TECDOC 0641 Geothermal Latin America 1993

IAEA-TECDOC-641
Estudios geotérmicos
con técnicas isotöpicas y geoquimicas
en America Latina
Actas de una Réunion final de coordination de investigaciones
celebrada en San José, Costa Rica, 12-16 de Noviembre de 1990
Geothermal investigations
with isotope and geochemical techniques
in Latin America
Proceedings of a Final Research Co-ordination Meeting
held in San José, Costa Rica, 12-16 November 1990
ORGANISMO INTERNACIONAL DE ENERGIA ATOMICA

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ESTUDIOS GEOTERMICOS CON TECNICAS ISOTOPICAS Y GEOQUIMICAS
EN AMERICA LATINA
GEOTHERMAL INVESTIGATIONS WITH ISOTOPE AND GEOCHEMICAL TECHNIQUES
IN LATIN AMERICA
OIEA, VIENA, 1992
IAEA-TECDOC-641
ISSN 1011-4289
Impreso por el OIEA in Austria

Marzo de 1992
PREFACIO
Publicamos en el présente volumen las memorias

presentadas en la ultima Reunion para coordinar las
investigaciones del Programa Coordinado de Investigacion
(PCI) del OIEA para America Latina sobre empleo de técnicas
îsotopicas y geoquimicas en la exploraciön de recursos
geotérmicos. La reunion se célébré en San José de Costa Rica
del 12 al 16 de noviembre de 1990 y se organize» con la
cooperaciön del Institute Costarricense de Electricidad, al
cual expresamos nuestro profundo agradecimiento.
Anteriormente se celebraron reuniones para coordinar las
investigaciones con el fin de examinar la labor en curso, en
diciembre de 1986 en el Instituto de Asuntos Nucleares de
Bogota (Colombia) , y en noviembre de 1988 en el Instituto
Ecuatoriano de Electrificaciön de Quito (Ecuador).
Cientificos de nueve paises de America Latina
(Argentina, Bolivia, Colombia, Costa Rica, Ecuador,
Guatemala, Mexico, Peru y Venezuela), que participaron en el
PCI, presentaron los resultados de sus estudios sobre el
terreno en la reunion de San José. Ademas de éstos,
cientificos de otros très paises latinoamericanos con
importantes recursos geotérmicos, que no participaron en el
PCI (Chile, El Salvador y Nicaragua), y expertos de Italia,
Nueva Zelanda y los Estados Unidos de America, que cooperaron
en la ejecuciôn del programa, asistieron a la reunion y
presentaron informes sobre sus actividades.
En términos générales, las investigaciones cientificas
realizadas en el marco del PCI del OIEA constituyen el primer
estudio geoquimico sistemâtico de los recursos geotérmicos de
America Latina. La reunion de San José permitio obtener una
panorâmica actualizada de las exploraciones de recursos
geotérmicos que se vienen efectuando en la région utilizando
la geoquimica e isötopos ambientales, que constituyen también
un instrumente geoquimico.
Los resultados estân ahora a la disposicion de las
autoridades nacionales interesadas, que deben decidir acerca
de la continuaciön de las investigaciones, especialmente en
el caso de aquellos campos geotérmicos en los que se han
obtenido resultados particularmente prometedores, habida
cuenta de una posible explotaciön con fines de generacion de
energia. La ejecuciôn de la siguiente etapa de las
investigaciones, que es mas costosa, y que puede incluir
sondeos exploratorios, podria demorar un tanto en aquellos
paises que disponen de fuentes de energia mas economicas,
taies como petröleo o centrales hidroeléctricas, o cuyos
campos geotérmicos estân ubicados en regiones remotas,
escasamente pobladas. Aun asi, consideramos que valiö la pena
llevar a cabo las investigaciones dado que contribuyeron a la
evaluaciön de los posibles recursos energéticos que podrian
utilizarse en el futuro, asi como a la capacitaciOn de un
numéro de geoquimicos latinoamericanos en el empleo de las
técnicas isotopicas y geoquimicas.
FOREWORD
We are publishing in this volume the papers presented at

the last Research Co-ordination Meeting of the IAEA Co-ordinated
Research Programme (CRP) for Latin America on the Use of Isotope
and Geochemical Techniques in Geothermal Exploration. The
meeting was held in San José de Costa Rica from 12 to 16 November
1990, and was organized with the co-operation of the Institute
Costarricense de Electricidad, which is warmly acknowledged.
Previous Research Co-ordination Meetings to discuss the work in
progress were held in December 1986 at the Institute de Asuntos
Nucleares in Bogota, Colombia, and in November 1988 at the
Institute Ecuatoriano de Electrificacion in Quito, Ecuador.
Scientists from nine Latin American countries, i.e.

Argentina, Bolivia, Colombia, Costa Rica, Ecuador, Guatemala,
Mexico, Peru and Venezuela, which took part in the CRP, presented
the results of their field studies at the San José meeting. In
addition to these, scientists from three other Latin American
countries with important geothermal resources, which did not take
part in the CRP, i.e. Chile, El Salvador and Nicaragua, and
experts from Italy, New Zealand and the United States of America,
who co-operated in the programme implementation, were present and
reported on their activities.
On the whole, the scientific investigations carried out

within the frame of the IAEA CRP constitute the first systematic
geochemical survey of the geothermal resources of Latin America.
The San José meeting provided an updated picture of the current
explorations of geothermal resources in the region using
geochemistry and environmental isotopes, which are also a
geochemical tool.
The results remain now at the disposal of the interested
national authorities, which have to decide about the continuation
of the investigations, especially for those fields where the
results have been particularly promising, in view of a possible
exploitation for power production. The next, more expensive
stage of investigation, which may include exploratory drillings,
might not take place soon in those countries which dispose of
cheaper sources of energy like oil or hydroelectric plants, or
where the geothermal fields are located in remote, scarcely
populated regions. Even so, however, we believe that the
investigations have been useful and worth being carried out,
because they helped to assess potential energy resources which
may be used in future, and to form and train a number of Latin
American geochemists in the use of isotope and geochemical
techniques.
NOTA EDITORIAL
Al preparar esta publication para la imprenta, el personal correspondiente del Organismo

International de Energîa Atômica ha montado y paginado los manuscritos originales facilitados par
los autores y ha procurado una présentation satisfactoria.
Las opiniones expresadas en las mernorias, las declaraciones formuladas y el estilo general
adoptado son propios de los autores citados. Dichas opiniones no reflejan necesariamente las de los
Gobiernos de los Estados Miembros o las de las organizations bajo cuyos auspicios se han elaborado
los manuscritos.
Las denominaciones concretas de paîses o territorios empleadas en esta publication no implican
juicio alguno par parte del OIEA sobre la condition juridica de dichos paîses o territorios, de sus
autoridades e institutions, ni del trazado de sus fronteras.
La mention de determinadas empresas o de sus productos o mar cas comer dales no implica
ningun généra de aprobaciôn o recomendaciôn por parte del OIEA.
Corresponde a los autores obtener el permiso necesario para reproducir textos ajenos sujetos a
derechos de propiedad intelectual.
EDITORIAL NOTE
In preparing this material for the press, staff of the International Atomic Energy Agency have
mounted and paginated the original manuscripts and given some attention to presentation.
The views expressed do not necessarily reflect those of the governments of the Member States or
organizations under whose auspices the manuscripts were produced.
The use in this book of particular designations of countries or territories does not imply any
judgement by the publisher, the IAEA, as to the legal status of such countries or territories, of their
authorities and institutions or of the delimitation of their boundaries.
The mention of specific companies or of their products or brand names does not imply any
endorsement or recommendation on the pari of the IAEA.
INDICE
Resumen del Programa coordinado de investigation .................................................. 9

Summary of the Co-ordinated Research Programme .................................................. 11
Reservoir characteristics of the vapor dominated geothermal field of Copahue, Neuquén,
Argentina, as established by isotopic and geochemical techniques .............................. 13
J.L. Sierra, F. D'Amore, H. Panarello, G. Pedro
Isotopic and geochemical study of the Domuyo geothermal field, Neuquén, Argentina ........ 31
H. Panarello, J.L. Sierra, F. D'Amore, G. Pedro
Flow patterns at the Tuzgle-Tocomar geothermal system, Salta-Jujuy, Argentina:
An isotopic and geochemical approach ................................................................ 57
H. Panarello, J.L. Sierra, G. Pedro
Informe geoquimico sobre la zona geotérmica de Laguna Colorada, Bolivia ..................... 77
G. Scandiffio, M. Alvarez
Geochemical report on the Empexa geothermal area, Bolivia ....................................... 115
G. Scandiffio, W. Cassis
Geochemical report on the Sajama geothermal area, Bolivia ........................................ 141
G. Scandiffio, J. Rodriguez
Geochemical and isotopic exploration of the geothermal area of Paipa, Cordillera Oriental,
Colombia .................................................................................................... 169
R. Bertrami, A. Camacho, L. De Stefanis, T. Medina, G.M. Zuppi
Isotopic composition and origin of thermal and non-thermal waters from the
Miravalles geothermal field, Costa Rica .............................................................. 201
W.F. Giggenbach, R. Corrales, L. Vaca
Modelo geotérmico preliminar de areas volcânicas del Ecuador, a partir de estudios
quimicos e isotöpicos de manifestaciones termales ................................................. 219
E. Almeida, G. Sandoval, C. Panichi, P. Noto, L. Bellucci
Avance de las pruebas de radiotrazado en el campo geotérmico de Ahuachapân,
El Salvador ................................................................................................. 237
W.J. McCabe, E. May en, P. Hernandez
Isotopic and chemical composition of water and gas discharges from the Zunil
geothermal system, Guatemala .......................................................................... 245
W.F. Giggenbach, D. Paniagua de Gudiel, A.R. Roldân Manzo
Investigaciones geoqufmicas realizadas en los campos geotérmicos de Zunil
y Amatitlân, Guatemala .................................................................................. 279
A.R. Roldân Manzo
Caracterfsticas geoqufmicas e isotöpicas de los fluidos producidos por los pozos
de Los Humeros, Puebla, Mexico ..................................................................... 307
E. Tello Hinojosa
Geochemical report on the Challapalca and Tutupaca geothermal areas, Peru ................... 345
G. Scandiffio, D. Verastegui, F. Portilla
Geothermal exploration by geochemical methods of the thermal area El Pilar-Mundo Nuevo,
State of Sucre, Venezuela 377
F D'Amore, G Gianelh, E Corazza, J Jauregui, P Varela
Origins of acid fluids m geothermal reservoirs 423
A H Truesdell
IAEA mterlaboratory comparative geothermal water analysis program 439
W F Giggenbach, R L Goguel, WA Humphries
Lista de participantes 457
RESUMEN DEL PROGRAMA COORDINADO DE INVESTIGACION
El PCI para la America Latina sobre el empleo de técnicas

isotöpicas y geoquimicas en la exploraciôn de recursos
geotermales se iniciö en 1984. Los recursos financières para
la ejecuciôn del programa fueron facilitados por el Gobierno
italiano, al cual el Organismo desea expresar su
agradecimiento. La primera actividad realizada fue el
seminario sobre el empleo de técnicas isotöpicas y
geoquimicas en la exploraciôn geotérmica, celebrado en junio
de 1984 en Morelia (Mexico) , en las instalaciones de la
Comisiön Federal de Electricidad, Gerencia de Proyectos
Geotermoeléctricos. Durante el seminario, al cual asistieron
représentantes de las instituciones que posteriormente
participaron en el programa, se examinaron los objetivos, las
principales lineas de investigaciôn y los campos geotérmicos
que se estudiarian durante el PCI.
Los primeros contratos de investigaciôn se adjudicaron
hacia finales de 1984. Los trabajos de campo empezaron en
1985 y continuaron hasta 1990. Durante la ejecuciôn del PCI
se estudiô un numéro considérable de campos geotérmicos, en
los nueve paises participantes. Mas adelante figura una
relaciôn de dichos campos. Las investigaciones efectuadas
fueron bastante amplias desde el punto de vista geoquimico,
en la mayoria de los casos, pero en algunos otros se
encontraban todavia en una etapa de reconocimiento cuando
finalize el PCI; estos Ultimos estudios no son tema del
présente documento, pero, en principio, se puede tener acceso
a los datos obtenidos solicitândolos a las instituciones
nacionales correspondientes. Si bien las investigaciones
utilizando técnicas geoquimicas convencionales ya se habian
iniciado en varios de los campos antes de 1985, los métodos
isotôpicos se aplicaron por primera vez en todos los casos
durante este PCI.
Debido a la localizaciön de muchos de los campos
estudiados en lugares remotos y de gran elevaciôn y a las
condiciones meteorolôgicas adversas durante prolongados
périodes del ano, las investigaciones no avanzaron
râpidamente; esa es la principal razôn de la duraciôn
anormalmente prolongada del PCI, que solo pudo concluir tras
mas de cinco anos de haberse iniciado.
Las zonas geotérmicas investigadas en el transcurso del
PCI son las siguientes:
Argentina; Volcan Copahue, Volcan Domuyo, Epulafqué, todos en
la provincia de Neuquén, zona occidental de Argentina;
Tuzgle-Tocomar en el altiplano del norte de Argentina,
provincias de Salta y Jujuy;
Bolivia: Laguna Colorada, Empexa y Volcan Sajama, en el
extremo occidental del altiplano boliviano y en la cordillera
occidental, cerca de la frontera con Chile;
Colombia; Paipa en la Cordillera Oriental;
Colombia-Ecuador ; Narirïo-Tufino-Chiles-Cerro Negro: lo que
constituye un solo campo geotermico compartido por los dos
paises;
Costa Rica; Volcan Miravalles en la Cordillera de Guanacaste;
Ecuador; Chachimbiro, Papallacta, Tungurahua, Chimborazo y
Cuenca, todos en la Cordillera Central;
Guatemala; Lago Amatitlan, Zunil, San Marcos y Tecuamburo, en
la Sierra Madré al noroeste de la Ciudad de Guatemala;
Mexico; Los Humeros, Estado de Puebla;
Peru; Challapalca, Paucarani, Calacoa, Calientes y Tutupaca,
Todos en la Cordillera Andina en el sur del Peru;
Venezuela; Las Minas, Mundo Nuevo y Aguas Calientes en el
Estado de Sucre, nordeste de Venezuela; Merida, Tachira y
Trujillo en la region andina en el oeste de Venezuela.
Los isotopos ambientales se utilizaron principalmente
para identificar el origen de los componentes del fluido
geotermico, la mezcla de aguas geotermicas con otras aguas, y
los procesos que ocurren en profundidad que producen
fraccionamiento isotopico, como por ejemplo, las
interacciones agua-roca y las perdidas de vapor. Por primera
vez se sugirio la presencia de una hipotetica "agua
andesitica", de una composicion isotopica bastante bien
definida, derivada del agua de mar transportada por
subduccion junto con sedimentos marinos en zonas de
subduccion (vease memoria de Giggenbach y otros, sobre el
sistema geotermico de Miravalle, Costa Rica).
La geotermometria isotopica se limito a unos pocos
casos, posiblemente debido a la complejidad de las
mediciones; no obstante, los pocos resultados disponibles
(Colombia, Mexico y Peru) confirman que el sistema de
sulfato-agua constituye un buen geotermometro, mientras que
los sistemas basados en componentes fluidos gaseosos
(metano-CO2 y metano-hidrogeno) probablemente reflejan el
equilibrio isotopico a la temperatura de formacion, que es
superior a la de la zona de almacenamiento geotermico.
Los analisis quimicos de los fluidos geotermicos se
utilizaron ampliamente en geotermometria, asi como paia el
estudio del origen y la historia geoquimica de los
componentes fluidos.
Otra actividad que vale la pena mencionar, organizada
poco despues del inicio del PCI, fue la intercalibracion de
los analisis quimicos de aguas geotermicas entre los
laboratories participantes en el PCI. Asimismo, laboratorios
de instituciones geotermicas de otros paises pudieron tomar
parte en el ejercicio. Los resultados de dicha
intercalibracion se dan a conocer en la ultima memoria de
este volumen.
10
SUMMARY OF THE CO-ORDINATED RESEARCH PROGRAMME
The CRP for Latin America on the Use of Isotope and

Geochemical Techniques in Geothermal Exploration started in
1984. The financial resources to implement the programme were
assured by the Italian Government, to which the Agency would like
to express here its gratitude. The first activity carried out
was a Seminar on isotope and geochemical techniques in geothermal
exploration, which took place in June 1984 in Morelia, Mexico, at
the premises of the Comision Federal de Electricidad, Gerencia de
Proyectos Geotermoeléctricos. During the seminar, which was
attended by representatives of the institutions which later took
part in the programme, the objectives, main research lines, and
geothermal fields to be studied during the CRP were discussed.
The first research contracts were awarded towards the end
of 1984. The field work started in 1985 and continued through
1990. During the implementation of the CRP a considerable number
of geothermal fields, the list of which is reported below, were
studied in the nine participating countries. The investigations
carried out were geochemically quite comprehensive in most cases,
but in some others they were still in a reconnaissance stage when
the CRP ended: the latter studies are not reported in these
proceedings, but the data obtained are in principle available
from the relevant national institutions. While investigations
with conventional geochemical techniques had already started in
several fields before 1985, isotope methods were applied for the
first time in all cases during this CRP.
Due to the remoteness and high elevation of many of the
fields studied and the adverse meteorological conditions during
long periods of the year, the investigations could not proceed
rapidly: this is the main reason for the unusually long duration
of the CRP, which could be concluded only after more than five
years after its inception.
The geothermal areas investigated in the course of this
CRP are:
Argentina: Volcan Copahue, Volcan Domuyo, Epulafquén, all in the
Neuquén Province, western Argentina; Tuzgle-Tocomar in the
altiplano of northern Argentina, provinces of Salta and Jujuy;
Bolivia; Laguna Colorada, Empexa and Volcan S a jama, on the

western edge of the Bolivian altiplano and on the Western
Cordillera, close to the border with Chile;
Colombia: Paipa in the Cordillera Oriental;
Colombia- Ecuador ; Narino-Tufino-Chiles-Cerro Negro: this
constitutes a single geothermal field shared between the two
countries;
11
Costa Rica: Volcan Miravalles in the Cordillera de Guanacaste;
Ecuador: Chachimbiro, Papallacta, Tungurahua, Chimborazo and
Cuenca, all in the Central Cordillera;
Guatemala: Lake Amatitlan, ZuniL San Marcos and Tecuamburo, on
thé Sierra Madré north-west of Ciudad de Guatemala;
Mexico: Los Humeros, state of Puebla;
Peru: Challapalca, Paucarani, Calacoa, Calientes and Tutupaca,

all in the Andean Cordillera in southern Peru;
Venezuela: Las Minas, Mundo Nuevo and Aguas Calientes in the

state of Sucre, north-eastern Venezuela; Mérida, Tâchira and
Trujillo in the Andean region in western Venezuela.
Environmental isotopes were mainly applied to identify the

origin of the geothermal fluid components, mixing of geothermal
water with other waters, and processes occurring at depth which
produce isotopic fractionations, such as water-rock interactions
and vapour losses. The occurrence of a hypothetical "andesitic
water", with a rather well defined isotopic composition, deriving
from sea water subducted together with marine sediments in
subduction zones, was suggested for the first time (see paper by
Giggenbach et al. on Miravalle geothermal system, Costa Rica).
Isotopic geothermometry was limited to a few cases,

possibly because of the complexity of the measurements:
nevertheless, the few results available (Colombia, Mexico, Peru)
confirm that the sulphate-water system constitutes a good
geothermometer, while the systems based on gas fluid components
(methane-CCU and methane-hydrogen) probably reflect the
isotopic equilibrium at the temperature of formation, which is
higher than that of the geothermal reservoir.
Chemical analyses of geothermal fluids were extensively

used for geothermometry, and for studying the origin and
geochemical history of the fluid components.
Another activity worth mentioning, organized shortly after

the beginning of the CRP, was the intercalibration of geothermal
water chemical analyses among the laboratories taking part in the
CRP. Also, laboratories of geothermal institutions of other
countries could take part in the exercise. The results of this
intercalibration are reported in the last paper of these
proceedings.
12
RESERVOIR CHARACTERISTICS OF THE VAPOR
DOMINATED GEOTHERMAL FIELD OF COPAHUE,
NEUQUEN, ARGENTINA, AS ESTABLISHED BY
ISOTOPIC AND GEOCHEMICAL TECHNIQUES
J.L. SIERRA*, F. D'AMORE**,

H. PANARELLO***, G. PEDRO*
* Ente Provincial de Energîa del Neuquén,
Neuquén, Argentina
**Istituto Internazionale per le Ricerche Geotermiche,
Consiglio Nazionale delle Ricerche,
Pisa, Italy
*** Institute de Geocronologia y Geologfa Isotöpica,
Buenos Aires, Argentina
Resumen-Abstract
CARACTERISTICAS DE ALMACENAMIENTO DEL CAMPO GEOTERMICO DOMINADO FOR LA

FASE VAPOR DE COPAHUE, NEUQUEN, ARGENTINA, ESTABLECIDAS MEDIANTE TECNICAS
ISOTOPIC AS E GEOQUIMICAS.
El caiapo geotérmico de Copahue-Caviahue, se puede définir como

del tipo "dominado por vapor" con estratificaciôn horizontal y capas
conectadas por fracturas y buena permeabilidad vertical dentro del
reservorio.
Los isôtopos oxigeno-18 y deuterio, asociados con anâlisis de
gases y el estudio de la evoluciôn de la relaciôn gas/vapor, permi-
tieron demostrar la existencia de por lo menos dos nivelés producti-
ves: el was superficial a unos 800-1000 m y el mas profundo a mas de
4000 m (todas las medidas respecte de la boca de pozo).
Las temperaturas obtenidas por métodos quimicos e isotôpicos ron-

dan los 200° y 250°C para la capa mas superficial y mas profunda res-
pectivamente.
Los valores de carbono-13 y las concentraciones de NZ, He y Ar

caracterisaron los gases acompanantes como principalmente magmaticos.
RESERVOIR CHARACTERISTICS OF THE VAPOR DOMINATED GEOTHERMAL FIELD OF COPA-

HUE, NEUQUEN, ARGENTINA, AS ESTABLISHED BY ISOTOPIC AND GEOCHEMICAL
TECHNIQUES.
îhe geothenal field of Copahue has been defined has vapor dominated field tiith stratified layers con-
nected by fractures »ith good vertical peneability vithin the reservoir.
2
H and J< 0, associated gas analysis and the study of the gas vapor ratio, alloyed to prove the existence of at
least i?o productive layers, the shallower at ca. 800-1000 t and the deeper at sore than 1400 a (both bellon the
sell top level).
Isotopic and geotheraosetric teeperatures are rounding 260'C and 250'C respectively, HC, H}, àr and Se analyses
allotted to hypothesise the origin of geothertal gases.
13
l. INTRODUCTION
1.1. LOCATION AND GEOLOGY
The area of Copahue is located in the AW sector of the Neuquén

province (Argentine Republic) near the border with Chile. The latitude
is ca. 37 deg 50' S. and the longitude about the 71 deg 0.5' N. It
cover a zone on the Andean Cordillera between 1600 and 2300 m a.s.l.
Domuyo
Copahue \*fj^";,'
FIG. 1.
The climate is Patagonic, and that of high mountain, depending of

the altitude, with snow and rain precipitations from autumn to spring,
and vinds prevailing from the AW. (Pacific ocean).
The effusive complex Copahue-Caviahue started to develope in the

Pliocene and its eruptions originated the large lavic mantle of the
Hualcupen Formation. This episode Mas over with the formation of a 17
km average radius calders.
Because of the draining, result of the continous magmatic activi-

ty and to the great explotions produced by variations in the dynamic,
all the volcanic building was seated. This fact determined that the
bottom was constituted by numerous fragmented blocks that originate an
14
area of high permeability. Latter a diastrophyc phase allowed the ac-
cumulation of lacustrine sediments in the base of the caldera. A fur-
ther magmatic evolution originated an effusive focus that produced
lavic flows covering the bottom of the system. The location of this
effusive focus would have been in the nearness of the volcano Copahue
and is known as Las Mellizas Formation.
During the Pliocene-Holocene the magmatic activity continued,

leading to new effusive points, favoured by the deep dislocations in
the border of the caldera that produced a set of périphérie eruptions.
This postcaldera volcanism can be classified into three effusive sta-
ges. The last one is represented by the Copahue volcano.
In the area two wells have been drilled: COP-1 and COP-2. The
former was drilled in March 1982 reaching 1414 m depth and lead to the
discover of a géothermie reservoir producing dry vapor. Two productive
levels have been detected, one between 800-900 m and a second into the
well bottom. The COP-2 was finished in 1986 with a total depth of 1236
m and is producing dry vapor of similar characteristics of COP-1 from
the shallower layer.
2. METHODOLOGY
Information available in the ENTE PROVINCIAL DE ENEBGIA DEL NEU-
QUEN (EPEN) i.e. production curves, build ups, pressure and temperatu-
re records of COP-1, COP-2 as well as chemical analyses of geothermal
manifestations and wells was recovered.
During three field trips performed in the 1985/1987 period, were

sampled and analysed COz, H2S, HZ, CH4, NZ, Ar, He and CO on gaseous
samples (tab. 1 and 2).
pH, alkalinity, majoritary ions, Fez +, Fe3 + , SiO? and Li+, stable
isotopes-' deuterium, oxygen-18 and tritium contents were determined on
vapor condensâtes, cold and hot waters (tab. 3 and 4). In addition
carbon-13 was measured in CÜ2 coming with gas in wells and selected
toani fes ta ti ons.
The large number of analysis and the high precision achieved,
allowed to distinguish the productive layers, to calculate the
physicochemical conditions within the reservoir, and to reformulate
the geothermal field model. Based on this model, a third exploration
well is being drilled (COP-3) and is intended to reach 1800 m below
top well level in order to verify the results of this work.
15
1 .
Z 0
o T UJ ( (Tl
n o T N O O O Q Q r- Ü. i
•-H T in m O Q co LÜ
1
O
"X
a Pi o rH « N , T CE
CE CO CT' O -
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ri rH
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0 o (0 o cr> o O a
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0 D pH T
r a rH IO Z •
CO kü O
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pH _i o in M o
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pH CO (T' O CO ro T pH
Z X Q a> 'N C?
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X
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z <N
n O T m ^
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JURI
er O O rH rH
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REFERENCES:
m
> S i: C n
UJ a. a. a. -- in
-- - -- --
u. u. ü.
CE •j UJ ^ ^ i" n
O T t ^
r^ fj ^ c c
N X 1- 0 UJ Z ;>, ;j CL. a. û.
0 X I. U Z X <J ÜJ irf w ;^; v ;-j CL CL a
oE OC v/ V l-* \j \^
Q UJ OJ '/i T
u. O OJ I OJ l. ç i*^
UJ o I r z <X i. U
ce.
16
N° 3: CHtniCfiL flND ISOTOPIC flNflLVSIS OF CONDENSEES ONO COLD ONO HOT UWrERS C>O .
: SAMPLE i LOCRÎION ; r : rvPE ! F» 1 5i02 ! N« : K ! Li

: <°o : ! H «.«.1.1 «O : e.V.. > ; <T.u.y ; : ng/l : «g/l : «g/i : «q,a : «.3/i1 «g/1 ! ng/1 ! w g / 1 ' Hg/1 ! Mg'l
icopH-i s: L« rUqumit« ; 130 I Y.por ! : -10,8 :-84,2 !O,8+/-0,7: ! ! I ! I
ICOPfl-2 ft! Poro COP I 1 242 I V»poi-: 2000 : -9,6 ; -82,7 :o,6«/-o,7i : : : : i
:CÛPfi-3 H! L« riiqum«- ! 8S ! V*por ! i -10,6 I-85,1 :o,o»/-o,6: : : : ; :
: COP«-« : Ffrrugi no** ' 51 î Liquid : 2000 : -11,9 : -84,7 : t,7«/-C,7: 5,9 ! 489 13 : 19 ! S9 I 29 : , o, i : • : i
:copfl-5 ; Sulûro* • î 61 î " . 2020 : -11,9 : -84,2 :2.5>/-0,7! 6,6 1 474 12 13 : SI : 30 . o,iu: 90 : 53 : 23 : o,0b
: copfl-e. ; d«-i rut» :si,s: : 2020 : -n,9 ! -84,3 ! I 5,9 I 282 1 < 1 1 23 : 39 ! 13 : o,i8 : 100 38 ; 19 : < u.os
: copfl-7 :d* Vi cKy I 3*1 ! " ; 2010 ; -12,0 : -84,3 :3,3»/-0,7l 5,9 ! 287 ! 2 ! 12 1 61 : 9,5 ,0,1 i so : 19 : 6,2 :< 0,05
: copn-6 ifto- d» lo* &*Ros ! ! " : 20-40 -11,8 : -83,3 !2.4»/-0,71 6 , 9 ! 286 12 ! 12 1 52 1 20 ; 0,28 ; 71 ; 24 : 7,8 I < 0,05
: ; -12,2 :
1 1 1 . >
l f rtpu 1 ^ ' / 1 L » ... : 2010 : -11,9 l -84,6 :3,6*/-o,7: i ; : : :
:copfi-i3 ; flgu-i d«*l vol c-in î 30 ! " : : -3,7 : :o.9./-0,7! : : : :
: copft-20 ; Cc.p-.hue ! : V.por ; : -12,8 ; -90,2 : : : : : : : : : : : i
:cwi-i !flgu* d«- conxuHO ! i
13 I Liquid ; -ii.s : -81,7 !3,9./-o,4: : : : : : : : ! i !
: ravi -2 !run..»*:!-! ; 7 : » : ; -13,5 : -97,2 !1,3»/-0,4: 6,2 ! : i i 1 : : : , :
:CfWI-3 ! n*n-anti «1 Loncopu*! 10 ! " ! 1424 ; -12,9 !-92,5 :4.s*/-o,4i 6,6 ! : : : : i ; : : :
;ciwi-i i C«£C*d* Excondzd* I 12 ! " ! 1670 ; -11,3 : -8i,9 ;3.6»/-o,s: 6,8 ! 21 : -i : 13 : 2,9 : 2,4 : ; 12 : 2,9 : 0,8 :< o.os
H'flF-l ! V»rti»nt* ! 8 ! ; : -12,5 :-90,1 if,8»/-o,7: : : i : ; : : : : ;
! WF-2 ! n»n«ntl»l ! 10 : : 1670 : -12,9 :-93,5 !3,2*/-0,7: 7,4 : 42 ; ' 1 1 <S : 3.3 ! 1,2 : 0,25 : 20 : 5.3 : 1,7 : <. o.os
!WF-3 ! n.n.ntl»l ! 11 ! ! 1674 : -13,6 : -94,5 ! 1,8«/-0,7! 7,1 ! 30 < 1 ; <S 1 1,8 : 0,9 0,1 : 20 : 3,6 : 1,7 ! < o,os
C>O Ch«-nic»l ftn«lylis: flPft-EPEM. Isotop] c fln«lyin: INGEIS.
TRBLE N" 1: ISOTOPIC HNftLVSIS OF COP-1 RNO COP-2 UELLS.
COP-1 COP-i
DfirE : s/ei : i/85 : u/86 : 1 1/86 ! 1/87 DOTE i 1/86 :

I 3/86 ! 11/86 : 1/87
REFERENCES: OURIO ; INGEIS : INGEIS : IIRG : INGEIS REFERENCES; INGEIS ! INGEIS : IIRG ; INGEIS
Oxyg.n-13 : -10.5 ! -9.6 ; -8.3 : -8. .2 : -9.1 QHyg.n-16 : -10.8 : -7.6 ; -7.7 ; -lO.l
o»u-t*i-i ,JM ; -81 : -33 : -78 : -76 1 D»ut»r-jLUM ; -es ; -si ; -83 :
3. RESULTS AND DISCUSSION
3.1. METEORIC WATER LINE
As established by Panarello et al., 1988, cold samples CAVI-1-2-

3-4, VAF-1 and COPA-4-5-6-7-8-9 fit closely the average world meteoric
water line defined by Craig (1961) i.e.
62H - 8 + 10 o/oo
Othervj.se doesn't exist a good correlation between isotopic com-

position and altitude due mainly to the following:
- Precipitation mainly as snow.
- Hest origin (Pacific) of the vapor mass that make the altitude
gradient reverse.
- Small altitude differences that do not allow the sampling of
the water at a well established height. (Panarello et al . , op
ci t)
Vapor condensate samples are shifted in oxygen-13 and define a

line that intercepts the m.w 1. in the isotope composition of waters
feeding the system This waters would have infiltrated at highly frac-
tured area known as "El Anfiteatro" (fig. 8).
3.2. CALCULATION OF THE PHYSICOCHEMICAL CONDITIONS INTO THE

RESERVOIR
As it is showed in fig. 2, static pressure and temperature profi-

les in the bottom of the COP-1 well (the well then has collapsed) it
is possible to differenciate two zones into the reservoir. The former
PRESSURE P (bar)
T
-200 -
D -400
e
P
t
h -600
i
n
m -800
0
t
e
r
8 -1000 -
-1200 -
ont or i
-1400
i BAKU Qias* nun BM i
90 110 130 150 170 190 210 230 250

Temperature ( C)
FIG. 2. COP-1 static pressure and temperature profiles
18
between 800-1000 m »ith a temperature between 195'C and 220'C and the
second at 1400 m, a temperature of about 250"C and static pressure of
4 MPa. This is the last information available that is then compared
with those obtained through chemical and isotopic considerations.
Q ( In/h) g/t (IN/K« yapor)

25 80
50
20
i
40
15
BX\ Eb
30
10 ^——
20
P- 8 ata
5
10
C
0 i i i i i 0
3/8 1 1/82 1/83 1/84 1/85 1/88 1/87 YEARS
— - Q (tn/h) n g/v (m/Kg vapor)
FIG. 3. COP-1: production and gas/vapor ratio.
Q (ta/h) I/Y (IN/Ki vapor)
5 -
3/86
(IN/Kg vapor)
FIG. 4. COP-2: production and gas/vapor ratio.
19
-IÛO .45
HSH = 3 log I H 2 S / H 2 0 J - t o g ( H 2 / H 2 0 >
FIG. 5. FT-HSH diagram (D'Amore and Truesdell, 1985).
In the FT-HSH diagram (fig. 5) (D'Amore & Truesdell, 1985) all

gas analyses and gas to vapor ratio available are plotted in order to
calculate temperature (T°C) and vapor fraction (Y) simultaneously.
It should be taken into account that the gas/vapor ratios are not
accurate because oftently are measured in the well without to stabili-
ze. In addition the method reflects a very located situation and not
that of the whole reservoir, since it is based in the gas/vapor ratio
in the influence area of the well.
20
The advantages are that there is no need of measuring the CO con-
centration to calculate the temperature, and the method shows an ap-
proximate historical evolution.
For the «ell COP-1 at the beginning of the production (1982) a
temperature T= 175°C and a vapor fraction Y= 1 is computed. This fact
can be interpreted as a "gas cap" as observed in The Geysers, geother-
mal field (Box, 1987). That cap has been consumed, probably, during
the first months of production.
The results in February, 1985 were: T= 195-200'C, Y= 0.7. This
situation came as a consequence of the loss of the "gas cap" and the
further production from a biphasic system. Then the yield of this well
fall down in 40 % and simultaneously a shift towards more positive
values in deuterium and oxygen-18 was observed, indicating that the
shallow reservoir was becoming exhaust.
In November, 1986, when the well was reopened, after to be closed

by 10 months, a temperature of 200-205°C and a Y= 0 25 are calculated,
an increase in the production was observed. This could be explained as
the contribution to the production of the residual liquid from the
precedent exploitation. The calculated value of temperature doesn't
indicate a deep contribution. This hypothesis is in agreement with the
more positive values of oxygen-18. Also must be noticed that the H 2$
value is the same in 1982 and 1985 (0.4-0.5 %) .
In April, 1987 an strong increase in the HzS content (1.0 %) was

observed. The calculated temperature T= 245-250°C, Y= 0 45, and a re-
turn to more negative oxygen-18 values correspond to the depletion of
the residual liquid (the yield also declines) and to the existence of
a deep contribution. The discharge declined because there is no good
connection between both reservoirs. The gas/vapor ratio increased to
2-5 % due to the deep contribution of gas and vapor First migrate the
residual liquid, then the vapor and the deeper gas (fig. 6).
Q (lu/h)
30
20 r««Jdaal l
2/83
d««p contribution
•xhaarta
4/VI
HZ* - 1.0 (COP-2 nlu« 11/6«)
10 T T» wo c
2/88
-11 -10.5 -10 -9.5 -9 -B.5

-8 -7.5 _™
Delta Oxyieu-18 (X.)
FIG. 6. COP-1: production vs oxygen-18.
21
For the »ell COP-2 on March, 1986, a value of T= 200°C and Y= 1
is obtained (similar to the beginning of COP-1) and is also producing
from a shallow reservoir
On November, 1986 when the well was reopened and assuming Bg/v-
1.6 x 10-3 a temperature T= 235"C an Y= 0.03 is calculated. This va-
lues do not correspond to the "gas cap" but to a residual liquid cha-
racterized by high oxygen-18 values and a deep contribution of gas and
vapor.
In April, 1987 an strong decrease in the discharge was observed

A temperature T= 235"C and a vapor fraction Y= 0.35 is computed. Ta-
king into account the analytical error the COP-1 and COP-2 show the
same local origin; mainly deep (vapor and gas).
In addition, also in the COP-2, the oxygen-18 value became more

negative, indicating that the residual liquid has been fastly removed
In fig. 7 the evolution of the gas/vapor ratio vs the delta oxy-

gen-18 is showed for the COP-1 and COP-2 wells. The evolution for both
from the beginning (vapor cap) until November, 1986 (when they were
reopened) fits on a straight line (I)
Ca«/Vnpor (IN/Kg vnpor)

60
3/6«
v ' «« T«por cap
.S/W
40 -
dwp «xmlrlbuliem
of f«« uid Tmpor
30 -
20
10 -
rmidiua Uifoll
production \\
____o "/•• ^ o
-11 -10.5 -10 -9.5 -9 -8.5
-8 -7.5
Delta Oxygen-18 (X.)
A
COP-1 0 COP-2
FIG 7. Gas/vapor ratio vs oxygen-18.
In fig. 8 (o*H vs $1*0 plot) the evolution for the COP-1 well,
starting from its drilling until it was reopened November, 198fi is
plotted. COP-1 follows a line with a slope of about 200°C and then the
values became more negatives. The same evolution is observed for the
COP-2 well, but with a slope of 210-220'C, in shorter intervals, indi-
cating that the shallower reservoir is smaller
Using the chemical analysis of gas sampled in November, 1986 some

physicochemical parameters of the fluid in the reservoir were computed
with a methodology proposed by D'Amore et al, 1987
22
Delta Deuterium (%.)
-60
-70
11/88
-80
-90
-100 -
-110
-18 -17 -16 -15 -14 -13 -12 -11 -10 -9 -B
Delta Oxygen-18 (%.)
A
'" Las Maquinitas COP-1 ^ COP-2
FIG. 8. Deuterium vs oxygen-18.
They are: minim T("C), maxim T('C), C02 pressures (PC02), vapor
fraction (Y), gas/total water ratio (g) and redox conditions (pO2 and
pS2).
In table 5 maxim and minim temperatures calculated through CO
analysis are presented. It roust be noticed that all the samples shot?
the temperature of the shallower reservoir, excepting that of the COP-
2 (T= 240°C) that was already producing from the deeper layer
Table 6 exhibits the maxim values (method without CO to fixed
temperatures). Two temperature values are presented: that without (*)
is a assumed one, that with (*) is a maxim value. The value of the
gas/total water ratio in. the reservoir has two different significate
according to the temperature considered. The corresponding to max T
represent an almost total evaporation into the reservoir, for instance
at the COP-1 is similar to the gas/vapor ratio measured at the well
top.
The maxim temperature calculated for November, 1986 for the COP-1
is 200 °C in agreement with that estimated by other methods, as resul-
ted from a shallow production. Conversely for the COP-2, Tmax= 270"C is
accounting for the deep contribution. A value of Y- 0.046 (Sl = 0.30)
complete the conditions of the deeper reservoir (1400 m).
"Las Maquinitas" and "Las Maquinas", exhibit a Tmax= 208-216°C
indicating that the main contribution is from the shallower reservoir.
At the area of the "Termas de Copahue" the value of Tmax- 245°C indi-
cate a strong deep con tri bution.
By using the diagram PC02 vs T (fig. 9) for the sampling of No-

vember, 1986 for "Las Maquinitas", COP-1 and COP-2 is possible to see
that the points are aligned on the equilibrium straigh line:
Muscovite (and clay minerals) + Calcite + Quartz =
K-Feldespar + Epi do ta (Xps- 0.275)
in full agreement with the minerals observed during the drilling above
850 m. Assuming the PC02 calculated using the gas/vapor ratio from
23
a
a
PROXIPO C f l R R E T E
CD) PROXIMO CflRRETERR
CL
UJ D
Q Z
a
1-1 UJ
L_
»^J
OBSERVRTIONS
LIMON
rtftQUINrïTRS
CDJ
u z
MftQUINrtS
UJ
LU
t/1 o
S tlBQUINITfiS
RIO BLflNCO
o u
Cfl)
D
o z
DEL
CQ
JRE C 11/86)
S MflOUINflS
v/
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t- «a er
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03 LP (V p-
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LO ro in LP LO IP LO in a
'/l
û. T T O 0? --* o CD in O T o
i 1 oi in T •N
u in
N UO N fO U) ~+ <£• CO CD
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X a i i
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u o OJ or OJ OJ u. '/l 0
T ro T T T T l/) 1)^ •-0 in ro T
?iC CO CQ H h-*
r
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z
u
CL 1 i 1 \ i J-
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rj
D
T IN
IN N
1 1
r- in
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r CO CM 2 ("0 [v ? £ o S LP
CO
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X ÛT
t- OJ eo O) OJ rv T OJ ^ tj a: UJ O K<
o i 1 ! 1
1
1 1 1 o Jj O HI n 'jd O) OJ N «i cr< o et a:
UJ '
i"0 ÛO r- T r-l O"1 Cv f •- CG ("0 T T
1- D •H V^ CL
fO LO ,-t 1J- CO -H .£,
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X UJ M
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w cö
'Ï? CC i tT' fO T £ UV T /O CD CO Cö 5 Z _J O
CT> UJ ^ r-< JV 0 -l O T o in T O CD UJ M CÜ 8
10 en O M l/l
_J UJ _J '/l X
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O o o o O O o o o O O oo -N O oo Q
oo LP tP O Z O »-H UJ
fO N Q r^- •-< ro o a. je ij
o T T in 10 LO U> T CD ro T l/> CO CO o a _i
o w r er
Q U. ^> X Z1 UJ
'J1 r- l—l CO g •£ ^ ^^ a t- V- X Q
T T ro T UV T Œ a t~ uj
u 0 0 o 0 0 O 0 0 UJ 3 t-* UJ ^P. O
a _i a a M uj
n^ t- x: a
Û. n^ o x x X K X X X CD UJ U CC
LU a: 0 0 U 15 0
(TV (p mN 0 0 o^ p- OJ T
X O N in LO p- o T •N
3 /~ O =•
i- cc n *• OJ CJ f-H
0 0
O4 f -4
CO O C Œ
i- ^ :> u
K O T o O o <r <r j- M x x
UJ O IH nn
O o. i; a c M UJ X
0 n ^ uj 4» 'S. UJ X 1-
UJ t- UJ a CÛ O a cr x »- (-.
\- i- o a r a. Q. OJ r-j ro CD T 1= V- ^ 3
nr 3 O
>-* û i: ~ * W
I i er u LJ Œ M <r tr «
û. O. OJ N CD T n oon
O O u u o O 0 ro (J
CJ U u x
X X
X X I *
24
R E F E R E N CES
o COP l
LAS MAQUINI1AS
LAS M AQUINAS
COP l 11/86
DEEP RESERVOIR P(C02)

SIMULATED g/v 1987-2SQOC
10
1987 and T= 250 °C a reaction of equilibrium where PCO^ would be con-
trolled by the equilibria of the alteration minerals Epidota and Pre-
nhite is obtained (cross in the diagram)
3.3. HYPOTHESIS ON THE ORIGIN OF THE INERT GASES

The values of 813C obtained in 1985 from Las Maquinas - -10 7
o/oo, Las Maquinitas --68 o/oo and COP-1 - -10 9 o/oo range bet-
ween -7 and -11 o/oo approximately These values are typical of active
volcanic zones, where could have existed the following interaction
during the magmatic activity
Calcite + Silicates = C02 + Hollastonite (Ca-Silicate)
Epstein and O Neil showed that this reaction produce a carbon

isotope fractionation leading to more depleted values in the ramaining
cal cite The shifting to more negative values depend on the degree of
progress of the reaction
If the relative quantities of N2 Ar and He are considered is

possible to see the following
1 The Nz/Ar ratio, taking into account all the sampled manifes-
tations and wells range from 300 to 1000 The value for the meteoric
water recharging the system is close to 40 Therefore could be said
that the N2 and the Ar are not from atmospheric origin
2 In the diagram (fig 10) the position for the points corres-
ponding to all the samples indicates a strong deep magmatic contribu-
tion that can explain the primary origin of the N2
N 2 /1CO
1 COP I
2 COP a
3 LAS MAQUNIJAS
i LAS MAQU NAS
Hex 10
FIG 10 Relative N2, He and Ar contents m geothermal gas discharges
26
4. CONCLUSIONS
Based on isotopic and chemicals considerations and on the produc-
tion data, the following conclusion can be established:
- Copahue is a typical vapor dominated geothermal field, where

the pressure into the reservoir is fixed by a biphasic (vapor/
liquid) system (Sierra. 1981).
- This kind of reservoir have been proposed by D'Amore (1979) and
confirmed in deep perforations at the Geysers by Box (1987) and
in Santa Lucia Island by Aqua ter. They are characterized as
stratified systerns.
The reservoir is constituted by several productive layers se-
parated by low permeability zones. The productive layers have
différents physicochemical characteristics and productions. For
the Copahue field, a first level with the following characte-
ristic have been established:
Depth - — ---------- — - 850 to 1000 m

Temperature ---------- 200 to 215'C (excluding the primary
gas cap)
v — — _ — — __ — — — _ _ __ _ _
1 _ _ __ nL / .nff O C ' Ln/ . É*?j
L / C I y-,-i
PC02 --- ----------——— 50 kPa
Production data for the COP-1 and COP-2 indicate that the sys-
tem has been quickly depleted.
The shallow reservoir would have a low lateral permeabylity,

thus the original fluid, near COP-1, would have undergone a
strong drop of pressure, gas and vapor loss (lowering of the
gas/vapor ratio and the discharge) due to the exploitation.
Also shows an isotopic enrichment, mainly in oxygen-18, and a
relative decrease of soluble gases.
After the reopening of the COP-1 and COP-2 wells in November,
1986 the first fluid produced by the COP-1 was originated in a
local residual liquid (condensate) that migrates laterally to-
wards the well. In addition for the COP-2 a deep gas and vapor
source contributed to the production.
The local liquid is fastly consumed, and after five months both
COP-1 and COP-2 fluids exhibits characteristics belonging to
the deep level (below 1400 m) with the following thermodynamic
pa rame t ers •'
Temperature ----- —— — - ————— _ _ _ _ 250-260 °C

Discharged vapor temperature ----- 200-220°C
Vapor fraction ----—-——-—------ 0.03-0.05
G/V ratio ----------------------- 20-30 L.N./kg
T>nn« _ _ _ _ _ _ _
IT \~t\J % _ _
—_ _ _ _ _ _ _ — _______ —— _ ~~ J_1 nn~
U U ?nn
& U U I-Pêt
J\.JT
H2S/H2 -------------------------- > i

018Q --------------------------- -10.0 0/00
The future COP-3 well would must find a fluid with this
characteristics typical for a vapor dominated system of high
enthalpy. In order to explain the present discharges of COP-1
and COP-2 a system with good vertical permeability must be
assummed (fig. 11).
27
PHASE I VHPUR ERS
g
i '" • """"" • • ' • " ":
FIRST LEUEL T =3an-2Q5
y + G ^^ L V: D.QS -D.2
==J> =l> 3= _ r : 3,5

<F=
jîm
xxy--vfoxxfi;:xxxx«»:^>fixxrex*>y^
SECOND LEUEL
L » <J * G
PHASE II
y
LEVEL
V = U dti
X^RESIPUBL LIQUID 's-..
SECDrtD LEytL .^ R?-.

'_ » U » G T =2SD-SBD_ n
v = D -Ü3 - Q..Û5
L: LIQUID
G: GRS
Y: URPDR
FIG. 11. COP-1 well (evolution).
àciaosledgtKstts - Tiis sork has been perforted sithin the fraiesork of tie làSt Coordinated Research Prograne on the
application of Isotope and Geocheiical Techniques in Geothertsl Exploration in Latin iierica (Research Contract N'
39S8/IG), financially supported by the Gorerntent of Italy.
REFERENCES
Bolognas! L. , Noto P. e Nuti S. (1986) Studio chimico ed isotopico

della solfatara di Pozzuoli: ipotesi sull 'origine e sulle tempera-
ture profonde dei fluidi. Ftendiconti Soc. It. Min. e Petr. , 41 (2),
pp. 281-295.
Box H. T., D'Amore F. and Nuti S. (1987) Chemical and isotopic com-
position of the fluid sampled during drilling at The Geysers (Ca,
USA). Int. Symp. on Development and Exploitation of Geothermal Be-
sources, Cuernavaca, Mexico, oct. 5-10, in press.
D'Amore F. and Truesdell A. H. (1979) Models for steam chemistry at

Larderello and The Geysers. Proc. 5th Workshop Res. Eng., Stanford
University, pp. 283-293.
28
D'Amore F., Celati B. and Galore C. (1982) Fluid geochemistry appli-
cations in reservoir engineering (vapor dominated systems). Proc.
8th Workshop Res. Eng., Stanford University, pp. 295-308.
D'Amore F. and Gianelli G. (1984) Mineral assemblages and oxygen and
sulphur fugacities in natural water-rock interaction processes. Geo-
chim. et Cosmochim. Acta, 48, pp. 847-857.
D'Amore F. and Pruess K. (1985) Correlations between vapor satura-

tion, fluid composition and well decline in Larderello. 10th Work-
shop Bes. Eng., Stanford University, pp. 113-121.
D'Amore F. and Truesdell A. H. (1985) Calculation of geothermal re-
servoir temperatures and steam fractions from gas compositions. GBC
Symp. on Geothermal Energy, Kona, Hawaii, 9, pp. 303-310.
D'Amore F., Fancelli R. and Saracco L. (1986) Development of a me-
thodology for measuring CO and its geothermometric applications.
Part J. Model development. CNR Report to European Communities (Con-
tract 0022-1).
D'Amore F. and Truesdell A. H. (1986) A review of solubilities and

equilibrium constants for gaseous species of geothermal interest.
Appendix to CNR 1987 Report to European Communities (Part II),
(Proposal A2/083/I, Contract 0022-1).
D'Amore F. , Fancelli R. , Mussi M. , Saracco L. , Caprai A. , Calvi E. ,

Del Chicca G. (1987) Development of a methodology for measuring
carbon monoxide and its geothermometric applications (Part II). CNR
Report to European Communities (Proposal A2/083/I, Contract 0022-1).
D'Amore F. (1987) Some geochemical techniques for reservoir tempera-
ture computation. Int. Symp. on Development and Exploitation of Geo-
thermal Resources, Cuernavaca, Mexico, oct. 5-10, in press.
D'Amore F., Fancelli R. and Saracco L. (1987) Gas geothermometry

based on CO content. Application in Italian geothermal fields. Proc.
12th Workshop Res. Eng., Stanford University, in press.
D'Amore F., Sierra J. L., Panarello H. (1988) Informe Avance del
Contra to de Investigaciôn 01EA N° 3988/IG.
Jurio R. L. (1977) Caracteristicas geoquimicas de los fluidos terma-

les de Copahue (Neuquén - Argentina). Principales implicancias geo-
térmicas. Apartado de la revista "Mineria", N" 172, 11 pp.
Mas L. C. (1986) Estudios petrogrâficos de minérales de alteraciôn y

algunos parâmetros fisicos sobre rouestras de roca de perforaciones.
Informe CNR - Int. School of Geo thermies. IIRG, Pi sa.
Panarello H. 0. , Levin M. , Albero M. C.,
Sierra J. L. and Gingins M.
0. (1986) Isotopic and geochemical study of the vapor dominated geo-
thermal field of Copahue (Neuquén, Argentina). Int. Meeting on Geo-
thermics and Geothermal Energy, Guaruja, Brasil, 10-14 äug. 1986, 16
PP. (A).
Panarello H. O. , Sierra J. L. , Gingins M. O. , Levin M. y Albero M.
C. (1986) Estudio geoquimico e isotôpico de los sistemas geotermales
de la Provincia del Neuquén, Repûblica Argentina, primera parte:
area Copahue. Informe anual de avance del contrato OIEA N" 3988 IG.
(B).
Saracco L. and D'Amore F. (1988) C02B, a computer program for

applying a gas - geothermometer to geothermal systems. Submitted to
Computers and Geosciences (Pergamon Press).
29
Secretarîa del COPADE (Provincia del Neuquên) (1982) Consideraciones
brèves sobre antécédentes hidroquîmicos de vertientes, condensados
acuosos y gases no condensables del area geotérmica de Copahue
(Neuquên - Argentina). Informe LATINOCONSULT - ESIN S.A., 59 pp.
Secretarîa del COPADE (Provincia del Neuquên), LATINOCONSULT - ELC.

Estudio de factibilidad geotérroica en Copahue: primera etapa. Infor-
me COP-I-5284.
Sierra J. L., Gingins M. 0. , Panarello H. 0., Levin M., D'Amore F. y

Gianelli G. (1986) Estudio geoquimico e isotôpico de los fluidos
geotermales de la Provincia del Neuquên. Informe de avance OIEA
(Convenio N° 3988/IG), nov. 1986, 15 pp.
Truesdell A. H., Haizlip J. P., Box H. T. and D'Amore F. (1987)

Fieldwide chemical and isotopic gradients in steam from The Geysers.
Proc. 12th Workshop Res. Eng., Stanford University, in press.
30
ISOTOPIC AND GEOCHEMICAL STUDY OF THE DOMUYO
GEOTHERMAL FIELD, NEUQUEN, ARGENTINA
H. PANARELLO*, J.L. SIERRA**,

F. D'AMORE***, G. PEDRO**
*Instituto de Geocronologfa y Geologfa Isotopica,
Buenos Aires, Argentina
**Ente Provincial de Energfa del Neuquén,
Neuquén, Argentina
***Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italy
Resumen-Abstract
ESTUDIO ISOTOPICO Y GEOQUIMICO DEL CAMPO GEOTERMICO DE DOMUYO, NEUQUEN,

ARGENTINA.
Se realizaron analisis isotôpicos y anâlîsis quimicos en sôlidos
disueltos y gases con el objeto de establecer un modelo de circulaciôn
y determinar la temperatura de reservorio.
De acuerdo a 2 os nivelés de tritio registrados y los va lores de
los isôtopos estables deuterio y oxigeno-18, la recarga del sistema se
produce a una al tara de ça. 2900 m s.n.m. en la falda oeste del cerro
Domo.
El agua muestreada en un geyser, "El Humazo", se reconoce como la

mas relacionada al agua primaria, aunque contiene una pequena propor-
ciôn de agua meteôrica reciente. La temperatura del reservorio de don-
dé proviene "El Humazo", séria de unos 225 °C de acuerdo con el geo-
termômetro de Na-K-Ca. Asimismo se puede inférir la existencia de otro
reservorio mas superficial con temperaturas de alrededor de 176°C de
donde provendrian las aguas de "Las Olletas" y "Los Tachos", también
afectados por procesos de diluciôn y pérdida de vapor.
Finalmente las manifestaciones templadas como "Aguas Calientes" y

"Banos de agua caliente", serian el resultado de mezclas entre aguas
del tipo de "Las Olletas" con acuiferos frios superficiales.
La termometria gaseosa y las temperaturas obtenidas a través de
consideraciones termodinâmicas sobre el equilibrio entre flui dos y
minérales arro.jan temperaturas entre 220-248 "C para el reservorio mas
profundo en concordancia con la temperatura quimica. Asimismo sugieren
un valor cercano a cero de la fracciôn de vapor en el reservorio (Y)
confirmando el estado liquido del fluido en el reservorio.
ISOTOPIC AND GEOCHEMICAL STUDY OF THE DOMUYO GEOTHERMAL FIELD, NEUQUEN,

ARGENTINA.
SnvironËental isotopes, 2S, II0 and }S as sell as cheiical analyses of dissolved solids and gases have
been perfoned in order to establish a circulation todel and reservoir teiperature
according to tritiai levels and isotope content, recharge occurs 2900 i above sea level on the vest slope of the
Doio volcano.
Hater fro* a geyser, "El Buiazo", sas recognised as the tore related to the pritary deep geothenal fluid, altough
sith a linor proportion of fresh sater.
31
Reservoir temperature as estimates by the Na-K Ca geotheraoaeter on this tamfestation yield a value of 225'C
A shallower reservoir mth température of about lïô'C (Ha tf Ca geotheraoaeter) is evidenced in "Las Olletas" and
'Los îachos" also affected by dilution and steaa loss processes
finally, teaperate Manifestations as "/tguas Calientes" and "SaSos de tguas Calieates" are the result of sizing bet
veen Las Olletas type eaters vith fresh eeteoric shallover vaters
Gas theraotetry and coiputation of fluid and sineral equilibria yield teaperatares betveen 220-248'C for the deep
reservoir, in agreement sith sore classical techniques and suggest a value near to zero for the vapor fraction (7)
at depth and confire the liquid state of the fluid into the reservoir
1. INTRODUCTION
The Domuyo geothermal area is located at AW of the Neuquen Pro-

vince c a 36° 45' S and 70° 47 W, 40 km away from the Andes Cordi-
llera
The climate is defined as Semiarid Patagonic in the lower zones

and as Andino high mountain type in the upper areas
The basement is constituted by acid plutonites, metamorphites and

Jurasic sediments from the Neuquenian Basin The upper part is covered
by tertiary vulcanites (Pliocene) and quaternary lava, the last cor-
respond to emissions of domic vulcanism whose magmatic chamber is res-
ponsible of a thermic anomaly
Domuyo
Copahue
FIG 1.
32
Great regional faults cross the zone with E-W. N-S and N-M direc-
tion. In these faults intercepts, wain thermal manifestations as ther-
mal spring and geysers are found.
The study of the zone began in 1982 »hen a geological interpreta-
tion of satellitary images and air photography was made. An area of 40
km2 was selected at the west of the Domuyo mount. On this area a geo-
logical survey was performed. In adittion geochemistry, gravimetry,
heat flow measurements, geoelectric and seismic prospections were
done.
2. METHODOLOGY
During 1985 and 1988 two field trips were performed. In the first
pH. conductivity, Na + , K+. Ca2 + , Mg2 + , Li+, Al , Si02, NH3, B, Cl~,
SO42-, 32-, F-, 1*0, 2H and 3ffwere analysed.
In the second one a more detailed chemistry of water and gases in

selected manifestations was made.
The information obtained during the first stage allowed the che-
mistry and isotopic classification of water samples, geothermometry,
determination of mixture of waters, altitude and area of recharge,
extension of the reservoir and to establish a circulation model. With
data of the second stage saturation indexes and physicochemical condi-
tions within the reservoir were modelled.

3.1. CHEMICAL COMPOSITION OF THE HATERS
In table 1 results of chemical analyses are presented. According
to their temperature and conductivity, water can be classified into 3
groups :
Group I: Comprises the samples corresponding to "El Humazo'

(EH1), "Las Olletas" (LO) and "Los Tachos" (LTD, they are alkaline
clorurated, mainly Na + , K+, with low concentration of Ca2+ and Mg2 + .
Conductivity oscilate between 5.38 and 6.42 mS/cm. Emergence tempera-
ture is near to the boiling point at these altitude (~93°C).
pH round 8.2.
Group II: Cold waters, MAF 3,4, 5, 6, 8, 10, 11. 12, 13 are in-
cluded. They are HC03- Na + Caz+ . Conductivities are lower than 102
uS/cm. Surface temperature is less than 13°C. pH ranges between 4.5
and 8.1.
Group III: Aguas Calientes (AC) 4, 5, 6, Banos de Aguas Calientes
(BAC 7), LT12 and MAF 1, 5 and 7 These samples present intermediate
values between group I and II i.e. conductivities between 629 and 4200
US/cm, temperatures of 16 to 64°C and pH of 5.9 to 7.9.
Tritium values showed in table 3 confirm the existence of this 3
groups being of (0 to 1) T.U. for the first, (1 to 6.5) T.U. the se-
cond and (1 to 3.5) T.U. for the third.
33
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a X kl rH -1 o rH r- Œ CE CE œ a Œ <X CE tr er <r CE er U. U. k. u. u_
4 r t- CQ n C C n E r: c n c a Œ a a Œ
ïï S VI UJ E: n r: c C
ta o 1
<t in 1
36
3.2. LIQUID PHASE THERMOMETRY
Table 6 presents the temperature values obtained by mean of dif-

ferent geothermometers Silica, Na/K, Na-K-Ca, Na-K-Ca corrected by
Mg, Na-Li, Mg~Li, K-Mg and in figure 2 the graphic method of Giggen-
bach (1986) is presented
Assuming as more reliable the Na-K-Ca geothermometer, the highest

temperature correspond to EH1, 225,5°C On LO and LT1 similar tempe-
ratures of 176"C and 179 °C respectively are obtained AC and BAC 7
yield lower values of 150 and 156°C
The triangular diagram of Giggembach (op cit) (fig 2) shows two

groups of samples, aligned on two isotherms EH1 and LT12 lie on the
isotherm of 245°C, LO, LT1 and all AC on the isotherm of about 190°C
Sample EH1 fits close to the full equilibrium curve, however it
shows a dilution since it is not on the curve, LT12 is more diluted
The position of LO and LT1 on the 190°C isotherm suggests the reequi-
libration of the system to a lower temperature As can be seen in fig
2, all the remaining manifestations are more diluted
The silica geothermometers yield lower temperatures for EH1 than

those obtained by the Na-K-Ca one, they are 191 °C for the quartz equi-
librium, without steam loss, and 177°C if steam loss is considered
Thus boiling with SiU2 precipitation is evidenced
TABLE N* 6: 6EOTHERHONETERS
BEOTHERHOI1ETERS AC4 ACS AC6 BAC7 LO LT1 LT12 EH1 RP
Na/K (F) 178,9 187,4 188,5 198,6 173,3 176,0 228,2 232,4 175,9
Na/K (T) 140,9 151,0 152,5 164,7 134,2 137,4 201,8 207,1 136,7
Na-K-Ca 177,5 177,5 183,4 186,6 176,0 178,7 211,3 225,5 159,7
Na-K-Ca («q> 161,6 168,9 159,1 137,6 172,8 174,2 206,1 225,5 29,7
Na-Li 148,1 134,6 138,3 145,3 141,0 138,6 144,6 143,0 227,7
K-tlg 131,2 133,4 129,8 118,8 151,1 149,8 168,9 212,8 101,2
Hq-Li 209,9 198,2 194,3 175,6 242,7 236,1 233,1 297,5 151,1
TQC 174,3 165,4 178,2 172,0 177,5 181,6 168,8 191,2 149,6
TQfi 163,6 156,2 166,7 161,6 166,2 169,5 159,0 177,3 143,8
TCH 152,4 142,2 156,8 149,7 156,0 160,8 146,0 171,9 124,3
Na/K (Fl: FOURNIER

Na/K ( î ) : TRUESDELL
Na-K-Ca (ttq): CORRECTION BY HAGNESIU«
TQC: QUARTZ CONDUCTIVE
TCH: CHALCEDONY
~ NOTE: TEHPERAÏURES ARE IN 'C
37
Na/1000
%-Na"=c Nü /10S
'o-Mg" = 100 Vct
.<:,• in mg/kg
LO
EHI LTI
a 12
20 X <U M 10 70 M / 90
Mg
"V.-Ma' ',
enbach, G r a p h i c a l Techniques, 11B6.- MAE 7 FIG. 2.
S1O2 (ppm)
600
400 -
300 -
ZOO -
100
0 20 40 00 80 100 120 140 180 180 200 220 240

Rnthalpj (Koal/Kf)
FIG. 3. Enthalpy — silica.
m HLBITE L[1 ^rj^'
a
HC5.^'"^°LT1?
K _^-''
H No-nBMT
2 MICRDCLINE
a KHOLINITE
__ .^„„IT,
?
"
-H
B IQ
SVST. Hci,Hea
«t ana oC i„ q oH;J',tiH: -a 3 5 = û
FIG. 4. Activity diagram.
38
BORON VS CHLORIDE LITHIUM VS CHLORIDE
Boron (ppm) Lithium (ppm)
20
KBl
12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
mi
+ +..+. .
£T
15 - ........................................... . +. . . . . . . . . . . . .
10
B
10 - 1C* «"
+ U> +LT1 1C8 + +
6
LT1Z +
? +« aicrqk-
+1C6 4
5 -
BlCTfWlï B
2 - ' ' * ' '•+' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2 -H +
0
) 500 1000 1500 ZO00 () 500 1000 1500 ZO
Chloride (ppm.) Chloride (ppm)
SULFATE VS CHLORIDE SODIUM VS CHLORIDE
Sulfate (ppm) Sodium (ppm)

zoo EB1 1400
+
1200
LO
150 LO 1000 -
les BOO
100 1C»
600 -
uiz
8
+ 400 -
50
200 -
•ll+-
0-1»
500 1000 1500 2000 500 1000 1500 2000
Chloride (ppm) Chlorid* (ppm)
FIG. 5.
-fe-
es
POTASSIUM VS CHLORIDE MAGNESIUM VS CHLORIDE
Potuilum (ppm) UH an»«i nrn

«"«u. ""* fU>F
ppm)
^
m+ 1
1*0
4-
120 - 1 + 7
!
100
-
BO
m j t
1
, -f ACS
AC« ,
to + i 1 -r 4-
LT1Ï ACS + 2 (- + AC* ttl
80
+ AC« AC* 4- +
i -r +
BAC7 + 4. i ">
40 +
,
20
++ m2
*- .K -f-
f «w
k+
£ * T"
± f +
0« 0T —————————— i—————————— i—————————— i——————————
0 500 1000 1500 2000 0 500 1000 1500 2000
Chloride (ppm) Chloride (ppm)
SILICA VS CHLORIDE ENTHALPY VS CHLORIDE

Silica (ppm) En.th.alpy (Kc«l/kg)
m LO läi i
20
4 BAC7 T_^ + + 80-
"tin« LT12
AC*
ACS
4- ACS
150 1- 60k + f
_P
BAC7 ACe
7 •i-
100 S-f 40r
• H- ' 9
< B S 7
50 ' ; +
20. r 1"^
I+ 2 ••'4-2
I
0 Ol ——————————— i———————————— i———————————— i———————————— I
0 500 1000 1500 ZOOO 0 500 1000 1500 2000
Chloride (ppm.) Chlorid« (ppm)
FIG. 6
Enthalpy (Kcal/leg)
300 i———————————————— -*
500 1000 1500 2000 2500 3000

Chloride (ppm)
FIG. 7 Enthalpy vs chloride

-100
-21 -20 -19 -18 -17 -16 -15 -13

Delta Oxyfen-18 (X.)
FIG 8 Deuterium vs oxygen-18
3.3. GAS GEOTHEBMOMETBY
A. METHOD l
Starting with the composition of the sample EH3, the following
reservoir parameters Here determined t, partial pressure of CÛ2
(PCOs), vapor fraction (Y) and gas to water ratio
The used methodology is that proposed by D'Amore et al (1987)

It is reliable for reservoirs with temperatures over 140°C and take
into account the gaseous species C02, HzS, CH4, H2 and CO The follo-
41
wing reactions are considered-
H20 = H2 + 1/2 02 H
H3S - H 2 +1/2 S z S
CH4 + 2 H20 = 4 H? + C02 C
CO ? -f- H 2 = CO + H20 CO
1/2 Fe304 + S z - FeS2 + 2/3 02 MP
Taking into account this 5 equation and the equilibrium cons-

tants, partial pressures of 82 and 02 can be eliminated and the follo-
wing equations to be written:
4 log P(H2) + log P(C02) - log P(CH4) -

log AV + 2 log P(H20)
3 log P(H2S) -log P(Hz) -

2 log KH - 3 log Ks - 3/2 log KMP + 2 log P(H20)
4 log P(CO) - 3 log P(C02) - log P(CH4) -

4 log Kco + log KC - 2 log P(H20)
The partial pressure of every gas specie may be written as a

function of its molar concentration ( n ± ) respect water in the dischar-
ge point (d), the molar fraction of the vapor (Y) and the molar coef-
ficient of distribution between vapor and liquid -S2 •
log Pi = log (nl/nH20)d - log A, + log P(H2O)
where A, - Y + (1 - Y) for Y > 0
for Y < 0
and log B1 - a + b t where t - temperature ( "C )

a, b = constant for each
gaseous specie.
Replacing in the 3 equations above, partial pressures by their

expression we have:
4 log(H2/CU2) - log(CH4/C02) ~ fi(t) + fi(t,Y) - 4 logP(C02)
3 log(H2S/C02) - log(H2/C02) = f2(t) + f2(t,Y) - 2 logP(CO2)
4 log(CO/CO2) - log(CH4/C02) - f3(t) + f3(t,Y)
fi(t), f2(t) and fs(t) are functions expressing the dependence of

the equilibrium constants with temperature and fj(t,Y), f2(t,Y) and
f y f t , Y) represent the termins A^ that are function of both, temperatu-
re and vapor fraction
42
Solving this system for EH3 we obtain:
t - 220'C reservoir temperature
PC02 =300 kPa
Y = 0.003 vapor fraction
log H2/H20 - - 6
Gas/water = 4.7 x 10-*
logP(Oz) = - 39.9
B. METHOD 2
In this method is taking into account the system C02. CH4, H2 and
CO. H2S is excluded, thus one constant must be assumed; in this case
Y=0.
The obtained results for EH3 are the following:
t - 240'C
log P(C02) - - 38.3
PCO2 - 300 kPa
In the manifestation at the border of the geothermal field Rincôn
de las Papas (RP) we obtain:
t - 210"C
log P(02) - - 41.2
PCO? - 2 MPa
C. METHOD 3 (D'Amore et al., 1989)
In this method the reservoir temperature is calculated by using

the simultaneously composition of the va ter and the gas. in the gas
the concentrations of CE4. H2 and CO refered to the CO2 are conside-
red.
In the reaction:
CO + 3 H2 = CH4 + H20 (1)
considering Y=0 we have:
+
log Pj - log n2/nC02 + log B! - log B(CO2) log P(C021 (?)
Taking into account equations 1 and 2 we arrive to an expression

only depending on T and P/cost-
In the same »ay is no» possible with aid of computer programs
calculate the P(co2) from the water composition, alkalinity and pH at
different temperatures. At the equilibrium temperature both pressures
calculated from water and gas must be equals.
With water from EH1 and gas from EH3, it was obtained:
t - 248°C
P(co2) =150 kPa
As can be observed the three methods yield values between 220 and
248°C in agreement with those obtained by classic thermometry. The
obtained value for Y, virtually equal to zero define the field as li-
quid dominated.
43
3 4. ENVIRONMENTAL ISOTOPES RESULTS
A. COLD HATER SAMPLES
Samples representatives of cold water springs £2 1 close to the

meteoric water line o^H - 8 <5 1 »0 + 10 o/oo MAE 1U 11, 12 13 and 14
exhibits more depleted in 2H and l S0 values indicating a higher alti-
tude of the recharge Conversely the more enriched samples correspond
to MAF 1 5 and 8
In fig 14 the oxygen- 18 contents of cold va ter springs are plot-

ted as a function of altitude An altitude effect of (0 18 ±0 02)
o/oo/lOO m is estimated fitting the equation
6160 - (18 ± 2) x 10 •* /fn h CIO 8 + 05) o/oo
with a coefficient of correlation r-0 9
In similar form (fig 15) an altitude effect of (1 3+0 2)o/oo

per 100 m is found for deuterium The regression equation is
Ô2H - (13 ± 2) x 10 3 /m (80 98 ± 0 Ob) o/oo
r~ 0 83
One pole of these lines are determined by samples MAb 1 and 8

with high tritium contents representing local recent precipitation
Conversely the other pole is represented by samples MAF 3 10 11, 13
and 14 with lower tritium contents corresponding to spring located at
the west slope of the Domo mount over 2900 m a i l assumed as the re
charge area
B HOT HATER SAMPLES
In figures 9A and 9B the isotope content 01S0 and 62H of samples

EH LO and LT show to be near of the isotopic equilibrium at the tem-
perature of emergence This fact and the Cl' enthalpy diagram allow to
calculate the isotopic composition prior to the steam separation LO
LT1 and HI O^H vs Cl ~ and 6 1 *O vs Cl - diagrams (fig 10 and 11),
lead to the calculation of the composition of the deep reservoirs HI*
and LO*LT*
From the 62H vs 8iaO diagram can be concluded that watei rechar-
ged at the Domo mount recharge the reservoirs corresponding to El Hu-
mazo ( H I * ) and that of Las Olletas-Los Tachos (LO*LT*) with the major
oxygen-18 shift for HI* AC and BAC manifestations are produced by the
mixing of waters LO type with local recent meteoric waters
Tritium contents of hot water samples indicate a minor meteoric

water proportion for EH1 and a significative contribution of fresh
water to AC and BAC samples
44
Temperature { C)
250
200
150
100
50
8 10 12 14 16
10E3 In
FIG 9a Oxygen-18 enrichment as a function of the emergence temperature
Temperatur« ( C)
250
200
150
100
50
-10 10 20 30 40 50 60 70
10E3 In
FIG 9b Deuterium enrichment as a function of the emergence temperature
45
Delta Deuterium (% )
-100
500 1000 1500 2000 3000

Chloride (ppm)
FIG 10 Deuterium vs chloride.
Delta Oxygen-IB (X)
500 1000 1500 2000 3000

Chloride (ppm)
FIG. 11 Oxygen-18 vs chloride
46
Tritium (T.U. +/- 0.6)
8
7
i
6
4ir.12
13
11
2'-
ice ACE
1- BAC? KH1
ÀC4 LO
Ht»
0 4
0 500 1000 1500 2000 2500 3000
Chloride (ppm)
FIG. 12. Tritium vs chloride.
3.5. CIRCULATION MODEL

In figure 13, a circulation model is presented. It consist of a
central area with a fluid HI* feeding the manifestation of El Humazo y
Los Tachos and a second system less hot, responsible of Las 01 le tas
and Banos de Aguas Calientes (LO*LT*) diluted with cold water in dif-
ferent proportion.
All the system is recharged in the neighboring of the Domo mount.
3.6. HYPOTHESIS ON THE ORIGIN OF GASES
13C composition of gases from EH1, EH3 and PP are -7.6, -7.3 and
-8.2 o/oo respectively, indicating magmatic or atmospheric origin.
This results would be partially confirmed by the study of concentra-
tion of non reactive gases (Giggenbach, 1983).
The source of the Ar, N2 and He can be characterized as follows:
1. Recent waters, air saturated, with low He content and N^/Ar
ratio depending on the quantity of gases withdrawn from waters. It can
range between 78 (low proportion of extracted gas) and 38 (all the gas
extracted).
2. A deep magma tic contribution with low He content, N 2/He grea-

ter than 3000 and Nz/Ar ratio higher than 500.
3. Cortical component typically observed in systems with slow

circulation. They have an He content increasing as a function of the
residence time of the fluid at the crust.
In figure 16 these parameters are presented as a triangular dia-

gram.
47
FIG. 13. Circulation model
-13.0
2000 2500 3000

Altitude (m)
FIG. 14. Delta oxygen-18 vs altitude.

-95
-100
-105
-110
'7
•U
-115
-120
1500 2000 2500 3000
Altitude (m)
FIG. 15. Delta deuterium vs altitude.
49
M - Mantle N^/IÛO
C • Cruitul
ASW - Air Saturate Water at JO'C
COIWUL
Ar
i - --
FIG 16 Triangular diagram N2-Ar-He for some geothermal fields of the world (D'Amore et al , 1989)
The PP sample shows a clear origin in air saturated groundwater

Conversely EH3, with higher values of He is shoving a deeper origin
EH3 gases can be considered as a mixture between a cortical and a man
tie contribution The sample from Copahue exhibits a typical composi
tion of gases coming from the mantle It must be noted that is possi-
ble, at the Domuyo area, not far from El Humazo the existence of a
basaltic magmatic chamber This chamber would contain gases of similar
characteristics to those of Copahue The further circulation through
methamorfic and granitic rocks, could explain the high He concentra-
tion making the crustal component became important
3 7 SILICATE SOLUBILITY PRODUCT
The most of problems related to the suitability of a given geo-

thermometer on aqueous samples is frequently due to the unknown inte-
raction between the host rock and water, and to the value of the pH at
depth Also to the difficulty for reaching the equilibrium in low en-
thalpy systems local cooling effects and mixing processes
The use of secondary mineral equilibrium fixing the water chemis-

try, could eliminate any unknown related to the estimated temperature
for the aquifer
It can be achieved by determining the monomeric aluminium (A1+3)

and (Al(xy)H)z with x= OH- F~, 504 =, etc and z~ (3 wy) In the pro
cess of leaching of the host rock into microfractured system d certain
quantity of polimeric aluminium is produced in addition to other
anions and cations Only a part of this polimeric aluminium produces
monomeric aluminium, being the latter a function of the solution com-
position and temperature This monomeric aluminium participates in the
formation of hydrothermal altered silicates in equilibrium
50
Using adecuate computer programs and field data like pH, tempera-
ture and alkalinity as well as laboratory chemical data, it is possi-
ble to calculate the composition of the fluid at depth and the satura-
tion indexes (S.I.) of several minerals at any temperature (Arnonson &
Sigurson, 1982; Worley, 1979).
The S.I. are computed and plotted for a selected group of mine-
rals that are compatible with the local minéralogie matrix For each
mineral, the intercept of the line S.I.= 0 vs temperature yield the
calculated equilibrium temperature.
Taking into account the uncertainty in the thermodynamic data,
the interval considéra ted as "in equilibrium' for a given mineral
falls into a range of S I. = 0 ± 0.25
In table 7 the value of S.I. for selected alteration minerals of
the manifestation EH1 are presented. The program was run assuming the
system descompression occured at 180°C.
fflBLE N° 7: S*tur.»tion ind*n»I of «on* «lt#r.»tion Hin*r*l*

**l*ct*d t»np*r*tijr»s CfroM U*tch 3 progr»M for
d*sco«position t»np«r-atur-* td« 180 °O.
EH1 hot spring, DoMuyo.
t -»c t °C
tllNERRL
200 225 250 275 for 5.1 .« 0
1> rig-Chlorit» -2. 11 -0.96 1.20 3.16 236
2~> Zoisit* -2.51 -1.52 -0.26 1. 17 251
3") Epidot» -0.96 -1.06 -0.29 1.40 254
4> Pr*hnit» -0.57 0. 16 1.31 2.6-4 220
5") Rlbit«-
-KF*1 d»sp*r -0.3$ 0.04 0.48 0.90 223
6> KF«.ld»*p»r-
-tluscovi t« -0. 10 -0.05 O.'J« 0.90 225
7) flrihydrjt«.
+ Fluorit» -0.44 -0. 19 0.05 0.27 245
t - 237 +/- 15 °C Cfor S.I. - 0 . 0 5
t - 238 +/- 17 °C Cfor S . I . " 0.0 »/- 0.253
Sup»r**turation with r»»p»ct to Ctlcit*.

Ur»d»rs*tur*-fcl on MI th r**p»ct to2 U*ir*kit* f LuoMontit*^ MontNori 11 orri t«
In figure 17 an average temperature of 238+ 17°C is obtained

The recalculated pH is 6.8 for a PC02= 120 kPa, for each temperature
value, the silica concentration corresponding to quartz saturation was
assumed. The obtained results are in agreement with those calculated
by the triangular diagram (Giggenbach op. cit ), classical geothermo-
meters and gas geothermometers.
The computed pH- 6.8 is lower than such measured at the field=
8.2. It can be explained as a descompression phenomena with C02 loss.
In figure 19 the pH= 6.8 at a temperature of 240°C is consistent

with the K-feldespar and K-mica-quartz and the salinity.
In table 8 are presented the values of S I. for Pinçon de las

Papas (RP) manifestation and in figure 18 a temperature of 166 ±17
'C for the mentioned sample is obtained.
51
_4 _
-2 -
150 175 200 225 250 275

Temperature ( C)
k«-chlor. + Zolstte # Kpldote
Prhenlte X JUb-KFeld <>
FIG. 17. Saturation indexes at selected temperatures,

El Humazo (EH1).
SI
(1) Qwt*
(t) Cttuomtta
(3)
— &l
(4) UrwoorlU
(8)
UfCblmiU(UUU)
(8)
_<
-3
0 25 50 75 100 125 150 175 200 225 250 275
Temperature ( C)
' (D + (2) * 0)
D (4) X (6) 0 (6)
FIG. 18. Saturation indexes vs temperature,

Rincön de las Papas (RP).
52
Solution pH
8
. BT«r«i«r<il(O.OOB)
T« KopU(O.OOe)
m(N«+K)-0 01
«Hl DOUUTO-1988
(0.060)
m(N«+K)-0.1
»«lr«lc«l(0 044)
•Js Bro«dl«n4«(0 034)
lfoblo(0 1)
ahob«ra(0 07)
C«rro Prl«lo(0.2B)
(12)
150 200 250 300 350
Température ( C)
FIG. 19. pH vs température.
TR8LE N° 8ï Saturation ind»H*s fot~ SOM*

»•l»ct»d t»np»r»tur»*.
RP hot spring, Dowuyo.
t ->c t °C
MT MP*DCII
100 125 ISO 175 200 for S.I .- 0
15 Ou*i-tr 0.41 0. 165 -0.01 - -0.37 148
25 2 Muscowit»-
-3 L*UMontit* - 2. -120 1.5-1 -0.27 -1.94 171
35 Huscoî t*-
- 3 fllfc.it* - 0.45 0.6S -0.25 -1.13 i&e
*O tluscoyi'fc* —
-Zoisi t» - 3.65 1.82 0.10 -1.52 177
55 Muscoî t*—
+ n^Chlorit» - -1.32 0.05 2.97 - 119
65 riuffcovi t*~
- 2 fldul^ri» 1.36 0.95 0. 15 -0.52 181
t - 16& +/- 14 &C <for S.I. - 0.05

t • 166 +/- 17 °C Cfor S.I. - 0.0 */- 0.255
SuperA^tur *tl on HI irh r»*p*c^ t
Und»rs«t'jr»tlon MI th r**p»ct to! Epldot», Prehnlt», U«ir»kit», flnhidrit*.
53
4, CONCLUSIONS
The important number of hot and cold springs and their relatively
high discharge, allowed to get a great number of data to formulate an
hydrologies! model
By mean of chemical data, isotope analysis and enthalpy data »as

possible to calculate the chemical and isotopic composition of the
parent water as well as the recharge altitude
The methodology based in the chemical composition of gases and

saturation indexes have led to a better and more accurate knowledge of
the geothermal field
The Domuyo geothermal field have a Hater dominated reservoir The

field has a central zone between El Humaô v Los Tachos having the
parent water the following characteristics
Ô2H (o/oo) -115

Oi*0 (o/oo) -13 U
t CO 220-248
Y O 03
PC02 (kPa) 150-300
Cl (ppm) 2500
A second zone with a shallower reservoir comprising a more extent

area with a similar isotopic composition a temperature of about 170
°C and a chloride concentration of ca 2000 ppm
In addition a third zone (Rincon de las Papas) exhibit strongly

bicarbonated waters, typical of the boundary of geothermal aiea^ The
more reliable temperature is that obtained by using the S I
166 ± 17°C Gas geothermometers and classic geothermometers yield
higher and erratic values
Acknoiledgeients - fhis vork has been perforied mtbia the fraievork of the Hlk Coordinated Research Prograste on the
application of Isotope and Geocheaical techniques ID Geotberial Exploration in Latin tterica (Research Contract K'
3988/IG), financially supported by the Governtent of Italy
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exploration in Djibouti: Stratigraphy, authigenic mineral assemblage
and temperature data of the drilled wells. Structural data from the
Asal rift. Geothermics. In press.
Giggembach W. F. (1980) Geothermal gas equilibria. Geochim.Cosmochim.

