Kamphaugite-(Y).

KAMPHAUGITE-(Y): AN HYDROTHERMAL CARBONATE OF LOW

TEMPERATURE

J. GONZÁLEZ DEL TÁNAGO1, A.LA IGLESIA1 & A. DELGADO2

1
Deprt. Petrología y Geoquímica & Instituto de Geología Económica CSIC, Facultad
de Ciencias Geológicas, Universidad Complutense, 28040 Madrid, Spain (e-mail:
tanago@geo.ucm.es)
2
Dept. Ciencias de la Tierra y Química Ambiental, Estación Experimental de El
Zaidín, CSIC, 18008 Granada, Spain

§ Author for correspondence: tanago@geo.ucm.es

text 3378 words; referentes 1090 words, 2 tables and 5 figures

Abstract Kamphaugite-(Y) occurs as white-to-cream coloured spherical to half-

spherical aggregates of radial crystals in the La Cabrera granitic pluton (Spanish Central
System). It is mainly formed on the free surfaces of K-feldspar, quartz, calcite,
kainosite-(Y) and laumontita, inside some miarolitic cavities.
The La Cabrera Kamphaugite-(Y) shows a chemical composition close to the
structural formula: Ca0.94Y0.89REE0.21(CO3)2[F0.05(OH)0.95] · 1.19H2O.
Negative δ13C values (<15.1‰) indicate a meteoric source for their carbon.
Textural relationships between kamphaugite-(Y) and associated minerals, its relatively
high δ18O values (+25.8‰), and the occurrence of laumontite inclusions in
kamphaugite-(Y), point to a genesis at <50 ºC, by a very low temperature postmagmatic
hydrothermal event.

Keywords: kamphaugite-(Y), yttrium-carbonate, stable isotopes, Spanish Central

System

Introduction Kamphaugite-(Y) – ideally Ca(Y,REE)(CO3)2(OH)·1.5H2O – is a rare

mineral. It was first described by Raade & Brastad (1993) and its crystal structure by
Rømming et al. (1993), from Hørtekollen, Norway, and reported in addition in two
Norwegian granitic pegmatites, occurring either as an alteration product of kuliokite-(Y)
or as crystallized rosettes along cracks in quartz and feldspars (Raade et al. 1993).
Raade & Brastad (1993) suggest that an unknow mineral UN-21 of the Evans Lou

1
 Kamphaugite-(Y).

granitic pegmatite, Canada (Hoggarth 1972) would be kamphaugite-(Y). This mineral

was later reported by Orlandi (1997) and Gamboni & Gamboni (1998) associated with
stilbite in the Maddalena Island granite, Italy; by Petersen, et al. (2001) in the Rössing
uranium mine granite, Namibia; by Wallwork et al. (2002) on decrespignyite-(Y) in the
Paratoo copper deposit, Australia; and by Fehér et al. (2003) on fissures in the
Szarvaskő granite, Hungary. None of the above studies have provided information on
the conditions of formation of this mineral.
Kamphaugite-(Y) in La Cabrera is scarce, and so far it has only been found in
miarolitic cavities of pegmatitic bodies. It occurs as spherical to half-spherical
aggregates of radial crystals -up to 1.5 mm in diameter - grown over the free surfaces of
K-feldspar, quartz, pyrite, clinochlore, calcite, kainosite-(Y) and laumontite. This
zeolite has also been found as inclusions in the outer zone of the kamphaugite-(Y)
aggregates.
The aim of this study is to report, for the first time, stable isotopic values (δ13C,
δ18O), that will aid to place constraints on the origin of kamphaugite-(Y). In addition,
new crystal-chemical and mineralogical data are reported.

Geological setting. The La Cabrera massif is located in the NW of the Madrid

province, Spain. It is one of the late-variscan granitic plutons which forms part of the
Spanish Central System (Bellido 1979; Villaseca et al. 1993; Villaseca & Herreros
2000). This massif shows geochemical I-type characteristics and an evolutionary trend
from marginal amphibole-bearing granodiorites towards a dominant biotitic
monzogranite and intrusive leucogranites. In the most evolved facies garnet, cordierite
and occasional muscovite can be found (Bellido 1979). Rare element, LYF-type,
pegmatites with gadolinite-(Y) occur in the most differentiated granite facies, (González
del Tánago et al. 1986; González del Tánago 1997). A remarkable postmagmatic and
recurrent hydrothermal activity is recorded throughout the Eastern Spanish Central
System, with several main events lasting 300 My (Caballero et al. 1992; Tornos et al.
2000). This hydrothermal activity (ascending hydrothermal solutions and downward
percolating groundwater) is recorded in the La Cabrera pluton by a medium-to-low
temperature hydrothermal history that, through a compact microfault system as well as
several major faults, affects all the pluton (González Laguna et al. 2000; Lozano 2003).
One of the most important effects of this hydrothermal process is Na/Ca ratio increase
of plagioclase which raises the calcium activity in the hydrothermal fluids. As a