Acta 44, N° 12, pp. 2021-2032.
Giggembach H. F. (1986) Graphical techniques for the evaluation of

water/rock equilibration conditions by use of Na, K, Mg and Ca con-
tents of discharge waters. Proc. 8th New Zealand Geothermal Horshop,
PP. 37-43.
Gingins, Mario (1986) Estudio Geoquimico-Isotopico de los Fluidos Geo-

termales de la Provincia del Neuquén (Convenio OIEA 3988/IG). Ente
Provincial de Energia del Neuquén, Neuquén,Argentina.
Helgenson H. C., Delany J. M., Nesbitt H. ». and Bird D. K. (1978)

Summary and critique of the thermodynamic properties of rock-forming
minerals. Amer. Journal of Science, Vol. 278, A, pp. 729-804.
Henley R. M . , Truesdell A. H. and Barton P. B. , with a contribution of

Whitney J. A. (1984) Fluid Mineral Equilibria in Hidrothermal systems.
Reviews in Economic Geology, 1. Published by the Society of Economic
Geologists.
JICA-COPADE (1982-1984) Proyecto de Desarrollo Geotérmico en la Zona
Norte de la Provincia del Neuquén-Domuyo.
Michard G., Ouzounion G. , Fouillac C. and Sarazin G. (1979) Contrôle

des concentrations d'aluminum dissous dans les eaux thermales. Geo-
chim.Cosmochim. Acta 43. pp. 147-156.
Michard G. and Roekens E. (1983) Modeling of the chemical composition

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resultados isotôpicos del Area de Domuyo. Convenio OIEA 3988/IG. Ins-
titute de Geocronologîa y Geologia Isotôpica, Buenos Aires, Argentina.
55
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aqueous solution and minerals the EQ3/6 software package Laurence
Livermore Laboratory
56
FLOW PATTERNS AT THE TUZGLE-TOCOMAR GEOTHERMAL
SYSTEM, SALTA-JUJUY, ARGENTINA
An isotopic and geochemical approach
H. PANARELLO
Institute de Geocronologia y Geologfa Isotöpica,
Buenos Aires
J.L. SIERRA, G. PEDRO
Ente Provincial de Energia del Neuquén,
Neuquén
Argentina
Resumen—Abstract
MODELO DE FLUJO EN EL CAMPO GEOTERMICO DE TUZGLE-TOCOMAR, SALTA-JUJUY,

ARGENTINA: ESTUDIO ISOTOPICO Y GEOCHIMICO.
En este trabajo se han ernpleado técnicas isotôpicas (tritio.

deuterio y oxigeno-181 asi como anâlisis quimicos de aniones y ca-
tiones mayoritarios y minoritarios y anâlîsis de gases para establecer
las condiciones hidrogeolôgicas y las tempera taras de reservorio.
Los contenidos en isotopos estables exhiben una buena correlaciôn

con la altitud y permiten diferenciar las areas posibles de recarga.
Debido a las condiciones climâticas altamente rigurosas del am-

biente Puneno, como gran ampli tad térraica, baja humedad y près ion at-
mosférica y escasa precipitaciôn, se producen importantes fracciona-
mientos cinéticos fundamentalmente en oxigeno-18.
La termometria guîmica de sôlidos disueltos y gases, definen el

area como un sistema de baja a media entalpia con temperaturas de re-
servorio del orden de 90 a 140°C.
FLOW PATTERNS AT THE TUZGLE-TOCOMAR GEOTHERMAL SYSTEM, SALTA-JUJUY, ARGEN-

TINA: AN ISOTOPIC AND GEOCHEMICAL APPROACH.
Environiental isotopes '#, *ff and J'O, aajor and linor anions aad cations, and gas analysis have been
lade in order to establish hydrological conditions and reservoir tetperatures.
Isotope contents of gaters, 2S, ISO shon good correlation sith altitude and alloy to differentiate the possible
recharge areas.
Due to the rigorous feather conditions prevailing at the high altitud in the Puna environtent i.e. great theraic
amplitude, los precipitation, los huaidity and ataospheric pressure, gross kinetic fractionation aainly in oiygen-
IS has been found.
Chetical of dissolved solids and gas geotheraoieters define the area as a lov to lediui entalpy mth reservoirs
teiperatures range fron 30 to 140'C.
Circulation of cold and bot water shots a pattern vhere are recreated tost of cases of stable isotope fractiona-
tion.
57
l. INTRODUCTION
The area under study is located in the border zone of the

provinces of Sal ta and Jujuy at the AW of the Argentine Republic The
geographic coordinates are aproximately 24 S and 66 30 H The area
covered is ca 400 km2, where the thermal manifestations of El Tuzgle,
Tocomar and Pompeya are located The higher picks, correspond to the
Tuzgle Volcano (5500 m) and to the Colorado creek (5220 m) The zone
is extremely arid and the basin have no drainage
The climate is particular, since that the average ctltitLide of the

field is more than 4500 m a s l Températures are very low all the
year long, showing a daily amplitude as big as 36°C
The main town is San Antonio de los Cobres, if ff m a s l distant

25 Km from the geothermal field A 4 yeat record of the meteorological
conditions for this town account for the following
Average annual temperature ti 8°C

Average annual atmospheric pressure 649 hPa
Highest temperature 27°C
Lowest, temperature 16"C
Average annual precipitation 1Ü3 mm
Freezing frequence 223 day/year
In the géothermie area studied 800 m above, the climatic condi

tions are by far more rigurous Hinds prevailing fiom H-NW and W-SW
have a velocity between 2-20 m/s, blowing during 10 to 18 hours per
day
ifrom the geological point of view the region presents metamorphic

and cristaline rocks from the Proterozoic Eruptive rock with great
significance have been originated in four principal phases, i e
Dacitic eruption of the Upper Miocene (old dacites), eruption of
andésites during the early to medium Pliocene, early Pleistocene
dacites (new dacites) and finally, eruption of basalts in the Boloce-
ne All this metamorphic cristaline sedimentary and eruptive rocks
were affected by tectonic movements Tertiary diastrofism of great
intensity, have masked the less important effects of other precedent
diastrophic cycles
2. METHODOLOGY
The samples for this work were collected at an area of about 400
km2 comprising all the thermal manifestation of Tuzgle, Toc^nar and
Pompeya (map 1) on October, 1989 and January 1990 9 cold waters and
17 hot water samples 8 corresponding to hi Tuzgle, 6 to Tocomar, 3 to
Pompeya and 7 samples from creeks
pH and conductivity were determinated at field Fe, Mn, Al Na+,

+ ::
K+, Ca2 + , Mg2 + , Li . As. NH3 , S = , S04 . C03=. HCO3~, Cl~, F- Band
SiC>2 at the Administracion Provincial del Agua (APA) and tritium,
deuterium and oxygen-18 at the Institute de Geocronologia y Geologia
Isotöpica (INGEIS) (Tables 1, 2, 3 and 5)
58
Toeomar
TOP 3 (4262. I SO) »r? «TOFt(4324.13B)
MAP 1
59
TRBLE N° 1: CHErilCHL RNftLVSIS OF UfiTER SRHPLES FROH FUZGLE.
i ruc-i : ruc-2 : ruc-3 : ruc-1: TUC-S : ruc-6 : ruc-7 : Tuc-8 : TU ruF-2 ; ruF-3 :
f l r -i: TU flr-2! TUF-I
T C°O : 19 : 56 ; 18.5 ; 15 : 12 : 39 : 11 : 13 : 10 : 12 ; 8 : ;
coNDUcr. : soo o : 6630 l 3220 l 3950 : 6710 i 6170 ! 6300 : 592 : 1250 : 108 : 183 ; 329 : 122
pH : 6.1 : 6.2 : 6.7 : 6.1 : 6. i : 6.0

: 6.1 ; 6.1 ; 7.9 : 6.1 : 6.7 l 7.6 ! 7.0
HC03 : 370; 111 ; 110 : 100 126 : 118 : 132 : 190 : 311 ; 36 : 182 : 113 : so
Cl : 1110 : 2120 ! 808 : mo l 2220 : 2000 : 2000 ; 73 : 1238 : 7 . 1 : 18 : 11 : 6.1
501 : us ; 101 ; 9i ; 89 : 80 1 7l : 63 i 36 : 80 : 5.9 : 33 : 32 ; 11
F : 0.70 ; 0.72 ; 0.37 : 0.37 : 0,10 : 0.15 l 0.62 : <0.20 : 0.12 ; <o.20 ; <0.20 : <0.20 ! <0.20
Na i 900 ; 1230 : sso ! 690 : 1260 : mo ; 1120 : 13 ; 750 : 9.5 : 31 I 12 i 7.2
K : 13l : 111 : 62 : 75 ; 137 ; 123 : 129 : 9.3 : 91 : 2.6 ; 6.3 1 2.3 ; 2.2
C* : 101 i 123 : 13 ; 13 ; lös : 98 ; 88 ; 6i : 95 : 6.5 : 51 ! 39 ! 11
Hg : is : 21 ; ; 11
7.9 ; 22 ; ig ; 22 ; 11 : 16 : 2.2 i 11 : 11 : 2.8
Si 02 ! 72 : 71 : 72: 75 ; 75 : 73 : 75 ; 10 : ! ! ; ;
B : 68 ; ei ; 32 : 11 : 83 i 72 : 76 : 2.5 ; 11 : o.si ; 1.7 ; 0.63 ; 0.13

L» : 13 : 17 ; 7.10 ; 9.20 : 17 : is : 16 : 0.30 : 10 : 0.01 : 0.17 : 0.01 : 0.03
Rx : 10 : 12 ; 5.20 ; 3.90 : 13 : s ; 7.20 ; 0.08 : 7.10 : <o.02 : 0.08 : <o.02 : <o.o2
F» ; o. 17 : 0.22
: i. 80 : o. 10 : 0.32 l 0.23 ! 0.32 : < o . i : • : '•
lin : 2.20 ; 2.00 l 0.57 ; 0.68 : i.io ; 1.30 : 1.10 : <o.os : • '•
; ;
M2S : 0.22 ; 0.22 ; <o. i 1 <0. 1 l 0.29 : <o. i ; <o. i : :

NH3 ; i.io ; 1.30 : 0.16 : 0.58 : i.oo : 0.92 : i.oo ; ; ; ; ' '
Corfr»n-fcr-»ti on* »r » in
TflBLE N° 2: CHEniCRL HNRLVSI5 OF UHTER SRMPLES FROH TOCOHRR.
! TOC-1 TOC-2
i ! TOC-3 : TOC-4 : TOC-5 : TOC-6 !TO flr-1! PO flr-2! TO flr-3! TO fir-4! TOF-l i TOF-3 ! TOF-4 ! TOF-5
T C°C> ; 35 : 45 i 62 : 57 : 55 : 60 ; 17 : is : 14 ! 0.5 ! i 11 ! : 5
CONDUCT . : 3680 : 3640 ! 3640 ! 3640 ! 3640 : 3300 ; 1734 : 1190 : 4970 ! 1013 : 104 : 420 ! 222 ! 104
pH : 6.7 ; 6.5 ; 6.8 i 6.6 ; 6.6 : 6.8 : 7. s ; ?.i : 6.2 ! 8.2 : 7.3 : 8. l : 7.2 ! 6.5
HC03 : 725 : 730 ! 740 ! 720 : 720 : 700 ; 352 : 247 ! 965 ! 321 : 44 : 197 : 76 :
Cl : 808 : 828 i 828 ! 828 : 828 : 727 ; 339 ; 218 ! 1162 : 154 : 6. i ; 14 ; 11 :
S04 : 192 : 185 : 187 i 183 : 166 i 176 : 104 : 199 i 229 ! 52 : 5.9 : 47 ; 30
F : 1.40 : 2.80 : 2.40 ! 1.50 i 2.50 ; 2.30 ; i . 70 :1.20 1 i.oo : 1.40 : <o.20 : 0.25 :<o.20 :
N* ! 740 : 730 ; 740 ! 740 : 725 : 650 ; 342 : 215 1 1125 : 175 : 5.5 : 27 ; 16 ;
K : 65 : 64 : 66 : 66 : 69 : 61 : 30 : 20 : 98 : is : 2.4 : 4.2 : 2.8 :
C* : 7.3 i s.e : 12 : 8.6 : 12 : 5.8 i 17 : 28 : 4.4 : 22 : 11 : 24 : 23 :
ng : 4.2 : 4.2 : 3.7 : 3.7 ; 3.6 : 5.6 : 6.4 ! 5.2 ! 5.1 : 18 : 1.8 : 24 : 2.9 :
Si02 ; 67 : 67 : 69 i 66 : 6i : 55 : : : : : 6.7 ! : :
8 : 42 : 43 : 44 ; 44 : 44 ; 38 : 20 : 13 : 64 12 : 0.33 : 0.90 ; 0.76 l
Li : 10 : 10 : 10 : 10 i 10 : 9 ; 4.50 i 2.80 : is : 2.90 : 0.03 : 0.24 : 0.07 !
R* : o.64 : 0.87 i 0.79 : 0.64 : 0.50 : 0.73 : 0.44 ! 0.23 : 1. 10 : 2.30 ! <o.o2 : <o.o2 ; 0.05 :
F* : 0.12 : o.ii : 0.18 ; <o.i : 0.29 : 0.16 : : : i : 0.13 : : i
n r, : <o.os : <o.os ; <o.os : <.o.os : <o.os : <0.05 : i '• ! ; <o.os : : :
H2S : 0.35 ; 0.67 ! 0.55 : 0.67 : i.io : 0.42 • ' '• ; : <0.1 ! : :
NH3 : 8.40 : 8.00 : 8.80 I 8.80 ! 7.60 : 7.60 • ' '• ; i ! ; :
«r» in ng/1.
fflBLE N° 3: CHEniCflL HNfiLVSIS OF UflfER SRHPLES FROh
POHPEVR - niNfi BETTV - SEV
: pool : POC-2 ! POC-3 ; PO flr-i; ne : SEV

r c<»C3 so : 35 : 52 ; 19 : 20 ; 12
CONDUCT. : SEID : 6110 ! 5670 : 5950 ; 1307 : 230
pH : 6.5 : 6.7 : 6.8 : e . i ; 6.7 : 7.0

HC03 : lose : 1210 : 1120 : 1077 : 162 : 57
Cl : 136« : 1262 ; 1338 ; 1161 : 317 : 26
S01 : 25: : 298 I 251 : 278 ; 31 : 28
F ; 0.70 i 0.90 : 0.80 : o.80 : <0.2 : <o.2
N* : 1200 : 1350 : 1187 : 1325 : 180 i 15
K ; 109 ; 128 : 111 121 i 23 1 1.6
C* : 8.9 : 11 : 11 : 7.7 : 53 : 22
rig : 21 : 25 ; 25 : 26 : 15 : 3.7
Si02 ; 11 ; 16 : 11 ! 23 : 61 i 9
B : si : 60 : 51 ! 56 I II : 1.8
Li : 11 : 13 ; 12 : 12 ; 2. 10 ; <o.o2
fll : 7.30 i 7.80 i 9.20 ; 7.10 ; 0.56 i <0.02
F» : i.io : 0.30 1 <0.1 i <o.i : <0.1 : <o. i

Hn : 0.12 ; 0.22 i 0. 15 ; <o.os : <0.05 i <0.05
H2S : 0.16 : o. 16 : 0.55 ; ; <0. 1 i <0. 1
NH3 ! 2.60 : i.eo : 1.30 ; ; <0. 1 : <o.i
on* -»r» l n Mg/1 .
FfiBLE N° 1: GRS RNHLVSIS FROH
ruc-ii TUC-2 ruc-s roc-3 TOC-1 roc-5 POC-1 POC-2
C02 98.11 99.10 95.80 99. 1 99.35 95.93 91. 18 91.11

C<0.093 C<0.093 «0.093 C<0.093 C69.323 C<0.093 'KO.og 1 C<0.093
H2S <0.0002 ND <0.0002 0.035 0. 16 0.01 0.03 0 . 005

C-3 C-3 C-3 c-o <-> C-3 C-3 C-3
N2 1.11 0.16 3.99 7.22 0.31 3.51 5.56 a. 61

C80.9S3 C68.713 C87.683 C37.373 C21.993 C82.25J C91 .96) C93.S83
02 0. 16 0. 11 0. 17 0. 10 0. 13 0.06 0. 18 0.20
C18.733 C31.033 Cll. 86) C7.573 C2.013 Cll. 893 t?. 573 C5. 753
CH1 0.01 <0.022 0.0305 0.53 0.0201 0.3733 0.0399 0.011

CO. 285 CO. 253 CO. 11> C5.013 C3.593 C5.813 CO. 123 CO. 313
H2 <0.001 <0.001 0.001 <0.001 0.001 <0.001 <0.001 <0.001

CO. 00 13 CO. 0025 CO. 00 13 CO. 0063 (0.08793 CO. 0123 CO. 0005) C<0.001)
H. 0.01 <0.002 0.0031 0.0012 <0.002 0.002 O.OÛ2 0.0072

CO.O351 CO. 01? co.osn CÛ.O113 fO. 00973 CO. 0363 CO. 018) C<0.063
62
TOBLE N° 5: ISOTOPIC ftNflLVSIS OF THERflflL fiND COLD UfiTERS.
! SflrtPLE : LOCflTION !flLTITUDE!OKVGEN-l!3 ÏDEUTERIUH ! TRITIUM

J ï ! H a . s . 1 :X.3«X-0.2!
. .' ( «.> + /-! : CTU>»/-0.6
: Tuc-i : Turgl* ! 1190 ! -9.6 : -76 :
: TUC-2 ! Turgl* ! 1190 : -9.2 : -76 i 0.0
: TUC-3 ! Turgl* ! 1190 ; -10.2 ; -77 ! 0.0
: TUC-I ! Turgl« ! 1190 : -9.9 : -77 !
! TUC-S ! Turgl* ! 1220 : -9.1 : -77 ! 0.0
: TUC-6 ! Turgl* ! 1220 : -9.2 : -76 !
: TUC-7 ! Turgl* ! 1190 i -8.9 : -77 ! 0.0
!TU ftr-l ! Turgl v ! 1218 : -9.0 : -72 :
: TU ftr-2 ! Turgl* ! 1218 : -9.5 ! -77 :
: Toc-i ! TocoHar ! 1230 : -lo.i : -81 :
: TOC-2 î TocoMar ! 1230 : -10.3 ; -81 :
: TOC-3 ! TocoHar ! 1230 : -10.2 i -81 :
: TOC-I ! Tocowar- ' 1250 : -10.2 i -si :
: TOC-5 ! Toconar ! 1250 : -10.3 : -86 !
: TOC-6 ! Toconar ! 1250 : -lo.o : -79 :
!TO fir-l ! TocoMar
I
! : -9.1 ! -79 :
: TO flr-2 ! TocoHar ! : -8.1 : -79 !
: TO fir-3 ! TocoMar ! : -8.2 : -79 :
!TO flr-1 ! TocoHar i ; -7.0 i -79 :
IPOC-1 ! PoHp*ya ! 3838 i -lo.i : -81 :
: POC-2 ! Ponp*u.a ! 3836 : -10.2 : -82 :
: poc-3 I PoHp#y» t 3838 ! -10.6 : -83 :
!PO flr-1 ! Po«p.ya i 3838 ! -9.1 : -79 :
: TUC-S i Turgl* ! 1160 ! -9.8 : -76 : 0.0
ÎTUF-2 ! Turgl* ! 1160 : -10.0 i -76 : 0.6

ÎTUF-3 ! Turgl* ! 1261 : -10.2 : -75 ! 1.5
i TUF-1 ! Turgl* ! 1700 : -10.1 : -79 : 2.1
: MB î Mi n* B*fc-ty ! : -10.1 ! -83 : 0.0
JSEV :s*y : 1025 ! -11.7 : -83 i 0.0

i TOF-1 \ TocoM*r- ! 1701 ; -11.7 : -83 ! 2.1
! TOF-3 • Tocoh**r- ! 1262 ! -9.3 : -76 : o.o
! TOF-1 ! TocoHar ! 1321 : -9.5 : -77 : 0.1
: TOF-5 ! TocoHar ! 1380 ! -10.7 : -77 : 0.0
63
3.1. PHYSICOCHEMICAL CHARACTERISTIC OF THE HATERS
3.1.1. TÜZGLE
There is chemical similitude between hot water samples TUC-1. 2,

3, 4, b, 6, 7 snd the TU Ax - 1 creek obtained down stream the thermal
manifestations They are alkaline clorurated and can be classified
according the salt content into two subgroups:
I. Conductivity between 5000 and more than 6700 uS/cm. sam-

ples TUC-1 ,' 2, 5, 6 and 7
11. Conductivity between 3200 and 4250 uS/cm. samples TUG 3,

4 and TU Ar-1
pH of samples belonging the subgroup I is slighty lower (6.0-6.2)

than those of the subgroup II (6.4-7 9) The temperature of all hot
waters oscilate between 39 and 56°C. The other set of samples are of
cold water TUF 2, 3. 4 and the TUC-8. All they are alkaline
bicarbonated, pH between 6.1 and 7.6 and conductivities between 329
and 592 uS/cm, with exception of TUF-4 (122 uS/cm)
Finally the sample of the TU Ar-2 creek sampled upstream

thermal manifestations is bicarbonated aIka1ine-terrea1 alkaline.
pH is 6.4 and the conductivity 108 uS/cm.
Concerning TUC-8, it was sampled and classified as thermal water,

but latter due to its physicochemical caracteristics, was considered
like a cold water with superficial circulation.
3.1.2. TOCOMAB
Hot waters at Tocomar TOC-1, 2, 3, 4 and 6 constitute an homoge-

neous group from the chemical point, of view. They are sodium clorura-
ted. Temperatures oscilate between 35 and 62°C and conductivites bet
ween 3300 and 3700 uS/cm. Their pH range from 6.b tc 6.8. Creeks sam-
ples TO Ar-1, 2, 3 and 4 are the result of a mixing among thermal and
cold waters.
TO Ar-3 is still more concentrated than the thermal manifestations It
can be explained as result of the process of evaporation, as
demostrated by the iso topic content of the samples (see forward)
Cold water samples TOF-1, 3, 4 and 5 are bicarbonated-terreal

alkaline. Their conductivity oscilates between 5600 and 6450 uS/cm
Temperatures range 35 to 52°C Sample of the creek PO Ar-1 is more
alkaline (pH= 8.1), 5950 uS/cm and a temperature of 19°C
In addition two sampled waters at Mina Betty and Sey, have the
following characteristics:
Mina Betty: alkaline clorurated, high calcium and magnesium, pH~
6.7, temperature 20°C and a conductivity of 1.3 uS/cm.
Sey: Ca -Mg-Bicarbona ted, pH- 7, T- 12"C and a conductivity of 230
fi S/cm.
3.2. ISOTOPE HYDROLOGY
3.2.1. METEORIC LINE AND MIXING LINES.
With data of rain samples taken at Mina Providencia at similar

altitude and climatic conditions the local meteoric water line is
obtained. Points fit on a straight line whose parameters are slightly
64
différents to those of the world meteoric water line defined bj- Craig
(1961) They are
Ô2H- 7 8 Ô1&U + 13 o/oo

Samples falling closer this meteoric line are TOF-1 and SEY (fig
t> ) The remaining samples are located under the m l mainly due to
evaporation phenomena after precipitation They fit lines with slopes
of 3-6 characteristics of very dry zones
Delta Oxygen-18 (% )
-6
4
D
3
2
D
D
I
n
(y-o oa)
10 3-t
2-8
11
12
200 400 600 800 1000 1200 1400
Chloride (ppm)
D x
TOF 4- TOC * POC TOAR TUF
FIG 1 Chlonde-oxygen-18
-75 'à 28
• XX
-77
4 2
-79 n__ru
-81
i
,
ErmporvtloQ
(Y--0 08)
-83
-ffZ-3-4
-85 -f
-87
200 400 600 BOO 1000 1200 1400
Chloride (ppm)
TOF + TOC * POC O TOAR < TUF
FIG 2 Chloride-deuterium
65
-8.3 i———
-fl.8
-9 3 L',
»2
-9.8 r-x'
-10 3,
-10.8
-11 3
-11.8
500 1000 1500 2000 2500
Chloride (ppm)
n
TOF X TUF + TUC TUAR
FIG. 3. Chloride-oxygen-18.
-72 0 -
-84.0
500 1000 1500 2500 2000
Chloride (ppm)
x n
' TOF TUF + TUC TUAR
FIG. 4. Chloride-deuterium.
66
-65 -
-12 -115 -11 -105 -10 -95 -9 -8 5

Delta Oxygen-18 (% )
TOF X TUF WORLD METEORIC WATER
FIG. 5. Oxygen-18-<Jeuterium
Samples of hot Hater from El Tuzgle (fig 6), have a trend

towards more positive values of S^Ô, however the limit between cold
and hot waters is not sharp No oxygen-18 shift is observed due to the
relative low reservoir temperature and to the kind of rock of matrix
mainly siliceous
Samples at Tocomar and Pompeya (fig 7) are différents to those

of El Tuzgle with an apparent oxygen-18 shift
In the 6180 vs Cl - and O^H vs Cl- plots (fig I and 2)
corresponding to the Tocomar-Pompeya zone, two différents groups one
for each zone is evidenced There are no evidences of mixing between a
ffeothermal fluid and shallow waters, neither in Tocomar nor in Pompe-
ya Only samples at the Tocomar creek and their tributaries allow to
see clearly that TO Ar-1 is the sum of the contributions of TO Ar-2
3, 4 and cold waters (fig 2) but they are separated from the source
thermal manifestation due to a strong evaporation process This fact
is also evidenced in the Ô^H, ô i *0 plot (fig 7)
At the Tuzgle area a mixing line between a geothermal fluid as
TUC 2, 6, 5 and 7 with shallow cold water (isotopically similar to
that of the creek) is evidenced Concerning samples of the TU Ar-2
creek, this would correspond to a shallow circulation, while TU Ar-1
to a mixing of TU Ar-2 type waters with a geothermal fluid The slope
of the mixing line is higher, since is repeated the phenomena descri-
bed in Tocomar due to the evaporation of the creek With dashed line
the evolution due to this phenomena is indicated
67
-59 0
-640
--69 0 l
D
a
-740 3 3-«
X * «
• +V3 4
-79 0 x
-84 0
-69 0 - -L _
-13 -12 5 -12 -115 -11 -105 -10 95 B5

DelU Oxygen-18 (7. )
TOF TUF TUC TUAR
FIG 6 Oxygen-18-deuterium
-60 0 -
-65 0 -
*
IJ D n
-85 0
- 9 0 0 '———L ———L -
' —— ' *• ' i -t -i _i J— -i ——
-13-125-12-115-11-105-10-95 -9-85-8-75-7 65
Delta Oxygen- 18 (X.)
p
• TOF + TOC POC TOAR > TUf
FIG 7 Oxygen-18-deuterium
J ^. 2 RECHARGE AREAS
In fiff 8 the 62H is plotted a fa in the dltitude of zechazge If

samples corresponding to Mina Betty and El S?y ?2~e not considered (the
altitude of the recharge is not veil known) the following equation j s
obtained by linear regression a
62H- 1 47 x 10 2 h - 11 3 o/oo
It means a variation of about 1 b o/oo per 1 OU m altitude
68
Recharge altitude (m x 1000)
5.4 -
-88 -88 84 -82 -80 -78 76 -74 -72 -70

x
• TOP TUF
FIG. 8. Deuterium-altitude.
In the case of the oxygen-18 vs altitude plot (fig. 9) also sam-

ples TUF-4, TOF-3 and 4 have been excepted due to the evaporation that
affects mainly the oxygen-18 content.
The resulting equation is:
Oi8O= - 0.30 x 10-2 h + 2.9 o/oo
With a variation of 0.3U ô 180/100 m.
As result of this correlations the following altitude of recharge

were determined:
62H 0180
Tuzgle --------- 4400 m 4500 m
Tocomar -------- 4900 m 5000 m
Mina Betty ----- 4800 m
Sey ------------ 4800 m
Recharge altitude (m x 1000)
5.4 -
5.2
-12.5 -12 -11.5 -11 -10.5 -10 -9.5 -9 -8.5 -8

Delta Orygen-lB (%.)
x
• TOF TUF
FIG. 9. Oxygen-18-altitude.
69
Tritium (T.U. +/- 0.6)
3 r
TUF-4-rOF-l
TUF-3
l •
TUF-2
TOF-4
TOr-3 TUC-5
TUC-8 TUC-3 TUC-7
ffr
500 1000 1500 2000 2500
Chloride (ppm)
FIG. 10. Chloride-tritium.
The altitude of the sampling point of Nina Betty suggest that

water emerge from a point distant to the recharge zone The tritium
content T- O T.U. confirm the hypothesis. The same consideration is
valid for El Sey.
In the map 2, the probable recharge zone in accordance with the

isotope data are located. In map 3 the possible recharge areas having
into account the hidrology are indicated
3.3. AQÜEOÖS PHASE THERMOMETRY
In table 6 maximum, minimum and average reservoir temperatures as

computed by différents geothermometers in liquid phase are showed. The
following conclusions may be outlined:
- The Na-K geothermometers yield excesively high temperatures

because the equilibrium Na-Feldespar -K-Feldespar is not achieved.
These thermometers are reliable only to temperatures over 150°C, not
probable in this case.
The Na-K-Ca is not applicable too because although more com-

plete than the Na-K. also requière equilibrium between feldespars.
- Temperatures obtained from K-Mg geothermometer may be conside-

red as reasonables. The K-Mg couple equilibrates faster and at lower
temperatures than the couple Na-K In addition the measured activities
are not in correspondence with a high temperature system, being
correct the interpretation of such equilibrium.
- Temperatures yielded by the Na-Li geothermometer are rather

high. This fact is due to their calibration in granitic systems.
70
AREA 06 RKARGA PROBABLE PARA AGUA CALI6NTE DEL
AREA DE RKAR&A PROBABLE PARA ZONAS DE ' TOCOMAR r POMPEYA'
MAP 2
71
FA A ERJPT A
3ASAMEN 0 FCRMACON «CO C*
FORM AC ON PJNCC"i!SCÂ
MLY PERMEABLE
, BASAL O
FORMAL ON RINCHERA
MEDIANAKNTE ANCCSinS Q A C I T A S Y SLBuPUPO P
POCO PERMEABLE F O R M A C ^ ^ CAUCH^PI
MpfRMEAatE F RMAC ON PASTOS CHCOS
MAP 3
72
TABLE No. 6. GEOTHERMAL RESERVOIR TEMPERATURE BY
CHEMICAL GEOTHERMOMETERS
GEOTERMOMETROSJ AC4 AC5 AC6 BAC 7 LO LTI LTI2 EHI RP
Na/K (F) 178.9 187.4 188.5 198.6 173.3 176.0 228.2 232.4 175.9
NA/K (T) 140.9 151.0 152.5 164.7 134.2 137.4 201.8 207.1 136.7
Na-K-Ca 177.5 177.5 183.4 186.6 176.0 178.7 211.3 225.5 159.7
Na-K-Ca (Mg)161.6 168.9 159.1 137.6 172.8 174.2 206.1 225.5 29.7
Na-Li 148.1 134.6 138.3 145.3 141.0 138.6 144.6 143.0 227.7
i
K-Mg 131
133.4
.2129.8 118.8 151.1 149.8 168.9 212.8 101.2
Mg-Li 209.9 198.2 194.3 175.6 242.7 236.1 233.1 297.5 151.1
TQC 174.3 165.4 178.2 172.0 177.5 181.6 168.8 191.2 149.6
TQA 163.6 156.2 166.7 161.6 166.2 169.5 159.0 177.3 143.8
TCH 152.4 142.2 156.8 149.7 156.0 160.8 146.0 171.9 124.3
Na/K (F): Fournier

Na/K (T): Truesdell
Na-K-Ca (Mg): Correction for Mg
TQC: Quartz without vapour loss
TCH: Chalcedony
The temperature is expressed in °C.
- Silica geothermometers shows a probable equilibration with

chalcedony for El Tuzgle and Tocomar, while that in Pompeya the equi-
librium is controlled by the christobalite, if is considered that the
water produced by the well have a temperature similar to that of the
reservoir.
3.4. GAS PHASE THERMOMETBY

The sami empirical geothermometer developed by Panichi, D'Amore
(1981) is used. Its error is ±15°C and gave reasonable values at
high temperature geothermal manifestations. In addition, gas/water
ratio (fas measured on thermal manifestations zones.
Pompeya: The calculated temperature is 71 ± 15°C and the maxi-

mum possible is 91°C. The gas chemical composition is typical of low
enthalpy manifestation, and probably connected to the boundaries of
the geothermal field.
73
Tocomar The geothermometer indicates a temperature of 139 ± 15
°C The gas/water ratio decreases from west to east, in agreement with
the reservoir geometry Although, the gas/water ratio is low in all
the area along, in agreement with the calculated température
Tuzgle The calculated temperature are lower (80 °C) than those
of Tocomar area In this zone, there are interferences with a shallow
cold water acuifer The gas/water ratio increase from north to south
4 CONCLOSIONES
Nina Betty The origin of the thermal anomaly is a deep circula-

tion, with a heat exchange between rock and water The calculated re
charge altitude is 4800 m a s l
It is not completely explained the relatively high value of t80
Sey In this point, the sample has got an isotopic composition

similar to TOF-1 The chemical analysis indicates that it was not
heated during its circulation The calculated recharge altitude is
4800 m a s l , therefore the distance between the infiltration zone
and the discharge point is big
Tocomar Is a medium enthalpy geothermal reservoir, with a

calculated deep temperature of 134~143°C and a low gas/water ratio
the fluid conductivity of 3300 3680 uS/cm The calculated recharge
altitude 5000 m a s l There are neither mixed geothermal fluids nor
shallow water detected
Tuzgle The conditions seems to be similar to those of the Toco

mar area a calculated deep temperature of 132-142"C A low gas/water
ratio but a higher fluid conductivity (up to 6 7 mS/cm) The recharge
altitude is 4500 m a s l The sampled water is a mixture between re
servoir fluid and shallow cold water
Pompeya The sampled water is similar to the well water in the

vicinity from a chemical and isotopical point of view In that way is
possible to say, they originate in the same reservoir with a
temperature close to that measured at the well head (52"C)
ackaotledgefeats - Part of this sort has been perfoned mthin the fraiesorï of the làSî Coordinated Research Prograite
on tie Application of Isotope and Seochetical Techniques in Geotherial Exploration in Latin Aienca (Research Contract
«' im/IG), financial!? supported b? the Coteraient of Italy
REFERENCES
1 Arias J (1979) Areas hidrotermales de las piovincias de Salta y

Jujuy V Convencion Anual Nacional de la frederacion Argentina de
Geologos
2 D Amoie F and Panichi C (1980) Evaluation of deep temperatures of

hydrothermal systems by a new gas geothermometer Geochim cosmo-
chim Acts vol 44, pp 549-556
3 D Amore F and Panichi C (1987) Geochemistry in geothermal explo-

ration Applied Geothermics, Ed by M Economides and P Ungemach,
pp 69-89
74
4. Hidroproyectos S.A. SETEC S. P L -CEP1C S C con la colaboracion de
Geologia de Servicios S A (1985) Estudio de la Segunda Fase de
Prefactibilidad Geotérmica del Area denowinada Tuzgle, Departamento
de Susques.
5 International Atomic Energy Agency (1981) Stable isotope hydrology

Deuterium and oxigen-18 in the water cycle TRS N° 210, pp 103-
142, 223-240. 241-271.
6. International Atomic Energy Agency (1983) Isotope techniques in the

hydrogeological assessment of potential sites for the disposal of
high-level radiactive wastes. TRS N° 228, pp 44-57
7. Vilela C. (1969) Descripciôn geolôgica de la Hoja 6C, San Antonio

de los Cobras, Provincias de Salta y Jujuy Direccion General de
Geologia y Mineria, bole tin N° 110
75
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA
DE LACUNA COLORADA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per l'Energia Elettrica,
Pisa, Italia
M. ALVAREZ
Universidad Mayor de San Simon,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE LAGUNA COLORADA, BOLIVIA.
La zona geotérmica de Laguna Colorada esta situada en el extremo sur de

Bolivia, cerca de la frontera con Chile y con la Argentina.
Hasta la fecha se han perforado cinco pozos de sondeo: API, SM1, SM2,
SM3 y SM4; salvo el ultimo, todos los demâs son productives.
La composiciôn quiraica e isotopica de los fluidos obtenidos es casi idén-

tica a la del campo geotérmico de El Tatio (Chile), que se encuentra a poco
mas de 20 km de alli.
La verdadera diferencia entre los dos campos consiste en las actividades

de superficie: contrariamente a lo que ocurre en El Tatio, ninguno de los
caudales térmicos de Laguna Colorada muestra una penetraciön importante en la
fase liquida profunda; tan solo unos cuantos manantiales térmicos al borde
del salar de Challviri, a unos 10 km al SE de los pozos, tienen una ligerisima
contaminaciön. Sin embargo, hay varias zonas con entrada de vapor y gas deri-
vada de la separacion en la fase profunda: estanques calientes y fumarolas
forman sistemas irapresionantes que se localizan cerca de los pozos SM1, SM2 y
SM3 (zona de Sol de Mariana), y a 10 km al 0 de los pozos (zonas de Huaylla Ja-
ra y Aguita Brava).
GEOCHEMICAL REPORT ON THE LAGUNA COLORADA GEOTHERMAL AREA, BOLIVIA.
The geothermal area of Laguna Colorada is located at the
southern end of Bolivia, near the border with Chile and Argentina.
To date five boreholes have been drilled: A P I , SM1, SM2, SM3
and SM4; except the last one all of them are productive.
77
Chemistry and isotopic composition of the produced fluids are
almost identical to those of the geothermal field of El Tatio
(Chile), just over 20 km away from there.
The real difference between the two fields regards surface

manifestations: otherwise than at El Tatio, no thermal discharge
of Laguna Colorada shows a substancial inflow of deep liquid
phase; only a few thermal springs at the edge of Salär de

Challviri, some 10 km to the SE of the wells, have a very little
contamination. Several are instead the zones with an inflow of
steam and gas derived from phase separation at depth: impressive

systems formed by hot pools and fumaroles occur in the
neighbourhood of SM1, SM2 and SM3 wells (Sol de Manana area) , and
10 km to the W of the wells (Huaylla Jara and Aguita Brava areas).
1. Lineamiento historico della exploraciön geotermica en

Bolivia
Como todos los paises de la cordillera Andina, Bolivia posée

condiciones geolögicas muy favorables para la explotaciön de
fuentes geotérmicas para generar energia. El gobierno de Bolivia,
tomando en cuenta tal potencial, promoviö las actividades de
exploraciön desde 1974.
Casi todos éstos estudios fueron llevados acabo con cooperaciön
internacional por expertos en Geotermia, en 1976 el gobierno de

Italia enviö una firma de consultores Italianos para un estudio de
reconocimiento de las areas al oeste de la codillera Andina,
realizado por el Programa de las Naciones Unidas para el

Desarrollo (U.N.D.P ) dentro el proyecto BOL/71/532.
Posteriormente fue hizo un estudio de prefactibilidad en dos
areas seleccionadas en base a los estudios de reconocimiento:

Salar de Empexa y Laguna Colorada/Salar de Challviri distantes una
de la otra aproximadamente 150 Km.
78
Como una consecuencia de los resultados favorables obtenidos y
en base a consideraciones econömicas se escogiö Laguna Colorada
como area para empezar la factibilidad del proyecto. El estudio de
factibilidad fué después ejecutado en el arnbito del Proyecto
BOL/84007 [1] de las Naciones Unidas entre los anos 1985 - 1990.
Todas las informaciones de caractér geolögico que se presentan
en continuaciön han sido tomadas del informe citato.
1.1. Desarrollo geolögico de la zona en estudio
El area del proyecto forma parte de un arco volcânico de edad

mioceno-pleistocénica y esta situada en la parte méridional de
Bolivia cerca del limite con Chile.
La morfologia es tipicamente volcânica, caracterizada por
grandes extensiones ignimbriticas, que han nivelado las asperezas
morfolögicas, y sucesivamente modelada por fenömenos de érosion
glacial.
Las estructuras prédominantes en escala régional tienen dos
direcciones principales: una aproximadamente N-S paralela a la
cadena y una NO-SE que muestra un componente transcurrente
izquierdo.
La evoluciön geolögica de la zona puede esquematizarse de la
siguiente manera:
- en el Plioceno, probablemente por encima de plataformas
ignimbriticas, estaban présentes unos aparatos volcânicos con

actividad escencialmente efusiva que emitian productos de
composiciôn dacitica y andesitica;
- en el Pleistoceno inferior el ârea examinada fué cubierta
por grandes volumenes de ignimbritas de composiciôn dacitica y
andesitica que nivelaron la morfologia preexistente;
después de las erupciones ignimbriticas la actividad
volcânica continua hasta el présente con edificios situados a
lo largo del eje N-S de la cadena. La actividad es mixta pero
79
prevalece aquella de tipo efusivo de composiciön andesitico-
dacitica;
- en la parte mas elevada del area son evidentes las huellas
de una glaciaciön post-ignimbritica occurrida probablemente
hace 35000 y 16000 anos;
- en el periodo post-glacial se mantiene una actividad nco-
tectônica evidenciada por fallas activas que afectan a las
plataformas ignimbriticas y que permiten el ascenso de los
fluides calientes que alimentan las varias manilestaciönes
termales de la zona.
Todos los datos geolögicos, vulcanolôgicos y estructurales, y
en particular: 1) la persistencia de la actividad volcânica por un
largo periodo con pocas variaciônes de la composiciön de los

productos emitidos, 2) el gran volümen de las igniinbritas y 3) las
caracteristicas quimicas y petrogrâficas de los productos

subactuales similares a las de los productos mas antiguos,
sugieren la existencia de câmaras magmaticas volumétricamente
importantes situadas por debajo del eje volcânico activo, y por lo
tanto, la persistencia de una importante fuente de calor

localizada inmediatamente al Oeste de la zona de las
manifestaciones.
En lo que se refiere al reservorio geotérmico, este se

encuentra en formaciones volcânicas profundas como ha sido
confirmado por el pozo SM1 .
2. Muestreo, determinaciones de campo y de laboratorio
2.1 Generalidades
Los datos que se refieren a las manifestaciones superficiales
muestreadas en 1986 provienen de] Informe Final sobre Exploraciön
de Superficie realizado para el proyecto BOL 84/007 [1], y del
reporte de la IAEA [2]. También los datos de 1989 relatives a las
80
manifestaciones fueron obtenidos en el ambito del programa de la
IAEA, el mismo que permitiö todas las determinaciones isotöpicas
de las muestras de los pozos.
Estân actualmente disponibles, ademâs de las informaciones
sobre las manifestaciones y drenaje superficial, los datos de los
pozos API, SM1 y SM2. Los resultados incluyen anâlisis realizados
en el campo o en laboratorio de muestras de vapor condensado,
fluido total, liquido en el vertedero, adémas de dos muestras de
fondo pozo.
El estudio de los datos quimicos de Laguna Colorada tuvo el
objeto de définir de manera preliminar las caracteristicas de los
fluidos geotérmicos asi como de proponer algunas hipôtesis sobre
la extension del reservorio y los procesos de circulaciôn y
procedencia de los fluidos profundos.
La ubicaciön de los pozos y manifestaciones superficiales es
reportada en la fig. 1. La fig. 2 muestra el esquema de aparato de
cabezal de pozo con los puntos de muestreo.
2.2. Metodologia de muestreo y anâlisis
Los liquides fueron recogidos en 6 distintas muestras para

analizar los prinipales costituentes y aquellos in traza, alumino
monomerico, silica, isotopos stables ( O y D) y tritio.

Se realizaron en el campo las determinaciones de temperatura,
Eh, Ph, condutividad eléctrica, alcalinidad y âcido suifihidrico.
Las muestras de fluidos seleccionados fueron analizadas en los
laboratories de ENEL (Ente Nazionale per l'Energia Elettrica)
determinando los siguientes paramètres : pH, Conductividad
Eléctrica, Alcalinidad, Ça, Mg, K, Li, Rb, Cs, Sr, Fe Total, B, As
Total, Zn Total, Pb Total, Alcalinidad, Sulfates, Cloruros,
Fluoruros, Bromuros, Acido Bôrico, Silice.
81
V
// ) °*wa, jf^ - ^rX»-A^
•v ,'_'--> ^- Ô-i •~ >~.
J
__>^v*
sfe^Mt^"1"^^
âss*^SHJ
^l^^- / 5>V V-" ^ ^<A-^ J(" •=•- / / /OV^r h-<««,oJ
^t^ f^^ ^-^k i S-^! ^ ^ f / <-^-V4°r^
Û^'^S^rtpx <V^ J / ^-i~ _,—— ^^>yA K_ v ^-, I \ cf««d-yiscACM£i«s ^/KT.,1 \i=
^^s^^Ci^^^^
^~-Ci'->(/LT!X-—vi Sî- I ^^1^^
^>Ro",<riCAMo«'>»;vO'raro^ .aa^fo^ -'KJ XT ,/nv S^l
^^{SM^Â1™ "i1 fHJ? i^^^^^^^fe^^sTir^
^««1^-^«
LODOS CALIENTES
SURGENTES
7
rs^sjT ^- POZOS
SUPERFICIALES
Escala 1 250000
FIG 1 ' MAPA DE IDS PUNTOS DE HUESTREO
82
LEYENDA Boca pozo
Punto de m u e s t r e o de fluido t o t a l y liquido de condensado
despues del separador p o r t a t i l
Separador a t m o s f e r i c o
Punto de muestreo de liquide de veriedero
Uertedero
à /(5)
Fluido t o t a l y gas ( D e s p u e s de Lit|uido s e p a r a d o a c o n d i c i o / i e s a t m o s l e n c a s ( V e r t e c l e r o )

separation con separador p o r t a t i f )
Fig. 2 Esquema de los puntos de muestreo
En lo que se refiere a los componentes isotöpicos fueron

analizados en su totalidad en Viena por la Agenda Internacional
de Energia Atömica a través del programa que se habia mencionado
anteriormente.
En las tablas 1-5 estän reportados los datos de las muestras
de agua consideradas, en las cuales se presentan general-
mente desviaciones porcentuales < 10 %.
En la tabla 6 estân reportados los datos de las muestras de
gases.
Text cont. on p. 93.
83
Tabla 1 - Analisis quimico de los pozos AP1.SM1, y SM2(mg/l)
oo T.M. = ST (vertedero), = FT (fluido total)
-t-
T.M. = UB (en pozo), = C (condensado)
Muestra Fecha T. M.. T.c. pH.c. Con.c. Alc.c. 1r.l. pH.l.

Cod. Con.l. Alc.l. Rlc.l. 1:a Mg Na K Cl S04 HC03 Si 02 H3B03 Br I
°C MS meq/l °c MS meq/l meq/l
AP1 20/12/88 15 FT 20.0 6.41 3820 0.6 20 6.18 3500 0.6 0.5 47,.0 0.140 770.0 128.0 1270.0 80.240.5 251.0 245.0 1.40 0.00
AP1 07/01/89 965 ST 74.5 7.2017400 0.8 20 6.78 12700 0.7 0.5 186,.0 0.075 3620.0 631.0 6500.0 168.0 37.6 617.0 806.0 0.00 0.00
AP1 04/01/89 958 FT 17.0 5.95 7100 0.8 20 6.89 6780 0.4 0.4 76,.6 0.040 1640.0 269.0 2770.0 82.053.0 301.0 394.0 2.60 0.34
SM1 03/02/89 980 FT 18.5 7.3218300 0.5 20 6.73 16300 0.4 0.2 212,.0 0.060 4560.0 707.0 8400.0 30.022.5 665.0 980.0 8.50 0.89
SM1 15/10/89 2921 UB 20 6.27 6910 1.7 1.6 56,.0 0.160 1390.0 180.0 2340.0 24.6 106.8 1100.0 231.0 2.50 0.29
SH1 03/02/89 979 ST 80.5 0.0017500 0.5 20 6.75 18600 0.4 0.2 249,.0 0.079 5230.0 829.0 9560.0 35.524.9 686.0 1070.0 0.00 0.00
SM2 23/06/89 1697 ST 83.0 7.35 19300 0.5 20 6.89 17700 0.4 0.0 232,.0 0.076 5230.0 925.0 9310.0 35.9 7.4 755.0 1070.0 0.00 0.00
SM2 23/06/89 1695 FT 20.0 7.0018100 0.5 20 6.75 16900 0.6 0.1 189,.0 0.050 4130.0 675.0 7830.0 30.727.6 678.0 936.0 8.30 0.84
SM2 13/10/89 2922 WB 20 6.70 1570 2.8 2.6 10,.3 0.070 296.0 37.5 347.0 119.0 170.2 372.0 48.9 0.54 0.17
AP1 06/01/89 963 C 14.5 5.45 158 0.6 20 6.64 261 0.4 0.4 .6
1, 0.006 28.5 4.2 43.3 4.4 46.7 4.6 3.0 0.00 0.00
SM1 03/02/89 978 C 20.5 5.18 112 0.3 20 6.48 252 0.1 0.1 0..2 0.000 9.4 1.7 12.8 2.0 41.1 2.4 4.5 0.00 0.00
SM2 23/06/89 1696 C 13.0 5.15 45 0.2 20 5.57 72 0.1 0.1 0..0 0.000 3.3 0.0 5.5 0.0 38.6 0.0 4.1 0.00 0.00
Muestra Codigo F H2S Li Rb Cs NH4 Sr Ba Zn Sb Pb As Fe Al. T Al. M TDS TAN TCAT 018 Deut. Trit. Prof.
meq/l meq/l 0/00 o/oo U.T. m.
AP1 15 14 .00 5.10 8.20 1.50 3.10 5 .800 0.48 0.002 0.900 0.280 0.005 5.80 1.200 0.096 0.000 2840 38.3 40.6 -9.69 -83.5
AP1 965 37.00 3.110 12569 187.0 188.0 -5.94 -67.8 0.12
AP1 958 1.80 10.60 16.80 2.90 5.40 4 .820 0.99 0.080 0.023 0.270 0.000 3.30 0.680 0.060 0.000 5584 80.5 84.7 -8.82 -83.3
SM1 980 3.90 15.70 48.50 8.30 15.90 2 .040 3.70 0.330 0.010 0.630 0.000 25.90 0.120 0.320 0.000 15689 247.0 234.0 -6.39 -79.5 0.04
SM1 2921 0 .66 12.30 1.80 5.20 11 .700 2.20 0.500 0.220 0.140 0.030 0.72 4.400 1.500 0.720 536S 66.5 70.3 -7.27 -79.6 1000
SM1 979 0.00 14.30 47.50 2 .680 17724 270.0 268.0 -5.53 -72.8
SM2 1697 0.00 16.70 53.00 2.300 17630 277.0 270.0 -5.55 -74.9
SH2 1695 3 .90 12.30 45.00 8.20 14.90 1 .890 3.50 0.320 0.720 0.000 25.90 0.120 0.280 0.000 14596 227.0 213.0 -6.26 -78.1
SM2 2922 3 .30 3.60 0.41 1.20 7.300 0.12 0.060 0.020 0.010 1.20 0.350 2.800 2.400 1255 12.3 15.3 -6.88 -74.5 1240
AP1 963 1.36 0.280.04 9.110 0.02 0.002 0.019 0.012 0.000 0.16 0.310 102 1.4 2.0 -11.81 -99.4
SM1 978 6.80 0.09 0.20 3 .590 0.004 0.210 0.000 0.06 0.060 45 0.5 0.7 -11.29 -103.9
SM2 1696 10.20 5 .110 0.000 0.000 0.05 0.000 29 0.3 0.4 -11.25 -102.1
Tabla 2 - Analisis quimico de todos calientes y fumarolas
T.M. = HP (lodos calientes), = F (fumarolas)
Muestn3 Fecha Cod. T. M. T.c. pH.c. (:on.c. A Ic.c. T.I. pH.l. Con. l. Ale. 1. Rlc.l. Ca Mg Na K Cl S04 HC03 S i 02 H3B03
°c MS meq/l "C fiS meq/l meq /l
HAB1 15/03/86 867 HP 79.0 4.58 1670 23 4.09 1590 3.4 1.000 2.3 1.4 1.0 572.0 0.0 43.3 1.0
HAB2 15/03/86 868 HP 81.0 3.57 2650 23 3.12 2680 8.2 3.300 3.4 2.8 0.6 1010.0 0.0 103.0 0.7
HHJ2 15/03/86 14 HP 82.9 3.14 1830 20 3.22 1830 0.0 0.001 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HHJ3 16/02/89 996 HP 70.0 2.44 3600 20 2.04 4050 21.6 8.600 19.8 7.9 1.4 1530.0 0.0 286.0 70.4
HSM 17/01/89 988 HP 81.5 3.04 2010 20 2.40 2130 44.5 13.900 36.4 16.4 5.5 941.0 0.0 300.0 2.9
HSM3A 13/03/86 10 HP 53.6 2.25 4030 2.21 10.8 14.000 18.4 12.5 0.8 1740.0 0.0 0.0 9.0
HSM4 13/03/86 11 HP 84.0 3.38 1580 31.0 18.400 87.0 30.5 34.8 732.0 0.0 0.0 63.0
HSH7 13/03/86 12 HP 67.2 6.57 841 0.8 20 6.12 0.6 1.1 0.800 12.9 21.1 5.4 276.0 49.7 0.0 598.0
HSH8 13/03/86 13 HP 73.2 2.16 3140 1.6 0.090 1.8 2.9 0.7 600.0 0.0 0.0 130.0
FAB 15/01/89 999 F 15.0 5.10 250 0.6 20 6.88 58 0.3 1.4 0.014 0.4 0.0 0.5 4.6 65.9 0.2 0.0
FAB3 15/03/86 1002 F 84.5
FAB6 15/03/86 1001 F 84.4
FHJ 16/01/89 1000 F 17.0 5.53 108 4.5 20 6.62 89 0.6 0.3 0.005 0.5 0.1 0.7 4.6 285.6 0.1 0.0
FHJ1 12/03/86 15 F 84.6
FHJ2 12/03/86 16 F 84.6
FSM1 13/03/86 17 F 84.5
FSM2 13/03/86 18 F 84.5
FSM5 13/03/86 19 F 84.7
FSM6 13/03/86 20 F 84.7
FSHA 17/01/89 1001 F 12.0 4.10 41 20 6.58 0.3 0.8 0.013 2.3 0.4 1.6 5.9 19.2 3.9 0.6
FSMB 17/01/89 1002 F 20.0 4.80 6 0.3 20 6.10 58 0.3 0.2 0.013 0.4 0.1 0.5 3.4 80.5 1.7 0.8
FSHD 17/01/89 1003 F 19.0 5.00 114 0.8 20 6.42 117 0.3 0.1 0.002 0.0 0.1 0.2 23.4 83.0 1.0 0.0
SMO 17/01/89 1004 F 16.0 4.30 2 20 4.48 18 0.0 0.2 0.005 0.2 0.1 0.3 6.3 0.0 0.8 0.3
SMO 13/03/86 21 F 118
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Tabla 2 - ( cont.)
Muestra Codigo H2S NH4 TDS TAN TCAT 018 Deut. Trit. Altitud
meq/l meq/l o/oo o/oo U.T. s.n.m.
HAB1 867 219.00 11. 9 12.5 0..78 -42. 0 4890

HAB2 866 284.00 21. 0 16.6 -0..28 -43.2 4890
HHJ2 14 0.010 373 0.0 0.0 -0..60 -42. 2 4760
HHJ3 996 89.600 2035 31.9 7.8 1..47 -36.9 0.42 4760
HSM 988 109.00 1470 19.7 11.4 -2..27 -46. 2 0.13 4850
HSM3A 10 129.00 1935 36.2 10.0 5..89 -34. 0 4850
HSM4 11 125.00 1122 16. 2 14.6 1..27 -37. 1 4850
HSM7 12 9. 640 926 5.9 1.8 4850
HSM8 13 54.400 792 12. 5 3.3 3..72 -37. 8 4850
FAB 999 29.10 7.600 45 0.4 0.5 -10,.36 -80. 8 4890
FAB3 1002 0.0 -9..66 -77. 2 4890
FAB6 1001 0.0 -12..78 -87. 3 6.5 4890
FHJ 1000 15.10 13.600 40 0.5 0.8 4760
FHJ1 15 -8,.49 -79. 5 4760
FHJ2 16 -9.95 -86. 2 4760
FSM1 17 -9.,32 -81. 9 4850
FSM2 18 -9.,14 -80. 8 4850
FSM5 19 -9.30 -83. 6 4850
FSM6 20 -10. ,38 -90. 2 4850
FSMA 1001 44.20 0.130 60 0.2 0.2 -8.,79 -77. 8 4850
FSMB 1002 29.10 8.200 46 0.2 0.5 -8.82 -78. 7 4850
FSMD 1003 0.48 15.800 42 0.5 0.9 -9.,05 -80. 2 4850
SMO 1004 27.20 0.630 36 0.2 0.1 -9.,13 -80. 1 4850
SMO 21 -8.,64 -79. 7 4850
Tabla 3 - Analisis quimico de las surgentes (mg/l)
Muestra Fecha Cod. T.M. T.c. pH.c. Con.c. Alc.c. T.l. pH.l. Con.l. Alc.l. Rlc.l. Ça Hg Na Cl S04 HC03 SÎ02 H3B03 Br I
°C * meq/l °C us meq/l meq/l
LC1 11/01/89 993 S 22.5 7.19 377 1.1 20 6.50 362 0.9 0.9 8.4 3.600 63.4 8.1 59.1 30.1 67.1 80.9 4.4 0.00 0.00
LC1 18/07/86 1 S 21.5 7.71 381 1.2 24 6.48 391 1.1 1.1 7.5 3.800 56.0 9.0 57.7 28.6 71.4 74.0 5.1 0.00 0.00
LC11 23/02/89 998 S 31.0 7.03 1480 3.1 20 6.95 1470 3.1 3.1 37.1 21.400 259.0 28.8 337.0 145.0 189.2 96.9 20.2 0.27 0.00
LC11 17/03/86 7 S 30.1 7.31 3.2 20 7.23 1670 3.5 38.0 24.100 246.0 35.6 358.0 149.0 194.6 116.0 20.9 0.00 0.00
LC4 11/01/90 994 S 22.0 7.61 512 1.1 20 6.90 523 1.2 1.1 9.4 5.500 99.4 10.9 106.0 42.6 70.2 80.9 6.5 0.00 0.00
LC4 18/07/86 2 S 21.1 7.74 447 1.2 24 6.38 447 1.2 1.2 7.9 4.000 66.9 9.6 71.2 32.6 70.2 76.0 5.6 0.00 0.00
LC5 28/02/89 995 S 21.0 8.20 820 0.7 20 6.90 903 0.7 0.7 6.8 4.200 187.0 12.6 202.0 104.0 43.3 89.8 15.1 0.00 0.00
LC5 18/07/86 3 S 20.8 8.10 946 0.8 24 6.29 1000 0.7 0.7 6.2 4.200 172.0 14.4 201.0 104.0 45.2 82.0 15.1 0.18 0.00
SAB7 15/03/86 0869 S 8.2 7.68 264 1.1 23 6.57 253 1.4 1.4 19.0 8.000 16.8 9.9 3.6 42.4 67.1 52.0 1.2 0.00 0.00
SC1 10/01/89 989 S 40.0 7.50 1150 1.6 20 6.67 1120 1.6 1.4 51.5 6.300 188.0 30.0 160.0 267.0 97.0 141.0 24.2 0.17 0.00
SC1 18/07/86 0861 S 40.0 7.79 1140 1.5 24 7.15 1130 1.5 1.5 54.7 6.700 160.0 26.0 125.0 271.0 92.7 133.0 19.9 0.14 0.00
SC11 10/01/89 991 S 36.5 7.84 485 0.7 20 6.60 484 0.7 0.7 36.4 2.900 66.8 4.4 3.6 190.0 43.3 60.7 1.9 0.00 0.00
SC11 18/07/86 0865 S 36.2 8.25 496 0.8 23 6.71 501 0.8 0.8 36.6 2.900 60.0 1.1 2.6 180.0 47.6 70.0 2.2 0.00 0.00
SC2 18/07/86 0862 S 41.0 7.69 1180 1.9 24 7.15 51.6 6.800 190.0 31.0 180.0 250.0 112.9 139.0 30.0 0.00 0.00
SC21 10/01/89 992 S 30.5 7.78 487 0.8 20 6.81 370 0.9 0.9 16.8 0.480 66.1 3.1 6.4 118.0 51.3 71.2 2.9 0.00 0.00
SC21 18/07/86 0866 S 29.3 8.50 376 0.9 23 6.48 377 0.9 0.9 16.7 0.440 59.0 2.8 2.6 113.0 56.1 69.0 2.9 0.00 0.00
SC4 18/07/86 0863 S 33.9 8.25 701 1.1 24 7.03 727 1.1 1.1 29.8 2.900 102.0 14.0 59.4 174.0 65.3 107.0 10.8 0.00 0.00
SC4 10/01/89 990 S 34.5 7.50 650 1.6 20 6.67 670 1.1 1.1 28.9 2.800 110.0 15.5 65.0 175.0 97.0 104.0 10.2 0.00 0.00
SHJ1 14/02/89 997 S 30.0 7.05 400 4.3 20 7.09 517 4.3 4.2 43.3 24.300 34.2 8.7 3.2 56.4 262.4 116.0 0.7 0.00 0.00
SHJ2 17/03/86 4 S 29.4 7.22 440 4.6 20 7.34 509 4.6 38.5 25.000 28.7 11.4 1.2 50.9 280.1 122.0 1.6 0.00 0.00
SHJ3 17/03/86 5 S 26.7 7.65 189 0.8 20 6.87 158 0.8 4.8 2.550 19.0 5.9 1.0 69.5 45.8 92.0 1.6 0.00 0.00
SHJ4 17/03/86 6 S 27.5 7.09 375 3.1 20 7.23 432 3.4 31.0 19.200 28.5 9.0 1.0 68.2 189.2 116.0 1.9 0.00 0.00
SPB1 21/01/89 986 S 12.0 7.48 86 0.6 20 6.32 94 0.5 0.5 7.2 2.000 9.8 1.5 3.6 13.3 33.6 21.5 1.1 0.00 0.00
SPB1 16/03/86 0870 S 10.9 6.05 362 0.6 21 7.10 98 0.5 0.5 7.0 2.100 9.0 1.6 3.0 12.9 34.8 31.8 1.5 0.00 0.00
SPB2 16/03/86 0871 S 12.0 6.95 130 0.4 21 6.67 89 0.4 0.4 6.8 1.700 5.6 3.1 4.1 15.0 24.4 47.8 1.6 0.00 0.00
SPB3 16/03/86 0872 S 10.6 6.60 98 0.3 21 6.58 74 0.4 0.4 5.9 1.600 3.9 2.5 2.0 12.6 19.5 41.2 1.2 0.00 0.00
WP1 22/01/89 983 S 37.0 7.66 374 0.9 20 6.65 370 0.9 0.9 22.2 2.900 59.8 6.6 3.4 126.0 56.1 83.5 6.9 0.00 0.00
oo
oc Tabla 3 - ( cont.)
Muestra Cod i go F Li Rb Cs NH4 Sr Ba Sb Pb As Fe Al. T TDS TAN T CAT 018 Deut. Trit. Altitud
meq/l meq/l o/oo o/oo U.T. s.n.m.
LC1 993 0.00 0.21 0.00 0.00 0.000 0.00 0.000 0.000 0.000 0.16 0.000 0.000 326 3.4 3.7 -12.55 -95.9 4280
LC1 1 0.42 0.19 0.00 0.00 0.011 0.08 0.000 0.000 0.000 0.17 0.000 O.OOÛ 314 3.4 3.4 -12.38 -93.4 4280
LC11 998 0.28 1.00 0.09 0.00 0.000 0.39 0.010 0.000 0.000 0.40 0.000 0.017 1137 15.6 15.8 -10.48 -76.6 0.04 4280
LC11 7 0.22 0.12 0.03 0.00 0.011 1.50 0.018 0.000 0.002 0.50 0.000 0.000 1185 16.4 15.5 -10.57 -74.6 4280
LC4 994 0.00 0.33 0.00 0.00 0.000 0.00 0.000 0.000 0.000 0.18 0.000 O.OOÛ 432 5.0 5.6 -12.42 -94.6 4280
LC4 2 0.44 0.23 0.00 0.21 0.011 0.08 0.000 0.000 0.000 0.17 0.027 0.035 345 3.8 3.9 -12.48 -92.7 0.00 4280
LC5 995 0.00 0.68 0.00 0.00 0.120 0.00 0.000 0.000 0.000 0.38 0.000 0.000 666 8.6 9.2 -11.51 -85.8 4280
LC5 3 0.34 0.64 0.00 0.00 0.012 0.11 0.000 0.000 0.000 0.44 0.000 0.000 646 8.6 8.6 -11.36 -85.5 0.00 4280
SAB7 0869 0.00 0.00 0.00 0.00 0.050 0.10 0.010 0.000 0.000 0.00 0.047 0.059 220 2.1 2.6 -9.09 -67. Z 7.50 4890
SC1 989 0.63 0.87 0.17 0.26 0.000 0.34 0.020 0.000 0.012 0.40 0.000 0.150 968 11.7 12.2 -11.01 -88.4 4400
SC1 0861 0.64 0.63 0.10 0.33 0.009 0.36 0.020 0.012 0.000 0.66 0.026 0.000 892 10.7 11.0 -11.01 -88.4 0.00 4400
SC11 991 0.26 0.05 0.00 0.00 0.000 0.08 0.000 0.000 0.028 0.03 0.000 0.028 410 4.8 5.1 -10.94 -86.6 4400
sen 0865 0.26 0.03 0.00 0.00 0.010 0.08 0.000 0.024 0.000 0.02 0.000 0.000 403 4.6 4.7 -10.94 -86.6 0.00 4400
SC2 0862 0.66 0.77 0.13 0.33 O.OOÛ 0.34 0.020 0.000 0.000 0.73 0.044 0.000 994 12.1 12.3 4400
SC21 992 0.22 0.07 0.00 0.00 0.000 0.03 0.020 0.011 0.000 0.10 0.000 0.018 337 3.5 3.8 -10.94 -83.8 4400
SC21 0866 0.21 0.03 0.00 0.00 0.008 0.02 0.020 0.032 0.000 0.05 0.012 0.040 323 3.4 3.5 -10.96 -82.7 0.00 4400
SC4 0863 0.52 0.32 0.08 0.00 0.010 0.20 0.010 0.024 0.000 0.41 0.000 0.000 567 6.4 6.6 4400
SC4 990 0.44 0.42 0.08 0.00 0.000 0.20 0.000 0.000 0.000 0.37 0.000 0.000 610 7.1 6.9 4400
SHJ1 997 0.00 0.03 0.00 0.00 0.000 0.00 0.000 0.000 0.000 0.03 0.000 0.000 549 5.6 5.9 -10.45 -68.8 0.25 4640
SHJ2 U 0.00 0.06 0.05 0.00 0.007 0.14 0.000 0.000 0.000 0.00 0.000 0.000 560 5.7 5.5 4640
SHJ3 5 0.28 0.06 0.06 0.00 0.008 0.07 0.000 0.000 0.000 0.00 0.000 0.000 243 2.2 1.4 -11.35 -75.5 4620
SHJ4 6 0.16 0.06 0.06 0.00 0.008 1.30 0.000 0.000 0.000 0.00 0.000 0.000 466 4.5 4.6 -10.51 -70.5 0.70 4580
SPB1 986 0.00 0.00 0.00 0.00 0.000 0.00 0.000 0.000 O.OOÛ 0.00 0.000 0.000 94 0.9 1.0 -11.85 -94.3 0.00 4700
SPB1 0870 0.21 0.01 0.00 0.00 0.015 0.04 0.000 0.000 0.000 0.00 0.260 0.000 104 0.9 1.0 -12.06 -91.4 0.16 4700
SPB2 0871 0.00 0.01 0.00 0.00 0.020 0.05 0.000 0.000 0.000 0.00 0.000 0.000 110 0.8 0.8 -11.57 -89.7 4700
SPB3 0872 0.00 0.00 0.00 0.00 0.010 0.04 0.000 0.000 0.000 0.00 0.000 0.000 90 0.6 0.7 4700
WP1 983 0.25 0.05 0.00 0.00 0.000 0.09 0.000 0.000 0.000 0.03 0.000 0.000 368 3.7 4.1 -9.70 -79.0 0.20 4860
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Tabla 4 - A n a l i s i s quimico de aguas supcrficiales (mg/l)
T - M . = LA (lagunas), = R (rios), = N (nieve)
Muestra Fecha Cod. T. M. T . c . pH.c. Con.c. A l c . c . T . l . pH.l . Con. I. A l e . I . R l c . l . Ca Mg Na K Cl S04 HC03 S i 02 H3B03 Br
°C MS meq/l •c MS meq/ 1 meq/l
LC12 17/03/86 8 LA 19.2 8.05 206

31. 8.42 200000 27.2 276.0 669.00 41000 3580 53900 .0 22600 1909.8 93.0 4180.0
RAB 22/01/89 985 R 16.0 6.95 189 0.8 20 6.44 196 0.8 0.8 17.8 6.100 14.3 2.8 2 .2 55,.6 4 5 . 8 62.2 0.6 0.00
RHJ 19/01/89 984 R 2.0 8.50 241 3.5 20 7.37 439 3.4 3.4 33.9 19.800 33.8 9.0 2 .9 64,.6 210.5 91.7 0.8 0.00
RS 21/01/89 987 R 16.5 7.50 288 2.3 20 6.79 224 2.3 2.3 15.2 7.200 30.7 3.0 4 .4 7,.0 139.7 57.4 1.7 0.00
SC10 18/07/86 0864 LA 24.0 8 . 2 5 31600 2.7 23 7.51 2.6 2.1 336.0 174.00 5700.0 236.0 8780 .0 1790,.0 162.3 76.4 4 1 0 . 0 3.60
SNOW / / N
Muestra Codi go F Li Rb Cs NH4 Sr Ba Zn Sb Pb As Fe ALT TDS TAN TCAT 018 Deut. Tri t . A l t i t u d
meq/ 1 meq/ 1 o/oo o/oo U. T s. n. m.
LC12 8 0.89 165.0 12.80 21.30 0.000 0 . 0 00.084 0.080 0.020 0.100 76.00 1.230 0.500 128486 2020 1970.0 -0.51 -28.1 4275
RA8 985 0 . 0 0 0 . 0 0 0.00 0.00 0.200 0.00 0.000 0.000 0.000 0.000 0.01 0.000 0.000 208 2.0 2.1 -10.22 -75.5 0. 6 4760
RHJ 984 0.00 0.03 0.00 0.00 0.210 0.00
0.000 0.000 0.000 0.000 0.03 0.000 0.000 467 5.1 5.0 -7.68 -54.2 0. 5 4310
RS 987 0 . 0 0 0 . 1 5 0.00 0 . 0 0 0 . 1 3 0 0.000.000 0.000 0.000 0.000 0.13 0.000 0.000 267 2.6 2.8 -12.10 -96.1 0. 2 4340
SC10 0864 1 . 5 0 2 . 6 0 1.60 3 . 4 0 0.900 8.800.000 0.060 0.000 0.000 3 . 5 0 0.230 0.460 17691 288.0 285.0 -8.04 -68.3 4600
SNOW -8.00 -47.4 5000
Tabla S - Analisis quimico de fluidos del Tatio (mg/l)
T.M. = FT (fluido total), = S (surgentes)
T.M. = HP (lodos calientes), = H (nieve)
Muestra Fecha l.M.

T.c. pH.c. T.I. pH.l. Ale. I. Ca Mg Na K Cl S04 HC03 SÎ02 H3B03 Li Rb Cs NH4 TDS 018 Deut.
°C °C meq/l
H28 01/11/68 HP 78.0 0.00 15 6.70 0.5 37 0.00 53 18 0 180 28.1 88 404 -0.90 -44.0
H324 01/10/69 HP 78.0 0.00 15 3.60 0.0 37 0.00 32 9 0 345 0.0 112 535 7.50 -26.0
H347 01/10/69 HP 56.0 0.00 15 4.90 0.0 26 0.00 28 5 0 245 1.2 87 392 6.30 -31.0
HC1 01/11/68 HP 20.0 0.00 15 7.10 2.7 99 0.00 16 8 0 14 164.7 60 362 -8.60 -55.0
HC3 01/11/68 HP 86.0 0.00 15 6.90 0.2 45 0.00 44 15 0 228 15.3 127 474 -3.70 -49.0
HC4 01/11/68 HP 85.0 0.00 15 6.40 0.1 27 0.00 15 10 0 180 3.7 0 236 -3.30 -44.0
S227 01/11/68 S 85.0 0.00 15 7.40 0.7 280 0.30 4600 520 8220 38 45.2 256 1070 47 6.70 15.80 2.900 15106 -5.50 -69.0
S241 01/11/68 S 85.0 0.00 15 7.40 0.7 278 0.00 4320 525 7870 26 43.9 280 972 45 6.40 14.90 14381 -5.70 -68.0
S319 01/11/68 S 83.0 0.00 15 6.30 1.1 171 0.00 3000 367 5370 22 64.7 149 704 27 4.20 10.30 9889 -6.00 -67.0
S56 01/11/68 S 85.0 0.00 15 7.60 1.4 232 0.00 3060 150 5380 46 87.3 207 726 27 2.10 9.90 9927 -6.10 -68.0
S65 01/11/68 S 86.0 0.00 20 0.00 1.6 225 7.20 2880 145 5240 42 777 704 28 2.10 10.00 10061 -6.50 -67.0
SA4 01/08/70 S 14.0 0.00 15 7.50 0.5 4 0.00 35 4 53 0 31.7 64 11 0 0.01 0.00 203 -8.20 -58.0
SA5 01/08/70 S 25.0 0.00 15 6.70 0.1 4 0.00 6 1 0 5 4.9 38 0 0 0.00 0.00 59 -8.80 -53.0
SA7 01/08/70 S 12.0 0.00 12 8.40 0.6 8 0.00 52 4 90 6 37.2 33 23 0 0.01 0.00 253 -7.70 -48.0
SA9 01/08/70 S 55.0 0.00 15 8.20 14.3 28 0.00 540 64 760 5 860.3 188 97 4 0.30 0.70 2547 -8.40 -0.6
SNOW 01/11/68 N -9.70 -55.0
W1 01/12/69 FT 211 6.80 15 7.46 0.3 196 0.81 3340 310 5820 47 20.7 293 727 23 3.50 11.30 1.400 10796 -6.00 -73.0
U2 01/06/70 FT 227 6.80 15 7.36 0.6 197 0.54 3430 431 6020 33 34.8 298 727 28 4.80 12.30 2.170 11221 -6.30 -78.0
W3 01/10/70 FT 254 6.60 15 7.65 0.1 198 1.52 2570 127 4490 44 9.2 173 612 21 1.70 9.50 0.000 8259 -6.80 -75.0
W5 01/03/71 FT 212 6.70 15 7.40 0.8 219 0.80 3760 519 6690 34 48.2 343 858 32 5.60 13.10 1.500 12527 -5.60 -72.0
Tabla 6 - A n a l i s i s quimico de gases, res = gases residuales
1 = Chiodim and C i o n i , 1989. 2 Giggenbach, 1989.
Muestra Cod Fecha C02% H2S% CH4% H 2% N2* 02% co% fH20% N2% 02% CH4% H2% He% Ar% T PC02 T
res res res res res res °C bar °C
1 1 2
FSMO 1004 18/01/89 93.98 2.79 0.83 0 . 1 1 0 .0000 0 .00160 73.2 0.0 13.70 12.30 0.025 1 . 1 1 0 240
FSHA 1001 17/01/89 95.38 2.17 1.00 2.03 0 .0000 0 .00174 73.2 0.0 13.30 15.80 0.036 0.411 250
FSMB 1002 17/01/89 91 .08 2.65 1 .67 6.17 0 .0000 0 .00062 74.1 0.0 18.60 6.91 0.029 0.330 220
FSMD 1003 17/01/89 96.59 3.21 0.86 1 . 76 0.0000 0 .00058 74.7 0.0 12.30 12.80 0.024 0.464 220
FAB 0999 15/01/89 94.63 0.69 0.59 2.32 0 .0000 0 .00245 78.9 17.2 0.62 1.52 0.006 0.000 300
FHJ 1000 11/01/89 95.34 0.00 0.20 3 22 0.0000 0 .00078 80.8 0.0 6.90 14.80 0.036 0.389 240
FSMO 21 13/03/86 96.03 1.17 0.36 0.36 2.07 0 .0081 0 .00073

99.17 248 1 .07 290
FSM2 18 12/03/86 97.35 1.39 0.22 0.13 0.91 0..0035 0..00018
98.21 207 4.15 267
FSH3 13/03/86 97.48 1.12 0.01 0.07 1 22 0..0100 0..00012
98.16 201 5.30 244
FSM5 19 16/03/86 95.01 0.73 0.75 0.30 2.22 0..0085 0..00028
98.37 211 2.80 256
FSM6 20 16/03/86 95.90 1.08 0.22 0.58 2.23 0..0091 97.92
FSM9 16/03/86 95.36 0.86 0.63 0.30 2.82 0..0120 98.86
FAB3 15/03/86 96.48 1.09 0.28 0.35 1 .71 0..2800
0..00130 98.62 271 11 .93 310
FAB5 15/03/86 95.42 1.23 0.81 0.39 2.12 0..0150 97.90
FHJ1 15 12/03/86 97.61 0.82 0 10 0.28 1 00 0. 0030 97.76
FHJ2 16 12/03/86 95.57 0.83 0.11 0.24 1.23 0..0040 97.89
SM1 1968a 02/02/89 93.80 0 90 1 .33 6.30 0. 0000 0. 00238 267

SM1 1968b 02/02/89 96 91 1 32 1.67 0.43 0..0000 0..00267 262
3. Pozos, reconstruction del fluido profundo y equilibraciôn
con el reservorio
Los pozos productives SM1, SM2 y SM3, que no estan ubicados

lejos de las manifestaciones de Sol de Mariana, tienen una
profundidad variable entre 1200 y 1500 m aproximadamente. Durante
el periodo de perforaciön ha sido reconocidos distintos nineles
productivos con permeabilitad y temperatura diferentes. La

temperatura maxima encontrada ha sido de 244°C y en las prevuas de
produciôn la entalpia se ha mantenido siempre entre 1050 y 1060
KJ/Kg. El pozo API profundo 1600 m, que se encuentra a unos 5 km a
SO de los anteriores tiene una temperatura maxima de 260°C y una
permealidad mas reducida. Durante las prevuas la entalpia era, en

principio, muy elevada, luego se establizö en 1380 KJ/Kg. Esto
indica la existencia de fenomenos de ebulliciôn en las cercanias
de la zona de produciôn.
Tenendo en cuenta solamente los pozos SM1 y SM2, de los quales

existe un numéro suficiente de datos (considerando que el
reservorio es del tipo liquido dominante y que el fluido producido
es el resultado de un proceso isoentâlpico) con un balance de

masa y energia del sistema puede ser calcolada la composicion
total del fluido del reservorio y de esta el pH y el estado de
saturaciôn del mismo, respecte a un grupo de minérales (Ver fig. 3
Y 4) .
Para esta reconstrucciön fueron utilizados los valores medios
de los anâlisis de agua de vertedero, de vapor condensado y de gas
separado muestreados en el periodo enero-junio 1989; en el periodo

considerado la entalpia del fluido producido no ha sufrido
variaciones, manteniendose en el rango 1055 KJ/Kg (244°C).
93
Pozos SW —1 y SM —2 — Fluido de reaervorio
Carbon total:
13.07 mmol/Kg
120 160 200 240 280 320

Température
FIG. 3 INTERACCION AGUA-ROCA. LOG (SI) Vs TEMPERATURA

(CON CONTENIDO DE CARBON TOTAL = 13 mg/1)
Pozos S M ~ 1 y SM—2 — Fluido de reservorio
Ccrbon totol:
80 mmol/Kg
160 200
Température
FIG. 4 INTERACCION AGUA-ROCA. LOG (SI) Vs TEMPERATURA

(CON CONTENIDO DE CARBON TOTAL = 80 mg/1)
94
Debido al tipo de équipe usado durante las pruebas los datos
analiticos disponibles se refieren a 2 tipos de muestras:
a) liquido en la salida del separador atmosférico funcionando a
84° C y 0.56 bar (vertedero) , tales muestras ha sido indicadas en
la tabla 1 con el codigo ST;
b) fluido total tornado en un punto del equipo que tiene una
temperatura de 123-132°C y presion de 2.2-2.7 bar, tales muestras
ha sido indicadas en la tabla 1 con el codigo FT.
Para esto tipo de muestras fueron realizadas correciones,
porque como consequencia de fenomenos de canalizaciön en la
planta, la fracciôn de agua muestrada resultaba major de aquella
teoricamente possible aquellas condiciones de presion y
temperatura. Los anâlisis de gas (ver tabla 6) se refieren a
muestras tomadas en el mismo punto.
El valor de la relaciön gas/vapor se refiere al mâximo medido
en el periodo considerado y es de 1.1 NL/kg.
La reconstrucciön efectuada utilizando un programa de câlculo,
estudiado para este objeto, entrega como resultado per i pozzi SM1
e SM2 a una temperatura de reservorio de 244°C, un fluido con un
valor de pH = 6.31 y una alcalinidad total de 1.69 meq/1.
La composicion total, (valores en mg/kg), esta representada en
la siguiente tabla:
Pozo Condicion pH Ça Mg Na K Cl S04 HC03 H3B03 Si 02 TDS
SM1-, Reservorio 6.31 175 0.056 3807 579 6615 25 802 779 500 13350
SM2J
La asociaciön mineralögica résultante a la temperatura de

reservorio (Ver fig. 3 y 4), esta de acuerdo con aquella
observada en las muestras de perforaciön.
Los minérales que llevan Calcio en soluciön (Calcita y
Anortita) estân sobresaturados.
95
Si se acepta un modelo mineralögico del reservorio en el cual
la calcita es un minéral secundario que se produce de la reaccion
del tipo:
Anortita + CCu + H2O --•> CaCC>3 + "arcilla"

el echo del desequilibrio con la calcita, para una temperatura
de la soluciön de 244°C, no es consistente.
Para llevar la calcita a un nivel de saturacicn compatible con

el modelo es necesario anadir CCu al fluido de reservorio.
La cantidad necesaria résulta ser 80 mmol/kg, con una prcsiôn
parcial de CO2 en reservorio de 7.95 atm.
4. Quimica del aqua
4.1. Clasificaciön quimica de las muestras de agua
Los resultados ana]iticos de los fluidos muestreados durante la
investigaciön en esta àrea son reportados en las tablas 1, 2, 3,

4, 5,. La clasificaciön de las aguas fué cfectuada mediante
diagramas de correlaciön utilizando concentraciones de los

const ituyentes mas fundamentales: Ca, Mg, Na, K, HCO3 , SO4 y Cl.
Durante la interpretaciön no fueron consideradas aquellas
surgentes muestreadas en el ano 1986, quimicamente eran idc-nticas
a las muestreadas en 19B9, (Ver tablas 2, 3, 4).

Fueron utilizadas sin embargo las que tenian distintas
caracteristicas para comparar los datos de las muestras, 969 y
2921 para el pozo Sol de Mariana! (SM1), de las muestras 1695 y
2922 para el pozo Sol de Manana2 (SM2) y la mucstra 958 para el
Pozo Apachetal (API), (Ver tabla 1).

En las figuras 5, 6, 7 son reportados los clâsicos diagramas de
Piper. En la figura 5 podemos observar que esta dividida en cuatro
cuadrances, en el cuadrante Sud-Este encontramos aguas del tipo
Alcalino-Cloruradas. En el cuadrante Nort-Oeste son del tipo
Alcalino-Térrea-Bicarbonato, generalmente coligadas a circula-
96
Cl- 100
n
-. Q)
+
fPBl
+
(D IQ
Z
feie
- pozos
100 HC03- + S04— 0

FIG. 5 DIAGRAMA DE PIPER CON Cl~ COMO ION SEPARADO.
504 —— 100
4-
POZOS
100 HC03- + Cl- 0

FIG. 6 DIAGRAMA DE PIPER CON 504 COMO ION SEPARADO.
97
Cl- + S04-- 100
+
ra
100 HC03- + C03—
FIG. 7 DJAGRAMA DE PIPER.
clones superficiales, finalmente en el cuadrante Nort-Este del
tipo Suifato-Calcica.
Como habiamos considerado las muestras colectadas del area en
estudio, 19 de ellas, las que se ubican en el primer cuadrante son

del tipo Alcalina-Clorurada, cuatro en el cuadrante Nort-Este y
quedan ocho, ubicadas mas abajo en el cuadrante Nort-Oes'e (ver
fig. 5) .
Todo esto mejor se visualiza en las fig. 6 y 7 los diagramas
fueron construidos de modo tal que el ion aislado fuese SO^ en una
de las figuras y Cl en la otra.

Por comparaciôn de esos diagramas, très grupos de agua son bien
individualizados, (el primero de los cuales como se vera después
98
puede ser ulteriormente dividido en dos) las caracteriscas de
ellos se pueden resumir como sigue:
GRUPO « A » conformado por las muestras SHJ1, SJH2, SHJ4, RHJ,
SAB7, SPB1, SPB2, SPB3, RS y RAB. Las très primeras son fuentes
tibias situadas al Nort-Oeste del rio Huaylla Jara (RHJ), emergen
de lava ignimbritas y son caracterizadas por la temperatura y
conductividad variable en los rangos que se indican a continua-
ciön: 27.5°C-30°C y 430/iS-520/iS. La muestra SAB7, 8.2°C y 250/iS,
es ubicada al Sud- Este de las fumarolas de Aguita Brava, las
surgentes frias SPB1, SPB2 y SPB3 con conductividad de
aproximadamente 100/xS ubicadas a 1.5-2 Km del Cerro Lagunitas.
Finalmente las muestras RAB y RS aguas superficiales del Rio
Aguita Brava y del Rio Silala, esta ultima esta ubicada muy lejos
del area en estudio. Todas las muestras de agua se pueden
considerar como una mezcla de porcentajes variables de los très
componentes Bicarbonato-Alcalino Térreo, Sulfato-Alcalino Térreo y
Bicarbonato-Alcalino.
COTOO ya se habia afirmado, el grupo « A » se puede todavia
subdividir, porque las muestras RAB, SAB7, SPB1, SPB2 y SPB3
tienen componentes Bicarbonato-Alcalino Térreos levemente mas
bajos y un componente Sulfato-Alcalino Térreo mayor que SHJ1,
SHJ2, SHJ4, RHJ y SPB1.
La muestra del Rio Silala se caracteriza por un elevado compo-

nente Bicarbonato-Alcalino.
GRUPO « B » esta formado por las muestras SHJ3, WP1, SC2, SC4,
SC11 y SC21, estas tienen conductividad y temperatura en el rango
de valores: 158-1130juS y 26.7-41°C.
Este grupo se diferencia del précédente por la falta total del

componente Bicarbonato-Alcalino Térreo; quimicamente es
prédominante el componente Sulfato-Alcalino-Alcalino Térreo con
una contribuciön de Sodio-Bicarbonato. En las muestras SCI, SC2, y
99
SC4 hay también una considerable cantidad de Sodio Potasio
Cloruro.
La muestra SHJ3 es una fuente tibia de modesta salinidad
(158jiS) ubicada cerca de las otras caracterizadas con la misma
sigla y discutida anteriormente en el grupo « A », mientras que la

muestra WP1 (30°C y 370/iS) proviene de un pocito profundo de 127m,
esta ubicada a un Km al sud del pozo Sol de Manana.
Las otras cinco fuentes éstan ubicadas en la esquina Oeste de

la Laguna Salada (area del Salar de Challviri) y se encuentran
localizadas a un nivel mas alto de la laguna, excluyendo asi un
primer grado de contaminaciön directa.
De las numerosas fuentes, cuyo caudal de agua es de 100 1/seg y
cuya conductividad y temperatura disminuyen progresivamente hacia

el Norte, solo las mas importantes fueron muestreadas.
Es interesante observar los datos de muestreo realizados en
Laguna Salada, la temperatura es inversamente proporcional a los

porcentajes del componente Suifato-Alcalino y directamente
proporcional al Alcalino-Clorurado, con la sola excepciön de SC11.
(Ver fig. 8 y 9)
42
SC2
40- .SCI
SC 11
(1989)
38-
ô 36- 'SCII C989)

SC11
o
SC4 (1989)
• SO.
O)
32-
SC21
(19891
30-
SC21
28-
26- —I— —i— —i—

20 25 30 35 40 50
NQ-K-S04 %
FIG. 8 TEMPERATURA Vs. Na - K - SO,
100
42
SC2
.SCI
40-
"SC 1(1989)
38-
36
• SC 11 (1989)
"
.SC 4 (1989)
SC4
I 32
SC 21 (1989)
30-
28-
26-
10 15 20 25 30 35 4
Na-K-Cl (%)
FIG. 9 TEMPERATURA Vs. Na - K - Cl
GRUPO « C » Formado de LC1, LC4, LC5, LC11, LC12, SC10 y las
muestras de los pozos. Este grupo de muestras es del tipo

Alcalino-Clorurado se puede dividir en dos subgrupos: el primero
comprende las muestras LC12 (Laguna Colorada), SC10 (Salar de
Challviri) y cuatro fuentes tibias LC1, LC4, LC5, LC11 localizadas
alrededor de Laguna Colorada. La temperatura y la conductividad de
estas ultimas varian respectivamente entre 28.1-30.1°C y 390-
1670/zS.
El quimismo consiste principalmente en el componente Alcalino-

Clorurado mayor al 50%, en las lagunas puede aumentar mas del 75%.
El componente restante puede ser subdividido en Bicarbonato-
Alcalino, y Sulfato-Alcalino Térreo. En alguna de estas muestras
hay cierta interacciôn con las aguas de Laguna Colorada.
El segundo subgrupo, como ya se ha mencionado, comprende
fluidos de pozos profundos gué, a excepciôn de SM2 (2922), tienen
un componente Clorurado-Alcalino mayor del 95%. La muestra SM2
(2922) que ha sido muestreada del pozo a una profundidad de 1240
m, résulta mas compleja presentando una suma total de los dos
componentes Bicarbonato-Alcalino y Sulfato-Alcalino mayor del 15%.
101
4.2. Consideraciones générales de las caracteristicas del agua
La evaluaciön de la composicion quimica de las muestras tomadas

a fines del 1986 ponen en evidencia que cada una de ellas
corresponde a tipos de circuitos superficiales y ninguna a
mostrado mezcla con una fase liquida originada por la interacciôn
a altas temperaturas con un reservorio de naturaleza volcânica.
El calentamiento de las aguas discutidas en el pârrafo anterior
podria explicarse por el flujo de vapor; en el ârea en estudio

existen numerosas manifestaciones localizadas a diverses
kilometros unas de las otras (Sol de Manana, Huaylla Jara y Aguita
Brava), originadas por fenömenos de ebulliciön.
La investigaciön de componentes trazas como Amoniaco y Acido
Börico excluyen esta hipôtesis. Por ejemplo las muestras SCI y SC2
(en el ârea de Salar de Challviri) tienen una temperatura de 30°C

mayor a la temperatura estacional promedio. Un flujo de vapor del
9% en peso, a 200 "C, es la cantidad requerida para calentar
convectivamente el agua de 10° a 40°C. En ese caso se tiene que
tomar en cuenta el contenido de NH3 en las "Steaming pools" y en
las fumarolas respectivamente. Un tal flujo de vapor produciria en
SCI y SC2 una concentraciôn de NH3 500 veces mayor a los valores
observados. Las mismas consideraciones son para el H 3 BO 3 , este
mismo mecanismo deberia implicar concentraciones de
aproximadamente 500 mg/1 contra los 30 mg/l de los actualmente
encontrados. Un proceso de este tipo necesariamente implica una
proporcionalidad directa entre la temperatura y el porcentaje de
sulfates (oxidaciön del H2S présente en el vapor), la fig. 9
muestra que esta proporcionalidad existe solo con el componente
Clorurado-Alcalino.
Por otra parte teniendo en cuenta la pequena extension de ârea
y la cantidad de agua caliente confluiente en la laguna, la
temperatura de esos fluidos no puede ser explicada solo por el
102
mécanisme» de conduciön. La disponibilidad de los anâlisis del
fluido de pozos a permitido aclarar mejor el origen de las fuentes
calientes del Salar de Challviri; si se considéra el diagrama
triangular Li, Rb, Cs (ver fig. 10), los puntos representativos de
SCI y SC2 resultan extremadamente vecinos a los pozos profundes.
LEYENDA
o Muestras de L Colorado
û Muestras del Talio
i i i i i i i l : l l i l i l l l i M ri l i i i l l r M l l l l l i l l l l l i l i
Rb (mg/l) * 4
FIG. 10 DIAGRAMA TRIANGULAR Li, Rb, Cs.
La presencia de éstos componentes en agua asi diluida no puede

ser atribuida a procesos de interacciôn agua roca superficiales a
una baja temperatura, se puede explicar unicamente por
contaminaciön del acuifero en cuestiön por parte del fluido
profundo.
Un aporte del 3-4 % de un fluido con las mismas caracteristicas
de aquellas encontradas en la perforaciôn profunda no solo
justificaria el contenido de Cl, Li, Rb, y Cs encontrados en estas
fuentes termales, sinö también un incremento en su temperatura de
103
aproximadamente 1CTC. Reconsiderando la Fig. 9 si se extrapola a
cero el components Clorurado-Alcalino, la temperatura teorica del

acuifero resultaria aproximadamente 28°C, con un incremento
respecto a la temperatura estacional media de aproximadamente 15 a
20°C. Esto es debido probablemente al mecanismo de conducion.
Para concluir también la temperatura de las otras fuentes
termales que emergen alrededor de Laguna Colorada y Cerro Huaylla
Jarita deben ser ligadas a factores conductivos.
Las caracteristicas de las fuentes frias SPB1, SPB2 y SPB3
muestreadas a déclive en el cerro Lagunitas son definitivamente
anomalas: estas ultimas, no obstante tienen una temperatura baja y
muestran cantidades de NH4 y H3BO3 mucho mayor de aquellas que se
deberian esperar razonablemente con respecto a los solidos totales
y podrian ser efectivamente contaminadas por un levé flujo de
vapor. Finalmente en la fig. 10 fueron indicados con triangulos
pequenos las muestras de pozos y manifestaciones del campo geo-
termico del Tatio (Chile), la casi perfecta sobreposicion de
puntos representativos, da una vez mas la estrecha similitud de
los fluidos geotermicos originados en los dos campos distintos
(Sol de Mariana y El Tatio) distantes entre si 20 Km.
5. Geotermometros
5.1. Consideraciones générales
Por lo que se menciono anteriormente no es posible hacer

ninguna evaluacion basada en la composicion quimica de los puntos
de agua superficiales disponibles, porque ninguna de ellas fue
reconocida como un fluido de origen profundo; tambien las muestras
SCI y SC2 son contaminadas seguramente a un nivel mas bajo y no
pueden ser utilizadas para tal objeto.
En lo que se refiere a fluidos profundos la interpretacion es
simplemente hecha usando el diagrama ternario de Giggenbach [3]
104
(ver Fig. 11) basado simultaneamente en dos funciones
termométricas Na/K y K/Mg.
LEYENDA
7 _ Na/1000
* Agua superficial On
o Muestras de fluido total
* Muestras de vertedero
<> Muestras de pozo
a Muestras del Tatio
Curya de full
equilibrio
2 x Dilucio'n
10 * Dilucio'n
K/100 0
% Mg
Fig 11- Diagrama de Giggenbach Na, K, Mg
Los puntos representativos de pozos profundes del area Sol de

Manana se colocan todos sobre la isoterma t Na/K de 280°C., la
mayor parte, ya sea muestras tomadas al vertedero (ST) o de fluido
total (FT) , se encuentran a la izquierda de la curva de "full
equilibrium". Una posible explicaciön es que durante la salida del
fluido profundo se verifica un fenömeno de precipitaciön que
reduce la concentracion inicial de Mg.
Las muestras tomadas en los pozos, SM1(1000 m) y SM2(1240 m)
que respecto a la composiciön teörica del reservorio son mas
diluidas (aproximadamente 2.2 y 10 veces), en este diagrama se
colocan mas alto y en el caso del pozo SM2 también a la derecha
respecto a la posicion que deberian tener si fueran diluidas con
105
agua destilada en la proporcion encontrada por los anâlisis. Todo
esto nos hace considerar que los pozos presentan distintos nivelés
de permeabilidad, caracterizados por fluidos con temperaturas y
composiciones distintas; las muestras tomadas en condiciones
estäticas son una mezcla, con relaciones distintas respecte
aquellas muestreadas en el curso de la producciön.

La temperatura obtenida de la concentraciôn de SiO2 en el
vertedero, corregida por la pérdida de vapor [4], résulta para SM1
y SM2 respectivamente 249° y 258°C. Estos valores son cercanos a
los medidos directamente en los pozos, mientras los obtenidos de
las funciones geotermométricas iönicas t K/Na y K/Mg indican de
hecho temperaturas superiores de 40-50°C.
La hipötesis mas probable es que el fluido producido en el area

de Sol de Mariana proviene de horizontes mas profundos de las
fracturas productivas que se encontraron en la perforaciön.
La temperatura en la parte mas profunda del reservorio esta
dada por la relaciôn Na/K, reequilibrandose lentamente sodio y
potasio, mientras la temperatura en la zona donde se produce
actualmente estaria por la concentraciôn de Sicu. La relaciôn K/Mg

indica una temperatura mayor que la anterior, esto podriase
explicar con un fenomeno de ebulliciôn y degasificaciôn en el
reservorio.
Esta hipötesis se confirma:

- por la presencia fisica de numerosas fumarolas y "hot pools"
en el ârea Sol de Manana cuya extension superficial esta
necesariamente ligada a un gran fenomeno de separaciön de fases.
- por calcules teôricos, considerando que la Anortita es el
ünico minéral présente en el reservorio que proporciona calcio en
soluciôn. A la temperatura de 240°C, con la cantidad de calcio
présente en el reservorio (175 mg/1) la presiôn parcial de C02 que
106
détermina el equilibrio entre la Anortita y la Calcita es de 7.9
atm, mientras que la calculada de los datos analiticos de los
fluidos producidos en el pozo es de 1.37 atm.
La concentraciôn de SiCu queda en cambio inaltérable y esta de
acuerdo con las medidas de temperatura efectuadas.
6. Geoquimica isotôpica
6.1. Reconstruction isotôpica del fluido de reservorio,

generalidades y métodos
Como ya indicado anteriormente, durante las pruebas de

producciön no ha sido posible efectuar un muestreo representativo
del condensado de los pozos. Esto obviamente, hizo imposible el
calcule de la composicion isotôpica del fluido en el reservorio,
por simple balance de masa entre el vertedero y el condensado.
Esta problemâtica fué afrontada utilizando el anâlisis del fluido
total (muestras FT) oportunamente corregido como ya hemos indicado
en el capitulo 3. La comparaciôn entre el contenido analitico de
Cloruro en el fluido total y el resultado teôrico calculado a
partir de los cloruros présentes en la muestra del vertedero
indican de hecho que las muestras fuéron tomadas a una fracciôn de
agua mayor de aquellas teôricas.
Los resultados asi obtenidos fuéron controlados con los valores
calculados a través de la composicion isotôpica en el vertedero
(ver fig. 2 punto 2) hipotetizando que el proceso en la producciön
sea reconducible a dos mecanismos fundamentales: un fenômeno de
separaciôn de vapor que ocurre entre el reservorio y el boca pozo
(asimilable a una continua pérdida de vapor) y a un proceso de
"single stage steam loss" lo que opéra entre el boca pozo y el
separador atmosférico.
107
En la siguiente tabla aparecen los resultados obtenidos:
METODO 1 METODO 2
POZO <518O 6 D <S180 6 D
SM1 -7.05 -81.7 -6.70 -77.3
SM2 -6.85 -80.8 -6.77 -79.9
MEDIA -6.95 -80.9 -6.73 -77.6
Considerando la medida de valores calculados se verifica una

diferencia muy reducida, estos valores son ademâs estrechamente
cercanos aquellos postulados por Giggenbach [5] para el vecino
campo geotérmico de El Tatio (618O = - 6.9, 5D= - 78).
Fueron escogidos como valores de referenda para el fluido de
reservorio 618O = -6.9 y <5D = -78; sobre esta base se elaboraron
las consideraciones relativas a las manifestaciones superficiales.
En el caso del pozo Apachetal (API) no fué posible ap] icar
estas metotologias porque el exceso de entalpia medido esta casi
seguramente ligado a fenomenos de segregaciön de fase con o sin
cesiön de calor de parte del reservorio.
Esta circunstancia se traduce en el flujo en el pozo de una
cierta cantidad de vapor, cuya composicion con los datos
disponibles no es évaluable. Tal mecanismo no obstante es
18
consistente con los valores de O y D los cuales en Apacheta 1
(API) son resultados mucho mas negatives que los correspondientes
a las muestras de los pozos SM1 y SM2.
6.1. Fuentes termales y frias
En la figura 12 son reportados los resultados analiticos

pertinentes a los isötopos, observamos variaciones en el contenido
de <S18O y 6D las cuales no son fâcilmente explicables frente a la
altitud. Las variaciones parecen bastante reguläres con una
108
Agua residua despues
de «Single step poilmg
enlre 2<0 y 85°C
Vapor pnmano de agua L E Y E N D A

de reservor'o pnmaria
diluida con agua de tipo
LW
Agua superficial ( Rios, Lagunas. Nieve)

Vapor pnmaoo de agua Surgentes de aguas termales y f r i e s
de
no dtluid
Muestras de fumarolas corregidas por el fraccionamient
Vapor pnmano de agua
de reservofio primana en el curso de la condensacidn
diluida con agua de tipo
R W
Muestras de fumarolas sin correccion
Lodos calientcs Laguna Colorada
Aguas profundes
FIG. 12 DIAGRAMA <S 18 O Vs 5D EN AGUA.

tendencia hacia de valores mäs negativos en la direcciön N-E (esta
tendencia puede llegar también al Salar de Empexa).
No es fâcil entender la razön de ese desarrollo probablemente
ligado a fenömenos metereolögicos (debido a la masa de nubes que
originan la precipitaciön). Esas ultimas pueden venir predomi-
nantemente del Oceano Pacifico.
En particular considerando los datos pertinentes de Huaylla
Jara y Aguita Brava, nieve del Volcan Michina (N) y el Rio Huaylla
Jara (RHJ), los puntos muestreados, en absoluto los mas positivos,
se unen con el punto D, que séria el agua meteorica local
postulada por Giggenbach para el campo geotermico del Tatio [5].
RAB , SHJ3, WP1, LC11 y de modo menor, SHJ1, SHJ4 y SAB7 tienen
una composicion mas negativa. Por el contenido de deuterio,
pudiera ser considerada como una posible recarga de los campos
geotérmicos de Chile y Bolivia. La intersecciön de la paralela al
eje de la absisa que pasa por el punto DW (composiciön isotöpica
de los pozos) con la recta meteörica da el punto RW (agua de
recarga).
Los puntos de agua muestreados al norte de Laguna Colorada RS,
LC1, LC4, y aquellas mas al sud SPB1, SPB2 en proximidad al Cerro
Lagunitas, resultan pues en absoluto mas negativas del area entera
en estudio.
Por lo que se refiere a las surgentes en torno a Laguna Salada
y la muestra LC5 sus composiciones son intermedias a aquellas dos
de los grupos anteriores.
No obstante los puntos de aguas frias, de origen local o
sublocal, son muy pocas, por lo tanto es dificil dar un cuadro de
la distribuciön de los valores isotöpicos, haciendo asi una vez
mas, complicada la explicaciön de las variaciones observadas.
La impresiön final es que las variaciones isotöpicas y quimicas
no son vinculadas a las anteriores, son mayormente causadas por
mecanismos metereolögicos.
110
18
Resumiendo, las variaciones de O y deuterio identifican una
linea local meteörica con la ordinaria pendiente de 8 pero con una
intersecciön menor de 10 probablemente 5. Ciertamente la falta de
cambios isotöpicos en las fuentes, sugiere que ninguno de esos
fluidos reaccionan con el reservorio a alta temperatura.
6.2 Fumarolas, "steamed pools" y aguas profundas
El vapor de las "hots pools" en el lado derecho de la grâfica

6O vs 6D del diagrama (ver fig. 12) , esta bien alineado a lo
largo de una recta con una pendiente alrededor de 1.6; este valor
es el misrtio que caracteriza el campo de El Tatio [5].
En la intersecciön de esa linea con la linea de las aguas
meteöricas se obtiene el punto LW (local ground). Este punto, muy
cerca a los puntos N (nieve del Volcan Michina) y RHJ (Rio Huaylla
Jara) , puede ser considerado representativo de la composicion
isotöpica de aguas freâticas en la zona donde estân présentes
estas manifestaciones.
La fumarolas, cuyas composiciones fueron corregidas por causa
del fraccionamiento durante la condensaciön, (solamente para las
muestras tomadas en el area de Huaylla Jara y Sol de Mariana de
1986 y para las muestras SMO tomadas en 1989), se encuentran a lo
largo de la linea con una pendiente alrededor de 8, extendiéndose
3 unidades 518O a la derecha, lejos de la linea meteorica
interceptada a +10.
El punto DW représenta la composicion media del liquido del
reservorio que alimenta los pozos de Laguna Colorada, similar al
que al présente alimenta el campo fronterizo de El Tatio. La recta
C représenta la composicion de los liquidos residuos que se
originan en DW por "single stage boiling".
La ausencia de puntos representativos debajo de la linea C esta
de acuerdo con la falta de muestras representativas del liquido
profundo en el area investigada.
111
Con la excepciön de FAB6 (que no ha sido corregida por el
fraccionamiento durante la condensaciön), todas las fumarolas
estân localizadas dentro la region comprendida entre las curvas A,
B y B1 como se puede observar en la figura 12.
En las mismas curvas estân también incluidos todos los vapores
que teoricamente se pueden formar:
- por ebulliciön del liquido primario DW a temperaturas mas
bajas de 240°C por un enfriamiento conductivo (curva A).

- por ebulliciön de un liquido primario DW después de la
diluciôn con diferentes porcentajes de agua de recarga
representadas por el punto RW (curva B).

- por ebulliciön de un liquido primario DW, sucesiva a la
diluciôn con diferentes porcentajes de agua freâtica local
representada por el punto LW (curva B 1 ).
7. Geotermometria de los gases
Durante la producciön de los pozos SM1 y SM2 fueron tomadas

muestras de gas natural con modalidades distintas entre ellas
(salida del separador atmosférico y muestreo de fluido bifase).
Las muestras mas representativas fueron corregidas por la
contaminaciön de aire y sobre estas fueron aplicadas técnicas
geotermométricas. La composiciôn del gas producido por el pozo SM1
esta presentada en la tabla 6; la Fracciön de Vapor calculada por
el Flash de 244° a B5°C y la relaciön Gas/Vapor son respectiva-
mente O.304 y 1.10 NL/Kg.
Desafortunadamente no existe medidas de H2 para el pozo en

examen, por lo tanto es posible aplicar solo el geotermometro que
utiliza el CO de Giggenbach [6]; por lo que se refiere a las
fumarolas puede ser utilizado también el geotermometro de
Chiodini y Cioni [7], esto ultimo permite de obtener,
contemporaneamente, la presiön de CO2 en el reservorio.
112
En la tabla 6 estan representados los resultados por el pozo
SM1 (265°C) y las fumarolas.
Estos risultados, a pesar que entre los dos geotermometros
existe una diferencia costante de 50°C aproximadamente, de toda
manera indican que la temperatura y la presiön de CO2 mas elevadas
se encuentran en la zona de Aguita Brava muy cercana al Volcan
Micina. Este ultimo es, sin lugar a dudas, la fuente de calor mas
importante de toda el area estudada.
Como se puede observar en la figura 13, en la que se
representan los contenidos relatives de N2/ Ar y He, estas
muestras de gas, aun sendo contaminadas por una componente
meteorica, parecen indicar un origen de los gases mas crustal que
magmatica.
No/100
IOOO
30
10He
FIG. 13 CONTENIDOS RELATIVOS DE N Ar y He.
£1
113
REFERENCIAS
[1] ENEL - Estudio de factibilidad geotérmica en el area de

Laguna Colorada, Naciones Unidas/PTCD, proyecto BOL
84/007, 1986.
[2] ENEL - Final report of the ENEL technical mission to
Bolivia (Laguna Colorada), 10-16 March 1986.

[3] Gigghenbach, W.F. - Geothermal solute equilibria.
Derivation of Na-K-Mg-Ca geoindicators. Geochimica et
Cosmochimica Acta, 52, 2749-2765, 1988.
[4] Fournier, R.O. and Potter, R.W. - A revised and
expanded silica quartz geothermometer. Geothermal
Research Council Bullettin, v. 11, 3-9, 1982.
[5] Gigghenbach, W.F. - The isotopic composition of waters
from El Tatio geothermal field. Geochimica et
Cosmochimica Acta, V. 42, 979-988, 1978.
[6] Gigghenbach, W.F. and Goguel R.L. - Collection and

analysis of geothermal and volcanic waters and gas
discharges. DSIR Report n. CD2401, 1989.
[7] Chiodini G. and Cioni R. - Gas geobarometry for

hydrothermal systems and its application to some Italian
geothermal areas. Applied Geochemistry, v. 4, 465-472,
1989.
114
GEOCHEMICAL REPORT ON THE EMPEXA
GEOTHERMAL AREA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per 1'Energia Elettrica,
Pisa, Italy
W. CASSIS
Empresa Nacional de Electricidad,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE EMPEXA, BOLIVIA.
La zona de Empexa esta situada cerca de la frontera con Chile, en la pro-

vincia de Daniel Campos, Departamento de Potosi, a aproximadamente 68°30' de
longitud y 20°22' de latitud. Se caracteriza la zona por la presencia de un
vasto salar en una cuenca volcànica a una altura de 3 717 m sobre el nivel del
mar. Muchas de las actividades térmicas tienen lugar en los limites de este
salar, pero las mas calientes se encuentran en una zona limitada; la cantidad
y la circulaciön de gases libres son muy reducidas.
Toda la parte sur de la zona es riquisima en azufre y âcido borico.

Existen diversas minas de las que se extraen grandes cantidades de azufre. La
presencia de estas materias y la intensa filtraciön de los depösitos salinos
evaporiticos, causada por el continuo retroceso del salar, hacen muy dificil
caracterizar las muestras de agua y calcular la composicion original del flui-
do termal profundo. La temperatura maxima calculable del depösito a juzgar
por las muestras de superficie, no deberia sobrepasar los 180°C.
GEOCHEMICAL REPORT ON THE EMPEXA GEOTHERMAL AREA, BOLIVIA.
The area of Empexa is situated near the border with Chile in

the province of Daniel Campos, Department of Potosi, at roughly
6 8 ° 3 0 ' of longitude and 2 0 ° 2 2 ' of latitude. It is characterized by
the presence of a vast salar in a volcanic basin at an altitude of
3717 m above the sea level. Many of the thermal manifestations are
located at the edges of this salar, but the hottest are found in a
restricted area; the presence and the flowrate of free gases is

very limited.
115
All the south of the area is highly rich in sulphur and boric
acid. There are various mines from which high quantities of
sulphur are extracted. These occurrences and the strong leaching
of the saline evaporitic deposits, caused by the progressive

receding of the salar, make very diffucult to characterize the
water samples and to estimate the original composition of the deep
thermal fluid. The maximum computable temperature in the reservoir

from surface sample should not exceed 180°C.
1. Sample collection and field determinations
The sampling in the Rio Empexa Valley was carried out over a
period of four days, from the 17th to the 20th of March 1986. A
total of 18 samples of hot and cold springs were taken, 2 of free
gas, 3 of residual gases collected from two water points and one
fumarole in the sulphur mine Mina conception.

The limited amount of time did not allow the carrying out of a
complete survey. Some of the water points recorded in previous
surveys, conducted in 1976 and 1977, were not found [1], the
location of these points was imprecise and the organization of the
field work did not permit an inventory of all the water points
present in this area and the collection of a suitable brine sample
of the salar.
The analysis of the fluids sampled during the 1986 survey are
shown in tables 1 (waters) and 2 (gases) . During the elaboration
of this report, the data from previous studies on water points not
found at the time of collection, have been also taken into
consideration.
Samples location (fig- 1) defines an area of about 300 km2 ;
the most significative manifestations are located on the southern

edge of the salar. The flow rate of the water points at the
highest temperatures (t > 65°C) varies between 0.3 and 4 1/s for a
116
i =.--'-. ^_ CmCX ALTAM1KA Z ~
/°iM-*"?*^ r S1,1 . E«.ne,.w,i

"' ~
X
=? v *'(- --
MM "CAUEJONl *f>t- .
~'SALAR DE EMPEXA
• = Surface water points

A = Test holes
•äfe- = Mina conception (fumarole)
Fig.l - Location map of Empexa area samples.
117
Table 1 - Empexa water samples analyses
s = spring, r = stream, w = well, b = brine
Sample; Date Cod. S. T. T. f. pH. f. Con. f. /Uc.f. r. l. pH. l. Con. l. /MC. l. Rlc.l. Ca Mg Na K Cl S04 HC03 S i 02 H3B03 Br l
°C /'S meq/l •c ßS meq/ 1 meq/ 1
E01 17/03/86 0841 S 11.0 7.18 141 25 6.24 155 0.8 0.8 12.5 6.00 8.9 5.6 7.4 30.3 0.0 51.8 4.5 0.00 0.00
E02 17/03/86 0840 S 14.0 7.86 520 1.1 25 6.60 463 1.0 1.0 62.0 11.60 2 4 . 7 6.8 7.6 196.0 67.1 40.4 2.4 0.00 0.00
E03 17/03/86 0839 S 14.0 7.25 370 1.8 25 6.66 372 1.7 1.7 40.0 11.80 2 0 . 4 9.8 14.4 97.4 107.4 59.6 3.6 0.00 0.00
E04 07/05/78 S 13.0 6.50 690 1.4 25 56.3 12.80 30.1 12.0 13.0 194.0 86.6 60.0 4.0
E05 17/03/86 0842 S 22.0 3.34 1190 25 3.50 1160 120.0 13.00 108.0 110.0 156.0 391.0 0.0 71.0 7.6 0.15 0.00
E 06 29/04/78 S 30.0 4.30 15200 25 965.0 131.00 2440.0 71.4 4750.0 1620.0 0.0 38.0 39.6 c
E07 17/03/86 0843 S 35.0 4.85 13000 25 4.78 12700 930.0 107.00 2350.0 64.0 4580.0 1600.0 0.0 20.0 38.0 1.40 0.42
E 08 29/04/78 R 15.0 4.15 7550 25 518.0 56.70 1030.0 40.9 1890.0 1150.0 0.0 58.0 25.0
E 09 01/05/78 S 15.0 6.80 15100 0.7 25 696.0 187.00 2230.0 131.0 4300.0 1410.0 2013.6 65.0 43.5
E10 29/04/78 S 13.0 5.70 2490 0.2 25 186.0 26.30 136.0 6.8 121.0 682.0 0.0 53.0 25.4
E11 10/05/78 S 18.0 7.50 8910 0.8 25 769.0 103.00 940.0 30.0 2960.0 179.0 4 5 . 7 41.0 13.5
E12 10/05/78 S 25.0 6.70 10500 12.0 25 252.0 196.00 1780.0 89.7 2960.0 907.0 732.2 80.2 37.8
E13 20/03/86 0853 S 25.0 6.60 6260 5.5 23 6.99 6450 5.4 5.4 390.0 118.00 898.0 74.0 1440.0 1150.0 335.6 105.0 41.0 0.42 0.31
EH 20/03/86 0852 S 34.0 6.61 6160 5.6 23 6.84 7050 5.4 5.4 390.0 130.00 1030.0 8 4 . 0 1660.0 1140.0 341.7 112.0 45.0 0.49 0.31
E15 07/05/78 S 32.0 6.80 8080 9.4 25 385.0 161.00 1280.0 108.0 2040.0 1310.0 573.6 118.0 50.2
E16 12/05/78 S 75.0 1.70 49500 25 753.0 405.00 6750.0 646.0 13500.0 36.4 0.0 563.0 792.0
E17 07/05/78 U 17.0 0.90 57700 25 1260.0 240.00 9000.0 913.0 18800.0 5 7 . 1 0.0 330.0 1100.0
E18 20/03/86 0854 S 18.0 7.04 6730 2.1 24 6.78 67Ï.J 2.0 2.0 171.0 92.00 1110.0 67.0 1910.0 446.0 128.1 82.0 38.6 0.90 0.31
E19 18/03/86 0848 S 16.0 4.50 4190 23 5.81 4560 0.6 0.6 290.0 48.60 580.0 74.0 1160.0 589.0 0.0 105.0 65.0 2.00 0.54
E20 18/03/86 0846 S 68.0 5.90 24500 7.3 25 6.73 26400 7.0 6.8 83.0 203.00 5100.0 187.0 8100.0 956.0 445.4 174.0 177.0 3.20 0.84
E21 18/03/86 0847 S 22.0 5.70 15.9 25 6.73 43100 15.4 15.2 509.0 405.00 8500.0 310.0 13600.0 2340.0 970.2 146.0 280.0 4.60 1.00
E22 19/03/86 0849 S 69.0 5.75 4.7 23 6.58 54100 4.6 4.6 125.0 522.00 11100 412.0 17900.0 2020.0 286.8 164.0 288.0 4.40 0.77
E23 17/03/86 OS44 S 86.0 8.27 6940 5.1 25 8.72 6580 4.4 3.8 3.0 0.25 1410.0 5 3 . 0 1800.0 338.0 87.3 244.0 120.0 2.40 0.97
E24 18/03/86 0845 S 87.0 7.67 6550 23 8.11 6370 4.9 4.5 6.6 0.17 1380.0 5 2 . 5 1760.0 326.0 274.6 278.0 115.0 2.40 0.84
E25 04/05/78 S 45.0 5.80 6070 7.2 25 0.00 7.4 2.80 1320.0 4 4 . 8 1700.0 342.0 4 4 4 . 8 400.0 164.0
E26 27/04/78 S 9.0 7.40 4910 0.8 25 0.00 196.0 13.50 338.0 4 3 . 3 759.0 226.0 4 5 . 6 80.0 32.0
E27 19/03/86 0851 S 11.0 7.08 621 23 6.51 642 0.8 0.8 5 2 . 2 12.60 4 5 . 0 20.8 2 7 . 2 202.0 0.0 78.6 9.0 0.00 0.00
E 28 27/04/76 S 10.0 6.70 5920 0.2 25 0.00 0 0.0 0.0 266.0 16.90 486.0 59.2 1040.0 301.0 12.9 7.0 41.9
E29 19/03/86 0850 S 35.0 6.75 1550 0.5 23 6.50 1830 0.5 0.5 128.0 8.30 201.0 23.4 459.0 128.0 30.5 118.0 23.0 0.74 0.42
E30 02/05/78 S 15.0 8.20 125 1.1 25 0.00 6.4 2 . 6 0 5.0 2.7 4.4 1 5 . 4 63.5 38.0 3.4
E31 02/05/78 S 13.0 7.50 1960 2.9 25 0.00 80.7 47.00 118.0 2 3 . 4 262.0 159.0 176.3 78.0 60.9
E32 20/03/86 0855 S 24 4.22 210 13.6 2.60 11.6 5.8 4.7 69.6 0.0 72.0 3.2
E33 26/04/78 W 11.0 3.80 1240 25 0.00 83.8 12.00 58.4 8.9 8.8 372.0 0.0 108.0 8.5
UE1 01/01/78 U 36.0 7.50 8000 6.3 25 0.00 421.0 133.00 1060.0 121.0 1740.0 1430.0 380.7 246.0 54.9
WE2 01/01/79 W 64.0 8.40 8000 2.7 25 0.00 150.0 59.00 1380.0 7 4 . 0 1840.0 1150.0 55.3 397.0 74.2
WE4 01/01/79 W 29.0 6.90 5400 1.7 25 0.00 261.0 37.50 736.0 101.0 1280.0 672.0 103.7 90.0 74.2
UE5 01/01/79 W 111 6.80 7100 9.1 25 0.00 28.1 2.90 1430.0 50.8 1740.0 399.0 536.9 246.0 124.0
WEG 01/01/79 W 23.0 7.60 5400 1.3 25 0.00 341.0 21.80 644.0 74.3 1380.0 437.0 78.1 90.1 74.1
SE135 01/09/76 135 B 20.0 7.00 20 7.00 420.0 3000.0 60000 9200 131000 13400 17085
SEUO 01/09/76 140 8 20.0 7.00 20 7.00 580.0 10000 90000 6100 200000 1630020746
SEK1 01/09/76 141 B 20.0 7.00 20 7.00 440.0 11000 85000 8500 190000 11000 14034
Table 1 - ( cont.)
Sample Code F Li Rb Cs NH4 Sr Ba Zn Sb As Fe AI. T Al. H TDS TAM T CAT ,5180 SO Trit. 5180/S04 534S/S04 Alt.
meq/l meq/l o/oo o/oo U. T. o/oo o/oo m.
E01 0841 0.00 0.00 0.00 0.00 0.000 0.10 0.020 0.000 0.000 0.00 0.000 0.000 0.000 127 0.8 1.6 -14.82 -117 .2 4250
E02 0840 0.00 0.00 0.00 0.00 0.014 0.29 0.010 0.000 0.000 0.00 0.000 0.000 0.000 352 5.4 5.3 -14.75 -113 .6 0.3 4100
E03 0839 0.00 0.00 0.00 0.00 0.007 0.24 0.020 0.000 0.019 0.00 0.000 0.000 0.000 259 4.2 4.1 -14.01 -108 .8 0.2 4100
E04 0.010 384 5.8 5.5 3800
E05 0842 0.44 0.140.06 0.00 0.018 0.36 0.010 0.046 0.020 0.00 0.025 4.200 2.000 982 12.5 14.6 -15.30 -118 .2 3900
E 06 0.056 10055 168.0 167.0 375
E07 0843 1.40 4.20 0.32 0.35 0.068 8.10 0.020 0.043 0.000 0.12 1.600 0.570 0.260 9708 162.0 159.0 -14.94 -114 .4 3900
E08 0.011 4769 77.3 76.4 3710
E09 0.006 9096 184.0 150.0 3780
E10 0.020 1236 17.6 17.5 3760
E11 3.017 5036 88.0 88.5 3750
E12 0.020 6315 114.0 108.0 3750
E13 0853 0.75 2.00 0.21 0.00 0.200 4.60 0.020 0.000 0.000 0.42 0.011 0.050 0.000 4225 70.1 70.1 -11.41 -89 .0 3750
EH 0852 0.76 2.40 0.26 0.00 0.005 4.80 0.020 0.000 0.000 0.50 0.010 0.050 0.000 4601 76.2 77.1 -11.62 -87 .9 9.30 7.60 3750
E15 0.005 5462 94.2 90.9 3750
E16 0.288 23446 382.0 381.0 3750
E17 0.000 31700 531.0 497.0 3750
E18 0854 0.00 2.20 0.18 0.00 0.061 1.60 0.020 0.007 0.000 0.26 0.000 0.000 0.000 3919 65.3 66.1 -14.73 -110.5 0.4 3750
E19 0848 0.22 2.70 0.40 0.24 0.300 1.60 0.010 0.018 0.011 1.40 0.000 0.000 0.000 2921 45.0 45.6 -13.68 -102 .8 3750
E20 0846 0.96 13.40 0.96 1 .30 0.300 2.70 0.210 0.033 0.056 4.70 0.012 0.070 0.000 15009 256.0 247.0 -12.96 -98 .7 4.90 8.30 3750
E21 0847 1.70 21.40 1.80 2.40 0.100 6.60 0.170 0.034 0.016 8.10 0.130 0.000 0.000 26138 448.0 436.0 -8.45 -80 .6 3750
E22 0849 0.67 25.00 1.80 1 .60 0.504 2.70 0.130 0.230 0.023 4.30 0.180 0.080 0.000 32573 552.0 543.0 -12.52 -V6 .8 0.3 7.00 8.90 3750
E23 0844 2.60 6.00 0.49 1 .10 0.056 1.40 0.040 0.000 0.069 4.40 0.000 0.039 0.020 3989 59.3 62.9 -13.06 -99 .3 0.4 -1.20 9.10 3800
E24 0845 2.60 6.?0 0.44 1 .40 0.043 2.60 0.190 0.000 0.070 4.10 0.000 0.039 0.020 3937 61.0 61.7 -12.77 -100 .3 3800
E25 0.041 3988 62.4 59.2 3800
E26 O.OOU 1688 26.9 26.7 3835
E27 0851 0.00 0.01 0.05 0.00 0.041 0.34 0.020 0.000 .0.000 0.02 0.000 0.048 O.OUO 448 5.0 6.1 -15.42 -113 .8 0.4 3900
E 28 0.020 2218 35.8 37.3 3870
E29 0850 0.42 1.00 0.08 0.22 0.012 2.20 0.000 0.000 0.000 1.70 0.000 0.000 0.000 1096 16.1 16.4 -15.06 -106 .8 3950
E30 0.007 79 1.5 0.8 4010
E31 0.006 832 13.6 13.6 3630
E32 0855 0.00 0.00 0.00 0.00 0.000 0.04 0.010 2.600 0.000 0.00 0.039 0.032 0.000 186 1.6 1.6 -9.16 -85 .3 4000
E33 0.001 660 8.0 7.9 4270
UE1 0.063 5212 85.1 81.2
WE 2 0.167 5125 76.8 74.3
WE 4 0.198 3254 51.8 50.7
WE5 0.324 4030 66.2 65.1
WEC 0.054 3064 49.3 48.7
SE135 135 190.0 234510 4250 3110.0
SEKO 140 260.0 344040 6320 4920.0
SE141 141 440.0 320380 5820 4840.0
Table 2 - Empexa gas samples analyses
Total gases (vol. %)

C02 H 2S H:> CH4 N2 He CO
(ppm) (ppm)
E8a 96. 30 0 .00 0. 000 0.018 3,.60 3.3 8.0
FE 95. 70 4 .00 0. 000 0.004 0..30 415.0 38.9
FE(Aquat. ) 98. 66 1 .11 0. 001 0.001 0..20
Residual gases (vol. %)
C02 H2S H2 CH4 N2 02+Ar NH3
E6b 97. 50 <0.05 <0 .005 CO. 005 2 .10 0. 58 -

E8b 95. 10 <0.05 <0 .005 <CO. 005 4. 60 0. 27 0.06
FE 92. 30 4.20 0 .034 <CO. 005 3. 30 0. 03 0.08
total of roughly 11 l/s. The total flow rate of other less warm
springs, still having temperatures exceeding 30°C, is more than 40
1/s.
The emission of gases, associated principally with water points

at the highest temperatures, is very weak; a fumarole (FE) is
present in the Mina Conception with a temperature of 85.6°C.
Water samples were collected generally in 6 separate aliquots
for analyses of major and trace constituents, monomeric aluminum

silica, stable isotopes (18O and D) and tritium.
Temperature, pH, conductivity and alcalinity were determined in
the field. Major and trace chemical costituents were analyzed in
ENEL laboratory in Italy; isotopes were analyzed in IAEA and DSIR
laboratories.
2) Previous studies
As mentioned above, in the period April-May 1977, a prefeasi-

bility study was carried out by the Italian company Aguater [1],
24 water points and some gases were sampled.
120
Subsequently, in 1978, some springs and fluids encountered
during the drilling of 6 thermal gradient test holes were re-
sampled. The temperatures could not be measured with exactitude,
but at least in two cases they were above 100°C (WE3 = 121°, WE5 =
115°) .
The geochemical interpretation of collected data was based on
statistical factors and on the individuation of leakage anomalies.
No particularly favorable results emerged in this connection.
In the summer of 1976 a geological study was conducted [I], the
most important results of which are summarized in the next
paragraphs.
2.1 Stratigraphy
The stratigraphie sequence in the area is made up of Miocene to

Recent age formations, essentially volcanics or sediments of
volcanic origin.
The lowest unit of the sequence is the "Quemez Formation" with
a radiometric age of 16.1, 9.4 m.y. This is made up of numerous
ignimbritic units with an estimated maximum thickness of 300 m.
The base of the "Quemez Formation", not outcropping, is
probably made up of older volcanites (lower Miocene) of the
Formation of Yoza which outcrops east of Rio Empexa.

At the summit of the "Quemez Formation", Pleistocene volcanites
occur which are linked to the renewed andesitic volcanic activity
during the Quaternary period with differentiated dacitic and
rhyolitic products.
In heteropia with the products of the Quaternarian volcanism,
sedimentary lacustrine and fluvial series of a prevalently muddy
and conglomerate nature with local peat intercalations are
present.
121
Volcanics cover the entire period of the Quaternary glaciations
during which they were intensively moulded. The related morainic
deposits are associated to the glacial phases.
The only post-glacial volcanites are found between the Cerro
Milluri and the Cerro Pilaya Khollu.
2.2 Tectonics
A compressive phase of the lower Pliocene (Quechua phase) has
weakly folded the "Quemez Formation". This was followed by a

tensional phase with the development of hörst and graben
structures. The latter one gave origin to closed basins during the
isostatic uplift of the erogenic chain and, as a result of the
progressive development of evaporitic processes, have become the
present Salars (Empexa and Uyuni).
Two principal systems of regional fractures can be indi-
viduated: the first and the oldest with W-NW, N-NE direction, and
the second, still active, with a NE, NW direction.

Locally, structures of vertical collapse connected to volcanic
activity may be individuated.
2.3 Volcanism and geothermal implications
The area of recent post-glacial volcanism is located between

Cerro Milluri and Abra de Napa. A number of acid volcanoes occur
here: C. Pico Loro, C. Cayti, C. Mucellcani. The volcanic products
of this area show an evident evolutive trend from andésites -»

dacites -<• rhyolites in relation to a process of subsurface
differentiation caused by fractional crystallization. This seems
to suggest the presence of a magmatic body in the process of
cooling (the dating of an ignimbrite sample of the volcanites of
the Cerro Pico Loro and Huallcani gave a value of 0.8 m.y.).
122
The magmatic chamber, of great dimensions, could be centred at
the swelling structures along the belt of thermal anomaly which
stretches from Abra de Napa to Fuente Towa, and which is
characterized by springs and thermal manifestations.
As far as the geothermal model is concerned, distinct reservoir
units and covers cannot be clearly individuated. The outcropping
volcanites present locally a fair degree of permeability, which
becomes high at times, both of primary origin (pyroclastics and
volcanic breccias) and of secondary origin (fissures). The
lacustrine terrains and volcanic sediments, whenever present, act
as an impermeable cover. Nevertheless, the same outcropping
volcanites reveal quite a variable degree of permeability and, in
many cases, none at all as a result of self sealing because of
hydrothermal alteration processes.
3. Classification of water samples
The classification of waters was carried out by means of

correlation diagrams based on main chemical costituents. In the
classic formulation of the Piper diagram all samples are found in
the quadrant of the alkaline-earth sulphate ones and in the
alkaline-chlorides ones. In order to obtain a better
discrimination, we have preferred to use two modified diagrams, as
in figs. 2 and 3, which consider Cl and S04 respectively as
separate anions. The two diagrams differ only in the distribution
of the points in the two upper quadrants.
Apart from Ell, a spring emerging west of the salar, cold
waters are situated between ten and a few hundred metres above
the level of the salar. The maximum temperature of these samples
is 14 °C and the T.D.S. is less than 1000 mg/1. As shown in fig. 3
and in table 1, most of these have a high sulphate content and
sometimes acid pH.
123
0 Cl- 100 S04 —— 100
n
QJ
4-
(D
H——————t-
100 HC03- + S04- 100 HC03- + Cl-
F i g . 2 - P i p e r d i a g r a m w i t h Cl as s e p a r a t e d am on. F i g . 3 - P i p e r diagram w i t h s u l p h a t e as s e p a r a t e d anion

These characteristics are uncommon in freshwaters, but can be
explained locally by the presence, in the past, of intense
hydrothermal activity. This activity led to the formation of
large, intensely altered zones and to numerous sulphur deposits
which culminate in the Mina Conception. During circulation, the
air-saturated shallow waters encounter these formations and
sulphur is transformed by oxidation into sulphuric acid and then
to sulphate.
All these surface samples belong to Group A, subdivided into
subgroups Al and A2 respectively located in the NW and NE
quadrant of fig. 3. E5 (t = 22°C, T.D.S. = 980 mg/1) , a surface
water slightly contaminated by thermal fluid, falls just below the
NE quadrant.
The other water points, which make up Group B, are located in
the quadrant of alkaline-chloride waters. Normally these waters
are associated with a deep origin, but the chemical composition of
many of these, in the Empexa valley, may be explained with the
leakage of evaporitic deposits. These deposits derive from the
progressive receding of the Empexa salar, as shown by the numerous
concretions of calcium and magnesium sulphates and carbonates
located few kilometres away from the present edge defining its
past extension.
In fig.3 the position of the fluids originating from theoretic

isochemical leaching of three brine samples of the salar (SE 135,
SE 140 and SE 141) sampled in 1976 for a mining study [2], is
close to the warmest thermal fluids.
The points distribution in fig. 3 allows only a dilution
process of the B group samples with Al or A2 freshwaters without
discriminating in any way between thermal springs and high
salinity hypothermal or cold waters.
125
The A-B section of the fig. 2 Piper diagram vs. T.D.S., as
shown in fig. 4, although confirming a dilution process does not

supply further information.
Fig.4 - Correlation diagram between T.D.S. and the A-B section

in the Piper diagram of Fig.2.
This suggests that, in most manifestations, deep and sub-

superficial circulations are widely interconnected. Fluids rising
from the geothermal reservoir interact with the superficial saline
deposits and the original internal ratio of the major costituents
changes. So it is very difficult not only a reliable individuation
of the original deep composition, which is necessary for any
geothemometric evaluations, but also an estimate of the actual
extension of the circuit.
126
The Na/K ratio contributes greatly to the solution of these
problems. The points distribution in fig. 5 shows two trends;
samples E6, 7, 8, 11, 20, 21, 22, 23, 24 and WE5 fall on line A
(Na/K = 50), while samples E13, 14, 15, 16, 17, 19, 26, 28, 29,
WE1, WE4 and WEC fall on line B (Na/K = 16.7). This last one is
very close to the average Na/K ratio of the three brine samples of
the salar SE135, SE140 and SE141 (= 15.5). The rest of the B group
samples fall in the area between the two lines A and B.
30
Slit-
Na = 2610 Na = 3700.0
17
9
20
x O
O
Lu
10
0-
0 100 200 300 400 500
NA(MEQ/L)
Fig.5 - K vs. Na diagram.
127
4
W
o
&/
/
/''
^
.-- " °
/
o / 0
/' Na= 21p S
20
o" ' ' #
/ ° /
Qj<° 0 s
2 ^
o o / o / 18
i ^ "" O
O
29 /
o
/ °
ô' / i
o --
,- " " °
,, - "o
23 /
0/
o °
/ ^
0/
o
SV^ n
P - " ^
0 I I 1 I I I I ! I ) ! 1 I 1 1 I 1 1 1 1 [ ! 1 1 1 1 1
) 20 40 60 80 1C)0 12!0
NA(MEQ/L)
Fig.Bb - K vs. Na diagram.
As regards the water points of the first trend (line A): E6, 7
and 8 (Rio Quebrada Calorno), are located very close together in
proximity of the Cerro Wichu Kkollu. They have temperatures of
30°, 35° and 15°C; T.D.S. are around 10000 mg/1 for the first two
and 5000 mg/1 in the last. The Ell sample is a cold spring which
emerges from the westernmost edge of the salar with T.D.S. of 5000
mg/1. E20, 21, 22, and fuentes Towa (23, 24, 25) are a group of
very interesting springs located in the Estancia Towa area, while
the WE5 test hole is situated roughly 2 km west of the fuentes
Towa. The temperatures of these 6 springs range from 22"C for E21,
to 87° for E24, for the test hole, at a depth around 150 m, was
registered a temperature of 115°C. The T.D.S., around 4000 mg/1 in
E23, 24, 25 and WE5, increases considerably (15000 - 32000 mg/1)
in E20, 21, and 22 situated between 3 and 5 km north of fuentes
Towa.
128
The main chemical differences among these samples regard the
percentages of sulphate and of earth alkaline contents. These are
higher in the water points E6, 7, and 8, but are practically
halved in E20, 21, and 22; for the hottest samples (fuentes Towa
and WE5) , the sulphates percentage is the same as in the three
previous water points, but the concentration of the earth
alkalines practically disappears.
Among the samples falling on line B: E13, 14, 15, 16, and 17
are located in a restricted area a little north of Mina
Conception. Their temperatures range between 14° and 75°C, while
the T.D.S. varies between 4000 mg/1 and 32000. Spring E16, which
emerged at 75°C at the salar edge with a 23000 mg/1 T.D.S., was
covered in 1986 by the dump of Mina Conception; its pH (1.7) was
extremely low compared to the S04 content (50 mg/1) and the
concentration of Cl (in meq/1) was considerably higher than the
sum of Na and K. Very little is known of the E17 sample (17°C and
35000 mg/1), collected not far from the preceding one, of which
maintains the characteristics, except for temperature. The three
samples E13, 14, and 15, which emerge 2-3 km north-west of E16,
have a temperature of 34 °C, a maximum T.D.S. of 5400 mg/1, SO4
always exceeding 1000 mg/1 and Cl content stechiometrically equal
to the sum of Na and K. E19 (14°C, 3000 mg/1) located near
Estancia Towa, because of its moderate acidity and Cl in excess of
the sum of Na and K is similar to E16 and 17, although has a much
higher percentage of SO4. The E26, 28 and 29 samples (temperatures
between 10° and 35°C, T.D.S. between 1100 and 2200 mg/1), are
situated on the south eastern edge of the area; their chemism is
identical and characterized, once again, by an excess of chlorides
compared to the sum of Na and K, apart from the higher content of
SiO2 in E29 (the warmest of these springs, although less saline) .
129
The other samples, E9, 12, 18, and WE2, located in areas rather
distant from one another, fall in the diagram of fig. 5 in an
intermediate position between the two lines A and B.

Finally, in fig. 6 and 6b, sum of Na and K vs. Cl, the samples
are well discriminated and may be distinguished thus:
- a cluster of points constitued by Fuentes Towa and the
test holes WE2 and WE5, defined as subgroup Bl;

- samples falling on line A (subgroup B2);
- samples falling on line B (subgroup B3), all
characterized by an excess of chlorides as regards

the sum of Na and K, including the three representative
brines of the Empexa salar.
500 ö
x/"
31 Jj -
Na =36950^
X
. . -ißu ,
Na = 56400^
â'Na = 5360
.400
/-'
O 0
Lu
^,"X « s'
/ O '
300
20 ^
-P*" /
/ ^
O 200
X
UJ
/;6X / ^
100 'V X*
0
£^'°
^ I 1 1 ! 1 1 l ! 1 ! 1 1 1 f 1 1 I 1 1 1 ! J i 1 1 I 1 1 I t l I 1 1 I I I 1 1 1 I 1 [ 1 [ 1 1 1 1 i 1 1 1 1
D 1C )0 2C 0 3C10 4C 0 5C 0 6C0
CL(MEQ/L)
Fig.6 - Na + K vs. Cl diagram.
130
120 X
X
X
X O x
X
X 9
o^ 0 x
X
0«x^ X
O ^f' X
X
LJ <
y/ > X
X
80 i^ /!2 X
SUBGROUP E 1 X
X ^"
\,_ X
' / -^ ^
+ i' csi?v "" r?> ' - ""
', 0 ^ / 3- X
X
X
v^» X
X
O X° Ox'
11
O
O X
by 40 ,
X
x
/o X
X »c
<f x
X ig
ox
XO
X 28 X
X ^
X :ex
X ,
X X
1 1 1 M 1 1 1 1 1 1 1 M 1 1 1 1 1 1 M 1 ! 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I II 1 ! 1 1 I I I I I I I I I I I 1 I I I ! I
D 2D 4D 6D 80 1C 0 12 0 14 -0
CL(MEQ/L)
F i g . 6 b - Na + K vs. Cl d i a g r a m .
It is supposed, therefore, that the composition of all the

water points which are situated along the latter line is greatly
influenced by leakage of evaporitic salt deposits, a process which
has certainly modified the original ratios between the different
constituents even in the warmest fluids. An additional
confirmation of this hypothesis is represented by the ratio Cl/Br

(mg/1) ; this, in the samples E23, 24, is slightly over 700, not
very far from the typical one for formation waters, whereas for
the others it varies between 3000 - 4000, values which distinguish
statistically waters that interact with the evaporites. The
principal variations which occur in this case as regards the
original composition in the reservoir, are the considerable
decrease of the ratio Na/K and the increase of the original
concentration of Ca and Mg.
131
Even the samples with a higher temperature which belong to
subgroup B2 present modifications, although lower than those of
subgroup B3. These are a result of the last phase of circulation:
in effect, while the ratio Na/K remains similar to that of Fuentes

Towa and of WE5, the concentrations of earth-alkalines and the
ratio Cl/Br increase considerably.
Finally, the samples of subgroup Bl, for lack of any surface
contamination, can be considered the most representative of the

deep fluid; its possible modifications depend only on processes
of riequilibration during its uplift to the surface.
4. Geothermometric Considerations
Fig. 7 and 8 show the Na, K, Mg triangular diagram according to

Giggenbach [3]. The difference between the two figures consists of
the different scales used for the Na, K, and Mg concentrations. In
the latter case, this permits a clearer visualization of the
fluids thermically more degraded and/or more mixed with
freshwaters.
In Fig. 7 the E23 and 24 (Fuentes Towa) samples are situated
slightly above the "full eguilibrium" curve, at an estimated deep
temperature of about 170 "C. The shift is probably due to the

boiling and degassing phenomena which occur during the upflow with
subsequent precipitations of Ca and Mg. The E25, WE5, E20, 21, and
22 samples, fall on a line which joins Fuentes Towa to the
f reshwaters (right corner) . This is in accordance with an
enrichment process in earth-alkaline components at constant Na/K.
Fig. 8 shows a second trend, which joins points E16, 17, WE4,
WEG and E28. This first two as a proof of the leakage process of
evaporitic deposits discussed in the previous paragraph, are
located in proximity of the points representing the brines of the
Empexa salar; we may, however, think that they could, originally,
132
•OQ No/1000
20 40 60 80 100
K/100 % Mg MG ÎO.5
Fig. 7 - N a , K , V M g t r i a n g u l ä r d i a g r a m .
, Na/400
V
40
K/10 x Mg MgfO.5
Fig.8 - Na, K, ViMg triangulär diagram.
133
be found in a higher position from which they moved away because
of a Na/K ratio decrease (evaporite contamination). Dilution
phenomena of the E16 and 17 samples could originate points E28,
WE4, and WEG.
The temperatures that can be calculated from SiO2 [4], assuming
the equilibration of chalcedony as the most probable, on the basis
of values calculated with ionic geothermometers, resulted for E23
and 24 175° and 186°C respectively.
Therefore, the results obtained using the most common solute
geothermometers are in accordance among them, (also the empiric
geothermometer Na/Li [5] gives values of 175° and 180°C). This
lead us to assume that the maximum temperature in the reservoir
does not exceed 180°C.
4.1 Examination of the State of Equilibrium
By using the activities of aqueous chemical species computed

for homogeneous equilibria at temperatures ranging from 150° to
20CTC, it is possible to compute the degree of under- or super-
saturation of the aqueous components with different mineralogical
phases.
This can be expressed for any mineral in terms of log AP/K.
AP/K refers to the activity product of the species concerned in a
given solute chemical equilibrium compared with the equilibrium
constant K for that hydrolysis reaction at a prefixed temperature.
This ratio is greater than zero for supersaturated minerals and
less than zero for the undersaturated ones. These log AP/K values
are plotted vs. a proper temperature range (based for example on
geothermometers results) ; the paths of convergence of the
resulting curves to the zero value establish the possible mineral
assemblages of the reservoir and enable the identification of the
fluids equilibration temperature by using only their chemical
analyses and some proper constraints.
134
The E24 spring can be considered the most representative fluid
of the Empexa deep reservoir, but pH, calcium and magnesium
content at the sampling point are the result of riequilibration at
shallow levels after degassing; this process explains the thick
travertine deposition characterizing all the hot springs around
the Fuentes Towa area. The only simple and reasonable way to
compute the possible concentration of these components in the deep
fluid is based on. the constraint of calcite equilibration at
180°C.
Fig. 9 shows the log AP/K values for the E24 spring, corrected
composition are plotted vs. temperatures ranging between 150" and
200 °C. The fluid is well equilibrated with both a series of
minerals that are typical components of volcanic rocks present in
the Empexa area and the phases deriving from their hydrothermal
alteration at a temperature of around 175°C. This confirms the
geothermometers values.
^:
Q_
cn
o
-1.0 -
-2.0 -
3.0 - i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i
Temperature °C
F i g . 9 - Log AP/K vs. T diagram.
135
Another interesting aspect to be pointed out is the calcium
concentration, computed according to this method, in the reservoir
condition (23.4 rog/1); this is very close to the 28.1 mg/1 found
in the gradient test hole WE5 during production.
3.4 Remarks on the isotopic data
Before this survey no isotopic analyses of thermal
manifestations and cold springs had ever been performed in the
Empexa area. The results of the 1986 sampling are shown in table
1, the relative 618O vs. <5D diagram in fig. 10. With the exception
of samples E21 (stagnant pool) and FE (condensed steam of the Mina
Conception fumarole), no fluid exists that significantly deviates
from the meteoric line; in other words no appreciable exchanges of
18
O between fluids and host rocks are observed. As the hypothesis
of chemical equilibration at depth is strengthened by the low
tritium values of the waters, the lack of isotopic shift can be
explained only in terms of the low temperature in the reservoir.
~>u
ACT^-
6'
^^ -^ -^
O ®
CN
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\
-
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»^'
130- I I 1 I I 1I I I
-16 -15 -14 -13 -12 -11 -10 -9
180 IN H20 (%o)
Fig.10 - oD vs. 0180 diagram.
136
This confirms the estimated values according to the solute
geothermometers and the AP/K logs. The 159 °C temperature
n o
computable for the exchange reaction of -LOO between dissolved
sulphate and water for the E23 sample also agrees with the
previous results.
5) Conclusions
The general situation in the Rio Empexa valley, on the basis of

the information available and of this geochemical survey, can be
summarized as follows:
a) - Three water groups with well identified chemical
characteristics exist.
The first is a surface one constituted of cold meteoric waters
emerging at a higher level than the salar, with low salinity and
mainly of an earth-alkaline sulphate type.
The second of subsurface character, includes cold and thermal
springs spread over the whole Empexa area, with salinity ranging
from medium to high values. The chemistry, due to the leakage of
evaporitic deposits, is mainly alkaline-earth-alkaline chloride;
the chloride content is higher than the sum of Na and K.
The third, representative of a deep circulation, consists of
the Fuentes Towa and others hot springs located very close to
these. In this zone favorable structural patterns for the uprising
of thermal fluids are present. The chemistry is mainly sodium
chloride with the exception of the most peripherical springs that
can leach evaporitic deposits; the salinity and the temperature at
depth should not exceed 4000 mg/1 and 180°C.
b) - There is a general absence of leakage anomalies and a very

limited presence of free gases. These, with the exception of the
Mina Conception fumarole, are completely lacking in H2S and have
an extremely low content of H2. These conditions make most of the
137
gas geothermometers practically useless; with the use of the
formulation based on carbon monoxide the calculated temperature is
approximately 100"C higher than that obtained by considering the
liquid.
Despite the fact that the thermal information of the gases

normally refers to the deepest part of a geothermal system and
that notable differences can sometimes be found in the calculated
temperatures based on equilibria involving different phases, the
gas results in this area are unreliable.
c) - In no sample was observed an appreciable isotope shift.
On the basis of all this, the conclusions that may be drawn for
the Empexa area, at least from a geochemical point of view, are
not very promising. In theory, higher temperature fluids could be
present in deeper levels than ones in which the waters of E23 and
24 type circulate. With these premises, a geoelectric survey could
be of use for the evaluation of subsequent developments.
References
[1] APPROVECHAMIENTO DE LOS RECURSOS GEOTERMICOS DEL
SUDOESTE BOLIVIANO - Areas de Salär d 1 Empexa y Laguna

Colorada - Aquater 1979.
[2] ERICKSEN, G.E. & VINE, T.D. (1976) - Preliminary re-
port on the lithium rich brines at Salär de Uyuni and

nearby salars in southwestern Bolivia.
[3] GIGGENBACH, W.F. (1980) - Geothermal solute equilib-
ria. Derivation of Na - K - Mg - Ça geoindicators.

GEOCHIMICA ET COSMOCHIMICÄ ACTA, 52, 2749-2765.
[4] FOURNIER, R.O. & POTTER, R.W. (1982) - A revised and
expanded silica quartz geothermometer. GEOTHERMAL

RESEARCH COUNCIL BULLETIN, V. 11, 3 - 9 .
138
[5] FOULLIAC, C. & MICHARD, G. (1981) - Sodium-lithium
ratio in water applied to the geothermometer of geo-

thermal waters. GEOTHERMICS 10, 55 - 70.
[6] REED, M. & SPYCHER, N. (1984) - Calculation of pH and
mineral equilibria in hydrothermal waters with appli-

cation to geothermometry and studies of boiling and
dilution. GEOCHIMICA ET COSMOCHIMICA ACTA, 48, 1479 -
1492.
139
GEOCHEMICAL REPORT ON THE SAJAMA
GEOTHERMAL AREA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per 1'Energia Elettrica,
Pisa, Italy
J. RODRIGUEZ
Universidad Mayor de San Simon,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE SAJAMA, BOLIVIA.
La zona geotérmica de Sa jama, al noroeste de Bolivia, esta muy cerca de

la frontera con Chile y a unos 60 km de distancia de la frontera con el Peru.
La actividad volcànica, durante el Terciario, se relacionaba con dos sis-

temas principales de fallas, formados durante la fase orogénica del periodo,
con tendencias N-S y E-0. Mas tarde se desarrollo un vulcanisrao cuaternario
relacionado con sistemas NO-SE y NE-SO. Este ultimo vulcanismo se caracteri-
zaba por volcanes compuestos que producian lavas y rocas piroclâsticas, que
cubren ahora las ignimbritas terciarias.
Las actividades térmicas mas importantes, que se manifiestan en un flui-

do profundo que llega a la superficie tras su evaporaciôn, se producen junto
al rio Junthuma, a una altura de 4 400 m sobre el nivel del mar, y se relacio-
nan directamente con el sistema NO-SE. Se dan otros casos a 7 km al este y
200 m mas abajo, con menos salinidad, que pueden considerarse como flujo de
salida lateral del mismo sistema. Este flujo latéral parece estar diluido con
agua meteorica que tiene una composicion isotôpica mas negativa que las aguas
térmicas junto al rio Junthuma.
Segûn geotermometros ionicos, la temperatura del depösito es de entre 230

y 250°C; los datos isotôpicos apoyan estos valores.
Solo se han recogido muestras de gas en depôsitos alimentados por fluido

residual (tras su evaporaciôn); estas muestras carecen de oligoelementos, por
lo que no pueden utilizarse como geotermometros y no son representativas del
estado del depösito.
141
GEOCHEMICAL REPORT ON THE SAJAMA GEOTHERMAL AREA, BOLIVIA.
The geothermal area of Sajama, Northwestern Bolivia, occurs

very close to the border with Chile and about 60 km away from
the border with Peru.
During Tertiary the volcanic activity was related to two
main fault systems, formed during the orogenig phase of the
period, with N-S and E-W trends. Later on a quaternary
volcanism developed in relation to NW-SE and NE-SW systems.
This latter volcanism was characterized by stratovolcanoes
producing lavas and pyroclastic rocks, that are now overlying
the tertiary ignimbrites.
The most important thermal manifestations, representing a
deep fluid coming at the surface after flashing, occur near Rio
Junthuma at an elevation of 4400 m a.s.l. and are directly
related to the NW-SE system. Seven kilometers eastward and
200 m downward other occurrences are found, with lower
salinity, that can be regarded as a lateral outflow of the same
system. This lateral outflow seems diluted with a meteoric
water having an isotopic composition more negative than the
thermal waters near Rio Junthuma have.
Reservoir temperature, according to ionic geothermometers,
is between 230 and 250°C; isotopic data support these values.
Only gas samples from occurrences fed by residual fluid
(after flashing) have been collected, they are depleted of
trace components and so cannot be used as geothermometers,
being not representative of reservoir conditions.
142
1). Geologic outline
In the year 1977 a geological reconnaissance study was

carried out by Geotecneco [1], the results of which are
summarized in this chapter.
The Sajama area consists of Tertiary and Quaternary
terrains of volcanic origin. It is characterized by numerous
strato-volcanoes producing lavas and pyroclastites which have
grown over an older ignimbritic cover with vast lateral
extension. The most recent volcanic activity occurs west of Rio
Sajama, along the border between Bolivia and Chile where the
volcanoes Huallatani (Chile), Parinacota, Pomerape, Kakepe and
Condoriri volcanoes are present.
1.1 Stratigraphy
The most ancient stratigraphie unit is an ignimbritic

sequence of unknown thickness. The upper part, with a maximum
thickness of some tens of meters, is composed of intensely
fractured ignimbrites. The lower levels consists, instead, of
tuffs intercalations with variable, but often very reduced
permeability. The base of the ignimbritic body is not
outcropping. It probably rests in stratigraphie unconformity on
the sedimentary sequence of Corocoro. The latter occurs in
other places in the region with a thick succession of
prevalently muddy, Tertiary continental sediments containing
arenaceous horizons, conglomerate and tuff levels.
Above the oldest ignimbritic unit, volcanic units of
various age and composition, which refer to distinct centres of
emission, are found. These do not form uniform covers. In
143
chronological order they are:
- Andesitic porphyritic lavas of Nevado Sajama.
They are probably of Pleistocene age as proven by the
intense development of forms of glacial erosion associated to
morainic deposits and traces of fossil fumarole activity.
- Intermediate andesitic lavas, partly vesicular, of the
Cerro Quisi Quisini.
Acid porphyrites of Cerro Condoriri, Nevado Kakepe
Junthuta, and Nevado Payachata.
In the most pronounced depressions of the Sa jama basin
incoherent deposits with fine and intermediate granulometry
have accumulated, composed of tuffs and ash materials
intercalated with muddy levels. The origin of these deposits is
attributed to episodes such as mud flows (Lahars), ash flow and
explosive activities (ash fall - pomices) connected to the most

recent volcanic activity. These terrains have been abundantly
eroded.
1. 2 Tectonics
The area is characterized by tensional structures. The

principal structural elements have conditioned both the
volcanism and the hydrologie surface structure.
Two principal fractures systems may be distinguished. The
first, and seemingly older system, with N-S/E-W direction on
which the Rio Kasilla and tracts of the Rio Sajama have
positioned themselves. Traces of this system can be
individuated on the Nevado Sajama.
The second, more recent system with NW-SE/NE-SW direction,
has influenced to a larger extent the present morphology
conditioning the alignment and the development of the most
144
recent eruptive centres. The Rio Junthuma has its location
along an element of this system.
1.3 Volcanism and geothermal implications
On the basis of stratigraphie data, a possible sequence of

volcanic events is the following:
- first phase with intense fissure eruptive activity,
probably along the oldest structural N-S/E-W systems, with
emission of viscous acid products which form the basal
ignimbrites.
- There follows a phase in which the eruptive activity
becomes less frequent, it is concentrated along limited sectors
of the fractures system, forming central volcanoes. The
products emitted are andésites with a porphyritic texture. To
this phase belongs the formation of the Sajama Volcano but the
same materials make up the lower parts of other volcanic
structures in this zone.
- Volcanic activity moves west as time passes with central
effusive, and more rapid and tranquil eruptions of intermediate
andesitic lavas (Cerro Quisi Quisini).
- There follows the most recent phase of a partially
explosive nature, with the emission of great quantities of
porphirytic acid material. This is composed of rhyolites and
rhyodacites with phenocrystals of plagioclase, pyroxene, and
biotite (normative quartz > 20%) .
The centres of this activity are: Cerro Condoriri, Nevado
Kakepe Junthuta, Nevado Payachata and Huallatani. Among these,
the most recent seem to be the Huallatani volcano, still in
fumarole activity, and the Payachata, which has two eruptive
145
centres; the Cerro Parinacota, and the Cerro Pomerape which
shows evident collapse structures and has a solfataric
activity. The Nevado Condoriri and Nevado Kakepe are older and
without present manifestations, even though the latter volcano
still shows thermal anomalies (hydrothermal manifestations).
- After the deposition of acid porphyrites comes a period
of mud flows with formation of lahar-type deposits in the most
depressed zones of the Sajama basin. These deposits are, at
present, highly eroded, and are mostly along the Rio Junthuma.
- On top of the lahars there are deposits of ash flow,
partly consolidated and containing also organic material. The
summit of these deposits is transformed into paleosoil. This

would indicate a period of lacking eruptive activity during
which vegetation developed.
- The paleosoil is covered by a level of 30 - 40 cm of

uniform thickness, of piroclastic products, mostly ash and
pumice of acid composition with sedimentary lithic intercalated
fragments. This level records a particularly violent explosive
event, perhaps phreato-magmatic, during which materials
belonging to deep stratigraphie levels have been torn from the
walls of the pipe (Corocoro formation?). This episode could be
attributed to the Cerro Parinacota or Pomerape or even to the
most recent Huallatani, despite this being the furthest away
from the deposits.
- Above the pumices occur again levels of fine and medium

ash flow material which form the present soil.
From a geothermal point of view there are numerous

indications of a volcanologie nature in favour of the
hypothesis that today there exists a not very deep magmatic
146
body in the process of cooling. Among these there are: active
fumarole and solfataric activity of some volcanoes; the recent
age of the last volcanites emitted; their evolutive trend from
andésites to rhyolites with femic phenocrystals as witness of a
acid differentiation process caused by fractional
crystallization in a quiescent stage; the overall volume of the
youngest differentiated volcanites suggesting the presence of
magmatic chambers with considerable possible storage and long
cooling periods.
As regards the hydrogeologic model, the relict lahars
deposits, together with the ashes, form an impermeable cover
sufficiently continuous and extensive in the lowest parts of
the basin. The outcropping volcanites at the highest altitudes
along the slopes of the volcanoes have quite variable degree of
permeability. In theory, these are permeable because of
fracturing and could provide an important recharge area, but
thermal fossil manifestations in all the zone must be noted as
evidences of self-sealing processes connected with a previous
rather intense activity. This makes the permeability of the
volcanites very discontinuous with rapid horizontal variations
and the development of independent (closed?) circuits, as shown
by the existence of cold and warm springs a few meters away

from each other. The identification of the reservoir is also a
problem. This should develop under the strato-volcanoes in the
basal ignimbrites, the permeability of which is ascertained
only for the first tens of meters. The volume of the entire
ignimbritic body does not seem sufficient to form a reservoir;
therefore, if this reservoir exists, it should continues at
depth in the pre-volcanic substratum. We have no direct
knowledge of this substratum, apart from the sedimentary
147
intercalation in the pumices, deriving from the fragments torn
by the explosions. One hypothesis is that this substratum
consists of the continental terrigenous succession of Corocoro
but the presence of this group under the Sajama area is not
certain. Furthermore the Corocoro group presents a considerable
variation in composition and, therefore, in permeability (clay
members, arenaceous conglomerates, etc.). As a result of
intense tectonic deformation, the members of the sequence are
not always mantained. Therefore, even if the existence of the
Corocoro Group in the Sajama area were ascertained, this would
not necessarily constitute a permeable reservoir.
2). Sample collection and field determinations
The Sajama geothermal area is located in the north-west

part of Bolivia, very closed to the boundary line with Chile
and about 60 Km away from the border with Peru. The area, with
an average elevation of 4400 m. a.s.l., shows an uneven
morphology; the most important manifestations are localized in
a small valley along Rio Junthuma.
Two more springs of lower flowrate occur at a level of
approximately 4200 m a.s.l., located some 7 Km east of the Rio
Junthuma ones. The sample location map is shown in fig. 1
The survey in this area was carried out over a period of
seven days from the 5ht to the llth of June 1988. A total of 15
samples of hot and cold springs were taken, 3 of both free
total and condensate gases. Unfortunately more than 50% of gas
samplers were damaged during the freight to Italy.
Water samples were collected generally in 6 separate
aliquots for analyses of major and trace constituents,
148
}f<\f ^'Äf^â^V V
T»M60 QUEMAOO
HUALL/iTANI
= Cold waters Q = Hot waters

Fig. I - Location map of Sajama area samples.
149
monomeric aluminum silica, stable isotopes (180 and D) and
tritium.
Temperature, pH, conductivity and alcalinity were
determined in the field. Major and trace chemical costituents

were analyzed in ENEL laboratory in Italy; isotopes were
analyzed in IAEA and DSIR laboratories.
3). General outline of the Rio Junthuma manifestations
In this area (fig. 2) occur several active and fossil
manifestations: the active ones (more than fifty), showing

temperatures ranging between 50 °C and over 85° C (that is the
boiling point for this altitude " 4400 m a.s.l.), are
distributed for a length of two kilometers. Their location
range between some centimeters to a few tenths of meters from
Rio Junthuma. In some springs occurs appreciable gas and the
total hot water flow rate can be estimated around 45 1/s; fig.
2 shows how manifestations are located in two structurally
separated zones. The first one, northward, provides more
occurrences at a temperature close to boiling than the southern
one does. This latter one, however, besides showing a slightly
higher conductivity for the most important water points,
presents mud pools and at least two fumaroles. Sampling of
these manifestations was impossible because of the dangerous
access to them.
150
1.10000
Fig. 2 - Location map of the thermal manifestations

of the Rio Junthuma .
151
4). Water chemistry
4.1. Classification of the water samples
The analytical results of the fluids sampled during the

survey are reported in tab. 1 (waters) and 2 (gases).
The classification of the samples was carried out by means
of cartesian diagrams and correlations existing between some
chemical components.
The classic Piper diagram is shown in fig. 3. The latter is
divided into four quadrants and samples are generally
distributed as follows. In the first NW are found the earth-
alkaline-bicarbonate waters, generally linked to shallow
circulation; in the second SW the alkaline-bicarbonate ones; in

the third SE alkaline-chloride waters occur, normally
considered of deep origin; in the fourth, NE, the earth-
alkaline-sulphate ones.
Among the samples of the Sajama area only SA16 and 16B
occurring before the Rio Junthuma hot springs start, are
located in the NW quadrant; both are low salinity cold waters
with an anomalous SiO2 (75.5 mg/1), the first one is a stream,
the latter is the Rio Junthuma itself. Samples SA41 and SA42
fall in the NE quadrant; SA41 is a streamwater, SA42 (31°C,
T.D.S. around 500 mg/1), a spring located 30 Km to the north of
the main manifestation area, on the base of its chemical
composition can be considered as a freshwater conductively
heated. The SiO2 and SO4 content, respectively 120 mg/1 and 226
mg/1, is higher than for the others freshwaters. Regarding
water points located in the SE quadrant: SA40, collected near
SA42, is a low salinity hypothermal spring with a noticeable
sulphate content; SA37 (29°C, T.D.S. 1427 mg/1), is another Rio
152
TABLE 1 - Lab. analytical results for water samples.
OODE Tf pHf Condf Alkf Ça Hg Na K Cl S04 Si02 H3S03 NH4 H2S Li Rb Br F AIT Fe Sr Ba
mS/cm meq/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l
ipg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l
SA1 84.5 7.30 6170 4.06 18.5 2.00 1250.0 127.0 1790.0 339.0 192.0198.0 0.660 1.9 6.70 1.10 5.70 1.90 0.033 0.06 2.50 0.130
SA11 68.9 6.19 5830 3.18 12.8 0 . 2 0 1420.0 144.0 1950.0 372.0 240.0 214.0 0.780 0.0 7.20 1.30 5.90 2.10 0.022 0.00 2.20 0.120
SAU 71.7 6.30 6350 3.11 7.4 0 . 2 4 1380.0 138.0 1950.0 371.0 236.0 217.0 1.100 0.0 7.40 1.30 5.80 2.20 0.250 0.21 2.20 0.100
SA13 87.8 7.43 6590 3.30 25.0 3.20 1180.0 118.0 1630.0 313.0 184.0
213.0 0.560 0.8 5.90 1.10 4.60 1.80 0.000 0.00 1.80 0.100
SA16 12.0 6.45 516 1.40 14.4 8.00 9.9 3.1 1.6 15.0 78.8
0.5 0.000 0.0 0.01 0.00 0.00 0.25 0.000 0.00 0.14 0.005
SA16B 9.8 6.31 168 1.56 14.6 8.20 9.8 3.4 1.7 14.9 0.4
78.4 0.000 1.3 0.01 0.00 0.00 0.25 0.044 0.16 0.15 0.006
SA18 51.5 6080 8.9 0.48 1340.0 123.0 1870.0 358.0 207.0 208.0 0.410 0.0 7.00 1.20 5.20 2.00 0.000 0.15 2.10 0.100
SA21 53.3 6160 7.9 0.07 1430.0 129.0 1930.0 374.0 243.0 216.0 0.400 0.0 7.20 1.20 5.90 2.10 0.047 0.02 2.20 0.110
SA35 86.5 5240 4 3 . 4 7.60 1140.0 115.0 1560.0 294.0 201.0 175.0 0.390 0.8 3.00 1.10 4.50 1.90 0.000 0.00 2.50 0.130
SA36 79.0 5670 28.7 2.80 1290.0 127.0 1740.0 340.0 197.0
214.0 0.480 Û.Û 6.70 1.20 5.10 1.80 0.000 0.01 2.40 0.120
S A3 7 29.1 2240 18.9 6.50 442.0 4 6 . 5 591.0 124.0 119.064.7 0.140 0.0 2.20 0.39 1.70 0.81 0.000 0.45 0.91 0.050
SA38 39.3 2270 43.5 28.30 439.0 56.0 476.0 188.0 47.9
155.0 0.290 0.6 2.20 0.30 1.40 0.43 0.000 0.03 0.90 0.020
SA39 45.2 1670 27.1 17.10 300.0 49.0 30.5
319.0 163.0 148.0 0.310 0.8 1.50 0.23 0.86 0.31 0.000 0.00 0.61 0.005
SA40 19.3 193 14.8 6.90 31.8 3.5 2.8 62.0 0.8
74 . 1 0.000 0.0 0.09 0.00 0.00 0.30 0.000 0.00 0.20 0.004
SA41 12.3 270 16.7 9.00 20.3 4.6 6.3 65.3 64.4 1.4 0.000 0.0 0.02 0.00 0.00 0.44 0.023 0.01 0.17 0.020
S A4 2 31.0 82 68.8 18.00 2 6 . 4 13.2 0.4 226.0 120.0 0.3 0.000 0.0 0.01 0.06 0.00 0.17 0.036 0.04 0.50 0.006
OODE Date pHl Condl A l k l Ralkl As Alm Cs Zn Pb Sb 1 TDS A. S. L 018_H20 D_H20 H3_H20 018. .504 S34_S04
mS/cm meq/l meq/l mg/l mg/l mg/l mg/l mg/l mg/l
mg/l mg/l m 0/00 o/oo T.U. 0/00 0/00
SA1 06/06/88 7.33 5 . 8 5 4.00 3.80 4 . 4 0 0.00 1.90 0.00 0.00 0.700.00
3948 4380 -13.99 •107.9 0.9
SA11 06/07/88 7.21 6.35 3.16 2.96 4.70 0.00 2.30 0.01 0.00 0.00 0.80 4372 4410 -12.73 -108.6
SA13 06/06/88 7.21 5 . 4 0 3.24 3.04 3.90 0.00 2.10 0.00 0.00 0.70 3692
0.00 4410 -14.14 -110.8 0.8 6 .00 11..50
SAH 06/07/88 6.90 6.47 3.16 3.00 4.80 0 . 0 0 2.30 0.00 0.00 0.00
1.00 4331 4410 -12.68 -107.0 -2 .00 12..20
SA16 06/07/88 6.32 0.18 1.34 1.34 0.00 0.00 0.00 0.00 0.00 134
0.00 4430 -16.52 •120.9' 2.7
SA 168 06/11/88 6.31 0.17 1.38 1.38 0.00 0.00 0.00 0.00 0.00 0.00 139 4430 -16.54 -118.0 2.3
SA18 06/08/88 6.87 6.29 2.92 2.76 4.70 0.00 1.20 0.00 0.000.6U
0.00<,144 4400 -12.83 -105.6 0.1 3 .90 11. 30
SA21 06/08/88 7.02 6.25 2.84 2.68 4.80 0.00 1.20 0.00 0.000.700.00
4346 4410 -12.56 -105.6 1.1
SA35 06/08/88 7.36 5.21 5.68 5.48 3.90 0 . 0 0 1.90 0.00 0.003565
0.50 0.004415 -14.00 -110.2 0.6
SA36 06/08/88 7.18 5.67 4.18 4 . 0 2 4.10 0.00 2.10 0.00 0.50
0.14 3964
0.00 4425 -13.74 -110.2 0.7
SA37 06/08/88 6.76 2.31 2.40 2.40 1.30 0.00 0.68 0.00 0.30
0.00 0.00 4370
1427 -15.63 -115.6 1.8
SA38 06/09/88 7.05 2.35 6.84 6.74 1.80 0.00 0.45 0.00 0.00 0.00
0.30 1450 4290 -16.60 -123.1 1.0
SA39 06/09/88 7.24 0.28 4.82 4.72 0.95 0.00 0.34 0.00 0.00 0.00
1021 4290 -16.92 -123.3 0.6
SA40 06/09/88 6.60 0.30 1.12 1.12 0.14 0.00 0.00 0.00 0.00 0.00 202 4400 -17.65 -126.7 0.6
SA41 06/10/88 6.56 0.14 0.92 0.92 0.86 0 . 0 0 0.00 0.00 0.00 0.00
196 4400 •16.92 -123.3 1.5
SA42 06/13/88 7.13 0.63 1.38 1.38 0.00 0.00 0.00 0.00 0.00 0.00 476 4410 -17.26 -125.4 0.6
TABLE 2
Sajama gas sample analysis (vol, 7«)
CODE C02 H2S H2 CH4 N2 CO (ppmV)
SA14A 99.78 0.0 0.0 0.007 0.0 11.20
SA-36 99.52 0.0 0.0 0.011 0.47 9.65
0 Cl- -t- SQ4 — 100

———— 1_____ 1———— 1———— 1———————— i———— i———— i———— i———— '
+SA42
+BA16B
+ SA41 n
- 0)
-f
+ SA40
-f 2
(D (D
Z .
+ SA37
+$44( 3
—— _.....,.. ! . . - . -J—————————— J——— ..._....!.-. . . . . . . —— 3*
100 HC03- + COS— 0
Fig.3 - Piper diagram for Sajama area water samples.
Junthuma sample taken a little downstream from the last

occurring manifestation; SA38 and SA39 are the two thermal
springs located ~7 km eastward of the main springs area. These
show temperatures of 39.5°C and 45.2°C with T.D.S. of 1450 and
"1000 mg/1 respectively. All the other water points, collected
along the Rio Junthuma, have temperatures ranging between
51.5°C and 87.8°C and T.D.S between 3700 mg/1 and 4400 mg/1.
154
In fig.4 the Piper diagram was plotted with chloride as a
separated anion: all samples appear well correlated on a
straight line.
0 Cl- 100
4.SA41
.. Ql
n
+
+SA40
ro 3:
IQ
100 HC03- + 504— ß O
Fig.4 - Piper diagram with Cl as separated anion.
In fig,5 the correlation between total salinity, expressed

in meq/1, and an A-B section of the previous diagram confirms
a dilution process of the deep hot water with a local ground
water.
Only SA38 and SA39 slightly shift from the dilution trend.
This is mainly due to a percentual increase in alkalinity and
sulphates. As later on explained, considering the isotopic data
these springs are characterized by dilution with a ground water
that is not the same interacting with the thermal occurrences
along Rio Junthuma.
155
-14
Fig. 5 - Gorrelation diagram between TDS and A-B section

in the Piper diagram with Cl as separated anion
Besides this difference SA38 and 39 can be related to the

same deep thermal inflow that feeds the main system. In fact
considering the representative points of all the thermal
springs in the study area in the triangular diagram correlating
Li, Rb and Cs [fig.6], they result quite close.
Concluding their location 7 km to the East and their
altitude, "200 m below the Rio Junthuma springs, make of SA38
and 39 a likely lateral outflow of the same system.
156
' l1} T I I l i l l | l i l l l l l l l
100 80 60 20 0
Rb * 4 (mg/!)
Fig.6 - Li, Rb, Cs triangular diagram,
4.2. Geothermometry
The temperature of the deep fluid on the basis of the

triangular Na, K, Mg diagram [2] (fig.7) should run not below
230°C. The mixing process of this deep water with different
percentages of freshwater is highlighted by a perfectly
straight lining up of the water points until the bottom-right
corner of the diagram (shallow waters representative zone).
157
Na/1000
V
100
MgtO.5
Fig.7 - Na, K, \/Mg triangulär diagram.
Again the plotting of 10*CMg/(10*CMg+CCa) vs.

10*CK/(10*CK+CNa) [2] (fig. 8) supports this dilution with the
only difference that the extrapolation of the line, connecting
the samples representative points, up to the theoretic
equilibrium curve at the different temperatures gives a
reservoir fluid at 250°C of temperature.
In fig. 9 [3] are shown the log AP/K values for SA21 spring
composition vs. temperatures ranging between 150 and 260°C
(with the only constraint of the calcite equilibration at the
different temperatures). The curves for a series of volcanic
158
10 Mg
10 K
o.o l l l l f l l l J l i l ! l l l l l l l l l l l l L l l l l l l l l l l l I l i i l I l
Fig.8 - 10K / (10K + Na) vs. lOMg / (lOMg + Ca) diagram.
Sample SA21
Added Carbon (o solution

133.8 mmol/Kg (at 240»C)
l l l l l l l l l | l l Ml l l l l | l l l l l l l l l | l l l l l l l l l | l l l l l l l l l | l l l l l l l l l | l l l l Ml l l | l l l l l l l l l |
'100 120 140 160 180 200 220 240 260
Temperature C
F i g . 9 - Log AP/K values vs. t e m p e r a t u r e -
159
rock components, and the phases derived from their hydrothermal
alteration, converge at a temperature around 240°C. The curves
match at a value of log AP/K below zero, this could be
explained by a poor computation of theoretic pH values due to a
lack of the pH value in the field. In the same way can be

explained the apparent equilibration of fresh minerals at a
lesser temperature of the altered ones.
For this reason it is been assumed as the equilibration
temperature value the one correspondig to the lines crossing
point instead of the conventional log AP/K = 0.
As far as concerning the SiO2 geothermometer [4] may be
interesting to examine fig. 10, here SiO2 is plotted against
1000/T°K.
T Amorphous Silica
O
to-
(N
o:
cn
Eo
"—^LO-
T—' ,
:
(N
o :
c/)gj
o.
in-
O--T-T i i i ir t i | i i r i i IT i ijiiiiiiiii[iiiifi
1.50 2.00 2.50 3.003.50 4.00
1000/T
Fig.10 - Si02 concentration vs. 1000/T0 K.
160
Many representative points fall along the solubility curve
of amorphous silica, this agrees with the presence of
ignimbritic layers at depth and with an equilibration process
at the temperature of outflow. Because of it, the Si02 content
cannot be used to estimate the temperature at depth.
4.3. Remarks on the isotopic data
No isotopic analyses of thermal manifestations or cold

waters present in this area had ever been performed before,
besides in the course of this survey only very few cold springs
were found; so the relative results presented in tab. 1 are
only enough to draw a tentative meteoric model of the
circulation patterns.
The highest chloride content and the most isotopically
positive springs SAH, SA14, SAIS and SA21, despite their
temperatures are not the highest in the Rio Junthuma area, have
been considered as residual waters originated from a deep fluid
single step boiled from a 260°C reservoir temperature to 85°C.
As the representative points of these springs in fig. 11
(diagram 5180 vs. SD) are slightly scattered, to reduce
possible errors to a minimum, the boiled water composition (BW)
has been computed extrapolating to zero the tritium content in
the three diagrams of fig. 12, 13 and 14, respectively 3H vs.
S18O, 3H vs. 6D and 3H vs. Cl.
The values obtained in such a way: 518O « -12.65, <SD « -
105.1 and Cl « 1950 mg/1 are comparable to those resulting
averaging the analytical results for SA14, 18 and 21. On the
base of the single step flash the 260°C deep water composition
(DW) should be: 518O = -14.64, SD = -116.6 and Cl = 1290 mg/1.
161
-95
•105
O
C\J
X
-1 15
-125
•1354-7
-18 -16 -15 -14 -12
180 IN H20(%o)
Fig.11 - £> D vs. £ 180 d i a g r a m .
o. u -
16
o
2 5 -„
£,•.•*-)
/I5\s
x
o 2.0 -_
3
C\l
n: o\
\
1.5 -E Q
\_/ —————————
n:
1.0 -E
/ 38
\ 21
1
40 ,42 ;a
o 35
o /o o
0 5' _~
*—' * «—
0.0 - l l 1 l 1 1 l l l 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
\^
1 1 1 1 1 1 1 1 1 1 I ! 1 1 1 1 1 1
-1?3.0 -17.0 -16.0 -15.0 -14.0 -13.0 -12

180 IN H20(%o)
Fig.12 - Tritium content vs. 180 diagram.
162
3.0
2.5
,16B
O 2.0
(N O
X
1.5 T -0e
O:
1.0
O1
oQi;
Q
0.5
0.0
-130 -125 -120 -115 - 1 -105
10 -100
D IN H20(%o)
Fig.13 - Tritium content vs. o D diagram.
3.0
2.5 -E
H
O 2.0
CN
n:
1.5
O
1.0 -e-
o o
,3 O
31
O
0.5
0.0
400 800 12001600 2000
CI (mg/l)
Fig.14 - Tritium content vs. Cl diagram.
163
The resulting oxigen shift from the GMWL is around 2 delta
units of 180 and the recharge water should have an isotopic
composition similar to that of Rio Junthuma.
Considering now samples SA1, 13, 35 and 36 they both for
salinity and tritium content, look like a dilution with

percentages between 15% and 35% of local groundwater.
This process is supported by their location on the diagrams
in fig. 12, 13 and 14.
In the c518O vs. SD diagram of fig. (11) they occur in
intermediate position with respect to lines A and B. The first

one, A, represents the dilution line along which fall all
possible mixture between the local groundwater (SA16B) and the
undiluted single step boiled deep water BW. Curve B shows in
turn the theorical isotopic composition of the residual waters
originated, according a single step flash, from the possible

mixtures between local groundwater and deep water ranging
temperatures between 85°C and 260°C.
The first hypothesis (superficial mixing) is automatically

excluded because SA1, 13, 35 and 36 have temperatures always
close to or even higher than boiling temperatures, despite the

evident dilution (chloride and tritium content). Also the
second hypothesys (mixing at the depth) can be excluded, the
location points of these springs in fig. 11 could be explained
only by low contributes of local groundwater that again do not
fit the analyzed chlorides and tritium.
The SD vs. Cl diagram (fig. 15), shows that such mixtures

arise at a subsuperficial level. The representative points of
SA1, SA13, SA35 and SA36 are well below the curve B (theorical
location of residual waters originating from diluited deep

fluid) and can be explained on the basis of a boiling process
164
for the undiluted deep water up to about 120°C, and afterwards
a mixing with the local groundwater (SA16B). This fit properly
both the analytical chlorides and tritium contents.
Finally considering the location of samples SA38 and 39 in
the diagrams 518O vs. 5D (fig. 11) and SD vs. Cl (fig. 15) is
evident:
1) The groundwater that acts as superficial end member for
the mixing has an isotopic composition more negative than the
one interacting with the Rio Junthuma springs; the tritium
content very close to 0 entails long circulation time peculiar
to regional patterns. The more positive values for samples SA16
and SA16B can be better explained with daily cicling process of
freezing and melting than with a lower infiltration level.
2) The deep component again seems to be an actual reservoir
fluid more than a residual water. This confirms the hypothesis
of a lateral outflow.
-95
-135
1000 1500 2000
CI (mg/l)
Fig.15 - oD vs. Cl d i a g r a m .
165
4.4. Extimation of the Rio Junthuma springs total flowrate
Given the particular morphology in which manifestations

along Rio Junthuma lies, it is possible to compute the total
deep water flowrate. As measured water flow rate at points Ql
and Q2 (fig.2) are respectively 106 1/s and 150 1/s, the deep
water contribution should be 44 1/s (~30%).
The chlorides and tritium contents of BW, SA16B and SA37
agree closely with this value.
5). Gases
The only two available gas analyses (tab. 2) belong to

springs which are fed by a deep fluid that underwent a boiling
process during its raise.
Such gases, besides being not representative any more of
the deep condition, are therefore depleted of the trace
components.
In order to estimate a geothermometry or, in any case, to
have an idea of the original reservoir composition it should be
advisable to sample gases from mud pools or fumaroles fed by
the steam produced with the boiling process.
References
[1] APPROVECHAMIENTO DE LOS RECURSOS GEOTERMICOS DEL
SUDOESTE BOLIVIANO - Areas de Salär d'Empexa y

Laguna Colorada - Aquater 1979.
[2] GIGGENBACH, W.F. (1980) - Geothermal solute equilib-
ria. Derivation of Na - K - Mg - Ça geoindicators.
GEOCHIMICA ET COSMOCHIMICA ACTA, 52, 2749-2765.
166
mineral equilibria in hydrothermal waters with
application to geothermometry and studies of boiling
and dilution. GEOCHIMICA ET COSMOCHIMICA ÄCTA. 48,
1479 - 1492.

RESEARCH COUNCIL BULLETIN. V. 11, 3 - 9 .
167
GEOCHEMICAL AND ISOTOPIC EXPLORATION OF THE
GEOTHERMAL AREA OF PAIPA, CORDILLERA ORIENTAL,
COLOMBIA
R BERTRAMI*1, A. CAMACHO**, L. DE STEFANIS***,

T. MEDINA**, G.M. ZUPPI***
* Ente Nazionale per 1'Energia Elettrica,
Pisa, Italy
**IAN,
Bogota, Colombia
***Dipartimento di Scienze della Terra,
Università di Torino,
Turin, Italy
Resumen-Abstract
EXPLORACION GEOQUIMICA EISOTOPICA DE LA ZONA GEOTERMICA DE PAIPA, CORDILLERA

ORIENTAL, COLOMBIA.
La explotacion de la zona geotérmica de Paipa (150 km al N de Bogota) se

realize durante el période de 1987-1989, obteniéndose los siguientes resulta-
dos y conclusiones principales:
I - Las aguas geotérmicas tienen una faciès de cloruro-sulfato sôdico.
II - El componente gaseoso principal es CO , aunque también estân pré-

sentes CH , H S y N .
Ill - La composiciön isotôpica estable del agua muestra efectos importan-

tes de evaporaciön y de separaciön del vapor. El fraccionamiento
Ö
isotôpico indica una temperatura entre 200° y 230 C.
IV - La presencia de componentes que indican pérdida de vapor geotérmico,

taies como NH. , , H„
NH, H„ yy H„BO„,
H B0„, sugiere
sugiere 1también que existe un
4 2 3 3
depôsito profundo de agua a alta temperatura.
V - Todos los geotermômetros quimicos senalan una temperatura del depô-

sito de 220°C o mas.
El modelo de la zona geotérmica que se saca de los datos geoquimicos e

isotôpicos indica que existe, al menos en la parte sur, un protnetedor poten-
cial geotérmico.
1
Present address: ENEL Pietrafitta, Perugia, Italy.
169
GEOCHEMICAL AND ISOTOPIC EXPLORATION OF THE GEOTHERMAL AREA OF PAIPA, COR-
DILLERA ORIENTAL, COLOMBIA.
In the period 1987-89 the geochemical and isotopic

exploitation of the Paipa geothermal area (150 km N of Bogota)
was carried out with the following main results and
conclusions :
I - The geothermal waters have a sodium chloride-sulphate
faciès
II - The main gas component is C02, but also CH4, H2S and
N2 are present
III - The stable isotope composition of water shows important
evaporation and steam separation effects. The isotopic
fractionation indicates a temperature between 200° and
230° C
IV - The occurrence of components indicating loss of
geothermal steam, as NH4, H2 and H3BO3 also suggest the
exsistence of a high temperature water reservoir at depth
V - All chemical geothermometers indicate a reservoir
temperature equal to or higher than 220° C
A model for the geothermal area, derived from geochemical

and isotopic data, indicates a promising geothermal potential,
at least in the southern part.
1 Introduction
The Paipa geothermal district, located 150 km north of

Bogota and 250 km east of Nevado del Ruiz volcano (Fig.l),
belongs to the Altopiano Cundi-bayacense in the Cordillera
Oriental; its geological setting, typical of this region,
consists of a Mesozoic-Cenozoic substrate, generally acting
as a geothermal reservoir, overlying a Precambrian and
Paleozoic metamorphic basement (Fig.2). The Cretaceous-Miocene
sediments are formed by shales alternated by quartzitic
sandstones, mudstones and dolostones. Levels of evaporites
(Upper Cretaceous) and coal (Eocene) are present (1,2).
170
Figure 1 Geographical location of Paipa geothermal district.
The area belongs to the Altopiano Cundi-bayacense in
the Cordillera Oriental.
The volcanic rocks, intruded in previous sediments, are

composed of an extensive sequence of riolitic and porphiritic
lava flows and pyroclastic deposits. The Upper Pliocene to
Pleistocene sediments are an assemblage of coarse grained
volcanogenic rocks derived from Cuerpo Volcanico de Oolitas
and Pan de Azucar (1,2).
The Paipa geothermal field is strictly connected to the
Colombian Andes tectonics, which strike the north-south
parallel to the Ecuador-Colombia trench. The geothermal field,
in fact, is located in the central axis of the Tunja
sinclinorium and is limited to the east side by the NNE-SSW
El Salitre fault (1,2,3).
171
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Figure 2 Geological setting of the Paipa area.

tip: Cretaceous-Eocene sediments (shales alterned with
quartzitic sandstones, mudstones and dolostones).
dotted: Upper Pliocene-Pleistocene sediments
(coarse-grained volcanogenic rocks).
dark: volcanic rocks (riolitic and porphiritic lavas)
gray: alluvial sediments
dash: lake Sochatoga
lines: main faults
172
The main aim of the present study is the evaluation of
the chemical and isotopic characteristics of water and gas
samples collected by Colombian members of IAN and IAEA
experts, in order to define the relations between the
different types of water in this area as well as the probable
distribution of temperature at depth.
2 Field and analytical methods
Ground-based field work was carried out in July 1987 and

in August 1989 at all the hot discharges and steaming grounds
present in the area. Samples of cold waters were collected
at the same time from streams and springs adjacent to the
thermal discharges. The hot water points (> 50°C) of this
area received attention during reconnaissance studies of the
geothermal energy potential of Colombia since the early 1980s
(4,5); therefore, detailed sketches or models for the Paipa
geothermal system are available. Altogether 19 water samples
were collected for chemical and isotopic analyses.
Temperature, Eh, pH and conductivity were measured in situ
using portable meters. All samples were filtered through
Millipore membrane filters.
The major dissolved constituents were determined at
Institute de Asuntos Nucleares (IAN), at ENEL laboratory
(Lardarello) and at Dipartimento di Scienze della Terra ( DST
- Torino) by atomic absorption spectrometry (cations), by ion
chromatography (anions) and by titration (alkalinity) using
standard methods. Moreover, some analyses of anions (HC03-,
SO4=, S=, PO4=, N03-) have been performed in the field using
a portable spectrometer.
The gas samples from steam vents as well as from
discharges were collected in evacuated vessels previously
filled with 500 ml of 4N NaOH; the gases were analysed in
ENEL laboratory by a combination of wet chemical and gas
Chromatographie methods. The non absorbed gases were analysed
by chromatography.
Isotopes of water molecule were analysed in the IAEA
laboratory, while Sulphur-34 and Oxygen-18 of dissolved
173
sulphates precipitated with BaCl2 carried out at the Paris-Sud
University.
The results are reported in tables 1-2 (chemistry) and

table 3 (isotope).
3 Chemical composition of water discharges
3.1 Major elements
On the basis of a preliminary survey of the analytical

data given in table 1 and reported in figure 3, the major
part of water can be classified as acid-sulphate-chloride,
as defined by Giggenbach (6). The chemical composition
appears to be rather homogeneous and only cations can mark
the differences between the cold and hot waters. High
temperature waters are mainly characterized by the
significant presence of Na-K, whereas waters from a partial
or total superficial origin show a variable Ca-Mg component.
Moreover, the temperature of hot discharges ranging
between 30 and 75°C does not present a regular areal
distribution, as could be suggested by the groundwater flow
inside the Paipa district. On the other hand the Ca and
Mg content increases from Rio Salitre-La Playa (P08 ) to
Banos Termales (P01-P03, P05, P20) following the water
movement, irrespective of temperature.
As shown in figure 4, it is correct to consider P08
the closest sample to the chemical end-member of the Paipa
waters, even if it indicates an intermediate temperature
(50°C). The second pole is formed by environmental
temperature waters that flow in the shallow aquifers and
are characterized by a neutral chloride chemistry. In this
case, the chemical content is mainly controlled by the
hydrolysis of volcanic porphyrites as indicated by samples
collected in the hydrographie network (Q.Honda) or by the
solubility of the Cretaceous-Eocene deposits (Mina de
Carbon). However all the samples do not contain
bicarbonates. A gradual intermixing between two groups
appears.
174
tab. 1 Chemical data of water samples - L indicates laboratory analysis; F, field analysis. Elements are
expressed in p.p.m.
Sample Year TF CondF pH F Eh F ALK F CondL pH L Ca++ Mg++ Na+ K+ HCQ3 Cl- S04 = H2S Si02 NH4 + U+ Fe Sr++ Ba-H- AI tot B F- Br- N03- P04 =
°C US/cm L
P-01 87 525 6 7 105 40000 134 23 14600 2300 56 5800 19700 48 72 088 53 17
89 506 33500 68 25 43 39000 66 90 16 11200 1200 45 5400 18200 47 70 04 26 10 06 42 25 08 55
P-02 87 525 ES 98 33000 144 15 13300 3650 48 5700 18400 56 35 094 33 14
89 51 8 35500 68 40 40000 65 80 16 10500 1200 42 5400 19200 42 90 05 1 10 003 29 22 18 7
P-03 87 725 59500 68 -312 129 15 12500 2900 50 5800 18200 14 60 83 075 28 16
89 740 41000 69 20 41 51900 72 83 16 11000 1200 43 5300 18400 1 4 43 80 04 1 15 0 11 33 19 24 33
P-04 87 21 5 3630 58 105 21 34 963 159 23 438 1435 5 03
89 20 1 4130 64 44 335 4200 65 16 5 720 77 35 164 1520 85 4 02 04 02 25 007 05 14 03
P-05 87 732 72 -42 21000 36 13 9115 2375 29 3698 10100 82 32 049 02 17
89 720 24200 76 -30 265 24700 77 30 12 5300 592 26 9 2700 6900 48 44 03 07 12 004 42 24 10 07 16
P-06 89 19 7 72 45 150 O B 95 47 3 140 14 3 09 43 23 ! 6 28 2 05 16 29 0 13 46 02
P-07 87 459 6 4 -91 20000 33 46 7813 1000 26 3270 10318 61 035 1 6 102
P-08 87 56 5 6 8 -232 44000 22 32 17708 1593 50 7430 23814 58 468 46 185
89 56 3 48300 4 7 147 43 49500 52 15 5 13000 1200 45 4800 16250 34 100 03 04 03 008 37 21 65 11 5
P-09 87 380 1018 70 37 49 58 130 187 66 53 236 53 252 03 08
P-11 87 24 8 140 59 225 13 06 52 07 1 5 20 19 99 03 33
89 242 152 62 59 1 8 158 64 12 1 23 3 6 27 15 48 2 03 03 021 29 1 6 02
P-13 89 44 56 812 09
P-18 89 51 2 38300 73 8 42 4000 76 76 17 11000 1100 40 5300 19000 08 43 80 03 04 05 05 326 18 77 33
P-20 89 720 40900 68 29 40 41500 73 70 15 10200 950 45 5200 18500 1 6 40 75 05 1 3 15 09 33 16 25 1 7 07
P-22 89 166 6300 78 -32 65 11 4 1500 155 725 750 135 10 09 03 23
OH 89 128 20 75 0 05 1 05 2 04 5 1 1 5 11 6 2 1
MC 89 185 5670 3 1 236 450 300 52 6 3 4500 1 5 118 1 5 550 08 190 1 2
tab. 2 Chemical data of gas samples. Analyses are expressed in per cent,
Sample Year H2 02+ Ar N2 CH4 C02 H2S Ha C2H6 CO

ppm ppm ppm
P-01 87 0.23 1.4 0.05 98.3 0.021 10.3 2.3
89 88 3.29 11.8 0.77 84.14 4.7
P-02 87 0.05 0.33 0.02 99.6 0.027
89 0.06 7.35 21.81 0.78 70 2.16
P-03 87 0.06 0.3 0.01 99.6 0.055 0.82 0.63
89 0.009 1.43 0.32 0.06 98.11 0.012 2.69
P-06 87 0.1 1 01 0.29 98.6 — 38 15
89 0.05 0.77 16 86 4.37 77.5 n.d.
P-07 87 - 0.07 0.37 0.06 99.5 - 5.8 33
P-13 87
89 0.001
0.11
0.12
1.66
1 03
0.61
0.06
97.6
98.79 : 0.717
P-13a 89 0.009 0.03 2 16 0.79 97 0.003
P-20 89 0.006 13.94
tab. 3 Isotopic data of water samples, referred to international
standards.
Sample Year 5 D 5 180 T 5 34S 5 180

%. SMOW %. SMOW T.U. (S04) (S04)
P-01 87 -6.55
89 -68.0 -6.61 0.3±0.2 8.90 4.0
P-02 87 -6.68
89 -67.2 -6.89 0.0+0.2
P-03 87 -7.05
89 -67.0 -7.32 0.3+0.2 10.20 6.4
P-04 87 -9.47
89 -72.0 -9.67 0.4+0.2 8.00 11.5
P-05 87 -8
89 -68.4 -7.91 2.0+0.2 9.50 7.2
P-06 89 -63.2 -15.01 3.7+0.3 11.00 17.0
P-07 87 -8.44
P-08 87 -6.54
89 -67.4 -6.08 0.4±0.2 10.00 6.0
P-09 87 -8.69
P-11 87 -9.97
89 -72.6 -9.99 0.3+0.2
P-18 89 -67.4 -6.72 0.010.2 9.10 4.9
P-20 89 -68.0 -6.9 0.0+0.2 9.70 5.1
P-22 89 -8.73 10.30 13.5
Q.H. 89 -9.25
M.C. 89 -9.57 7.60 15.0
100
100 100
CI
Figure 3 Relative HCO3, Cl, SO4 contents (mg/kg) of waters

collected in 1989 and listed in table 1. The major
part of waters can be classified as
acid-sulphate-chloride.
176
8\ 100
O/
Figure 4 Particular of relative Na+K, Mg, Ca contents. Only

cations can mark the differences between surface and
deep waters. Sample P08 could be considered rather
close to the chemical end member of Paipa deep waters.
The S:C1 ratios are smaller than those of the magmatic

discharges in the Nevado del Ruiz volcano (7-10) which
supports the assumption that the chemistry of these waters
is due to the partial absorption of deep gases (9, 10).
Although the water temperature is higher than 30 °C,
thermal spring discharges show a low content of dissolved
silica. This could be explained either by an aquifer matrix
relatively depleted in quartz and silicates, or by waters
heated without reaching complete chemical equilibrium. This
second process needs slow reactional kinetics (11, 12)
which could be favoured by the presence, in the volcanic
rocks, of quartz phenocristals (1-3). The undersaturation
with respect to quartz no longer appears in the equilibrium
177
diagrams (Fig.5) of aqueous phases at a temperature of
60°C. Therefore, as at this temperature, which corresponds
to the mean temperature of all the Paipa thermal springs,
waters are always saturated with respect to quartz, it is
correct to consider that in rising up, the fluids could
be thermically equilibrated with external conditions. The
new equilibrium allows precipitation of exceeding SiO2, as
indicated by the presence of hydrothermal calcedony in the
sedimentary formations.
16.0
1 2.0
m
01
o
80
QUARTZ
SATURATION
4.0
OH
AMORPHOUS
SILICA
SATURATION
MC
0.0
-6.0 -4.0 -ao
Figure 5 Equilibrium diagram of acqueous phase at 60°C. The

fluids are equilibrated with external conditions: this
allows precipitation of excess SiO2 as indicated by
the presence of hydrothermal calcedony in the
sedimentary formations.
178
At the same time, figure 6 showss the different stages
of maturity reached by waters during dynamic hydrothermal
alteration. The most important alteration process consists
of attack by acids formed through absorption of deep gases
into groundwaters and leads to rock destruction (6, 11,
12). In the Paipa geothermal district, separation of the
C02 rich vapour phase and its absorption into water generate
an environment of increasing acid alteration. However, when
the volume of waters reacting with gases is small (P08),
or when the exchange reaction time between the water and
the gases is long (Pll), the continuous gas flow permits
the waters to reach equilibrium with C02, leading to a
rapid increase in their reactivity. Besides, when the gas
volume is smaller than that of water (P18) or when the
exchange reaction time is short (QH), the amount of
dissolved CO2 is reduced, decreasing the reactivity of the
water towards the aquifer matrix. The principal processes
Na
1JÛOO
so
X
/ / / /shallow \
/ f i f waters \
/ 220°/ /Z00° / 11 \
/ / / / 60*
50 /
100 QH
Figure 6 Relative Na, K, Mg, content of thern