2
 Kamphaugite-(Y).

consequence of this process epidote, allanite-(Ce), ferro-axinite, prehnite and a large set
of secondary minerals are formed, mainly low temperature calcium silicates and
carbonates (titanite, zeolites, fluorapophyllite, kainosite-(Y), bavenite, etc.). This
hydrothermal process is of particular interest in many miarolitic cavities of the
pegmatite bodies, where the hydrothermal fluids were concentrated and where the most
important secondary minerals are formed (González del Tánago 1997; González del
Tánago & La Iglesia 1998; Lozano 2003).
The most abundant magmatic high-yttrium mineral in the La Cabrera pluton is
zircon which in crystal rims may reach up to 2.22 wt% of Y2O3 and, occasionally, some
pegmatite zircons reach up to 7.39 wt% (Perez Soba et al. 2003). Xenotime-(Y), and
monazite-(Ce) up to 4.34 wt% of Y2O3, are less abundant. In the garnet facies and
pegmatite bodies the most important yttrium minerals are zoned garnet, whose zones
can contain up to 2 wt% Y2O3 and gadolinite-(Y), González del Tánago (1977).

Metodology X-ray powder diffraction patterns were obtained using a Philips X’PERT
diffractometer. Powder of silicon was used as standard. Due to the small amount of
sample available (∼ 10 mg), an obliquely cut silicon crystal was used as sample holder.
Differential thermal analysis (DTA) and gravimetric analysis (TG) were
simultaneously carried out with a Seiko Exstar 6000 instrument, using about 6 mg of
sample, static air atmosphere and heating rate of 10 ºC min-1.
Semi-spherical aggregates of kamphaugite-(Y) were mounted in epoxy and
polished. Wavelength-dispersive electron microprobe (EPMA) data were collected
using a Jeol JXA-8900M instrument at the Universidad Complutense, Madrid. Main
operating conditions were: acceleration voltage 20 kV, probe current 50 nA, and
variable counting time among 10 and 30 s and among 5 and 15 s, in peak and
background respectively. Beam diameter was between 2 to 5 µm to minimize the
electron damage. The standards used were albite, kaersutite, and REE-phosphates
described by Jarosewich et al. (1980) and Jarosewich & La Boatner (1991), For Th and
U commercial glasses were utilized. An on-line ZAF correction program was finally
used.
CO2 determination, as well as isotopic analyses were carried out at the Stable
Isotope Laboratory of Estación Experimental de El Zaidín (CSIC), Granada, Spain. CO2
was obtained from carbonate using 100% phosphoric acid for 12 hours in a thermostatic
bath at 25 ºC (Mc Crea 1950). The acid fractionation factor used for calcite was 1.01044

3
 Kamphaugite-(Y).

at 25 ºC (Kim & O’Neil 1997). Isotopic ratios were measured in a Finnigan MAT 251
mass spectrometer. The international standards NBS-18 and NBS-19 were measured
concurrently yielded experimental errors of less than ± 0.1‰ (1σ) for δ13C and δ18O
determinations.

X-ray diffraction and thermal analysis From the X-ray powder patterns, and
considering a tetragonal symmetry, the following unit cell parameters have been
calculated for La Cabrera kamphugite-(Y): a = b = 7.449(4) Å, c = 21.793(4) Å, RW
factor 0.00151, and V = 1209.3(0) Å3. These data are in excellent agreement with those
given by Raade & Brastad (1993) and Rømming et al. (1993), which are the only
cristallographic data published to date for this mineral together with those of Fehér et al.
(2003).
The DTA curve for kamphaugite-(Y), Fig. 1, shows three endothermic effects at
342, 430 and 754 ºC. The first one, a very small effect, is ascribed to dehydration and
the second and third one to dehydroxilation and decomposition reactions. The curve TG
shows four steps at temperature intervals 80-380, 400-450, 450-600 and 600-780 ºC
with weight losses of 4.0, 12.4, 10.8 and 12.6%, respectively. The first step, with a
weight loss at a very low rate, may correspond with the existence of zeolitic water,
which agrees with the structural considerations of Rømming et al. (1993) and Fehér et
al. (2003). The following steps correspond to the OH and CO2 groups loss through
complex reactions probably with metastable formation of CaCO3, in a process similar to
the one described by Wiedemann & Bayer (1987) for dolomite decomposition.
Moreover, the TG cooling curve shows a weight increase of 1.2% in the temperature
interval of 450-400 °C which can correspond to the CO2 absorption by carbonatation of
CaO.
Chemical composition EPMA results for the La Cabrera kamphaugite-(Y), with their
standard deviations, are given in Table 1. The measure of C by volumetric
determination as CO2 is 29.7 %wt. Using the H2O-TG measure, including zeolitic
water, and assumed (F+OH)=1, results to 7 oxygen the structural formula:
Ca0.94Y0.89REE0.21(CO3)2[F0.05(OH)0.95] ·1.19H2O. The 1.19 H2O per formula unit (pfu)
seems to agree with the considerations of Fehér et al. (2003).
The kamphaugite-(Y) spherical aggregates display a concentric and alternative
composition zoned, as can be observed in Fig. 2. The boundaries between zones are not
always sharp, and the most significant chemical variations are in the REE and Y