Isotherms calculated according to Giggenbach equations
(6) are given together with the full equilibrium
curves.
179
affecting geothermal fluids during their further rise to
the surface are summarized in figure 7, where dissolved
C02 is reported with respect to discharge temperature.
Dissolved CC>2 shows the same order of magnitude in hot as
in cold waters. Therefore, waters do not precipitate the
travertine deposits in all the geothermal district, as
could be suggested by the high partial pressure. In the
case of Mina de Carbon and of water point P06 (steam
heated pool), superficial oxidation of H2S provides a source
of acidity and an excellent environment for intense rock
leaching. The waters thus show a high content of dissolved
sulphate.
o- 08
MC
o
u
-1-
11
O
0!
-2-
o <0 18
5
0
0
3
0
4
-3 — 0 0
20
J2L
10 30 50 70 t C
Figure 7 Dissolved CÛ2 as fonction of discharge temperatures.
3.2 Trace elements
The most significant trace elements in Paipa waters,

halogens (F and Br), B and Li, could complete interpretation
of the water origin and circulation. By including analytical
data obtained during a comprehensive study of Nevado del
Ruiz gases (7, 9, 10, 13), the relative Cl, Br and F
180
contents are compared in (Fig. 8). The most striking feature
of this plot is the pronounced mixing line between the
Nevado del Ruiz gases and magma and marine evaporites (14).
The volcanic pole is formed by samples P06 and Pll, whereas
P04 represents the evaporitic pole. The thermal water
samples appear to be partially enriched in F and Cl,
confirming the attack of strong acids (HC1 and HF), formed
through the absorption of magmatic gases, on the aquifer
matrix. The destruction of evaporitic layers follows a
selective evolution, thus enriching thermal waters in the
dissolved chlorides. However, agreement of Br:Cl and F:C1
ratios is not merely a coincidence. Other "markers"
dissolved in the waters, such as B and Li, plotted in
Nevado del Ruiz

V V
100 Br
Figure 8 Relative Cl, Br, F contents plot. The most striking

feature is the pronounced mixing line between magmatic
and evaporitic points.
181
figure 9 confirm the double origin of fluids. The most
striking feature of this plot is the pronounced mixing
line described by cold groundwater collected inside the
geothermal area and trending towards the Li pole. Similarly
B:C1 and SO4:C1 ratios suggest that acid waters are mixtures
in the depth of water from an acid-sulphate-chloride
reservoir, with various proportions of shallow groundwaters.
The principal source of sulphate and halogens may be done
by high-temperature deep gases interacting with the
sedimentary deposits that cover the reservoir.
CI/100
100
gases from Nevado
del Rui z
marine
evaporites
100 Li
Figure 9 Relative Cl, Li, B contents plot. The double origin

of fluids is confirmed. The diagram emphasizes the
mixing at various proportions of waters from an
acid-sulphate-chloride reservoir and a shallow
aquifer.
182
marine
evaporites
Nevado del Rui

magma
Paipa t h e r m a l
waters
Nevado del Ruiz

gases
50B
100
Figure 10 Relative Cl, B, SO* contents plot. The principal

source of suphate and halogens may be the high
temperature deep gases interacting with the
sedimentary deposits.
However the lack of any intermediate water suggests

the existence of two separate circulation systems: a deep
one, concerning water rock interaction and involving
sedimentary rocks of Cretaceous-Eocene age, and a shallow
one, where cold waters interact with volcanic rocks or
adsorb deep gases of steam vents.
4 Gases chemistry
The areal distribution of gas discharges shows the absence

of steam vents in the southern sector of the Paipa area
inside the Cuerpo Volcanico de Olitas. Moreover, a preliminary
analyses of gas chemistry (Tab.2) indicates that the
183
discharged gases are mainly formed by C02, followed by N2,
and show a rather constant chemical content. Because of the
comparatively high discharge temperatures, the relative
proportions of more soluble (H2S) to less soluble (H2, N2 and
CH4 ) gases in the free gas phase sampled are likely to be
similar to those found in the deep fluid, thus permitting
the evaluation of the equilibrium temperatures.
The O2+Ar content is normally lower than the error
affecting samples during collection. The contribution of
atmospheric gases seems fairly small and is strictly
controlled by hydrogeological conditions; in fact, in 1989,
collection took place after an heavy wet period and surface
cold waters significantly diluted deep fluids, as pointed out
by the high N2 content. However two major groups of gas
discharges may be distinguished (Fig.11). The samples
collected in the Rio Salitre sector indicate a high H2 and
saturated hydrocarbons content. The presence of H2 and CH4
observed in all discharges of this sector suggest a very
high temperature of interaction with deep matrix and a
relatively short residence time of the rising fluids at a
comparatively lower temperature. In addition, samples
collected in the northern sector show the presence of volatile
sulphur compounds. The H2S system is controlled by the redox
conditions during the upward movement of fluids; in this
case, a short residence time of gases in a likely oxydizing
environment near the surface and a short interaction of the
fluids with areated groundwaters is suggested. Moreover, He
contents are relatively higher than in the Rio Salitre sector,
indicating a longer residence time of fluids in the depth.
In other words, the reservoir cap must be more important and
show a lower permeability in Paipa than in the southern
sector, where the holocene aquifer, although probably having
a higher storage capacity, does not show a very significant
thickness.
Thus, the chemistry of the gases collected in the
geothermal district provides additional information about the
mineralogical matrix of the deep reservoir, about the
fracturation intensity of the upper system and the hydraulic
conductivity of the cap.
184
CO./100
100
Figure 11 CO 2/ N2, CH4 relative contents plot. Full and

empty circles indicate respectively gas samples
collected during 1987 and 1989. Two major groups of
gas discharges may be distinguished: samples collected
in Rio Salitre district (P06, P07 and P13 ) and in
Banos Termales (P01, P02, P03 ).
The spatial distribution of gases probably reflects the

relative proportions of magmatic gases interacting with the
shallow groundwater layer overlying the carapace. The small
amount of liquid stored in the Rio Salitre area only provides
a low buffer capacity with respect to chemical variation.
185
5 Isotopic composition of waters
5.1 Water molecule isotopes
The isotopic composition of water samples is given in

table 3 and the results for Deuterium and Oxygen-18 are
reported in figure 12. The best fit for sample data points
is a line described by the equation
62// = (1.44±0.20)6180-(S7.8±0.8)
intercepting Local Meteoric Line at 62 H = 74.0 and

18
& O = -10.5. Using the correlation linking 18O of local
precipitation to altitude, as reported by Torres et al.
(15), an "isotopic altitude of recharge" of 2700 m is
obtained. This altitude is in agreement with the mean
elevation of Cordillera Oriental in the Paipa district.
-40.
-60-— EXCHANGE WITH C02 (=50%)

e
-80- 5 D = ( 1.44 ± 0.20) 6180 - (57.78 1 0.7?)
^RECHARGE
-100.
-1 5 -10 —5
, 18_
0 0
Figure 12 Deuterium versus Oxygen-18. Sample P06 that does

not fall on the evaporation line as all the other
samples is interpreted as a continuous isotopic
exchange ( of about 50% ) between «O of local
precipitations and deep CO2.
186
The slight slope of the 6 2 H-6 18 o correlation line could
be explained by the isotopic enrichment for steam heating
and non-equilibrium evaporation of deep waters at a
temperature higher than 220°C. The waters have the same
hydrogeological origin, as indicated by the good correlation
coefficient (r? = 0.95). A similar conclusion could be
drawn from figure 13 where 5 L8 O is reported in relation to
chloride content :
Ô I8 O = 0.75[CZ"]- 1CT3- 10.1
Moreover, the upward movement of fluid is accompanied

by boiling and phase separation, and secondarly by mixing
with cold waters. Nevertheless the lack of observed steam
points in the district allows for neither quantification
of the steam production nor the measurement the isotopic
composition of the separated water phase. Considering the
water collected in P08 as very close to the end-member of
deep fluids, and assuming a cooling process as boiling and
-4
-6
-8
18
l -\ ~3
ô O= (0.75CI ) 10-10.1
-10
-12
-14
- -1
CI mg I
-16
2000 4000
Figure 13 Oxygen-18 versus chloride content.
187
multistage steam loss, the vapor isotopic composition should
be -15.2 for 618O and -82.5 for o2//. The liquid-vapor
separation strongly partitions dissolved salts, increasing
in our case to about 1.2 times the chloride concentration
in the Paipa thermal waters.
The cooling processes are recognizible in the central
sector of Paipa district, where mainly gaseous vents are
present, not only because of the major role on steam loss
played by Rio Salitre fault but also because of the
proximity to the hydrogeological recharge areas and thus
because of superficial groundwater movement absence.
Moreover, in the northern area the mixing with cold
groundwaters takes place.
However, sample P06 does not follow the scheme described
above. This sample was collected in a small pool in the
Rio Salitre sector. The pool is filled with surface waters
in relation to the meteorological and hydrogeological
cycles. Sample P06 could be interpreted either as a
continuos isotopic exchange between ISQ of summer
18
precipitations (6 0~-9%.) and CO2 or as Deuterium enrichment
of an hypothetical residual vapour phase in the whole
geothermal system.
The first hypothesis is in agreement with the C02
discharged in the pool; the gas volume is larger than that
of the water. Taking in account a mean isotopic composition
18
of O in C02 equal to -14 %. (16) and a f ractionation
factor of 42.5 %. valid for a temperature of 15 °C (mean
yearly temperature), it is correct to consider
precipitations isotopically depleted of 5.8 %. and exchanged
for 50%.
Due to the lack of vapour steam in the area, as

previously mentioned, it is not possible to take in account
the second hypothesis. Moreover, the Hydrogen exchange
kinetic seems faster than the required and, at the same
time, the reactional temperature needed (more than 300°)
is not in agreement with that evaluated in Paipa geothermal
district.
188
Tritium activity in thermal and cold waters is always
lower than in Bogota precipitations (15, 17) during the
same period. The Tritium low level indicates a non
significant component of present precipitation, defining in
this way a mean residence time higher than 50 years. Only
P06 shows a Tritium content close to that of actual
precipitations, confirming the hypothesis of an isotopic
exchange betweeen meteoric waters and C02 steam vents.
5.2 Isotopes in dissolved sulphates
In table 3 the isotopic composition of stable isotopes

in dissolved sulphates is reported. The 534S values of
thermal waters are consistent with a mixing between an
evaporitic mineral source and a deep sulphide; but M.C.
sample appears to be quite enriched in the heavy isotope
if the oxidation from a secondary sulphide is considered
(Fig. 14).
18
Cretaceous evaporites
14
,22
10 — O
O O 20
" is
MC
O
Figure 14 Sulphur-34 versus sulphate-chloride weight ratio.
189
In fact the isotopic composition of Sulphur with a
magmatic origin ranges between 0%. and + 2%. vs. C.D. (11,
12) and the 634s of Cretaceous evaporites, like those present
in the subvolcanic stratigraphy, ranges between +15%. and
+ 18%. vs. C.D. (17).
Dissolved sulphate formed by the oxidation of subsurface

sulphides preserves the original isotopic signal; in this
way the solid sulphide pole in the Paipa aquifer matrix
should have a 634s of about +8%. (M.C. sample). This
composition should be considered as a result of the
absorption of volatile Sulphur compounds inside carbon
levels of the Guadua formation, which forms the cap of
the geothermal reservoir.
In a 634s vs. 6 18 O diagram (Fig. 15) all representative

points of thermal waters fall on a straight line. Because
of its slope (about 1.5), this line could be considered
as a reduction line. It cannot be considered as a
+ 20
o
to + 15
22 • 6
+ 10
MC
+ 5
+• 5 +10 + 15
„18
Q/
0 O xoo
(so4)
Figure 15 Sulphur-34 versus Oxygen-18 of dissolved sulphates.
Star indicates isotopic composition of Cretaceous
evaporites. All thermal waters fall on a straight
line with a slope of about 1.5, that could be
considered as a reduction line. Samples at low
temperature (P04, P06, P22, M.C.) do not achieve
isotopic equilibrium during subsurface oxydation.
190
precipitation line of gypsum and anhydrite since the thermal
water always remains undersaturated with respect to these
minerals. Thus, this line is interpreted as a mixing line
where the end-members have to be identified in the
Cretaceous sulphates and the geothermal gases. During
subsurface oxydation, the isotopic equilibrium between
molecular Oxygen and water is not achieved for low
temperature samples. On the basis of classical equilibrium
equations (18, 19), the percentage of molecular Oxygen
ranges between 90 and 100%. Nevertheless it is possible
that the C02 Oxygen participates to the sulphide oxydation.
Sample M.C. indicates that the oxydation takes place
instantaneously at an environmental temperature and a low
pH. Under such conditions the equilibration time for
isotopic exchange reaction is a few hours.
The other water samples indicate reactional conditions
close to the equilibrium and a participation of water
Oxygen of more than 50%. In this way the reaction half-life
ranges between 50 ( P08 ) and 300 years ( P01 ). The time
herewith obtained is in agreement with water age calculated
by Tritium content, confirming once more that the aquifer
where all isotopic exchanges take place is confined and
has a low permeability.
Similar conclusions can be drawn from figure 16, where
the 180 content of dissolved sulphates is plotted versus
that of corresponding waters. The isotherms representing
the mean fractionation factors for isO exchange between
sulphate and water are determined according to Lloyd (18)
and Mizutani & Rafter (20) equations. The plot of thermal
waters indicates a close approach to equilibrium
temperatures, similar to those evaluated by the means of
water isotopic enrichment in Deuterium and Oxygen-18.
Moreover, cold waters oxidizing close to surface conditions
with molecular Oxygen indicate temperatures generally lower
than those measured at the discharges.
191
-5
Figure 16 Oxygen-18 in dissolved sulphates versus Oxygen-18

in corresponding waters. The isotherm are determinated
according to Lloyd (18) and Mizutani & Rafter (20)
equations.
6 A model for the Paipa hydrothermal system
The use of classical geothermometers Na-K (21), Na-K-Ca-Mg

(22) and CO (23) defines a reservoir temperature close to
200 °C (tab.4). As expected, the same geothermometers applied
to cold water indicate an equilibrium temperature similar to
the one measured at the discharge. Only TNK2 gives for cold
groundwaters of Cuerpo Volcanico (Pli), a temperature in
disagreement with the one measured, because of Na excess in
volcanic rocks.
tab. Reservoir temperatures defined by classical geothermometers

Sample TQA TNK TNKCM T C02 T CO T 18 0
P-01 100 200 240 - 250 170
P-02 95 210 245 - 230 -
P-03 95 205 240 105 240 130
P-04 40 200 140 - - 65
P-05 100 210 240 115
P-06 80 75 55 — — 10
P-08 90 190 265 - - 150
P-11 100 230 50 — - 50
P-13 80 175-200 -
P-18 95 200 220 - - 160
P-20 95 195 220 — — 150
P-22 55 200 60 55
Q.H. 50 300 40 -
M.C. - 210 40 45
192
Silica geothermometer, as previously shown, indicates a
lower temperature than the one obtained with the other
geothermometers. Thus, the Si02 content of thermal waters
does not reflect the fluid-rock equilibrium reached in the
reservoir and underevaluates dissolution temperature. By the
use of Triangular diagram (6), evaluation of analytical Na,
K, Mg contents allow the definition of deep equilibration
temperatures and the effects of water mixings (Fig.6).
The position of all data shows either a trend towards
the partial equilibrium or a complete immaturity. Only water
sample P08 reaches full equilibrium at a temperature of about
250 °C. Because of the faster rate of equilibration in the
system K-Mg with respect to K-Na, a difference of about 40°C
can be evaluated between conditions in the shallower levels
(K-Mg) and those in the depth (K-Na) for the Paipa thermal
waters. Gas geothermometers are affected by surface or
subsurface oxidation of H2S, CH4 and other non-absorbed gases.
Moreover, mixing with cold waters leads to an incorrect
evaluation of the last equilibrium temperature. Nevetheless
for sample P13 collected in a steam vent, temperatures
obtained with gas geothermometers must be compared with those
evaluated by dissolved geothermometers in the close area
(P08); in this sector of Paipa geothermal district, the deep
temperatures are always higher than 200°C as indicated by CO
geothermometer ( 23 ).
The water maturity index (6) is always above 2.0;
therefore it is correct to evaluate the CO2 fugacity in the
geothermal system using K, Mg, Ca relative contents. All
thermal waters are aligned and trend towards sample P08,
confirming once more, that it could be considered like, or
very close to, deep end-member (Fig.17).
For the Paipa geothermal system a fugacity of 100 bars
could be taken into account. Considering a water column in
equilibrium with such a pression in an open system, a depth
of about 1000 meters must be evaluated.
All thermal waters have a constant value of mole ratios
n CO2/n H20 for vapour phase (about 5 ), indicating homogeneous
conditions inside the system. Starting with equation 30 of
193
/° \
40 60 100 200 t(c)
KC
5 _ _ 100
-1 0 1 7 L (Km)
Figure 17 Evaluation of CO2 fugacities in Paipa area by using

K, Mg, Ca contents in discharge waters according to
Giggenbach equations ( 6 ).
Giggenbach ( 6), water fugacity of about 20 bars could be

obtained, indicating a reservoir temperature higher than
210°C.
Thermal waters are in equilibrium with minerals forming

the sedimentary cap (tab.5). Using the heat and mass balance
equation, the composition of waters before separation were
recalculated. In this case at a temperature of 220°C, waters
reach, or are close to, equilibrium with respect to
hydrothermal or metamorphic minerals.
The influence of deep uprising fluids is higher in Banos
Termales (northern sector) than in La Playa (southern sector),
as indicated by the presence of discharges at high
temperatures.
194
tab. 5 Saturation index with respect to some sedimentary and metamorphic minerals.
Sample Anhyd. Laum. Low Alb. Microcl. K Mica Analc. Calced. Prehn. Calc. Quartz
P-Q1 -0.59 -3.245 -1.161 -0.16 -3.167 -3.009 0.24 -8.421 -1.91 0.632
P-02 -0.618 -6.15 -2.69 -1.68 -7.08 -4.468 0.18 -11.5 -2.086 0.566
P-03 -0.51 - — — — - -0.02 — -1.439 0.298
P-04 -1.769 — - — - - -0.26 — -3.744 0.298
P-Û5 -1.073 -1.193 -0.58 0.26 -2.009 -2.044 0 -3.449 -1.272 0.313
P-06 -3.6 - — — — — 0.25 — -6.5 0.75
P-08 -1.391 -20.843 -9.741 -8.86 -24.318 -11.347 0.04 -30.027 -4.449 0.407
P-11 -3.199 - — — — - 0.43 — -2.34 0.916
P-18 -0.662 0.589 0.723 1.7 1.883 -1.07 0.19 -3.677 -1.579 0.579
P-20 -0.589 - - - - - -0.04 - -1.651 0.287
(Ji
Moreover, the southern sector, being closer to the aquifer
recharge area, is characterized by the presence of diffuse
steam vents for the local hydrostatic conditions and sediments
hydraulic conductivity. The low upward movement of gases, as
indicated by the low fracturation intensity of pelitic
formations and the depth of resevoirs as previously defined
could force the uprising gases, mainly the more reactive
ones, to equilibrate with the new thermal and geochemical
conditions.
This model is valid for the sectors where volcanic rocks
are covered by a significant thickness of sediments. When
volcanic rocks outcrop (Cuerpo Volcanico de Oolitas and Cuerpo
Volcanico Pan de Azucar) steaming grounds and thermal
discharges are completely absent.
The temperature difference between fully equilibrated
waters (P08 at 250°C) and partially equilibrated waters
(P01-P03 at 220°C) allows the evaluation of chemical and
isotopic composition of the deep end-member:
a2!! = -65.5; 6180 = -5.80; Cl- = 5720
The potential source for high chloride content may include

the dissolution of evaporites within the subvolcanic
stratigraphy, incorporated into fluids.
7 Conclusions
The above geothermal model was constructed for the Paipa

district assuming uniform permeability conditions of the
sedimentary cap; therefore, it is likely to indicate only
the potential distribution of fluids inside the system.
The actual model is governed by the scarce knowledge

about the local stratigraphy and the presence and rate of
faults and fissures. Because of these geological problems,
exploratory drilling in Paipa and La Playa sould be seriously
considered.
196
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CAMACHO, ZUPPI, G.M. (1990)
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(20) MIZUTANI, Y., RAFTER, T.A. (1969) Oxygen isotopic
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(24) BERTRAMI, R., CIONI, R., CORAZZA, E., D'AMORE, F.,
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199
ISOTOPIC COMPOSITION AND ORIGIN OF THERMAL AND
NON-THERMAL WATERS FROM THE MIRAVALLES
GEOTHERMAL FIELD, COSTA RICA
W.F. GIGGENBACH
Division of Chemistry,
Department of Scientific and Industrial Research,
Petone, New Zealand
R. CORRALES, L. VACA
Institute Costarricense de Electricidad,
San José, Costa Rica
Resumen-Abstract
COMPOSICION ISOTOPICA Y ORIGEN DE LAS AGUAS TERMALES Y NO TERMALES DEL YACI-

MIENTO GEOTERMICO DE MIRAVALLES, COSTA RICA.
Si se va del norte al sur a lo largo del yacimiento geotérmico de Hirava-

lles, en Costa Rica, se comprueba que los contenidos de deuterio y de oxige-
no 18 de las aguas en movimiento que représentai! sistemas freâticos locales,
o o
disminuyen un 25 /oo y un 3 /oo respectivamente a lo largo de uiia
distancia de solo 40 km. Las aguas fluviales con flujos de il 000 kg/s, que
transportan la mayor parte de las aguas de escorrentia de la zona, tienen com-
posiciones isotâpicas parecidas a las del agua freâtica del norte, lo que su-
giere que los vientos del norte hacen que la mayor parte de la precipitaciön
se produzca en la ladera norte de la cordillera. El contenido de deuterio de
los caudales de agua de pozo geotérmico y cloruro natural se corresponde con
el de las corrientes del norte, lo que indica que se produce un proceso de
realimentaciön a partir de las aguas freâticas del norte cuya cantidad es pré-
dominante. Las aguas termales con mayor contenido de cloruro se enriquecen
con oxigeno 18, lo que posiblemente se debe a que se produce un intercambio
isotôpico con la roca. Sin embargo, a la vista de los recientes hallazgos en
sistemas hidrotérmicos situados a lo largo de plaças con limites convergentes,
se considéra como mas probable que el enriquecimiento con oxigeno 18 se deba a
la mezcla del 15 al 20% con un agua "andesitica" cuyo contenido en deuterio es
o o
-20 /oo y +10 /oo en oxigeno 18. La absorciôn de esta agua andesi-
tica, que se desprende en forma de vapor de las masas profundas de magma en
proceso de enfriamiento y cristalizaciôn, conduce inicialmente a la formacion
de aguas âcidas cloruro-sulfatadas. La llegada de estas aguas a un pozo geo-
térmico tras el proceso de profundizaeion sugiere que la conversion de aguas
cloruro-sulfatadas inmaduras en aguas de cloruradas neutras maduras se produce
en nivelés comparât!vamente poco profundos.
201
ISOTOPIC COMPOSITION AND ORIGIN OF THERMAL AND NON-THERMAL WATERS FROM THE
MIRAVALLES GEOTHERMAL FIELD, COSTA RICA.
Progressing from the n o r t h e r n to the s o u t h e r n

extent of the M i r a v a l l e s G e o t h e r m a l F i e l d , Costa Rica, the
d e u t e r i u m and oxygen-18 contents of stream waters,
representing local groundvaters, decrease by 25°/oo and 3°/oo
r e s p e c t i v e l y over a distance of only 40 km. R i v e r waters with
flows >1000 kg/s, carrying most of the d r a i n a g e f r o m the area,
have isotopic c o m p o s i t i o n s close to those of n o r t h e r n ground-
water suggesting that most of the p r e c i p i t a t i o n , c a r r i e d by
n o r t h e r l y winds, falls to the n o r t h of the C o r d i l l e r a . The
d e u t e r i u m content of g e o t h e r m a l w e l l and n a t u r a l c h l o r i d e
water d i s c h a r g e s agrees w i t h that of northern streams,
p o i n t i n g t o recharge from t h e q u a n t i t a t i v e l y p r e d o m i n a t i n g ,
northern g r o u n d w a t e r . The h i g h e r c h l o r i d e t h e r m a l waters are
e n r i c h e d in oxygen-18 p o s s i b l y due to i s o t o p i c exchange w i t h
rock. In v i e w of recent f i n d i n g s on hydrothermal systems
located along convergent plate boundaries, however, the
e n r i c h m e n t in oxygen-18 is c o n s i d e r e d more l i k e l y to be due to
the a d m i x t u r e of 15 to 20% of an "andesitic" water w i t h a
d e u t e r i u m content of -20°/oo and oxygen-18 of +10°/o». A b s o r p t i o n
of this andesitic water, released as vapor from cooling and
c r y s t a l l i s i n g magma bodies at depth, leads i n i t i a l l y to the
formation of acid sulfate-chloride waters. Incursion of such
waters into a geothermal well a f t e r d e e p e n i n g suggests that
the conversion of immature sulfate-chloride to m a t u r e neutral
c h l o r i d e waters takes place at c o m p a r a t i v e l y shallow levels.
INTRODUCTION
The Miravallec Geothermal Field, Costa Rica, lies some 125 km

to the NE of the capital San José. Following an i n i t i a l
assessment in 19G3 by United Nations experts, more detailed
geochemical investigations into its potential for electric
power production began in 1975 (Gardner and Corrales, 1977).
These studies suggested that a suitable geothermal reservoir
with temperatures of around 240°C underlies the study area.
Three wells were d r i l l e d from 1979 to 1980, all proving
productive. Until 1990 a further five wells were completed
202
comprising a total electric power production potential of
about 40 MW e .
The present investigation was carried out within the framework

of the IAEA Coordinated Research Program on the Application of
Isotopic and Chemical Techniques to Geothermal Exploration in
Latin America. Most of the stream and river samples were
collected by S Arnorsson and R Corrales during a mission of
the former in September 1985. The isotopic analyses of the
waters were carried out at the IAEA laboratories in Vienna,
the geochemical data for thermal waters used here are those
reported by Giggenbach and Corrales (1993).
The major aim of this study was the application of isotopic

techniques to obtain information on possible source components
making up the thermal discharges and on the d i s t r i b u t i o n and
movement of the waters within the Miravalles geothermal
system.
THE ISOTOPIC COMPOSITION OF THERMAL AND NON-THERMAL WATERS
The isotopic composition of samples of thermal and non-thermal

waters collected from the Miravalles Geothermal Field are
given in Table 1. For non-thermal waters estimated flow rates
are shown, they are uêd to distinguish rivers (R), w i t h flows
fclOOO kg/s, from streams (Q). For thermal waters, discharge
temperatures, in °C, and c h l o r i d e contents, in mg/kg, are
g i v e n . On the basis of a n a l y t i c a l data reported by Giggenbach
and Corrales (1991), thermal waters are also classified in
terms of their major anion into chloride (c), bicarbonate (b)
and sulfate (s) waters. The well discharge compositions are
weighted means of separated water and steam samples and,
therefore, represent total discharge compositions. They also
represent averages of the compositions reported by Giggenbach
and Corrales (1991). The samples are arranged with regard to
their geographic distribution from north to south, sample
locations are shown in Fig. 1.
203
TABLE 1
The isotopic composition of river (R), stream (Q), thermal

spring and geothermal well (P) discharges over the Miravalles
Geothermal Field, from north to south, together with estimated
flows, in kg/s and temperatures and chloride contents, In
mg/kg, for thermal waters. Thermal waters are classified in
terms of their major anion: c- chloride, b- bicarbonate, s-
sulfate.
temp . flow 02H a18o Cl

Location ( °C ) type ( °/oo ) ("/o«) (mg/kg)
R Guacalito 10000 -26 .5 -4. 74 -

R La Chepa 3000 - -4. 89 -
R San Isidro 1000 -26 . 3 -4 .92 -
R Los Angeles 6000 -25 .0 -4. 88 -
R Las Huacas - 1500 -27 . 7 -4 .70 -
Q Frijoles 50 -27 .2 -4 .90 -
Q Los Chiles 10 -26 .5 -4 .84 -
R Higueron 2000 -28 .5 -4. 98 -
QC Q de la Chepa 20 b -27 .9 -5. 04 3
Q Raudales 500 -30 .3 -5. 35 -
LT La Torre 32 s -29 .9 -5. 20 12
LQ Los Quesos 18 b -40 .6 -6. 52 4
Q Stream N of GB 150 -35 .5 -5. 86 -
GB Guayabal, pool 70 s -24 . 5 -4. 43 660
R Guayabal, river s -38 .1 -6. 44 7
Q El Carmen 80 -37 .6 -6. 30 -
36 PH-36, well 140m 67 s -24 .0 -4. 52 701
Q Herrumbre 350 -37 .9 -6. 08 -
QG Gaveteros, stream 20 s -38 .1 -6. 50 4
34 PH-34, well 280m 115 b -34 .9 -5. 10 9
R Guayabo River - -34 .1 -5. 48 -
Pl PMG-1 245 c -28 .9 -3. 48 2570
P2 deep PMG-2 220 c -29 . 1 -2 .86 3090
P5 wells PMG-5 240 c -34 .8 — T 89 2370
P10 PMG-10 2 c -29 .0 -3. 00 2830
Pll PMG-11 2 c -31 . 3 -3. 23 2630
EG El Gomes 37 b -38 .0 -6. 40 52

Q La Fortuna 70 -45 .9 -7. 08 -
Q Peje 300 -40 .7 -6 .72 -
R Cuipi lapa 3000 -30 .2 -5. 42 -
Q Las Palmas 30 -49 .2 -7. 52 -
Q Arena 10 -41 .7 -6. 68 -
Q Blanco 50 -38 .2 _ ^
96 -
BN Benaçon 50 b -48 .9 -7. 46 8
BB S Bernardo Arriba 46 b -48 .8 -7. 12 155
SB Salitral Bagaces 72 c -34 .9 -3. 92 2560
BJ S Bernardo Abajo 50 b -48 .3 -7. 43 112
Q Estanque 10 -52 .9 -7 .51 -
RO Rio Blanco 45 b -50 .8 -7 .59 81
PP Punto de Palo 25 s -44 .0 -6. 68 37
Q Rio Bagaces 60 -53 .7 -7 .53 - -
Q Villa Vieja 70 -52 .2 -7. 22 -
R Rio Tenor io 30000 -39 .2 -5. 76 -
204
rvers
streams
Chloride waters
bicarbonate w.
sulfate waters
Fig. l- Sketch map of Miravalles Geothermal Field showing

sample locations for thermal and non-thermal waters
The isotopic compositions of the waters listed in Table 1 are

plotted in Fig.2. Both river and stream samples follow a trend
close to that indicated by the global meteoric water line, but
somewhat shifted to higher deuterium, or lower oxygen-18,
values suggesting that the formation of groundwaters over this
area may be governed by a "local meteoric water line" with a
somewhat steeper slope of 9. Most of the thermal waters, with
the clear exception of the chloride waters, follow a similar
trend suggesting that they are largely derived from local
groundwaters.
205
62H
Woo)
-30-
-40
-50
-7 -6 -4 6'80(%o) -3
Fig. 2- Plot of <3 2 H versus 0 •*•8 0 for thermal and non-thermal

water discharges over the M i r a v a l l e s Geothermal Field
For symbols see Fig. 1 and Table 1.
Comparison of the isotopic composition of all these waters

with their geographic position shows that there is a
pronounced decrease in heavier isotopes on going from north to
south, a trend most clearly reflected in the composition of
streams. Rivers can be assumed to represent the weighted- mean
of groundwaters over a much larger catchment area (Fritz,
1981). The compositions of river waters, close to those of
northern groundwaters, suggest that they are recharged largely
from the northern part of the M i r a v a l l e s area and that most of
the r e g i o n a l p r e c i p i t a t i o n falls over the northern, "Atlantic"
parts of the study area, carried there by predominantly
northerly winds (Vialc et al., 1986).
The chloride waters, as discharged from deep wells and at

Salitral Bagaces (SB), are "shifted" to higher oxygen-18
contents. The shift of thermal waters to higher oxygen-18
contents is generally ascribed to isotopic exchange of the
thermal waters w i t h rock d u r i n g t h e i r r i s e to the surface
206
(Craig, 1963). Accepting this process to be active at
Miravalles, the deuterium content of the most shifted water
(P2) would point to recharge from northern groundwaters. The
pattern exhibited by individual wells and the discharge from
Salitral Bagaces points to subsequent m i x i n g of a deep parent
water with southern groundwater.
The waters most enriched in deuterium of the area are

represented by the acid sulfate-chloride waters discharged
from a spring at Guayabal (GB) and a nearby shallow well PH-36
(36). None of the groundwaters is isotopically heavy enough to
qualify as the recharge water suggesting these waters contain
an as yet undefined component even more enriched even more
1 Q
enriched in deuterium. A slight " 0-shift" is also indicated
for the other shallow well PH-34 (34). The water discharged
there, however, is a very d i l u t e bicarbonate water.
The large variability in the isotopic composition of

groundwaters renders the Miravalles area especially suitable
to investigate recharge processes and the origin of possible
source components of the geothermal discharges. In order to be
able to establish the isotopi<~ identity of the various groups
of waters more clearly, variations in deuterium and oxygen-18
contents as a function of geographical position are
investigated in more detail.
ISOTOPIC COMPOSITIONS AS A FUNCTION OF GEOGRAPHIC POSITION
Variations in deuterium contents of waters discharged over the

Miravalles Geothermal Field are shown in Fig. 3. For the non-
thermal waters, two groups are distinguished: r i v e r c w i t h
estimated flows fclOOO kg/s, and streams with lower flow rates.
This distinction allows probable differences in the size of
the respective catchment areas to be taken into account. Small
streams are more likely to represent local groundwaters while
the waters of rivers usually contain contributions from much
more distant groundwaters. Generally river waters are
isotopically depleted as compared to smaller tributaries
because of the presence or predominance of isotopically
207
-50-
(km) 30
Fig. 3- Deuterium contents of waters discharged over the

Miravalles Geothermal Field from north to south.
Reference point for distances is summit of Miravalles
volcano. For symbols see F i g . 1 and Table 1.
depleted, higher altitude p r e c i p i t a t i o n (Fritz, 1981;

Giggenbach et al., 1983).
Over the Miravalles area the pattern is reversed, river waters

being isotopically considerably enriched as compared to most
of the streams. Also, in contrast to the generally observed
depletion in heavier isotopes of groundwaters with increasing
a l t i t u d e , waters of the Miravalles area become isotopically
enriched on moving north from the coast u p h i l l to the
Cordillera. The most likely explanation for such behavior is
based on the assumption that the isotopic composition of these
groundwaters is governed by a "continental" effect rather than
an "altitude" effect (Eriksson, 1983). In this case
atmospheric moisture moving predominantly from north to south
(Viale et al., 1986) would lose its heavier isotopes on
approaching the Cordillera leaving isotopically more and more
depleted moisture to fall on the areas to the south.
208
Both stream and river waters follow distinct trend lines, the
deuterium content of the streams together with that of most of
the bicarbonate springs decreasing much more rapidly on going
from north to south than the river samples. The close
correspondence in the composition of streams and bicarbonate
springs suggests that the latter are essentially derived from
infiltrating local groundwater. The preservation of high
d e u t e r i u m contents in river waters collected far to the south
of the C o r d i l l e r a , e.g. Rio Tenorio, indicates that the
composition of river waters all over the study area is d o m i -
nated by groundwaters forming over the northern parts of the
Miravalles area, from essentially "Atlantic" p r e c i p i t a t i o n .
The chloride waters have deuterium contents corresponding to

those of the northern groundwaters. In the case of Salitral
Bagaces, the waters would have travelled a horizontal distance
of some 25 km without losing their isotopic i d e n t i t y . Such
long horirontal travel paths for thermal waters are not very
common, but have been identified isotopically e.g. for the El
Tatio geothermal system in Chile (Giggenbach, 1978). As
a;ready pointed out, the deuterium content of the acid
sulfate-chloride waters from the Guayabal area (GB and 36) are
higher than those of any other thermal or non-thermal water.
The only water likely to be affected by an isotopic "altitude"
effect is that discharged at Los Quesos (LQ). Its comparative
isotopic depletion is probably due to admixture of higher
altitude precipitation falling on the h i g h e r slopes of
Miravalles volcano.
The overall pattern is repeated with the oxygen-18 contents as

shown in Fig. 4, except that chloride waters are much more
enriched than any of the other waters. Again, the two acid
sulfate-chloride waters (GB and 34) are isotopically heavier
than any of the potential recharge waters. Further insight
into the relative importance of the various source components
making up the thermal waters may be obtained by taking into
account variations in one of the chemical components of the
1p
waters, e.g. by comparing 0 and Cl contents of the thermal
waters, as done in Fig.5.
209
6180
-4-
("/oc )
Y
-5-
-6-
-7-
N
1O 0 10 2O (km)
Fig. 4 - Oxygen-18 c o n t e n t o f w a t e r s d i s c h a r g e d over t h e
Miravalles Geothermal Field from north to south.
0 1000 2000 300O CI (mg/kg)

Fig. 5 - P l o t o f oxygen-18 v e r s u s c h l o r i d e c o n t e n t f o r t h e r m a l
waters f r o m the Miravalles Geothermal Field.
210
The correlation between chloride and oxygen-18 contents can be
fully explained in terms of intermixture of three endmember
1 P n
components: northern groundwater with 0 of -4.8 /oo.
southern groundwater with 180 of -7.5°/oo/ both low in
chloride, and a deep, high chloride, "parent" water with 3300
mg/kg of Cl and a 180-content of -2.5°/oo All the stream, river
and bicarbonate waters can be assumed to be derived from
groundwaters present over the M i r a v a l l e s area. Geothermal well
and the Salitral Bagaces discharges are likely to o r i g i n a t e
from a common parent water and to be diluted to varying
degrees by southern precipation.
The position of the data points for the two acid sulfate-
chloride waters from the Guayabal area would also agree with
derivation from this common deep Cl water, but through
d i l u t i o n w i t h northern p r e c i p i t a t i o n . Because of the large
d i f f e r e n c e in the degree of m a t u r a t i o n (Giggenbach, 1988)
between the Guayabal and deep well waters, however, it appears
unlikely that they are derived from the same deep source
components or have been generated under similar conditions.
The Guayabal waters are likely to have formed at much
shallower levels. The simple pattern of Fig. 5, corresponding
to dilution of a common deep chloride component to form both
the well and Guayabal waters, is likely to be only be
accidental .
SOURCE COMPONENTS OF THERMAL WATERS
Based on an allegedly generally observed close correspondence

in the deuterium contents of thermal waters and local
groundwater, Craig (1963) concluded that geothermal waters
have a predominantly local meteoric origin, with contributions
from any common "magmatic" component being too small to be
detected. The frequently observed enrichment in oxygen-18 for
higher temperature waters was ascribed to an 1 R 0-shift caused
by isotopic exchange between the waters and rock generally
enriched in oxygen-18.
By use of a large set of isotopic data for a wide range of

geothermal systems along convergent plate boundaries
211
(Giggenbach, unpublished results), however, it becomes
apparent that deuterium contents of thermal and local
groundwaters generally do not agree. Deuterium contents of
most higher temperature geothermal discharges appear to be
affected by an a d d i t i o n a l , d i s t i n c t shift to heavier values,
the m a g n i t u d e of this apparent "deuterium shift" increasing
w i t h decreasing d e u t e r i u m content of the local groundwater.
By p l o t t i n g the isotopic compositions of pairs of geothermal

and local groundwaters for a number of such "andesitic"
systems, Giggenbach (1991) concluded that much of the
-i P o
d e v i a t i o n s in both 0 and ^H of thermal waters from those of
local groundwater may as well be explained in terms of mixing
between local groundwater and a quite well defined, common
endmember water with a deuterium content close to -20°/oo and an
oxygen-18 content of + 10°/oo.
The isotopic composition of this water coincides with that of

a large number of fumarolic condensâtes from andesitic
volcanoes e.g. in Kamchatka (Taran et al., 1989) and Japan
(Sakai and Matsubaya, 1977) and many other such centers. At
present the origin of this "andesitic" water is still quite
uncertain, but is likely to represent modified seawater,
subducted together with marine sediments (Taran et al., 1989).
"Magmalic" waters from other tectonic environments, such as
hot spots and r i f t s and r i d g e s along d i v e r g e n t plate
b o u n d a r i e s , may well be q u i t e different and similar to that of
the frequently invoked "juvenile" water w i t h a H content of
about -SO 0 /oc
A c c e p t i n g a d m i x t u r e of "andesitic" water to be the m a i n cause

of isotopic enrichment of the M i r a v a l l e s Cl waters, p o s s i b l e
rel a t i o n s h i p s among the v a r i o u s source components may be
discussed by use of F i g . 6. Both the acid s u l f a t e - c h l o r i d e
waters i s s u i n g at Guayabal and the neutral c h l o r i d e vaters
discharged from the wells are assumed to have formed through
absorption of "andesitic" vapors into the northern
groundwater, quantitatively predominating over the Miravalles
area. In the case of neutral chloride waters, this process is
thought to lead to the formation of an i n i t i a l l y acid parent
212
water with a <32H of -25° /ooand 0180 of -2.0 °/oo. Subsequent
water-rock interaction and dilution with now southern
groundwater gives rise to the formation of the range of
neutral chloride waters as encountered in the wells.
The very fact that no a d d i t i o n a l oxygen-18 shift is rbserved

for the Salitral Bagaces waters, even rafter having travelled
for another 10 to 15 km, suggests that isotopic exchange with
rock, under "geothermal" conditions, may be a process
affecting the isotopic composition of thermal waters only
little.
The presence of comparatively immature waters within the

Miravalles geothermal system is indicated by the incursion of
an acid sulfate water into well PGM-2 after deepening from
1200 m to 2000 m in 1984 (Giggenbach and Corrales, 1992). The
similarly acid, high sulfate waters of Guayabal, however, are
more likely to have formed at more shallow levels, through
absorption of volcanic gases higher up within the Miravalles
volcanic system.
F i g . f> contains contour l i n e s corresponding to the fraction x a

of andesitic vapor absorbed to form a geothermal discharge, if
the above model is correct. Values of x a may also be obtained
from
*a = '"g - <V/(fla ~ <V
Where the subscripts a, g and m refer to the respective

andesitic, geothermal and meteoric waters. Inserting values of
-2 %o for <5180g/ -4.8°/oo for <3180m and +10°/oo for fl 1 ?> a/
the fraction of andesitic vapor contributing to the formation
of the hypothetical geothermal parent water becomes 0.39 or
19%. Subsequent d i l u t i o n by southern groundwaters reduces this
proportion to about 15%.
For the Guayabal waters a value of xa of 2.5% is obtained.

Their S/Cl mol-ratio of 1.5 is close to that of many volcanic
vapor discharges (Giggenbach et al., 1990) suggesting that
both Cl and SO^ in these waters are derived through direct
absorption of volcanic vapors rising within the system.
213
-6CH
18,
-5 &'öO(°/oo) 10
Fig. 6- Plot of ö H versus 00 illustrating possible

formation of Miravalles thermal waters through
absorption of "andesitic" vapors into groundwater.
Contours x a correspond to fraction of andesitic vapor
absorbed.
Assuming all the Cl present in the well discharges, 3000

mg/kg, to have been introduced with the magmatic vapor, its Cl
content would have to be about 20 000 mg/kg or 2°* b.w.. This
value is somewhat above the range of 0.4 to 1.8% b.w. usually
observed for HC1 contents in high temperature vapor discharges
from active volcanoes (Giggenbach et al., 1990), but of the
same order. While not providing conclusive proof as to the
cause of the "oxygen-18" shift observed for the Miravalles
chloride waters, the above findings may s t i l l be used to
derive a hydrological model of the Miravalles geothermal
system compatible with geochemical evidence.
GEOCHEMICAL MODEL OF MIRAVALLES GEOTHERMAL SYSTEM
A geochemical model describing the origin and distribution of

the various fluid components w i t h i n the Miravalles geothermal
system, compatible w i t h the isotopic composition of the water
discharges, is shown in Fig. 7. The procedures used in its
construction follow closely those described for the Nevado del
214
bicarbonate w
chloride waters
sulfate-chloride w
cooling magma
N
(km)
0 10 15 (km)
Fig. 7- Cross-section through Miravalles geothermal system

along line N - S of Fig. 1 showing distribution of
fluids compatible with geochemical evidence. Upper
numbers in boxes are deuterium ratios, lower numbers
oxygen-18 values of respective waters.
R u i z volcanic-magmatic-hydrothermal system (Giggenbach et al.,

1990). P e r m e a b i l i t i e s dre assumed to be isotropir and u n i f o r m ,
the model, therefore, describes only the potential
distribution of the fluids underground. Actual fluid movement
is governed by the generally unknown distribution of faults,
fissures and permeable strata.
The overall direction of fluid movement is assumed to be

dominated by the influx of the quantitatively most important
groundwater component, that forming from precipitation falling
to the north of the Cordillera. Vapors released from cooling
and crystallising bodies of magma at depth are absorbed into
this deeply percolating groundwater forming initially quite
acid, sulfate rich waters. Ongoing water-rock interaction
leads to the gradual conversion of these early primitive
waters to neutral chloride waters (Giggenbach, 1988). Because
of the general direction of groundwater flow from north to
south, the halo of neutral chloride waters is
likely to be deflected to the south where it mixes to varying
degrees with minor proportions of groundwater there.
215
Over the northern, "upstream" parts of the rising thermal
plume, and w i t h i n the Miravalles volcanic structure, residence
times of the fluids are probably too short to permit
conversion of the acid sulfate-chloride to neutral chloride
waters and they are able to reach the surface at Guayabal
(GB). Interaction of these immature waters with rock at
shallow levels, especially after dilution, may give rise to
quite neutral bicarbonate-sulfate waters as discharged e.g. at
Los Quesos 'LQ), El Gomes (EG) and from well PH-34 (34).
The tongue of neutral c h l o r i d e waters is obviously able to

travel underground for a distance of some 10 km m a i n t a i n i n g
its i s o t o p i c and c h e m i c a l i d e n t i t y . M a r g i n a l layers of this
water, still containing dissolved CC>2, interact f u r t h e r with
rock l e a d i n g to the f o r m a t i o n of the b i c a r b o n a t e - c h l o r i d e
waters as discharged, again in d i l u t e d form, from springs at
San Bernardo (BB, BJ) and Rio Blanco (RO). The appearance of
acid sulfate-chlor i de waters in the easternmost w e l l PGM-2,
a f t e r d e e p e n i n g from 1200 to 2000 m in 1984, suggests that
immature water reach shallow levels over t h i s part of the
field.
On the basis of the above model, the optimum siting of wells

will have to take into account several conflicting tendencies:
d r i l l i n g close to the center of thermal upflow enhances the
l i k e l i h o o d of encountering higher temperatures, but also that
of incursion of acid waters. Drilling farther "downstream"
reduces the risk of a c i d i f i c a t i o n but also lowers discharge
enthalpies or temperatures and with them increases the risk of
calcite deposition (Vaca et al., 1989).
ACKNOWLEDGMENTS
The present i n v e s t i g a t i o n was carried out w i t h i n the framework

of the IAEA Coordinated Research Program on the "Application
of Isotopic and Chemical Techniques to Geothermal Exploration
in Latin America" (COS/8/002) with financial support from the
Government of Italy.
216
REFERENCES
Craig H, 1963: The isotopic geochemistry of water and carbon

in geothermal areas. In Nuclear Geology on Geothermal
Areas, CNR Pisa, 17-53.
Eriksson E, 1983: Stable isotopes and t r i t i u m in p r e c i p i -

tation. In Guidebook on Nuclear Techniques in Hydrology.
IAEA Techn. Report 91: 19-33.
Fritz P, 1981: River waters. In Stable Isotope Hydrology -

Deuterium and Oxygen-18 in the Water Cycle. IAEA Techn.
Report 210: 177-201.
Gardner M C and R Corrales S, 1977: Geochemical investigations

of the Guanacaste Geothermal Project, Costa Rica.
Geothermal Resources Council, Trans., 1: 101-102.
Giggenbach W F, 1978: The isotopic composition of waters from

the El Tatio geothermal field, Northern Chile. Geochim.
Cosmochim. Acta: 42, 979-988.
Giggenbach W F, 1988: Geothermal solute equilibria. Derivation

of Na-K-Mg-Ca geoindicators. Geochim. Cosmochim. Acta,
52: 2749-2765.
Giggenbach W F, 1991: What is the real cause of the oxygen-18

shift of waters from geothermal areas along convergent
plate boundaries? Geotherm. Resources Council, Trans.,
Reno .
Giggenbach W F, Gonfiantini R, Jangi B L and Truesdell A H,

1983: Isotopic and chemical composition of Parbati Valley
geothermal discharges, North-West Himalaya, India.
Geothermics, 12: 199-222.
217
Giggenbach W F, N Garcia P, A Londono C, L R o d r i g u e z V, N
Rojas G and M L Calvache V, 1990: The chemistry of
f u m a r o l i c vapor and thermal-spring discharges from the
Nevado del Ruiz volcanic-magmatic-hydrotherma1 system,
Colombia. J Volcanol. Geotherm. Res., 42: 13-39.
Giggenbach W F and R Corrales S, 1991: The i s o t o p i c and

chemical composition of water and steam discharges from
volcanic-magmatic-hydrotherma1 systems of the Guanacaste
Geothermal Province, Costa R i c a . Appl. Geochem., (in
press ) .
Sakai H and Matsubaya 0, 1977: Stable isotopic studies of

Japanese geothermal systems. Geothermics, 5: 97-124.
Taran Y A, Pokrovsky B G and Esikov A D, 1989: Deuterium and

oxygen-18 in fumarolic steam and amphiboles from some
Kamtchatka volcanoes, "andesitic" waters. Dokl. Akad.
Nauk. USSR, 304: 440-443.
Vaca L, Alvarado A and Corrales R, 1989: Calcite deposition at

M i r a v a l l e s Geothermal Field, Costa Rica. Geothermics, 18:
305-312.
Viale P, Corrales R, M a n i e r i A, Mayra C and Vaca L, 1986:

Mineral alteration and fluid characteristics of
Miravalles Geothermal Field - Costa Rica. Extended
Abstr . , Fifth Int. Symp. Water-Rock Interaction,
Reykjavik, Iceland, p. 667-670.
218
MODELO GEOTÉRMICO PRELIMINAR DE ÁREAS VOLCÁNICAS
DEL ECUADOR, A PARTIR DE ESTUDIOS QUÍMICOS E
ISOTÓPICOS DE MANIFESTACIONES TERMALES
E. ALMEIDA, G. S ANDO VAL

Instituto Ecuatoriano de Electrificación,
Quito, Ecuador
C. PANICHI, P. NOTO, L. BELLUCCI
Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Resumen-Abstract
MODELO GEOTÉRMICO PRELIMINAR DE ÁREAS VOLCÁNICAS DEL ECUADOR, A PARTIR DE

ESTUDIOS QUÍMICOS E ISOTÓPICOS DE MANIFESTACIONES TERMALES.
fi partir de 1986 se mostrearon y anaii:aron las aguas y gases de ocho áreas geotéraicas, para establecer
su composición quiíica e isotópica, En Chachisbiro y Cuicocha, se observan enriqueciaientos de hasta el 5X.
en {) y SOS, en Beuteno. La evaporación de una hipotética agua geotersica profunda, desde 2WC hasta la
teaperatura en superfice, puede ser responsable de las variaciones isotópicas observadas en Chachisbiro,
Por otra parte, en Cuicocha, un proceso de sezcla entre agua subterránea caliente y agua fresca de una
laguna es responsable de los valores observados. En otras áreas, la coiposicién isotópica de las aguas
térsales corresponde escencialsente a aguas aeteóncas que caen a diferentes altitudes, desde 2500 nasta
4200 a sobre el nivel del sar. Las relaciones Na/K indican teiperaturas del reservono de aproxiaadasente
EW, 210 y EOfl'C, para aguas cloruradas que eiergen en las áreas geoterncas de Chacbíibiro, Cuenca y
p
apaliacta respectivasente. En la caldera de Chalupas, los datos no peralten hacer ninguna hipótesis
razonable sobre la existencia de jn acdfero profundo de alta teiperatura. Muestras procedentes del -olean
Tungurahua son de aguas sulfatadas-acidas, que tienen una coiposicién isotópica concordante con aguas
calentadas por gases a teiperaturas de 200'C aproxisadanente. En el área de Chiiborazo, la reducida
cantidad de suestras disponibles no peralten dar ninguna inforaación acerca de sus características
térsales. En Tufií5o, las aguas provienen de aculferos superficiales aodificados por gases calientes, cuyos
geotersfisetros dan teaperaturas de SSO'C.
PRELIMINARY GEOTHERMAL MODEL OF VOLCANIC ÁREAS IN ECUADOR BASED ON CHEMICAL

AND ISOTOPIC INVESTIGATION OF THERMAL INDICATORS.
Since 1986, the waters and gases of eight geothermal áreas have been
sampled and analysed to establish their chemical and isotopic composition. In
Chachimbiro and Cuicocha ^0 enrichment up to 5% and deuterium enrichment up
to 20% have been observed. The isotopic variations seen in Chachimbiro could
be explained by hypothetical deep geothermal water with a temperature range
from 240°C to surface temperature. The valúes observed in Cuicocha, on the
other hand, are due to mixing of hot groundwater with fresh lagoon water. In
other áreas, the isotopic composition of the thermal waters basically
corresponds to that of meteoric water falling from various altitudes ranging
from 2500 to 4200 m above sea level. The Na/K ratios indicate reservoir
temperatures for the chloride waters emerging in the Chachimbiro, Cuenca and
Papaliacta geothermal áreas of approximately 240°C, 210QC and 200°C,
respectively. From the data on the Chalupas caldera it is impossible to
construct any reasonable theory regarding the presence of a deep,
high-temperature aquifer. Tungurahua volcano samples consist of sulphuric
219
acid water with an isotopic composition similar to waters evaporating at about
200°C. The number of samples from the Chimborazo área was too low to justify
any assumptions about the thermal characteristics of the water. The waters in
Tufiño origínate in surface aquifers modified by hot gases registering 230°C
on the geothermometers.
1 INTRODUCCIÓN
En el marco del Programa de Exploración de los Recursos Geotérmicos de la

República del Ecuador, ejecutado por INECEL, se han efectuado estudios
geocientificos exploratorios en las áreas de Tufiflo, Chachimbiro, Cuicocha,
Papallacta, Chalupas, Tungurahua, Chimborazo y Cuenca, a fin de determinar
las posibilidades de utilización del recurso geotérmico en la generación
eléctrica. Parte importante de estos estudios, constituyen las
investigaciones geoquímicas e isotópicas llevadas a cabo con el apoyo de la
Organización Internacional de Energía Atómica (OIEA), a través del Contrato
de Investigación 3991/IG, suscrito con INECEL. Los resultados finales de
estas investigaciones se resumen en este documento.
2 SITUACIÓN GEOLÓGICA REGIONAL
El margen continental activo del Ecuador es caracterizado por la subducción

de la placa Nazca, que transporta a la Cordillera de Carnegie creada por el
paso de la Nazca sobre el punto caliente Galápagos. La subducción de Nazca
y Carnegie es muy importante en la evolución de la Cordillera de los Andes,
particularmente de su volcanismo. El Ecuador continental se divide en tres
regiones: Llanura costanera (Costa), Cordillera de los Andes (Sierra) y
Cuenca superior amazónica (Oriente).
La Costa esta1 formada por la parte emergida de un prisma acrecionado,

constituido por basaltos tolelticos cretácicos que representan corteza
oceánica C13 y sedimentos volcanoclásticos que yacen bajo sedimentos
pertenecientes a cuencas terciarias y cuaternarias (Figura 1).
La Sierra tiene en su mitad septentrional dos cordilleras paralelas, la

Occidental y la Real, separadas por un valle angosto conocido como
Depresión Interandina. La mitad meridional, es una cordillera de menor
altura y sin un valle central. La Occidental es formada por rocas
volcánicas básicas e intermedias de edad cretácica, emplazadas en un
ambiente submarino (arco volcánico oceánico), y cubiertas de sedimentos
pelágicos. La Real es un cinturón metamórfico barrowiano, cuyos protolitos
son sedimentos de plataforma y pendiente continental metamórfizados en el
Cretácico y Terciario inferior CE],
El Oriente forma parte de la cuenca amazónica; tiene un basamento

precámbrico sobre el cual se encuentran potentes depósitos sedimentarios
marinos de plataforma continental, sedimentos lacustres y detríticos
continentales.
los terrenos volcánicos continentales se extienden a lo largo de la Sierra,

con un ancho promedio de 80 km. La actividad terciaria fue importante en
toda la cordillera, en tanto que la cuaternaria esta' restringida a la
mitad septentrional, donde se localizan casi todas las áreas geotérmicas
estudiadas (Figura 1).
220
80° 79° 78°
SIMBOL06IA
CUENCA SEDIMENTARIA CUATER-

NARIA DE LA COSTA
VOLCÁNICO CUATERNARIO Y
TERCIARIO DE LOS ANDES
BASAMENTO TOLEITICO; SEDI-

MENTOS MESOZOICOS Y TER-
CIARIOS DE LA COSTA
ARCO VOLCÁNICO MESOZOICO DE
JJ LOS ANDES
CUENCA AMAZÓNICA .MESOZOI-

CO HASTA CUATERNARIO
BASAMENTO METAMORFICO W-
LEOZCHCO DE LOS ANDES
O ÁREA GEOTÉRMICA
FIGURA I. ESQUEMA GEOLÓGICO DEL ECUADOR
El volcanismo durante el Cuaternario es muy importante; han sido

identificados aproximadamente EOO centros de emisión C33 y muchos de ellos
presentan una evolución magmática muy desarrollada. Los volcanes más
voluminosos y activos se caracterizan por una compleja alternancia de lavas
básicas e intermedias, domos ácidos y productos piroclástícos de
composiciones dacíticas y riollticas. El volcanismo en la parte meridional
de la Sierra es fundamentalmente terciario C4-, 53 y ha sido poco estudiado.
3 ASPECTOS QUÍMICOS E ISOTÓPICOS
3.1 TUFINO
Se encuentra en la frontera entre Ecuador y Colombia; los volcanes Chiles y

Cerro Negro se sitúan en su interior. La cámara magmática que alimento' a
este complejo volcánico constituye la fuente de calor [6, 73 del sistema
geotérmico estudiado.
La mayoría de las aguas analizadas tienen temperaturas comprendidas entre

los 32 y 5E°C, su composición química e isotópica esta1 resumida en la
Tabla I. El 75% de las muestras son bicarbonáticas; el 12,57. son sulfatadas
y corresponden a los manantiales más salinos y calientes, representando la
interacción de aguas superficiales con gases volcánicos CB3. Las restantes
muestras son cloruradas y magnésicas, que se ubican a varios kilómetros de
distancia del área de interés. En la Figura E están las relaciones entre
el 'I) y el Deuteno, donde se aprecia que tanto las aguas termales como las
frías se encuentran sobre la recta meteórica y no se ve un enriquecimiento
del '13, lo que no permite evidenciar fenómenos de intercambio agua-roca, de
particular interés.
221
- 70
+ T< 30° C
QT>30°C
-110
-15 -14 -13 -12
¿ B 0(% 0 . V - S M O W )
FIGURA Z. D I A G R A M A DE VARIACIÓN ¿**0/¿0 DE TU FINO
El análisis de los datos permite concluir que todas las manifestaciones

termales de Tufíflo, incluso las más calientes, pertenecen a un acuifero
superficial alimentado por aguas meteóricas de circulación bastante
restringida, según lo indica el contenido de tritio. Estas aguas han sido
modificadas química y térmicamente por el aporte de gases calientes de
origen magmático (1!C del orden de +2,7*/,. hasta +5,6*/.. PDB) C8] y,
probablemente mínimas cantidades de vapor.
El único indicio geoquímico sobre la posible existencia de un sistema

geotérmica de alta entalpia es constituido por la notoria presencia de gas,
cuyos geotermómetros dan temperaturas del orden de los 230 °C.
3.2 CHACHIMBIRO
Se encuentra en un segmento de la Cordillera Occidental, que tiene una

gran concentración de aparatos volcánicas y un volcanismo persiste desde el
Plioceno. La característica básica, desde el punto de vista de la fuente de
calor, es que los centros eruptivos del complejo volcánico de Chachimbiro
han sido alimentadas por varias cámaras magmáticas evolucionadas C9].
El reservorio estarla localizado en rocas volcánicas a profundidades

variables entre los 10OO y EOOOm. Evidencias para su existencia están dadas
por: Zonas de alteración hidrotermal; Fuentes termales, y; Emanaciones de
gases. Las aguas termales son Cloruradas con temperaturas de ^¿"C, caudales
de 70 1/min, salinidad de 7000mg/l. El contenido de 5iOB varia entre 180 y
EOOppm; además, tienen una gran cantidad de gas disuelto, fundamentalmente
COE CIO].
La Figura 3 presenta las relaciones entre el "D y el Deuterio; alli' se

evidencian dos grupos de aguas: Aguas frías de circulación somera, con la
misma composición isotópica de las aguas meteóricas, y; Aguas termales que
se desvian fuertemente de la recta de las precipitaciones.
222
-40
-50 - ¿>D- 86 0+ 10
-60 -
-70 -
> SINGLE STAGE

-80 -
o STEAM LOSS
-90 -
A (AGUA PROFUNDA ORIGINAL . T= 240° C; Cl =1 5 g / Kg )

-100- B (AGUA PROFUNDA RESIDUAL : T = 60° C; CI = 2.4g/Kg)
• AGUAS CLORURADAS
D AGUAS BICARBONATADAS
- 110- T
-14 -12 -10 -8 -6 -4
8
S' o 3 ,V. SMOW)
FIGURA 3. DIAGRAMA DE VARIACIÓN 5 * 0 / 8 0 DE CHACHIMBIRO
Las aguas termales muestran una evidente evolución química, desde aguas
bícarbonatadas hasta aguas cloruradas, en donde el 'ti se incrementa de -11
a -6%.; los sólidos disueltos también se incrementan conforme aumentan los
isótopos pesados en solución, sugiriendo un mecanismo de enriquecimiento de
solutos, debido a una evaporación del agua meteórica original en
condiciones termales anómalas, o también, por procesos de mezcla de aguas
termales salinas con aguas frías.
La evaporación del agua desde una temperatura relativamente alta (p.e.

2^0°C), hasta condiciones superficiales (cerca de 60°C), ocasiona un
incremento del "Ü en aproximadamente 2,8%. y, un enriquecimiento del cloro
hasta el 30% de los valores originales. Para el caso de Chachimbiro,
solamente este proceso no explica como, partiendo de aguas meteóricas que
inicialmente tienen contenidos de "O y cloro más bajos que -10%. y lOOmg/kg
respectivamente, se observe que el "D alcanza un desplazamiento del 57.. y
el contenido de cloro llegue a 2250mg/kg. Una explicación puede
encontrarse considerando, adicionalmente, otro proceso en el cual las aguas
meteóricas que circulan por rocas más oxigenadas del reservorio profundo,
si la temperatura es más alta que EOO°C Cll, 123, incrementan su contenido
de "O en aproximadamente el 3%., por intercambio con la roca. Estos dos
procesos están esquemáticamente indicados en la Figura 3, donde, partiendo
de un agua meteórica se llega a un agua geotérmica "A" que experimenta un
proceso de evaporación en profundidad (single stage steam loss), hasta
alcanzar un valor composicional como el de "B". Esta agua residual se
mezcla con aguas subterráneas someras para dar el conjunto de aguas que se
encuentran sobre la linea de mezcla.
En la Figura ^ se indican las variaciones del "O con la altura de

emergencia, en las aguas de Chachimbiro y Cuicocha. Para Chachimbiro, es
evidente la existencia de dos diferentes grupos: El primero, son aguas
subterráneas someras de circulación restringuida, por cuanto las áreas de
infiltración están muy próximas a la zona de emergencia; El segundo grupo
223
4000
a n
= O 18 %o
LAGUNA DE
3000 - ° CUICOCHA
E
o
< 2000
D CHACHIMBIRO
O CUICOCHA
—r
- 14 -12 -10 -8 -6
6 "o (%0 , v SMOW)
FIGURA 4. DIAGRAMA DE VARIACIÓN <J18 O/ALTITUD DE CHACHIMBIRO Y CUICOCHA
D CHACHIMBIRO
O CUICOCHA
1000 2000 3000

Cl(ppm)
FIGURAS. DIAGRAMA DE VARIACIÓN C I / B DE CHACHIMBIRO Y CUICOCHA
224
400
B ( AGUA ORIGINAL PROFUNDA 240° C }

O CHACHIMBIRO
O CUICOCHA
50
1000 2000 3000
Cl ( p p m )
FIGURA 6. DIAGRAMA DE VARIACIÓN C L / S I O E DE CHACHIMBIRO Y CUICOCHA
(muestras que se desvian a la derecha de la recta), refleja procesos de

mezcla puestos en evidencia en la Figura 3, asi 1 como, en las Figuras 5 y
6, donde los contenidos de boro y sílice son confrontados con el cloro.
En el diagrama Cl/SiOe existe una correlación positiva entre las aguas

termales y frías de tipo bicarbonatado, con las cloruradas, que se desvian
hacia la derecha de la recta de dilución, porque tienen altos contenidos de
cloro con respecto al sílice. Por el contrario, en el diagrama Cl/B, todas
las muestras presentan una correlación lineal. Esta discrepancia puede ser
explicada tomando en cuenta que tanto el boro como el cloro son parámetros
"conservadores", y, la solubilidad del sílice varía con el enfriamiento de
las aguas termales emergentes C13]. Esto implica que, aparte de la mezcla,
el enfriamiento también puede considerarse en las aguas cloruradas que
emergen a la superficie. La simultánea existencia de los dos mecanismos,
explica las composiciones presentadas en las Figuras 5 y 6, donde es
interesante notar que las lineas de mezcla definen un componente profundo
similar al obtenido del modelo isotópico presentado en la Figura 3.
3.3 CUICOCHA
Incluye los volcanes Cotacachi y Cuicocha cuyas características

vulcanológicas permiten inferir una importante fuente de calor. El Cuicocha
tuvo un estilo eruptivo explosivo C5, l¿f, 15] emitiendo flujos
piroclásticos daciticos [16]. La actividad se inicio' en el limite
Pleistoceno-Holoceno, durante la cual se formo' una caldera, hace 3100 arios
[173. El Cotacachi es un estratovolcán andesltico de edad pleistocénica al
cual se asocian varios domos daciticos de edades holocénicas.
Las aguas que afloran en el sector son Bicarbonatadas, con temperaturas de

45°C, notándose que hacia las cercanías de la caldera existe un
significativo aumento en el contenido de cloruros CIO].
225
De la relación "Ü/Deuterio (Figura 7) se desprende que el desplazamiento es
consecuencia de la mezcla entre el agua de la laguna de Cuicocha y las
aguas termales de los alrededores. La linea de mezcla corta a la de las
aguas meteóricas en la abscisa -1S'¿., que puede representar el contenido de
I!
D en las aguas de alimentación de la laguna. La pendiente de esta linea es
igual a 4,8 que es concordante con con una evaporación superficial a baja
temperatura C18]. Si este es el caso, un enriquecimiento del 67,. en el "t)
ocurre en las aguas del lago hasta alcanzar condiciones estacionarias. Sin
embargo, este fuerte enriquecimiento no esta' acompasado de un sensible
incremento en la salinidad total de las aguas evaporadas. En efecto, las
aguas del lago presentan un muy bajo contenido de sal (^20 ^Siemens), donde
el ion dominante es el bicarbonato. Esto sugiere que las aguas meteóricas
que lo alimentan, son escencialmente constituidas por nieve fundida, la
cual esta' presente en el vecina volcán Cotacachi. En realidad, la mezcla
del agua de la laguna con las aguas termales ocasionara1 una desigual
dilución de las soluciones termales, porque acurre solamente a lo largo de
fracturas y fallas. Por esta causa, las dos muestras ubicadas en la linea
de mezcla (Figura 7) contienen cada una el 70 y el 30'/, del agua del lago y,
los sólidos disueltos totales son de 3800 y 500mg/kg respectivamente,
sugiriendo con esto, que estas dos aguas termales representan dos
reservorios distintos.
En la Figura 4, se aprecia a un grupo de aguas que se desplaza a la

izquierda de la recta, esto se interpreta como aculferos con larga
circulación, parque las áreas de alimentación están a alturas mucho más
elevadas. Particularmente el lago de Cuicocha, ubicado a mayor altura que
las fuentes termales.
-40
-50-
LAGUNA DE
CUICOCHA
-60 -
o -70- LINEA DE MEZCLA
-80-
-90-
-100-
-110
-14 -IZ -10 -8 -6 -4
¿ I 8 0 (% 0 , V - S M O W )
FIGURA 7. DIAGRAMA DE VARIACIÓN <5~'8 O/ f D DE CUICOCHA
226
3.4 PAPALLACTA
Esta área tiene manantiales de composición clorurada sódica con un

importante componente sulfato calcico, una elevada salinidad C193 y
temperaturas de 66°C. Estas aguas afloran en una zona de fallamiento, en el
contacto entre el basamento metamórfico de la Cordillera y el volcánico
terciario. Una compleja situación tectónica y volcánica, dificulta
establecer hipótesis sobre el origen de la fuente de calor, a nivel de
reconocimiento.
Si bien los datos disponibles son pocos, lo que condiciona fuertemente la

interpretación, desde el punto de vista térmico la situación parece
interesante. La Figura 8 presenta la relación "D/Deuterio de las tres
vertientes muestreadas; una de ellas esta' enriquecida en "D con respecto
a las otras dos, que se ubican en la linea de las aguas meteóricas. Por lo
tanto, suponemos que un posible mecanismo de intercambio con las rocas pudo
tener lugar; además, las características geomorfo lógicas del área y la
relación "D/altura indican que esta agua tiene una zona de alimentación
600m más elevada que las otras dos. Todo esto, permite asumir que esta agua
experimento' condiciones de alta temperatura en profundidad, lo que parece
confirmarse al aplicar los geotermómetros químicos reportados, más
adelante.
-70
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-80
-65-
INTERCAMBIO CON LA ROCA ?

-90 ¿O- 86 0+10
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HCO3 SO4 CI
-105- PAPALLACTA
TUNGURAHUA D EB
CHWBORAZO ^
-12.5 -12 -10.5 - 10

.V-SMOW)
FIGURA 8. DIAGRAMA DE VARIACIÓN cfÔ/ 6 D DE LAS ÁREAS DE PAPALLACTA

TUNGURAHUA Y CHIMBORAZO
3.5 CHALUPAS
Se trata de una 14)k<n, formada por el colapso del

caldera (16 x
estratovolcán Chalupas, emitió' por lo menos 100 km
luego de que éste
cóbicos CEO] de materiales riollticos C163; posteriormente, el volcanismo
se reactivo' en el interior de la caldera. Las particulares características
227
del sistema de alimentación magmatica de este complejo volcánico, activo
desde hace un millón de aftos, son buenas evidencias de la existencia de una
fuente de calor.
En la Figura 9, las muestras relativas al área de Chalupas, caen sobre la

recta de las aguas meteóncas en un amplio intervalo de composición. Esto
permite suponer la existencia de una fuerte circulación superficial sin
encontrarse condiciones anómalas de temperatura, esto confirma el modelo
geovulcanológico de INECEL CEO] en el cual se indica que la caldera esta'
rellenada por materiales impermeables (piroclástos y sedimentos lagunares)
que constituyen un efectivo sello al sistema geotérmico. Las variaciones en
el contenido isotópico corresponden a diversas cotas de infiltración,
situadas entre los 3500 y 4c?00m de altura.
-7O
-75-
-80
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o
2
o
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AGUAS BICARBO NATA DAS
(J) A G U A S SULFATADAS
FIGURAS DIAGRAMA DE VARIACIÓN s'80/,5 D EN CHALUPAS
3.6 TUNGURAHUA
En los flancos del activo volcán Tungurahua, existen abundantes

manifestaciones de aguas bicarbonatadas acidas y sulfatadas, con temperatu-
ras hasta de 53°C [21]. Tres muestras fueron analizadas (EUI-42, 43 y M de
la Tabla I), la correlación entre el "D y el Deuterio es una recta de
pendiente +1,8 (Figura 8) sugiriéndonos que las aguas pudieron ser
sometidas a procesos de evaporación-condensación a una temperatura de
aproximadamente EOO°C C18].
La EUI-^4 es agua subterránea local que durante su descenso por el interior

del cono, interacciona con gases volcánicos calientes (S0e , I-JS y C0¡, ),
dando como resultado un fuerte incremento de HC03 y SQ en la solución y, un
simultáneo incremento de la temperatura del liquido hasta alcanzar
probablemente los 200°C. Bajo estas condiciones, se produce la evaporación
parcial de la solución, formándose vapor que se condensa en la parte alta
del volcán, originando un aculfero termal con una composición química e
228
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isotópica similar a la de la muestra EUI-42. Por otra parte, las aguas
residuales de la evaporación circulan hacia la base del cono, originando
aguas termales similares a la muestra EUI-*f3, que tiene al sulfato como
ion dominante en la solución, y presenta además, un alta concentración de
los isótopos pesadas.
3.7 CHIMBORAZQ
Es el estratovolcán más alto del Ecuador, su actividad se inicio' en el

Pleistoceno y fue prácticamente continua hasta el Holoceno. La
interpretación petrológica de los productos emitidos en sus tres etapas
evolutivas, sugiere la presencia de una cámara magmática en donde el magma
basáltico-andesítico de las etapas iniciales, evoluciono' hasta un producto
final de composición dacltica- nolítica C16Ü. Durante su evolución, el
magma transfirió' calor provocando una anomalía térmica, cuya primera
evidencia en superficie son fuentes termales con temperaturas de 46°C.
La única muestra que ha sido analizada puede ser considerada como agua
subterránea cuyo origen esta' en los deshielos del Volcán Chimborazo, a
alturas superiores a los 4500m. La desviación que se observa en la Figura
B, respecto a la recta de las aguas meteóricas no encuentra, en este
momento, una explicación satisfactoria debido a la falta de otros datos
anal iticos.
3.8 CUENCA
Esta área es conocida por la existencia de fuentes termales con una

elevadlsima salinidad, alta conductividad y caudales del orden de los EO
1/s CIO, 193. Estas aguas tienen las mayores temperaturas (73,3°C)
registradas en el país y, precipitan travertinos que son explotados como
roca ornamental. Esta zona termal se encuentra en una cuenca sedimentaria
cretácica y los materiales volcánicos más próximos son de edad terciaria.
Las manifestaciones aflorantes son de dos clases: Aguas cloruradas con

temperaturas mayores que 48°C, concentradas en un área de aproximadamente
un kilómetro cuadrado y que son aprovechadas como balnearios (Baños de
Cuenca), y; Aguas bicarbonatadas frías (17 a £2°C), diseminadas en una
zona relativamente amplia, varios kilómetros alrededor de los balnearios.
En esta zona marginal existe un manantial frío de tipo clorurado que tiene
el menor contenido de "ÍD y una elevada salinidad (TDS - 8,£g/kg).
Las aguas termales tienen una zona de alimentación situada aproximadamente

a una elevación de 3EOOm, esto es, 500m sobre la altura de los balnearios.
En el área de Baftos se muestrearon 11 vertientes cuya temperatura de
emergencia varia entre 48 y 73,3°C. No obstante tal diferencia térmica, la
composición isotópica de los diversos manantiales es muy homogénea (Figuras
10 y 11), situándose sobre o muy próximos a la linea de las precipita-
ciones; al mismo tiempo, el contenido de ion cloruro se mantiene constante.
Todo esto permite suponer que el agua profunda alcanzo' condiciones de
equilibrio químico con las rocas de un reservarlo somero, en el tope de la
potente cuenca sedimentaria.
232
o
2
tf)
O
"o
U AGUAS BICARBONATADAS
AGUAS CLORURADAS
F AGUAS FRÍAS
-90
-13 -11.5 ,,Q -IV.^
00 (%o,V- SMOW)
FIGURA 10. DIAGRAMA DE VARI ACIÓN &18,O / ¿ D EN CUENCA
80 80
óo
70 70
o
IX) o
60 60
ce
$ ce
ce ui
a
50 50
4O 40
30 30
-12 -II -10500 1000 1500
<5'80 (%0 V-SMOW) CI(mg/Kg)
FIGURA II. DIAGRAMA DE VARIACIÓN 6'% Y Cl CON LA TEMPERATURA

EN CUENCA
4 EVALUACIONES GEOTERMOMETRICAS
La Figura IB presenta un diagrama triangular donde se relacionan las

concentraciones relativas de K, Na y Mg en todas las aguas analizadas. Este
diagrama ha sido modificado de un original propuesto por Giggenbach CE23,
con el fin de ampliar el área correspondiente a la esquina del magnesio, en
la cual generalmente están localizadas las aguas inmaduras. Muchas de las
233
Na/5
200°
CHACHIMBIRO
CUICOCHA
CHALUPAS
CUENCA
CHIMBORAZO
PAPALLACTA
TUNGURAHUA
\T Mg
FIGURA 12. CONCENTRACIONES RELATIVAS N o . K , M g ( m f l / k g ) DE

TODAS LAS AGUAS ESTUDIADAS
muestras de agua caen entre las dos lineas que describen la temperatura
K/Mg en el rango de 40 a 60°C, indicando con esto que este par iónico es
incapaz de reflejar las condiciones termales profundas. Por otra parte, la
relación Na/K parece más útil para evaluar las temperaturas profundas, pero
esta1 restringuida a pocas muestras. Realmente, la Figura 1E indica que
muchas de las muestras tienen temperaturas Na/K mas altas que E50°C pero,
no parecen ser reales si se toma en cuenta las características isotópicas
ya discutidas.
Solamente pocas muestras de Chachimbiro, Papallacta, Chimborazo y Cuenca

parecen admitir la aplicación del geotermómetro Na/K, ellas son aguas
cloruradas y parecen ser maduras o parcialmente equilibradas con rocas de
los acuiferos (segán la definición dada por Giggenbach CEED).
Consecuentemente, temperaturas de E*tO, EOO, 100 y EOO'C pueden ser
obtenidas, respectivamente, en las áreas indicadas.
En cuanto se refiere a Tufiflo, las manifestaciones termales, incluso las

más calientes, son aguas superficiales modificadas por el aporte de gases
calientes, no existiendo una evidencia segura de la contribución de un
componente liquida profundo. La evaluación de la termalidad, por
consiguiente, es posible únicamente con ayuda de la geotermometria de
gases. Las temperaturas obtenidas de esta manera, dan un máximo de EEO a
E30°C CE3,
5 CONCLUSIONES
Los indicadores químicos e isotópicos presentados, ratifican el interés

geotérmico de las áreas de Tufiflo, Chachimbiro y Cuenca. Además,
constituyen argumentos positivos que justifican la iniciación de
234
investigaciones geocientlficas detalladas en Papallacta y Chimborazo. Con
respecto a Chalupas, los métodos químicos e isotópicos no han sido de mucha
utilidad, debido a las características de las aguas muestreadas.
AGRADECIMIENTOS
Los autores agradecen a INECEL y al IIRG por las facilidades para elaborar
el presente trabajo, elaborado en el marco del "Programa Coordinado de
Investigaciones para América Latina, sobre la Aplicación de Técnicas
Geoquímicas e Isotópicas en la Exploración Geotérmica", financiado por el
Gobierno de Italia. Especial reconocimiento a la OIEA y, particularmente,
al Dr. Roberto Gonfiantini quien brindo' su total apoyo a las gestiones
técnicas del Contrato de Investigación 3991/IG mediante el cual se
realizaron las investigaciones de las áreas ecuatorianas.
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Costa Ecuatoriana" Politécnica, Monografía de Geología. Vol. V, No.
2, (1980) 7-45 p.
C23 FEININGER, T. "El Basamento Metamórfico del Ecuador" Politécnica,

Monografía de Geología 3, Vol. VIII, No. 2, (1983) 37-48p.
[33 ALMEIDA, E. "El Riesgo Volcánico en el Ecuador Continental" Memorias

Segundas Jornadas Nacionales de Geología, Minas y Petróleo.
Universidad Central del Ecuador, (1988), 57-60 p.
[43 HALL, M., CALLE, J. "Control Geocronológico de los Principales

Eventos Tectónico-Magmáticos del Ecuador" Politécnica, Monografía de
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República del Ecuador" Inf. Int. INECEL, Proyecto Geotérmico. Quito,
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Cuenca-Chalupas-Chachimbiro en la República del Ecuador, Síntesis de
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Guidebook on Nuclear Techníques ín Hydrology. IAEA, Tecnical Reports
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[13] TRUESDELL, A., FOURNIER, R. "Procedures for Estimating the

Temperature of Hot Water Component ín a Mixed Water Usíng a Plot of
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[14] HALL, M. "El Volcanismo en el Ecuador" Inst. Pan. Geografía e

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l.aurea in Scíenze Geologiche, Uníversita* Degli Studí di Pisa,
(1984).
[17] von HILLEBRANDT, Ch. "Estudio Geovulcanológíco del Complejo

Volcánico Cuicocha-Cotacachi y sus Aplicaciones, Provincia de
Imbabura" Tesis, Escuela Politécnica Nacional, Quito. (1989).
[18] TRUESDELL, A., NATHENSON, M. "The Effects of Subsurface Boilíng and

Dílutíon on the Isotopic Compositíon of Yellowstone Thermal Waters"
J. Geoph. Res. V. 82, No. 26, (1977), p. 3694.
[19] AQUATER. "Proyecto de Investigación Geotérmica de la República del

Ecuador, Estudio de Reconocimiento" Informe preparado para OLADE e
INECEL, San Lorenzo ín Campo, Italia, (1980).
[20] INECEL. "Estudio de Exploración de los Recursos Geotérmicos en

Chalupas, Primera Fase Prefactibi1idad". Informe interno preparado
por el Proyecto Geotérmico, (1983).
[213 INECEL. "Estudio Geológico de las Fuentes Termales de Palíctahua,

Provincia de Chimborazo". Informe interno preparado por el Proyecto
Geotérmico, (19B4).
[22] GIGGENBACH, R. "Geothermal Solute Equilibria. Derivation of

Na-K-Mg-Ca Geoindicators". Geochím. Cosmochim. Acta, 52: 2749-2765.
[23] AQUATER. "Proyecto Geotérmico Binacional Tufiflo-Chiles-Cerro Negro,

Estudio de Factibi1idad" Informe interno preparado para OLADE.
(1987).
[24] BARBERI, F., PATELLA, D., SCANDIFFIO, G. "Proyecto Geotérmico

Binacional Tuf iflo-Chí les-Cerro Negro, Informe de la Reunión Final de
la Junta Asesora" Informe interno preparado para OLADE. (1988).
236
AVANCE DE LAS PRUEBAS DE RADIOTRAZADO EN EL CAMPO
GEOTÉRMICO DE AHUACHAFAN, EL SALVADOR
W.J. McCABE
Instituto of Nuclear Sciences,
Petone, Nueva Zelandia
E. MAYEN, P. HERNÁNDEZ
Centro de Investigaciones Geotérmicas,
San Salvador, El Salvador
Resumen-Abstract
AVANCE DE LAS PRUEBAS DE RADIOTRAZADO EN EL CAMPO GEOTÉRMICO DE AHUACHAFAN,

EL SALVADOR.
Con el fin de encontrar las rutas hidrológicas de las aguas geotérmicas y localizar tan-
to áreas productoras, como áreas idóneas para realizar el proceso de reinyección de las aguas
residuales, cinco pruebas con el trazador radioactivo 1-131, se han realizado en el Campo Geo_
térmico de Ahuachapán (S.O. de la República), desde diciembre de 1987 a marzo de 1990. En la
primera experiencia, el trazador fue inyectado en el pozo AH-5 y únicamente fue detectado en
el pozo AH-1; en la segunda prueba, fue inyectado en el AH-2, no lográndose obtener respues-
ta radioactiva, la tercera inyección fue realizada en el AH-29, obteniéndose respuesta en el
AH-1 y escasamente en los pozos AH-20 y AH-22. Todas las pruebas anteriormente mencionadas
fueron llevadas a cabo a reinyección estática, con agua residual proveniente del AH-1. Poste-
riormente se hizo una cuarta inyección, en el mismo AH-29 a reinyección constante por tres
meses, y se obtuvo respuesta significativa en los pozos AH-1, AH-5, AH-20 y AH-22. Una quinta
prueba fue iniciada inyectando el 1-131 en el pozo AH-2, a reinyección constante con agua del
AH-1 por 3 meses pero problemas con el detector de centelleos líquido, obligaron a suspender-
la a 10 días de inicio.
En todas las pruebas fueron recolectadas muestras de aguas de la mayoría de pozos del
campo, tanto aguas residuales en superficie, como muestras a profundidad.
Las muestras fueron llevadas al laboratorio y procesadas químicamente por método gravi-
métrico, separando el compuesto radioactivo en forma de ioduro de plata y cuyo rendimiento
fue comparado con un segundo análisis usando el método del electrodo específico para iodo.
Posteriormente se realizó el conteo del iodo radioactivo por el método instrumental de cente-
lleo líquido.
PROGRESS IN RADIOTRACER TESTS IN THE AHUACHAFAN GEOTHERMAL ÁREA, EL

SALVADOR.
Five tests were carried out with the radioactive tracer 131j ^n the
Ahuachapán geothermal área, in the SW of the country, over the period
December 1987 to March 1990, to lócate the hydrological courses of geothermal
waters and to find both productive áreas and áreas suitable for residual water
reinjection. In the first experitnent, the tracer was injected into the AH-5
well and detected only in the AH-1 well. In the second test, the tracer was
injected into AH-2, but no radioactive response was obtained anywhere. The
third injection was into AH-29 and a response was obtained in AH-1, with a
slight response detected in the AH-20 and AH-22 wells. All the above tests
were carried out with static reinjection of residual water from AH-1. A
fourth injection was subsequently made, also into AH-29, using constant
reinjection over a period of three months, and this gave a significant
response in the AH-1, AH-5, AH-20 and AH-22 wells. A fifth test was
started. 131j was ô be injected into the AH-2 well with constant
reinjection of AH-1 water for three months, but problems with the liquid
scintillation detector forced the test to be abandoned after ten days.
237
In all the tests, samples of both residual surface water, and deep
water were collected from most of the wells in the área.
The samples were taken to the laboratory and subjected to gravimetric

cheroical processing. The radioactive constituent was separated out in the
form of silver iodide and the yield compared to a second analysis using the
iodine-specific electrode method. Afterwards, a count was made of the
radioactive iodine using a liquid scintillation detector.
INTRODUCCIÓN
El Campo Geotérmico de Ahuachapán, El Salvador, es un campo "líquido dominan

te", con temperaturas máxima de 240°C, y que inició operaciones en 1975, con
una unidad de 30 MWe. En 1976 y 1980 fueron instaladas dos unidades más (30 y
35 MWe respectivamente) para un total de 95 MWe. Posee 14 pozos productores
(600 - 1200 mts) de un total de 32 perforados, con presiones de separación de
6-7 Kg/cm2 (150-160°C) y porcentaje promedio de vapor de 20% en peso. El agua
residual ha sido eliminada por dos nétodos: Por reinyección al reservorio a
presión de separación (suspendida temporalmente desde 1982) y por descarga su-
perficial por gravedad al Océano Pacífico a través de un canal de concreto de
80 Km de longitud.
Diversos estudios han sido realizados desde su inicio, con el fin de opti-
mizar la explotación del yacimiento y prolongar la vida útil del mismo. Estu-
dios recientes (1) han revelado la conveniencia de expansión a la zona Sur del
campo y de la reinyección de las aguas residuales como acciones a corto y me-
diano plazo, que mantengan y amplíen la explotación del recurso. Como parte de
lo anterior, y con la colaboración del Organismo Internacional de Energía Ató-
mica (OIEA) , se han implantado experimentos de radiotrazado y estudios de isó-
topos ambientales en el área, desde 1986. El 1-131 ha sido el elemento radioac-
tivo escogido como trazador en los experimentos realizados al presente, en ba-
se a experiencias exitosas en otros campos geotérmicos y en pruebas de corta
duración, ya que su tiempo de vida media es de 8 días. (2, 3)
PRIMERA PRUEBA RADIOTRAZADO
Con el objetivo de corroborar una prueba previa llevada a cabo en 1971

con tritio antes de iniciada la explotación del campo, y de chequear el siste-
ma de tratamiento de muestras y análisis en el laboratorio de isótopos inesta
bles del Centro de Investigaciones Geotérmicas de CEL, el 11 de diciembre 1987
se ejecuta la primera inyección de material radioactivo, 1-131, con una con-
centración de 0.8 curies (31 GBq); este fue introducido en el pozo AH-5 con
un volumen de agua residual de 140 m^ proveniente del pozo AH-1. (Ver Figura
1). La recuperación radioactiva obtenida en el pozo AH-1 fue más del 25% en
los 76 días monitoreados, obtuvo su máxima concentración a los 20 días de in-
yectado y comenzó a detectarse a los dos días de iniciada la prueba. Fueron
significativas las recuperaciones detectadas en los pozos AH-20 y AH-26. No
se detecto en ninguno de los demás pozos en el campo. El sistema de inyección
del trazador es mostrado en la Figura 2.
Comparando con los resultados obtenidos de la prueba en 1971, aún cuando
en esta oportunidad fue recuperado en un 10% y detectada una concentración pi-
co a los 3 días, parece ser que es consistente con la prueba actual, teniendo
en cuentra las diferentes condiciones del campo antes y después de su explota-
ción. En la Figura 3 se muestran las dos curvas, donde se puede apreciar dos
concentraciones pico o trayectorias de llegada en la prueba reciente y alguna
posibilidad de una tercera alrededor del día 50. La prueba con tritio dio una
similar dimensión de la trayectoria del flujo, pero no dio una resolución su-
ficiente para mostrar una segunda trayectoria.
Aparentemente existe un flujo preferencial entre el pozo AH-5 y el AH-1
con una velocidad de 100 m/día y aproximadamente un tercio del agua desde la
vecindad del AH-5 es descargada al AH-1. Esta buena conexión podría estar aso-
ciada a una falla o contacto plano; ya que el AH-1 es uno de los pozos mas pro
fundos en la parte principal del campo, esto sugiere una paralelismo con otros
238
312
SIMBOLOGIA
|> POZO SEOT. PERFORADOS
^ POZO SEOT. PROYECTADOS
XFALLA GEOLÓGICA
5
ÍFUMAROLAS
310
O 25O 5OO______lOOOmr»
ESCALA I 25,000
309
411 412 413 414
FIG. 1. Pozos profundos — campo geotérmico de Ahuachapán.
SEPARADOR CICLÓNICO
POZO REINYECTOR AH-I
SILENCIADOR
I I CANALETA
Válvula cuten
2 Válvulas dr «•quridad
3 Válvula at ••gurldorj
4 Válvula d* compuerta 000 PSIG
5 Válvula d* «tgurldad
Mi ManálMtra iKttma Inyiccltfn
MüMane'mitro dtl cobtial
n»a d» mny*ccla<<
LP'Lmvo d* purga
LBPiLl'nto O* Bypaii
Wi,Wg.-Caudal «n poto» AH-I.AM-5
Hu-Entolpi'o dtl agua
FIG. 2. Esquema del sistema de inyección del trazador, pozo AH-5.
239
Ah-1 1987
t£
O Ah-1 1971
Q
<
NI
¡
O
O 2000 -
gj
o 1500 -
z
CC «M
o ,-
íu O
a: T-
X 1000
1 T
o —
u
fl
(£
U.
500 -
O l*
80
DÍAS DESPUÉS DE INYECCIÓN
FIG 3 Prueba de radiotrazado en el pozo AH-5, Ahuachapán
campos como Wairakei N.Z., en donde se ha demostrado, después de muchas prue-

bas con trazadores, que agua ligeramente enfriada (160-200°C), entrando al cam
po desde arriba a la zona principal de producción a través de fallas, se mue-
ve a gran velocidad a nivel de zona de contacto con el basamento. Este movi-
miento podr£a ser ayudado por fallas abiertas que coincidan con ese plano, lo-
grándose de esa forma que sólo los pozos que penetran a la formación del basa-
mento sean detectados, no así los pozos menos profundos cercanos al pozo inyec-
tor, en donde el trazador es descargado hasta que ha sido mezclado con el cuer-
po de agua varios días mas tarde. Probablemente la segunda curva del AH-1 po-
dría representar el trazador mezclado en el reservorio.
SEGUNDA PRUEBA RADIOTRAZADO
Con el ob]eto de comprobar la influencia del sistema de reinyección utili-

zado en el campo de 1975 a 1982, se realizó una segunda inyección (9/Jul/88)
en el pozo AH-2 con una concentración de 0.6 curies (21 GBq) y 216 mts^ de
agua residual proveniente del AH-1; fueron monitoreados por 56 días todos los
pozos del campo, tanto muestras a profundidad como en superficie. A pesar de
la profundidad del AH-2 {1200 m) , comparable con alguno de los pozos cercanos
como el AH-29 (1200 m) y el AH-1 {1205 m), no se obtuvo ninguna señal radioac-
tiva en estos, ni en los restantes con respecto al rumbo tomado por el agua den-
tro del reservorio, por lo que probablemente, se haya encausado hacia un reser-
vorio mas profundo. Debido a lo anterior, esta prueba puede considerarse posi-
tiva, y si en la prueba programada a reinyección constante se obtiene similar
respuesta, podría considerarse una zona idónea de reinyección al reservorio
geotérmico.
TERCERA PRUEBA RADIOTRAZADO
Esta prueba se realizó en el pozo AH-29 el día 12 de marzo de 1989, con el

objeto de corroborar también el grado de incidencia de la reinyección en el
campo, ya que desde 1975 hasta 1982 se mantuvo la reinyección de agua residual
en el AH-29, produciéndose cambios termodinámicos en pozos adyacente al mismo,
240
lo que llevo a suspenderla. En esta oportunidad se inyectaron 2.0 curies (72.6
GBq) de 1-131 con 738 mts3 de agua residual del pozo AH-1, monitoreándose el
campo por 45 días y obteniéndose señal radioactiva solamente en el AH-1y some-
ramente significativa en el pozo AH-20 y AH-22. Las Figuras 4 y 5 ilustran a
diferente escala (normal y semilog), los resultados de esta prueba.
0.0
10 20 30
FIG. 4. Prueba de radiotrazado en el pozo AH-29, Abril de 1989.
! . . . i i . i . i
' 1
'
M
"o POZO N.°-

X
U 100.0. o ——— o AH-I -

z • • ñ 1 1 <
"*l"1>
a ———— KI i
/ ^
^—-*^ -o'V°" "•*%-•-:
00
g v*- 0 :
Üi
0
o'
A
r /i\i 1
- / tf ^'1\
rir~~
/ J
2 1.0
tj- 1^1
O
4
8 I———— "
< \I •
í/
0 /
£
0.1 . . . . . . . . I . .. '
-
c 10 20 zo 40 5l
FIG. 5. Prueba de radiotrazado en el pozo AH-29, Abril de 1989.
241
CUARTA PRUEBA RADIOTRAZADO
Esta inyección del 1-131 se llevó a cabo el 29 de junio de 1989 en el mis-

mo pozo que se utilizó para la tercera prueba (AH-29), solamente que se reali-
zó a reinyección constante con un flujo de agua de 49 Kg/seg durante el perío-
do del monitoreo, el cual tuvo una duración de 67 días. En esta oportunidad se
introdujo una concentración de 1.7 curies (62 GBq) y fue detectado en 4 pozos,
los cuales en orden de aparición fueron: El AH-5 (apto en esta oportunidad para
monitorearlo) y el AH-20 se comenzaron a detectar al primer día y los pozos
AH-1 y AH-22 al cuarto día, variando solamente en la concentración o fracción
de radioactividad detectada, de acuerdo a la cercanía desde el pozo inyector
al pozo monitoreado. Debido a acciones operativas propias del campo, los pozos
AH-5 y AH-22 fueron monitoreados sólo por 30 días. Las Figuras 6 y 7 ilustran,
a diferente escala (normal y semilog), los resultados de esta prueba.
500
IM
"b POZO N": T
o————o AH-I
4OO
• ———— • AH-5
Q &———& AH-20
o
•————• AH-22
300
ÜJ
z
200
./
r5 100
°o°°ou -'
10 20 30 +0 50 60 70
FIG. 6. Prueba de radiotrazado en el pozo AH-29, Junio de 1989.
1000
o
X
TJ
Z
O
o
<
ce
o
U)
h-
o
o
o
10 20 30 4-0 50 60 70
FIG. 7. Prueba de radiotrazado en el pozo AH-29, Junio de 1989.
242
QUINTA PRUEBA RADIOTRAZADO
Esta correspondió al mismo esquema que la segunda, sólo que a reinyección

constante del pozo AH-1 (38 Kg/seg) y tuvo que ser suspendida a los 10 días de
iniciado por desperfectos del equipo contador de centelleos liquido, utilizado
para detectar el radiotrazador. La concentración del 1-131 inyectado el 7 de
marzo de 1990 fue de 2.0 curies (72.6 GBq) y en una muestra a profundidad del
pozo AH-29 colectada al tercer día de la prueba, indicó ya la presencia del
1-131 en ese punto.
PROTECCIÓN RADIOLÓGICA DURANTE LOS EXPERIMENTOS
El procedimiento para inyectar el trazador es simple y sencillo. Esta di-

señado de tal forma se obtenga una mínima dosis de radiación al operador. Trans-
ferir el frasco con el 1-131 del contenedor al sistema de inyección toma nor-
malmente de 10 a 20 segundos. Con una cantidad de 2 curies (74 GBq) de 1-131
(valor típico utilizado) resultará en una dosis equivalente efectiva menor de
3 mrem (0.03 mSv), la cual es mucho menor que la dosis ambiental anual de 200
mrem (2 mSv).
Para todas las pruebas, se realizan las siguientes medidas de seguridad rja
diológica:
a) El sistema de inyección es chequeado visualmente a condición de la prueba
antes de realizarse para detectar fugas y defectos en válvulas y acceso-
rios .
b) Material plástico es colocado debajo del sistema de inyección.
c) El personal encargado del experimento se protege completamente con gaba-
chas y accesorios de caucho y plástico.
d) El frasco con el elemento radioactivo es manejado con largas pinzas espe-
ciales, y colocado internamente en una válvula de compuerta, recubierta de
plomo, en el sistema de inyección.
e) Las dosis de radiación se miden y registran adecuadamente durante la inyec-
ción del radiotrazador.
f) Se construye una fosa de 1 mt. de profundidad cercana al sistema de inyec-
ción, como prevención y desecho del material descartable utilizado.
SEPARACIÓN DE IODO DE LAS AGUAS GEOTERMALES PARA EL CONTEO RADIOACTIVO
La siguiente técnica gravimétrica es utilizada para recuperar el iodo sin

precipitación de sílice o cloruros: El sulfhídrico es oxidado con permanganato
de potasio acidificado, sulfito es adicionado para reducir el iodato a ioduro,
y ácido fluorhídrico es agregado para complejar y prevenir la precipitación de
la sílice. Esta solución se filtra a través de una membrana. Posteriormente se
adiciona nitrato de plata para precipitación de los cloruros. Debido a la reía,
tiva solubilidad de los haluros de plata, el iodo es cuantitativamente precip_i
tado, mientras sólo se forma una pequeña cantidad de cloruro de plata. Esta so-
lución es filtrada nuevamente a través de una membrana previamente tarada y los
cloruros de plata fijados, son removidos con amoníaco diluido.
DETERMINACIÓN DEL IODURO EN AGUAS GEOTERMALES CON ELECTRODO DE ION ESPECIFICO
El electrodo para ioduro es sensitivo al sulfhídrico y también a los bro-

muros, pero en menor capacidad. Por lo tanto, es necesario oxidar el sulfhí-
drico de las aguas geotermales antes de la determinación de ioduro. Los bromu-
ros no pueden ser usados como agentes oxidantes sin introducir un apreciable
"blanco reactivo". El permanganato de potasio alcalino oxida el sulfhídrico a
sulfato pero el ioduro existente es también oxidado a iodato. El iodato tiene
que ser entonces reducido a ioduro nuevamente con la adición de ácido y sulfi-
to de sodio.
Para evitar problemas con el electrodo, es aconsejable mantenerlos fuera
de la solución mientras hay un excedente de agente oxidante y ninguna forma-
ción de ioduro.
243
CONTEO DE CENTELLEO LIQUIDO DEL IODO SEPARADO DE LAS AGUAS GEOTERMALES
Es la técnica mas sensitiva para la detección y cuantificación de radioac-

tividad. Es aplicable a todas las formas de medición de emisiones con desint£
gración nuclear (Alfa, Beta, etc.). La técnica analítica esta definida por la
incorporación de un elemento radioactivo distribuido uniformemente en un medio
líquido capaz de convertir la energía cinética de las emisiones nucleares en
emisiones de fotones. El elemento radioactivo colocado en un frasco con la so_
lución centellante, encerrado en la oscuridad, permite que la intensidad del
fotón sea observado en la región ultravioleta del espectro de energía electro_
magnética. Esta señal es ampliada y detectada después de procesos que crean
un pulso eléctrico representativo de los fotones. El registro de cada pulso
durante el tiempo de medición, provee una indicación del número de eventos cen-
tellantes que ocurren en ese tiempo.
CONCLUSIONES
Los resultados obtenidos al presente en Ahuachapán, han demostrado la uti-

lidad de esta técnica de avance, como una herramienta extremadamente poderosa
que conlleva a poseer un conocimiento hidrológico de las condiciones de opercí
ción de los campos geotérmicos, en un tiempo relativamente corto, lo que ayu-
da a planificar estrategias inmediatas de explotación-reinyección del recurso.
REFERENCIAS
(1) Aunzo, Z.P., Bodavarsson, G.S., Laky, C., Lippman, M.J., Steingrimsson,
B., Truesdell, A.H., and Witherspoon, P.A., 1989. The Ahuachapán Geo-
thermal Field, El Salvador: Reservoir Analysis, Lawrence Berkeley Labo-
ratory, Report LBL-26612, U.S.A.
(2) McCabe, W.J., 1990. Artificial Tracers in Geothermal Hydrology. Institute

of Nuclear Sciences, Department Science and Industrial Research, New
Zealand.
(3) McCabe, W.J., Barry, B.J., Manning, M.R., 1983. Radioactive Tracers in
Geothermal Underground Water Flow Studies. Geothermics, Vol. 12, No.2/3,
pp 83-110.
244
ISOTOPIC AND CHEMICAL COMPOSITION OF
WATER AND GAS DISCHARGES FROM THE
ZUNIL GEOTHERMAL SYSTEM, GUATEMALA
W.F. GIGGENBACH
División of Chemistry,
Petone, New Zealand
D. PAÑI AGUA DE GUDIEL, A.R. ROLDAN MANZO
Instituto Nacional de Electrificación,
Guatemala City, Guatemala
Resumen-Abstract
LA COMPOSICIÓN ISOTÓPICA Y QUÍMICA DE LOS CAUDALES DE AGUA Y GAS PROCEDENTES

DEL SISTEMA GEOTÉRMICO DE ZUNIL, GUATEMALA.
Las diferencias en la composición química e isotópica de los caudales de

agua y vapor sugieren que el sistema geotérmico de Zunil es un típico sistema
volcánico magmático-hidrotérmico estrechamente relacionado con el complejo
volcánico de Cerro Zunil - Domo El Azufral que se encuentra al SE de la zona
térmica principal. Los vapores magmáticos originales llegan a la superficie
del depósito de azufre de Azúfrales con mínimas alteraciones. Su interacción
con aguas subterráneas locales en niveles comparativamente poco profundos ori-
gina la formación de aguas acidas sulfatadas que se descargan sobre las lade-
ras de la estructura volcánica. El movimiento de aguas primitivas más profun-
das hacia el N y el O conduce a su neutralización y conversión en aguas acidu-
ladas con CO , con predominio de Cl, tal como se encuentran en los pozos
profundos. La proporción del agua originalmente magmática en las aguas pro-
fundas con Cl es de ~20%. La posterior interacción agua-roca transforma la
mayor parte del CO en disolución en HCO , y las aguas bicarbonatadas re-
sultantes se descargan a través de manantiales situados a lo largo del río Sá-
mala. Los vapores que se desprenden de las aguas profundas calientes sirven
de alimento a fumarolas y depósitos vapocalentados. A medida que disminuye la
distancia con las zonas ascendentes principales de los fluidos térmicos rela-
cionados con el complejo de Cerro Zunil, puede esperarse que aumenten las tem-
peraturas profundas del agua. Al mismo tiempo, sin embargo, existe un peligro
creciente de que lleguen a los pozos fluidos ácidos y oxidantes inmaduros de
origen magmático.
245
ISOTOPIC AND CHEMICAL COMPOSITION OF WATER AND GAS DISCHARGES FROM THE ZUNIL
GEOTHERMAL SYSTEM, GUATEMALA.
Variations in the chemical and isotopic composition of water and steam
discharges suggest that the Zunil Geothermal System is a typical volcanic magmatic-
hydrothermal system closely associated with the Cerro Zunil - Domo El Azufral
volcanic complex to the SE of the main thermal area. The originally magmatic vapors
reach the surface least altered at the Azufrales sulfur deposit. Their interaction with
local groundwater at comparatively shallow levels gives rise to the formation of acid
sulfate waters discharged over the flanks of the volcanic structure. Movement of
deeper primitive waters to the N and W leads to their neutralisation and conversion
to CÛ2 charged, predominantly Cl waters as encountered in the deep wells. The
proportion of originally magmatic water in the deep Cl waters is --20%. Further
water-rock interaction converts most of the dissolved CC>2 to HŒ>3, the resulting
bicarbonate waters are discharged from springs along the Samalâ River. Vapors
released from the deep hot waters feed fumaroles and steam-heated pools. Deep
water temperatures can be expected to increase with decreasing distance to the major
upflow zones of thermal fluids associated with the Cerro Zunil complex. At the same
time, however, there is increasing danger of the incursion into wells of immature acid
and oxidising fluids of magmatic origin.
INTRODUCTION
The Zunil Geothermal Field lies some 200 km west of Guatemala City. On the basis
r\
of geoscientific surveys in 1973 and 1977, a 4 krrr area was cosen for the drilling of
six deep exploration wells during 1980 to 1981 to a maximum depth of 1310 m, the
highest temperature encountered was 288°C. According to these early investigations,

the heat source of the field was thought to lie to the west of the Samalâ River
(Caicedo and Palma, 1990). Initial production testing indicated rapid pressure
drawdown due to restricted permeabilities (Bethancourt and Dominco, 1982). In a
246
recent series of papers, Adams et al. (1990a) evaluate the geochemistry and
hydrology of the Zunil Field and agree that a plume of high temperature water
originates in the western part of the existing well field to travel south and east and to
mix with shallow steam-heated water there; Adams et al. (19905) describe another set
of hydrogeochemical investigations and suggest that the reservoir at Zunil is
geochemically inhomogeneous and that the recharge to the field comes primarily from
the north and east. Menzies et al. (1990) report the results of an integrated well test
program and conclude that steam output from the presently drilled wells could sustain
a 15 MW power station, however, additional wells would have to be drilled to
maintain production. Foley et al. (1990) discuss the geology and geophysics of the
Zunil geothermal system and suggest that fluid production is controlled by the
intersection of NW and NE trending faults.
The present investigation was carried out within the framework of the IAEA
Coordinated Research Program on the Application of Isotopic and Chemical
Techniques to Geothermal Exploration in Latin America. The major aim of this study
is the development of an internally consistent hydrological model of the system
possibly useful in the selection of more favorable drilling targets. The model is based
largely on the isotopic and chemical composition of water and steam discharges.
CHEMICAL COMPOSITION OF WATERS
The chemical composition of samples from well and spring discharges collected during
the present investigation are given in Table 1. The results agree closely with those
reported by INDE (1978) for earlier much more extensive surveys. The three well
samples were taken from the weirbox, but are corrected for steam loss and therefore
represent total discharge compositions. Sample locations are shown in Fig. 1. AR is
the composition of a solution resulting from the "dissolution" of 10 g of average
crustal rock in 1 kg of water. For all neutral to alkaline waters Al contents were < .05
247
Table 1.- The chemical composition of well and spring discharges from the Zunil
Geothermal Field, in mg/kg.
pH Li Na K Rb Cs Mg Ca B H(:O3 SiO2 SO4 Cl réf.
wells, weirbox samples

Z3 8.1 8.70 933 231.0 2.33 2 .02 .012 15 40.0 51 951 31 1810 a
Z6 8.4 8.10 1028212.0 1.89 2 .01 .040 11 45.0 157 889 61 1700 a
ZU 7.8 6.31 1092 101.0 0.55 2.26 .070 30 50.8 41 580 105 1740 a
Chloride springs
cl 9.0 2.70 545 51.1 - 0.3 7 26.2 96 404 210 728 c
C2 8.3 6.05 788 33.9 0.39 1 .35 0.2 48 34.2 32 396 115 1236 a
Bicarbonate waters
Bl 9.2 0.13 79 7.4 0.02 .003 11.6 22 0.7 79 160 64 31 a
B2 7.0 0.18 65 10.0 0.02 .012 5.4 11 1.3 140 132 22 57 b
B3 7.0 0.28 166 12.2 0.03 .027 5.9 17 2.8 259 138 103 101 b
B4 8.4 0.37 199 18.6 0.05 .037 18.1 25 3.4 340 161 129 114 a
B5 7.8 0.56 286 37.2 0.07 .030 36.2 42 4.7 463 194 210 180 a
B6 8.7 0.56 372 36.6 0.07 .022 40.5
41 4.7 491 196 194 163 a
B7 8.7 0.57 258 27.3 0.08 .025 45.2 43 4.6 501 200 193 168 a
B8 6.1 0.91 157 19.0 0.09 .019 30.8 18 2.5 503 146 235 71 b
sulfate water AI
SI 2.1 0.12 43 14.5 0.04 .009 18.9 76 0.2 7 242 117 15 b
S2 3.1 0.08 80 7.7 0.04 .009 45.0104 <.l 42 292 633 10 b
S3 2.1 0.05 89 30.9 0.11 .004 14.6 43 1.8 59 209 1600 7 a
S4 2.0 0.07 134 32.3 0.23 .010 28.3 72 1.7 39 287 2060 8 a
surface waters HCO3

Rl 7.0 <.01 9 4.4 0.01 .002 5.6 9 0.3 74 28 15 b
R2 7.1 <.01 8 3.3 «c.Ol < .01 3.8 8 <.l 69 52 56 15 b
R3 6.1 <.01 16 5.9 0.01 < .01 3.6 7 0.2 38 22 18 20 b
solution of average crustal rock (10 g/kg of water)

AR 0.30 240 210.0 1.50 0 .04 230.0 420 0.12 2 d
a.- DSIR C.- INDE (1984)

b.- pH, HCO3, SO4, Cl by INDE d.- Taylor (1964)
248
NW
chloride wate
bicarbonate w.
sulfate waters
fumaroles
proposed drill sites
Fig. l - Sketch map of Zunil Geothermal Field showing positions of collection points
for water and steam samples, the inferred flow of deep fluids (arrows) and the
suggested position of drillsites.
mg/kg. An initial classification of the waters, on the basis of relative Cl, SO^ and
HCC>3 contents is carried out in Fig. 2. The samples belong to three distinct groups:
The first group consists of chloride waters discharged from the three wells (Z3, Z6,
Zll), the only natural high chloride spring Z-20 (Cl), and an abandoned exploration
well, ZP-6 (C2),
The second group covers all the neutral bicarbonate springs along Rio Samalà (Bl to
B8) and also includes the much less mineralised waters of rivers entering (RI, R2)
and leaving the thermal area.
249
neutralised
deep
/water
HCO:
Fig. 2 - Relative Cl, 804 and HCO-j contents of waters from the Zunil Geothermal
System.
The third group is made up of acid, high sulfate waters. Samples SI and S2 represent
boiling, evidently steam-heated pools. Waters S3 and S4, discharged from over the
slopes of Dome El Azufral, have considerably higher sulfate contents, but are well
below boiling.
There appears to be very little mixing among the three groups of waters. Cl and C2
are to a minor degree affected by possible admixture of a high sulfate water. The
waters from the central group of bicarbonate springs, B3 to B7, form a tight
cluster,those farther to the north, Bl and B2, show deviations to higher and lower
804 contents respectively. The trend described by these data points may be
interpreted in terms of mixing of sulfate waters with a hypothetical bicarbonate-
chloride water possibly resulting from direct partial or complete conversion of the
CC»2 in the deep Cl waters to HCO3.
250
B8 at the southern end of the thermal area has lower Cl contents. Together with the
other HCOj springs it may delineate another trend corresponding to mixing of deep
Cl waters, as represented by the wells, with a low Cl, sulfate-bicarbonate water
possibly formed through underground absorption of CC^ rich vapors into local
groundwater. The composition of the river waters, R2 and R3, is likely to reflect
admixture of minor proportions of HCO^ waters. The existence of three distinct
groups of waters is likely to reflect three distinct environments of water-rock
interaction and three distinct degrees of attainment of water-rock equilibrium.
The interaction of fluids within hydrothermal systems with close volcanic-magmatic

associations can be evaluated in terms of two endmember processes: initial rock
dissolution adding cationic components in proportions close to those in the original
rock, and eventual rock equilibration with minerals thermodynamically stable over the
major water-rock equilibration zones within the system (Giggenbach, 1988). An initial
evaluation of the Zunil waters in terms of these processes is carried out in Fig. 3 on
the basis of relative Na, K, Mg and Ca contents. The two deep well discharges (Z3,
Z6) plot close to the rock equilibrium line at temperatures close to those measured,
the more shallow well Zll at a correspondingly lower temperature. The water
discharged from the abandoned exploration well reflects water-rock equilibrium at
considerably lower temperatures, ~18(to that from the only natural high C] spring C1
the effects of admixture of the more shallow bicarbonate waters. Extrapolation onto
the full equilibrium line suggests a temperature close to that of Zll.
Assuming relative Na, K contents of the HCOj springs to reflect those of deeper
equilibration, temperatures of 220 to 240°C are indicated. Their highly increased Mg
contents point to extensive interaction with rock at lower temperatures (Giggenbach,
1988). The data points for both river waters and acid sulfate springs approach the
composition expected for rock dissolution. Again all three groups are well separated
suggesting distinctly different formation conditions.
251
10 Mg
l t
R 3 rivers
0-8
S3
rock
HCO3 - waters acid ËJ dissolution
waters
0-6-
Na 10K
0-4 -
0-2-
wa ter-
rock
equilibrium
0-2 0-4 0-6 0-8
Ça
Fig. 3 - Plot of 10cMg/(10cMg + cCa) versus 10cK/(10cK + cNa) (in mg/kg) for
water discharges from the Zunil geothermal Field.
Other techniques to evaluate water-rock equilibration temperatures are based on
dissolved silica and relative K, Mg contents. Corresponding temperatures may be

obtained by use of the relationships (Giggenbach, 1988)
ts = (1000/(4.55 - log csi02)) - 273 (1)

and tkm = (44107(14 - log(c^/cMg)) - 273 (2)
where the temperatures t are in °C and Cj are the concentrations of SiO2, K and Mg
in mg/kg. In Fig. 4 a line is shown for ts = t^m. For the three well discharges, both
temperatures are very similar, again close to those measured suggesting attainment of
full equilibrium among the waters and a mineral assemblage containing Na and K
feldspars, chlorite, a CaA^-silicate and chalcedony.
252
50 tfcn, (°C) 100 150 200 250 300
-300
U
2.!
2.0-
1.5-
50
0 1 2 3 4 5 6 Lkm
Fig. 4 - Evaluation of silica, ts, and K-Mg, tj^, temperatures .
The two surface samples of Cl waters, Cl and C2, plot above this line possibly
indicating equilibration with a more soluble polymorph of silica or quenching of
higher chalcedony equilibration temperatures, 240°C. The differences between ts and
tfcm are even more

pronounced in the case of the HCC«3 and 804 waters. Their data
points plot close to the line representing the most soluble silica polymorph,
amorphous silica. In this case, equilibration temperatures for both silica and K-Mg are
close to those measured in the surface pools (—70°).
Many of the solution components depicted in Figs 2 and 3, such as HCO^, 804, Mg
and Ca, are greatly affected by shallow processes. In order to obtain information on
deeper processes and to establish possible genetic links among the various types of
waters, relationships among the more "conservative" constituents such as Cl, B, Li, Rb
and Cs are investigated in Figs. 5 and 6. Relative Cl, B and Li contents confirm the
253
Cl/10
.01
02
03
.05
B/CI
.10
B 1O Ll
Fig. 5 - Relative Cl, B and Li contents of water dischatges from the Zunil Geothermal Field.
Li/10
Rb/4 Cs
Fig. 6 - Relative Li, Rb and Cs contents in waters from the Zunil Geothermal Field.
254
close relationship between Cl and HCOß waters as already proposed by Bethancourt
and Dominco (1982) an the basis of B/C1 ratios. The two groups of sulfate waters
occupy distinct positions. The low B content of the two obviously steam heated pools
SI and S2 is likely to reflect the low B content of the comparatively low temperature
steam injected. The position of the acid waters S3 and S4 suggests interaction with a
much more B enriched, probably much higher temperature vapor at greater depth.
There is no obvious genetic relationship between the 804 and the Cl-HCO^ waters.
The overall pattern is confirmed by reative Li, Rb and Cs contents shown in Fig. 6.
Again, 804 waters occupy positions approaching that of dissolved rock suggesting
much of their solute contents to be derived from straightforward rock dissolution. The
Cl, HCC>3 waters desribe a trend corresponding to removal of Cs from the deep Cl
waters at close to constant Li/Rb ratios. The most likely process giving rise to this
pattern is incorporation of Cs into secondary zeolites at lower temperatures (Goguel,
1983). The degree of Cs removal, therefore, may reflect variations in the distance
travelled by the waters. Accepting this explanation, Waters B3 and B4 have travelled
the shortest distance or are closest to the major flow path of the thermal waters, Bl
and B8 are likely to represent waters having moved farthest or having resided
underground longest.
According to this evaluation, the natural upflow of thermal waters is centered on the
area represented by springs B3 and B4, with the waters approachig the valley floor
either from the NW or SE, but probably not from the SW or NE. Relative Cl, B, Li,
Rb and Cs contents of the Zunil waters point to the existence of a common parent
water for both Cl and HCOß waters. Information on the origin of this deep water may
possibly be obtained from their isotopic compositions.
255
ISOTOPIC COMPOSITION OF WATERS AND STEAM
The isotopic composition together with sampling dates and temperatures, tritium and
Cl and SÛ4 contents of the samples listed in Table 1 are given in Table 2. The
isotopic composition of steam discharges, together with the 6^S and mole fraction of
F^S are given in Table 4. Isotopic relationships among the samples are best discussed
on the basis of Figs. 7A and B.
Table 2.- Isotopic compositions (%o) and tritium (TU), Cl and 804 contents (mg/kg) of
well and spring discharges from the Zunil Geothermal Field.
INDE date temp. 5 180 62H 3

H Cl SO4 ref
wells (total discharge)

Z3 ZCQ-3 09 .85 260 -8 .74 -79 .3 1.3 1140 20 a
Z6 ZCQ-6 09 .85 280 -8 .36 -75 .9 1.3 1070 38 a
Zll Z-ll 08 .87 250 -7 .25 -70 .1 992 60 b
chloride springs
Cl Z-20 01 .80 93 -8 .20 - 1.1 700 202 c
C2 ZP-6 11 .88 93 -7 .22 -74 .2 1236 115 b
bicarbonate waters
Bl Z-23 08 .87 40 -11 .89 -85 .2 1.1 31 64 b
B2 Z-29 06 .86 50 -10 .38 -77 .0 1.2 57 22 a
B3 Z-4 06 .86 63 -10 .75 -79 .7 0.0 101 103 a
B4 Z-9 07 .87 62 -11 .39 -77 .5 4 129 b
B5 Z-17 07 .87 70 -11 .30 -83 .3 1.1 180 210 b
B6 Z-10 07 .87 67 -11 .89 -84 .1 0.3 163 194 b
B7 Z-13 07 .87 87 -11 .54 -84 .7 168 193 b
B8 Z-15 06 .86 64 -11 .05 -82 .4 3.2 71 235 a
sulfate waters
SI ZF-38 06 .86 91 -7 .25 -70 .6 15 117 a
S2 Z-36 06 .86 90 -7 .58 -67 .4 10 633 a
S3 Z-19 08 .87 56 -9 .38 -75 .8 7 1600 b
S4 Z-31 08 .87 74 -10 .02 -80 .7 8 2060 b
surface waters
Rl ZR-1A 06 .86 18 -11 .64 -84 .7 15 - a
R2 ZR-2A 06 .86 16 -12 .23 -85 .7 15 56 a
R3 ZR-16 06 .86 18 -12 .22 -85 .4 20 18 a
R4 rain 06 .86 - -8 .47 -55 .3 4.8 - - a
a.- IAEA b.- DSIR c.- Fournier and Hanshaw (1981)
256
-60-
-80-
&2H
-80-
-100'
-14 -12 -10 S180(%0) -8
Fig. 7 - The isotopic composition of waters (A) and steam condensâtes (B) from the
Zunil Geothermal Field. In Fig. 7A a line is shown representing the
composition of residual waters after single step steam separation at a given

temperature, in Fig. 7B the compositional area of steam having separated
from the deep chloride, DW, or the more shallow bicarbonate (SW) waters
or their mixtures.
Data points for the HCO^ waters plot close to the meteoric water line suggesting that
they are largely made up of local groundwater. By assuming the river waters to be
most representative of this local groundwater, its composition is represented by point

LG. Most of the bicarbonale waters, however, are isotopically considerably "heavier"
possibly pointing to the existence of a distinct type of shallow thermal water, its
isotopic composition, SW, is taken to correspond to the mean of all bicarbonate
waters.
257
The two deep well discharges, Z3 and Z6, show increased 18O contents. Such 18O-
shifts are generally explained in terms of water-rock isotope exchange (Craig, 1963).
Recent findings on water and vapor discharges from hydrothermal and volcanic
systems along convergent plate boundaries, however, suggested that much of this
"oxygen shift" may be due to admixture of a so-called "andesitic" water with 6180 Qc
f\
+ 10±2%o and 6ZH of -20±10%o . In this case their should also be some "deuterium
shift". Comparing the isotopic compositions of the two deep well discharges and that
of the range of possible groundwaters as represented by the bicarbonate springs and
the river waters, there appears to be indeed a ^H enrichment in the well discharges.
The isotopic composition of the deep Cl water, DW, is assumed to correspond to the
mean of the two well waters. Before discussing possible admixture of a magmatic
water further, an attempt is made to interpret the isotopic composition of the
remainder of the samples.
Again the two groups of acid sulfate waters occupy distinct positions. The two steam-
heated pools, SI and S2, show clearly the effects of isotopic enrichment due to surface
evaporation (Giggenbach and Stewart, 1982). The much higher 804 contents of S3
and S4 are not accompanied by higher isotopic enrichment suggesting that they are
probaby formed through absorption of S-rich vapors undergound. The composition of

the two lower temperature Cl waters, C2 and Z11, would be in agreement with
possible isotopic enrichment due to vapor loss as indicated by the line marked "steam
separation".
The isotopic composition of fumarolic vapors and the effects of vapor separation
processes are discussed by use of Fig. 7B. Two of the fumaroles were re-sampled
about one year apart, their isotopic compositions are quite different. For both Paxmux
(PX) and Fumarola Negra (FN), the 1988 samples appear to be isotopically conside-
rably depleted compared to the 1987 samples. All five data points including that of
the fumarolic area of Las Fresas to the west, however, fit into an area delineated by
258
the theoretical composition of vapors possibly produced from the deep Cl water, DW,
or the shallow water (SW), representing the HCO^ waters, or their mixtures. The
vapor at Las Fresas is most likely separated from the deep Cl water at a temperature
of around 200 °C. The compositions of the 1987 samples from Paxmux and Fumarola
Negra suggest derivation from an intermediate water, between DW and SW, the 1988
samples from SW only at quite low temperatures of about 140°C. The shift in isotopic
composition for these two vents from 1987 to 1988 may reflect differences in rainfall
giving rise to differences in the underground distribution and temperatures of the feed
waters.
The isotopic compositions of the vapor from the "dry" well ZCQ-5 (Z5) and from the
Azufrales area on Domo El Azufral (Fig. 1), are close to that of D W and therefore
show also both an 1°O and ^H shift. The similar isotopic compositions of the Azufral
vapor and of the well discharges suggests that they are derived from a common, high
temperature parent water and that the body of this parent water extends from the
main drilling area, to the west of Samalâ River, to well underneath Domo el Azufral.
According to Fig. 7A, the isotopic composition of samples Zll and C2 may be
explained in terms of isotopic enrichment due to underground vapor loss. A check as
to the validity of this conclusion can be made by use of Fig. 8 taking into account
variations in Cl contents with those in the isotopic composition of the waters. The Cl
content of the deep water is again assumed to be that of the mean of the total
••}
discharge compositions of the two deep wells of 1100 mg/kg. In the case of ZH
contents, the position of sample C2 corresponds to that of the residual water after
steam separation from DW at temperatures close to 210°C. The increased ^H content
at a reduced Cl content of sample Zll suggests that its composition is due to a
process other than simple steam loss from DW.
This conclusion is supported by the position of data points in Fig. 8B. None of the
more shallow Cl waters lies along the line representing steam separation from DW.
259
-60-
4OO 80O 120O Cl (mg/kg)
Fig. 8 - Deuterium and oxygen-18 contents versus Cl contents. Lines indicatind thé
effects of dilution and steam loss on deep water DW are shown.
1S
All three show considerable enrichment in 10 O at Cl contents too low to be
compatible with simple single step underground steam separation. Their compositions
are likely to reflect, in addition to steam separation, the effects of surface evaporation
or mixing with shallow waters, other than local groundwater LG, but resembling SI
and S2. A similar mixing process is likely to be responsible for the variability in the
isotopic composition of the bicarbonate waters.
As pointed out above, the increased 1°O and ^H contents of the deep well waters
with respect to the isotopic composition of local groundwater LG, may be explained in
18
therms of the admixture of a magmatic, in this case "andesitic" vapor with 610O of
260
around +10%o and 52H of about -20%o (Giggenbach, 1991). The derivation of the Zunil
waters from an "andesitic" water is evaluated by use of Fig. 9. Again assuming the
composition of local groundwater to be represented by LG, any admixture of an
"andesitic" water is described in terms of three lines representing the likely range of
compositions. The data point for DW falls within the expected range, as do those for
Zll and C2, and even those of the highly immature sulfate waters S3 and S4. The
isotopic compositions of all these waters would therefore be compatible with
formation through absorption of an andesitic vapor into local groundwater.
Fig. 9 also contains lines representing the possible fractions xa of andesitic water
involved in the formation of a thermal water. They may also be calculated by use of
the relationship
- 6m)
where the subscripts refer to the isotopic composition of the andesitic water (a), of
the thermal discharge sampled (d) and of the local meteoric water (m). For DW a
value of close to 0.2 is obtained implying that 20% of the water is of andesitic,
62H
-5O-
-100-
-10 -5 0 &18O Woo) 10
Fig. 9 - Derivation of Zunil geothermal waters through mixing of local groundwater,
LG, with "andesitic" water.
261
magmatic origin (Giggenbach, 1991). Assuming all the Cl to have been introduced
with the andesitic vapor, its Cl content is 1100/0.2 = 5500 mg/kg or 0.55% by weight.
ISOTOPIC COMPOSITION OF SULFUR SPECIES
The isotopic composition of sulfur species present in geothermal discharges can be

expected to provide additional information on the origin of the fluids and on the
conditions over the deeper parts of the system. The S contents of H^S in steam
samples are given in Table 3, the ™s and *°O contents in dissolved sulfate in Table
4. Possible correlations are discussed by use of Fig. 10.
Table 3.- Isotopic composition (in %o) and mol-fraction (Xj_j § in pmol/mol) and 6-^S
(in %o) of H2§ in steam condensâtes from the Zunil Geothermal Field.
date °C 6180H2O 62HH 0 X

H2S
634SR
2 2S
25 ZCQ-5 09 .85 170 -8.66 -75 .0 90 -

C2 ZP-6 11 .88 93 - - 28 -1. 6
LF Las Fresas 08 .87 94 -11 .5 -83 .6 257 -0. 8
PX Paxmux 08 .87 93 -12 .3 -82 .9 260 -0.4
PX it
11 .88 93 -14 .0 -94 .2 273 -5. 1
FN Fum. Negra 08 .87 94 -12 .9 -94 .0 178 + 0.1
FN n 11 .88 93 -14 .1 -97 .4 196 -1. 8
AZ Azuf rales 08 .87 91 - - 802 -0. 1
AZ " 11 .88 81 -9 .1 -83 .7 1143 """ J. •7
Table 4.- Sulfur-34 and oxygen-18 content of dissolved SO^ together with oxygen-18
content (%o) and 804 and Cl contents (mg/kg) of associated waters.
date ST so4 ci 634S 6180

°C (mg/kg) H2S S04 SO4 H2O
Zll 08.87 144 60 992 +3.6 +15.8 + 4.3 -7.3

B4 07.87 62 129 4 +7.6 +4.0 -11.4
B5 07.87 70 210 180 +8.6 +4.4 -11.3
B6 07.87 67 194 163 +9.7 +6.1 -11.9
B7 07.87 87 193 168 +8.9 +5.9 -11.5
S3 08.87 56 1600 7 +0.9 + 13.0 -9.4
S4 08.87 74 2060 8 +0.7 +9.5 -10.0
262
<518o S0
4
-10 -5 -5 0
518oHO(°/o«,)
Fig. 10 - Oxygen-18 contents in dissolved sulfate and waters (A) and sulfur-34
contents in dissolved sulfate and I^S (B) of Zunil geothermal fluid
discharges.
The isotherms shown in Fig. 10A are based on the temperature dependent
fractionation of 1°O between water and sulfate as determined by Lloyd (1968) and
Mizutani and Rafter (1969) according to
A
S04-H20 * looolnaS04-H20 = (3 °65 S00^2) - 4-9 (4)
where T is in K. For the two acid waters, S3 and S4, attainment of equilibrium is
indicated at temperatures close to those measured, a process greatly facilitated
by the low pH of the waters. The trend observed for the bicarbonate springs suggests
an increase in 1"O equilibration temperatures from just below 100° for the two
southern samples, B6 and B7, to 110 to 120°C for the two more northern samples, B4
and B5. This minor trend may reflect an actual difference in equilibrium
temperatures, but also differences in the residence time of the waters underground.
263
For the shallow well Zll a temperature of 155° is suggested if the total discharge
1°O content is used, 180° if that of the separated water is used. Both are, for
unknown reasons, below that measured of 250° (Table 2). Residence times of the
waters within the Zunil geothermal system are obviously long enough to allow 1°O in
sulfate to adjust to quite low temperatures.
A much "slower" process is 34S exchange between SO4 and H2S. Accepting the
isotopic composition of H2S within much of the Zunil system to be close to the range
of about -2 to 0%o, as observed for the fumarole discharges, apparent equilibration
temperatures may be evaluated by use of
A
S04-H2S ~ 100°lnS04-H2S = (6 04° ° 0 0 ^) + 2-16 (4)
as reported by Robinson (1973).
Both the two acid sulfate waters were collected from springs on the slopes of Domo
El Azufral. The most closely related discharge of H2S is likely to be that from the
Azufral fumaroles. Their 6 S values are within the range observed for the other
vapor condensâtes. By use of a value of -l%o for H2S, exceedingly high temperatures of
>1000°C are obtained for S3 and S4. The very low isotopic fractionation suggests that
formation of sulfate from a sulfur containing vapor proceeded under conditions
preventing attainment of equilibrium even for these acid waters. Such conditions are
likely to prevail over parts of the system were the originally magmatic, or "andesitic",
vapors first interact with groundwater. These vapors would contain much of their
sulfur in the form of SO2. In this case the acid sulfate waters form through
disproportionation of SO2 according to
4 SO2 + 4 H2O = 3 H2SO4 + H2S (5)
If the H2S and H2SO4 are separated shortly after their formation, the ™s content of
the sulfate may still reflect that of the original magmatic gas of around 0 to + l%o.
264
Sulfur-34 equilibration temperatures for the bicarbonate waters are also unrealistically
high, the shift to higher ^S values, however, would point to some equilibration.
The composition of sample Zll suggests reasonable equilibration temperatures of

350° if a value of -l%o is accepted for the l^S, 500° if equilibrium with coexisting Ir^S
(+3.6%o, Table 4) is assumed. Both temperatures are very high but may reflect the
occurrence of such temperatures deeper within the Zunil hydrothermal system.
The 34s content of 804 in the two acid waters S3 and S4 points to their formation
under conditions preventing even minor re-equilibration with I^S. Such conditions
are likely to occur if the zones of conversion of magmatic to hydrothermal fluids lie at
shallow levels. The isotopic compositions of sulfur species in fluids from the Zunil
geothermal field, therefore, strongly suggest that initial interaction of magmatic vapors
with groundwater takes place within Domo el Azufral structure. On moving away
from these zones the initially highly immature waters are converted to neutral chloride
waters as encountered in deep wells and lateron to more dilute bicarbonate waters
discharged from surface springs.
CHEMICAL COMPOSITION OF VAPOR DISCHARGES
The chemical compositions of steam samples from the Zunil Geothermal Field are
given in Table 5 together with typical analyses from other fields in Guatemala for
comparison. The samples were collected and analysed by use of procedures described
by Giggenbach and Goguel (1989). For the 1987 samples from Paxmux and Fumarola
Negra (Table 3) only data for the gases absorbed into the alkaline condensate are
given.
An initial assessment of the possible origin of the gases is carried out in Fig. 11 on the
basis of relative N2, He and Ar contents. The samples from Zunil, representing a
wide variety of steam discharges from wells (Z3, Z5, Z6, Zll) and fumaroles (LF, PX,
FN, AZ) still cover quite a limited range halfway between the composition of
265
K)
Os
Table 5.- Composition of vapor discharcjes fr om the Zunil Geotherma 1 Fiela, in ^mol /mol .
Os
°C ys H2° co2 H2S NH3 He Ne H2 Ar °2 N

2 CH4
wells
Z3 260 .30 997 700 2192 67 5.2 .0060 .00018 13.10 0.14 <.2 23 0.58
Z5 280 1.0 997 200 2691 90 4.0 .0059 .00014 12.30 0.08 <.2 11 0.39
Z6 280 .34 997 200 2682 56 5.1 .0056 .00039 11.90 0.25 <.3 36 0.67
Zll 250 .43 996 900 2994 43 3.1 .0040 .00040 12.31 0.28 <.3 46 1.02
fumaroles
C2 93 1.0 998 710 1230 28 6.5 .0061 .00051 1.31 0.30 0.6 33 0.44
LF 94 1.0 995 800 3797 257 1.3 .0206 .00118 40.65 0.76 <.2 101 2.77
PX 93 1.0 990 800 8942 260 0.3 - - - - - -
PX 94 1.0 989 120 10215 273 <.l .0534 .00330 3.60 2.94 <.9 389 20.00
FN 94 1.0 996 200 3620 178 0.3 - - - - - -
FN 93 1.0 994 500 5120 196 <.l .0248 .00121 35.40 1.10 0.8 139 6.98
AZ 91 1.0 994 200 4843 802 0.3 .0296 .00116 0.46 0.70 <.3 151 0.46
AZ 81 1.0 992 505 6165 1143 0.6 .0353 .00053 0.38 0.60 <.9 186 0.98
San Marcos
SM 93 1.0 998 700 1150 83 0.6 .0051 .00013 0.35 0.90 <.l 60 0.20
Tecuamburro
TA 95 1.0 956 000 36740 5764 0.7 .1280 .01230 0.44 6.60 <.4 1480 3.52
Amatitlân
LC 95 1.0 944 900 54300 110 7.7 .3700 .00055 14.30 0.11 606 19.3
Moyuta
MC 97 1.0 994 400 5387 44 <.l .0235 .00039 6.90 0.45 <.6 162 0.05
N2/100
air
air saturated
water
10He
Fig. 11 - Relative N2, He and Ar contents in gases from the Zunil Geothermal System.
meteoric gases (air, air saturated water) and "andesitic" gases as defined on the basis
of a large number of volcanic gases from around the world (Giggenbach, unpublished
results). The similarity in relative N£, He and Ar contents supports a common origin
of the gases within the Zunil system. The compositions of the gases from the San
Marcos (SM), Tecuamburro (TA) and Moyuta (MC) geothermal fields follow this
trend, typical of geothermal systems along convergent plate boundaries, that from
Amatitlan (LA) shows a somewhat increased He content.
Relative contents of the three quantitatively most important constituents of

geothermal vapors, Ô, CC>2 and ^S are shown in Fig. 12. Except for Paxmux,
data points for the Zunil field lie along a line indicating large variations in ^S
contents at close to constant CC>2 contents of about 0.3 mol-%. Well discharges and
C2, SM and MC show the lowest ^S content, the two low altitude fumaroles FN and
PX occupy intermediate positions, the highest relative ^S content is found for the
267
H2O/100
0-1
"/„CO
30H2S
5 CO2 /H 2 S
Fig. 12 - Relative HÔ, CC^ and H2S contents in vapor discharges from Zunil.
sulfur depositing vent at Azufrales. The high I-^S content there corresponds to that of
similar S-depositing vents at Tecuamburro (TA). The repeat samples from Zunil
occupy very similar positions suggesting no major changes in the chemistry of these
gases over the period from August 1987 to November 1988.
The major causes of variations in CC^/I^S ratios of geothermal steam discharges are
differences in the solubility of the two gases, I-^S being three times as soluble as CC>2
(Giggenbach, 1980). Vapors boiling off from a deep liquid phase, therefore, are
initially enriched in CC^, the residual solution becoming enriched in IH^S. The wells
then are likely to tap little degassed water having travelled deeply without much
opportunity to lose gas. The fumaroles discharge vapors from probably more shallow
bodies of already degassed water. The validity of this assumption may be checked by
including a gas with an even higher solubilty contrast, such as
268
Because of its very low solubility, CH^ contents can be expected to be highest in
"early" vapors, very low in vapors from already degassed bodies of water. Relative
CH4, CC>2 and I^S contents are plotted in Fig. 13 together with lines representing
the composition of vapors and residual fluids formed on removal of the fraction of
steam, y, at 150° and 300°C from a an original deep water with a composition close
that of the wells Z3, Z6 and Zll. The theoretical lines were calculated for closed
system, single step steam separation. The effects of temperature on the relative
position of the "early" and "late" steam separation lines are obviously quite small.
Separation of even very minor fractions of vapor, however, leads to marked shifts in
relative gas contents, especially at lower temperatures. Contrary to the findings

suggested by Fig. 12, PX and FN appear to represent very "early" vapor carrying much
of the little soluble CH^ while the vapor from Z5 is possibly derived from a body of
5000CH4
250
300
L
MC
350'
400'
\
30HoS
30 20 10
10 5 C0 2 /H 2 S
Fig. 13 - Relative CH^ CC>2 and H^S contents of Zunil vapor discharges. Lines are
shown illustrating the effects of vapor separation from the deep water DW, as
a function of y, the fraction of steam removed, in %, at 150° and 300°C.
269
water having lost a few percent of vapor. The composition of vapors from the
Azufrales fumarole may indicate derivation from an extensively degassed deep water.
The above evaluation, of course, assumes that all the vapor samples are derived from
a common body of deep water with a uniform composition. There are however a
series of other processes which could have affected relative CH^ CC>2 and ^S
contents. One of the most obvious is re-equilibration of CH4/CÜ2 ratios in response
to variations in temperature. Variations in this ratio are indicated in Fig. 13 in terms
of isotherms calculated by use of
tMC = (46257(10.4 + log(xCH4/xCo2))) -273 (6)
where tjyjc is the temperature for equilibrium of CH4 and CO2 with crustal rock
(Giggenbach and Goguel, 1989). According to this interpretation, the two gases in the
three wells (Z3, Z6 and Zll) and in C2 equilibrated at about 340°. The apparently
higher temperature derived for Z5 is probably due to some earlier underground steam
loss, while the temperatures of 360 to 380° for the steam discharged from vents on
top of Domo El Azufral (AZ) may be indeed those in deeper zones. The lower
temperatures of 270 to 300° indicated for PX, FN and LF may reflect equilibration in
more shallow, cooler zones of the system.
Additional gas phase equilibration temperatures may be obtained by use of recently

derived relationships (Giggenbach and Goguel, 1989)
lo
g(xH2/xAr) =
°-014t - 2-5 (7)
and
log(xco /XAT) = 0.0277t - 7.53 + 2048/(t + 273) (8)
where Xj are again the mole fractions as given in Table 5 and t is the temperature in
°C. In Fig. 14 a line is shown representing equilibrium for both H2 and CC>2 in a
single liquid and a single vapor phase. Tie lines represent equilibrium mixtures of
liquid and fluid.
270
equilibrium vapor
L
-HA HA=
1 '
0-
-1-
L CA =log(x c02 /x Ar )
1 2 3 4 5 . 6L
CA
Fig. 14 - Evaluation of temperatures of H2 and CC>2 equilibration with rock. Lines are
shown for attainment of equilibrium of the gases dissolved in a single liquid
and in a single vapor phase.
All the data points for the wells and for some of the steam vents (LF, FN) plot close
to the full equilibrium line at temperatures between 250 and 300°C. For the more
outlying vapor discharges (C2, PX), H2-Ar temperatures are below CO2-Ar
temperatures possibly reflecting the different rates of equilibration of the two gases
with H2 being considerably "faster" than CO2 (Giggenbach, 1987). Apparent H2/Ar
and CO2/Ar temperatures for the fumaroles are lower than those of the deep wells
suggesting long residence times at lower temperatures, in agreement with CH4/CO2
temperatures (Fig. 13).
Table 6 gives the hydrocarbon contents xj of the Guatemalan thermal vapor

discharges. The mole fractions given may be converted to total discharge mol-fractions
Xj, in nmol/mol, according to
X
i = vs XCH4 xi (9)
where ys and XCH are the steam fractions and CH4 contents given in Table 5.
271
Table 6.- Hydrocarbon contents of geothermal gases in Guatemala, in mmol/mol of
the hydrocarbon fraction.
met ete eta pre pra ibu nbu ipa npa ben toi ebe pmx o-x
Z3 969 4.0 8.8 1.4 1.5 0.2 1.2 0.8 1.5 3.9 1.5 0.9 1.0 0.8
Z5 980 1.4 4.6 0.4 0.8 0.3 0.8 1.0 1.2 4.0 0.9 0.7 0.9 0.7
Z6 978 1.1 8.5 0.8 1.2 0.2 0.6 0.4 0.7 3.7 0.5 0.3 0.4 0.4
Zll 535 <.5 5.2 <.5 0.7 <.5 <.5 <. 5 <.5 3.8 42 135 219 57
C2 349 1.1 7.2 <.5 1.5 <.5 <.5 <.5 <.5 6.5 70 225 215 59
LF 988 <.3 2.7 0.4 <.3 <.3 <.3 <.3 <.3 1.3 0.5 1.4 2.5 0.8
PX 993 .02 4.3 .01 1.0 0.2 0.2 .05 .05 1.0 .08 .03 .07 .02
FN 990 < . 0 2 4.1 < . 0 2 0.9 0.2 .25 .06 .14 2.1 .40 .78 .93 .31
AZ 970 <.5 3.1 <.5 <.5 <.5 <.5 <.5 <.5 2.0 1.7 7.8 11 3.9
AZ 841 <1 <.5 <.5 <.5 <.5 <.5 <.5 <.5 3.1 17 42 55 17
San Marcos
SM 950 0.5 3.2 0.7 1.1 <.8 <.8 1.3 1.5 1.4 1.5 4.2 2.7 2.5
Tecuamburro
TA 707 2.9 2.5 0.4 0.3 <.2 <.2 <.2 <.2 4.8 39 90 108 36
Amatitlan
LC 940 <.5 3 0 . 8 <.5 7.6 0.9 1.9 0.5 0.5 13.6 1.4 1.8 1.3 1.2
Moyuta
MC 910 3.2 5.6 <.5 2.1 0.7 <.5 <.5 <.5 3 8 . 3 7.9 9.3 16 4.0
met: methane pre: propene nbu: n-butane ben: benzene pmx: p+m-xylene
ete: ethene pra: propane ipa: i-pentane toi: toluene o-x: o-xylene
eta: ethane ibu: i-butane npa: n-pentane ebe: ethyl benzene
Hydrocarbons in geothermal vapor discharges are largely derived from the

decomposition of sedimentary organic material subjected to increased, up to magmatic
temperatures. The presence of unsaturated and aromatic hydrocarbons in the Zunil
well discharges points to the existence of very high temperatures (<500°C) of
interaction with sedimentary material (Giggenbach, unpubl. results).
Because of their higher solubility in water, aromatic hydrocarbons tend to accumulate

in residual waters, again allowing the differentiation between "early" and "late" vapors.
The very low contents of aromatic hydrocarbons in PX and FN, and possibly LF,
agrees with their position in the "early" vapor part of Fig. 13. Similar low contents in
the deep wells, Z3, Z5, Z6, would also classify them as "early" vapors. The extremely
272
high contents of aromatic hydrocarbons in the more shallow Cl water discharges Zll
and C2 can only be explained in terms of possible enrichment from percolating vapors
without affecting much relative CH^ Œ>2 and IH^S contents. The comparatively high
contents in samples from Azufral, AZ, agrees with their possible "late" nature as
already indicated by Fig. 13. Generally speaking, the hydrocarbon contents of all the
Guatemalan vapors are those expected for geothermal systems closely associated with
volcanic-magmatic systems.
The chemistry of gases associated with fluid discharges fom the Zunil Geothermal
Field suggests an essentially magmatic, or more specific "andesitic" origin. Gas
equilibration temperatures are close to those measured in the wells or higher pointing
to the possible presence of higher temperature zones within the system.
GEOCHEMICAL MODEL OF THE ZUNIL GEOTHERMAL SYSTEM
The evolution of fluids with close volcanic-magmatic associations generally proceeds

along the sequence magmatic vapor - acid chloride - msulfate waters - neutral
chloride water - bicarbonate water. Accepting this general pattern also for Zunil, both
chemical and isotope evidence clearly show that the first step, the conversion of
magmatic vapors to acid waters occurs within the andesitic structures of Domo El
Azufral and Cerro Zunil, to the SW of the discharge area. The next step, the
conversion of the initial acid waters takes place during further movement of the
waters to the north and west.
The driving force behind the upward movement of thermal waters is the buoyancy
caused by the density difference between hot thermal and surrounding groundwater.
The level to which the waters are able to rise is determined by the static groundwater
level. In the case of Zunil it is likely to be defined by the level od the Samalâ river.
Any water rising within the El Azufral - Cerro Zunil Complex will spread out to reach
the surface at the nearest hydrological low, the bed of the Samalâ River. Steam may
273
boil off from the spreading tongues of hot water as they approach the surface to
reach the surface as fumaroles or steaming ground. Vapors generally rise close to
verticallty thus marking the epicenters of deeper boiling zones.
Relative HCG^/Cl ratios of the bicarbonate waters correspond closely to CC^/Cl

ratios in the waters supplying the deep wells. The HCC>3 waters, representing most of
the natural thermal water discharge from the Zunil Geothermal Field, then are most
likely to have formed through virtually quantitative conversion of CC>2 to HCOß by
interaction with rock preceding or following about tenfold dilution with groundwater
The incresased sulfate content of these waters may be due to admixture of some of
the immature acid sulfate waters (S3, S4) at shallow levels or incomplete "maturation"
of the more primitive, deep parent water.
The extent of the deep body of high temperature waters can be expected to be
delineated by the occurrence of hot springs and vapor discharges. To the NW the
limit of the field is likely to be marked by the Los Vahos vapor discharges, to the N
by the Almolongo bicarbonate springs. The inferred flow paths of the waters
compatible with isotopic and chemical evidence is marked in Fig. 1 by arrows, the
likely distribution of the waters underground is shown in Fig. 15.
The model was constructed by assuming uniform and isotropic permeability conditions
underground and therefore is likely to represent only the potential distributuion of
fluids within the system. The actual distribution is largely governed by generally
unknown geological factors such as the nature and distribution of igneous and
sedimentary rocks and the presence and rate of formation of faults and fissures
facilitating fluid movement. Isotherms were drawn by assuming conductive heat
transfer and a thermal gradient of 50°/km outside the actual geothermal system. The
hydrothermal system is assumed to be associated with a body of cooling magma
beneath the El Azufral - Cerro Zunil complex. On the basis of models drived for the
White Island (Giggenbach, 1987) and Nevado del Ruiz (Giggenbach et al., 1990)
274
NW
C CANDÊLARIA
LLANO DEL FINAL

LosVohos
chloride waters -=
liquid+vapor
-2- sulfate waters
10 (km) 5 0
Fig. 15 - Cross-section through the Zunil geothermal system along line N W - SE of
Fig. 1. The distribution of fluids is that indicated by the geochemistry of the
fluids discharged.
volcanoes, the magmatic system is assumed to be surrounded by an extensive two-

phase, vapor-brine envelope. It provides the environment for initial conversion of
magmatic fluids to acid brines. Over the upper slopes of Domo El Azufral, the vapors
released from deeper primitive waters reach the surface leading to the formation of
extensive patches of steaming ground, the deposition of elemental sulfur and the
formation of the acid sulfate waters S3 and S4. At greater distance, continuing
intertaction with rock leads to the neutralisation of the acid waters, removal of most
of the magmatic sulfur in the form of alteration minerals such as sulfates (alunite,
anhydrite) and sulfides (pyrite). Much of the neutral Cl water appears to remain
stored underground. A small fraction was discharged naturally from spring Z-20 (Cl)
or is discharged in diluted form from the bicarbonate springs.
According to Fig. 15, the major upflow zones of thermal waters lie to the east of
Samalâ River. Because of permeability problems encountered over the present
production area to the west, exploratory drilling to the east should be considered
275
seriously. The choice of drillsite is largely a function of accessibility and depth to the
production zones. Another limiting factor which has to be taken into account when
drilling close to Domo El Azufral, is the possible ingression of immature, acid

waters both at shallow and deep levels. The potential for such ingression is likely to
increase with decreasing distance to the Azufral Dome. The position of drillsites
representing possibly the best compromise are indicated in Fig. 1.
ACKNOWLEDGMENT
The present investigation was carried out within the framework of the IAEA
Coordinated Research Program on the "Application of Isotopic and Chemical
Techniques to Geothermal Exploration in Latin America" (GUA/8/009-2) with
financial support from the Government of Italy.
REFERENCES
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and hydrology of the Zunil Geothermal System, Guatemala. Geoth. Res.
Council, Trans., 14, 837 - 844.
Adams A, Goff F, Trujillo P E, Counce D, Medina V, Archuleta J and Dennis B,
1990b: Hydrogeochemical investigatios in support of well logging operations
at the Zunil Geothermal Field, Guatemala. Geoth. Res. Council, Trans., 14,
829 - 835.
Bethancourt H R and Dominco E, 1982: Characteristics of the Zunil Geothermal

Field (Western Guatemala). Geoth. Res. Council, Trans., 6, 241 - 244.
Caicedo A and Palma J, 1990: Present status and development of the geothermal
resources of Guatemala. Geoth. Res. Council, Trans., JA, 97 - 105.
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Craig H, 1963: The isotopic geochemistry of water and carbon in geothermal areas.
In: Nuclear Geology on Geothermal Areas, CNR, Pisa, 17 - 53.
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Geology and geophysics of the Zunil Geothermal System, Guatemala. Geoth.
Res. Council, Trans., 14, 1405 - 1412.
Fournier R O, Hanshaw B B and Urrutia J F, 1982: Oxygen and hydrogen isotopes in

thermal waters at Zunil, Guatemala. Geoth. Res. Council, Trans., 6, 89 - 91.
Giggenbach W F, 1980: Geothermal gas equilibria. Geochim. Cosmochim. Acta, 44,

2021 - 2032.
Giggenbach W F, 1987: Redox processes governing the chemistry of fumarolic gas

discharges from White Island, New Zealand. Appl. Geochem., 2, 143 - 161.
Giggenbach W F, 1988: Geothermal solute equilibria. Derivation of Na-K-Mg-Ca

geoindicators. Geochim. Cosmochim. Acta, 52, 2749 - 2765.
Giggenbach W F, 1991: Isotopic shifts in waters from geothermal and volcanic systems
along convergent plate boundaries and the origin of "andesitic" water. Earth
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volcanic water and gas discharges. DSIR Chemistry Report CD 2401, pp 82.
Giggenbach W F and Stewart M K, 1982: Processes controlling the isotopic

composition of steam and water discharges from steam vents and steam
-heated pools in geothermal areas. Geothermics, 11, 71 - 80.
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Giggenbach W F, Garcia N, Londono A, Rodriguez V, Rojas G and Calvache M,
1990: The chemistry of fumarolic vapor and thermal spring discharges, from
the Nevado del Ruiz volcanic-magmatic-hydrothermal system. J Volcanol.
Geotherm. Res., 42, 13 - 39.
Goguel R L, 1983: The rare alkalies in hydrothermal alteration at Wairakei and

Broadlands geothermal fields, New Zealand. Geochim. Cosmochim. Acta, 47,
429 - 437.
INDE, 1978: Proyecto Zunil, Informe Geoquimico, pp. 65.
Lloyd R M, 1968: Oxygen isotope behaviour in the sulfate-water system. J. Geophys.

Res., 73, 6099-6110.
Menzies A J, Granados E E, Sanyal S K, Mink L L, Merida L and Caicedo A, 1990:
An integrated test program for the definition of a high temperature

geothermal reservoir: a case study from the Zunil Geothermal Field,
Guatemala. Geoth. Res. Council, Trans., 14, 1233 - 1239.
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Science, 12, 54 - 59.
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278
INVESTIGACIONES GEOQUÍMICAS REALIZADAS EN
LOS CAMPOS GEOTÉRMICOS DE ZUNIL Y AMATITLAN,
GUATEMALA
A.R. ROLDAN MANZO

Unidad de Desarrollo Geotérmico,
Instituto Nacional de Electrificación,
Ciudad de Guatemala, Guatemala
Resumen-Abstract
INVESTIGACIONES GEOQUÍMICAS REALIZADAS EN LOS CAMPOS GEOTÉRMICOS DE ZUNIL Y

AMATITLAN, GUATEMALA.
Los estudios geotérmicos en Guatemala se iniciaron en 1971 en el

campo geotérmico de Moyuta. En 1981 OLADE realizó un estudio
regional determinando trece zonas de interés geotérmico. Zunil y
Amatitlán, analizados en este estudio, fueron clasificados dentro
del grupo A o de prioridad uno.
Las aguas de Zunil se clasifican según tres tipos: cloruro-sódicas,

neutras o bicarbonatadas y acidas. Análisis de gases indican origen
meteorice y magmático, con recarga local, y la existencia de dos
acuíferos diferentes. Análisis isotópicos evidencian origen
profundo y un tiempo de residencia para el agua de aproximadamente
200 años. Geotermómetros de aguas, gases e isótopos proporcionan
temperaturas entre 180° y 400°C. Por medio de prospecciones de
mercurio y radón se identificaron zonas de alta permeabilidad.
Las aguas de Amatitlán se clasifican según dos grupos:
cloruro-sódicas y bicarbonáticas. Análisis isotópicos sugieren
origen profundo y un tiempo de residencia mayor de 100 años.
Análisis de gases indican origen magmático. Geotermómetros de
cationes proporcionan temperaturas de 240° a 245°C, mientras que las
temperaturas de equilibrio para gases van de 220° a 300°C. Estudio
de radón evidencia anomalías con orientación NO-SE las cuales
indican un rasgo estructural profundo.
GEOCHEMICAL INVESTIGATIONS IN ZUNIL AND AMATITLAN GEOTHERMAL FÍELOS

GUATEMALA.
Geothermic studies in Guatemala began in 1971 in the Moyta

geothermal field. In 1981 OLADE realized a regional study, finding
13 áreas as geothermal prospects. Zunil and Amatitlán, object of
this study, were classified in group A (priority one).
The Zunil waters are classified in three groups: sodium-chloride,

bicarbonate or neutral and acid. Gas analysis shows magmatic and
meteoric origin with local recharge and two different reservoirs.
Isotopic analysis yields deep origin and a residence time of
aproximately 200 years. Water, gas and isotopic geothermometers
279
yield temperatures between 180°C and 400°C. Mercury and Radon
surveys show high permeable zones.
The Amatitlan waters are classified in two groups: sodium-chloride

and bicarbonate. Isotopic analysis suggests deep origin and a
residence time greater than 100 years. Gas analysis yields magmatic
origin. Cation geothermometers yield temperatures from 240°C to
245°C and gas equilibrium temperatures ranging from 220° to 300°C.
Radon surveys show anomalies NW-SE oriented which could correspond
to a deeper subvolcanic structure.
1. INTRODUCCION
Dentro de la bûsqueda de fuentes alternas de energia para

contrarrestar los elevados precios del petroleo, en Guatemala, se
iniciaron las investigaciones geotérmicas en el ano de 1971 a traves
del Proyecto Minero de las Naciones Unidas conjuntamente con la
Direccion General de Mineria e Hidrocarburos. Posteriormente, el
Institute Nacional de Electrificaciön (INDE) ha sido el responsable
de la investigaciôn geotérmica en el pais; los primeros estudios se
efectuaron en el ârea de Moyuta, de 1971 a 1976. En el ârea de
Zunil, las investigaciones se iniciaron en 1973, con la colaboraciön
de Japan International Cooperation Agency, llegando a concluir en
1976 que Zunil es un ârea de alto potencial para el desarrollo de la
energia geotérmica (JICA, 1977).
En 1981 OLADE efectuô un estudio régional en el ârea limitada al

norte por la falla del Motagua, al sur por la costa del Pacifico, al
oeste por la frontera con Mexico y al este por la frontera con El
Salvador. Como resultado de este estudio se definieron trece zonas
de interés geotérmico clasificadas en très diferentes grupos. Los
campos de Zunil y Amatitlân, objeto de este estudio, fueron
clasificados dentro del grupo A o de prioridad uno. (Figura 1).
2. CAMPO GEOTERMICO DE ZUNIL
El campo geotérmico de Zunil esta situado al oeste de la ciudad de

Guatemala a aproximadamente 218 km por carretera asfaltada, a una
280
00
FIG. 1. Localization de los campos geotérmicos de Zunil y Amatitlän.

altura de 2000 ra.s.n.m. La temperatura ambiente varía entre 15° y
20°C, la precipitación promedio anual es de 2000 mm, mientras que la
evapotranspiración es de 750 mm por año.
El campo ha sido dividido en dos áreas: Zunil 1, donde se instalará
una planta generadora de 15 MW y Zunil 2 donde actualmente se
efectúan estudios de prefactibilidad. (Figura 2).
NW
O AGUAS CLORUROSODICAS
O AGUAS BICARBONATADAS
O AGUAS SULFATADAS
O FUMAROLAS
FIG. 2 Locahzación de muestras seleccionadas en el

campo geotérmico de Zunil y delimitación de las áreas
de Zunil 1 y Zunil 2.
2.1 GEOLOGÍA
Zunil se encuentra localizado en el borde sur de la depresión de

Quezaltenango, considerada una caldera de edad terciaria precedida
por un volcanismo efusivo del tipo andesítico dacítico. Se trata
de un graben de unos 3 kms de ancho con dirección noreste-suroeste
formado por un sistema de fallas a lo largo del cual se localizan
los domos Cerro Candelaria, Cerro Quemado y el Volcán Zunil.
El basamento es de naturaleza granítica y granodiorítica de edad

cretácica, sobreyaciendo discordantemente un fuerte espesor de lavas
andesíticas y piroxénicas de edad terciaria, tobas y brechas
tobáceas, tobas riolíticas, tobas soldadas, lahares, flujos
riodacíticos y flujos basálticos con espesor entre 800 y 1000 m.
(Figura 3).
282
COMPLEJO OE ROCAS
GRABEN DE ZUÑÍ L VOLCÁNICAS TERCIARIAS
COMPLEJO DOMICO DEL CERRO
QUEMADO
RIODACITAS DOMO LA PEDRERA. ANDESITAS DOMO EL AZUFRAL. P5RH ROCAS METAMORFICAS,
ROCAS PIROCLASTICAS RECIÉN- RTCpn COMPLEJO ROCAS VOLCANI- PTP,LAVAS RECENTES

TES. IS&ICAS TERCIARIAS. •ÍHDEL DOMO ZUNIL.
ANDESITAS Y LAVAS DEL DOMO ROCAS INTRUSIVAS.
CERRO QUEMADO.
FIG. 3. Geología del área geotérmica de Zunil (Tobías, 1977).
2.2 GEOQUÍMICA DE FLUIDOS
Como producto de las primeras investigaciones, se localizaron 70

manantiales los cuales fueron químicamente analizados y 20 de ellos
son analizados mensualmente hasta la fecha. Seis pozos productores
han sido perforados desde 1980 y sus fluidos químicamente
analizados. Las aguas de Zunil se clasifican en tres tipos (Tabla 1
y Figura 4) cloruro-sódicas (con alto contenido de Na y Cl )
neutras o bicarbonatadas (con alto contenido de HCO ) y acidas
(con alto contenido de SE~) (Giggenbach 1988, Bethancourt 1978,
JICA 1977). Se considera que las aguas del tipo ácido provienen del
calentamiento de las aguas superficiales por vapor de origen
profundo, rico en sulfates y que las aguas bicarbonatadas son el
producto de aguas superficiales calentadas por conducción, mientras
que las aguas cloruro sódicas tienen un origen profundo.
283
T A B L A 1
COMPOSICIOH QUÍMICA DE FOJOS 1I HARAHTIALES DEL CAMPO GEOTEBMICO DE 20NIL (ig/kg)
(Giggenbach 1988)
INDE «o. °C pH Li Ka I Bb Cs «9 Ca B Al HCO, SiOj S04 Cl reí
Pozos (vertedero)
«1 ÍCQ-3 92 8.1 8.70 933 231.0 2.33 2.02 .012 15 40.0 - 51 951 31 1810 A
« 2CQ-6 92 8.4 8.10 1028 212.0 1.89 2.01 .040 11 45.0 - 157 889 61 1700 A
K3 Í-1I 144 7.8 6.31 1092 101.0 0.55 2.36 .070 30 50.8 0.51 41 580 105 1740 A
(UDantiales cloruro sódicos
Cl J - 2 0 89 9.0 2.70 545 51.1 - - 0.3 7 26.2 - 96 404 210 728 C
Aguas bicarbonatadas
Bl 1-23 40 9.2 0.13 79 7.4 0.02 .003 11.6 22 0.7 (.05 79 160 64 31 A
B2 2 - 2 9 50 7.0 0.18 65 10.0 0.02 .012 5.4 11 1.3 0.09 140 132 22 57 B
B3 Z-4 63 7.0 0.28 166 12.2 0.03 .027 5.9 17 2.8 <.05 259 138 103 101 B
B4 S-9 62 8.4 0.37 199 18.6 0.05 .037 18.1 25 3.4 (.05 340 161 129 114 á
B5 !-17 70 7.8 0.56 286 37.2 0.07 .030 36.2 42 4.7 (.05 463 194 210 180 A
B6 2-10 67 8.7 0.56 372 36.6 0.07 .022 40.5 41 4.7 (.05 491 196 194 163 A
B7 M3 87 8.7 0.57 258 27.3 0.08 .025 45.2 43 4.6 (.05 501 200 193 168 A
B8 2 - 1 5 64 6.1 0.91 157 19.0 0.09 .019 30.8 18 2.5 (.05 503 146 235 71 B
Aguas s u p e r f i c i a l e s
El IB-1A 18 7.0 (.01 9 4.4 0.01 .002 5.6 9 0.3 0.08 74 28 - 15 B

82 ZE-2A 16 7.1 (.01 8 3.3 (.01 (.002 3.8 8 (0.1 0.06 69 52 56 15 B
B3 IB-16 18 6.1 (.01 16 5.9 0.01 <.002 3.6 7 0.2 4.40 38 22 18 20 B
Aguas sulfatadas
SI ZP-38 91 2.1 0.12 43 14.5 0.04 .009 18.9 76 0.2 6.70 - 242 117 15 B
S2 2 - 3 6 90 3.1 0.06 80 7.7 0.04 .009 45.0 104 (0.1 42.0 - 292 633 10 8
S3 Z-19 56 2.10.05 89 30.9 0.11 .004 14.6 43 1.8 59.0 - 209 1600 7 A
S4 2-31 74 2.00.07 134 32.3 0.23 .010 28.3 72 1.7 39.0 - 287 2060 8 A
AR Soca proiedio 3.00 2400 2100 15.0 .500 2300 4200 - - - - - - -
Befereccias:
A. DS1R
B. pB, flCOj, SO,, Cl INDE
C. INDE
284
AGUA PROFUNDA
NEUTRALIZADA
COMPLETAMENTE
lADA
HC03
FIG. 4. Diagrama CI-HCO3-S04 para las aguas de Zunil

(Giggenbach, 1988).
Varias zonas de fumarolización activa se localizan en el campo

geotérmico de Zunil y son denominadas: Fumarola Grande o Zona del
Geiser, Fumarola Negra, Fumarolas de Paxmux, Los Vahos, Alteración
Hidrotermal La Cascada y Fumarolas de las Fresas (Tobías 1971,
Figura 2). Alteración hidrotermal se observa en las áreas
adyacentes a las fumarolas, donde la roca original se ha
transformado produciendo minerales arcillosos y oxidaciones
ferromagnesianas, se observa especialmente caolinización y
silicificación; depósitos de azufre nativo se encuentran en al área
de Las Fresas, mientras que en la Fumarola Negra se ha localizado
mercurio.
Análisis de gases muestran un bajo contenido de gases no

condensables (0.85% aproximadamente) principalmente CO£* y H ¿i S.
Las concentraciones relativas de nitrógeno, helio y argón indican
origen tanto meteorice como magmático indicando la existencia de dos
acuíferos diferentes (Figura 5 y Tabla 2). Esta tesis fue propuesta
inicialmente por OLADE (1982) considerando que existe un acuífero
superficial producto de la dilución de aguas provenientes de un
acuífero profundo con elevada temperatura.
285
TABLi 2
CONPOSICIO» DEL VAPOR DEL CAKPO GEOTÉRMICO DE IDIIL
(liol/iol o ppi por voluien!
(Giggenbach 1988)
HDE Do. °C Is M C02 H2S «B, He
!3 2CQ-3 138 0. 30 997700 2192 67 5 .2 0.0060

26 ICO.-6 123 0. 34 997200 2682 56 5 .1 0.0056
!5 2CQ-5 - 1.00 997200 2691 90 4.0 0.0059
111 2-11 144 0. 43 996900 2994 43 3 .1 0.0040
LF FRESAS 94 1.00 995800 3797 257 1 .3 0.0206
PI PAIMDÍ 93 1.00 990800 8942 260 0.3 -
Pí F.IEGEA 94 1.00 996200 3620 178 0 .3 -
AZ AiDFRAL 91 1.00 994200 4843 802 0 .3 0.0296
IKDE Do. He Bj Ar Oj «a CH, R•
¡3 2CQ-3 .00018 13 .10 0. 14 0.2 23 0.58 -4.88

26 2CQ-6 .00039 11 .90 0. 25 0.3 36 0 .67 -4.92
25 2CQ-5 .00014 12 .30 0. 08 0.2 11 0.39 -4.91
211 Z-ll .00040 40 .65 0.28 0.3 46 1.02 -4.91
LF FRESAS .00118 40 .65 0. 76 0.2 101 2 .77 -4. 39
PI PAIHOÍ - - - - - -
PN F. NEGRA - - - - - -
AI A20FRAL .00116 0 .46 0. 70 0.3 151 0.46 -6. 33
AIRE SATURADO CON

AGUA SUBTERRÁNEA
OH*
FIG. 5. Diagrama N2-Ar-He para los gases de Zunil

(Giggenbach, 1988).
286
Análisis isotópicos fueron efectuados inicialmente para determinar
el origen de la recarga en el campo de Zunil (Fournier y Hanshaw
1981) concluyendo que la recarga es de origen local. Análisis
posteriores (Giggenbach 1986) confirman la tesis de Fournier y
Hanshaw, y en base a los mismos, Giggenbach propone una hidrología
tentativa del campo geotérmico de Zunil, la cual se muestra en la
Figura 6. Un modelo diferente fue desarrollado por West Jec (1990)
en base a los estudios de prefactibilidad efectuados en el área de
Zunil 2 (Ver figura 7). Los resultados isotópicos muestran un
enriquecimiento de 18O entre 2.2 y 5%o (Giggenbach 1988, Cordón y
Marida & M K Ferguson 1990), lo cual evidencia un origen profundo
luego de un equilibrio agua-roca; asi mismo puede observarse la
existencia de aguas calentadas por vapor (Tabla 3 y Figura 8). El
tiempo de residencia ha sido calculado en base al contenido de
tritio (1.3 Unidades de Tritio en promedio) utilizando la ecuación
de Pearson y Truesdell en aproximadamente 200 años (Cordón y Marida
& M K Ferguson 1990.
2.3 GEOTERMOMETRIA
Diversos geotermómetros han sido aplicados en el campo geotérmico de

Zunil los cuales revelan temperaturas dentro del rango de 180°a
400°C. Utilizando los geotermómetros de cationes, se considera la
existencia de dos acuíferos (OLADE 1982) como fuera mencionado en el
párrafo 2.2; uno profundo a temperatura de aproximadamente 260°C, y
otro más superficial, producto de la dilución del primero, a una
temperatura de 210°C. Estas temperaturas han sido confirmadas en
los pozos exploratorios y se sugiere que el acuífero puede presentar
mayor potencial a mayor profundidad. Geotermómetros de gases
aplicados a muestras provenientes de los pozos (Giggenbach 1986)
confirman la existencia de altas temperaturas en profundidad
(superiores a 200°C),zlas cuales se han obtenido además aplicando
geotermómetros isotópicos, (West-Jec 1990) y cuyos resultados
aparecen en la Tabla 4. Los valores más altos se obtienen con los
isótopos de carbono, cuyos valores corresponden a niveles muy
profundos, revelando que la temperatura se incrementa dentro del
basamento.
287
NW
C CANDELARIA
LLANO UL. PIÑAL
chlondewcters
hauíd-t vapor
sul'ate waters
lO(k-n)
Hidrología tentativa del sistema geotérmico de Zunil, compatible con la

composición química e isotópica de los fluidos descargados (Giggenbach,
1988)
chlonde waters
J bicarbonate
sulfate wate
^/ fumoroles
proposed dnlls
O 1 2 3 km
Trayectorias de flujo de las aguas propuestas por W.F. Giggenbach (1988)
FIG. 6. Modelo hidrogeoquímico del campo geotérmico de Zunil

propuesto por Giggenbach (1988).
288
NO SE
Volcan Altura (m s.n.m)
Altura (m) Cerro Quemado
Azufróles Volca'n de Zunll
3,000 -, Fuentes Gaoramos
- 3.000
- 2,000
- 1,000
otro«)~400°C Qiniolltnongo-Conl»l(7)T
pora Loa Sí»i«m<ji tí» Zunll-l

Almolonga y Funiorola Ntgro-Grond»
Flujo de fluidos
subterráneos
> Fluío de agua frfa -— Flujo de vopor

* Flujo de ogua callente ~~~ Flujo de aguo calentado poi
profunda del tipo Cl
SO
Altura rFumarolo Grande del tipo Cl
Aguas Amargas
I Fumarola Negro
Zona de mezcla —\—————— —
3.000 -
Agua callente
Agua caliente del tipo HCO,
del tipo SO,
2,000
1,000 -
Agua co'ivnh
d*l tipo Cl C-HCOj)
Ar«a d* recarga
paro lot >lit«mo»
t ~* d« lo Fumarolo N»oro y
rumorólo Crond*
Coi» mogmaHco» (C02 y olrot)
Flujo de fluidos
subterráneos
: Flujo de aguo fna - — -*• : Flujo de vapor
: Flujo de aguo callente

: Flujo de agua
profunda del upo Cl calentada por vapor
FIG. 7. Modelo hidrogeoquímico del campo geotérmico de Zunil

propuesto por WEST-JEC (1990).
289
TABLA 3
COMPOSICIOH ISOTÓPICA I COHTEHIDO TOTAL DE Cl 1 SO, DE (mg/Kg) -

POSOS í HASAIIT1ALBS DEL CAHPO GEOTÉRMICO DE SOSU
(Giggeabacb 1988)
2 3
ISDE 8o. 1, °C "0 fi B Cl S04 REP
0/00 0/00 o/oo ig/kg ig/kg
Pozos
«1 ÍCC-3 0.63 92 -8.74 -79. 3 1.3 1140 20 A

N2 JCQ-6 0.63 92 -8. 36 -75. 9 1.3 1070 38 A
K3 ¡-11 0.5?144 -7.25 -70. 1 - 992 60 B
Manantiales cloruro sódicos
Cl ¡-20 93 -8.20 - 1.1 700 202 C
Aguas bicarbo Datadas -90
Bl J-23 40 -11. 59 -85. 2 1.1 31 64 B -12

B2 ¡-29 50 -10. 38 -77. 0 1.2 57 22 A
B3 ¡-4 63 -10. 75 -79. 7 0.0 101 103 A
FIG. 8. Relación de deuterio-oxígeno 18 (A) y
B4 ¡-9 62 -11. 39 -77. 5 4 129 B
210 sulfato-oxi'geno 18 (B) para las aguas de Zunil
B5 ¡-17 70 -11 30 -83. 3 1.1 180 B
B6 ¡-10 67 -li 89 -84. 1 0.3 163 194 B (Giggenbach, 1988).
B7 ¡-13 87 -11 54 -84. 7 165 193 B
B8 ¡-15 64 -11.05 -82. 4 3.2 71 233 A
Aguas superficiales
TA BLA 4
Bl ¡R-1A 18 -11.64 -84 7 15 - A
56 TEMPERATURAS GEOQUÍMICAS BR °C BASADAS
R2 !R-2A 16 -12.23 -85 7 15 A
18 ES ISÓTOPOS Y GASES (HjS-Bj-CH.-COj)
R3 ZR-16 18 -12 22 -85.4 20 A
- - A EN EL ÁREA DE ¡ORIL. (NEST JEC 1990)
R4 LLOVÍA - 8 .47 -55.3 4.8
Aguas sulfatadas
ZP-38 91 - 7 .25 -70.6 15 117 A LOCALIZACIOS CARBOR OIIGÍHO HIDROGEHO GASES

SI
Z-36 90 - 7 .58 -67.4 10 633 A CO 2-C8« HjO-CO, Bj-CB4;HjO-B2
S2
S3 H9 56 - 9 .38 -75.8 7 1600 B
S4 ¡-31 74 -10 .02 -80.7 8 2060 B
ZCQ-3 383 272(304) — 175 329
Referencias:
Azúfrales 320 174 249
Puentes Georginas 344 14311451 — 227
A.- IAEA 8.- DSIR c.- Pournier and Bañaba* 119811
Chuitziquiná 339 282 ...
Puentes Geórgicas 378 140(157) — 291
Los Vahos ... 267 ...
Los Vahos 208 263 —
Azufralito 358 125(205) — 188
Las Presas 288 164(206) — 249
Puiarola Segra 399 157(186) 163 146 334
Panui 364 138 248
290
2.4 PROSPECCIONES DE MERCURIO Y RADON
Tanto el mercurio como el radón están relacionados con procesos de

actividad geotermal profunda (Tobías 1987, Koga 1989) y la
prospección de los mismos es ampliamente utilizada para determinar
zonas de ascenso de fluidos hidrotermales al localizar fallas y
fracturas activas (Gutierres y López 1983, West Jec 1990).
La primera prospección de mercurio en el área de Zunil fue efectuada

en muestras de agua y arcillas por Japan International Cooperation
Agency (1973), encontrando valores altos de mercurio (33 a 690 ppm)
principalmente en el área de la Fumarola Negra. Se reportan además
valores relativamente altos en la zona de Fuentes Georginas. En el
área de Zunil 1, el consultor Cordón y Marida & MK Ferguson (1989)
efectuó un estudio de mercurio en suelos, analizando 47 muestras a
66 cm de profundidad. Los valores encontrados varían de 55 ppb a
3.42% con los valores más altos entre los pozos ZCQ3, ZCQ5 y ZCQ6,
incluyendo áreas de fumarolización activa; además, la distribución
de los valores altos de mercurio indica la existencia de fallas
permeables con orientación NE y NO. (Ver Figura 9). Finalmente,
00o
• SSO LOCALIZACION DE MUESTRAS CON CONCENTRACIONES DE MERCURIO EN PARTES POR BILLÓN,

EXCEPTO CUANDO SE INDICA.
^~-^ FALLA MODIFICADA, DE FOLEY (1,989)', DISCONTINUA DONDE SE I N F I E R E ,
00 POZO PRODUCTIVO.
FIG. 9. Isoconcentraciones de Hg en el área de Zunil 1 (Cordón y Mérida, 1990).
291
N>
\O
K>
Ceri(o El Galápago
i
i
Las Majadas
—~, v
abor Pa|omaiuyup~\\
^=g^^ ^\
Tuncenlro Fuenles Georgmas

La Estancia
de la Cruz x 2700m
FIG. 10. Anomalías de mercurio y radón en el campo geotérmico de Zunil (WEST-JEC, 1990)
como parte del estudio de prefactibilidad del área de Zunil 2, la
firma consultora West Jec realizó prospecciones de mercurio y radón,
habiéndose analizado mercurio en suelo, mercurio en el aire del
suelo y radón, torón y radón total en el aire del suelo. Los
resultados indican que las anomalías de mercurio están orientadas en
dirección ESE-ONO y que las mismas coinciden con las anomalías de
radón y con una zona de baja resistividad determinada por el estudio
CSMAT. Las zonas anómalas encontradas en este estudio pueden
observarse en la Figura 10.
3. CAMPO GEOTÉRMICO DE AMATITLAN
El campo geotérmico de Amatitlán se localiza aproximadamente a unos

28 kms al sur de la ciudad de Guatemala dentro de los municipios
Amatitlán, San Vicente Pacaya y Villa Canales (Figura 1). Las
alturas dentro del área varían de 1,188 m.s.n.m. (nivel del lago del
mismo nombre) hasta mayores de 1,800 m.s.n.m. (Laguna de Calderas).
El lago Amatitlán recibe el agua proveniente de la cuenca del río
Villalobos y descarga hacia el Pacífico por medio del río
Michatoya. La temperatura media anual es de 22°C, se tiene una
precipitación promedio de 1,400 mm y una evapotranspiración
potencial de 800 mm.
3.1 GEOLOGÍA
Geológicamente, Amatitlán se ubica en el extremo sur del graben de

Guatemala dentro de una caldera de origen cuaternario antiguo, donde
actualmente se encuentra el lago del mismo nombre. El área
geotérmica se localiza en la parte norte del complejo dómico del
Pacaya, la cual está limitada al oeste por la falla de Mixco, al
este por la falla de Santa Catarina Pinula y al norte por la falla
de Amatitlán. Un sistema de fallas con orientación norte-sur
formado por las fallas Mal Paso, Laguna Seca, Los Humitos y otras
menores atraviesa el campo. Estratigráficamente la zona tiene lavas
andesíticas, andesitas basálticas, lahares y lavas intermedias del
293
período terciario; sobreyacen a ellas lavas andesíticas, rocas
dómicas dacíticas y riodacíticas, lavas básicas del Pacaya y
piroclásticos del período cuaternario. El basamento, cretácico
superior y de naturaleza granítica, se encuentra discordantemente
bajo las vulcanitas terciarias. Los domos El Limón y La Mariposa,
ubicados al suroeste del lago, son del tipo riodacítico y sugieren
la formación de cámaras magmáticas como probable fuente de calor del
campo geotérmico. En el extremo sur de la caldera se encuentra el
volcán Pacaya, actualmente en actividad, el cual está formado por
basaltos diferenciados. Cercano al Pacaya hacia el noreste, se
localiza el Cerro Grande de composición andesítico-dacítica. (Tobías
1987, Figuras 11 y 12).
DEPRESIÓN VOLCANO-TECTÓNICA DE AMATITLAN

COTA
Im 3 n m )
2500 C«rro C h i n o
Fallo de
2000 AmotitlOfl
I50O
1000
500
Kg(?>
O
Tv o Kg ( basamento granítico)
-500
-1000
O DISTANCIA 15 Kms
LEYENDA
Sedlm«nto» lacustres F u m a r e la
Qc £o°o° | Aluvión y Cokivlo'n a. estratificado*
Qb Lovat basáltico» de I Qc Conglomerado arenoso Manantial c a l i e n t e

« M volcan de P o c o y a (paleo- aluvldn)
ft111 > ' I Lavas ¿¿micas nodaclticas I———] Lava* t e r c i a r l a s andeeltlcos
Qr-d I ' "j f doclticas Ta
f < g r a n o d l o r l t b , c o l l z a s (? )
l.'.'.'.'l velcon ancestral
FIG. 11. Geología del área geotérmica de Amatitlán sección norte-sur (Tobías, 1987).
294
COTA
( m a. n m } NW SOUTHWESTERN OF EL L I M Ó N ANO MARIPOSA DOMES
--7^r---rr-¿6"~-Ji^2
*o o o o -Jsp oVo o o
O S-D O O- OÔ O ^- O AM-3
POZO EXPLORATORIO DE
DIÁMETRO REDUCIDO
600 E x p l o r o * o r y well of «molí
(Basament* Rock
dlameter.
Rocas básales (Basaments Rock»)
SKm
LEYENDA DISTANCIA
Qa y terrazas aluviales <Qs I— — 1 S e d i m e n t o s lacustres

I Aluvión and diluvial t e r r e c e s I—-'-^l L a c u s t n a n sediments AMATITLAN
Inst N a c i o n a l de Electrificado^
Qr-d P(l7l I Roca* domicas (Rlodacitas y d e c i t a ) |o o oí Conglomerado a r e n o s o Unidad de Desarrollo Geotérmico
I Domic rocks( Rhyodoclte and docite) Qc I » I Sondy conglomérate
SECCIÓN G E O L Ó G I C A NW-SE
Qp T*~>—=1 Pom«« de rlodoclto y d o c i t o To Lavas andesltlca* terciarlas
l> * 1 Dócil» and r h y o d o c l t e pumlce T e r t l a r y andesite*
Q» I* *, volcánica* cuaternarias |v v y] Volcánico terciario Indif erenciado
I Quoternary v o l c a n t e r o c k » I * * I T e r t i a r y volcanlc undlferenclated
(andesite) -80- Isotemperatura °C Isotemperature
FIG. 12. Geología del área geotérmica de Amatitlán sección noroeste-sureste (Tobías, 1987).
3.2 GEOQUÍMICA DE FLUIDOS
La primera localización y muestreo de manantiales en el área

geotérmica de Amatitlán se efectuó en 1977, luego se seleccionaron
los manantiales considerados representativos y estos se han
muestreado sistemáticamente hasta la fecha (Figura 13). En base a
su composición química los manantiales han sido clasificados en dos
categorías; (ELC 1989, Giggenbach 1986, Tobías 1987, Figura 14)
aguas cloruro sódicas localizadas a la orilla sur del lago Amatitlán
con valores hasta de 1450 ppm de Cl y temperaturas mayores de
90°C y aguas bicarbonáticas alrededor del domo El Limón y a lo largo
del valle del río Michatoya, con temperaturas entre 40° y 70°C, y
contenido de HCO de 750 ppm. El manantial AM-8, con la más
alta concentración de cloruros, se considera representativo de aguas
termales de origen profundo. Al resto de manantiales se les
295
t
Ciudad dt Guottmala a 23 Km
voLcan dt Pacaya O 5 4 km
FIG. 13. Localización de manantiales seleccionados en

el área geotérmica de Amatitlán (Giggenbach, 1986).
cu
Q INOE
HCOj
IOSO.
FIG. 14. Diagrama de CI-HCO3-S04 para las aguas de Amatitlán

(Giggenbach, 1986).
clasifica como derivados de este por dilución con aguas

superficiales. OLADE (1982) considera que los dos grupos de aguas
provienen de acuíferos diferentes; el grupo clorurado sódico con una
temperatura en profundidad de aproximadamente 200°C y el grupo
bicarbonático, mas superficial, con temperatura aproximada de 100°C.
296
Supone además, la existencia de un acuífero más caliente a mayor
profundidad el cual es mencionado también por ELC (1989) quienes
consideran que el fluido original puede llegar a 300°C.
Análisis isotópicos efectuados en manantiales seleccionados del área

sugieren una simple relación entre las aguas clorurado sódicas,
bicarbonatadas y superficiales, de tal manera que todos los
manantiales corresponden a mezclas de agua de origen profundo con
agua superficial (Giggenbach 1986, ELC 1989, Tabla 5 y figuras 15 y
16). El enriquecimiento en el contenido de 18O (aproximadamente
1.8% ) indica una considerable interacción agua-roca a temperaturas
mayores de 300°C. Por otro lado, si se considera el agua del lago
como representante del contenido actual de tritio, las aguas
cloruro-sódicas tienen más de 100 años.
Áreas fumarolizadas se localizan desde la orilla sur del lago hasta

Laguna Calderas. Básicamente son áreas calientes formadas por
material areno-arcilloso de color gris claro a blanco, provenientes
de alteración de piroclásticos o lavas neutras a acidas. Han sido
clasificadas en tres sistemas (Tobías 1987); uno alrededor del
T iB LA 5
COMPOSICIÓN ISOTÓPICA DE AGOAS DEL CAMPO

GBOTBRHICO DE AKATITtA» iCigseabach 19861
INDE do. re. < «0 0/00

l
Í3B o/oo JE (T.O.) Cl-dg/kg)
AK-1 72 -8.68 -61.2 0.0 166

AN-7 97 -6.44 -54.6 0.6 1250
AH-8 91 -6.22 -53.3 0.9 1420
AM-19 50 -8.88 -64.2 0.0 158
AH-24 64 -8.88 -64.0 0.4 105
AÜ-32 65 -8.49 -60.2 0.4 306
AH-44 84 -6.63 -52.9 0.5 1160
AH-57 57 -7.26 -57.5 1.6 235
AH-67 20 -9.36 -62.9 1.8 2
AH-69 50 -7.07 -49.4 13.2 245
AH-7Ü 20 -7.86 -52.5 11.4 5
AL-2 22 -1.61 -19.2 9.4 5
AL-4 25 -2.92 -26.4 3.9 101
297
Dilución con aguo
• ubt*rran«o " jov«n
CL(mg/Kg) I9OO
FIG. 15. Relaciones tritio-cloruros, deuterio-cloruros

y oxígeno 18-cloruros para las aguas de Amatitlán
(Giggenbach, 1986).
Precipitación d«
bala altitud
FIG. 16. Relación deuterio-oxígeno 18 para las aguas de Amatitlán

(Giggenbach, 1986).
298
cráter de Los Humitos, otro en los domos El Limón y La Mariposa y un
tercero en el extremo sur-oeste del lago. Dos muestras de gases
fueron analizadas por Giggenbach (1986); una cercana al lago
Amatitlán (ALA) y la otra cercana a la Laguna Calderas (ALC) Tabla
6). El contenido de gases para ambas es muy diferente; 0.9 mmol/mol
para el Lago Amatitlán y 55.1 mmol/mol para la Laguna Calderas. Se
considera que el bajo contenido de gases en la muestra de Amatitlán
es debido a una alta desgasificación del agua. La composición
relativa de los gases helio, nitrógeno y argón en ambas muestas
sugiere un origen magmático común con una dilución por nitrógeno y
argón provenientes de aguas superficiales (Figura 17). Por otro
lado, el contenido relativo de hidrocarburos confirma este origen
magmático (Figura 18, Tabla 6).
3.3 GEOTERMOMETRIA
Geotermómetros de sílice presentan valores de aproximadamente 200°C

tanto para las aguas bicarbonatadas como para las aguas clorurado
sódicas. Geotermómetros de cationes por su parte, indican valores
de 240° a 245°C. El uso del diagrama sodio-potasio-magnesio
(Giggenbach 1986) revela que las únicas muestras que han alcanzado
equilibrio agua-roca en profundidad son aquellas con valores altos
de cloruros, intersectando la línea de equilibrio a una temperatura
aproximada de 230°C (Figura 19). Por otro lado temperaturas de
equilibrio de gases presentan valores de 220° a 300°C (ELC 1989,
Giggenbach 1986). En base a los resultados obtenidos, Giggenbach
propone un modelo hidrogeoquímico el cual se presenta en la Figura
20.
299
AIRE
AIRE SATURADO CON

AGUA SUBTERRÁNEA
10 He
FIG. 17. Diagrama nitrógeno-argón-helio para

los gases de Amatitlán (Giggenbach, 1986).
ETANO/IO
PROPAKO BENCENO
FIG. 18. Diagrama etano-benceno-propano para

los gases de Amatitlán (Giggenbach, 1986).
300
TABLA 6
COMPOSICIOS QDIHICA DE GASES DEL CAHPO

GEOTÉRMICO DE AHATITLAK (ppt)
(Giggenbach 1986)
T°C C02 IB, Be
AlC 95 55.1 986 2.0 0.14 .0068 .00001 .26