4
 Kamphaugite-(Y).

contents. Quantitative measurements in several different section diameters yield a

positive correlation between Y and Yb, as is common in other yttrium minerals
(Voloshin et al. 1983), given the analogous physicochemical behaviour of both
elements. On the contrary, negative correlations were obtained between these elements
and the other REE as well as Ca. Thus, it seems that the main substitutions for
kamphaugite-(Y) are: Y-1REE1 and Ca-3REE2, which would explain the Ca cationic
deficit in this mineral. Th and U contents are highly variable, though always low. We
suggest that the actinide elements enter the kamphaugite-(Y) structure by means of
substitutions such as: Ca-2(U,Th)1.
The chondrite normalized REE pattern for kamphaugite-(Y) is showed in the
Fig. 3. For comparison the only other three kamphaugite-(Y) data available are shown.
The pattern show an enrichment in heavy REE, but an small negative anomaly in Yb is
observed. In the La Cabrera kamphaugite-(Y), it could be explained because a Yb-
enriched secondary xenotime-(Y) is formed during the hydrothermal process.

Stable isotopes Kamphaugite-(Y) and calcite from La Cabrera display very negative
δ13C values, ranging between -14.16 and –15.26‰ and from –18.45 to –11.40‰ (V-
PDB) respectively (Table 2). δ18O values in Kamphaugite-(Y) are +24.82 to +25.91‰
and for the calcites ranging between +19.3 to +23.2‰ (V-SMOW).

Discussion Possibly the world scarcity of kamphaugite-(Y) deposits has not allowed
much studies on its formation conditions, rarely temperature. Neither its yttrium origin,
except in the samples studied by Raade & Brastad (1993). Nevertheless, its associated
mineralogy suggests a low temperature hydrothermal origin (Raade & Brastad 1993;
Gamboni & Gamboni 1998; Petersen et al. 2001; Wallwork et al. 2002).
In the La Cabrera pluton yttrium has been removed from magmatic and
pegmatitic minerals by an hydrothermal process. This yttrium is incorporated in the
fluids probably in the form of CO32- and F complexes (Moller 1989). The occurrence of
fluorite, fluorapatite, fluorapophyllite and ubiquitous calcite, together with tvetite-(Y)
and bästnaesite-(Y) inclusions in garnets, suggest that such process has taken place.
As a consequence, several Y-rich minerals are formed during the temperature
drop: kainosite-(Y), neo-formed xenotime-(Y) and thalenite-(Y). The first one is the
most common, sometimes as a by-product of gadolinite-(Y) alteration by carbonatation
and Fe-1Ca interchange. Thalenite-(Y) is rare. Nevertheless we have showed that most

5
 Kamphaugite-(Y).

of the yttrium is incorporated to other medium to low temperature minerals such as

titanite (occasionally up to 6.15 wt% as Y2O3), allanite-(Ce), (occasionally up to 11.36
%wt as Y2O3), epidote and rarely vigezzite.
At low temperature, corresponding with the end of the zeolite cystallization,
appears agardite-(Y), González del Tánago & González del Tánago (2002), which is
formed as a result of arsenopyrite oxidation leading to local high As activity.
The textural kamphaugite-(Y) relationship with calcite, laumontite and
commented minerals, and postdate kainosite-(Y), suggest it is the latest yttrium mineral,
after zeolitic formation, perhaps contemporaneous to agardite-(Y).
Most of the yttrium entering kamphaugite-(Y) would be origined from the
alteration of gadolinite-(Y). Sometimes it is observed that bavenite occurs in close
association with kamphaugite-(Y). This could indicate that gadolinite-(Y) was the
yttrium and beryllium source for both minerals, although so far we have found no direct
evidence to support this hypothesis.
Kamphaugite-(Y) displays (Table 2) very negative δ13C values (–14.16 and –
15.26‰ V-PDB) close to the calcite values (–18.45 to –11.40‰ V-PDB). For this
reason, sources for this carbon such as sea water, dissolution of primary precipitated
marine limestone, atmospheric CO2 and magmatic CO2 can be discarded (Craig 1953;
Keith & Weber 1964; Hoefs 1980; Kyser 1986). On the contrary, these values are
typical of carbonates precipitated from meteoric waters, in which the main source of
carbon has an edaphic origin (Talma & Netterberg 1983; Salomons & Mook 1986;
Cerling 1984 and 1991). Although values as negative as –18.45‰ are not common in
this type of carbonates (Cerling 1991), they can be explained considering that in lightly
acid soil-water, typical of granitic rocks, the isotopic composition of the Dissolved
Inorganic Carbon (DIC) has a lower isotopic fractionation with respect to the edaphic
CO2, whereas at pH>7.5 the DIC is enriched around 10‰ (Romaneck et al. 1992).
Values similar to those from La Cabrera have been reported by Reyes et al. (1998) in
fracture-filling carbonates in the El Berrocal granitic pluton (also in the Spanish Central
System), where the DIC of the present underground waters have values between –20.7
and –17.4‰. The present δ13C values of DIC in La Cabrera ranging between –9.9‰ and
-21‰ (Lozano 2003). Consequently isotopic values of associate calcites and actual
water corroborate this superficial origin for the carbon of Kamphaugite-(Y), see Fig. 4.