ALA 95 0.9 961 4.5 5.17 .0061 .00073 .05
Ar 02 CH4 «"ClCOjl let ete eta
ALC .02 1.0 11 0.35 -2.8 940 (.5 30.8

ALA .40 1.2 25 3.42 -6.7 998 U 0.4
pre pra ibu be nbu ipa opa pe benz
ALC (.5 7.6 0.9 (.5 1.9 0.5 0.5 13.6

ALA 0.1 0.1 U U 0.7
tol ebe 1-1 p-z o-i
ALC 1.4 1.8 1.3 0.6 0.6

ALA 0.8 0.9 0.6 0.3 0.3
let: letano be: buteno tol: tolueno

ete: eteno nbu: n-butano ebe: etilbenceno
eta: eta no ipa: isopentano i: nleno
pre: propeoc npa: n-pentano ALC: Laguna de Calderas
pra: propano pe: penteno ALA: Lago de Aiatitlán
ibu: isobutano benz: benceno
301
FIG. 19. Diagrama sodio-magnesio-potasio para
los aguas de Amatitlán (Giggenbach, 1986).
FIG. 20. Modelo hidrogeoqutmico propuesto por Giggenbach

para al área geotérmica de Amatitlán (Giggenbach, 1986).
3.4 PROSPECCIÓN DE RADON
Con el objeto de detectar fallas y fracturas tectónicamente activas,

en 1985 se procedió a efectuar una prospección de radón en el campo
geotérmico de Amatitlán, cubriendo un área aproximada de 100
kilómetros cuadrados, mediante el sistema de cápsulas con películas
detectoras. Ciento dos cápsulas se colocaron cada 500 ó 1000 m en
302
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303
ocho líneas con dirección NO-SE, separadas 1 km cada una. El tiempo
de exposición fue de treinta días y posteriormente se efectuó el
análisis calculando el número de trazas por centímetro cuadrado y
2
por hora (T/cm -hr) . Se considera que la emisión de radón hacia
la superficie se efectúa a través del sistema de fallas norte-sur.
El análisis de los resultados evidencia tres anomalías en el rango
2
de 20 a 40 T/cm -hr, entre el domo El Limón y la falla Los
Humitos. Una cuarta anomalía se localiza superficialmente asociada
a la falla de Mixco (Figura 21). Las tres anomalías presentan una
alineación NO-SE, desplazadas ligeramente hacia el sur de las
manifestaciones geotermales; el eje de alineación puede corresponder
con un rasgo estructural profundo subvolcánico relacionado
directamente con el reservorio geotérmico principal (Tobías 1987).
REFERENCIAS
Bethancourt, Hugo R. 1978. Proyecto Zunil. Estudio de

Factibilidad Preliminar. Informe de Factibilidad Preliminar.
Instituto Nacional de Electrificación. Guatemala.
Cordón y Mérida & MK Ferguson Company. 1990. Planta

Geotermoeléctrica de 15 MW. Proyecto Zunil I, Quezaltenango.
Estudios Geocientíficos No. 1. Informe final.
ELC Electroconsult. 1982. Primera Unidad Geotérmica. Campo de

Zunil, Quezaltenango. Informe de Factibilidad Preliminar.
Milano, Italia.
ELC Electroconsult. 1989. Área Geotérmica de Amatitlán. Estudio

de Prefactibilidad. Informe de Geoquímica de los Fluidos.
Milano, Italia.
Fournier, Robert & Hanshaw, Bruce B. 1981. Oxygen and Hydrogen

Isotopes in Thermal Waters at Zunil, Guatemala, report
submitted to the Instituto Nacional de Electrificación (INDE).
Guatemala.
304
Giggenbach, Werner F. 1986. The Isotopic and Chemical
Composition of Water and Steam Discharges from the Lago de
Amatitlán, San Marcos and Zunil Geothermal Fields, Guatemala.
Chemistry División, DSIR. Private Bag. Petone, New Zealand.
Giggenbach, Werner F. 1988. Isotopic and Chemical Composition

of Discharges from Zunil, Tecuamburro and Moyuta Geothermal
Fields, Guatemala. IAEA Report. Chemistry División, DSIR.
Private Bag. Petone, New Zealand.
Goff, Fraser., Adams, Andrew., Meeker, Kimberley., Truesdell,

Alfred., Roldan Manzo, Alfredo Rene., Janik, Cathy. 1989.
Hydrogeochemical Exploration of Tecuamburro Volcano Región,
Guatemala.
Gutiérrez L.C.A. y López, Arturo. 1983. Concentraciones

superficiales de Radón en el Campo de Los Azufres, Mich.
Informe 32-83. Comisión Federal de Electricidad. México,
Japan International Cooperation Agency. 1977. Republic of

Guatemala. Report on Geothermal Power Development Project.
OLÁDE. 1982. Estudio de Reconocimiento de los Recursos

Geotérmicos de Guatemala. Informe Final.
Roldan Manzo, Alfredo Rene. 1989. An Outline of Geothermal

Development in Guatemala. Report presented in the 20th
International Group Training Course on Geothermal Energy, held
at Kyushu University, Japan.
Tobías, Edgar. 1977. Proyecto Zunil. Estudio de Factibilidad

Preliminar. Informe Preliminar Geológico y Vulcanológico.
Instituto Nacional de Electrificación (INDE). Guatemala.
Tobías, Edgar. 1987. Proyecto Geotérmico Amatitlán. Estudio de

Prefactibilidad. Instituto Nacional de Electrificación (INDE).
Guatemala.
305
CARACTERÍSTICAS GEOQUÍMICAS E ISOTÓPICAS DE
LOS FLUIDOS PRODUCIDOS POR LOS POZOS DE
LOS HUMEROS, PUEBLA, MÉXICO
E. TELLO HINOJOS A
Gerencia de Proyectos Geotermoeléctricos,
Comisión Federal de Electricidad,
Morelia, México
Resumen-Abstract
CARACTERÍSTICAS GEOQUÍMICAS E ISOTÓPICAS DE LOS FLUIDOS PRODUCIDOS POR LOS

POZOS DE LOS HUMEROS, PUEBLA, MÉXICO.
Los análisis químicos e isotópicos de los fluidos producidos

por los pozos del campo geotérmico de Los
Humeros,Puebla.,fueron estudiados con el objeto de conocer la
química del yacimiento y los procesos que ocurren en él. De
acuerdo con las características químicas de los fluidos se
encontró que la salmuera producida por los pozos productores
es una agua de b a j a salinidad,cuyo carácter geoquímico es
variable y depende del tipo de pozo y la zona donde produzca.
Los pozos más someros presentaron un carácter bicarbonatado-
sódico. Mientras que los pozos más profundos presentan un tipo
geoquímico clorurado-sódico.También se encontró que de acuerdo
con los datos de exceso de vapor el pozo Hl produce en una
zona de líquido dominante, mientras que el resto de los pozos
producen en una zona de dos fases. Debido a lo anterior para
el pozo Hl la composición química en la descarga total es
igual que a condiciones de yacimiento, para el resto de los
pozos no se puede decir lo mismo. Ya que, son pozos que
presentan un exceso de vapor alto, y la composición a descarga
total no es la misma que a condiciones de yacimiento cuando se
presentan estas características.
De acuerdo con su composición isotópica los p o z o s de
Humeros presentan un corrimiento de oxígeno-18 característico
de fluidos de origen geotérmico que se han equilibrado con la
roca a altas temperaturas. Los manantiales aledaños al campo
en su mayoría se ubican en la linea meteórica. La muestra
proveniente de Alchichica presenta una composición isotópica
típica de una agua que ha sido m o d i f i c a d a por procesos de
evaporación a temperatura ambiente.
GEOCHEMICAL AND ISOTOPIC CHARACTERISTICS OF THE FLUIDS GENERATED IN LOS

HUMEROS WELLS, PUEBLA, MÉXICO.
Chemical and isotopic analyses of the fluids produced by wells in the

geothermal área of Los Humeros, Puebla, were carried out to establish the
chemical composition of the field and the processes taking place in it. The
chemical characteristics of the fluids showed that the brine produced by the
wells is a low-saline water, whose geochemical character varíes according to
well type and production zone. Shallower wells produced sodium bicarbonate-
type water, whereas the deeper wells exhibited a sodium chloride geochemical
307
type. It was also found, according to vapour excess data, that the Hl well is
in a zone where liquid is dominant, while the remaining wells are in a
dual-phase zone. As a result, the chemical composition of the Hl well total
discharge is the same as that of the field as a whole, whereas that statement
cannot be made for the other wells. Thus there are wells which produce a high
vapour excess, and the total discharge composition is accordingly not the same
as for the field as a whole.
The isotopía composition of the Humeros wells shows an ^0 shift

which is characteristic of fluids of geothermal origin that have reached
equilibrium with the rock at high temperatures. The springs adjoining the
área are mostly located on the meteoric line. The Alchichica sample has an
isotopic composition typical of a water which has been modified by evaporation
processes at ambient temperature.
1. INTRODUCCIÓN
El presente t r a b a j o fue realizado dentro del marco del

programa de investigaciones sobre la aplicación de técnicas
isotópicas y geoquímicas en la exploración geotérmica en
América Latina.
El campo geotérmico de Los Humeros, Puebla se encuentra
ubicado en la porción Centro-Oriente del Estado de Puebla, en
límites con la porción Centro-Occidente del Estado de Veracruz
a 53 Km al noroeste de la ciudad de Jalapa,Ver.
El o b j e t o del presente estudio es r e a l i z a r una
caracterización geoquímica e isotópica de los fluidos produci-
dos por los pozos de Los Humeros. Además de incluir manant-
iales localizados en la periferia del campo, con el fin de ver
si existe alguna interacción de estos con fluidos geotérmicos.
Para la realización de este trabajo se seleccionaron los
datos químicos de los pozos que hasta el momento han sido
m u e s t r e a d o s . Por t a n t o , a q u í se c o n t e m p l a r o n los datos
químicos de pozos que se perforaron hasta diciembre de 1989.
32 pozos han sido perforados a partir de 1981 a 1990 de
los cuales 22 son productores, 4 están contemplados como
inyectores, 4 f u e r o n f a l l i d o s y 2 están en c a l e n t a m i e n t o
(Figura 1).
2. COMPOSICIÓN QUÍMICA DEL AGUA SEPARADA DE LOS POZOS Y AGUA

DE MANANTIALES
Con el fin de caracterizar el tipo de agua que producen

los pozos se utilizó la gráfica 2, la cual relaciona el conte-
nido relativo en peso de SO4, Cl, y HCO3 ( Giggenbach, W . , 1 9 8 9
). L o s pozos H 6 , H 7 , H 9 , H 1 0 , H l l , H 1 2 , H13, H17, H 2 0 , H 2 3 ,
H24, H 2 7 , H 2 8 , H 3 0 , H32 Y H33 presentan un carácter clorurado-
sódico. Este tipo geoquímico es característico de agua prove-
niente de un yacimiento geotérmico . Normalmente en un yacimi-
ento geotérmico el equilibrio agua-roca se lleva a cabo a
profundidad y a altas temperaturas. Ahora bien, el agua de los
pozos H 6 , H10, H l l , H12,H 2 3 , H 2 4 , H 2 7 , H 2 8 , H 3 0 , H32 y H33
308
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2172000 2172000
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FIGURA IrLOCALIZACION DE LOS POZOS DE HUMEROS, PUE.
caen en la zona de aguas equilibradas con la roca. En la tabla

1 están referidos los resultados del análisis químico del agua
separada de los pozos que la producen.
Los pozos Hl, H16 y H18 presentan un carácter geoquímico
bicarbonatado-sódico. Estas características son adquiridas
debido a que están produciendo en la parte más somera del
yacimiento. Esta parte del yacimiento corresponde o se compor-
ta como una zona de condensación ( Figura 2 ).
309
TABLA 1.- COMPOSICION OU/MICA DEL AGUA SEPARADA DE LOS POZOS DE LOS HUMEROS.PUEBLA.
LA CONCENTRACION DE LOS SOLUTOS ESTA DADA EN mg/1 Y LA CONDUCTIVIDAD
ELECTRICA ESTA ENjmhos/cm. LA ENTALPIA TOTAL ESTA EN kJ Ikg.
No ENTALPIA
DE FECHA DE PH C.B. A/a K Ça Mg Si02 Cl SO4 HC03 B Li
POZO MEZCLA
H-1 121089 1385 8.2 1200 282. 0 46.0 1.78 0.05 911 99.6 110.8 207.5 247 0.85
H-6 121089 2378 7.9 1025 227.0 41.0 0.80 0.05 1142 252.7 1.7 39.8 253 0.75
H-7 191089 2587 6.6 750 147.0 22.0 2.20 0.04 885 76.9 73.2 34.3 2410 0.30
H-8 121089 2168 8.0 1150 282.0 46.0 2.20 0.07 988 96.8 99.6 100.3 503 0.57
H-9 261089 2662 6.8 775 170.0 26.0 0.76 0.02 940 79.4 4.0 82.0 2648 0.76
H-10 190789 2662 6.0 1010 141.9 19.1 1.80 0.02 265.1 12.4 80.5 5331 0.34
H-11 111089 2636 4.8 3500 203.0 27.0 7.10 0.40 909 982.7 33.3 28.2 1716 0.83
H-1 2 121089 2596 7.1 440 180.0 32.0 0.50 0.04 1023 133.4 1.7 49.3 1743 0.58
H-1 3 121089 1671 8.1 1650 350.0 66.0 4.00 0.07 949 393.1 71.5 87.7 267 1.37
H-1 5 70689 2115 5.2 550 120.0 15.0 1.20 0.07 502 9.8 131.9 10.0 142 0.40
H-1 6 131089 2498 8.9 2100 586.0 32.0 0.90 0.05 551 99.3 142.0 463.8 220 0.85
H-17 131089 2662 7.6 635 112.0 19.0 0.84 0.03 519 158.8 75.3 41.5 184 0.40
H-1 8 131089 1747 8.0 1645 123.0 23.0 0.92 0.04 229 112.3 42.8 396.6 118 0.37
H-20 60989 2628 7.3 525 93.0 16.0 1.20 0.02 441 79.5 19.4 70.6 469 0.31
H-23 210189 2064 7.6 1060 146.0 10.0 6.00 0.06 163 193.6 107.7 2.4 73 0.20
H-24 180589 2491 7.6 1500 285.0 46.0 1.50 0.11 406 324.6 27.3 58.2 422 0.90
H-27 130489 2260 7.4 1075 75.0 6.0 1.70 0.07 252.5 21.0 10.3 187 0.10
H-28 180789 1731 8.4 2400 533.4 28.1 0.60 0.01 556.0 31.8 110.4 227 1.54
H-30 140389 2662 5.3 1925 112.0 14.4 0.80 0.08 152 498.4 13.9 259.6 5963 0.23
H-31 121089 2489 7.7 455 112.0 21.0 1.00 0.05 970 14.4 0.6 26.3 1192 0.42
H-32 131089 2637 5.7 1275 107.0 21.0 5.30 0.18 914 329.9 15.8 9.5 1628 0.24
H-33 261089 2662 7.2 900 180.0 27.0 1.70 0.04 911 178.0 5.7 33.2 1495 0.40
NOTA: C.E. CONDUCTIVIDAD ELECTRIC A

LOS ANALISIS FUERON REALIZADOS POR CFE
FIGURA 2.. CONTENIDO RELATIVO DE CI.S04
Y HCOi EN PESO (mg/Kg). LA

RAZON HCOi/CI ESTA EN RAZON
PESO. PO ZO S
MANANTIALES
OK)
0-25
% CI
HCOï/CI
1.0
4-0
SO 4 HCOi
60____% HCO»____80
Cuando los pozos están produciendo en una zona de
condensación normalmente se detectan bajas concentraciones de
cloruros. Sin embargo, se detectan altos contenidos de bicar-
bonatos y sulfatos. Esto se debe a que el vapor que transporta
consigo CO2 y H2S condensa en el acuífero (zona de
condensación). Bajo estas condiciones la reacción con la roca
produce soluciones bicarbonatadas-sulfatadas con pH ácido y/o
alcalino.
El pozo H15 presenta un carácter sulfatado-ácido, el cual
también es adquirido cuando el pozo está produciendo en la
parte más somera del yacimiento, la cual corresponde a una
zona de condensación. Esto hace que al interaccionar el H2S de
origen geotérmico con el agua de la zona de condensación parte
del H2S, es disuelto en la fase líquida enriqueciéndose ésta
en sulfatos. Como se puede ver en la figura 2 el pozo H15 cae
en la zona indicativa de aguas calentadas por vapor. Esto solo
puede ocurrir en la parte más somera de un yacimiento
geotérmico o bien en manantiales superficiales. Debido a lo
anterior se puede decir que también este pozo produce en una
zona de condensación.
Con respecto a los manantiales aledaños al campo, los
cuales están referidos en la tabla 2, en su mayoría son del
tipo bicarbonatado- sódico. Este carácter geoquímico sugiere
que se trata de aguas de reciente infiltración que han inter-
accionado con roca de origen volcánico a bajas temperaturas
(Figura 2). Cabe mencionar que solo el agua proveniente de
Arteziano (M7) presenta un carácter clorurado-sódico
característico de agua de origen geotérmico ( Figura 2).
Los geotermómetros de solutos iónicos tales como Na/K
(Ellis and Manon, 1964) y de Na-K-Ca ( Fournier and Truesdell,
1973) son una poderosa herramienta para evaluar las condi-
ciones profundas de sistemas geotérmicos. Normalmente el
problema que se presenta en la utilización de estos
geotermómetros es el que se deriva del uso indebido a muestras
que no se les puede aplicar. Una selección o depuración ini-
cial para determinar si es aplicable uno de estos
geotermómetros está basado en el valor del pH y los contenidos
relativos de Cl, SO4 y HCO3 ( Figura 2 ).
Recientemente ( Giggenbach, W. 1986 y Ginggenbach, W.
1988 ) desarrolló una técnica que da una indicación automática
sobre la aplicabilidad de geoindicadores de solutos iónicos.
Esta basada esencialmente en la dependencia de la temperatura
de las dos siguientes reacciones:
K-Feldespato + Na = Na-Feldespato + K ( 1 )
2.8 K-Feldespato +1.6 H20 + Mg =
0.8 K-Mica +0.2 Clorita +5.4 Sílice + 2 K (2 )
312
TABLA 2- COMPOSICIÓN QUÍMICA E ISOTÓPICA DEL AGUA DE MANANTIALES Y NORIAS DE LOS HUMEROS.PUE.
LA CONCENTRACIÓN DE LOS SOLUTOS ESTA DADA EN mg/l Y LA CONDUCTIVIDAD ELÉCTRICA ESTA
EN/ffnhos/cm.
NOMBRE
No FECHA DEL PH C.E. TIPO Na K Ca Mg S¡02 Cl S04 HC03 B DEUTERIO OXI-18 TRITIO
MANANTIAL
1 270188 HUICHOTITA 4.5 90 J M 5.0 3.6 17.0 0.9 45.0 1.3 0.0 31.5 0.00 -68.5 -10.6 9.7
2 300188 ATOLUCA 7.0 70 M 4.3 5.0 12.0 0.7 23.0 2.7 0.0 24.2 0.00 -64.8 -9.8 8.3
3 20188 MIXQUIAPAN 7.5 105 M 6.6 1.7 9.2 1.5 37.7 2.0 0.0 46.1 0.00 -67.1 -10.2 0.7
4 10288 CHACHAR 8.1 135 M 8.6 1.4 19.5 1.0 23.0 2.7 0.0 29.1 0.00 -72.2 -11.0 8.4
5 270188 SOTÓLA 7.6 120 M 5.6 3.2 7.1 1.3 47.5 4.1 8.9 9.7 0.00 -82.6 -12.0 11.7
6 270188 HUIZILPOPOCA 7.6 91 N 6.6 3.2 5.6 0.9 40.2 4.1 3.9 24.2 0.00 -80.4 -12.1
7 250188 ARTEZIANO 9.0 13100 N 3160 300.0 26.9 19.3 4.0 2364 1974 1379 37.80 -48.4 -5.3
8 250188 S.N. PIZARRO 8.5 5150 N 833.0 95.0 15.6 78.4 13.4 622.0 899.0 1128 3.34 -75.5 -10.2
9 260188 TEXCALPITZAHUAC 8.1 340 P 30.4 1.4 21.8 5.6 32.8 0.0 5.8 128.6 0.08 -74.2 -11.0
10 250188 BARRIENTOS 8.5 350 N 27.0 5.3 20.2 8.3 28.0 4.1 8.8 114.1 0.17 -71.4 -10.5
11 250188 SANTIAGUITO 8.3 400 P 39.6 3.9 32.4 12.2 23.0 15.2 18.3 179.0 0.08 -70.8 -10.3
12 250188 SAN ROQUE 7.8 134 N 42.0 2.1 18.8 8.7 23.0 11.1 7.8 182.0 0.04 -72.2 -10.8
13 260188 HUIZILTEPEC 8.2 540 N 17.6 4.6 28.0 3.3 30.5 4.8 2.8 152.9 0.00 -86.4 -12.3
14 260188 GONZAGA 8.7 400 M 47.6 4.2 25.0 1.1 32.8 8.2 9.4 0.0 0.00 -88.4 -11.0
15 290188 TZOCUILA 7.4 134 M 6.0 4.2 7.0 1.7 52.3 2.7 2.9 36.4 0.00 -57.1 -8.8
16 260188 MATLAHUACALA 8.2 540 M 8.3 2.5 76.0 2.8 13.4 8.2 34.8 223.3 0.00 -75.1 -11.1
17 290188 TEMOXIZA 7.6 106 M 7.0 1.7 20.0 1.0 42.6 1.3 0.0 38.8 0.00 -68.3 -10.6
18 30288 MAZAPA 7.3 137 M 9.6 2.5 17.0 2.2 45.0 5.5 0.0 53.4 0.08 -68.5 -10.6 3.5
19 30288 EL TESORO 7.6 1000 M 83.0 9.2 38.0 27.6 49.6 70.5 3.5 371.4 1.27 -77.3 -11.2 0.8
20 290188 CHIGNAUTLA 7.5 145 M 14.0 1.4 11.6 1.1 22.2 5.5 0.0 50.9 0.00 -68.2 -10.6 4.0
21 10288 S.J. XIUTETELCO 7.5 108 M 9.0 1.0 11.9 1.4 25.2 2.7 0.0 29.1 0.00 -71.4 -10.1 2.6
22 30288 ZOATZINGO 6.6 95 M 6.0 3.2 4.0 1.0 46.5 4.1 0.8 24.3 0.00 -53.3 -8.6
24 280188 TRES OCOTES 7.1 55 M 4.3 2.5 3.4 0.5 37.5 2.7 0.0 16.9 0.00 -67.9 -10.2
U)
( confinación Tabla 2 ~ página 2 de 2)
NOMBRE
No FECHA DEL PH C.E. TIPO Na K Ca Mg SiO2 Cl SO4 HCO3 B DEUTERIO OXI-18 TRITIO
MANANTIAL
25 20288 COATLAMINGO 7.3 76 M 5.0 2.5 4.8 0.7 34.4 17.9 0.0 31.5 0.00 -67.5 -10.5
26 20288 EL RANCHO 6.7 107 M 4.6 2.5 7.3 1.5 31.3 20.7 0.0 43.7 0.00 -52.7 -7.9
27 20288 EL ATRIO 6.9 180 N 4.6 6.0 12.5 1.7 19.2 4.1 0.0 82.5 0.10 -62.0 -9.6 4.2
28 10288 LA BARRANCA 7.7 100 M 6.0 2.1 7.0 1.4 31.3 2.7 0.0 38.8 0.08 -66.8 -10.3
29 20288 AHUACATLAN 7.7 77 M 4.6 3.2 6.7 0.9 58.7 2.7 0.0 31.5 0.08 -45.9 -8.1
30 10288 LA PASADA 7.1 65 M 3.6 2.5 4.3 0.6 40.4 2.7 0.4 16.9 0.00 -53.7 -8.6
31 280188 LA CUEVA 7.8 70 M 4.6 2.5 12.5 1.0 31.3 1.3 0.0 28.7 0.00 -65.5 -9.8
32 280188 ACUACO 8.2 200 P 7.6 2.1 21.4 1.5 46.5 3.5 0.1 71.9 0.00 -73.2 -10.9 2.5
33 260188 HUITZILAPAN 8.1 164 N 9.0 3.5 9.6 1.9 43.5 4.1 1.0 62.2 0.08 -75.0 -10.6 2.5
34 260188 XALTIPANAPA 8.1 740 N 73.0 15.0 69.3 4.4 25.2 4.1 28.3 0.0 0.00 -66.3 -10.1
35 270188 CALZACATENO 7.7 65 M 4.6 2.8 3.0 0.5 31.3 1.3 0.0 76.7 0.00 -66.3 -10.3
36 270188 SIETE AGUAS 7.6 58 M 4.0 2.1 2.9 0.4 19.2 2.8 2.8 24.0 0.08 -65.5 -10.3
37 11287 ALCHICHICA -12.3 0.7
NOTA : (M) MANANTIAL, (N) NORIA, (P) POZO ARTEZIANO, (C. E.) CONDUCTIVIDAD ELÉCTRICA
EL MUESTREO PARA ANÁLISIS ISOTÓPICO FUE REALIZADO DE OCTUBRE A DICIEMBRE DE 1987
EL ANÁLISIS QUÍMICO FUE REALIZADO POR CFE. DEUTERIO YOXIGENO-18 LO ANALIZO EL HE Y EL TRITIO
FUE ANALIZADO EN EL LABORATORIO DEL OIEA EN VIENA.

Ambas reacciones involucran minerales en equilibrio total
que se espera obtener después de la recristalización
isoqulmica de una roca de la corteza de composición promedio,
bajo condiciones de interés geotérmico. La reacción (2)
responde más rápido y entonces se obtiene la última
temperatura de reequilibración dando generalmente temperaturas
bajas. Combinando los dos subsistemas, se obtiene un método
que permite obtener el grado de equilibrio agua-roca, y
determinar si es factible aplicar los demás geotermómetros. En
la figura 3 está graficado el contenido relativo de Na, K y Mg
para el agua de los pozos y manantiales de Humeros,Puebla. Los
análisis de agua de los pozos, se sitúan en la zona de
equilibrio parcial, a excepción del H16 que está en equilibrio
a una temperatura de 200°C. El pozo H28 el cual se localiza
más arriba de la linea teórica indica que este pozo presenta
pérdida de vapor e incremento del contenido absoluto del
soluto (Giggenbach, W. 1989).
Las aguas que corresponden a manantiales están todas
desplazadas hacia la esquina del Mg. Esto indica que se trata
de aguas de reciente infiltración bicarbonatadas-sódicas que
se han equilibrado con roca de origen volcánico a temperaturas
inferiores a 100°C. Solamente la muestra proveniente de Arte-
ziano (M7) se ubica en la zona de equilibrio parcial con una
temperatura del geotermómetro K/Mg de 156°C.
3. EVOLUCIÓN DE LA COMPOSICIÓN QUÍMICA DEL AGUA DEL YACIMIENTO
Un muestreo sistemático de los fluidos producidos por los

pozos de Los Humeros se ha llevado a cabo por CFE desde 1982 a
la fecha. Para conocer la historia de los solutos en el yaci-
miento se seleccionó a los pozos Hl, H6, H8 y H13 los cuales
producen una mezcla vapor-agua.
En las figuras 4 y 5 esta graficado el contenido de cloru-
ros a descarga total y a condiciones de yacimiento contra
tiempo para los pozos Hl, H6, H8 y H13 desde su inicio hasta
diciembre de 1989. Para el caso del pozo Hl (Figura 4), se
puede observar que tanto a descarga total como a condiciones
de yacimiento los cloruros han permanecido constantes con
respecto al tiempo.
Para el pozo H6 (Figura 4) , se observa que la
concentración de cloruros tanto en la descarga total como a
condiciones de yacimiento también ha permanecido constante con
respecto al tiempo.Para el pozo H8 se puede decir que al
principio se detectaron los valores mayores de cloruros en el
yacimiento y en la descarga total. Sin embargo, a partir de
1986 a la fecha el comportamiento a sido asintótico.El H13 que
es otro de los pozos que producen una mezcla vapor-agua, la
composición química a descarga total y a condiciones de yaci-
miento se ha incrementado con respecto al tiempo. Esto se debe
a que este pozo estuvo produciendo en la zona de
condensación y ahora produce en la zona de dos fases de ahí
que los cloruros se incrementen con respecto al tiempo.
315
FIGURA 3 - CONTENIDO RELATIVO DE Na, K Y Mg No/1000
EN PESO ( m g / K g ) A POZOS
0 MANANTIALES
K/IOO
Lo* Mum«ros
H-l
110
100
90
80
70
60
f*
50
**
40
30
20
Cl de Y o c í m .
10
Cl en la M e z c l a
O —1——————i———
82 84 86 88 90
TIEMPO (AMOS)
300
280 -
H-6
260-
240 -
220 -
200- B
180 -
á
140 - g
120 -
100-
n
. °
80- •*• n D
60-
D
40 -
D Cl.de Y a c i m + .+ +* ^
20 -
+ Cl en la Mezcla
0- t i
86 87 88 89 90
TIEMPO (AROS )
Figura 4.— Cloruros contra tiempo
317
Los Humeros
zuu -
190 -
H-8
180 -
170 -
160 -
B
150 -
140 -
*"N
130 -
| 120 -
D
V-
' 110 - n
w 100 - D
§ 90 -
2 80 -
«
3u 70 - 2k Dn CL, Cpn'"1 n E
60 - + °g gana130 ntftijf1
50 - •f
40 -
* *+ + +
30 - *t- -H- "*"++
20 - +
* + +
10 -
0- ——— ———— • , , , •---- r- ——— -- ————i
85 87 89
TIEMPO (AÑOS)
280 - H-13
260 -
240 - P n
n
220 - n n
- 200 - a
£ 180 -
160 -
•*•
.
+
^.
+
+
V) Jf*B
o
K 140 - ^ +
3 __
¥ 120 - +
9 100 - +^
80 - +
60 -
40 - U Cl de Y a c i m .
20 -
+ C 1 en la M e z c l a
" 1 L 1 1 1 í 1 1 1 t 1 1 1 1 1 !
88.5 88.7 88.9 89.1 89.3 89.5 89
TIEMPO (AÑOS)
Figura 5.— Cloruros contra tiempo
318
4. COMPORTAMIENTO DINÁMICO DEL YACIMIENTO
La composición química del agua de los pozos puede cambi-

are Estas variaciones se pueden deber a reducciones en la
presión de yacimiento ó bien a fenómenos de mezcla, dilución,
evaporación, condensación, desgasificación etc.
Por varios años los pozos productores de Los Humeros han
sido muestreados para observar los cambios ocurridos en su
composición química. Además la variación en las temperaturas
del agua profunda durante la producción puede ser monitoreada
por medio de geotermómetros químicos.En las figuras 6 y 7 está
graficada la temperatura de los geotermómetros de sílice y
Na/K para los pozos Hl, H6, H8, y H13 con respecto al tiempo.
Se puede observar en estas figuras que los dos geotermómetros
concuerdan muy razonablemente y además han permanecido con-
stantes con respecto al tiempo para estos pozos.
La solubilidad de la sílice y la razón de Na/K al variar
la temperatura pueden ser usados para determinar que mecanismo
es el que causa cambios en la composición química. Por ejem-
plo, cuando la temperatura disminuye a causa de una ebullición
rápida o a la influencia de agua fría puede no afectar inme-
diatamente la razón Na/K. Sin embargo, una mezcla de dos aguas
previamente equilibradas a diferentes temperaturas podría
afectar ambas razones SiOo y Na/K (Ellis, A. J. and
Manon,W.A.J., 1977).
En las figuras 8 y 9 se ilustran los cambios que ocurren
en la concentración de cloruros y la temperatura de la sílice
para el pozo Hl durante el periodo 1982-1988. Además en estas
figuras se incluye un patrón de lineas las cuales cada una
indica un proceso diferente el cual puede ocurrir en el yaci-
miento. Por tanto, se puede decir que para el pozo Hl los
cambios son regulares y variables y se observa que estos
cambios están dominados por una serie de procesos complejos de
ebullición, evaporación, condensación, dilución y en el perio-
do de 1986 a 1988 predominan los procesos de pérdida y ganan-
cia de vapor. Para el pozo H6 los procesos que predominan
durante el tiempo de observación, que comprende de 1986 a 1988
fueron: condensación de vapor, ebullición, ganancia y pérdida
conductiva,dilución por aguas frías y aguas a 150°C ( Figura
10 ). En el caso de del pozo H8 se siguió el mismo procedimi-
ento encontrándose que los cambios en la concentración de
cloruros de yacimiento y temperaturas de sílice han sido
grandes los cuales han ido haciéndose menos variables con
respecto al tiempo. Los procesos predominantes son:
condensación de vapor, dilución por aguas a 150°C, ebullición,
evaporación, ganancia y pérdida conductiva.
5. EXCESO DE VAPOR Y COMPOSICIÓN EN LA DESCARGA TOTAL Y A

CONDICIONES DE YACIMIENTO
Si la entalpia de descarga de los pozos excede la de un

líquido saturado a la temperatura de reservorio, se considera
que existe un exceso de vapor. Las entalpias de descarga de
los pozos del campo geotérmico de Los Humeros varían de 1385 a
2662 kJ/kg. Una alta entalpia de descarga refleja dos fases
319
Los Humeros
H-i
400 -
300 -
+
n
200 -
100 -
i l i
82 84 86 88 90
TIEMPO (AÑOS)
500
H-6
400 -
n p D
300 -
a.
200 -
100 -
D T Nal K
T S¡0
-\—————i—————i—————r i—————r~
86 87 68 89 90
TIEMPO (AROS)
figura 6. Geotermómetros contra tiempo
320
Los Humeros
500
H-8
4OO -
300 -
2 nn
% 200-
100 -
—i—————— —r~
85 87 89
TIEMPO (ANOS)
500
H-13
400 -
g n
300 -
a n n n
200 -
100 -
D T NalK
+ T SÍ02
i i i i i i i i i i i i i i
88.4 88.6 88.8 89 89.2 89.4 89.6 89.8 90
TIEMPO (AROS)
Figura 7. Geotermómetros contra tiempo
321
u)
NJ
P E R I O D 0 2 4 - I O - 8 3 o 16-10-84 P E R I O D O 16-10-840 12-08-85
EVAPORACIÓN EVAPORACIÓN
0(
""""!lg Conductivo Ptrdldo Conductiva Oononcla C o n d u c t i v o
90 90
Cond * f t * o c t on Cond*n$aclon
80 80
12 14
CT 0>
E E
ÜJ
70 70
c/j co
O o
CE ce
D CE 10
cu
o O
_j 60 -J 60
o O
50 - 50
40 40
260 270 280 290 300 260 270 280 290 300
GEOTERMOME""RO DE S Í L I C E (°C ) GEOTERMOMETRO D E S I L I C E ( ° C )
FIGURA 8 .- CAMBIOS EN LA C O N C E N T R A C I Ó N DE C L O R U R O S Y T E M P E R A T U R A DE S Í L I C E CON

R E S P E C T O AL TIEMPO P A R A EL POZO H - l .
PERIODO 12-08-85 a 13-10-86
EVAPORACIÓN
100- 100 P E R I O D O 13-10-86 o 1 9 - 0 7 - 8 8
90- Perdida Conducta lando Conductiva

<?. *
90
Condtniaclon
80
80
o>
E
z UJ
UJ 70 3S-
V) 70
co O
o ce
CE
Z) ce
ce o
_i
3 60 O 60
o
50 50
40 _ 40
260 270 280 290 300 260 270 280 290 300 3/0
GCOTERMOMETRO D E S Í L I C E ( ° C ) GEOTERMOMETRO DE SÍLICE ( ° C )
K)
FIGURA 9 . - C A M B I O S E N L A CONCENTRACIÓN DE CLORUROS Y T E M P E R A T U R A DE S Í L I C E CON
RESPECTO AL TIEMPO PARA EL P O Z O H-l
PERIODO 11-07-86 a 1 9 - 0 7 - 8 8
150 -
140 -
130 -
LJ
o
o:
3
oc
o
_J
o
100 -
270 280 290 300 310 3 2O

GEOTERMOMETRO D E S Í L I C E ( ° C )
FIGURA 1 0 . - C A M B I O S EN LA CONCENTRACIÓN DE C L O R U R O S Y
T E M P E R A T U R A DE S Í L I C E CON RESPECTO A L T I E M P O
P A R A EL POZO H-6
(vapor y agua) en el yacimiento y su separación parcial en el

acuífero antes de entrar al pozo. En la tabla 1 está referida
la entalpia de mezcla de los pozos de Los Humeros. Si se
observa en la tabla 1 la entalpia de descarga del pozo Hl
corresponde a la de un liquido saturado a la temperatura de
reservorio; por consecuencia el exceso de vapor a condiciones
de yacimiento es pequeño. Esto sugiere que el yacimiento
penetrado por el pozo Hl es de liquido dominante ( Tello,H.E.,
1984a).
Para el resto de los pozos la entalpia de mezcla es mucho
mayor que la entalpia de un liquido saturado a la temperatura
de yacimiento, cuando esto se presenta se debe a que a condi-
ciones de yacimiento en forma natural existe una fracción de
vapor coexistiendo con la fase liquida.
324
Una de las causas del exceso de vapor o entalpia de los
pozos es que las fases de vapor y agua no son transmitidas a
través de la formación en el reservorio con igual facilidad
porque las dos fases tienen diferentes permeabilidades
relativas. Es también concebible que el exceso de vapor se
deba a la evaporación de agua por conducción de calor
proveniente de la roca del reservorio, ya que la caída de
presión causada por la extracción del fluido por los pozos
productores origina el enfriamiento ( por ebullición )de este
fluido y por esta razón hay flujo de calor conductivo de la
roca a ese fluido. Sin embargo, hay dificultades involucradas
en la evaluación química del agua del reservorio, basada sobre
datos de exceso de vapor de los pozos. Si el reservorio
contiene solamente agua, entonces es fácil relacionar la
composición de las muestras a superficie con las condiciones
de reservorio. En el caso contrario, si el fluido en el pozo
es un fluido de dos fases con exceso de vapor, no es posible
relacionar la composición química del fluido en la superficie
con las condiciones de reservorio, sin hacer algunas
suposiciones fundamentales. Por tanto, para este estudio la
composición química del agua en Los Humeros fue evaluada
suponiendo dos posibles causas del exceso de vapor de los
pozos: a) transferencia de calor conductivo de la roca b)
efectos de permeabilidad relativa para el flujo de ambas fases
vapor y agua. Se consideró que ambos procesos ocurren en forma
excluyente. El primer caso supone que la transferencia de
calor involucra evaporación de agua desgasificada (ya
hervida), de tal forma que se añade vapor libre de gas al
vapor formado con anterioridad. Este modelo supone que la
descarga total representa una sola fase líquida en el
yacimiento (Pozo Hl). En el segundo caso, se supone que el
exceso de vapor es debido a los efectos de permeabilidad
relativa para las fases agua-vapor. Aquí, los cálculos de las
concentraciones del agua en el yacimiento supone dos fases en
el reservorio, lo cual ocurre en los pozos H6, H8 y H13. Es
importante mencionar que para los pozos H9, H10, Hll, H12,
H16, H17, H18, H19, H20, H23, H27, H28, H29, H30, H31,
H33 el método de exceso de entalpia no es posible aplicarlo
para hacer alguna corrección de los solutos en el yacimiento
debido a que algunos pozos producen poca agua, y la poca que
producen es difícil muestrearla, o bien presentan entalpias
que corresponden a las de un vapor saturado. Por tanto, si se
aplicara este método de corrección de la composición química
del agua basados en los datos de entalpia se tendrían datos
erróneos para estos pozos.
6. COMPOSICIÓN A DESCARGA TOTAL Y EN EL YACIMIENTO
Dependiendo de la presión ejercida en la descarga, las

concentraciones de varios solutos varían en las fases indivi-
duales agua-vapor; mientras que la concentración en la
descarga total permanece constante para condiciones de
yacimiento constantes. Los componentes son distribuidos entre
las fases de acuerdo con la fracción de vapor, la cual es una
función de la presión.
325
Para la concentración de solutos de los fluidos evaporados
a presión atmosférica se corrigieren a descarga total usando
la siguiente ecuación:
Ao = Aa(l - Xv) (3 )
donde Ao es la concentración a descarga total del componente
A, Aa es la concentración a presión atmosférica del componente
A, y Xv es la fracción de vapor, la cual se calcula de acuerdo
con,
Xv = Ho - Ha / Hv - Ha (4 )
donde Ho es la entalpia de mezcla y Ha y Hv son la entalpia de

líquido y vapor a la temperatura de saturación respectiva-
mente, que en el caso de los Humeros es de 91°C.
Es importante determinar las concentraciones a condiciones
de yacimiento, ya que es posible detectar variaciones en la
composición del fluido del reservorio. Estas concentraciones
pueden ser calculadas por medio de la siguiente expresión,
Ay = Ao / ( 1 - Xv ) (5 )
donde Ay es la concentración a condiciones de yacimiento del
componente A, Ao es la concentración del componente A en la
descarga total y Xv es la fracción de vapor, la cual se calcu-
la de acuerdo con,
Xv = Ho - Ha / Ha - Hv (6 )
donde Ho es la entalpia de mezcla y Ha y Hv son las entalpias
del líquido y vapor a la temperatura del yacimiento.
En las figuras 4 y 5 están representados los cloruros de
yacimiento y en la descarga total contra el tiempo para los
pozos Hl, H6, H8, y H13. Se puede ver en estas figuras que
solamente las concentraciones del Hl concuerdan muy razonable-
mente tanto a descarga total como a condiciones de yacimiento.
Ahora bien, el hecho de que se agrupe el contenido de cloruros
en la descarga total como a condiciones de yacimiento signifi-
ca que el pozo está produciendo en una zona de líquido domi-
nante (Tello,H. E. 1984 a). Por lo tanto, cuando esto ocurre
la composición química a condiciones de yacimiento es igual a
la descarga total. Para el pozo H6 la composición química en
la descarga total no es la misma que a condiciones de yacimi-
ento. Esto indica que está produciendo en una zona de dos
fases ( Figura 4 ).
Para los pozos H8 y H13 nuevamente se presenta la
separación entre ambos valores, lo que indica que también
estos pozos producen en una zona de dos fases ( Figura 5 ).
Para el resto de los pozos como se mencionó en párrafos
anteriores no es posible aplicar este método para corregir la
concentración de los solutos a descarga total y a condiciones
de yacimiento. En la tabla 4 está referida la composición
química a descarga total y a condiciones de yacimiento de los
pozos Hl, H6, H8 y H13.
326
TABLA 3.- COMPOSICIÓN QUÍMICA DE LOS GASES DE LOS POZOS DE LOS HUMEROS .PUEBLA.
EL CONTENIDO DE LOS GASES ESTA DADO EN % PESO. LA ENTALPIA ESTA DADA
kJ/kg Y PRESIÓN DE CABEZAL ESTA DADA EN (MPA)
POZO FECHA ENTALPIA TEMPSEP xg COZ H2S NH3 HELIO H2 Ar N2 CH4 GGDP
H-1 121089 1385 126 5.69 98.27 0.92 0.64 0.0001 0.0006 0.00 0.154 0.009 155
H-6 121089 2378 133 3.51 91.87 6.26 0.71 0.0000 0.0061 0.00 0.546 0.546 269
H-7 191089 2587 137 2.27 93.64 5.59 0.20 0.0000 0.0309 0.00 0.504 0.025 277
H-8 121089 2168 177 5.61 96.73 2.37 0.39 0.0000 0.0240 0.00 0.466 0.013 269
H-9 261089 2662 128 1.39 84.96 10.52 1.74 0.0008 0. 1650 0.00 1.430 1.170 301
H-10 190789 2662 125 1.43 91.43 5.77 1.15 0.0000 0.0574 0.00 1.570 0.001 319
H-11 111089 2636 133 2.78 94.84 3.81 0.76 0.0000 0.0270 0.00 0.431 0.129 244
H-12 121089 2596 275 7.39 94.36 3.76 0.49 0.0000 0.0620 0.00 1.240 0.800 246
H-1 3121089 1671 144 3.43 93.60 4.61 0.49 0.0000 0.0590 0.00 1.030 0.217 264
H-15 70689 2116 136 2.89 84.86 11.26 0.37 0.0022 0.1440 0.00 3.180 0.180 310
H-16 131089 2498 241 1.94 89.27 8.60 0.45 0.0000 0.0810 0.00 0.795 0.800 300
H-17 131089 2662 134 3.02 95.49 3.11 0.73 0.0000 0.0270 0.00 0.333 0.249 249
H-18 131089 2530 105 36.5 95.66 1.73 0.22 0.0000 0.0990 0.00 0.186 2.100 239
H-20 060989 2628 143 2.38 91.77 6.13 0.64 0.0000 0.0709 0.00 0.486 0.916 257
H-23 210189 2064 160 5.17 90.30 7.99 0.19 0.0005 0.1140 0.00 1.060 0.322 287
H-24 180589 2491 124 6.42 96.48 1.58 0.33 0.0000 0.0754 0.00 0.650 0.879 238
H-27 130489 2260 143 4.67 91.29 5.10 0.41 0.0000 0. 1450 0.00 3.030 0.018 286
H-28 180789 1731 129 1.43 80.06 12.49 2.37 0.0000 0.2090 0.00 4.840 0.033 282
H-29 131089 2662 7.67 88.45 9.08 0.28 0.0000 0.1110 0.00 1.990 0.084 305
H-30 140389 2662 137 2.49 88.82 6.40 0.17 0.0000 0.2600 0.00 2.990 2.050 289
H-31 121089 2489 112 2.56 89.92 7.33 0.66 0.0000 0.1040 0.00 0.623 1.360 268
H-32 131089 2637 113 1.50 91.59 7.10 0.21 0.0000 0.0550 0.00 0.994 0.036 285
H-33 171089 2662 188 1.39 85.40 12.10 1.21 0.0003 0.0946 0.00 0.827 0.820 280
TEMPSEP.- TEMPERATURA DE SEPARACIÓN EN ( °C)
GGDP.-GEOTERMOMETRO DE GASES DE D'AMORE Y PANICHI EN ( °C )

UJ
K) LOS ANÁLISIS FUERON REALIZADOS POR CFE
-J
TABLA 4.- COMPOSICIÓN QUÍMICA DEL AGUA SEPARADA A DESCARGA
TOTAL YA CONDICIONES DE YACIMIENTO. LA ENTALPIA
ESTA DADA ENkJ/kgYLA CONCENTRACIÓN EN mg /1.
CONCENTRACIÓN EN LA DESCARGA TOTAL

POZO FECHA ENTALPIA Na K Ca Mg Si02 Cl B TNa/K
H-1 121089 1385 158 26 1.0 0.03 510 56 138 263
H-6 121089 2378 28 5 0.1 0.006 142 31 32 273
H-8 121089 2168 61 10 0.5 0.02 214 21 109 263
H-1 3 121089 1671 152 29 2.0 0.03 412 171 116 278
CONCENTRACIÓN A CONDICIONES DE YACIMIENTO

POZO FECHA ENTALPIA Na K Ca Mg SÍO2 Cl B TNa/K
H-1 121089 1385 182 30 1.0 0.03 596 65 161 263
H-6 121089 2378 110 20 0.4 0.02 552 122 122 273
H-8 121089 2168 160 26 1.0 0.04 562 55 286 263
H-1 3 121089 1671 213 40 2.0 0.04 577 239 162 278
TNa/K.- GEOTERMOMETRO DE SODIO / POTASIO ( °C )
7. EQUILIBRIO QUÍMICO DEL YACIMIENTO Y GEOTERMOMETRIA DE FASE

LIQUIDA
Se ha demostrado que el estudio del equilibrio

soluto/mineral es de gran ayuda para hacer una evaluación
completa de un sistema geotérmico. Esto está basado en el
hecho de que la química de los fluidos está primeramente
gobernada por la solubilidad de los minerales, lo cual es
importante para poder entender los factores termodinámicos que
afectan el equilibrio. Por ejemplo el uso de geotermómetros
químicos, y la predicción de la tendencia de la depositación e
incrustación de los minerales depende grandemente del estado
de saturación que se haya logrado entre el fluido y la roca.
Debido a la gran importancia que esto representa para el mejor
entendimiento del estado termodinámico del yacimiento. Se han
realizado estudios con este enfoque desde 1986 los cuales
fueron realizados por ( Tello, H. E. 1986 ) ,
(Tello,H.E.,1987), ( Tello,H.E.,1989ab). Ahora bien, sabiendo
el estado de equilibrio agua-roca sirve entre otras cosas para
predecir las tendencias de depositación de los minerales. Es
sabido que las especies químicas son controladas por la solu-
bilidad de los minerales y que el estado de saturación es
altamente dependiente de los procesos físicos que puedan
ocurrir durante el transporte del fluido del reservorio a la
superficie» Estudios sobre la cinética de interacción agua-
roca, ebullición,desgasificación,enfriamiento y dilución con
fluidos más fríos han demostrado que estos son los principales
procesos los cuales causan que algunos minerales se desvien de
su estado de saturación original ( Arnorsson et al.,1982b).
Por ejemplo se ha visto que una ebullición con una máxima
desgasificación produce un fluido supersaturado con respecto a
la calcita, y de una progresiva ebullición y enfriamiento a
temperatura más bajas se obtienen fluidos saturados en sílice
amorfa. Es por tanto, deseable para la propia interpretación
de los datos químicos, que cada factor sea tomado en cuenta.
328
8. ESTADO DE SATURACIÓN DEL FLUIDO PROFUNDO RESPECTO A
MINERALES SELECTOS
En las figuras 11 se muestra el estado de saturación del

agua a profundidad respecto a la calcita, anhidrita y cuarzo,
a la temperatura medida en la zona principal de producción.
Los valores de solubilidad para cada uno fueron calculados
a partir de los datos termodinámicos de Helgeson (1969), y
las actividades de las especies se calcularon a partir de los
datos analíticos, usando un programa de computadora desarrol-
lado por Arnorrsson et al (1982 a). El estado de saturación de
cada mineral es expresado como:
LOG K anhidrita = a Ca * a S04 (7)

LOG K calcita = a Ca * a CO3 (8)
LOG K cuarzo = a H4SiO4 (9)
En la figura llb puede observarse que los pozos Hl, H6,

H7, H8, Hll, H12, H20 y H23 están sobresaturados con respecto
a la calcita. El pozo H9 está insaturado con respecto a la
línea de equilibrio. Cabe mencionar que las aguas geotérmicas
a profundidad se equilibran con la calcita. Sin embargo, la
sobresaturación con respecto a la calcita que presentan la
casi totalidad de los pozos que producen agua, se debe a
procesos de ebullición que ocurren alrededor de la zona
productora de estos pozos. Por tanto, esas aguas profundas
parecen supersaturarse y este mineral tiende a precipitar.
Con respecto a la anhidrita se puede decir que los pozos
Hl, H8, y H12 están en equilibrio ( Figura lia ). El H7 y H6
tienden al equilibrio, mientras que el Hl, H20, y H23 están
sobresaturados con respecto a la anhidrita. El pozo H9 presen-
ta una gran insaturación con respecto a la anhidrita.
Con respecto al cuarzo (Figura lia) los posos Hl, H6, H8,
tienden al equilibrio aunque presentan una pequeña
insaturación con respecto a línea de equilibrio. El resto de
los pozos están insaturados con respecto al cuarzo. Ahora
bien, puede concluirse que la variación en la composición
química de los pozos que producen agua se debe a procesos que
ocurren en forma normal en un sistema geotérmico y que la
variación en la producción se debe a la depositación de los
solutos debido a los cambios en la concentración y temperatura
que originan dichos procesos. La depositación e incrustación
de algunos minerales depende de su estado de saturación. Cabe
mencionar que la depositación de algún mineral de alteración,
como regla general ocurre en aguas sobresaturadas. Con base en
lo anterior y después de observar el estado de saturación de
los pozos con respecto a minerales selectos, puede decirse que
los pozos Hl, H6, H7, H8, Hll, H20 y H23 pueden presentar
problemas por depositación de carbonato de calcio, debido a
que están sobresaturados con respecto a la calcita o El H9 es
probable que no presente depositación de este mineral por
estar completamente insaturado. Los pozos H7, Hll y H23 pueden
320
(a)
SOBRESATURADOS
H tO
H-ll
H-l H-r
-t
-IO
-II
-12
-1*
-14
-16
CdS04 =
-l<
-17
LOGK=6
-It
SOO IZO S40 340
TEMPCRATUKA MIOIOA (C)
soo ato 340 sao

TCMPCRATUMA WCMOA (c)
14
S08RESATURADOS (c;
H-6
¿^í-6 ®
®H-20
O
M
K
<
3 H-7 H-12
O H-23
O
o H-ll
-S
-Sí
INSATURADOS
H-9
-1.*
© LOO K Cuarzo= 0.41- -^
»4O MO ••O
MCOWA (C )
FIGURA. II SATURACIÓN DE SÍLICE, CALCIO, SULFATOS Y CARBONATOS

EN AGUAS GEOTÉRMICAS CON RESPECTO A LA SOLUBILIDAD
DE ANHIDRITA, CALCITA Y CUARZO.
330
presentar depósitos de sulfato de calcio por estar sobresatu-
rados con respecto a la anhidrita. Los pozos H6 y H9 es proba-
ble que no presenten depositación de sulfato de calcio por
estar insaturados con respecto a la anhidrita. Con respecto al
cuarzo la totalidad de los pozos están insaturados, por tanto,
es probable que no haya depositación de SiC>2 en la zona de
producción. Sin embargo es probable que deposite SiO2 donde
haya cambios de fase; o bien cuando haya presencia de
hidróxidos de algún metal, los cuales actúan como puente para
que se inicie la depositación de sílice. Esto puede ocurrir
como en el caso del pozo H16 presentó insaturación con respec-
to al cuarzo, sin embargo había depositación de sílice, pero
esto ocurrió debido a la presencia de hidróxidos de fierro
productos d& la corrosión (Tello, E.H. 1989).
9. CARACTERÍSTICAS ISOTÓPICAS DE LA FASE LIQUIDA DEL

YACIMIENTO Y GEOTERMOMETRIA ISOTÓPICA
En la tabla 5 se presentan los resultados del análisis de

concentración de oxígeno-18 y deuterio respectivamente, en
muestras de vapor de pozos de Los Humeros. Cabe mencionar que,
la base de datos incluye información sobre 16 pozos, los
cuales fueron muestreados en mayo de 1987, diciembre de 1988 =
Esto con el objeto de establecer la reproducibilidad de la
metodología de muestreo, y de esta manera poder detectar
variaciones reales correlacionables con cambios en otros
parámetros físicos y químicos. En las mismas tablas se presen
tan las temperaturas de separación de cada fase, y la entalpia
de mezcla solamente en los pozos Hl, H6 y H8, H13, H15 y H20
la muestra del vapor separado se tomó a una temperatura dis
tinta que la temperatura de la muestra líquida. En los casos
de pozos equipados con separador de producción, se tomó la
muestra de vapor a la salida de este. En el caso de no contar
con separador se usó un separador portátil para la toma de la
muestra de vapor, mientras que la muestra de agua separada se
tomó en el vertedor. Con los resultados del análisis de
concentración de oxígeno-18 y deuterio en el líquido separado
y en el vapor separado, se calculó la concentración de ambos
en la descarga total de los pozos, y los resultados se presen
tan en la tabla 5. Para estos cálculos se utilizaron 2 proce
dimientos los cuales se describen a continuación:a) Se utiliza
solamente los datos de concentración de oxígeno-18 y deuterio
en la fase líquida analizada. Esto es para cuando se toma la
muestra de agua en el vertedor, se hace uso de las siguientes
ecuaciones:
<S18Odt=£a180-eXv (10)
5Ddt=íaD-eXv (11)
Donde Xv es la fracción de vapor a la presión atmosférica, que
en el caso de Los Humeros es de (0.073Mpa) y se calcula de
acuerdo con la ecuación (4). Para el cálculo del coeficiente
de partición (e) se hace de acuerdo con las siguientes ecua-
ciones:
e180 = 9.2 - 0.04t°C (12)
eD = 68 - 0.4t°C (13)
331
TABLA 5.- COMPOSICIÓN ISOTÓPICA DEL VAPOR SEPARADO DE LOS POZOS DE LOS
HUMEROS. LA ENTALPIA ESTA DADA EN kj/kg.
TEMPSE
POZO FECHA ENTALPIA VAPOR OXIGEN-18 DEUTERIO CARBON-13 DESCARGA TOTAL
°C VAPOR VAPOR EN EL GAS OXIGEN-18 DEUTERIO
H-1 140587 1286 127 -5.45 -80.4 -3.5 -2.61 -77.6
H-1 290988 1248 160 -2.24 -65.9 -2.35 -72.3
H-6 140587 1830 144 -3.76 -70.6 -4.1 -2.09 -67.8
H-6 290988 2382 150 -4.51 -71.5 -3.88 -70.8
H-7 140587 2600 139 -3.18 -66.2 -3.7 -3.18 -66.2
H-7 280988 2492 136 -3.35 -70.8 -2.91 -70.3
H-8 140587 2034 138 -4.17 -73.8 -3.3 -2.89 -77.5
H-8 280888 2249 139 -4.33 -72.7 -3.42 -71.7
H-9 140587 2628 172 -1.47 -62.1 -4.5 -1.47 -62.1
H-9 270988 2757 170 -1.63 -68.0 -1.63 -68.0
H-10 140587 124 -3.56 -66.0 -4.0 -3.56 -66.0
H-10 280988 216 -4.93 -68.0 -4.93 -68.0
H-11 140587 2595 248 -2.52 -68.0 -3.5 -2.52 -68.0
H-11 280988 2662 248 -2.84 -64.3 -2.84 -64.3
H-1 2 140587 2636 261 -1.38 -60.1 -5.4 -1.38 -60.1
H-1 2 290988 2527 139 -3.21 -67.3 -3.21 -67.3
H-1 3 290988 1730 120 -4.19 -73.9 -2.2 -71.9
H-1 5 280988 2265 128 -4.11 -69.3 -3.23 -68.4
H-16 140587 2618 170 -4.34 -70.6 -4.4 -4.10 -70.4
H-16 270988 2431 163 -7.22 -82.2 -6.7 -81.6
H-17 140587 2595 175 -3.72 -64.9 -4.0 -3.72 -64.9
H-17 280988 2662 144 -3.48 -68.2 -3.48 -68.2
H-1 8 140587 194 -1.87 -46.0 -5.8 -1.87 -46.0
H-1 8 290988 178 -2.81 -53.4 -2.81 -53.4
H-1 9 140587 192 -2.96 -60.4 -3.2 -2.96 -60.4
H-20 280988 2528 152 -4.41 -71.7 -4.0 -71.3
H-27 290988 2662 119 -3.29 -66.2 -3.29 -66.2
DEUTERIO Y OXIGENO-18 FUERON ANALIZADOS POR EL HE, MÉXICO
EL CARBONO-13 SE ANALIZO EN EL USGS LABORATORY. MENLO PARK, Ca.
donde (t) es la temperatura de saturación a la altura de 2800

msnm que es la de Los Humeros.Estas ecuaciones 12 y 13 son
válidas para temperaturas entre 80 y 100°C.
b) Se utilizan los resultados de los análisis de la fase
vapor separada, de acuerdo con las siguientes ecuaciones:
5180dt=5v180 +10 3 lna(Xa) (14)

£D dt =<SvD+10 3 lna (Xa) (15)
donde Xa es la fracción de agua a la temperatura de separación
y se determina de acuerdo con la siguiente expresión:
Xa = Hv - Ho / Hv - Ha (16)
332
donde Ho es la entalpia de mezcla, Hv y Ha son la entalpia del
v a p o r y l i q u i d o r e s p e c t i v a m e n t e a la t e m p e r a t u r a de
separación. El coeficiente de partición (10 3 lna) se determina
de datos experimentales desarrollados por Botinga (1969).
En la figura 12 se encuentran graficados el contenido de
deuterio contra el contenido de oxígeno-18 de los pozos de
Humeros. Se puede observar en la figura que los pozos pre-
sentan un corrimiento de oxígeno-18 característico de fluidos
geotérmicos. Este enriquecimiento de oxígeno-18 se debe a que
el equilibrio agua-roca se llevó a cabo a altas temperaturas.
Además como referencia se incluyó en la figura la composición
isotópica del agua de manantiales y norias aledaños al campo.
Estos datos de deuterio, oxígeno-18 y tritio están referidos
en la tabla 2. Las muestras de Arteziano (47) y S.N. pizar-
ro (M8) presentan un marcado corrimiento de oxígeno-18 respec-
to a la linea meteórica, producto de la interacción agua-roca
a altas temperaturas. La muestra proveniente de la laguna de
Alchichica ( M 3 7 ) presenta una composición isotópica
c a r a c t e r í s t i c a de a g u a s m o d i f i c a d a s por p r o c e s o s de
evaporación a temperatura ambiente. El resto de los manant-
iales se u b i c a n en la l í n e a de agua m e t e ó r i c a ( T e l l o ,
H.E.1988).
A
/LCHCHIC*
-24 -
-48 -
O
Di
U
Ul
Q
-72 -
-96 -
MANANTIALES
I POZOS(DESQUEJA. TOTAL)
-120
-13 -11 -7 -5 -3 -1
OXIGENO 18
FIGURA 12.- COMPOSICIÓN ISOTÓPICA DE MANANTIALES Y POZOS

DEL CAMPO GEOTÉRMICO LOS HUMEROS, PUE.
333
10.GEOTERMOMETRIA ISOTÓPICA DEL CO2-CH4
Una extensiva investigación de la composición isotópica

del dióxido de carbono y metano presente en fumarolas, manant-
iales calientes y fluidos geotérmicos se han llevado a cabo en
los últimos 10 años. Estas investigaciones se han realizado
con el objeto de: 1) Determinar si el contenido de C en el
CO2 presenta alguna variación significante en relación con
cambios del gradiente geotérmico. 2) Probar la validez del
geotermómetro isotópico de CO2-CH4.
Ahora bien, el C02 es el compuesto más abundante en los
fluidos geotérmicos investigados los cuales varían de acuerdo
con su ubicación geográfica. Las variaciones que presenta no
son al azar, ya que valores más altos de 8 C están asociados
con anomalías termales (Panichi y Tongiorgi, 1975). Por tanto,
las variaciones de S C en el C02 natural puede considerarse
como una herramienta auxiliar en la prospección de nuevas
áreas geotérmicas.
Pequeñas cantidades de metano e hidrógeno siempre
acompañan al CO2 en fluidos geotérmicos. Suponiendo que el
equilibrio isotópico ocurre entre C02, CH4, H2, y H2O a través
de la reacción.
CO2 + 4H2 = CH4 + 2H2O (17)
El fraccionamiento isotópico observado entre los pares CO2

- CH4, H2O - H2 y H2 - CH4 han sido usados para evaluar la
temperatura a profundidad en varias áreas geotérmicas (Craig,
1953; Hulston y McCabe,1962; Los datos isotópicos del conteni-
do de SC en el CO2 y CH4 para dos de los pozos de Los Humer-
os se refieren a continuación.
5l3c 5l3c T C
POZO FECHA Tsep cH4 CO2 °
H17 14-V-87 175 -22.9 -4.O 400
H18 14-V-87 195 -24.6 -5.8 400
Cabe mencionar, que tanto el contenido de S C, como las

temperaturas fueron proporcionados por A.Truesdell
(comunicación personal, 1988) . La constante de equilibrio para
el sistema C02 -CH4 ha sido calculada usando los gráficos
elaborados
0
por Botinga (1969) para temperaturas entre O a 700
C. En el rango de temperaturas de interés geotérmico, por
ejemplo, de 100 a 400 ° C, los valores reportados pueden ser
determinados por medio de la ecuación:
l'o3lna = -9.01 + 15.301 * 103T~1 + 2.631 * 106T~2 (18)
donde a = (13C/12C) CO2/ ( C/ 12C)CR4 y T es la Temperatura
expresada en °K.
Si se aplica la ecuación (18) para la evaluación de la
temperatura, se debe suponer que existe equilibrio isotópico
entre el CO2 y CH4. Sin embargo, esta suposición ha sido muy
criticada por varios investigadores entre ellos (Craig, 1963).
Por lo tanto, es importante discutir la validez y limitaciones
del geotermómetro isotópico de CO2 - CH4:
334
I) En todos los campos investigados, incluyendo Los
Humeros, el geotermómetro isotópico CG>2 - CH4 da temperaturas
generalmente de 50 a 200°C más altas que la temperatura medida
directamente en el cabezal.
II) El C02 y CH4 pueden estar en equilibrio isotópico
solamente cuando ambos se originen del mismo proceso químico.
Esto es cierto para sistemas de baja temperatura como se ha
observado en gases naturales producidos por procesos bacteria-
nos y no hay razón porqué no sea cierto también para sistemas
de alta temperatura (Panichi, C. , Ferrara, C., Gonfiantini,
R., 1976).
III) La 513C del metano varía de -20 a -30 %. en sistemas
geotérmicos. Mientras que, el metano que se origina 13
a más
bajas temperaturas presenta valores más negativos de C. Para
el caso de Los Humeros los valores de <S13C varían de -22.9
(H17) a -24.6 (H-18).
Esto es una evidencia de que la composición isotópica del

CH4 refleja la alta temperatura a la cual se formó o bien a un
intercambio sucesivo con el CO2 dentro del sistema geotérmico.
IV) Generalmente se admite que la velocidad de reacción es
muy lenta en sistemas geotérmicos.
De acuerdo con lo anterior puede concluirse lo siguientes
a) Debido a la falta de equilibrio isotópico, las tempera-
turas evaluadas a partir de la composición isotópica de CO, y
CH4 pueden no tener sentido (400°C para el H17 y H18). b) Sin
embargo, también puede ser que estas temperaturas sean respre-
sentativas de fluidos más profundos.
11. GEOTERMOMETRIA ISOTÓPICA DEL DEUTERIO EN H2 y CH4
También se aplicó la geotermometría isotópica del deute-

rio en H2 y CH4 a los pozos H17 y H18. Los resultados se
refieren a continuación:
POZO FECHA Tsep. S DR2 S DCH4 T°C
H17 14-V-87 175 -435 -154 400 (D)
H18 14-V-87 195 -392 -155.5 430 (D)
530 (C)
donde (D) y (C) significa que el coeficiente de partición fue

calculado a partir de los datos experimentales desarrollados
p o r B o t i n g a ( 1 9 6 9 ) . Cabe m e n c i o n a r q u e estos v a l o r e s
analíticos fueron proporcionados por A. Truesdell (1988). Como
se puede observar las temperaturas calculadas son muy altas.
Esto sugiere o bien que no exista el equilibrio isotópico o
que estas temperaturas sean representativas de fluidos de
origen más profundo.
335
12o CONTENIDO DE 513C EN EL C02 (gas)
Se determinó el contenido de C en el CO^ en muestras de

gases de los pozos de Los Humeros.Como puede observarse en la
tabla 5 existe una diferencia bastante notoria en el contenido
de <S13C entre pozos localizados en ambientes volcánicos (Los
Azufres) y pozos localizados en ambientes sedimentarios (Los
Humeros). La S 13C de rocas sedimentarias13
marinas (calizas) es
del orden de cero. Mientras que la 6 C de CO2 de origen
magnético es del orden de -7 a -8 %. para los pozos de Los
Humeros el contenido de 513C de CO2 en la muestra de gas varía
de -3.2 a -5.8 de acuerdo con lo anterior puede decirse que
existe un aporte de carbón de origen sedimentario. Siendo los
pozos Hl, H6, H8, Hll y H19 los que presentan un mayor aporte
de C, además de estar más cercanos al alto estructural de
las calizas. Estos pozos están ubicados en la parte noroeste
del campo. Los pozos H6, H12 y H18 los cuales están ubicados
en la zona sur del campo, presentan valores más negativos de
6 C lo cual refleja que si hay aporte de C de origen
sedimentario, pero predomina el C de origen magmático0
Esto es cierto ya que los pozos H12 y H18 los cuales están
ubicados cerca del cráter de Maztaloya uresentan los valores
13
más cercanos al valor que presenta el C de origen magmático
-7 a -8 %.(Figura 13).
13. CAMBIOS SECUNDARIOS EN LA COMPOSICIÓN QUÍMICA E ISOTÓPICA

DE LOS FLUIDOS.
La composición química e isotópica de los fluidos produ-

cidos por los pozos productores de Los Humeros han sido utili-
zados en el modelo geoquímico del campo (Tello, H. E. 1989).
La existencia de procesos de mezcla, condensación dentro
del campo han sido evidenciados, por medio de los análisis
químicos e isotópicos, el problema ahora es definir y delimi-
tar las áreas dentro del yacimiento geotérmico que son afecta-
das por esos fenómenos secundarios.
El presente trabajo representa un intento por correlacionar
un cierto número de parámetros geoquímicos. Por tanto, se ha
considerado además de parámetros isotópicos, algunas especies
químicas encontradas en los fluidos geotérmicos.
I Q
Los análisis combinados de SO y 6D como se menciono en
párrafos anteriores nos han servido para definir la
características isotópicas del vapor profundo y nos puede
ayudar a conocer las propiedades del agua más somera que
pudiera estar recargando el acuífero geotérmico. Además de
indicarnos la dirección del flujo subterráneo.En la figura 14
se presenta una configuración de isovalores de oxígeno-18 para
los pozos de Los Humeros. Se puede observar en esta figura que
los valores menos negativos se encuentran al sur de la zona
perforada y estos valores siguen una tendencia SE-NW lo cual
coincide con el alto estructural de las calizas. Esto sugiere
que existe un enriquecimiento en isótopos pesados producto de
la interacción del agua con calizas, a altas temperaturas.
336
6S9500 662500 665500
2178000 ¿ - 2178000
2175000 - 2175000
2172000 - 2172000
2169000 2169000
659500 662500 665500
Figura 13.— Isovalores de carbono-13 (Los Humeros)
337
659500 662500 665500
2178000 ¿ - 2178000
2175000 <r - 2175000
2172000 - - 2172000
2169000 2169000
659500 662500 665500
Figura 14.— Isovalores de oxigeno—18 (1988) Los Humeros
338
En la figura 15 se presentan los isovalores de temperatu-
ras medidas en los pozos a condiciones de equilibrio se puede
ver en esta figura que las temperaturas más altas se encuen-
tran en la parte norte de la zona perforada, concretamente en
pozos localizados dentro del colapso central, los pozos H4,
659500 665500
2178000 - - 2178000
2175000 - 2175000
2172000 - 2172000
2169000 2169000
659500 662500 665500
Figura 15.— Isotemperaturas medidas en Los Humeros.
339
Hll, H20 son los que presentan estas temperaturas las cuales
son mayores a 300°C. Los pozos localizados en la zona sur del
campo en el Xalapasco Mastaloya también se detectan
temperaturas mayores a los 300°C. Es importante hacer notar
que los pozos H13, Hl, H7 , H8 están ubicados cerca de la
isolinea de 300°C, y están ubicados entre la falla de las
víboras y la falla de Los Humeros.
Al configurar los isovalores de temperaturas calculadas
por medio del geotermómetro de gases de D'Amore y Panichi
(1980) (Figura 16), se encontró que los valores más altos
corresponden a pozos localizados en la falla de Los Humeros
(H7, H8, H10) y otros dentro del colapso central H17, H15, H16
y H9 (Tabla 3) .
De acuerdo con lo anterior puede concluirse que las zonas
más importantes en cuanto a temperaturas se refiere pueden
clasificarse como sigue: 1) la zona del colapso central con
temperaturas medidas y/o calculadas de 307°C hasta 384°C. 2)
la zona del Xalapasco Maztaloya con temperaturas que van de
302 C a 356°C y 3) el corredor central o falla de Los Humeros
con temperaturas medidas y/o calculadas que van de 267 a 315°C
14. CONCLUSIONES
De acuerdo con su composición química el agua producida

por los pozos de Humeros se clasifica en bicarbonatada-sódica,
sulfatada-sódica y clorurada-sódica. Al hacer la corrección de
la composición química del agua separada de los pozos, se
encontró que el pozo Hl, produce en una zona de líquido domi-
nante. El resto de los pozos de Los Humeros se encuentran
produciendo en una zona de dos fases.
De acuerdo con el estado de equilibrio los pozos Hl, H6,
H7, H8, Hll, H12, H20 y H23 pueden presentar depositaciones de
carbonato de calcio, ya que están sobresaturados con respecto
a la calcita.El pozo H9 lo más probable es que no presente
depositación de carbonato de calcio ya que está insaturado con
respecto a la calcita. Con respecto a la anhidrita se concluye
que los pozos que pueden presentar depositaciones de sulfato
de calcio son los pozos Hll, H20 y H23 por estar sobresatura-
dos con respecto a la anhidrita. El pozo H9 puede no presentar
depositaciones de sulfatos de calcio ya que presenta una gran
insaturación con respecto a la anhidrita. Los pozos Hl, H8,
H12 están en equilibrio soluto/mineral y los pozos H6 y H7
tienden al equilibrio por tanto, es probable que se deposite
sulfato de calcio. Con respecto al cuarzo la totalidad de los
pozos están insaturados, por tanto, es probable que no haya
depositación de sílice en la zona de producción. Sin embargo,
es probable que deposite SiO2 donde haya cambios de fase. O
bien cuando haya presencia de hidróxidos de algún metal, los
cuales actúan como puente para que inicie la depositación de
la sílice.
340
659500 662500 665500
2178000 - 2178000
2175000 - 2175000
2172000 - - 2172000
2169000 2169000
659500 662500 665500
Figura 16.— laovalores del geotermo'metro de gases.
341
1 fi
Los pozos de Humeros, presentan un corrimiento de SO
característico de fluidos geotérmicos. Esto indica que la
interacción agua-roca se efectuó a altas temperaturas. La
composición isotópica del agua de los manantiales se agrupan
en su mayoría en la linea de agua meteórica (Tello, H.E.1988)o
También se analizó el contenido de 513C en el CO2 en mues-
tras de gases de los pozos de Humeros. Se13 encontró que existe
una gran diferencia en el contenido de <S C entre pozos local-
izados en ambientes volcánicos (Los Azufres) y pozos localiza-
dos en ambientes sedimentarios (Los Humeros), ya que en primer
lugar se sabe que la 8 C de rocas sedimentarias marinas
(calizas) es del orden de cero. Mientras que la <S13C de CO2 de
origen magmático es del orden de -7 a -8 %. . Para los pozos
de Humeros la £13C de C02 en la muestra de gas varía de -3.2 a
-5.8, por lo que puede concluirse que existe un aporte de
carbón de origen sedimentario. Siendo los pozos Hl, H6, H8,
Hll y H19 los que presentan un mayor aporte de 513C de origen
sedimentario, lo cual se debe a que están más cercanos al alto
estructural de las calizas. Ahora bien los pozos H6, H12 y H18
los cuales están ubicados cerca del cráter de Maztaloya pre-
sentan valores más negativos de 8 C (-4.1 a -5.8) lo cual
refleja que si hay aporte de 8 C de origen sedimentario, pero
predomina el 513C de origen magmático.
De acuerdo con las temperaturas geotermométricas de agua y
gases complementados con temperaturas medidas se encontró que
existen 3 zonas bien definidas, los cuales pueden definirse de
acuerdo a sus temperaturas como sigue 1) la zona del colapso
central con temperaturas medidas y/o calculadas de (307C a
384C), 2) la zona del xalapasco Maxtaloya (302 a 356°C) y 3)
corredor central o falla Los Humeros con temperaturas de 267 a
315°C.
RECONOCIMIENTO
El autor agradece al Ing. Marco Antonio Torres R., por el

apoyo recibido en la impresión final de este trabajo.
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pp.2749-2765.
Giggenbach, W., 1989. Techniques for the interpretation of

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Hulston, J.R. and McCabe, W.J.,1962. Mass spectrometer measure
ments in the thermal areas of New Zealand carbon isotopic
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Tello, H. E., 1984a. Qulmica de los fluidos de descarga del
pozo Humeros 1.CFE. Gerencia de Proyectos Geotermoeléctricos
Informe 16-84. Morelia, Michoacan, Mexico.
Tello, H. E., 1984b. Metodologia para la estimacion de la
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344
GEOCHEMICAL REPORT ON THE CHALLAPALCA AND
TUTUPACA GEOTHERMAL AREAS, PERU
G. SCANDIFFIO
Ente Nazionale per 1'Energía Elettrica,
Pisa, Italy
D. VERASTEGUI, F. PORTILLA
Unidad Investigaciones Geotermales,
ELECTROPERU SA,
Lima, Peru
Resumen-Abstract
INFORME GEOQUÍMICO SOBRE LAS ZONAS GEOTERMALES DE CHALLAPALCA Y TUTUPACA,

PERÚ.
Se muestran brevemente las características más sobresalientes de cinco

zonas termales que se encuentran en la parte sur del Perú a lo largo de la
cordillera andina y cerca de la frontera con Chile y Bolivia. Se han organi-
zado estas zonas en dos regiones:
Challapalca, que comprende Challapalca y Paucarani;

Tutupaca, que comprende Calacea, Calientes y Tutupaca.
Los datos geoquímicos se refieren principalmente a la composición química

e isotópica del agua en determinados puntos; si bien la composición del gas
de estos caudales geotérmicos es casi desconocida, se obtuvieron indicaciones
muy favorables. En las zonas de Calientes y Challapalca existen amplios cir-
cuitos termales; sus temperaturas profundas deberían sobrepasar los 200°C.
GEOCHEMICAL REPORT ON THE CHALLAPALCA AND TUTUPACA GEOTHERMAL AREAS, PERU.
The most outstanding characteristics of five thermal zones,

located in the southern part of Peru along the Andean Cordillera
and near the border with Chile and Bolivia, are briefly discussed.
These zones were organized into two areas:
- Challapalca, comprising Challapalca and Paucarani;
- Tutupaca comprising Calacoa, Calientes and Tutupaca.

The geochemical data mainly regard chemistry and isotopes of
water points; even if the gas composition of these geothermal
345
discharges is almost unknown, very favourable indications came
out. In the Calientes and Challapalca zones wide thermal circuits
exist; their deep temperatures should exceed 200 °C.
1. Previous studies
The Challapalca and Tutupaca areas have been the subject of

studies by AQUATER-INGEMET [1] and Burgess [2],
The AQUATER survey regarded a region covering tens of thousands
of square kilometres, so that it can only be of interest for
general informations.
BURGESS, instead, carried out, with financial support of OLADE,

an a detailed study of the areas in question sampling 70 water
points. Only chemical data were found in the records of
ELECTROPERU, the peruvian Agency attending to the development of
this Coordinated Research Programme. Isotopic data and the
sampling map of the manifestations were missing.
2. Geologic outline and stratigraphy
This study regards an area of approximately 4500 sq km running

between the Western Cordillera and the Peruvian Plateau. The
geological and structural setting is constitued by Mesozoic Units,
made up of terrigenous sediments, intensely deformed and folded
over which lie in unconformity the products of several volcanic
cycles spanning from Lower Tertiary to Quaternary, and clastic
glacial or glacio-fluviatile quaternary deposits. However
volcanics are the most widespread formations in the area.
346
From top downward the stratigraphie sequence is made up of:
- Quaternary glacial or glacio-fluviatile erosion deposits;

- Purpurini=îi
- Tutupaca Upper Tertiary-Quaternary volcanic units;
- Chila =!l
- Capillune formation=i|
- Seneca volcanics Limnic-Volcanic sequence;
- Maure formation =="
- Huaylillas Volcanic Complex;
- Huilacollo formation=i| ow1"^
- Tarata formation =* Centre and SW Toguepala Group;
- Toquepala formation NW =^
- Chachacumane format ion=ii Yura Grou
- Atascapa formation =^ P-
This stratigraphie sequence can be recognized in the AA'

section of Appendix 1C traced on the geological map of the
Tutupaca area in Appendix 1A.
2.1 Tectonics, volcanism and thermal features
During Tertiary the Andean tectonic in this area was

characterized by brittle tensional features. The main phase dates
back to Miocene. In places there was a reactivation of older
lineaments. As a result the region was divided into blocks
unevenly displaced, which could be responsible for the arising of
geothermal reservoirs.
Three main fault trends are distinguished, though some other
orientations occur: NW-SE (Andean), NE-SW (anti-Andean) and E-W;
some of thes trends can be seen in Appendixes 1A, IB and 1C.
Over the older ignimbritic basal complex (Huaylillas) several

central volcanic apparatuses built up in various periods of
activity and their products covered the whole area. Glacial or
glacio-fluviatile erosion have partly modified the morphology due
to the different volcanic cycles, but the most recent volcanics
remained almost unaffected by weathering.
Three main volcanic phases are recognized: a) Chila;
b) Tutupaca; c) Purpurini.
347
a) In a first period spanning between 5 and 8.4 M.a. the
activity was mainly effusive from central volcanoes (Nazaparco,
Loma Pabellön, Novena, Jucure, Chila and San Francisco. The second
period reactivated the former apparatuses between 2 and 4 H.a.,
and gave rise predominantly to effusions but also explosions
producing andésites.
b) This second phase distributed its products over the whole

area, as isolated blocks, over the former volcanics. The glacial
and glacio-fluviatile erosion has strongly altered the Chila
products while it has just touched the Tutupaca ones. The age of
Tutupaca volcano is estimated around 0.7 M.a., to the same period
should be ascribed also Yucamane, Yucamane Chico, Calientes, San
Francisco, Casiri and a few domes; again effusive activity is
predominant with acid products (dacites), noteworthy are the
pyroclastic deposits of Yucamane.
c) The last volcanic phase (Purpurini), displaced superficial

domes, probably the most differentiated products of regional
magmatism. These domes of dacitic compositions could point to the
existence of magmatic chambers not at a great depth. In the local
morphology the domes appear as isolated shapes, untouched by
erosion, at times related to collapse structures.
Radiometrie age of Purpurini volcanics is around 0.1 Ma, of the
same cycle are Kere, Casiri and Paucarani.
The volcanic apparatuses related to the study zones of Tutupaca
and Challapalca are singled out in Appendixes 1A and IB.
Several thermal manifestations are known (thermal waters,

fumaroles, solfataras, geysers), almost all occurring close to the
youngest volcanic apparatuses, along Andean and anti-Andean fault
systems.
348
Fumaroles and geysers are mainly sited toward Tutupaca and
Calientes, while solfataras occur mostly around Paucarani sector.
Thermal waters spring almost always where there are fractures,
even having sometimes their final seepage through glacio-fluvial
covers.
Three circuits can be distinguished on the basis of spring

features :
1) subsurface freshwaters of meteoric origin infiltrating in
the volcanics and outcoming at the contact between lavas and
pyroclastics as cold waters;
2) waters that through deeper circuit become contaminated by
geothermal fluids hosted by the permeable portion of the Capillune
formation, and rising as thermal waters of low salinity;
3) waters with higher temperatures and salinities, probably
from deep aquifers developed through regional fractures well below
the Huaylillas ignimbrites.
It is however difficult to distinguish "reservoir" and "cover"

geologic units because of the nature of the outcrops.
Mesozoic terrains have various lithologies and permeabilities
with a noteworthy silt-clay component; the limnic-volcanic upper
tertiary sequence can make up for a partial cover and is well
spread; volcanics could act as recharge areas or covers as a
function of fissuring or/and hydrothermal alteration achieved. In
fact such alteration processes are known in the whole area, mostly
related to the occurrences at the highest temperatures, mainly as
deposits of kaolinite or silica/carbonate incrustations.
3. Sample collection and field determinations
The sampling carried out over a total of 11 days was mainly

performed in three zones: Challapalca, Paucarani and Tutupaca.
349
Thirtyone manifestations were visited, 28 samples of water were
taken and 3 of gas; samples location is shown in Appendixes 1-1B.
Some of the water points recorded in the previous studies were not
found owing to imprecision as to their location or to the
impossibility of reaching them.
Water samples of others zones not visited (Calientes and
Calacoa) were later sent to Italy for further analyses.
Unfortunately, for these samples, that proved to be of maximum
importance, some field determinations were not carried out and no
sample of gas is avalaible. Water samples were collected generally
in 6 separate aliquots for analyses of major and trace
constituents, monomeric aluminum silica, stable isotopes (18O and
D) and tritium.
Temperature, pH, conductivity and alcalinity were determined in
the field. Major and trace chemical costituents were analyzed in
ENEL laboratory in Italy; isotopes were analyzed in IAEA and DSIR
laboratories.
4. Water Chemistry
4.1. Classification of water samples (Tutupaca)
The analytical results of the fluids sampled in this area are

shown in tables 1 (waters) and 3 (gases) . The code CA and CS
identify manifestations in the Calacoa and Calientes zones
respectively.
The sample classification was mainly done by simple correlation

diagrams involving both major and trace chemical components.
In the Piper diagram of fig.l, all the samples of the Tutupaca
area (with the exception of TP12) are distributed in the NE and SE
350
Table 1 - Tutupaca water samples analyses
s = spring
Samplt; Date Cod. S.T

. T.f.pH.f. (:on.f. /Uc.f. 1r.i. pH.l. (:on.l. /Uc.l. (¡Ic.l. Ca Mg Na K Cl S04 HC03 Si 02 H3B03 Br I
•C MS meq/l °c MS meq/l meq/l
CA1 30/05/86 1755 S 60.0 6.30 1710 3.8 20 6.27 1740 3.6 3.6 58.8 5.70 319.0 30.1 404.0 126.0225.8 530.0 67.5 0.98 0.00
CA2 30/05/86 1756 S 91.0 7.96 4130 3.2 20 8.30 2920 3.6 3.6 67.4 9.70 602.0 53.0 702.0 368.0 195.3 766.0 121.0 1.76 0.60
CA3 30/05/86 1757 S 14.0 20 7.12 331 1.1 1.2 32.7 7.30 19.2 4.6 9.5 77.1 73.2 0.0 1.1 0.00 0.00
CS1 30/05/86 1758 S 86.0 7.65 5480 2.0 20 7.54 5600 2.1 2.1 42.4 0.49 1270.0 99.1 1960.0 93.4122.0 969.0 323.0 3.44 0.50
CS2 30/05/86 1759 S 86.0 7.04 3980 2.9 20 8.23 5670 3.2 3.2 45.0 3.50 777.0 54.9 1140.0 100.0176.9 836.0 194.0 2.10 0.30
CS3 30/05/86 1760 S 80.0 6.94 5160 2.2 20 6.95 5580 2.4 2.4 48.3 4.30 1000.0 42.5 1550.0 112.0134.2 850.0 255.0 2.70 0.30
CS4 30/05/86 1761 S 14.0 20 7.60 353 0.4 0.4 31.3 10.90 16.3 6.7 1.2 124.0 24.4 50.0 0.2 0.00 0.00
TP10 21/05/86 1669 S 50.0 2.70 2100 0.0 20 2.72 2390 0.0 0.0 152.0 39.00 166.0 19.9 162.0 1040.0 0.0 185.0 30.5 0.35 0.00
TP11 21/05/86 1670 S 46.0 2.90 2050 0.0 20 2.85 2260 0.0 0.0 151.0 41.00 163.0 18.7 150.0 1020.0 0.0 178.0 28.9 0.42 0.00
TP12 21/05/86 1671 S 14.0 7.56 62 20 6.50 67 0.4 0.4 3.3 1.80 5.5 2.5 1.2 8.6 24.4 46.0 0.2 0.00 0.00
TP1B 19/05/86 1660 S 31.0 6.41 1790 20 7.50 2260 7.9 7.9 44.8 5.80 472.0 36.6 322.0 314.0 0.0 109.0 56.0 0.97 0.70
TP2 20/05/86 1661 S 36.0 6.40 2470 10.9 20 7.97 2760 10.3 10.3 30.1 9.40 589.0 45.9 428.0 372.0 659.0 172.0 72.7 1.24 0.50
TP3 20/05/86 1662 S 56.0 6.44 2840 10.8 20 7.76 2810 10.1 10.1 55.5 6.30 619.0 43.6 444.0 390.0 659.0 120.0 75.7 1.30 0.80
TP4 20/05/86 1663 S 56.0 6.56 3080 11.2 20 8.00 3030 10.8 10.8 23.2 6.15 641.0 49.9 452.0 412.0 683.4 126.0 79.1 1.32 0.00
TP6 20/05/86 1665 86.0 3.63 577 0.0 20 3.10 7230 0.0 0.0 19.8 13.70 29.9 18.1 1.7 248.0 0.0 190.0 0.7 0.00 0.00
TP7 21/05/86 1666 S 3.0 6.75 230 0.0 20 6.45 243 0.7 0.7 21.3 6.50 12.8 3.4 1.5 66.4 0.0 42.0 0.3 0.00 0.00
TP8 21/05/86 1667 S 12.0 6.79 144 20 6.20 149 0.5 0.5 11.4 2.60 10.1 4.8 2.0 32.2 0.0 38.0 0.2 0.00 0.00
TP9 21/05/86 1668 S 60.0 3.00 2100 0.0 20 2.88 2420 0.0 0.0 152.0 40.30 179.0 23.8 168.0 1000.0 0.0 196.0 32.5 0.37 0.00
Table 1 - ( cent.)
Sample Code F Li Rb Cs NH4 Sr Ba Zn Sb As Fe ALT Al.M TDS TAN TCAT 5180 5D Tnt. 5180/S04 534S/S04 A l t .
meq/l meq/l o/oo o/oo U.T. o/oo o/oo m.
CA1 1755 2.00 1.70 0.27 0.50 0.200 1.10 0.080 0.037 0.000 1.60 0.420 0.270 0.000 1550 17.7 18.3 - 1 1 . 78 -91.0 1.2 3600
CA2 1756 3.20 3.00 0.49 0.00 0.300 1.50 0.050 0.016 0.000 2.80 0.220 0.000 0.000 2703 30.7 32.2 -11.28 -89.3 0.4 2900
CA3 1757 0.00 3.00 0.49 0.00 0.000 1.50 0.050 0.016 0.000 0.01 0.000 0.000 0.000 157 3.1 3.6 -11.36 -82.6 2.0 3000
CS1 1758 2.70 9.80 1.30 3.40 0.600 1.10 0.020 0.000 0.000 9.30 0.030 0.200 0.000 4789 59.2 61.4 -12.67 -111.4 0.4 -6.00 9.20 4340
CS2 1759 1.50 5.80 0.54 1.90 0.500 0.99 0.040 0.000 0.000 5.60 0.080 9.000 0.000 3179 37.1 38.6 -13.36 -112.3 0.4 -3.00 8.20 4315
CS3 1760 1.80 7.60 0.50 2.80 0.500 0.86 0.060 0.007 0.000 8.00 0.440 0.120 0.000 3892 48.3 48.5 -14.04 -118.4 0.00 4280
CS4 1761 0.00 0.00 0.00 0.00 0.000 0.11 0.018 0.000 0.000 0.00 0.020 0.000 0.000 241 3.0 3.3 -14.13 -111.3 2.7 0.00 4320
TP10 1669 4.30 0.50 0.12 0.34 0.100 0.14 0.018 0.400 0.000 0.33 29.00 35.50 0.000 1866 26.2 18.6 -13.44 -103.4 0.00 4390
TP11 1670 4.60 0.50 0.13 0.00 0.200 0.09 0.018 0.400 0.000 0.29 27.20 34.90 0.000 1821 25.5 18.6 -14.11 -104.9 0.7 0.00 4330
TP12 1671 0.00 0.00 0.00 0.00 0.000 0.03 0.000 0.000 0.000 0.00 0.000 0.000 0.000 69 0.6 0.6 -13.16 -96.6 2.2 0.00 4260
TP1B 1660 0.96 1.40 0.19 0.46 1.100 1.20 0.035 0.000 0.000 0.49 0.760 9.000 0.170 1858 23.5 24.4 -13.36 -102.8 0.6 0.00 4120
TP2 1661 1.00 1.80 0.25 1.50 1.00 0.001 0.000 0.000 0.67 0.000 0.000 0.000 1727 30.6 29.3 -13.39 -105.8 2.10 12.80 4140
TP3 1662 1.04 1.90 0.24 0.70 1.400 1.50 0.039 0.000 0.000 0.51 0.470 0.050 0.000 1764 31.4 31.7 -13.46 -103.3 0.7 2.50 12.60 4050
TP4 1663 0.00 2.10 0.24 0.70 1.100 1.40 0.028 0.000 0.000 0.61 0.000 0.000 0.000 1797 32.5 31.2 -12.86 -100.4 0.00 4040
TP6 1665 0.28 10.00 0.06 0.00 0.200 9.00 0.011 0.081 0.000 0.00 1.800 6.500 0.210 550 5.2 5.3 -11.84 -102.6 1.7 0.00 4480
1H7 1666 0.16 10.00 0.00 0.00 0.000 0.17 0.010 0.000 0.000 0.02 0.000 0.000 0.000 165 1.4 3.7 -12.73 -98.2 0.00 4140
TP8 1667 0.00 0.00 0.00 0.00 0.000 0.13 0.024 0.000 0.000 0.02 0.000 0.000 0.000 102 0.7 1.3 -13.34 -96.2 0.3 0.00 4140
TP9 1668 4.80 0.59 0.15 0.28 0.200 0.04 8.000 0.420 0.000 0.35 32.20 23.80 0.000 1864 25.6 19.4 -14.20 -106.1 0.4 0.00 4290
Table 2 - Challapalca water samples analyses
s = spring
SampU; Date Cod. S.T. T.f.pH.f. (:on.f. /Uc.f. •r.i. pH . I .:on.l.

( /Uc.l. Pilc.l. Ca Hg Na K Cl S04 HC03 Si 02 H3B03 Br !
°C MS meq/l °c MS meq/l meq/l
PA1 17/05/86 1656 S 45.0 6.59 1010 11.2 20 7.53 1120 10.6 10.6 75.6 35.40 127.0 42.9 3.7 116.0 677.3 192.0 4.0 0.00 0.00
PA2 17/05/86 1657 S 9.0 5.05 294 0.0 20 3.84 274 0.0 0.0 15.8 5.80 12.8 4.2 0.6 125.0 0.0 53.0 0.4 0.00 0.00
PA3 17/05/86 1658 S 62.0 6.50 1880 4.5 20 7.28 1930 4.4 4.4 65.3 38.30 241.0 90.3 498.0 70.8 274.6 244.0 147.0 1.65 0.50
PA4 17/05/86 1659 S 38.0 5.98 890 4.5 20 7.12 1040 4.3 4.3 93.8 29.10 93.1 31.0 6.1 344.0 268.5 132.0 4.5 0.00 0.00
PC1 14/05/86 1673 S 43.0 6.81 1350 3.8 20 7.17 1470 3.7 3.7 35.2 16.30 249.0 29.4 354.0 41.4 231.9 137.0 91.8 1.18 0.30
PC10 16/05/86 1682 S 18.0 6.72 473 1.9 20 6.84 611 1.9 1.9 23.2 17.00 67.2 16.4 95.0 58.7 115.9 85.4 8.4 0.12 0.00
PC2 14/05/86 1674 S 87.0 7.92 5460 1.4 20 7.35 6190 1.2 0.6 67.6 0.44 1420.0 91.9 2320.0 75.5 85.4 273.0 591.0 7.42 1.30
PC3 14/05/86 1675 S 8.0 9.02 339 0.0 20 6.75 314 1.0 1.0 18.1 3.60 37.2 8.9 5.4 79.0 61.0 37.4 1.7 0.00 0.00
PC4 15/05/86 1676 S 12.0 8.20 292 0.0 20 6.67 291 1.2 1.2 28.9 7.30 16.4 5.1 6.5 66.2 73.2 43.4 1.5 0.00 0.00
PC5 15/05/86 1677 S 72.0 6.12 207 0.7 20 6.75 220 0.6 0.6 8.7 0.72 26.6 8.2 1.0 41.7 42.7 120.0 0.6 0.00 0.00
PC6 15/05/86 1678 S 22.0 6.28 475 0.0 20 6.75 506 1.5 1.5 15.6 12.20 59.1 14.8 102.0 16.4 90.3 93.9 10.2 0.21 0.00
PC7 15/05/86 1679 S 58.0 6.10 4570 4.4 20 7.05 4050 3.7 3.7 43.1 17.60 848.0 98.1 1330.0 107.0 268.5 210.0 233.0 5.28 0.60
PCS 16/05/86 1680 S 24.0 6.72 550 1.8 20 7.06 502 1.7 1.7 16.5 10.90 65.9 10.1 84.2 29.6 109.8 99.9 17.7 0.36 0.00
PC9 16/05/86 1681 S 68.0 6.10 4630 3.1 20 7.10 3860 2.9 2.9 38.7 10.10 807.0 84.0 1240.0 98.7 189.2 165.0 220.0 4.96 0.70
Table 2 - ( cont.)
Sample Code F Li Rb Cs NH4 Sr 8a Zn Sb As Fe A l . T Al.M TDS TAN TCAT ¿180 ¿D T r i t . 5180/S04 ¿34S/S04 A l t .
meq/l meq/l 0/00 o/oo U.T. o/oo o/oo m.
PA1 1656 0.12 0.16 0.19 0.00 0.400 0.71 0.120 0.000
0.000 0.35 5.500 0.050 0.000 605 13.6 13.3 -15.84 -117.5 0.7 4600
PA2 1657 0.27 10.00 0.00 0.00 0. 000 0.11 0.000 0.00 0.250 6.400 0.100 235 2.6
0.010 0.073 1.9 -14.37 -111.5 4600
PA3 1658 0•22. 1.00 0.38 0.28 0.600 0.60 0.210 9.000
0.000 4.50 0.140 0.050 0.1701416 20.0 19.2 -14.74 -118.6 0.5 4750
PA4 1659 0.21 0.15 0.17 0.50 0.900 1.10 0.000 0.36 5.400 0.070 0.000 742 11.7
0.023 0.000 11.9 -15.96 -121.7 0.1 1.20 -1.50 4540
PC1 1673 0.22 1.75 0.19 0.76 0. 100 0.53 0.016 8.000 0.000 3.30 0.000 0.110 0.090 971 14.6 14.7 -15.25 -119.0 0.3 4370
PC10 1682 0.20 0.15 0.00 0.00 0. 000 0.24 0.020 0.000 0.000 0.11 0.000 0.000 0<t)00 372 5.8 5.9 -16.76 -125.6 0.0 4420
PC2 1674 1 .84 11.50 1.10 5.70 0.700 1.50 0.065 0.026 0.000 18.60 0.000 0.070 0.050 4893 68.4 67.5 -10.95 -104.9 0.2 4395
PC3 1675 0.22 0.03 0.00 0.00 0.000 0.15 0.010 0.000 0.000 0.05 0.000 0.000 0.000 192 2.8 3.0 -11.68 -99.2 3.0 4360
PC4 1676 0.30 0.03 0.00 0.00 0.000 0.19 9.000 0.000 0.000 0.05 0.000 0.000 0.000 185 2.8 2.9 -12.96 -103.0 6.4 4370
PC5 1677 0.15 0.00 0.00 0.00 2. 400 0.13 0.043 0.007 0.000 0.02 0.390 1.100 0.210 212 1.6 1.9 -3.76 -89.2 0.5 4700
PC6 1678 0.20 0.17 0.00 0.00 0. 000 0.17 0.000 0.014 0.000 0.32 0.020 0.080 0.000 416 4.7 4.7 -16.64 -124.6 2.8 4200
PC7 1679 0.86 4.90 0.76 2.50 1. 500 1.50 0.170 0.000 0.000 12.30 0.070 0.050 0.050 2917 44.1 43.0 -14.57 -116.9 0.0 4350
PCS 1680 0.24 0.30 0.04 0.00 0. 000 0.15 0.000 0.000 0.000 1.30 0.000 0.000 0.000 337 4.8 4.8 -16.58 -126.2 0.5 4380
PC9 1681 1 .04 4.70 0.76 2.60 1. 500 1.500.1900.000 0.000 11.400.2000.0000.000 2698 40.1 40.0 -14.58 -116.3 0.0 4370
Tab. 3 - Chemical analyses of gases
Sample Date C02 N2 H2S CH4 H2 CO

% % ppm ppoi ppm ppm
TP1B 20/05/86 65.65 34.00 2 363 4.2 2.0

TP4 20/05/86 93.54 6.17 0 277 2.9 15.4
TP6 20/05/86 98.75 1.24 0 0 450.0 48.6
PC6 15/05/86 22.90 77.10 0 2 4.2 6.5
Cl- + S04— 100
..TP7
n
::TF
+ TP12
ra
2 +
+
CAÍ
+ TP2
+ TP4
100 HC03- + C03—
Fig. 1 - Piper diagram for Tutupaca area water samples.
quadrants. Points TP7, TP8, TP12, CA3, and CS4 are cold meteoric
waters with a maximum temperature of 14 "C and a TDS ranging
between 70 and 240 mg/1.

TP6, TP9, TP10 and TP11 are hot acid waters, the first of wich
is a boiling pool (86 °C) with a TDS of 550 mg/1, whereas the
others have a temperature varying between 46 and 60.4°C and a TDS
around 1850 mg/1. TP6 and TP9 are located in the quebrada Azufre
Grande, the other in the quebrada Azufre Chico. Along the shores
of these torrents, located in two large faults beneath the slopes

of Tutupaca volcano, many warm and hot springs are present.
Their chemical characteristics are similar displaying a high
earthy-alkaline sulphate component (approximately 60%) and a
alkaline sulphate component of some 25%; the rest is alkaline
chloride.
355
All the other samples of the Tutupaca area are located in the
SE quadrant, where the alkaline chloride waters are found.
For better discrimination the Piper diagram was plotted with
chlorides as separated anión (fig.2). In this figure the rich
chloride samples can be clearly distinguished into three
subgroups.
The first includes the samples TP1B, TP2, TP3 and TP4, which
are hot samples with temperature ranging between 31 and 56°C and a
TDS around 1750-1850 mg/1; their composition is alkaline
bicarbonate chloride with a high sulphates percentage. In the zone
where these samples are located there are many emergences of warm
and hot springs and numerous streams with considerable flowrate
that may interact.
Cl- 100
n
Q)
+ TP8
TP9
+ TP6
TP12
ra
-2.
CAÍ
+ CA2
T ^TPS
+ TP4
.00 HC03- S04--
Fig. 2 - Piper diagram w i t h Cl as separated a n i ó n .
356
The second subgroup is composed of the samples CAÍ and CA2,
these were taken in the zone of Calientes, several kilometres away
from the water points with the code TP. Their temperature values
are 60.5 and 91'C respectively (this latter, decidely higher than
the water boiling point at the emergence altitude, is probably
justified by the formation of superheated steam); the sodium
chloride component exceed 65%, the TDS ranges between 1550 and
2700 mg/1 and the SiC>2 content, very high, is respectively 530 and
766 mg/1.
The third and last subgroup includes the samples CS1, CS2 and
CS3, located about 15 km to the west of the Tutupaca volcano.
Their temperatures and TDS are very high ranging 80°-86°C (boiling
point) and 3200-4800 mg/1 respectively; the sodium chloride
component varies between 86 and 93% and the SiOo content between
836 and 969 mg/1.
In fig. 3 is shown the relative Cl, S04 and HCO3 content of all
the previous described water points. On the basis of this diagram,
excluding the cold waters from the discussion, the samples TP6,
TP9, TP10 and TP11 (hot acid waters), located in the left corner,
could be considered as steam heated waters enriched mainly in
geothermal H2S. This statement is actual for the water point TP6,
the upper one sampled in a creek where some mud pools and steaming
pools are present; as regard the others three, the total absence
of gas, along the lower part of both the streams Azufre Grande and
Azufre Chico, leads one to believe that the conspicous presence of
sulphates, rather than to an H2S oxidation, is linked to a sulphur
oxidation. This is a product of the past activity of the Tutupaca
volcano in such large amounts that not far from the summit a
sulphur mine exists.
357
STEAM HEATEa WATERS
o.
100 80 60 40 0
S04 (mg/l)
Fig. 3 - Relative Cl, S04, HC03 content.
The samples TP1B, TP2, TP3 and TP4 (alkaline bicarbonate

chloride with a high sulphates percentage) are found in the
"peripheral" waters sector of the diagram. These mixed samples can
be considered the boundary part of a geothermal system, leaving

the central core, the deeper chlorinated inflow uprising at the
surface reduces, but the CO2 and H2S, reaching surface nappes rich
in oxygen, give aggressive solutions that can considerably alter
the host formations and produce alkaline bicarbonate-sulphate
waters. In the Tutupaca area the peripheral waters retain a slight
deep liquid phase contribution and this explains its chloride

content.
358
All the samples in the SE quadrant of fig. 2 are also in the
upper sector of fig. 3, in particular CS1, CS2 and CS3 are located
in the "mature waters" zone and can be used for geothermometric
purposes.
The linking between these alkaline chloride waters and the
previous "mixed waters" is clearly appears in fig. 4, where the
relative content of Li, Rb and Cs is shown: the representative
points cluster in the same area of the diagram proving that a
single deep liquid feeds the manifestations.
Another diagram that provide general informations about any
steam and gas inflow contribution is the fig. 5 one, where the
relative content of Cl, H3BO3 and NH4 is shown. The chloride
¿o
0,
i i i i i i i i i i i~i i i i i i i ] i i i i
100 80 60 0
RB (mg/L) * 4
Fig. 4 - Relative content of Li, Rb, Cs.
359
60 40 0
Cl (mg/i)
Fig. 5 - Relative content of NH4, Cl, H3BO3.
concentration is a direct function of the water-rock
equilibration process, H3BO3 behave in a similar way, but prove to

be enriched where phenomena of steam inflow occur; the NH4
concentration, finally, in addition to phase separation phenomena,
may depend on gas inflow.
Excluding the cold waters, whose NH4 content is zero and lie on
the diagram base, in the lower part are located the most
representative alkaline chloride samples, where the NH. content is
very reduced. Subsequently the group of acid waters TP10, TP9 and
TP11 is encountered, this confirms their low steam inflow; at
higher values of NH4 content the samples TP4, TP3 and TP1B is met,
for this "mixed water" group the supply of deep gases has already
been underscored.
360
At the top of the diagram is located TP6, where the presence of
condensed steam were evident even if the presence of gas is not
particularly abundant. The gas sample associated with this water
point (see table 3) contains H2, relatively high quantity of CO,
but H2S and CH4 are below the detection limit, making any gas
geothermometry unreliable; the tritium content of the associated
liquid phase (1.7 T.U.) is, finally, quite comparable with that
found in the cold waters. This situation agrees with a mixing
between a local groundwater, that circulates in hot subsurface
rocks and boils without reaching high temperature and pressure,
and a deeper gas which encounter this fluid and considerably
enriches it in NH¿ and SO..
4.2. Classification of water samples (Challapalca)
The analytical results of the fluids sampled during the survey

in this area are reported in tables 2 (waters) and 3 (gases) . The
samples with PA code identify manifestations of the Paucarani
zone.
The classification of samples was carried out in the same way
as for the preceding area.
In the NE quadrant of Piper diagram ( fig. 6) the earth-
alkaline sulphate bicarbonate samples PA4, PC4 and the earth-
alkaline sulphate sample PA2 are found; the first has a
temperature of 38 °C and a TDS of 740 mg/1, the others are cold and
characterized by a TDS lower than 250 mg/1. Sample PA1 (45°C and
605 mg/1) located along the dividing line between the NW and SW
sectors is a alkaline earth-alcaline bicarbonate sulphate water.
In this latter sector the PC3 and PC5 samples are found; their
TDS, aroud 200 mg/1, is similar, but the temperature quite
different: the first is a cold water, the second a steaming pool
(72°C).
361
At the boundary between SW and SE sectors are located PCS and
PC10, alkaline earth-alkaline bicarbonate chloride tepid samples
with a TDS around 350 mg/1.
Other 6 samples, PA3, PCI, PC2, PC6, PC/ and PC9 are found
well inside the SE quadrant. These mainly alkaline chloride waters
have temperatures ranging between 42°C and 86.9 °C and TDS between
1 and 5 g/1. Excluding PA3 belonging to Paucarani thermal zone,
all these last samples either line up in the diagram or show a
good correlation between chloride content and temperature.
The same conclusions can be drawn from the triangular Cl, SO4
HCO3 diagram (fig. 7) , where, the all the water points found in
the SE quadrant of fig. 6, fall into a line in the "mature waters"
area.
Cl- 100
+ PC4
fPA2
n
>PA4 - 0)
+
+ PAi . +
ra + PC 10 ia
z .- +PC3
+
i PCS
+ PA3
+ PC5
+ PC1
+ CS
+PC
............ .1...... .. i..... .,..__,.. i _..._.. — i... — ........
100 HC03- + S04—
Fig. 6 - Piper diagram with Cl as separated anión for

Challapalca water samples.
362
TI I I I I I I I T I I I I I I I I I T I I I I I I I I M I I I I I I I I I II I I I I I I I I
S04 (mg/l)
Fig. 7 - Relative content of Cl, SO¿, HCO-,.
This trend is evidently due to a dilution process of a deep

water whose most representative uprising end-member is the PC2
sample.
4.3. Geothermometry
Fig. 8 and 9 show the Na, K, Mg diagram [3] for the two areas
samples of Tutupaca and Challapalca. The deep temperatures for the
most representative springs CS1 and PC2, evaluable from the Na/K
ratios, are respectively 215°C and 20CTC that is 20°- 30°C higher
than those computable with the K/Mg ratios. This shift could be
explained in terms of the different re-equilibrations rates
363
Na1000
100
K/100 Mg Í0.5
Fig. 8 - Na, K, /~Mg triangular diagram for Challapalca area water samples.
involving the considered cations during the deep fluid uprising at

the surface. Both the geothermal areas present dilution phenomena
are as confirmed, in the corresponding diagrams, by the samples
points lining between the most important springs (CS1, PC2) and
local groundwaters (right corner in the diagrams).
Also in fig. 10 (where the values of 10*Mg/ (10*Mg+Ca) are
plotted vs. lO*K/(10*K+Na)[3]) springs CS1 and PC2 fall very close
to the equilibrium curve confirming the reliability of the
geothermometric estimation. These temperatures, however, should be
considered as the minima to be found in the reservoirs.
As regard the SiO2 geothermometer values, these must be
critically evaluated: PC2 spring (Challapalca area) and CS1, CS2,
364
Na/1000
100
MGÍ0.5
Fig. 9 - Na, K, 7~"Mg triangular diagram for Tutupaca area water samples.
CS3 springs (Tutupaca area) are steaming ones; on the hypothesis

of the "quartz adiabatic cooling" the resulting deep temperatures
are over 186°C [4] for the the former area and 265°C for the
latter.
The former value is consistent with the Na/K and K/Mg results
for the same water point, the second is decidedly higher. As above
200 °C the re-equilibration speed of SiO2 is very high and not even
massive phenomena of boiling can explain this incongruence, the
only explanation to justify the concentration found is that the
thermal fluids meet formations with SiO2 which can easily be

leached. These latter could be the ignimbrites schematized in the
365
10 Mg
10 K
Fig. 10 - 10 K/(10 K + Na) vs. 10 Mg/(10 Mg + Ca) diagram for both the areas.
geological section of the Tutupaca area (see appendix 1C). In this

case, the SiO2 content would be controlled by the amorphous phase
and the resulting equilibrium temperature ranging between 185 °C
and 200°C [4] perfectly merging the solute chemical
geothermometers values.
At last in fig. 11 are shown the log (AP/K) values for PC2
spring composition vs. temperatures ranging between 120°C and
240 °C (with the only constraint of the calcite equilibration at
the different temperatures)[5]. The curves for a series of
volcanic rock components, and the phases derived from their
hydrothermal alteration converge at a value around 210°C, very
closed to the Na/K temperature.
366
Sample PC2
Added Carbon to solut.

13.17 mmol/Kg
120 140 160 180 200 220 240 260

Temperature °C
Fig. 11 - Log AP/K values vs. temperature.
5. Remarks on the isotopic data
The relative results of water points sampled for isotopic

analyses are given in tabs. 1 and 2. The SD vs. <518O diagrams for
the Tutupaca and Challapalca areas are shown in figs. 12 and 13.
The first shows a substantial shift (at least two <S18O units)
for the samples CS1, CS2 and CS3 confirming that these are fluids
with high deep temperatures.
The second (fig. 13) the cold samples PC3, PC4 and PC11, which
considerably swerve from this one, are brook waters subjected to
daily cicles of freezing and thaw and could, in the warmer hours,
partially evaporate. This last process certainly is at the base of
367
-70
-90
O
<N
X
-110
1 30~ I I I I I I 1I I I I I 1I I I 1I I I I I I I I I I I I I I I 1! I I 1I I I I I I I I II I I i 1 I I ! I I I I I I I I I I I I I I I 1I I I I I I
•15 -13 12 -11

180 IN H20
Fig. 12 - 6 D vs. <518O diagram for Tutupaca water samples.
-60-1
-80-
o
IE
zj •100-
-120
-140
-18 -16 -14 -12
Fig. 13 - S D vs. £^°0 diagram for Challapalca water samples,
368
the isotopic composition of PCS (72°C, 212 mg/1) which,
characterized by a small flow rate, results isotopically very
increased: <S18O = -3.76, SD = - 89.2.
These evaporation phenomena are confirmed by the lining of all
the points till now mentioned on a straight line with the equation
<SD = 1.53*<S18O - 81.6 (R2 = 0.96) which can exatly taken as the
"evaporation line". A further support is constituted by the
position of sample TP6, which also evaporates, that even located
in the Tutupaca area, falls on the same line.
As regard the remaining points, sample PC2, the most

representative of the reservoir deep fluid, shows an appreciable
oxygen shift of about three <518O units; PC7, PC9, PCI, PC6, PC8
and PC10 can be considered as mixings in different percentages of
this deep fluid with a surface groundwater whose isotopic
composition should be: <518O = -16.85, SD = -126.5.
The SD vs. Cl content diagram of fig. 14, furtherly confirms

this hypothes is.
f.3
100- O
O
CM
X
)ñ i.
C)
o
-120* o o
O
500 1000 15002000 2500

Cl (mg/l)
Fig. 14 - 5 D vs. Cl diagram for Challapalca water samples.
369
To end up, the tritium content of the samples decreas,
generally, as a function of TDS and temperature with the exception
of TP6; here, notwithstanding a temperature of 12°C, the tritium
value is 1.7 T.U. confirming the large supply of groundwater.
The 180°C and 240°C temperatures computable for the exchange
18
reaction of O between dissolved sulphate and water [6] for the
CS2 and CS1 samples also agree with the chemical geothermometers
results.
6. Gas chemistry
The number of free gases found in the two areas, not taking
into account the Calacoa and Calientes zones not visited, is
rather small. The manifestations are characterized by a very
reduced gas flow. Moreover, some samples were damaged during the
air freight.
Shortly, for the Tutupaca area only three gases are available,
while for Challapalca the only gas resulted so polluted to loose
any meaning. The few analytical results are in tab. 3.
The composition of TP1B and TP4 agree with the assumption of a
mixture between a thermal fluid and surface waters initially in
equilibrium with the atmosphere. Instead TP6 contains an higher
quantity of H2 confirming a stronger interaction of surface water
with a deeper gas of vulcanic origin.
7. Conclusion
In the Tutupaca and Challapalca areas exist geothermal fluids,

their temperatures should be higher than 200°C. As regard the
former, samples coming from the Calacoa and Calientes zones, even
if some tens of kilometers far each from the other, seem to be the
emergecy of the same big thermal system or, at least, two
different hydrologic circuits with similar characteristics.
370
References
[1] AQUATER - INGEMET (1980) - Proyecto de Investigación

Geotérmica de la República del Perú - Región V. Lima -
PERÚ.
[2] BURGESS W.G. (1985) - Proyecto Integrado del Sur,

PERU: contribution to the geothermal assessment.
WD/OS/85/19.
[3] GIGGENBACH, W.F. (1988) - Geothermal solute equilibria.

Derivation of Na-K-Mg-Ca geoindicators. GEOCHIMICA ET
COSMOCHIMICA ACTA. 52, 2749-2765.

RESEARCH COUNCIL BULLETIN. 11, 3-9.

mineral equilibria in hydrothermal waters with appli-
cation to geothermometry and studies of boiling and
dilution. GEOCHIMICA ET COSMOCHIMICA ACTA. 48, 1479 -
1492.
[6] MIZUTANI, Y. & RAFTER, A.T. - Oxygen isotopic

composition of sulfates. NZ J SCIENCE, 12, 54-59.
371
U)
~J
to
Appendix 1
LOCATION OF THE INVESTIGATED THERMAL ZONES IN SOUTH PERU
Appendix 1A
GEOLOGICAL MAP OF THE TUTUPACA AREA
Appendix 1B
MAP OF THE CHALLAPALCA AREA
-j
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I l \ \ u \ ^ll ^ * /^
1 7
• ^» j-^-^t.'"?"';^!-*\ ''* /^-^ '" v TV.,, / " /N^'x ^x N;^^ f *-
i,c»i^.1,^ vi.'Giv/ S\ ,-,<l^L '••<• ^-p-rv-v '-*%¿;""; / ^ „ x / ^\^ \-) X\ 4 - >¿__
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^^^^S^^-^^'^rV/v^^í^tv V<, v
-
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\ V ^'J-- '-
-V— *v
Appendix 1C
SCHEMATIC GEOLOGICAL SECTION OF THE TUTUPACA AREA
(see Appendix 1A)
VOLCAN TUTUPACA
avas
pi roc last i cos (tufos)
_ " " " (redeposition)
ignimbrite
VOL CAN LOP E7 EX TRA NA

5500
RIO CALIENTES
5000
«500
4000
-igmmbrite
J50U
-areniscas
3000
LEYENDA
DEPÓSITOS ALUVIALES Y FLUVIO. KTI-to f'PUPO TOOUEPALA
GLACIARES
\ Qp-VlcZ VOLCÁNICO TUIL'PACA CALIENTES JSKI-/U GRUPO YURA
lUv-XVl TtO-Vicl VOLCÁNICO Pf?E-TUTUPACA CALIENTES MANANTÍA C A L I E N T E
L"l'\-':';] T«-Co Fm. CAPILLUNE

GEOTHERMAL EXPLORATION BY GEOCHEMICAL METHODS
OF THE THERMAL AREA EL PILAR-MUNDO NUEVO,
STATE OF SUCRE, VENEZUELA
F. D'AMORE, G. GIANELLI
Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italy
E. CORAZZA
Istituto di Geocronologia e Geochimica Isotópica,
Pisa, Italy
J. JAUREGUI, P. VÁRELA
Dirección General Sectorial de Energía,
Ministerio de Energía y Minas,
Caracas, Venezuela
Resumen-Abstract
EXPLORACIÓN GEOTÉRMICA MEDIANTE MÉTODOS GEOQUÍMICAS EN EL ÁREA TERMAL DE EL

PILAR-MUNDO NUEVO, ESTADO DE SUCRE, VENEZUELA.
En 1985-1986 se efectuó un estudio geoquímico en la zona de El Pilar -

Hundo Nuevo, península de Paria, Estado de Sucre, Venezuela. El objetivo era
hacer comprobaciones para una posible explotación geotermoeléctrica de la zo-
na, que se caracteriza por muchas manifestaciones naturales con temperaturas
del orden de 80-100°C.
Mediante una serie de clasificaciones diferentes de las muestras de agua

y gas, fue posible hacer una selección de las composiciones químicas más im-
portantes que permitieron obtener indicaciones geotermométricas útiles. Para
evaluar algunos de los parámetros del depósito, se han aplicado al mismo tiem-
po varias técnicas geotermométricas basadas en la interacción fluido-roca.
La zona en cuestión parece prometedora respecto a la recuperación de re-

cursos geotérmicos de entalpia elevada; parece que hay un depósito profundo
con salinidad relativamente baja (< 5 000 ppm), con salmuera neutra a tempera-
turas que se calculan entre 250 y 300°C y con presión parcial de CO eleva-
da. Se supone que existe un segundo depósito a menos profundidad, con tempe-
raturas del orden de 200-220°C. La acción de ambos depósitos está dominada
por el agua, y parece que se produce la ebullición a 160°C, a un nivel muy po-
co profundo. El nivel piezométrico (elevación de 150 m) regula la distribu-
ción en la zona de fumarolas y manantiales de agua. La autoobturación hace
377
posible la acumulación de fluidos, al menos en el depósito profundo, el cual
puede realimentarse con agua meteórica del lugar. Se deduce que a cierta pro-
fundidad hay un batolito que proporciona calor a los fluidos profundos.
GEOTHERMAL EXPLORATION BY GEOCHEMICAL METHODS OF THE THERMAL AREA EL

PILAR-MUNDO NUEVO, STATE OF SUCRE, VENEZUELA.
A geochemical survey was carried out in 1985-86 in the El Pilar - Mundo Nuevo area, Paria
peninsula, state of Sucre, Venezuela. The aim was to ascertain a possible geothermoelectric
exploitation of the area, characterized by many natural manifestations with temperatures in the range
80- 100°C.
Through a series of different classifications of water and gas samples it was possible to operate
a selection of the most significant chemical compositions that allowed useful geothermometric
indications. Several geothermometric techniques based on fluid-rock interaction have been applied at
the same time to evaluate some reservoir parameters.
The area of concern seems to be promising for the recovery of high enthalpy geothermal
resources; a deep reservoir appears to be constituted by a relatively low salinity (< 5000 ppm), neutral
brine with computed temperatures between 250 and 300°C and high CÜ2 partial pressure. A second
shallower reservoir is supposed to exist, with a temperature of the order of 200 - 220°C. Both
reservoirs result to be water-dominated, and boiling appears to take place at 160°C, at a very shallow
level. The piezometric level (elevation 150 m) regulates the areal distribution of water springs and
fumaroles. Self-sealing allows accumulation of fluids at least in the deep reservoir which can receive
its recharge from local meteoric water. A batholith is inferred at some depth, supplying the heat to the
deep fluids.
INTRODUCTION
From the Preliminary Report on the Evaluation of the Geothermal Potential of north-eastern
Venezuela (Gonzales et al., 1981), and also from the results obtained in the Geothermal Resources
Inventory in eastern and central Venezuela (Hevia and Di Gianni, 1983; Urbani, 1984), the El Pilar -
Mundo Nuevo area, located in the isthmus of the Araya-Paria peninsula, state of Sucre, Venezuela
(Fig. 1), was selected as the one with the highest priority. The geothermal assessment of the Paria
peninsula allowed this area to be selected as the most promising for a geothermoelectric exploitment.
The reason for this choice is due to some characteristics suggesting a local accumulation of
geothermal fluids, like the highest density of surface manifestations in Venezuela as well as of high
temperature springs (80 - 100°C) and of the peculiar chemical composition of the discharged fluids.
Urbani (1989) gave a preliminary assessment of the area and proposed a model implying a
geothermal reservoir with a temperature of 200 -250°C.
378
.SEA*
*£ ATI ANTIC
Stau of SMCftÑ O C E A N
CPAB - Cariaco pull-apart

basin
CG - Cariaco graben
GG - Guaraünos graben
SOG - San Juan graben
EPFS - El PHar fault
system
SFF - San Francisco fault
UF
BF
- Úrica fault
- Bohordal fault r Area of interest (El Pilar-Casanay

geotherraal district) © Towns
22 39
LBF - Los Bajos fault r

r
Geolonical map
sc."1:25.000
Geological map
• Springs
x Tree hydrocarbons
ESF - El Soldado fault sc. 1:10.000 A Cerro La Pica
P Zone of highest temperature springs ""-• Fault traces o 20km
Fig. 1. Location of thermal springs in the Araya-Paria isthmus, stale of Sucre (from Urbani,1984,
modified), and geostructural sketch map (from Várela and Hevia, 1990, modified). The
center-most rectangle is represented in detail in Fig. 2.
In the years 1985 and 1986 several thermal manifestations were sampled and analyzed with the
purpose of a regional survey from the Cariaco gulf to the Paria gulf, and inland to the San Juan
valley, thus characterizing the boundaries of the interest area outlined in Fig. 2 (Campos, 1981;
Gonzales, 1981; Jáuregui etal., 1985; Jáuregui et al., 1986; D'Amore and Gianelli, 1986; Hevia and
Jáuregui, 1988). Many more analyses of diluted waters, both from cold and hot springs, are reported
in Hevia and Jáuregui (1988), namely for the central area. The location of springs in Fig. 2 was
derived from the map in the same article by Hevia and Jáuregui (1988).
The marginal springs shown in Fig. 1 have been included in the present work with the purpose
of a better evaluation of the thermal anomaly in the central area. In spite of their thermality (up to
55-60°C) and of their salinity, since the beginning of the survey these springs demonstrated by their
compositions to be related to marginal circuits. Their locations are roughly aligned E - W on the active
El Pilar fault trace or on secondary ones related to it.
The geothermal manifestations in the area of concern (Fig. 2) form a hydrothermal system,
constituted by several boiling springs of sodium chloride type, associated with large alteration zones
with fumaroles and mineral deposits of sulfur, gypsum, anhydrite, calcite, and silica. Being only of
shallow origin, fresh diluted waters are found sparsely in the whole area, including also the
fumarolic zones.
In this study several geothermometric techniques based on fluid-rock interaction have been
applied at the same time, with the aim of a better definition of the thermal potential of the field. The
survey allowed also a thorough test and intercomparison on the reliability of different methods in
evaluating the main reservoir parameters. The interpretation of data is based also on a selection of
available samples, depending on their modifications that might occur during their ascent to the
surface; this selection was applied both to water and to gas samples. Notwithstanding the high
density of the tropical vegetation covering the studied area, enough geological and structural
information has been obtained, as briefly exposed in the geological chapter.
Though the above limitations are objective, the study encouraged by the involvement of IAEA
certainly allowed some conclusions to be reached about the high geothermal potential of the El Pilar -
Mundo Nuevo system, positively ascertaining high thermal conditions at depth and possibly a sealing
that produces the condition necessary for a true geothermal field: the fluid accumulation.
The interpretation given in this work may give useful indications for further steps of the
survey, like deep explorative drillings.
GEOLOGICAL BACKGROUND
The northeastern region of Venezuela is located in a transition zone at the contact between the
SE end of the Caribbean plate and the NE edge of the South American plate. Such a contact is poorly
defined, and it is marked by a wide strip affected by deformation and block faulting. This character is
the consequence of the stress generated by the right transcurren! movement and the oblique collision
of the Caribbean plate toward ESE, against the counterclockwise turning South American plate. The
result at depth is a transcurrent strain (at the base of the thinned continental crust which is near the
380
- '\
\ m
/ \\ MV.™J\/
rW*
O NH 4 -S0 4 springs (fumaroles) • N a - C l springs A Diluted w a t e r s • Houses
Fig. 2. Location of thermal springs in the area of concern, El Pilar - Mundo Nuevo. Elevations are in
UJ
m a.s.l. (from Hevia and Jáuregui, 1988, modified). Dashed lines represent the
00
hydrogeological pattern.
ductile-fragüe limit, at a depth of some 15 km) and pressure deformation along the dominating
directions NNW-SSE, E-W, and NW-SE; in turn this is complicated by the pre-existing directions
(e.g. N 70 E) as well as by some more directions complementary to the previous ones (SW-NE,
N-S). The block faulting takes place either through faulting with variable directions around NW-SE,
or through reactivation of old faults (Úrica, San Francisco, Santa Rosa, and others more,
delimitating the Caribbean plate), or else through recent faults like Bohordal, Los Bajos, El Soldado
(Fig. 1).
An important feature is the clear steady decrease from W to E of the right transcurrent E-W
movement, between the Cariaco graben (almost 100 km), the Cariaco gulf (25-40 km) and the
western part of the Araya-Paria isthmus (20-25 km), reaching a full stop in the Cerro Las Minas
"push-up" block (Vierbuchen, 1984). This is in agreement with the interpretation given by Speed
(1985) about the present transcurrent activity of the El Pilar fault system, as the consequence of a
suture resulting from the angular collision in this area between the two plates.
After the Paleocene-Eocene great displacements that gave the region its basic architecture, the
main deformations took place in middle Miocene (Macsotay et al., 1986), in Pliocene-Pleistocene,
and in Quaternary. The most recent evidence are the marine terraces in the Araya peninsula, uplifted
12 and 8 m, 125000 and 25000 years ago respectively; another consequence is the subsidence proved
by microgravimetric methods in the area around and ESE of El Pilar (Bravo et al., 1986), as well as
in other areas of the SE quadrant. According to all authors working in the area the above inference is
supported by the interpretation of the present seismicity.
In the central area Mundo Nuevo - Las Minas - El Pilar the compressive deformation toward S
and SE produced many scales, faulted folds, wedges either raised or lowered, structures like
semigraben or klippen, all of them with an average vergency to SE.
Since in the region almost all contacts and the same stratigraphic column have been altered
tectonically, the following list represents the formations and the lithologies of the area:
- Barranquin formation (KB): average or very coarse quartz sandstones, shales, calcarenites
and limestones. Age: Barremian. Thickness: 600-1200 m.
- El Cantil formation (KEC): clear massive limestones and some calcarenites. Age: Albian.
Thickness: 300-700 m.
- Querecual formation (KQ): limestones with alternated dark shales. Age: Turonian-Coniacian.
Thickness: 150-300 m.
- San Antonio formation (KSA): limestones, hard siliceous shales and some shales and
sandstones. Age: Maestrichtian. Thickness: 200-400 m.
- Tunapuy formation (KMT): phyllites and calcareous schists, either quartz-graphitic or
micaceous, with intercalations of lenses of metamorphic limestone, of some quartzites and of
quartz-mica-chlorite schists. Age: lower Cretaceous. Thickness: 800-1500m.
- Gliinimita formation (KMG): sericitic-graphitic phyllites, marls, meta-arenaceous limestones.
Age: lower Cretaceous. Thickness: 200-300 m.
- Lechozal complex (KTpL): informal name for a mixture of deformed fragments of
metamorphic rocks (KMT, KMG, KM Macuro, etc.) and of sedimentary rocks (BB, KSA, etc.).
Age: undetermined, later than Paleocene-Eocene. Thickness: 100-150 m.
382
- Chaguaramas complex (Ts-QCH): informal name for a polymictic conglomerate or mixture of
reworked clasts, ranging from a coarse conglomerate to a fine sandstone and to a pelite, of greenish
color. It results from the demolition of the southern edge of laminations and scales, and from other
erosive products of metamorphic rocks (KMT, KMG, etc.) as well as of sedimentary rocks like KB
and KSA. Thickness: 500-800 m.
- Los Arroyos formation (TmLA): informal name for deep trench turbiditic sediments with a
composition generally pelitic. Age: middle Pliocene. Thickness: 600-1000 m.
- Guatamarito formation (TpsG): informal name. Clear calcareous shales and greenish-gray
clays from lagoons and marshes of upper Pliocene. Thickness: 150-400 m.
- Mamporal formation (QM): clear polymictic conglomerate, poorly cmented, with layers of
fine sandstone. Age: upper Quaternary. Thickness: 300-800 m.
- Recent sediments from alluvium and flooded plains. Thickness: from a few meters to more
than 100 m.
The recharge of water takes place through the intensive faulting of the rocks all over the area.
The sealing could be provided by some low permeability lithologies of the above mentioned
formations, or by a self-sealing, or else by the compression of certain sections of the fault planes.
Approximately 8 km to the north of the area with thermal manifestations several apophyses of
a granitic porphyrite outcrop, with an age of 5 Ma (Moticska, 1987). This area corresponds to a
gravimetric anomaly suggesting the presence of a great sized intrusive body, either granitic or
granodioritic (Vierbuchen, 1984); possibly this intrusion is constituted by rocks derived from the
recent igneous phase related with the volcanic activity in the southernmost section of the Lesser
Antilles arc (Schubert and Sifontes, 1983). According to the gravity model by Vierbuchen (1984) the
top of the intrusion can be located at a depth of 6-9 km. The batholith has a maximum extension of
about 10 km, and a maximum thickness of 5 km (undefined width). A hypothesis about the heat
source can be forwarded, attributing it to the pressure stresses producing the fracturing and the
deformation of the plate edges, and capable of generating heat anomalies in the deep crust, up to the
local melting. The heat anomaly would produce a high heat flow capable of generating deep
reservoirs of hot fluids. The hot fluid uplift can take place through fracture systems associated to
faults, the most known directions of which are NNW-SSE and N-S, as resulting from the
distensional discharge of the compression of blocks limited by minor faults.
The geological conditions of the region are highly favourable to the presence of reservoirs at
depth, with a medium-high enthalpy.
CLASSIFICATION OF WATER SAMPLES
The results of water analyses are given in Table 1 for the main components; trace elements for
selected samples are given in Table 2. Table 3 reports dÔ, QD and tritium values for samples
collected in May 1985. Fig. 3 is a ¿r °O vs. dD diagram for the rainwater values of the Maracay area
(Venezuela, Lat. 10.25°N, Long. 67.65°W) and Barranquilla area (Colombia, Lat. 10.88°N, Long.
383
TABLE 1. Chemical analyses for main components of the springs in the El Pilar area. All analyses
$ performed at 25°C, expressed in mg/\; temperature and pH are measured in the field;
conductivity is in nS/cm; blanks = not determined.
sample date t'C pH conductivity Na K Ca Mg Cl SO4 HCO3 SiO2 NH4 B
7 5/85 983 677 4930 763 290 136 11 7 1540 166 129 150 27 36 5
12 2/86 86 5 596 675 287 229 252 1900 177 350 144 309
13 5/85 80 68 4780 689 273 181 13 5 1415 168 222 143 26 33 7
14 5/85 100 794 4030 634 188 122 21 7 1220 63 5 262 78 1 13 24 5
15 5/85 99 5 69 5710 939 364 110 082 1870 827 49 152 33 5 45 2
106 2/86 97 5 577 650 263 371 42 1 1400 154 430 109 42 3
114 6/86 480 825 400 130 179 16 1 705 144 76 76 5 17 7
4 5/85 497 595 5060 779 147 466 373 1190 877 465 59 5 54 16 6
17 5/85 87 622 1070 6 7 1 2 106 15 68 287 257 28 5 61 5 0 05
18 5/85 954 650 1331 3 6 1 6 28 3 39 4 7 474 117 26 8 i75 0 05
45 5/85 904 575 2660 1 3 1 4 25 040 2 2 1160 0 25 1 462 065
46 5/85 82 285 2750 0 8 0 6 66 092 2 2 1140 0 86 4 403 0 04
47 5/85 42 280 1300 3 5 2 6 74 8 34 4 7 482 0 29 3 45 0 03
49 5/85 85 435 6930 07 2 9 10 035 0 4 3170 0 36 8 1080 <001
50 5/85 536 236 5640 3 1 19 7 8 8 55 4 4 1870 0 201 304 008
51 4/86 435 364 3 2 5 3 30 1 579 10 545 0 45 2
109 3/86 394 285 3 7 3 7 162 21 5 0 9 1130 0 77 3
110 3/86 493 240 3 2 35 78 3 743 2 5 123 0 53 8
111 3/86 275 278 6 4 85 381 276 2 5 116 0 70 9
112 3/86 599 1 83 2 5 7 5 16 1 251 1 8 157 0 68 8
22 5/85 476 6 16 2430 477 21 2 176 52 341 7 4 1090 33 8 1 9 2 6

24 5/85 244 691 3600 908 18 2 191 98 85 3 103 2590 21 5 23 0 24
39 5/85 284 605 3490 1030 15 7 232 203 537 187 1720 22 9 3 4 62
77 5/85 392 667 3020 816 42 4 141 36 8 149 25 8 1420 26 2 5 4 4 5
88 5/85 565 588 1130 176 195 106 295 657 39 637 35 4 3 8 29
M2 5/85 240 70 658 87 1 5 143 29 152 62 2 348 8 9 I 4 0 05
19 5/85 305 697 990 94 8 12 3 146 13 147 20 2 329 28 7 0 2 3 1
31 5/85 324 684 725 31 1 5 904 279 56 5 96 3 262 13 6 0 2 0 06
36 5/85 37 661 713 28 1 1 7 124 167 36 1 139 182 12 3 0 3 0 5
42 5/85 32 63 888 63 8 82 144 13 98 5 24 8 399 18 7 0 2 1 7
52 5/85 53 63 573 6 3 1 5 179 66 87 24 4 338 42 4 0 8 0 04
53 4/86 465 632 52 1 4 169 691 12 16 0 540 25 5
59 5/85 295 67 461 50 05 108 29 11 5 9 6 281 13 2 0 3 <0 01
65 4/86 340 738 38 03 95 5 353 6 4 0 290 13 1
66 5/85 33 635 852 69 5 8 8 147 11 4 111 14 8 336 24 0 0 2 2 2
71 5/85 32 65 927 63 2 57 142 11 3 96 19 9 420 18 2 02 1 7
78 4/86 43 5 701 4 8 09 78 3 435 9 8 0 241 15 2
83 5/85 37 58 609 6 2 4 0 304 89 10 5 5 3 409 58 9 0 4 008
115 2/86 355 644 4 0 0 7 143 137 8 1 22 314 15
116 2/86 332 654 39 0 7 136 85 80 10 3 345 15
TABLE 2. Chemical analyses for trace elements of selected springs, El Pilar area. All analyses performed at 25°C, expressed in ppb; n.d. - not determined
sample u Rb Cs As Br NO3 Ba Sr F Al AlOnXO Fe Sb Pb Zn H2S
7 11800 5200 2700 1000 8100 2500 370 1800 1800 40 20 «10 230 500 <5 1600
13 11400 5100 2400 1100 7100 910 270 1700 1900 <30 <20 150 180 460 <5 1200
14 9900 4000 2500 1500 5000 <200 390 1100 1600 90 <20 30 130 390 <5 290
15 15400 6300 3200 1100 9300 <200 620 2100 1700 60 40 20 870 530 <5 1100
4 9000 1800 1500 110 6500 <200 50 3600 1800 60 <20 1900 190 470 9 <100
17 <10 <40 <400 <10 120 <200 40 180 <500 720 160 1100 30 <20 <5 4400
18 <IO <40 <400 <10 <100 <200 40 300 <500 800 320 90 <30 <20 <5 13800
45 <10 <40 <400 80 160 <200 <30 <100 <500 1000 60 1900 <30 <20 10 2800
46 <10 <40 <400 20 100 <200 100 <100 <500 500 n.d. 2100 120 <20 50 920
47 <io <40 <400 40 <100 <200 70 140 <500 10600 n.d. 22500 <30 30 60 770
49 <10 <40 <400 40 740 <200 <30 <100 <500 430 130 560 <30 <20 30 4000
50 30 <40 <400 100 200 <200 40 <100 <500 54900 n.d. 6100 30 60 130 160
*
22 740 <40 <400 10 570 3700 3600 4600 1100 <30 <20 80 170 260 20 1700
24 110 <40 <400 30 <100 115000 2030 1700 1200 40 <20 10 220 400 <5 100
39 980 <40 <400 80 1000 7900 80 910 <500 <30 <20 130 190 460 180 670
77 1400 <40 <400 20 870 2800 930 3900 3400 <30 <20 <10 150 600 <5 380
88 540 <40 <400 190 <200 440 3900 1100 <30 <20 60 90 150 <5 790
52 <10 <40 <400 <10 <IOO 240 80 210 <500 100 <20 250 20 40 7 790
59 <10 <40 <400 <20 <100 <200 <30 130 <500 <30 <20 140 <30 30 7 <100
83 50 <40 <400 <10 <100 <200 130 400 <500 <30 <20 30 40 60 <5 730
M2 <40 <400 20 <100 3300 20 <100 <500 30 <20 80 <30 20 7 590
19 1200 <40 <400 50 590 <200 160 370 600 <30 <20 <10 40 70 <5 <100
31 <10 <40 <400 10 260 3300 40 410 <500 <30 n.d. <10 30 30 <5 <100
36 <10 <40 <400 10 130 <200 90 500 <500 <30 n.d. 20 <30 30 <5 660
42 610 <40 <400 20 330 10200 180 360 <500 <30 <20 <10 30 50 <5 <100
66 830 <40 <400 50 380 4000 140 300 <500 <30 <20 <10 <30 90 <5 730
71 580 <40 <400 20 120 6900 180 320 <500 <30 <20 <10 20 80 <5 380
O Al is expressed as total Al and monomeric Al (separated in the field)
oo
TABLE 3. Isotopic composition of HÔ. 5 is in °/°° SMOW. *518O for 804.
sample 6 18 O 6D T.U. (±1.0)
7 -2.45 -17.8
13 -2.59 -20.0 1.2
14 -3.14 -17.3
15 -1.88 -16.0 0.1
15 +6.6*
4 -3.63 - 1 9 . 2
17 2.2
18 -2.77 - 7.4 3.1
45 -0.33 + 0.7 1.4
45 -0.18 + 7.3
46 -1.88 - 0.4
47 -2.67 - 6.9
49 -3.76 - 4.8 1.5
50 -0.39 + 0.2 1.1
22 -3.81 -21.2 3.4
24 -3.29 - 9.2
39 -3.61 -18.4
77 -3.91 -23.6 0.5
88 -3.90 -20.5
M2 -3.45 -16.8
19 -3.91 -19.5 0.6
31 -4.06 -19.5
36 -3.70 -18.5 5.1
42 -3.88 -19.2 0.7
52 -3.73 -18.6 9.4
59 -3.71 -18.1 4.2
66 -3.86 -20.0 0.9
71 -4.00 -20.2
83 -4.24 -20.2 0.3
74.78°W), as well as some average rainwater values of Venezuela and Colombia (from IAEA,
Vienna; R. Gonfiantini, personal communication). A slope of 8 seems fairly reasonable, although the
average rain values might not be fully representative of the average ones in the El Pilar area.
The chemical classification of waters was accomplished taking into consideration: i) absolute
concentrations of the main components characterizing each type of water; ii) correlations among
selected components.
Five types of waters can be recognized on the basis of the former method. In Fig. 4 the five
water types are exemplified by particular samples.
386
10-
-10-
Q
-30H
-50- O • a
1 2 3 4
-70-
-10 -8 -6 -4 -2
Ó180
Fig. 3. Rainwater 5^80 versus 5D (°/°° SMOW) in northern Venezuela and Colombia. 1: average in
Venezuela; 2: average in Colombia; 3: Barranquilla area (Colombia); 4: Maracay area,
Venezuela.
Na K Ca Mg Cl HC03 S04 NH4 B Li Rb Cs SiQ2 Na K Ca Mg Cl 4B Li Rb Cs SiO?

xlO «10 KlO «10 xlO 3 «!03 «10 «ID »10 x10»10 <103 «103 xlO
NACÍ water Mixed water

80-
o n nnn
NH4 SÜ4 water Na HC03 water
80
O XL ñu -Q. H n
diluted water diluted water

80
»40-
n n n___n n n PI 1 1 n n n
Fig. 4. Examples of the Five types of waters, as described in the text.
387
Group 1). The first group consists of seven samples (7, 12, 13, 14, 15, 106, 114). Complete
chemical analyses are available for springs 7, 13, 14, and 15 only, sampled in 1985. From Piper's
(1944) modified diagram (Fig. 5) it is evident that this is a homogeneous group of sodium-chloride
type waters. They are all located along an east-west strip of about 3 km in length, from El Palmar to
Los Chirriaderos (see map of Fig. 2). The most representative water sample (15) is reported in Fig. 4
for almost all chemical components (in meq/1). Despite its homogeneity some interesting differences
can be observed in Fig. 6 where sample 39 (located 15 km to the south) is also reported for
comparison (only samples collected in May 1985 are represented). In this figure several components
are plotted versus chloride (ppm). It is evident that, as the Cl concentration decreases, the Mg and
alkalinity increase, whereas Na, K, Li, Rb, Cs, Br, Nlfy, and B decrease. The SO4/H2^ ratio also
increases, due mainly to a decrease in H2S (oxidation). From stable isotope data (Table 3) the waters
show almost the same ÓD values (=18 i 1.5°/°°), while the d^°O value is -1.9%° for sample 15,
decreasing progressively towards -3.14%° of sample 14 and to -3.6%° for sample 39, in proportion to
the Cl content. The high arsenic content (over 1 ppm) in these waters is an indication of its
accumulation in the geothermal water from a deepe and hot source. Antimony also is quite high in
these waters: in sample 15 it is just less than 1 ppm.
Despite the fact that the tritium content of fresh water is about 13 T.U., little tritium is
apparent in these waters, at least in samples 13 and 15 which were the only ones analyzed in this
group.
Group 2). It includes spring 4 (Ño Carlos) only, located about 15 km east of the first group.
The water chemistry shows an unusual composition: it contains about the same amount of Cl as
spring 14, but more Ca, Mg, Na, as well as very high values of 804 and of HCC>3. Figures 4 and 5
show the complex chemistry of this water.
Group 3). One typical group of waters is that of the NH4-SÜ4 springs located in the fumarolic
fields of the Mundo Nuevo - Los Mereyes area (springs 45, 46, 47, 49, 50, 51, 112) and of El
Salvaje - Buena Esperanza area (springs 17, 18, 109, 110, 111). Their peculiar composition is put
into evidence in Figures 4 and 5.
Group 4). The fourth group of waters is of the Na-HCC>3 type (springs 22, 24, 39, 77, 88),
located far west and south of the area of concern El Pilar - Mundo Nuevo. They are all accompanied
by emissions of CO'2. Their chemistry is evidenced in Fig. 4 for sample 77, and in Fig. 5; they
usually contain large amounts of Mg. In Fig. 6 spring 39 is reported because of its Cl content in
excess of 500 ppm, despite its relative distance from the springs of Group 1. Compared to the
waters containing Cl reported in Fig. 6, its Na content increases with a decrease in Cl, whereas K,
Li, Rb, Br, B and NH3 decrease; this is the consequence of its high HCC>3 content.
Group 5). This is made of low salinity waters (< 1000 ppm), with pH between 6 and 7. A
distribution can be made on the basis of their geographic location. Springs 52, 59, 65, 78, 83 and
388
*í»
Fig. 5. Piper's (1944) modified diagram plotting compositions of waters from Groups 1, 2, 3, and 4.
M2 are located in the Mundo Nuevo area. Springs 115 and 116 are located west of El Salvaje and
north of Los Chirriaderos ( 1 - 2 km); these are typical local groundwaters of the Ca-HCC>3 type, as
shown in Fig. 4 (for sample 83). Springs 19, 31, 36, 42, 66 and 71 are all located west of the Los
Mereyes - Mundo Nuevo area (see example in Fig. 4). Springs 31 and 36 in the Casanay - La
Florida area are characterized by relatively higher Mg and 804 contents with respect to the others of
this group.
Fig. 7 shows the 3D versus dÔ diagram for the waters of Groups 1, 2, 4, and 5. All
samples but Group 1 are positioned on the meteoric line (Fig. 3) at dD = -19°/°° and d^°O = -4°/°°
approximately. Diluted waters can be considered as representative of the local meteoric ones. All
sodium bicarbonate waters except spring 24 fall on the meteoric line, at about the same point as
diluted waters. The lack of an isotopic shift of bicarbonate waters can be an indication of
low-enthalpy systems in spite of the emerging temperatures. The position of spring 24 can be
explained taking into consideration its recharge from Cerro El Pato, with an elevation in excess of
600 m; a negative shift for dÔ can also be explained by an exchange with CÜ2: the manifestation
emits a huge amount of free gas with respect to the water flow. Springs of Group 1 show an evident
positive shift in dÔ, up to two units (spring 15), suggesting a high temperature water-rock
interaction.
389
Fig. 6. Plot of some components against chloride for some selected springs, from the central ones
(center and right) to a peripheral one (left), showing the steady changes in major and minor
components. Chemical components are in ppmv.; 3'Ô in %<> SMOW.
390
20-
10-
0-
4,36.39.52.59
Q-10-
31,71.19,42,66.88
20- 83
-30-
-40 H
-7 -6 -5 -4 -2 -1
Fig. 7. 5D versus 5O diagram for the waters of Groups 1, 2, 4, and 5. The meteoric line is
reported also (from Fig. 3). The oxygen isotopic shift for Na-Cl waters is marked by a broken
line.
Fig. 8 shows the isotopic composition for the NH4-SÜ4 type waters (Group 3). The values
are scattered over the diagram from about 0 to about -4°/°° of 3Ô, across the meteoric line; the
exchange with CC>2 of the associated gas can displace the points toward more negative values. The
points fall along a straight line with a slope 3 which can be interpreted as due to condensation and
evaporation processes at about 100°C; this line intercepts the meteoric line at more positive 3D values
with respect to the springs of other groups. The positive shift in 5D can be explained by an exchange
with H2S of the associated gas phase, depending on the relative amounts of K^S and water.
"Most geochemical techniques may with confidence be applied only to specified types
of fluids with limited ranges of compositions. For instance, most ionic solute
geothermometers "work" only if used with close to neutral waters containing chloride as
the major anión. Any such interpretation of geothermal water samples, therefore, is best
carried out on the basis of an initial classification e.g. in terms of their major anions Cl,
SO4 and HC03" (Giggenbach and Goguel, 1989).
In the C1-HCO3-SO4 diagram of Fig. 9 the five groups of waters show the importance of
three main geochemical processes: a) steam heating from the absorption of high temperature,
H2S-containing, "geothermal" steam into groundwater; b) uprise of neutral, low sulfate, high
chloride, "geothermal" waters along the C1-HCÜ3 axis, close to the Cl corner; c) dilution by neutral,
but high-bicarbonate waters. Considerable caution is required in the application of most
"geo-indicators" for sulfate or bicarbonate waters, because the observed chemical composition is
mainly due to attack of acidic gases on the local matrix rock. It is evident that all waters of Group 1
follow almost a linear trend toward the shallow bicarbonate waters, starting from spring 15 which is
391
20-
Fig. 8. dD versus d^Ô diagram for the NH4-SÜ4 springs of Group 3 (see text).
0,50
HCO,/Cl
STEAM - HEATED WATERS
112-51-109-110-111 115-53-65-116
Fig. 9. Cl - HCO3 - SO4 diagram (after Giggenbach and Goguel, 1989) for all five groups of waters.
The hatched area represents "mature" waters; symbols represent: solid circles waters of Group
1, open circles waters of Groups 2 and 4, crosses waters of Group 3, open squares waters of
Group 5.
392
regarded as the most "mature" water and which is likely to be the most representative of the deep
reservoir. With respect to spring 15, the other Na-Cl waters become more and more enriched in Mg
and bicarbonate upon dilution; this has been evidenced also in Fig. 6. All low salinity waters (Group
5) fall in the vicinity of the bicarbonate corner; some waters far from the interest area show a certain
scatter, like the ones from Pantoño and Casanay areas (Fig. 1). Springs 22 and 39 (out of the interest
area) show a relatively high content of Cl, likely to be related to a mixing with salty waters in recent
sediments, from which they can strip also oxidized organic matter, like nitrates. Spring 4 also shows
a high Cl content associated with a high sulfate, consistent with a saturation temperature for anhydrite
close to 50°C. The relatively high Br (6 ppm), sulfate, Ca and Mg values, and its location subjected to
sea flooding, might indicate that a fraction of this water is likely to be related to a marine source. Its
isotopic composition, shown in Table 3, is consistent with a meteoric origin and a circulation within
marine sedimentary formations, at low temperature.
Spring 24, located few kilometers south of Las Minas, is a typical sodium bicarbonate water; it
shows anomalous contents of ammonium and mainly nitrate. The associated gas has a very high flow
rate and contains large amounts of methane (close to 20 % in volume). All these evidences are in
favor of a circulation in sediments rich in organic matter.
In the interest area the waters falling near the left corner of the diagram are generally acidic.
Fig. 9 shows that springs 17 and 18 also contain a significant amount of bicarbonates. These two
springs (not acidic) are associated with the most powerful gas emissions east of the Mundo Nuevo
area. All these waters are interpreted as cold groundwaters that have been heated and contaminated by
geothermal steam. Indeed, all these springs are characterized by a strong bubbling of gas containing
large amounts of H^S. One interesting feature of these waters is their large seasonal variation of pH.
During the rainy season oxidation of FTjS is stronger and the pH lower (less than 2).
It is interesting to point out that bicarbonate waters, such as 4, 22, 24, 31, 36, 39, are
surrounding the interest area of geothermal upwelling. Besides, the high sulfate and the steam-heated
waters in the interest area are encountered at the higher elevations (see Fig. 2). In particular in the
eastern area, while the Na-Cl waters (El Palmar - Los Chirriaderos) are found below 150 m, the
steam-heated waters and the main gas flows (El Salvaje - Buena Esperanza) are found at elevations
between 200 and 400 m. The piezometric level can be defined by the elevation of springs 14 and 15,
about 130 - 150 m. In the Mundo Nuevo - Los Mereyes western area only acidic springs (as well as
diluted bicarbonate waters) are found; indeed the whole area has an elevation between 350 and 400
m. Then (if locally present) the deep and chloride-rich waters are not allowed to reach the surface
because of their lower piezometric level. The circulation system is complicated by many shallow
waters which can also influence the composition of gases, e. g. oxidizing FÍ2S and H2-
The Cl-Li-B diagram shown in Fig. 10 is here proposed only for water samples where
chloride is above 10 % in weight among anions. According to Giggenbach and Goguel (1989):
"The alkali metal probably least affected by secondary processes is Li. It may, therefore, be
used as a "tracer" for the initial deep rock dissolution process and as a reference to
evaluate the possible origin of the two important "conservative" constituents of thermal
waters, Cl and B."
393
Cl/100
001
0.20
B/4
Fig. 10. Li - Rb - Cs diagram (Giggenbach and Goguel, 1989) for selected waters (Cl > 10% in
weight among anions) (see Table 2); SW = sea water.
All waters of Group 1 fall in a single cluster, showing a leaching of rocks, possibly reaching a
"maturation" stage. Sample 4, and to a further extent 22 and 39, show a chloride enrichment: this is
consistent with an addition of sodium chloride-rich waters (tectonic lows filled with marine
sediments and/or sea water at high tide).
In the Li-Rb-Cs diagram (Fig. 11) the Na-Cl waters cluster again around a composition which is
consistent with the dissolution of an acidic rock, like rhyolite. Rhyodacitic subintrusive rocks (as
discussed in the geological chapter) outcrop just north of the area, within a distance of 6 - 10 km.
These three rare alkali elements, being little reactive, are conservative of the rock composition and can
be leached only at depth; their ratios are not affected by shallow processes (Giggenbacb and Goguel,
1989). Only in waters of Groups 1 and 2 it was possible to find measurable concentrations of Rb
and Cs. These neutral waters (at least for their deep components) possibly have lost Rb due to uptake
in K-silicates, but not Cs.
As an introduction to the next chapter dealing with water geothermometry, the Na-K-Mg
diagram proposed by Giggenbach and Goguel (1989) has been used only for qualitative classification
(Fig. 12). All points representing waters of Group 1 fall aligned in a straight pattern from the Mg
corner of shallow waters to the farthest sample 15. This is an indication that they all form a single
family, confirming the previous observations. The relative position of the alignment is due mainly to
the Na-K and K-Mg geothermometric equations chosen by Giggenbach and Goguel. It is evident that
in this case the use of the two geothermometers yields an inconsistency. In spite of the general
reliability of Giggenbach and GoguePs (1989) geothermometer, the Ca concentration should be
taken into account in sedimentary rocks, like in this case. Different temperature calibrations of the
394
100
IOCS
Fig. 11. Triangular plot for Li, Rb, and Cs (after Giggenbach and Goguel, 1989, modified) for
selected waters (see Table 2).
Na/1000
A A A A A A A
K/100 "VMg
Fig. 12. Triangular plot for Na, K, and Mg (after Giggenbach and Goguel, 1989, modified).
Temperatures are in °C.
395
empirical K-Mg curve result in changes of the "full equilibration" and temperature lines. In any case,
the diagram suggests that all these waters are likely to be partially equilibrated or mixed waters, the
least immature being again spring 15.
CLASSICAL WATER GEOTHERMOMETRY
Empirical cation geothermometry has been used as a first attempt to calculate the sub-surface
temperatures of the springs. A particular emphasis will be given to the sodium chloride waters, with
the aim of evaluating the thermal conditions of the deep reservoir, even though all these waters appear
to be affected by some dilution processes, on the basis of the classification outlined above.
It is well known that many different geothermometers (Table 4) rarely give the same computed
temperatures. Table 5 summarizes the results obtained using some among the given geothermometers
for the high salinity groups of waters (Groups 1, 2, 4). Geothermometers should be used carefully,
and some comments are necessary for their application.
Silica geothermometer: Quartz (conductive cooling) can be used with a certain confidence for all
the sampled springs except for the Na-Cl waters. For this group in fact the relatively low computed
temperatures (of the order of 160°C in the El Palmar - Aguas Calientes zone) have been interpreted as
the ones at which the gas phase separates from the liquid phase owing to boiling and cannot be
assumed to be representative of the deep reservoir temperatures. Fig. 13 is a dissolved silica -
enthalpy plot (Truesdell and Fournier, 1977) for determining the temperature of a hot water
component mixed with a cold water, yielding a warm spring water. Group 1 only is reported in the
diagram; considering among the sodium chloride waters the ones between the boiling point and the
point where all local diluted waters merge, the extrapolation to the quartz solubility curve gives a
temperature of 250°C approximately. Of course, this temperature is only indicative of a high enthalpy
system, namely because of the few data available. For Na-bicarbonate waters (Group 4) temperatures
computed from the chalcedony equation are also reported in Table 4, considering low enthalpy
systems (t< 150°C).
Na - K geothermomcten Several Na-K geothermometers can be applied; all of them lie in a
broad band between the albite-microcline and the albite-adularia curves (Fig. 14; from Fournier,
1990); empirical curves tend to converge above 300°C. In Table 5 Arnorsson's (1983)
geothermometer only was used as an instance for Na-K calculated temperatures. For the Na-Cl
waters the Na/K ratio appears to give too high temperatures, as if Na were deficient with respect to
pure albite. For springs of Groups 2 and 4 a Na-K geothermometer based on montmorillonites has
been applied (as in Fig. 14) In fact, it must be taken into account that in sedimentary basins exchange
reactions involving clay minerals can substantially change the Na/K ratio (see also Henley et al.,
1984). The computed temperatures are much lower than the ones obtained by application of the Na-K
geothermometer based on feldspars.
Na - K - Ca geothermometer: It takes into account reactions involving exchanges of the three
elements with a mineral solid solution (Fournier and Truesdell, 1973). Fournier (1990) makes several
comments on the application of this geothermometer for waters with reservoir temperatures below
200°C, of sodium bicarbonate type, and/or rich in Mg (see also Giggenbach, 1989). The composition
396
TABLE 4 - Equations expressing the temperature dependence of selected chemical
geothermometers. For each geothermometer used in Table 5 there is an abbreviation;
concentration units are in mg/Kg, except for Fouillac and Michard (1981) (molar units).
Geothermometer Equation Source
Amorphous silica t°C = 731 ^- - 273 (<250°C) Fournier (1981)

4.52 - log SiO
Chalcedony (TCH) t°C = 4 69 1(32

S;Q
-273 (<250°C) Fournier (1981)
Quartz (maximum steam loss) t°C =

1522 -273 (<250°C) Fournier (1981)
5.75 - log SiO2
Quartz (no steam toss) (TQC) t°C = 5 ^ f c "2?3 (<25(f C) Fournier (1981)
Na-K t°C = 856 -273 Truesdell(1976)

0.857 +log (Na/K)
Na-K t°C = 833 -273 Tonani(1980)

0.780 + log (Na/K)
Na-K(TNK) ____ 933 273

ll5 Amorsson(1983)
0.993+
Na-K(TNK) AmOISson(1983)
Na-K f0/"*._ _____1L1 /_____ JTl Fournier (1981)

1.483 + log (Na/K)
Na-K t°r = ____*178____ . 273 Nieva and Nieva (1987)

1.470 + log (Na/K)
Na-K t o c= 1390 .2?3 Giggenbachetal. (1983)

1.750 + log (Na/K)
K-Mg(TKM) t«0————M1Í————-273 Giggenbachetal. (1983)

13.95-log (K2/Mg)
397
TABLE 4. (continued)
Li-Mg CTM L) ft>

2200 ==r-273 Kharaka and Manner (198 9)
5.470 -log(Li/VMg)
Na-Li t°C = 1590 ^-273 Kharaka et al. (1982)

0.779 + log (Na/li)
Na-Li (TNL) <ci<o 3 M) fC = 1000 >» rr *\ ~ ¿* i J Fouillac and Michard (1981)

0.389 + log (Na/Li)
T
Na-Li (ci>o 3 M) 1195 .x - 273 Fouillac and Michard (1981)

0.130 + log (Na/Li)
Na-Ca t°C = 1096.7 -273 Tonani(1980)

3.080 -log(Na/VCa)
K-Ca t°C =
1930 -273 Tonani(1980)
3.861 -log(Na/VCa)
Na-K-Ca(TNKC) fC = 1647 - 273 Foumier andTruesddl (1973)

bg(Na/K)+p[log(VCa/Na)+2.06]+2.47
P = 4/3 for t<100°C, = 1/3 for t>lOO°C
Na-Ca-Mg(TNKCM) t°OTNKC-DEL (see below) Fournier and Potter (1979)
1 Compute t by TNKC
If t<70°C, no correction to TNKC
2 Compute R = (Mg/(Mg + Ca + K)) 100 (in equivalents)
If R>50, no correction to TNKC (cold environment)
3 Compute DEL - correction to TNKC
If 5<R<50 and T is computed by TNKC
DEL - 10 66-4 7415R+325 87(log R) 2 -l 032 105(log R) 2 /T-1 968 107(log R) 2 /T 2 +l 605 107(log R)Vr 2
If 0 5 <R<5 and T is computed by TNKC
DEL = -1 03+59 971 log R+145 05(log R) 2 -3671 l(log R)2/T-1 61 10 7 log R/T2
If DEL <0 5, no correction
4 To compute R- Ca - Ca(ppm)/(1000 20 04)
K = K(ppm)/(1000 39 102)
Mg = Mg(ppm)/(1000 12 156)
18
5 O 1 000 In a - 2.88 (lO6!'2)- 4.1 MacKenzie and Truesdell (1977)
1000 + 5
1000
398
TABLE 5. Temperatures (in °C) computed by water geothermometers
sample TQC TCH TNK TNKA TNKC TNKCM TNL TML TKM
4 110 81 271 140 153 125 281 142 121

7 161 — 349 — 281 231 322 173 164
12 159 — 364 — 280 190 — — 150
13 158 — 355 — 278 228 333 169 159
14 124 — 319 — 258 145 324 155 138
15 162 — 352 — 291 291 331 246 231
22 84 53 125 54 93 63 100 67 66
24 66 34 74 29 94 34 — 23 55
39 69 37 59 -25 85 85 73 86 70
77 74 42 136 61 133 63 106 87 87
88 86 55 206 97 91 62 147 67 70
106 142 — 357 — 268 168 — ... 138
114 123 — 330 — 249 167 — — 129
TQC: quartz, no steam loss (Fournier, 1981)

TCH: chalcedony (Fournier, 1981)
TNK: Na-K (Arnorsson, 1983)
TNKA: Na-K from clay equilibrium (Fournier, 1990)
TNKC: Na-K-Ca (Fournier &Truesdell, 1973)
TNKCM: Na-K-Ca-Mg (Fournier & Potter, 1979)
TNL: Na-Li (Fouillac & Michard, 1981)
TML: Mg-Li (Kharaka & Mariner, 1989)
TKM: K-Mg (Giggenbach et al., 1983)
of CO2-rich waters tends to be controlled by the attack of carbonic acid on feldspars (and on other
mineral phases); this will cause water composition to plot off the empirical composition trends that
result from NaCl geothermal fluids in equilibrium with feldspars. The NKC temperatures for waters
of Group 1 appear to be significant of the deep reservoir conditions, ranging between 250 and 290°C.
Na-K-Ca-Mg geothcrmometcn The presence of relatively high contents of Mg tends to lower the
temperatures given by the previous geothermometer; Fournier and Potter (1979) introduced the Mg
correction. About this geothermometer, Fournier (1990) made the following comments:
"Mg concentrations in geothermal fluids decrease rapidly as temperature increases and all
Mg-rich fluids found in nature have undergone water-rock reaction at a relatively low
temperature. Furthermore, as geothermal fluid flows from a high-temperature environment
399
to lower temperatures, it appears to pick up significant amounts of Mg from the
surrounding rock relatively easily and quickly. This leads to major ambiguity in the
application of the Fournier and Potter (1979) Mg correction; that is, a truly
low-temperature water may require a Mg correction to give a correct temperature, but a Mg
correction applied to a high-temperature water that has picked up Mg during upflow will
yield too low a reservoir temperature."
The Mg correction for the springs here considered appears to give reasonable results only for
bicarbonate waters. For NaCl springs the decrease of the calculated temperature is in correlation with
the decreasing salinity; it seems to confirm that the whole Group 1 constitutes a family of mixed
origin waters, among which spring 15 is the purest term.
K - Mg and Mg - Li geothermometers: Giggenbach et al. (1983) and Kharaka and Mariner
(1989) proposed these two empirical geothermometers respectively, using equations based on water
compositions of well fluids. Application of both geothermometers to the springs of Group 1 yields
lower temperatures than the ones inferred in the deep reservoir because of the possible uptake of Mg
during ascent, along with dilution. According to Fournier (1990)
700-
600-
500-
O>
^¿
O5 400-
JE
CM
o
300 H
200-
100-
0-
100 200 300
Enthalpy (cal/g)
Fig. 13. Dissolved silica vs. enthalpy diagram (from Truesdell and Fournier, 1977) for selected
samples. Solid circles represent Na-Cl waters; all groundwaters fall within the solid square.
400
3.00
2.50-
2
_ -°°~
i¿
\
05
5 1.50H
1.00-
0.50-
60 100 200 250 300 C

i i . i i
3.50 3.00 2.50 2.00 1.50
1000/T(°K)
Fig. 14. Variation of log (Na/K) as a function of the reciprocal of absolute temperature. Theoretical
curves for low albite - microcline, low albite - adulada and Na-montmorillonite -
K-montmorillonite calculated using equilibrium constants in Arnorsson (1982). Various Na/K
geothermometers are labelled VG (Giggenbach et al., 1983), RF (Fournier, 1979), DN (Nieva
and Nieva, 1987), SA (Arnorsson, 1983), AT (Truesdell, 1976), FT (Tonani, 1980). (After
Fournier, 1990).
"Water-rock exchange reactions involving Mg proceed relatively fast at low

temperatures and K //Mg and Li//Mg ratios appear to be good indicators of the last
temperature of water-rock equilibration in an ascending water. A contributing factor in this
apparent fast reequilibration is that both Mg and Li tend to be minor constituents in most
thermal waters, so a relatively small amount of reaction involving one or both of these
constituents may have a large effect on the ratios of cations remaining in solution. When
there is good agreement in the temperatures estimated using K//Mg, Li//Mg, and other
geothermometers (particularly Na-K-Ca and silica), one can be fairly certain that
water-rock equilibration has occurred at the estimated temperature and that there has been
little water-rock reaction during subsequent flow to the surface. Agreement between
K//Mg and Li//Mg geothermometer temperatures, but higher temperatures estimated using
other geothermometers, may indicate a relatively short time in a reservoir at intermediate
depth and intermediate temperature where water-rock reequilibration occurs only in respect
to the most reactive phases."
In this study the Na bicarbonate waters follow the former proposition (equilibrium), while the
Na-Cl waters (as always, possibly except spring 15) contain significantly more Mg (and less Li) than
initially was present in the deep reservoir water (dilution).
401
Na - Li gcothermometen Two geothermometers of this type have been proposed by Fouillac and
Michard (1981) and by Kharaka et al. (1982) (Table 4). In Table 5 only the temperature computed
according to Fouillac and Michard's (1981) equation is given. Since Na is a major constituent and Li
a minor one, slight changes in the latter (e.g. exchanges in sedimentary formations) can heavily
modify the Na/Li ratio. It is used here only to differentiate the high temperature sodium chloride
system (Group 1) with respect to the low enthalpy sodium bicarbonate waters (Group 4). The high
temperature calculated for spring 4 by means of this geothermometer is worth of attention, because of
its geographic location: the temperature might be interpreted as the deep reservoir original
temperature, before any possible reequilibration in a shallow and low enthalpy reservoir. Moreover,
application of the TNL geothermometer often results in overestimated temperatures, possibly because
it has been calibrated mostly in granitic systems.
K - Ca geothermometer A chemical reaction governing CC>2 pressure through the formation of
calcite in a full equilibrium system corresponds according to Giggenbach (1988) to:
Ca-Al-silicate + K-feldspar + CÜ2 = K-mica + calcite (1)
The temperature dependance of this univariant reaction is given by:
log PC02 = o-° 168 t-3.78 (2)
where ?CO2 *s 'm ^>ar an& * m °C-

As an example, this equation gives 2.6 bar at 250°C and 18 bar at 300°C. A possible relation
linking CC>2, Kand Ca in a full equilibrium system is (Giggenbach, 1989):
3 K-feldspar + CC>2 + Ca2+ = K-mica + calcite + 2 K+ (3).
Its PcC>2 dependence corresponds approximately to:
log (CK2/CCa) = log PC02 + 3-0 (4)

where Cs are concentrations in mg/1.
For spring 15 this geobarometric equation gives a PcO2 °f 1-2 bar, consistent with a reservoir
temperature close to 230°C if calcite is considered a stable phase. This is the same temperature as that
computed by the K-Mg geothermometer.
As a general conclusion on the application of the aforementioned geothermometers, the general
remarks by Fournier (1990) are to be regarded consistent with the results obtained in this study:
"In evaluating cation geothermometer temperatures, attention must be given to possible

effects of continuing water-rock interactions and mixing of different waters during upflow.
In addition, variations in estimated cation geothermometer temperatures may result from
variations in the mineralogy of the reservoir rocks that are reacting with the fluid. The
complete conversion of all feldspar in contact with reservoir water to smectite or illite will
generally lead to erroneous cation geothermometer temperatures. In particular, this is a
likely source of error when dealing with CU2-rich waters that contain mostly NaHCO3-
Additional errors arise from not taking into account activity coefficients of both the solid
and ionic reactants. Under the best conditions cation geothermometers have an uncertainty
of at least ± 5 - 10°C, and commonly much greater than 20°C.
402
Even with their inherent uncertainties, cation geothermometers can be very useful for
estimating approximate temperatures in geothermal systems and for investigating effects of
water-rock partial reequilibration during upflow. Reactions involving Na and K appear to
proceed very slowly while those involving Mg appear to proceed relatively quickly. In this
regard, the salinity of a solution is an important factor because a given amount of reaction
of highly saline fluid with wall rock during upflow will have little effect on the ratios of the
major cations in solution. On the other hand, the same amount of reaction of a dilute
solution with wall rock may drastically change cation ratios. Therefore, cation
geochemistry applied to hot-spring waters is likely to be most reliable for saline waters and
least reliable for dilute water. Increasing Mg , in general, and decreasing K/V~Mg and
Li//Mg, in particular, are very sensitive indicators of water-rock reequilibration with
decreasing temperature and of mixing of high- and low-temperature waters."
Some more remarks can be made about the results reported in Table 5. The general trend of
temperatures follows the classification groups made on the basis of salinities and chemical
compositions. Sodium chloride waters of Group 1 show in general a strong thermal anomaly
centered in the area of the order of 1 - 2 km^ between El Palmar and Aguas Calientes. The thermal
anomaly is likely to be extended 3 - 4 km westward, as far as spring 14 (Los Chirriaderos). All these
waters appear to be more or less affected by dilution and mixing with a shallow diluted water, as
already outlined. In spite of this, the composition of spring 15 (El Palmar) allows a first evaluation of
the deep thermal conditions to be made through the geothermometers presented in Table 5. As
mentioned before, the temperature calculated from quartz for this spring might well represent the
temperature of the flashing point. One can suppose that a liquid phase (equilibrated at high
temperature with quartz) rising from the deep reservoir is cooled by conduction and becomes
oversaturated in silica; at a certain shallow depth, depending on local structural and physical
conditions, the liquid phase starts boiling, segregating a gas phase. The sudden increase in
concentration of silica and the violent expansion of the gas phase produce a stirring of the residual
liquid, and as a consequence precipitation of silica. The solid phase thus produced can be partially
deposited locally in the fractures and/or carried to the surface by the upflow; it is then eliminated at the
sampling point by filtration of the sample. The explanation for the whole process was proposed by R.
Celati (personal communication, 1986).
The average temperature calculated for spring 15 by means of the other classical
geothermometers is of the order of 290 ± 50°C, with all the already outlined limitations. It is worth
noting that the use of the isotopic SÜ4-H2O geothermometer reported in Table 4 (Mackenzie and
Truesdell, 1977) gives a temperature of 206°C for the same spring. This represents the isotopic
equilibrium temperature between water and sulfate ion. Of course, water collected from this spring
does not necessarily have the same isotopic composition as the deep hot water because of possible
steam losses or dilution and mixing phenomena which here are not accounted for. The temperature
obtained from the isotopic geothermometer can represent the equilibrium between water and
anhydrite, below which solid sulfates dissolve yielding sulfate ions. That is, above this temperature
SÜ4 and HSO4 species are not present in the solution; this is supported by the calculated
403
oversaturation of anhydrite found for this water for temperatures above 200 - 230°C. In the deep
reservoir instead sulfur is supposed to be controlled by the E^S - pyrite equilibrium.
Temperatures computed for spring 4 (Group 2) by TQC, TNKCM, TNKC, TNKA, TKM,
TML are of the order of 132 ± 16°C, indicating a situation of medium enthalpy as can be inferred by a
leak from a deep reservoir and a later reequilibration.
Temperatures computed for bicarbonate waters of Group 4 (ruling out the TNK and TNL
geothermometers) are all below 100°C. As an example, spring 22 can be considered representative of
the group; it is located south of the anomaly, with an emerging temperature of 48°C and an average
calculated temperature of 69 ± 15°C.
From the geothermal point of view Group 5, including all diluted waters, was not taken into
account, having been considered too immature for having any significance. The NKC computed
temperatures are in any case lower than 50°C.
GEOTHERMOMETRY AND SATURATION INDICES
Despite the fact that all the classical geothermometers indicate a strong thermal anomaly localized
in the El Palmar - Aguas Calientes area, the range of values is pretty wide for a precise temperature
evaluation. Application of fluid-mineral equilibria governing the chemical composition of water can
decrease the uncertainty with regard to the temperature estimates for the deep aquifers (e.g.
Amorssonetal., 1982; Michard and Rockens, 1983; D'Amore et al., 1987; Celati etal., 1991). This
can be achieved by the analytical determination of monomeric aluminum (AP+) and (AKxJOw)2' w¡th
x = OH", F-, SO^-, etc. and z = 3 - wy. Monomeric aluminum must be separated in the field.
The method by Arnorsson et al. (1982) was used through the computer program WATCH in
order to calculate the water speciation and the saturation indices for several hydrothermal minerals.
The Saturation Index (SI) is the logarithm of the ratio (at a given temperature) between the
activity product for hydrolysis reaction of a given mineral (AP) and its thermodynamic equilibrium
constant (K). Assigning a decompression temperature (that is when a two-phase system is produced
in the ascending fluid) equal to the quartz geothermometer temperature and a SiC>2 concentration
corresponding to quartz saturation, it is possible to calculate at selected temperatures the pH, the
speciation of the fluid (as activities of aqueous species), and then the saturation indices. These
saturation indices are plotted versus temperature for a number of selected minerals. For each mineral
the intersection of the SI vs. temperature curve with the zero line gives its equilibrium temperature.
Considering the uncertainty of measured Al concentration and of the thermodynamic data, the field of
stability for a given mineral is assumed to be between temperatures corresponding to a saturation
index of 0 ± 0.25. Table 6 reports the temperature range for selected minerals andsprings (4, 15, and
22). For sodium chloride waters spring 15 was chosen as the most representative. The values of the
saturation indices vs. temperature for spring 15 is reported in Fig. 15. Taking into consideration the
maximum temperatures of the ± 0.25 range, the following high temperature mineral assemblage can
be found for spring 15: albite (293°C), K-feldspar (288°C), Mg-chlorite (305°C), calcite (275°C),
epidote (268°C). The computed mean temperature is 286 ± 15°C; this is very close to the value of
291°C given by the TNKCM geothermometer. On the other hand, considering the minimum
404
temperatures of the ± 0.25 range, a different mineral assemblage can be also found in the diagram:
albite (226°C), K-feldspar (210°C), wairakite (225°C), prehnite (235°C), calcite (225°C), anhydrite
(225°C). This gives a mean temperature of 224 ± 8CC. This temperature is comparable with that of the
TKM geothermometer (231°C).
This bimodal distribution of temperatures can be interpreted as two limiting thermal conditions
existing in different and independent parts of the reservoir: a deep zone characterized by temperatures
close to 290°C and a relatively shallow zone with a temperature of about 225°C. If spring 15 is
partially mixed, the bimodal distribution is the result of the mixing. Of course, the choice of mineral
species is somewhat arbitrary, at least in the early survey phase, until proved by drill cores. This
method cannot be applied with confidence to the other sodium chloride waters because their higher
dilution and mixing produce large variations of the computed saturation indices of minerals.
Waters of spring 4 (Group 2) and of sodium bicarbonate springs (Group 4) appear to be in
equilibrium with the following minerals: albite, K-feldspar, laumontite, montmorillonites (Table 6
and Fig. 16). Undersaturation for alumosilicates such as epidotes, prehnite, Mg-chlorite, can be
ascribed to the incompatibility of the reservoir temperature with the stability ranges of these high
-6
200 250 300 350
T(°C)
Fig. 15. Saturation indices vs. temperature (see text) for selected minerals, for spring 15 (at quartz
saturation).
405
temperature mineral phases. This type of waters, always accompanied by free gas, may be the result
of a release of CC>2 at depth from hydrolysis of limestones and interaction of the produced carbonic
acid with silicate minerals at relatively low temperatures. All waters of Group 4 yield temperatures
lower than 100°C with the "classical" geothermometers; saturation indices give consistent indications
within a temperature range of 60 to 90°C.
For spring 4 (see Fig. 17) the computed temperature is 104 ± 8°C, in spite of its high chloride
content; it confirms a contribution of a deep component, with reequilibration at low temperature. The
presence of the deep component is witnessed by the relative abundances of conservative species like
Li, Rb, Cs, Cl. Waters of Groups 2 and 4 are noteworthy for the agreement between the temperatures
computed by the method of saturation indices and by the "classical" geothermometers.
TABLE 6. Computed temperature range (°C) for equilibrium conditions of selected mineral species.
Equilibrium occurs when SI = 0.00±0.25. Spring numbers as column headings.
mineral system 15 22
Albite Na-Al-Si-O 260±33 (x) 70±5 90±6 (x)

Adularía K-Al-Si-0 289±29 undersat. t>60 undersat. t>90
Microcline K-Al-Si-O oversat. t>232 undersat. undersat.
K-FeldsparO) K-Al-Si-O 249139 (x) 85±5 112112 (x)
Prehnite Ca-Al-Si-O-H 241 ±6 (x) undersat. undersat.
Epidote Ca-Fe-Al-Si-O-H 264±4 (x) undersat. undersat.
Zoisite Ca-Al-Si-O-H 232±5 (x) undersat. undersat
Wairakite Ca-Si-O-H 233±7 (x) undersat. undersat.
Mg-Chlorite Mg-Al-Si-O-H 302±2 (x) undersat. undersat.
Calcite Ca-C-O 250125 (x) oversat. t>48 oversat i>59
Anhydrite Ca-Si-O oversat. t>200 undersat. oversat. t>82
2
Na-Montm. Na-Al-Si-0-H oversat.< > 88±1 10311 (x)
K-Montm. K-Al-Si-0-H oversat. t>205 82±1 9911 (x)
2
Ca-Montm. Ca-Al-Si-O-H oversat/ ) 93+1 110+1 (X)
2
Mg-Montm. Mg-Al-Si-O-H oversat/ ) 94±1 110+1 (X)
2
Muscovite K-Al-Si-0-H oversat/ ) oversat. t<H5 oversat. t<!40
Laumontite Ca-Al-Si-O-H oversat/2) 79±4 10215 (x)
(x) This symbol indicates the use of the mineral for equilibrium temperature evaluation (see text)
(') Assumed with a structural state intermediate between microckne and adularía
(2) Oversaturated in the temperature range 200-325°C
406
-6-
80 100
T(°C)
saturation).
- 6-
~4Ó ' §T 80 100 "iío ' iSó ' Í8Ó~
TÍ°C)
saturation).
407
GAS GEOCHEMISTRY
Gas classification
In Table 7 the gas compositions as vol. % are given; analyses were carried out on total dry
gases. Data are reported after correction for C>2, considered as an index of air contamination. In order
to use the gas composition as a tool to evaluate deep temperatures, a classification of gases was made
by means of three suitable diagrams.
Fig. 18 is a diagram comparing the main component CÜ2 against two reduced and reactive
parameters: CH4 and the sum H2 + H^S. Methane is an ubiquitous component of all kinds of gases ;
it is one of the slowest species to equilibrate (Giggenbach, 1982) with respect to "faster"
components. The samples in the diagram follow a certain geographic distribution from E to W and to
marginal springs: the compositions of the eastern samples, occurring from El Palmar as far as El
Salvaje, show important concentrations of Ü2 and/or H^S. Moving farther to W (Mundo Nuevo -
Los Mereyes) the gases show lesser and lesser of these components, up to nil (or close) in the gases
associated with the marginal bicarbonate waters. An exception is the gas of spring 88, with high
concentrations of H2S (and to a lesser extent of H2) in spite of its marginal position, its low salinity
and its low (< 100°C) temperature computed by water geothermometry.
Another classification is given by the reduced and hydrogenated minor components H2, H2S,
CHÍ4, in the plot of Fig. 19. A geographic trend similar to what obtained from Fig. 18 can be seen in
this diagram, the marginal gases being richer in methane. The shift to the right, that is toward the
Ü2S - CFÍ4 edge, of gases associated with NaCl springs like 7, 14, and 15 can be explained as a
hydrogen loss. The most likely reason for this can be a steam loss from the original fluid, of which
the high elevation gas emissions like 17 and 18 represent the gas fraction; the NaCl springs instead
represent the liquid fraction. It should be pointed out that the former are within 1.5 km of the springs,
at an elevation about 200 m greater. The gas composition of 17 and namely of 18 samples is thus
here considered as the most representative one of the gas at equilibrium in the deep reservoir, the
corresponding water being represented by spring 15. A second hypothesis for the H2 loss can be
reequilibration in water during ascent. The gases from the Mundo Nuevo - Los Mereyes area lie in an
intermediate position between 17 and 18 gases and the methane corner. The explanation for not being
these gases in the same position in the diagram as samples 17 and 18 can be attributed to a certain
contamination of the deep gases in the latest stages of their ascent, that is after separating from the
liquid phase at the piezometric level (as already mentioned in the water classification): in the area in
fact the villages tap local water tables at very shallow depths. The least affected by this oxidation is
the gas from spring 45, the strongest gas manifestation in the area. The position of sample 52
(air-contaminated and associated with a diluted neutral water, the richest in tritium) is odd: it is clearly
the result of oxidation in the surface water. Because of the large amount of C>2 found in the gas, its
position in the diagram suggests that if no oxidation did occur (complete loss of Ü2 and partial of
Ü2S) its point would shift toward the position of gas 18. The same can be valid for sample 88.
408
TABLE 7. Composition of free gases in springs, El Pilar area. All analyses expressed in vol %; n.d. = not determined; blank = not detected.
sample C02 H2S CH4 H2 N2 AT He CO-104
7 98.5 0.51 0.074 2.9-10-4 0.85 0.018 traces 4.4

14 97.3 2.01 0.092 0.0084 0.57 0.012 traces 5.0
15 89.0 2.90 5.40 0.041 7.40 0.114 traces 6.3
17 93.2 0.97 3.49 0.43 1.89 2.5-10-3 2.4-10-3 3.1
18 92.4 1.90 1.54 0.52 3.65 4.3-10-3 2.5-10-3 3.3
5 94.6 1.09 3. HO- 4 4.27 2.7-10-2 4.2-10-3 3.3
45 95.9 0.33 2.25 0.063 1.71 5.7-10-3 1.5-10-3 4.8

45 96.4 0.27 1.84 0.076 1.38 3.6-10-3 1.1-10-3 n.d.
46 96.0 0.081 2.26 0.033 1.61 5.1-10-3 1.7-10-3 0.9
47 95.6 0.09 2.42 0.058 1.84 8.2-10-3 2.2-10-3 0.24
49 97.2 0.17 1.50 0.062 1.01 3.7-10-3 7.8-10-4 1.4
50 95.4 0.21 2.39 0.028 1.92 7.4-10-3 1.6-10-3 0.96
22 95.8 2.46 2.6-10- 4 1.73 4.6-10-2 traces 9.2

2 4
24 71.3 25.7 2.7-10' 4 3.0 5.5-10- 2.9. 10- 0.2
24 79.4 18.4 n.d. 2.73 3.9-10-2 traces n.d.
39 98.9 5.5-10- 4 4.0-10- 4 1.04 2.5-10-2 2.9-10-4 0.2
77 96.2 1.38 2.0-10- 4 2.37 1.6-10-2 1.1-10-3 1.0
88 67.2 0.45 3.50 6.5-10'4 28.3 0.49 1.6.10-2 1.8
52 72.0 1.15 3.11 23.4 0.34 5.9-10-3 n.d.

4 2.6.10-3
83 91.2 2.77 1.2-10- 5.93 6.6-10-2 0.37
COz/100
A————A————A————A————A————A————A————A————A————'(Hj.Hj.SJxK)
Fig. 18. Triangular diagram for CC>2, Cffy and (H2 + H^S). Crosses refer to the easternmost
springs in Fig. 2, from El Palmar to Los Chiorriaderos and from Buena Esperanza to El
Salvaje; open circles represent the Mundo Nuevo - Los Mereyes area; triangles represent
peripheral springs, as in Fig. 1.
/\ A A A A A A
Fig. 19. H2S-H2-CFI4 triangular diagram. Symbols as in Fig. 18, except solid circles identifying
true fumaroles (Buena Esperanza - El Salvaje).
410
The diagram built on the N2-Ar-He inert components (Fig. 20) (Giggenbach et al., 1983;
Giggenbach and Goguel, 1989) yields more information about the origin of gases as well as on the
effect of air contamination. The He corner, named "crustal", represents radiogenic helium, as can be
obtained from a long residence in old rocks; the N2 comer is close to the "magmatic" gases, nitrogen
being an ubiquitous component, also in its non-atmospheric fraction. Along the N2 - Ar edge the two
end points of air and water-dissolved air are lying; the air-saturated water generally represents the end
member on this side. Most samples cluster into two distinct compositions: one groups all fumaroles
(with associated condénsales as the acidic waters of Group 3) in a position intermediate between the
"crustal" and "magmatic" end members; the second group includes all gases associated with neutral
"real" thermal springs. Once more, samples 17 and 18 appear to be the most representative of the
deep gas, lying right on the "crustal"-"magmatic" line; the gases from the Mundo Nuevo - Los
Mereyes area appear to be more or less contaminated by an atmospheric component supplied by
air-saturated water. In particular, gases from springs 52 and 83 (diluted neutral waters) are more
heavily contaminated by dissolved air. For what the central study area is concerned, these results
confirm that any geothermometry based on gas equilibria becomes significant only when the air
contamination is small: reactive species (namely H2) in fact can reequilibrate at low temperature.
N,/100
HexlO
Fig. 20. Inert gas triangular plot (N2, He, Ar) (after Giggenbach et al., 1983).Solid circles represent
true fumaroles (Buena Esperanza - El Salvaje); open circles represent gases associated with
Na-Cl waters; X's refer to the Mundo Nuevo - Los Mereyes area; squares and triangle refer to
peripheral waters.
411
Among gases associated with bicarbonate waters (all falling near the air-saturated water end
member) exceptions are shown by gases 5 (Ño Carlos) and the two ones from the Cariaco gulf (77
and 88). All of these are right on the El Pilar fault trace or on secondary ones, and in spite of their
apparently odd location there can well be a contribution from deep gases. This anomaly was pointed
out also in the section dealing with waters, namely for conservative species, e.g. Li.
Gas Geothermometrv.
On the basis of the above information the geothermometric methods based on gas equilibria
will be applied only to some gases considered as the most representative.
The gases from manifestations 18 (El Salvaje, to the east) and 45 (Mundo Nuevo, to the west)
were tested by means of the method by Saracco and D'Amore (1989). This method takes into
consideration the three contemporary equilibria:
CH4 + 2H2O = CO2 + 4H2 (5)
H2 + 3/2FeS2 + 2H2O = 3H2S + l/2Fe3O4 (6)
CH4 + 3CO2 = 4CO + 2H2O (7)
A numerical approach is used to solve a set of three non-linear equations derived from the
above equilibria:
4 log (H2/CO2) - log (CH4/CO2) = 4.635 log T - 12144.08/T + 6.69
+ 4 lo A - 3 log A - l°g A -4
3 log (H2S/CO2) - log (H2/CO2) = - 0.412 log T - 10318. 15/T + 17.25
+ 3 log AH2S - 2 log ACOZ - lo« AH2 ' 2 '°g PCO2 (9)
4 log (C0/C02) - log (CH4/CO2) = 0.719 log T - 12913.84/T + 4.73

3 A
+ 4 log ACO - i°g co2 - i°g ACEU (1°)
IS
where T is in °K, PcO2 ê partial pressure of CO2 at equilibrium, and Aj is a term
containing the reservoir vapor mass fraction y and the distribution coefficient B¡ of the gas i between
steam and liquid (Bj is the ratio between the concentrations in the steam and in the liquid):
Ai = y + (l-y)/B i (11)
if y > 0 (steam present in a two-phase fluid), or:
A¡= l/Bjd + y - y B j ) (12)
if y < 0 (liquid, vapor-depleted system).
The unknowns are three: T, PcO2> an^ v-
412
For gas 18 the following results are obtained:
T = 250°C; y = 0.001; P C O2 = 2.8atm;
the computed redox conditions are the following:
log P02 = -37.7; log P S 2 =-13.4,
consistent with the values computed in many geothermal fields (D'Amore and Gianelli, 1984).
For gas 45 the results are:
T = 230°C; y = 0; Pcc>2=1.0atm.
As pointed out by Giggenbach (1987) this method, used to evaluate the reservoir parameters,
involves several species at the same time, with the limiting assumption that all of them are still found
in the sample in the representative proportions as originally present in the reservoir. Hence, the
computed temperatures above shown are to be considered minimum values for the reservoir if
reequilibration (and oxidation at shallow depth) are actually occurring during the ascent to the
surface, with different reaction rates for each species and with different solubilities.
Calculation of deep temperatures for "good quality" samples can be achieved through use of
carbon monoxide in equilibrium with the other main carbon components CC>2 and CIfy and with
water, according to equation (7) (Bertram! et al., 1985; D'Amore et al., 1987; Giggenbach, 1987;
Chiodini and Cioni, 1989). Fig. 21 was taken from Giggenbach (1987), plotting the CH4/CC>2
versus CO/CÜ2 molar ratios. In the figure two major redox buffers are considered: one supposing
Ü2 - SC>2 coexistence for a magmatic gas phase, and another (more interesting for geothermal
systems) involving a general reaction likely to control the redox state:
4(FeOL5) = 4(FeO) + 02 (13)
+ +
where the bracketed entities represent Fe2 and Fe^ incorporated in an unspecified iron
oxide or an iron-aluminum mineral assemblage. For this buffer two curves are shown, according to
different equilibrations in the liquid phase or in the vapor phase. In the upper right part isotherms
refer to the equilibration temperatures in the vapor phase, while in the lower part they refer to
reequilibration in the liquid phase. In Fig. 21 the four most representative gases for the study area are
reported: 17, 18,45, and 46. At the first glance the points fall on the curve of the iron buffer referring
to the liquid phase; the same result was found according to the previous method. The calculated
temperatures range from 250 - 260°C for the El Salvaje - Buena Esperanza area (eastern zone) to 220
- 270°C for the Los Mereyes - Mundo Nuevo zone. The other gases (not reported) fall in a scattered
way, outside the liquid-vapor area, for temperatures between 200 and 300°C. This does confirm the
local high temperature anomaly, but it confirms also what stated above about the non-equilibrium
state of these gases, due to vapor loss and/or oxidation phenomena during the late stages of ascent.
The carbon monoxide content can also be used to estimate the CC>2 partial pressure using
(Chiodini and Cioni, 1989) the following chemical equilibrium:
C02 + H2 = CO + H20. (14)
Arranging the expression of the equilibrium constant, the following relation is obtained
(D'Amore, 1990):
413
5-
0-
Cvj
O
o
C)
O)
- -5-
-10-
1
-8 -7 -6 -5 -4
log (CO/CO2)
Fig. 21. CH4/CO vs. CH4/CÜ2 molar ratios for the application of the CO geothermometer (after
Giggenbach, 1987) applied to selected samples (see text).
= °-491 + 192.4/T + 0.979 log T + log (CO/H2) -log ACÓ + log AH2 (15)
where T is in °K and A as defined in equations (11) and (12).
This equation is almost independent of the temperature and the steam fraction . Between 130
and 320°C, and neglecting the effect of "y":
log PC02 = 3.52(±0.1) + log (CO/H2) (16)
The effect of considering a pure liquid phase will increase the computed log ?CO2 by ab°ut
0.2 units, considering the difference in solubilities between CO and H2- Application of equation (16)
to the four samples appearing in Fig. 21 gives a range of CC>2 partial pressures close to 2 bar in the El
Salvaje - Buena Esperanza and of the order of 10 bar for the Mundo Nuevo - Los Mereyes areas
respectively.
414
The empirical gas geothermometer proposed by D'Amore and Panichi (1980) gives
temperatures of 264 and 289°C for gases of springs 17 and 18 respectively, considering a
PCQ2-dependent correction term of 10 bar because of the composition constraints:
t(°C) = 24775/(2 log(CH4/C02) - 6 log (H2/CO2)- 3 log (H2S/CO2)
-71ogPc02 + 36.05)-273 (17)
Considering a liquid-dominated geothermal system, an attempt was made to apply the H2/Ar
geothermometer proposed by Giggenbach and Goguel (1989). According to these authors in the case
of boiling springs the H2/Ar ratio (when no oxidation from O2 nor Ar pollution from atmospheric
sources occur) appears to provide valid information on the thermal conditions within the deep
equilibrated liquid phase. This method has been proposed and up to date tested only for high enthalpy
systems; in the case of low enthalpies it needs further refinement. The equation used is:
t(°C) = 70 (2.5 + log (H2/Ar)) (18)
The calculated temperatures are 321 and 331°C for gases 18 and 17 respectively, and 258 and
232°C for gases 45 and 46 respectively. These temperatures are in general agreement with the ones
already found by gas and water geothermometry, thus confirming a liquid-dominated system at high
enthalpy.
D'Amore et al. (1989) proposed a geothermometric method devised for low enthalpy systems
which can be applied to thermal springs where the gas is associated to water. The method is based on
the calculation of the CO2 pressure either from water chemistry and from gas composition. There is a
temperature at which the two PcO2>s are equal. This can be considered the temperature at which the
gases are in equilibrium with the water sample at some point in the reservoir. This method of
comparison of the two PcO2>s can
be use(^ as a
geothermometer if the water sample is truly
representative of the reservoir water, where it is possible to assume steam fraction to be totally absent
in the reservoir. Using the chemical equation (5) and expression (8) with y = 0, the computed ?CO2
changes very rapidly with temperature. Table 8 lists the temperature-dependent term (KBT) of the
following equation:
l°gPcO2 = KBT - log(H2/CO2) + 1/4 log(CH4/CO2) (19)
Using the water composition and starting from the field measured temperature, pH and
alkalinity it is possible to calculate the new values for pH and ?CO2 f°r eacn temperature, e.g. by
means of the program WATCH by Arnorsson et al. (1982). Change of P<X)2 w'tn increasing
temperature is moderate and smooth.
The limitations of this method are mainly due to attainment of full equilibrium of the gases
involved in the chemical reactions considered (different reactions can be used), and to the water
which must be representative of the liquid phase in the reservoir. As an example, this method was
applied to the Ño Carlos spring (water sample 4 and gas sample 5, a few meters away) and for spring
15 with the gas of samples 17 and 18. To calculate PcO2 in me water
of spring 15 a decompression
temperature of 160°C was chosen (as resulting from the silica geothermometer), taking into account
the loss of carbonic acid as CO2 during boiling. This method gives a convergency of computed
415
TABLE 8. Temperature-dependent term KBT in eq. 19
(t in °C)
KBT t KBT
40 -6.352 130 -3.516

50 -5.945 140 -3.290
60 -5.582 150' -3.100
70 -5.233 175 -2.607
75 -5.071 200 -2.169
80 -4.905 225 -1.796
90 -4.589 250 - 1 .443
100 -4.307 275 -1.110
110 -4.021 300 -0.808
120 -3.758 325 -0.470
125 -3.648
2's of 2.5 bars at about 90°C for Ño Carlos and between 13 and 15 bars at a temperature of 306
± 8°C for the high temperature example (15, 17, 18), as shown in Fig. 22. The obtained temperatures
are consistent with the ones calculated by the previous methods. Besides, the higher PcO2 obtained
at 300°C with this method is consistent with 2.3 atm calculated with the method by Saracco and
D'Amore(1989)at250°C.
CONCLUSIONS
The results of the geochemical survey indicate that the studied geothermal area can be
promising for the recovery of high enthalpy geothermal resources in the El Pilar - Mundo Nuevo
area.
About the springs outside the area of concern, chemical evidences indicate that some leaks
from the deep reservoirs must exist, namely for spring 4 (Ño Carlos), with computed reservoir
temperatures generally in excess of 100°C, but lower than 150°C. This temperature is still of interest
for the exploitation of a low enthalpy system. Its position right on a fault plane of the El Pilar fault
system is in favor of a deep contribution.
The springs with NaCl waters, located in the El Palmar - Aguas Calientes - Los Chirriaderos
' area and the fumaroles located both in the Buena Esperanza - El Salvaje and in the Mundo Nuevo -
Los Mereyes areas are the result of a high local convective heat flow. A local heat source can be
postulated in a young magmatic body at an indefinite depth of some kilometers. Its residual
temperature at the top can still be high enough to justify the heat transmission to the fluids. The
416
5-
ra
¿í
oo 3-
O
equilibrium
equilibrium
o
40 60 80 100 100 200 300
temperature (°C) temperature(°C)
Fig. 22. Computed ?CO2 vs- temperature for water and gas compositions, for selected samples, in
order to obtain the equilibration temperature between gas and water (see text).
inference of this magmatic body is justified by the occurrence of outcrops of rhyodacitic subintrusive
rocks (5 Ma; Sifontes and Santamaría, 1972), located in the metamorphic unit about 6 km north of the
main zone of thermal manifestations. These rhyodacitic subintrusives are likely to be apophyses of
the deep batholith, possibly granitic or granodioritic; other younger intrusions not outcropping are
also possible to exist in the region just below the thermal area.
The local permeability is a consequence of the long-lasting and intensive deformations of the
zone; the recent and present episodes are related to the active El Pilar right lateral strike-slip fault
system (and to other systems complementary to the main structural feature) connected with the
displacement of the southern end of the Lesser Antilles arc with respect to the continent. Possible
recharge areas are located on both sides of the El Pilar fault: north of it the metamorphic formations
are highly fractured, and south of it limestones are fractured too by secondary tectonics. Both sides
form elevations in excess of 200 - 400 m of the fluid manifestations.
The zones with higher temperature manifestations are affected by carbonate, sulfate, and/or
silica mineralizations. Self-sealing phenomena can exist at depth, thus allowing the formation of an
impermeable cover confining the fluid into a possible reservoir. Shallow oxidation is witnessed by
the remains of some old sulfur mining works in the study area; the fresh water wells in the villages
indicate the presence of shallow water tables that can mix with the thermal fluids of deep origin.
The processing of geochemical data led to some hypotheses on the chemical and physical
characteristics of the reservoir fluids, as well as on their modifications during ascent. All the
following considerations are summarized in Fig. 23.
417
--300
--150
GAS+STEAM |_J
«LIQUID
BOILING + GAS SEPARATION (t =160 °C --0
LLI ---150
O
ce
<
o
LU
ce 1000
Fig. 23. Sketch summarizing the possible model inferred for the geothermal field centered in Las
Minas (Fig. 2), in a section approximately N - S, from Aguas Calientes to Buena Esperanza
and farther uphill. Some selected springs and fumaroles are labelled along the topographic
surface. Symbols represent: 1, the gas phase; 2, the liquid + gas and steam (2 phases); 3, the
liquid phase; 4, the dominant phase(s). Stippled areas represent possible aquifers. The true
reservoir is the deeper one; the shallow resrvoir is not certain to exist: it can be merely the
mixing and partial reequilibration level (see conclusions in the text).
A deep hot reservoir is inferred at a temperature of about 300°C; it is constituted by a sodium

chloride neutral water, without any free steam (y = 0), with a CC>2 partial pressure of about 14 bar.
Considering all classifications, a mixing results to be active for all springs, the "purest" being water
15; various geothermometric methods give the highest calculated temperatures for this spring. Being
this the least diluted (TDS = 3650 ppm), the total salinity in the deep reservoir cannot be much
higher, of the order of less than 5000 ppm, taking into account a dilution of 10 % approximately
(from Fig. 9) and a silica loss.
The lower temperatures obtained by the SO4-FÍ2O geothermometer (206°C) and the bimodal
distribution of temperatures obtained by water geothermometry indicate that a second reservoir is
likely to exist, separated from the hotter one and with temperatures in the range of 200-230°C. The
mixing with water of this second reservoir yields a dilution of the NaCl water and increases the
relative concentrations of Mg, 804 and HCÜ3.
418
Considering the highest silica content (spring 15) a boiling temperature in the range
160-170°C is found; the result is the production of a two-phase system, in which the steam-gas phase
migrates toward springs 17 and 18, while the liquid phase outcrops as spring 15. The piezometric
level at an elevation of 150 m approximately controls this phase separation of the manifestations: all
fumaroles are found at higher elevations than the low-gas Na-Cl springs. For all fumaroles the most
reliable temperatures computed by gas geothermometry are found around 250°C. This difference from
the maximum temperatures of the deep reservoir obtained by water geothermometry can be due either
to «equilibration in the upper reservoir or to interaction with shallow fresh waters. Using the boiling
point curve for liquid H2O at low salinity and assuming a certain connection between the deep
reservoir and the surface, the high temperature reservoir can be estimated to lie at a depth greater or
equal to 1100 m. The shallow reservoir, with a temperature of the order of 220°C, may also be
present at a depth of a minimum of 300 m.
The relative position in the inert gas diagram (N2-He-Ar) of the most important fumaroles
(namely 17 and 18) indicates for certain a deep origin of these gases (no meteoric contribution). The
high He content can be explained only by a long residence of the fluid in the reservoir rocks (this was
found e.g. at Larderello). This supports a possible accumulation of the fluid in the deep reservoir,
which is inferred to be generally sealed by the rock alteration.
The geothermal system is supplied by groundwater derived from meteoric water which can
originate from the two high elevations on both sides of the El Pilar fault: Cerro La Pica to the north
and Cerro El Pato to the south, both higher than 600 m (recharge areas).
Heat and gas (mainly CÜ2) are assumed to be supplied by a buried batholith which heats a
convective cell of neutral pH, chloride type, water, and with a two-phase condition in the upper zone.
This steam separation process gives rise to the fumaroles; steam can be absorbed by local
groundwater, with oxidation of H2S and production of steam-heated sulfate and bicarbonate waters
rich in boron and ammonia. Hybrid waters can be the result of mixings between the deep waters and
shallow ones.
The outflow of chloride waters depends on local structural and topographic conditions:
because of lateral flow the spring can be found kilometers away from the hot upflow point of the
geothermal system. The high relative permeability for the gas phase generally yields a direct vertical
upflow from the reservoir, thus defining clear geographic distributions. In this area the main steam
upflows are localized at Las Minas and between Mundo Nuevo and Los Mereyes (Fig. 2), where
eventually exploratory wells can be localized.
ACKNOWLEDGEMENTS
This work has been performed within the framework of the IAEA coordinated research
program on the "Application of Isotope and Geochemical Techniques in Geothermal Exploration in
Latin America (Research Contract No. 3994/R2/IG), which is executed with the financial support of
the Government of Italy. The Italian National Research Council (CNR) also gave a financial
contribution to this program.
419
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422
ORIGINS OF ACID FLUIDS IN GEOTHERMAL RESERVOIRS
A.H. TRUESDELL
US Geological Survey,
Menlo Park, California,
United States of America
Resumen-Abstract
ORÍGENES DE LOS FLUIDOS ÁCIDOS DE DEPÓSITOS GEOTÉRMICOS.
Los fluidos ácidos en depósitos geotérmicos son raros. Su presencia en

sistemas geotérmicos relacionados con volcanismo reciente (Tatún, Sumikawa,
Miravalles) indica probablemente que el fluido en el depósito geotérmico pro-
viene de fluido volcánico incompletamente neutralizado por la reacción con
feldespatos y micas. El vapor recalentado que contiene HC1 (Larderello, Los
Geiseres) forma ácido cuando se condensa o se mezcla con líquido a temperatu-
ras moderadas (<300°C). El origen del vapor con HC1 es la reacción del NaCl
sólido con las fases minerales de la roca a temperaturas elevadas (>325°C).
En Los Humeros se produce criptoacidez cuando se forma y neutraliza la acidez
del HC1 sin alcanzar la superficie.
ORIGINS OF ACID FLUIDS IN GEOTHERMAL RESERVOIRS.
Acid fluids in geothermal reservoirs are rare. Their occurrence in geothermal systems
associated with recent volcanism (Tatun, Sumikawa, Miravalles) probably indicates that the geothermal reservoir
fluid was derived from volcanic fluid incompletely neutralized by reaction with feldspars and micas. Superheated
steam containing HCl (Larderello, The Geysers) forms acid where it condenses or mixes with liquid at moderate
temperatures (<300°C). The origin of steam with HCl is reaction of NaCl solid with rock minerals at high
temperatures (>325°C). Cryptoacidity occurs at Los Humeros where HCl acidity is formed and neutralized
without reaching the surface.
Introduction
The occurrence of acid fluid in well discharges from geothermal wells is of great theoretical and
practical interest. Chemical substances in geothermal fluids have been proposed to originate
from leaching of rocks by hot water (e.g. Ellis and Mahon, 1964) or from neutralization of
volcanic fluids (e.g. Giggenbach, 1981). Because volcanic gases and condénsales where they
discharge at the surface are acid, the occurrence of acid reservoir waters in some geothermal
fields associated with volcanic activity supports the hypothesis that neutral geothermal fluids
also originate from volcanic fluid. Deep, hot, acid water has not been successfully exploited
and some wells (and fields) have been abandoned as a result. Acid carried in superheated steam
that condenses only at the surface can be neutralized but at additional cost. Distinguishing the
cause of acid fluid production can assist in management decisions involving treatment or
isolation of acid reservoir fluids and possible abandonment of wells or fields.
423
In some fields, acid waters that come to the surface through springs or drill holes originate
from acid reservoir fluids. In others, boiling of high-temperature neutral or acidic brines or
reactions in vapor-halite-silicate assemblages generates HC1 gas that is carried in superheated
steam and becomes corrosive when the steam condenses, usually at the wellhead. Ascending
superheated steam containing HC1 may also mix with overlying neutral waters to produce acid
solutions that rapidly corrode and scale well casings, possibly without acid fluid appearing at
the surface. Analyses (in milliequivalents per liter) of related acid and neutral geothermal waters
and steam condénsales are given in table 1.
TABLE 1. SELECTED ANALYSES OF ACID GEOTHERMAL RESERVOIR WATERS AND RELATED

WATERS (in milliequivalents per litre unless otherwise specified)
No Well or Temp pH Na Ca Mg Fe a SO,) HCOj R Cation Aruon Cl

spring <C mmol mmol sum sum excess
Tatun
1 Hsinpeitou 70 13 424 103 12 62 48 104 66 28 46 93 6 170 104
2 E101 175 4 297 123 13 1 86 265 109 504 377 114 114 21 5
3 E102 250 396 854 4 35 19 48 8 158 172 407 136 175 70 8
Sumikawa
4 Tamagawa 98 12 496 1 66 105 66 376 91 4 277 45 !25 46 3
5 S-2 240 72 31 1 24 15 15 0206 169 128 341 11 13 1 367 33 1
6 S-2A 245 26 199 253 228 854 17 153 373 987 5 17 503 526
7 S-4 280 76 108 1 33 0005 018 0007 89 227 286 15 6 123 123 140
8 Yakeyama 88 04 67 972 101 42 8 34 8 564 175 107 361 293 739 274
Yellowstone
9 Green Drag 85 29 126 138 024 0041 0022 129 342 - 653 0741 153 165
10 Echinus G 93 3 696 1 28 0095 0041 0079 322 6 02 -- 4 27 0204 858 95
11 Ear 94 5 9 21 152 0532 003 00012 - 11 6 0521 308 27 0361 165 165
12 Unnamed 88 22 013 00128 001 00065 0011 0076 227 07 00093 0171 228
Miravalles
13 PGM 2 235 962 673 34 0 0 1 100047 112 1 96 0 574 10 5 83 107 115
14 PGM2A 235 22 108 849 19 1 26 1 39 113 15 6 11 5 657 122 129
15 PGM Av 238 8 1 977 683 325 0012 00036 109 1 17 0 689 10 6 5 37 109 111
16 G 2 250 59 0065 - 017 - 00683 482 0 065 0 169 0 1

17 G-4 >250 31 073 17 1 66 144 185 1 48 48 1 196 185 151
18 G-6 340 26 0957 00818 135 119 887 1600 0 667 0 777 78 6 1410 1600 1100
Krafla
19 KG 12 330 667 0826 0123010500008 000540592 0208 1 1 1 06 0808 -
20 KG 12v 330 348 00074 0021 00032 0932 3 16 - 0964 3 17 22
Los Humeros
21 H-4 300' 29 739 0665 48 - 143 024 - 0 19 214 137 145
22 H-16 316 77 215 0716 036 00033 742 398 236 109 154 227 138
23 H-l 270 85 128 1 25 001 - 272 2 56 2 84 11 3 222 145 812
Sources of analyses 1-3.CH Chen (unpublished), 4. Ozawa et a] (1973) 5-7, Sakai et al (1986), 8, White et al (1963): 9-12, Roweet al
(1973) and Thompson and Yadev (1979). 13-15. Majruen et al (1990). 16-20. Truesdell et al (1989) and Orkustofhun unpublished data,
21-23, CFE (1990)
Other significant consDtuents (in meq/1) for analyses (#) Al #1. 17 3. #Z 24, #3. 15 6, «4, 17 6, and #8. 37 8 NRi #17.41 6, #18,486. and
#21.05 F#4. 63. and #11. 14 Mn #1 0 6. #17. 6 8, and #18. 26 6 Li #9, 0.5. #11. 0 75. #13. 097. #14. 1 1, and #15. 1 0
424
Acid C1-SO4 Waters with Excess Chloride
Some reservoir water analyses show "excess" chloride defined as chloride equivalent
concentrations
+
significantly
++
greater
++
than the sum of equivalent concentrations of cations other
than H . (High Fe and Mn in well discharges originate from reaction of H+ with casings,
and these ions are also not included in the sum of cation equivalents.) These waters must have
had at least part of their acidity introduced as HC1, most probably from a volcanic source.
Chloride excess waters from geothermal reservoirs are apparently rare, although many
examples of similar waters are found in crater lakes or associated with active volcanoes (White
et al., 1963, table 19). Only the Tatun system in northernmost Taiwan has been sufficiently
explored to show excess chloride waters present in a distinctly geothermal reservoir. Other
areas may have similar reservoirs but have not been drilled.
The geology of the Tatun field has been described by Chen (1970) and the chemistry of
reservoir waters briefly reviewed by Truesdell et al. (1989). The Tatun geothermal field covers
an irregular area about 5 x 10 km within the circular Plio-Pleistocene Tatun volcanic group.
This volcanic center has a long history of activity and some morphologically young volcanoes
but there are no historic eruptions or published rock dates. The geothermal reservoir is
developed partially within andesitic flows and tuffs but mostly within the underlying 900-m
thick Miocene Wuchishan Sandstone consisting chiefly of thick beds of orthoquartzite
containing only quartz, kaolinite and minor alunite, and elemental sulfur. Within the reservoir
andesites are highly altered.
Reservoir waters range in salinity but have chemical compositions similar to each other and to
the Hsinpeitou spring at the western margin (table 1, analyses 1-3, and figure 1). The deep
reservoir water at Tatun probably has a pH of 1.5 to 2, chloride from 3500 to 13000 ppm, and
a temperature of 250 to 300°C (references in table 1). Steam boiled from this water contains
HC1 gas. Condénsales from a shallow well producing dry steam contained 3500 ppm HC1 at
pH 1 (Ellis and Manon, 1977) and condénsate with 400 ppm Cl was collected from a
superheated fumarole (Truesdell et al., 1989). The chloride excess at Tatun has not been
neutralized by reaction with rock because the reservoir contains no minerals (e.g. feldspar or
mica) capable of neutralizing acid. The Tatun field was finally abandoned because no means
was found to prevent rapid corrosion of casings.
a E-101
O E-102
+ Hsinpeitou
3
4->
JO
+-I
03
o 02
c
o
O D
O) ,
O 1
O
pH Na K Ca Mg Fe Cl S04 B Al
Figure 1. Schoeller diagram of analyses (in meq/1) of well waters and a spring water from the
Tatun, Taiwan field. In a Schoeller diagram the slopes of lines connecting logarithmic
concentrations indicate ratios and are not changed by boiling or mixture with dilute waters or
steam condénsate. pH values are shown directly. Data sources are given in table 1.
425
Other waters with chloride excess are closely associated with active volcanism. An example is
the famous Tamagawa hot springs on the western slope of Mt. Yake, north-central Honshu,
Japan. These springs (table 1, analysis 4, and figure 2) discharge 9300 1/m at 98°C containing
about 3 g Cl/1, comparable on a yearly basis to an erupting volcano in the amount of heat and
material transported (Ozawa et al., 1973). The Sumikawa geothermal field on the north slope
of Mt. Yake produces mostly low-Cl (100-400 mg/1) neutral waters with one well producing
acid SO4-C1 water (discussed later). The relation between the neutral waters, high-SU4 acid
water, and high-Cl acid waters occurring within 5 km has never been examined.
Acid discharge of well 4 at Los Humeros, Mexico, well 12 at Krafla, Iceland, and acid steam
condénsate at The Geysers, California, and Larderello, Italy, are also excess chloride waters
but were formed by a different mechanism involving transport of HC1 in superheated steam.
These areas will be described later.
Acid SO4-C1 Reservoir Waters
Acid waters with SO4-C1 acidity are found at the margins of several geothermal systems
associated with recently active andesite volcanoes. In these fields the acid zones were
penetrated by a small number of wells that produced acid fluid from the outset or after
deepening. These wells were soon abandoned or used as injectors so geochemical data are
limited. The best documented examples are well S-2 at Sumikawa, Japan, and well PGM-2 at
Miravalles, Costa Rica. Each of these wells became acid after deepening. Analyses of flashed
waters from these wells before and after deepening and of a typical neutral water of each field
are given in table 1 (references in the table).
Well S-2 at Sumikawa was originally drilled to 900 m and deepened 5 months later to 1065 m
with the intention of increasing the flow. The fluid produced before deepening had high excess
steam (2428 J/g total enthalpy) and elevated Cl, SC<4, Ca, Mg and Fe relative to other
Sumikawa well waters but was at near neutral pH (table 1, analyses 5-7, and figure 2). During
the first few months of production, Cl and SÜ4 increased but fluid pH remained neutral. After
10
o S-2
O S-2A
cr A S-4
QJ + Tamagawa
E 6 x Yakeyama
c
•B 4
cu
cu
o
c
o
U O
D3
O
-1 -2
-4
pH Na K Ca Mg Fe Cl S04 Al
Figure 2. Schoeller diagram of analyses (in meq/1) of waters from Sumikawa, Japan wells and
associated acid springs, on the flanks of ML Yake volcano. Data sources are given in table 1.
426
deepening (S-2A), the water no longer had excess steam (~1090 J/g enthalpy), but had much
higher $64, Fe, Ca and Mg, and lower Na, B and HCOs, with pH values below 3. Oxygen
isotope compositions were initially similar to those of other Sumikawa waters and increased
0.8 permil after deepening, but deuterium compositions were initially 5 permil higher than
other waters and became 12 permil higher after deepening (MMC, 1990). The Cl in the acid
water was a little lower than the initial Cl but still higher than Cl in other well waters although
there was no chloride excess.
The chemical evidence for the source of the acidity is equivocal. Higher Cl and SC»4 compared
to other Sumikawa waters might suggest less dilution with meteoric water and less reaction
with rock to neutralize acidity and precipitate SÜ4 as anhydrite. Alternatively, the S-2 acid
water could be a mixture of normal Sumikawa water with acid SO4-C1 spring water similar to
the Yakejama water (table 1, analysis 8) but higher in SÜ4 relative to Cl. Higher 6D and 5O are
consistent with evaporation at surface boiling temperatures, suggesting a component of
surface-evaporated, acid-sulfate water. The mixing of shallow high-SC»4 water with deep high-
Cl water has been suggested to be the origin of acid SÜ4-C1 waters in the Palimpanon and
Bacon-Manito fields of the Philippines (Robinson et al., 1987) and of acid SC»4-C1 hot-spring
waters at Yellowstone National Park, USA (table 1, analyses 9, 10, and figure 3). The
deuterium contents of the Yellowstone waters were intermediate between those of neutral high-
Cl waters and of evaporated, deuterium-rich acid-SU4 waters formed by oxidation of H2S
(Truesdell et al., 1977).
10
Green Dragon
Echinus Geyser
cr
o> Ear Spring
Unnamed
c
o
§
ü
8 o
O)
O
-2
pH Na K Ca Mg Fe Cl S04 B
Figure 3. Schoeller diagram of analyses (in meq/I) of acid and neutral spring waters from
Yellowstone National Park, USA. Data sources are given in table 1.
At Miravalles, Costa Rica, acid high-SC»4 water was discharged from well PGM-2 after it was
deepened from 1200 m to 2000 m in 1984 (table 1, analyses 13, 14, and figure 4). Before
deepening the well had produced water similar to other wells with neutral pH but slightly
elevated 804. After deepening (PGM-2A),pH decreased to 2.2 and SC<4, Mg and Fe increased
greatly with smaller increases in Na, K and B, and decrease in Ca. The increased Fe probably
resulted from acid corrosion of the casing suggesting that the reservoir pH was probably lower
than 2.2. This water showed almost no change in Cl and no excess Cl indicating that the acidity
was associated with higher SO4 not Cl.
427
10
o PGM-2
cr O PGM-2A
03
A PGM-Ave
E 6
«,
I 4
0)
u
c
o
U O
O)
o
-2
-4
pH Na K Ca Mg Fe Cl S04 B HC03
Figure 4. Schoeller diagram of analyses (in meq/1) of well waters from the Miravalles field,
Costa Rica. Data from Mainieri and Vaca (1990).
As at Sumikawa the chemical evidence does not indicate a definite origin for the acidity. Acid,
high-SO4 waters could have had a volcanic origin or could have been formed at the surface by
oxidation of H2S. These acid-SC>4 hot-spring waters are well known and occur in almost every
geothermal system where steam escapes at the surface. Most of these spring waters contain
cations leached from adjacent rocks but some are nearly pure, dilute sulfuric acid (table 1,
analysis 12). However, in order to increase SO4 in PGM-2 from 2 meq/1 to 16 meq/1 with only
1% change in Cl requires a concentration of SÜ4 in the mixing water exceeding 1400 meq/1 or
about 65000 ppm SÜ4. This is about 20 times the most concentrated acid-SU4 water reported
by White et al. (1963). An acid-SO4 water mixing to produce the acid S-2A discharge at
Sumikawa would have to be twice as concentrated. Although not impossible, the existence of
these waters seems very unlikely.
A Volcanic Origin for Acid C1-SÜ4 and SO4-C1 Waters

Acid SÜ4-C1 waters at Sumikawa and Miravalles seem most likely to be immature volcanic -
geothermal waters not fully equilibrated with feldspar, mica, and Fe minerals in the reservoir.
Giggenbach (1981, 1988) suggests that volcanic fluids containing acid, oxidizing gases
"mature" to form neutral, reducing geothermal waters by reaction with rock minerals including
feldspars, mica, and reduced iron oxides and silicates. HC1 is neutralized to NaCl, and SO2
disproportionates to H2S and H2SÜ4, which may then precipitate as alunite and anhydrite. The
chemically distinct acid waters at Tatun and at Sumikawa and Miravalles appear to have
resulted from different reaction paths during maturation. At Tatun, SÜ4 is present in variable
amounts but is not as important as HC1 in producing acidity. At Miravalles, acid and neutral
waters differ mainly in SÓ4 with nearly the same Cl. Sumikawa seems intermediate. At Tatun,
conversion of SO2 to SO4 and precipitation as anhydrite and alunite appears to have preceded
neutralization of HC1. At Miravalles, HC1 neutralization apparently preceded SC»2 dispropor-
tionation which produced additional acid. Sumikawa may be similar to Tatun but with more
neutralization of acid and less precipitation of sulfate.
Sulfur isotopes in SC»4 from Miravalles (Giggenbach and Corrales, this volume) and from
Palimpanon and Bacon-Manito fields in the Philippines (Robinson et al., 1987) have been
428
analyzed to determine whether SC«4 was produced by surface oxidation of H2S or by deep
addition of SO2- These isotope analyses were not entirely definitive and the interpretations
were quite different. In the Philippines fields most S^S values were near zero permil, which
was interpreted to indicate that all sulfur was originally present as H2S and that H2S had
oxidized near the surface to acid-SO4 water, which infiltrated the geothermal reservoirs.
Analyses of Miravalles SO4 were interpreted to show that mixing with surface-produced acid-
SC»4 water had not occurred and that SÜ4 was of deep origin. It is unfortunate that detailed
analyses of Philippine acid waters are not available for geochemical interpretation.
HC1 in Superheated Steam
The appearance of superheated steam containing HC1 at the major vapor-dominated geothermal
systems of Larderello and The Geysers has led to several studies of its occurrence and origin
along with programs to mitigate its corrosive effects. At Larderello, HC1 was first observed in
1960 (Allegrini and Benvenuti, 1970; D'Amore et al., 1977) and at The Geysers, in the mid-
1980s (Haizlip and Truesdell, 1988). The almost simultaneous appearance of HC1 in many
wells at Larderello was probably caused by widespread drying of the reservoir and to a large
extent HC1 disappeared when liquid injection was begun (Truesdell et al., 1989). The solubility
of HC1 in solutions differing in temperature, pH, and Cl concentrations was calculated by
Haizlip and Truesdell (op. cit.) who concluded that at The Geysers and Larderello (240-
260°C), HC1 is transported only in superheated steam because below 300°C it is very soluble in
neutral liquid and would have been removed from the vapor if condénsate were present.
Saturated steam from the normal Geysers reservoir (table 1, analysis 16, and figure 5) has little
Cl, but superheated steam at normal and high temperatures may have high HC1 concentrations
indicated by acid condénsate with high Cl and high Fe and Ca (analyses 17, 18). The origin of
the HC1 in these fields is related to high-temperature reactions but whether it forms mainly from
boiling of near-neutral NaCl brines or from reaction of halite with silicates (D'Amore et al.,
1990) is still controversial.
At The Geysers and Larderello, HC1 in steam seems closely related to the existence of high-
temperature zones below the main vapor-dominated reservoir (Walters et al., 1988; D'Amore et
al., 1990). At The Geysers these high-temperature zones are at the same pressure as the vapor
o G-2
- 6 C> G-4
cr A G-6
03
, 4
c
o
c
o
o
c
o O
u
D)
O
-2
-4
pH Na K Ca Mg Fe Cl S04 B SÍ02
Figure 5. Schoeller diagram of analyses (in meq/1) of water collected in condénsate traps from
a low-Cl (G-2), and high-Cl (G-4) normal-temperature wells and from a high-temperature,
high-Cl (G-6) well at The Geysers, USA.
429
reservoir and 50 to 100°C higher in temperature. Fluid in these zones must be superheated
steam with only absorbed liquid or high-Cl brines possibly present. These zones contain
distinct, high-gas, high-B, high oxygen-18 steam and HC1 that is either an original constituent
(if a volcanic origin is assumed) or has resulted from boiling of brine or from halite-silicate
reactions. In most areas of The Geysers where HC1 occurs, steam is sufficiently superheated
that the first condensation occurs at the wellhead and corrosion can be prevented by injection of
alkaline solutions.
HC1 in superheated steam occurs in many places, mostly related to active volcanoes. In well
KG-12 at Krafla, Iceland, superheated steam containing HC1 appeared in late 1979 and
disappeared in 1982 (table 1, analyses 19 and 20 before and after superheating) with HC1
content closely proportional to the degree of superheating and the rate of flow (Truesdell et al.,
1989). The KG-12 acidity was mitigated by mixing the steam with two-phase discharge from
another well. The Krafla occurrence was clear evidence that HC1 could appear in any high-
temperature (>325°C?) geothermal field in which superheated steam appeared. The Cl
concentration in waters from KG-12 (table 1, analysis 19) and nearby wells is normally
relatively low (<100 ppm) but brines are occasionally encountered and evaporation in the
reservoir may be the origin of the brine or possibly halite, which produced HC1 in KG-12. As
at The Geysers and Larderello, the appearance of superheated steam is related to the local or
widespread depletion of liquid in the reservoir and a decrease in reservoir pressure. Injection of
liquid water will recharge liquid in the reservoir and in most cases raise pressures and eliminate
HC1 in steam.
Los Humeros, Mexico, an Unusual Case

The Los Humeros geothermal field in the state of Puebla, Mexico, is located in a large caldera
at the eastern end of the Mexican volcanic belt. The productive reservoir is mainly developed in
andesites and andesite tuff underlain by hornfels and calcareous skarn. There are several
petrographic and fluid inclusion studies of Los Humeros reservoir rocks (Arnold and
Gonzales-Partida, 1987; Prol, 1988; Viggiano and Robles, 1988; Prol-Ledesma and Browne,
1989). Chemical analyses of fluids (tables 1 and 2) and some downhole-temperature
measurements were provided by the Comisión Federal de Electricidad (CFE) and the Instituto
Investigaciones de Eléctricas (HE). A report by Gutierrez-Negrin and Viggiano (1990) and one
by HE (1990) provided additional data on the history of well H-16.
Most wells of Los Humeros have high total fluid enthalpy and produce all or almost all steam at
the wellhead. Of well fluids collected before 1990 only those from well H-l (table 1, analysis
22, and figure 6) were low enthalpy and originated as almost entirely liquid water in the
reservoir (about 0.7 liquid fraction when produced to 4 bars). Other wells had liquid fractions
from zero to 0.4 but most were less than 0.1. With high total enthalpy and small liquid
fractions the reconstruction of reservoir fluid concentrations is difficult because boiling is
almost certain to have caused some mineral precipitation in the reservoir or wellbore.
Well H-l is one of the shallowest of the field (1450 m TD) and produces relatively little excess
steam (fluid enthalpy, 1311 ± 100 J/g). The measured temperature at bottomhole was 260°C in
agreement with geothermometer calculations (quartz saturation 260 ± 10°C; Na/K (Fournier)
265 ± 10°C). It is probable that H-l fluid is typical of the main aquifer at Los Humeros (table
2, analyses 1-5). Fluids from six other wells have average flashed Cl concentrations similar
(±25 ppm) to that of well H-l (95 ± 28 ppm) and give similar geothermometer temperature
indications (figure 7). Other wells have a wide range of measured and calculated Cl
concentrations but also have similar indicated reservoir temperatures (figure 7). Measured pH
values of all (except H-4) fluids after flashing are generally neutral to alkaline (pH 7.5 to 8.5,
rarely as low as 6.5).
430
TABLE 2. SELECTED ANALYSES OF FLASHED WATER FROM LOS HUMEROS WELLS H-l, H-16
AND H-4 (in mg/L unless otherwise specified)
Source: Comisión Federal de Electricidad (1990)
No. Date Enthalpy pH Na K Ca Cl HCOj SO4 B
1 82/06/10 1220 8.5 250 43 2 74.4 293 116 225 694

2 85/01/10 1240 8.5 294 49 0.2 96.4 173 123 240 675
3 89/06/06 1340 8.24 290 48 1.9 95.1 255 116 187 803
Well H-16
86/02/14 2660 7.79 540 28.8 7 208 393 150 1680 944
86/03/18 2660 7.76 600 26.6 7.7 208 450 197 1880 1020
6 86/06/12 7.73 695 32.2 10.3 309 900 1900 1080
7 87/07/14 2660 7.7 494 28 7.2 263 144 191 1660 651
8 88/06/24 2310 7.54 372 54 1.86 298 54.'
54.7 95.2 1180 1080
9 88/08/11 2330 8.21 430 40 1 212 73.: 166 691 534
10 89/01/20 9.24 636 29 — 210 524 192 248 194
11 89/02/14 9.12 632 29 — 210 523 197 187 367
12 89/09/09 8.64 420 44.2 1.2 212 279 94.6 270 875
13 89/10/13 2500 8.92 586 32 0.9 99.3 464 142 220 551
14 82/08/19 7.2 66 15.3 4 63.3 61 216 465 350

15 82/08/30 2.9 170 26 96 506 — 11 .3 2320 11.6
16 82/08/30 2.9 150 72 33 472 — 29 .2 4230 18.9
17 83/01/24 6.2 285 47 7 — 97 69 400 400
18 83/03/08 6.6 37.4 6.7 0.2 106 951 41 18.4 481
19 83/03/08 8.5 53 7.5 0.0 40 585 42 17.3 287
20 83/03/15 8.5 30 4 0.0 26.9 1150 52 .2 10.8 303
21 83/04/21 4.95 130 — 0.0 333 36.6 32 .7 376 372
Notes: 2-inch orifice plates were used for H-l samples after 1983 and all H-16 samples presented
here; orifice plate sizes for H-4 samples are not known. "--" indicates not available, not analyzed,
or not detected.
10
a H-4
cr O H-16
a A H-1
£ 6
1 4
2
+->
g 2
o
8 o
D)
-4
pH Na K Ca Mg Cl S04 B HC03
Figure 6. Schoeller diagram of analyses (in meq/1) of waters from two wells affected by deep
HCl and of a normal well at Los Humeros, Mexico.
431
3000
* Total discharge
a Aquifer liquid
a Flashed liquid
100 200 300 400 500 600
Chloride, mg/kg
Figure 7. Enthalpy-Cl diagram of average fluids from wells at Los Humeros, Mexico, with
lines showing steam loss for average H-l discharge and for the highest chloride well (H-l 1,
data for H-2, H-4 and H-19 are not sufficient to plot).
Well H-l6 was described in detail by Gutierrez-Negrin and Viggiano (1990) and IIE (1990).
This well was drilled to 2048 m total depth and showed several likely production zones as
indicated by intensive faulting and lost circulation, a definite deeper zone from 1750 m to total
depth, and shallower, less well-defined zones above 1650 m to possibly 1300 m or above. The
lower zone (in andesite and hornfels) was entirely in the amphibole facies characterized by the
appearance of amphiboles and garnet. The measured temperatures in the lower production zone
were 300-319°C but temperatures of 380-400°C have been measured in other wells. The upper
production zone (in andesite) was mainly epidote facies but extended to the amphibole facies.
Measured temperatures were 230-290°C. Quartz-saturation geothermometer temperatures of
fluid from this zone were variable but centered on 270°C similar to those from well H-1.
After initial production in 1985, the flow of this well progressively decreased and in 4 years
nearly stopped flowing. The partially slotted liner installed from 1400 m to total depth was
raised and found to be highly corroded in its lower part (1420-1432 m depth) with only 50 m
of unslotted and 20 m of slotted liner recovered. The middle part of the liner (1415-1420 m
depth) was scaled completely with Fe oxides and sulfides in the outer part and amorphous
silica with some Fe minerals in the inner part. The upper part of the liner was lightly scaled.
The chemistry of H-l6 well fluids (table 2, analyses 6-16, and figures 6 and 8) went through a
remarkable evolution (Gutierrez-Negrin and Viggiano, op. cit.) in which HCOs, which was
originally the major anión, decreased from 450 to 55 ppm and then increased to 520 ppm while
chloride increased from 210 to 300 ppm and returned to 210 ppm. During this period the pH
(after flashing) decreased from about 8.5 to 7.5 and then increased to 9.0, B decreased from
1900 to 600 ppm and Ca decreased from 7 to about 1 ppm. Other species (Na, SÍÜ2) showed
less definite decreases.
In December 1989 the lower zone was isolated by a plug at 1570 m and a new slotted liner was
installed, after which the well produced entirely from the upper zone and the fluid chemistry
stabilized. The flow after December 1989 was about that measured when the well was first
drilled but the enthalpy decreased from near 2660 to 2400 J/g (Luis Quijano León, pers.
commun., 1990) suggesting that the lower zone had contributed heat but little fluid.
432
3.5
2.5
g
'^
(o
•M
(U 1.5
o
c
o
o
05
O
0.5
-0.5
85.5 86.5 87.5 88.5 89.5
Year
Figure 8. Changes in concentrations (in mg/1) of selected constituents of flashed discharge

fluids from well H-16, Los Humeros, Mexico.
The chemical reactions that led to the corrosion and scaling may be interpreted from the
wellhead chemistry and the character of the scale. The initial production was from both deep
and shallow zones. The shallow water was similar to that of well H-l (table 2, and figures 6
and 8) and is represented by samples taken in early 1989 after the lower zone was sealed off by
scaling or had been cemented. The deep zone produced superheated steam containing HsBOs,
HC1, and H2S along with CÜ2 and other gases. In the upper part of the slotted liner the
superheated steam mixed with water from the shallow reservoir and partially condensed to
produce an acid high-Cl, high-B solution that attacked the casing and rock minerals including
plagioclase, other feldspars, and possibly calcite.
These reactions increased brine concentrations of Fe, SÍO2, Na, and Ca, and neutralized some
of the acid. Before complete neutralization, sulfide was present as H2S and did not react with
Fe++,+ and SiO2, present in high concentrations from solution of rock silicates, was stabilized
by H ions so that amorphous silica did not precipitate although it was highly supersaturated.
With further neutralization by reaction with casing, rock minerals, and HCC»3 from the upper
reservoir, H2S was converted to HS and stabilization of supersaturated amorphous silica
ended, producing the scale composed mostly of Fe sulfide and amorphous silica. Oxidation of
Fe+2 to Fe+3 caused by fluid mixing resulted in minor precipitation of Fe oxides. In the
mixture, SC»4 from the shallow water had been present as HSÓ4 along with elevated Ca++
(from acid attack of rock minerals) and with neutralization, HSO4 became SO4 and anhydrite
precipitated. With sealing off of the deep zone, acid attack of rock minerals ended so that Ca
decreased strongly (to equilibrium with anhydrite) and Na decreased moderately.
Concentrations of B and Cl decreased as contributions from the deep fluid ended. The
corrosion and scaling had continued from the first tests in 1986 with a decreasing contribution
of deep fluid caused by progressive scaling until the deep flow was cut off entirely between
September 1988 and January 1989. The lowest pH values and the highest B and Cl
concentrations were near the beginning when the proportion of deep flow was greatest. This
interpretation is similar to those of HE (1990) and Gutíerrez-Negrin and Viggiano (1990).
433
Other wells in the central zone probably produce from both upper and lower zones and may
have similar problems. Well H-4, just south of H-16, produced HC1 to the wellhead with so
much corrosion that it was necessary to plug and cement it shut (table 2, analyses 17-24, and
figure 6). The short history of well H-4 is similar to that of well H-16 but more extreme
(figure 9).
ra
E
03
o
c
o
u
O)
o
-1
82.5 83 83.5 84
Year
Figure 9. Changes in concentrations (in mg/1) of selected constituents of flashed discharge

fluids from well H-4, Los Humeros, Mexico.
Well H-4 was drilled to 1880 m total depth. There were two permeable zones between 900 and
1400 m and between 1700 and 1800 m. Measured temperatures were about 300°C at 1100 m,
significantly higher at this depth than in most other wells. Measured temperatures below 1100
m seemed to decrease but petrology of samples from 1400 m depth did not indicate low
temperatures (Prol-Ledesma and Browne, 1989). Initial fluid production in mid-August 1982
was neutral, but within 2 weeks, pH had dropped below 3.0. The well was flowed and
samples were taken intermittently until April 1983 but rapid wellhead corrosion was observed
and the well was finally cemented and abandoned. During the first 2 weeks of production,
flashed Cl concentrations immediately increased from 60 to 500 ppm and pH, initially 7.2,
decreased to 3.7 and stabilized at 2.9. Over the same period B increased from 460 to 4000 ppm
and HCOs, initially 60 ppm, disappeared entirely. Other species showed irregular changes; Na,
K and Ca increased and SiÓ2, NH4 and SO4 decreased. When sampled in January and March
1983, these changes had generally reversed, the fluid was neutral or alkaline (pH 6.6 to 8.5)
with B (18 ppm) and Ca (0.2 ppm) much lower and HCO3 (800-1100 ppm) much higher than
in any 1982 samples. Again other changes were irregular but Na, K and Cl generally decreased
while SiO2, NH4 and 864 generally increased. After March 1983, most of these changes were
again reversed, with lowered pH and HCOs ar>d increased B and Cl.
The changes in H-4 fluid with time are similar to those in H-16 fluids and undoubtedly H-4
went through the same history of liner corrosion and progressive plugging leading to
elimination of deep fluid influence. In H-4 the deeper fluid was blocked by scale in March
1983 but reappeared later, possibly having broken through or bypassed the scale.
434
Conditions in the Deep Los Humeros Reservoir
During the initial production from wells H-16 and H-4 a mixture of shallow and deep fluids
was produced. The wellhead enthalpy of early H-16 production, combining deep and shallow
fluids, was 2662 J/g and the enthalpy of the upper fluid alone (after scaling had blocked the
deeper fluid) was 2400 ±100 J/g. From mass balance calculations (using 2500 J/g shallow
discharge), the deep contribution would be 65% if it were saturated steam (2750 J/g at 300°C),
50% if it were superheated to 2830 J/g, and 25% if superheated to 3150 J/g. The observation
that the flow of the repaired well (producing from the upper zone only) was nearly equal to the
initial flow from both zones probably rules out major production from the deeper zone and
suggests that the deep fluid was highly superheated steam.
This high enthalpy steam probably was not produced by equilibrium boiling from liquid. Steam
from evaporation of 30% NaCl brines at 350°C would have an enthalpy of only 2890 J/g; and
higher temperature evaporation would produce steam with lower enthalpy (calculations by J.L.
Haas, Jr., quoted in Truesdell and White, 1973). If the deep zone fluid was 25% of the total
and had an enthalpy of 3150 J/g, then it would have a temperature of about 410°C at the
pressure of the upper reservoir (about 85 ba). This steam would not be compatible with liquid
water unless the water were highly saline or tightly adsorbed on rock surfaces. This suggests
that the lower reservoir contains only superheated steam and that temperatures near 400°C exist
not far below the bottom of well H-16. A temperature near 400°C has been observed at Los
Humeros (Gutíerrez-Negrin and Viggiano, 1990) although the well and depth are not available.
The high-temperature reservoir found at Los Humeros beneath a normal temperature reservoir
is analogous to the high-temperature zones underlying vapor-dominated reservoirs in the
northern part of The Geysers. The main difference is that the shallower reservoir at Los
Humeros is liquid dominated, and therefore, pressures in both reservoirs are higher.
The Origin of Deep Fluid Constituents

In the earlier discussion of changes in fluid chemistry it was shown that the constituents
contributed from the deep reservoir were all soluble in superheated steam or resulted from acid
attack of casing and wallrock. The "primary" constituents HC1, B and H2S are also present in
the shallow reservoir (with HC1 represented as NaCl). It is also observed that in the natural
state before drilling there is no evidence of acid fluids. The andesite contains calcite, feldspars,
and mica; the hornfels and skarn are composed in part of carbonate rocks and normally contain
calcite. If superheated vapor in the deep reservoir contained significant HC1 and B in its natural
state, then it would be expected that minerals such as calcite and feldspars would not occur and
that boron minerals such as tourmaline would be found. The lack of mineralogical evidence for
deep acid or high boron suggests that the deep fluids observed in H-16 and H-4 may be in part
artifacts of drilling formed by flows of shallow water down the wellbore.
A shut-in drill hole penetrating both the shallow, liquid-filled reservoir and the deep reservoir
containing only high-temperature steam would be a conduit for downward flow of liquid
between the two zones. Liquid flowing down the well would quickly vaporize as it reached the
high-temperature zone and it would precipitate salts and evolve gases. Some constituents such
as B (as HsBOs) would partition between solid and vapor. The continued downflow of upper-
zone water could cause accumulation of significant quantities of alkali chlorides (mainly halite)
and sulfates, boric acid, and amorphous silica and release CC>2 (from HCOs) and NH3 (from
NELO into the steam. The steam in contact with this deposit of salts would have high H3BÜ3
and significant HC1 formed by halite-silicate reaction. With production of the well, gases and
volatile salts would be drawn upward to mix with the shallow reservoir water with the results
discussed earlier. If this idea is correct, then shallower drilling at Los Humeros could have
avoided the formation of acid steam as well as its introduction into drill holes.
435
Summary
Acid reservoir fluids in geothermal fields seem to originate from either the introduction of
volcanic fluids or from the volatilization and transport of HC1 in superheated steam. A minor
source may be infiltration of surface acid-SO4 waters formed by oxidation of H2S. With the
exception of the high-Cl waters of the Tatun field, acid reservoir waters of volcanic origin seem
to exist on the margins of geothermal reservoirs and do not represent a major part of the total
fluid. Acid from volatilization of HC1 is expected to appear in boiling high-temperature
reservoirs as they lose reservoir liquid and start producing superheated steam. The occurrence
of superheated, high-HCl steam at Los Humeros, Mexico, is unusual because the steam is
produced by flow from a deep dry reservoir to a shallower water-saturated reservoir with
strong corrosion and scaling resulting from fluid mixing and reaction with casing and rock. It
is suggested that the acid steam is an artifact of exploitation and could be avoided by shallower
drilling.
Acknowledgments. The author wishes to thank Luis Quijano León and Enrique Tello Hinojosa
of the Comisión Federal de Electricidad de Mexico for the use of unpublished data for Los
Humeros and for enlightening discussions of well H-16. He also wishes to thank Alfredo
Mainieri P. and Leonel Vaca C. of the Instituto Costarricense de Electricidad for discussions
and data for Miravalles well PGM-2, and Mitsubishi Metals Corp. (Japan) for data on
Sumikawa well S-2. Partial support of the International Atomic Energy Agency in the Los
Humeros study is gratefully acknowledged. He also thanks his colleagues, in particular
Donald White and Werner Giggenbach, for many discussions of acid fluids in the earth.
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438
IAEA INTERLABORATORY COMPARATIVE GEOTHERMAL
WATER ANALYSIS PROGRAM
W.F. GIGGENBACH, R.L. GOGUEL, W.A. HUMPHRIES

Division of Chemistry,
Petone, New Zealand
Resumen-Abstract
PROGRAMA DEL OTEA PARA ANÁLISIS COMPARATIVOS DE AGUAS GEOTERMALES ENTRE

LABORATORIOS.
La composición química de tres muestras de aguas geotermales de Nueva

Zelanda se determinó en 22 laboratorios, incluyendo los que participan en el
programa coordinado de investigación para América Latina sobre "Aplicación de
técnicas isotópicas y geoquímicas en la exploración geotérmica". Aquí se pre-
sentan y discuten los resultados de esta intercomparación. Con arreglo a lo
previsto, los resultados indican que algunos laboratorios tienen capacidad
para realizar análisis químicos de elevada calidad, mientras que otros deben
mejorar considerablemente su rendimiento para obtener resultados que puedan
utilizarse en la exploración geoquímica de zonas geotérmicas. No obstante, en
gran medida corresponde a cada laboratorio evaluar su propio rendimiento y
adoptar decisiones con respecto a las posibles maneras de mejorarlo.
IAEA INTERLABORATORY COMPARATIVE GEOTHERMAL WATER ANALYSIS PROGRAM.
The chemical composition of three samples of geothermal waters from

New Zealand was determined by 22 laboratories, including those
participating in the coordinated research programme for Latin America on
"The application of isotope and geochemical techniques in geothermal
exploration". The results of this intercomparison are presented and
discussed. As expected, the results show that some laboratories have the
capacity to produce high quality chemical analyses, while others must
improve their performance considerably in order to obtain results which
can be used for the geochemical exploration of geothermal areas. To a
large degree, however, it is up to individual laboratories to assess
performances and decide on possible avenues of improvement.
439
INTRODUCTION
Application of recently developed techniques for the evaluation of chemical and

physical conditions over the deeper part of a geothermal system relies heavily on the
availability of sufficiently complete and accurate analyses of the fluid discharges. The
range and sophistication of these techniques can be expected to increase considerably
within the near future putting great demands on the reliability of laboratories
involved in geothermal fluid analysis. The most promising way to check on the
present state of reliability of laboratories involved in geothermal projects, and to
identify possible lines of improvement, consists of a comprehensive interlaboratory
analysis program.
A number of national or regional interlaboratory water analysis programs have been

carried out. Most of these, however, were restricted to little mineralised potable or
irrigation waters or waters of interest in environmental pollution studies. The
number and type of constituents covered by these programs are generally quite
different from those determined in geothermal investigations.
The only interlaboratory chemical analysis program involving many countries and
including geothermal water samples was organised by Chemistry Division, DSIR. The
results are reported by A J Ellis (1976). For a number of constituents (Li, SO4, As,
NH3, Rb, SiO2) more than half of the laboratories reported values outside an
acceptable range, for the rest only 80% of the data were considered acceptable. The
scatter exposed during this study revealed serious deficiencies in analytical accuracy
and the need for general improvement and standardisation of analytical procedures.
In view of this and its involvement in many geothermal projects, the International
Atomic Energy Agency decided to initiate a purely geothermal intercomparison water
analysis program within the framework of the Coordinated Research Program on the
Application of Isotope and Geochemical Techniques in Geothermal Exploration in
Latin America. Chemistry Division, DSIR, New Zealand was asked to organise the
collection and distribution of suitable samples and to carry out an initial assessment
of the results.
440
TIMETABLE
13.08.85 - Distribution of announcement of program to some thirty laboratories

involved in geothermal projects, together with a questionnaire as to the range of
species able to be analysed. Of the 25 replies received by the end of 1985, all stated
the ability to analyse for Na, K, Mg, Ca, Cl and SO4; 23 were able to determine pH,
Li, F, HCO3; 22 to determine Fe and SiO2; 21 B and NH3; 18 Rb, Cs, Al, As; 12
Hg, Br, I, D, 180.
30.12.85 to 1.1.86 - Collection of three sets of twenty liter, filtered and two preserved
one litre water samples.
15.01.86 - Distribution of three 500 ml samples by airmail to 25 laboratories together

with covering letter and reply forms to acknowledge receipt of samples (by end of
February) and to report analytical results (by end of April 1986). As expected, only a
fraction of laboratories acknowledged receipt or submitted results by the deadlines
and a reminder was sent on
02.07.86 - enquiring about the fate of the samples sent. In due course, it was learnt
that all had arrived safely, with some leakage reported for two or three bottles. By
the extended deadline of
31.10.86 - twenty more or less complete lists of analytical results had been received.
LIST OF PARTICIPATING LABORATORIES
The selection of laboratories participating in the Intercomparison Program is largely

based on their present or past involvement in IAEA projects.
Facultad Ciencias, Universidad Mayor de San Simon

Calle Sucre Final, Cochabamba, BOLIVIA.
Coordinador Área Materials Primas, Instituto de Asuntos Nucleares

Apartado Aereo 8596, Bogotá D.E., COLOMBIA.
441
Instituto Costarricense de Electricidad
PO Box 10032, San José, COSTA RICA.
Instituto Ecuatoriano de Electrificación (INECEL)

Casilla 565-A, Quito, ECUADOR.
Comisión Ejecutiva Hidroeléctrica del Rio Lempa

Avenida Norte, San Salvador, EL SALVADOR.
Institute Mixte de Recherches Geothermiques, BRGM

BP 6009, 45060 Orleans Cedex, FRANCE.
Laboratoire de Geochimie des Eaux, Universite Paris 7

F 75 251 Paris Cedex 05, FRANCE.
Instituto Nacional de Electrification

6a Ave. 2-73 Zona 4, Guatemala City, GUATEMALA.
Geological Survey of India

Ghandi Bawan, Lucknow 226 001, UP, INDIA.
P T Geoservices
JL Setiabudhi 81, Bandung, INDONESIA.
Oil and Gas Technology Development Center, LEMIGAS

PO Box 89 JKT, Jakarta, INDONESIA.
Isotope Hydrology, IAEA

PO Box 100, A-1400 Vienna, AUSTRIA.
Laboraterio Chimico Físico, ENEL-UNG

56044 Larderello (PI), ITALY.
442
Ocean Research Institute
1-15-1 Minami-Dai, Nakano-ku, Tokyo 164, JAPAN.
Comisión Federal de Electricidad

Apartado Postal 31-C, Morelia, 58000 Midi., MEXICO.
Geothermal Research Centre, DSIR Chemistry Wairakei

Private Bag, Taupo, NEW ZEALAND.
DSIR Chemistry
Private Bag, Petone, NEW ZEALAND.
Electropem S.A.
Edif. "La Torre" of. 903, Centro Cívico, Lima, PERU.
PNOC Energy Development Corpoation, Geothermal

Port Bonifacio, Metro Manila, THE PHILIPPINES.
Geological Survey Division, Dept. of Mineral Resources

Rama 6 Road, Bangkok 10400, THAILAND.
Vernadsky Institute of Geochemistry, Academy of Sciences of the USSR

Kosygin St. 19, 117 975 Moscow, 5-334, USSR.
Ministerio de Energía y Minas

Torre Oeste - Piso 17 - Parque Central, Caracas 105, VENEZUELA.
Four other laboratories had agreed to participate, but had failed to supply results by
the extended deadline of 31.10.86.
DESCRIPTION OF WATER SAMPLES
The three water samples used in the Intercomparison Program were obtained from
geothermal areas on the North Island of New Zealand.
443
TABLE 1
Chemical analyses reported for sample 001 collected from a clear, colorless,
boiling (97.5°) spring at Waikite on 31.12.85 (in mg/kg).
Lab No. PH Li Na K Rb Cs Mg Ca Al Fe As F Cl Br SO, HCOj B SiO,

01 8.1 2.0 197 7.2 0.09 0.29 0.21 7.9 <.05 <.01 <.20 1.8 138 - 34 278 1.2 150
02 7.6 2.0 2.3 6.0 . 0.30 0.20 8.0 - <.50 0.31 2.0 128 <.5 29 - 1.3 57
03 8.0 1.9 200 8.0 0.10 . 0.21 8.2 - . . . 133 - 35 344 1.2 149
04 7.7 2.5 178 2.5 . . 1.00 8.0 - 1.20 - - 298 - 23 303 1.1 -
05 8.0 2.0 200 6.9 0.70 2.60 1.25 7.9 - 0.51 0.92 1.9 137 - 29 307 3.5 283
06 8.4 0.8 186 5.8 <.10 <.10 0.54 16.4 - . . - 136 - 36 287 - 142
07 7.6 - 183 7.8 - - 0.21 8.0 - . 0.39 - 125 - 33 259 - -
08 8.2 2.4 220 8.0 - - 2.70 14.3 - . - 1.3 250 - - 299 - 185
09 8.1 2.2 197 7.5 - - 0.23 7.6 <.03 <.02 - 2.2 130 - 32 299 1.3 154
10 8.1 2.2 191 7.2 0.06 0.11 0.17 7.8 0.04 0.02 0.38 1.9 125 0.4 31 299 1.6 141
11 8.2 2.0 202 6.8 0.14 0.17 0.21 8.7 0.02 0.45 . 2.0 133 0.4 36 293 1.3 144
13 8.3 2.4 200 8.0 0.20 0.40 4.00 6.0 - - - 2.0 140 - 31 298 5.4 146
14 7.7 2.3 199 9.8 0.30 0.80 <.10 7.0 <.10 0.01 . 2.2 153 - 26 299 1.5 134
15 7.9 2.0 192 10.3 - - 0.20 7.0 - 0.80 - 1.9 109 0.8 96 301 - -
17 7.7 2.0 206 7.1 0.09 0.40 0.22 8.3 0.01 0.01 0.32 2.3 129 0.4 32 300 1.4 146
18 7.9 . - - . - . . - . - - 124 - 33 302 - -
19 7.8 2.0 193 6.9 0.10 0.26 0.18 7.3 - <.06 . 2.4 133 - 34 278 1.1 152
20 8.2 2.3 182 9.4 0.08 - 0.07 9.6 - . . 2.1 136 - 29 287 - 130
21 8.0 2.1 186 7.9 0.09 0.28 0.28 10.0 <.10 <.02 0.23 2.2 152 - 25 315 0.1 146
22 8.4 2.1 210 6.4 <.10 0.27 0.22 8.0 - . . - 135 - 36 295 1.5 160
23 8.4 1.6 144 6.8 - - 3.73 10.2 - 0.01 . 2.8 121 0.1 56 254 . 25
25 8.3 2.1 203 6.8 - - 0.23 7.9 - - - - 131 - 32 305 1.4 143
median 8.0 2.0 196 7.2 0.10 0.28 0.21 8.0 0.02 0.04 0.32 2.0 133 0.4 33 300 1.3 146
"true" 8.0 2.0 196 7.2 0.10 0.28 0.21 8.0 0.02 <.01 0.30 2.0 133 0.4 33 280 1.3 146
TABLE 2
Chemical analyses (in mg/kg) waters collected from the weirbox of well WK66 and Wairakei on 30.12.85. The enthalpy of the well
at the time of sampling was 1020 J/g, steam was separated at 166° and 100°C.
Lab No. PH Li Na K Rb Cs Mg Ca Al Fe As F CI Br SO, HCO3 B SiO,

01 8.5 10.7 1158 169 2.2 2.0 0.004 20.2 0.5 <.01 3.8 3.3 1950 . 32 <5 25 596
02 6.5 11.0 1130 149 - 1.9 - 20.0 - <.50 4.1 7.0 1970 5.3 34 - 33 283
03 9.5 10.7 1170 164 2.8 - .010 19.7 0.3 . - . 1960 . 34 54 25 588
04 8.5 12.6 1050 13 - - 2.70 18.0 - 1.00 - . 2710 - 30 49 23 -
05 8.6 9.4 1442 174 1.8 2.5 19.82 18.9 - 0.34 4.1 1.4 2363 - 27 39 52 234
06 8.9 1.2 1187 176 4.5 2.0 0.05 41.8 - - . . 2010 - 38 27 - 29
07 8.2 11.0 1200 230 - 5.0 - 12.0 2.0 - 2.0 . 2487 - 34 49 - 8
08 8.3 10.0 1225 200 2.3 - . 21.4 . . . 3.7 2700 . . 49 . 683
09 8.8 11.4 1150 167 - - <.01 18.7 427 <.01 . 7.6 1975 - 34 7 26 647
10 8.5 10.9 1090 168 0.2 0.3 0.16 19.0 0.5 <.01 4.7 9.5 1933 4.3 37 49 23 481
11 8.3 10.4 1170 186 3.3 2.2 0.20 21.6 0.6 0.04 . 7.6 1960 5.3 37 29 36 110
13 8.7 12.0 1100 160 2.5 2.5 - 12.0 . . . 8.0 1955 . 39 29 29 135
14 8.4 11.9 1180 156 2.5 3.2 <.10 17.3 0.2 0.05 - 6.9 1965 - 35 23 25 497
15 8.5 10.3 1308 187 - . 0.04 16.5 , 1.00 . 1.5 1991 1.6 90 96 . -
17 8.4 10.7 1170 163 2.1 2.0 0.002 20.0 0.4 0.004 4.2 7.8 1960 5.4 37 <1 28 590
18 8.6 - - - - - - - - - . . 1970 . 37 48 . -
19 8.5 10.2 1130 163 2.1 1.9 <.01 16.2 - 0.06 - 9.5 1960 . 35 48 24 610
20 8.0 10.4 1045 204 2.6 - - 19.6 0.3 . . 7.5 1969 - 33 5 - 175
21 8.7 11.2 1099 166 2.0 2.0 0.08 22.1 0.4 <.02 2.8 8.4 1995 4.1 28 81 27 105
22 8.5 10.8 1200 171 2.1 2.0 <.01 20.0 . . . . 1970 . 37 <5 26 580
23 7.7 7.8 7149 86 14.2 18.4 0.04 . . . . 9.3 1630 2.9 65 41 . 52
25 8.4 11.2 1180 168 - • 0.05 16.8 - - - 1952 - 35 33 27 582
median 8.5 10.7 1170 167 2.2 2.0 0.05 19.7 0.4 0.04 4.1 7.6 1970 4.3 35 40 26 382
"true" 8.5 10.7 1170 167 2.2 2.0 0.004 20.0 0.4 <.01 4.0 7.6 1970 4.3 35 <5 26 590
TABLE 3
Chemical analyses (in mg/kg) reported for waters collected at Morere, New Zealand, on 1.1.86
from a 47° spring associated with a natural gas discharge. The waters contained suspended
iron hydroxides, removed by filtration.
Lab No. PH Li Na K Rb Cs Mg Ca Al Fe As F CI Br SO4 HCO, B SiO2

01 7.2 4.5 6690 84 0.07 .004 9 2750 <.05 0.15 <.01 0.9 15670 - <3 28 44 28.4
02 6.9 5.0 7025 65 - <.10 75 3000 . <.50 . 1.0 16470 57 . - 42 13.7
03 7.0 4.8 6660 72 0.40 - 81 2770 - 0.14 - - 15800 - 26 44 44 30.0
04 7.2 20.8 6000 11 - - 406 2620 - 4.60 - - 26680 - 4 73 38 -
05 7.0 5.0 7208 198 2.10 1.16 90 2893 . 0.34 3.1 1.7 16072 - 47 44 84 50.1
06 7.4 0.8 6064 67 <.10 <.10 198 249 . - . - 15537 . <10 29 - 583.0
07 7.0 5.1 5200 162 - - 81 2800 . 0.12 . 1.0 15900 - 75 7340 40 3.6
08 7.1 4.8 640 108 0.50 - 168 3274 - . - 0.4 20000 - - 40 - 56.0
09 7.2 3.3 6770 83 - - 76 2660 <.03 <.10 . 1.4 16320 - <1 35 48 27.7
10 7.0 4.6 6540 82 0.04 <.001 76 2730 0.02 0.03 <.01 1.8 14775 57 <1 41 54 34.0
11 7.0 5.9 6780 85 0.17 - 77 2790 0.02 0.81 . 0.9 15600 58 6 46 45 27.6
13 6.9 6.0 6800 90 0.50 0.20 63 3506 . - - 0.2 15750 . . 39 46 26.0
14 7.0 12.0 6400 60 6.20 22.50 73 2738 0.40 0.14 - 0.6 15408 . 1 49 37 23.0
15 7.0 3.5 7692 583 - - 65 2225 - 200.0 - 1.5 17176 2 - 85 - -
17 6.9 4.8 6770 82 0.10 <.10 75 2720 - <.01 0.01 1.3 15650 63 <1 42 46 25.0
18 6.9 - - - - - - - . . - . 15800 . 60 38 . .
19 7.0 4.3 6590 74 0.10 0.15 74 2690 _ 0.28 _ 1.1 15660 . 6 39 42 25.5
20 7.1 2.4 6364 110 0.06 - 81 2856 0.11 0.29 - 0.8 15755 . - 31 . 25.4
21 7.2 4.9 6497 83 0.13 <0.01 83 2856 0.10 <.02 <.01 1.0 15964 51 _ 76 42 26.5
22 7.1 4.8 7000 82 0.12 <.10 100 2300 - . - _ 15800 . <5 45 45 <50.0
23 7.3 - 1580 71 - - 174 2882 - 0.06 - 1.1 13461 . 78 39 . 55.0
25 7.3 4.6 6880 90 - - 78 2600 - - - - 15374 - - 42 47 35.0
median 7.0 4.8 6660 82 0.13 0.10 80 2760 0.10 0.14 <.01 1.0 15800 57 6 42 44 27.0
"true" 7.0 4.6 6700 84 0.10 0.004 80 2760 <.05 0.15 <.01 1.0 15800 57 <3 30 44 27.0
The lowest salinity samples was collected on 31.12.85 at Waikite from a natural
boiling spring (97.5°). The waters are clear and colorless and deposit minor amounts
of silica. The springs are located at the NW- margin of the Taupo Volcanic Zone
and are possibly associated with the Waiotapu - Te Kopia geothermal systems.
The intermediate salinity samples represents the weirbox discharge from well WR66
at Wairakei collected on 30.12.85. The discharge enthalpy at the time of sampling
was 1020 J/g, steam was separated at 166° and 100°C. The water was clear and
colorless, minor amounts of amorphous silica accumulated on the cellulose filters.
The highest salinity sample was collected at Morere, an area of warm springs (47°) on
the East Coast of the North Island. The waters are associated with copious dis-
charges of methane and deposit considerable amounts of ferric hydroxide (FeOOH)
in flow channels. The waters are also characterized by high iodide contents which
impart a yellowish color to the samples after prolonged exposure to air.
Three samples were taken at each location. A twenty litre samples, pressure (N2)
filtered through cellulose acetate (Millipore) filters, two one litre samples each
filtered and acidified with 5 ml of cone. HNO3 and preserved with 5 ml 30% formalin
respectively. All sample containers, including sample bottles sent to participants, had
been cleaned by treatment with half-concentrated HNO3 and rinsing with distilled wa-
ter. The samples bottles were number with the first two digits representing the labo-
ratory, the last digit the type of water; Waikite (001), Wairakei (002), Morere (003).
RESULTS
The analytical results for the three geothermal water samples as received from 21
laboratories by mid November 1986 are given at least seven results were reported,
some laboratories reported results for a number of other species, they are shown in
Table 4.
Excess significant figures given are rounded off, otherwise the data are shown as
received in spite of some obvious typing, transcription or dilution errors such as a
value of 427 mg/kg of Al reported for 092, a Na-content of 640 given for 083, a Ca-
447
TABLE 4
Chemical results for constitutents analysed only sporadically

(in mg/kg and °/» (SMOW))
Lab. I Lab. NH, Lab. Sr Lab. Hg Lab. SD SIS0
Waikite (1)
15 44.0 01 0.04 01 0.0614 <.0002 01 -44.6 -6.53
17 <0.4 05 0.2510 49.00 21 .0009 09 -42.9 -6.32
06 <0.02 21 0.05 10 - -6.10
09 <0.02 16 -41.8 -6.45
11 0.04 18 -45.7 -6.70
14 0.04
15 0.70
17 <.10
median 0.04 - - - -45.2 -6.45
Wairakei (2)
11 0.1 01 0.2311 0.1014 <.0002 01 -41.8 -4.72
15 60.0 05 1.2510 88.50 21 .0006 09 -38.8 -4.65
17 <.4 06 0.30 21 0.11 10 - -4.60
21 0.3 09 0.32 16 -39.8 -4.65
11 0.34 18 -40.5 -5.00
14 0.84
15 1.00
17 0.22
median 0.2 0.33 - - - -40.2 -4.65
Morere (3)
11 26.901 10.20 01 231 14 .0076 01 -15.7 +3.90
15 30.0 06 8.1008 208 21 .0023 09 -12.0 +3.93
17 30.0 09 11.50 10 200 10 - +3.60
21 29.5 11 12.10 21 213 16 -35.4 +4.11
17 11.40
median 30.0 11.40 210 - - -15.0 +3.90
content of 249 for 063, a HCO3-value of 7340 for 073, a B-value of 583 for 063, and a
K-value of 583 for 153. Also Na-values for 232 and 233 are likely to have been
interchanged, Sr-values for 101 and 102 are likely to be ng/kg. The occurrence of
such errors even in data sets submitted to an intercomparison program illustrates the
need for rigid checking procedure of analytical data and for good "book-keeping"
practices.
Samples Oil, 012 and 013 were analysed at Chemistry Division, DSIR, New Zealand
by use of an iterative procedure. The waters were first analysed by comparison with
individual standards for each species. On the basis of these results, three artificial
waters were recreated gravimetrically with chemical compositions closely matching
those of the original waters. These artificial waters were then used as standards for
448
the re-determination of the original samples thus eliminating matrix effects and
chemical interferences. The results obtained can be expected to be as close to "true"
values as possible for the species Li, Na, K, Rb, Cs, Mg, Ca, Sr, Al, Fe, As, B and
SiO2 determined by atomic absorption or emission spectrophotometry.
The remaining parameters pH, F and NH 3 were determined by use of specific

electrodes against gravimetric standards on samples stabilised by HNO 3 or formalin,
sulfate was determined gravimetrically as BaSO4, HCO3 by blank-corrected alkalinity
titration (Giggenbach and Goguel, 1986).
Samples 001 and 002 were chemically stable and analytical values for all three sub-
samples (filtered, acidified, preserved with formalin) agreed closely. Both filtered
and formalin treated samples of 003 (morere) continued to precipitate minor
amounts of iron hydroxide, the filtered and acidified ones turned yellow due to the
oxidation of iodide, the formalin treated one remained colorless.
EVALUATION
Due to the large diversity of analytical techniques applied by a wide range of

laboratories of possibly highly variable standards, statistical techniques based on the
assumption of normal distribution around a mean are of little value. In order to
minimise the effects of far outliers, a technique based on the distribution of
observations around the median value of a given samples has been chosen. The "box-
whisker"-plots, as proposed by Tukey, (1977) were modified as shown in Figs 1 to 3.
There the analytical data for a given species, normalised to the median value are
presented on a logarithmic scale. The boxes extending to the left and right represent
each 25% (quartile) of the data deviating to higher or lower values thus
encompassing 50% of all data. Values outside this range are indicated by their
laboratory number. The size of the boxes *'c an indication for the error associated
with the determination of a given species by the "better half of laboratories.
Of the species considered in Figs 1 to 3, for some the scatter of results is within a
reasonable range (pH, Li, Na, K, Ca, F, Cl and B) for all three samples, for some,
however, the range of results exceeds the two order of magnitudes covered (Rb, Mg,
449
1/5 1/2 median 2x 5x
median
H* (§M2><SX!3EH 1— ®~ ©-©© 80
Li 20
?L ©
© ——————— ©-©
No 196
K © —————— @@§[ 72
Rb ®— @~c |I f\^
\u/ S*^t
\ii/ /f?^
û/ 010
Cs @@———— © ———I ———— ©———————© 028
IVg <ix v¿J vc5!ü(_ 21 06 1——————©— © ———1 06 23 J3021
Co (ÍISSí ]-@@d5i— ®-@ 80

Fe -*-§U 17 -«-09 1021 11 02 05 15 oT OO4
F ® —— 0 ^HD-0 20
a ©HIJ®@ —————©-© 133
sq <3SgHI ] ———————©———————© 330
MOO, D® 300
B to————————————————©it 130
so2 ]@<5^———© 146
(mg/kg)
o1 0.2 03 04 ' 06 ' ' 10 2 3 4 ' 6 ' ' ' 10 x
Fig. 1 - Comparison of analytical results for sample 001 (Waikite) in terms of

deviations from median. Best estimates of "true" values are indicated by
heavy bars Boxes contain 25% of values deviating to higher or lower
values. Arrowed boxes indicate data outside the range of the figure.
1/5
nedian
85
107
1170
167
22
20
005
Ca 197
Fe ••+J0910 _ J±?_L __ _ __ 11 U_ __ __ __ __ 0 2 W I 5 0.04
76
197O
35
40
26
382
0.1 Q2 03
Fig. 2 - Comparison of analytical data reported for sample 002 (Wairakei).

Dashed lines enclose values too widely scattered to permit meaningful
statistical evaluation. Arrowed number indicate detection limits given.
450
median
1/5
Csl'OHJ -"020617-22 19 13
Fig. 3 - Comparison of analytical results for sample 003 (Morere). For details see
captions Fig. 1 and 2.
Fe, SO4, HCO3). In these cases any statistical treatment with the aim to arrive at the
"true" composition of the samples is futile. In order to be able to select a range of
analytical results most likely approaching this "true" value, the laboratories were
classified in terms of the number of results outside the two quartiles shown in Figs 1
to 3 for pH, Li, Na, K, Cs, Ca, F, Cl, B and SiO2. Four groups of laboratories are
distinguished:
TABLE 5
Number of outliers: 0-1 2-4 5-10 10-20

09 02 06 04
11 03 07 05
Laboratory: 17 10 13 08
19 20 14 15
25 22 21 23
By use of the data reported by the first, most reliable group, together with those
obtained at Chemistry Division, DSIR (01) an attempt was made to derive a best
estimate of the "true" composition of the three samples.
451
For sample 001, these estimates are very close to the median values derived earlier,
except for iron for which a value below the detection limit of 0.01 mg/kg was
accepted. The same conclusion for iron was reached for water 002. In addition, the
DSIR value of .004 nig/kg was accepted for Mg and a value of <5 mg/kg for HCO3,
well below the median values. A HCO3 value of 40 mg/kg was obtained here at
DSIR as the result of a simple alkalinity titration. After correcting for the effects of
the considerable amounts of the weak acids H3BO3 and H4SiO2 present, by "back
titrating" the samples with NaOH from pH 3.8 to their original pH (Giggenbach and
Goguel, 1986), the amounts of HCO3, however, were found to be below the detection
limit of the technique employed. Most of the low values reported for SiO2 are likely
to represent monomeric silica contents. As most silica geothermeters are based on
total silica contents, the much higher total silica contents as determined by AA are
accepted as "true" values.
A special effort was made to determine Cs in sample 003, therefore, the very low
value of 0.004 mg/kg as measured by DSIR is adopted. Similarly an upper limit of
0.05 mg/kg is accepted for Al, of 0.15 mg/kg for iron. The iron content of the
acidified sample was 0.90 mg/kg but had dropped to 0.15 mg/kg in the filtered
samples by the time they were sent out. They may have decreased further during
shipment. Again a blank corrected lower value of 30 mg/kg was taken for HCO3,
with sulfate likely to be well below the limit of 3 mg/kg.
These best estimates of the true composition of the three waters are shown in Figs 1
to 3 as solid bars, they may be used to judge the accuracy of individual values.
DISCUSSION
A detailed point by point discussion of the results is beyond the scope of this general
evaluation. Some general conclusions, however, may be drawn.
One of the major uses of chemical data is geothermal investigations consists of the
valuation of water-rock equilibration conditions at deeper levels. Application of such
geo-indicators relies largely on Na, K, Mg, Ca and SiO2-contents of the discharges. A
look at the results reported by the "better half of laboratories , as indicated by the
size of "boxes" in Figs. 1 to 3, shows that the errors for Na, K and Ca are within
452
reasonable limits (5-10%) for all three samples. For Mg, however, scatter increases
rapidly with decreasing concentrations. For sample 003 containing 80 mg/kg, the
scatter is within 10-15%, it increases to a factor of three for sample 001 (0.21 mg/kg)
and spans several orders of magnitude for sample 002 (0.004 mg/kg).
The effects of these errors on the evaluation of water-rock-equilibration temperatures

by use of a recently proposed technique (Giggenbach, 1986) are shown in Fig. 4. For
Waikite (001) the apparent range of K/Na-temperatures extends from 100° to 200°,
K/Mg-temperatures from 60° to 140°. For wairakei (002), most data points are close
to the measured and the full equilibrium temperature of 260°. The results for 042,
052, 232, however, would give a completely unrealistic picture. Even for the high Mg
water 003, an unacceptable scatter is observed. The range of silica contents reported
for the low (27 mg/kg) to intermediate (146 mg/kg) silica waters (003, 001) are
reasonable.
CI/100
Li B
Fig. 4 - Evaluation of K-Na and K-Mg-water-rock equilibration temperatures

(Giggenbach, 1986) by use of analytical results reported for Na, K, Mg for
Waikite (001), Wairakei (002) and Morere (003) geothermal discharges.
453
There silica is largely present in the monomeric form and colorimetric and atomic
spectroscopic values agree. In the case of the high silica water from Wairakei (002),
however, the discrepancy of values obtained by the two techniques becomes
unacceptable.
Another application of geochemical data consists of the evaluation of possibly source

components by use of "conservative" components such as Cl, B and one of the alkalis
Li, Rb, Cs In Fig. 5 relative Cl, Li and B contents are shown for all three waters.
Again considerable uncertainties are introduced by the scatter in the data reported by
some laboratories.
The main reason for likely errors in the analysis of low HCO3 waters has been
discussed above (lack of back titration with NaOH to account for the presence of B,
Na/1000
K/100 300* 200* K / Mg - terrperatunt (*C)
Fig 5 - Relative Cl, L» and B - results reported for Waikite (001), Wairakei (002)
and Morere (003) geothermal discharges.
454
SiO2 and other weak acids). Sulfate results for the two higher sulfate waters (001,
002) are quite reasonable, most of the laboratories could not cope with the very low
sulfate water 003 for which much too high values were reported.
Accurate Al data are required in many computer studies of water-aluminium silicate

equilibration, but only less than half of the laboratories report results for this
constituent and then often only detection limits. The few values given are within an
acceptable range, in contrast to results for iron, another species required in the
computer simulation of mineral-water interactions. All three waters are likely to
contain iron in very low amounts (<.05 mg/kg), values reported, however, range
beyond 1.0 mg/kg.
Of the constituents determined only by a few laboratories, iodide values for Morere
(003) are very consistent but appear to be unreliable for the other two waters. The
variations in NH 3 reported may be due to some interference from biological activity
in the unstabilised samples. The agreement of the results by many laboratories for
Wairakei (002) and Morere (003) with the DSIR results, obtained on acidified and
sterilised samples, suggests that biological effects were not important. Strontium
values agree for the Morere water (003), as do Hg-data.
Interlaboratory checking procedures are obviously much better developed for isotopic
measurements. Most deuterium and oxygen-18 values are well within acceptable
ranges of ±27°° and ±0.27°° respectively, except for 003. There some problems may
have been introduced by the high salt content of this water.
RECOMMENDATIONS
The major purpose of the present intercomparison program was the identification of
deficiencies in the analytical procedures of laboratories involved in the geochemistry
of geothermal systems. The results obtained clearly show that there is ample room
for improvement. To a large degree, however, it is up to individual laboratories to
assess their performance and to decide on possible avenues of improvement. In some
455
cases this may involve upgrading of existing facilities, eg, analysis of Mg and SiO2 by
atomic absorption spectrometry rather than wet chemical techniques; the
introduction of more suitable techniques or the application of stricter calibration and
quality control procedures. Only very minor errors are likely to have been introduced
by the use of the simple sampling technique. Considering eg, the excessive range of
iron values reported, only little would have been gained by distributing a second
acidified sample.
REFERENCES
Ellis A.J. (1976) The IAGC interlaboratory water analysis comparison programme.
Giggenbach W.F. (1986) Geothermal solute equilibria, derivation of Na-K-Mg-Ca

geoindicators. Geochim. Cosmochim. Acta 52, 2749-2765.
Giggenbach W.F. and Goguel R.L. (1986) Methods for the collection and analysis of
geothermal and volcanic water and steam samples. Chem. Div., DSIR, Report, pp.60.
Tukey J.W. (1977) Exploratory Data Analysis. Addison-Wesley Publ. Comp. 27-56.
456
LISTA DE PARTICIPANTES
Eduardo ALMEIDA, Jefe del Proyecto Geotérmico, Instituto Ecuatoriano

de Electrificación, Quito, Ecuador
Peter BLATTNER, Institute of Nuclear Sciences, Department of
Scientific and Industrial Research, Lower Hutt, Nueva Zelandia
Egizio CORAZZA, Istituto di Geocronologia e Geochimica Isotópica,
Pisa, Italia
Werner GIGGENBACH, Chemistry Division, Department of Scientific and
Industrial Research, Petone, Nueva Zelandia
Roberto GONFIANTINI, Organismo Internacional de Energía Atómica,
División de Ciencias Físicas y Químicas, Vienna, Austria
Pablo HERNÁNDEZ PANAMEÑO, Jefe del Centro de Investigaciones
Geotérmicas, Comisión Ejecutiva Hidroeléctrica del Rio Lempa,
San Salvador, El Salvador
Julieta JAUREGUI, Proyecto Geotérmico, Ministerio de Energía > Minas,
Caracas, Venezuela
Alfredo LAHSEN, Decano de la Facultad de Ciencias Físicas y Naturales,
Universidad de Chile, Santiago, Chile
Alfredo MAINIERI, Jefe del Proyecto Geotérmico, Instituto
Costarricense de Electricidad, San José, Costa Rica
Karla MIRANDA, Proyecto Geotérmico, Instituto Nicaragüense de Energía,
Managua, Nicaragua
Rafael MURILLO, Jefe del Laboratorio Químico de Miravalles, Instituto
Costarricense de Electricidad, San José, Costa Rica
David NIEVA, Jefe del Departamento de Geotermia, Instituto de
Investigaciones Eléctricas, Cuernavaca, Morelos, México
Pietro NOTO, Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Hector PANARELLO, Instituto de Geocronologia y Geología Isotópica
(INGEIS), Universidad de Buenos Aires, Argentina
Costanzo PANICHI, Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Javier RODRÍGUEZ C., Departamento de Química, Universidad Mayor de San
Simón, Cochabamba, Bolivia
Alberto RODRÍGUEZ M., Decano de la Facultad de Ciencia y Tecnología,
Universidad Mayor de San Simón, Cochabamba, Bolivia
Alfredo ROLDAN M., Jefe de la Sección Geoquímica, Instituto Nacional
de Electrificación, Ciudad de Guatemala, Guatemala
Giovanni SCANDIFFIO, Unita Geotérmica Nazionale, Ente Nazionale per
l'Energia Elettrica (ENEL), Pisa, Italia
José Luis SIERRA, Dirección de Desarrollo Geotérmico, Ente Provincial
de Energía del Neuquén, Neuquén, Argentina
Paolo SQUARCI, Director, Istituto Internazionale per le Ricerche
Geotermiche, Pisa, Italia
Enrique TELLO, Oficina de Geoquímica, Comisión Federal de
Electricidad, Morelia, Michoacán, México
Alfred H. TRUESDELL, Geological Division, Branch of Experimental
Geochemistry and Mineralogy, U.S. Geological Service, Menlo
Park, California, USA
Leonel VACA, Proyecto Geotérmico, Instituto Costarricense de
Electricidad, San José, Costa Rica
Pablo VÁRELA, Coordinador General del Proyecto Geotérmico, Ministerio
de Energía y Minas, Caracas, Venezuela
Eulalia VIVES, Proyecto Geotérmico, Instituto Costarricense de
Antonio YOCK, Proyecto Geotérnr-,o, Instituto Costarricense de
Gian Maria ZUPPI, Dipartimento di Scienze della Terra, Universitá di
Torino, Torino, Italia
457
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ORGANISMO INTERNACIONAL DE ENERGIA ATOMICA

Dependencia de Intercambio de Informaciön del INIS

Los pedidos deben ir companados de un pago por adelantado de 100.-

Orders should be accompanied by prepayment of Austrian Schillings 100,

Impreso por el OIEA in Austria

Publicamos en el présente volumen las memorias

We are publishing in this volume the papers presented at

Scientists from nine Latin American countries, i.e.

On the whole, the scientific investigations carried out

Al preparar esta publication para la imprenta, el personal correspondiente del Organismo

Resumen del Programa coordinado de investigation .................................................. 9

El PCI para la America Latina sobre el empleo de técnicas

The CRP for Latin America on the Use of Isotope and

Bolivia; Laguna Colorada, Empexa and Volcan S a jama, on the

Mexico: Los Humeros, state of Puebla;

Peru: Challapalca, Paucarani, Calacoa, Calientes and Tutupaca,

Venezuela: Las Minas, Mundo Nuevo and Aguas Calientes in the

Environmental isotopes were mainly applied to identify the

Isotopic geothermometry was limited to a few cases,

Chemical analyses of geothermal fluids were extensively

Another activity worth mentioning, organized shortly after

J.L. SIERRA*, F. D'AMORE**,

CARACTERISTICAS DE ALMACENAMIENTO DEL CAMPO GEOTERMICO DOMINADO FOR LA

El caiapo geotérmico de Copahue-Caviahue, se puede définir como

Las temperaturas obtenidas por métodos quimicos e isotôpicos ron-

Los valores de carbono-13 y las concentraciones de NZ, He y Ar

RESERVOIR CHARACTERISTICS OF THE VAPOR DOMINATED GEOTHERMAL FIELD OF COPA-

1.1. LOCATION AND GEOLOGY

The area of Copahue is located in the AW sector of the Neuquén

The climate is Patagonic, and that of high mountain, depending of

The effusive complex Copahue-Caviahue started to develope in the

Because of the draining, result of the continous magmatic activi-

During the Pliocene-Holocene the magmatic activity continued,

During three field trips performed in the 1985/1987 period, were

: SAMPLE i LOCRÎION ; r : rvPE ! F» 1 5i02 ! N« : K ! Li

icopH-i s: L« rUqumit« ; 130 I Y.por ! : -10,8 :-84,2 !O,8+/-0,7: ! ! I ! I

TRBLE N" 1: ISOTOPIC HNftLVSIS OF COP-1 RNO COP-2 UELLS.

DfirE : s/ei : i/85 : u/86 : 1 1/86 ! 1/87 DOTE i 1/86 :

3.1. METEORIC WATER LINE

As established by Panarello et al., 1988, cold samples CAVI-1-2-

Othervj.se doesn't exist a good correlation between isotopic com-

Vapor condensate samples are shifted in oxygen-13 and define a

3.2. CALCULATION OF THE PHYSICOCHEMICAL CONDITIONS INTO THE

As it is showed in fig. 2, static pressure and temperature profi-

90 110 130 150 170 190 210 230 250

FIG. 2. COP-1 static pressure and temperature profiles

Q ( In/h) g/t (IN/K« yapor)

FIG. 3. COP-1: production and gas/vapor ratio.

Q (ta/h) I/Y (IN/Ki vapor)

FIG. 4. COP-2: production and gas/vapor ratio.

HSH = 3 log I H 2 S / H 2 0 J - t o g ( H 2 / H 2 0 >

FIG. 5. FT-HSH diagram (D'Amore and Truesdell, 1985).

In the FT-HSH diagram (fig. 5) (D'Amore & Truesdell, 1985) all

In November, 1986, when the well was reopened, after to be closed

In April, 1987 an strong increase in the HzS content (1.0 %) was

-11 -10.5 -10 -9.5 -9 -B.5

FIG. 6. COP-1: production vs oxygen-18.

In April, 1987 an strong decrease in the discharge was observed

In addition, also in the COP-2, the oxygen-18 value became more

In fig. 7 the evolution of the gas/vapor ratio vs the delta oxy-

Ca«/Vnpor (IN/Kg vnpor)

FIG 7. Gas/vapor ratio vs oxygen-18.

Using the chemical analysis of gas sampled in November, 1986 some