6
 Kamphaugite-(Y).

In order to estimate the formation temperature of kamphaugite-(Y), its δ18O

value has been measured, as well as those from calcites (Table 2). Although there are no
specific thermometric equations for kamphaugite-(Y), the use of other equations, such
as those for calcite or stroncianite (O’Neil et al. 1969) yielded similar temperature,
indicating always very low temperature values (< 50 °C), as can be seen in Fig. 5. In
addition, when the theoretical Meteoric Calcite Line (MCL) is represented it is possible
to observe that calcite and kamphaugite-(Y) samples are located near the MCL, shows
its superficial temperature origin (Fig. 4). The slightly more positive δ18O kamphaugite-
(Y) values can be related with an origin at lower temperatures and/or equilibrium with
less negative water (see Fig. 4). Consequently, calcite and kamphaugite-(Y) have been
originated at similar low temperature conditions but in different episodes. The cooling
18
of hydrothermal water, lightly enriched in O due to water-rock interaction and/or
evaporation processes, and the mixing with water from a more open system (rich in
DIC) could explain this values.

Acknowledgements. F. Rives, provided the first material for this study. Electron
microprobe analyses and photos were performed with the useful help of A. Fernández
Larios. The graphics assemblage was made by J. González del Tánago Chanrai. We
express our sincere thanks to all these persons, as well as to J. Suarez and C. Iñigo for
interesting suggestions and English version. G. Raade for the critical reading of a first
manuscript.

References

BELLIDO, F. 1979. Estudio petrológico y geoquímico del Plutón de La Cabrera. Ph. D.

thesis, Univerisdad. Complutense, Madrid.

CABALLERO, J.M., CASQUET, C., GALINDO, C., GONZÁLEZ CASADO, J.M.,

SNELLING, N. & TORNOS, F. 1992. Dating of hydrotermal events in the
Sierra de Guadarrama, Iberian Hercynian Belt, Spain. Geogaceta 11, 18-22.

CERLING, T.E. 1984. The stable isotopic composition of modern soil carbonate and its
relationship to climate. Earth Planetary Scinces Letters 71, 229-240.

7
 Kamphaugite-(Y).

CERLING, T.E. 1991. Carbon dioxide in the atmosphere: evidence from Cenozoic and
Mesozoic paleosoils. American Journal Science 291, 377-400.

CRAIG, H. 1953. The geochemistry of the stable carbon isotopes. Geochimica et

Cosmochimica Acta 3, 53-92.

FEHÉR, B., SKAKÁLL, S. & NAGY, G. 2003. Kamphaugite-(Y), a rare hydrous Ca-
Y-carbonate mineral from Szarvaskő, Bükk Mountains, Hungary. Acta
Minereralogy and Petrology., Abstracts series 1, Szeged, 30.

GAMBONI, A. & GAMBONI, T. 1998. Kamphaugite di Cala Francese. Revista

Mineralogica Italiana 12, 27-28.

GONZÁLEZ DEL TÁNAGO, J. 1997. Allanita-(Nd) y minerales de elementos raros en

las pegmatitas de La Cabrera, Madrid (Sistema Iberico Central). Revista Sociedad
Geológica de España 10, 83-105.

GONZÁLEZ DEL TÁNAGO, J. & LA IGLESIA, A. 1998. Zeolitas y minerales cálcicos

de baja temperatura en las pegmatitas graníticas del plutón de La Cabrera (Sistema
Central Español). Estudios Geológicos 54, 181-190.

GONZÁLEZ DEL TÁNAGO, J. & GONZÁLEZ DEL TÁNAGO CHANRAI, J. 2002.

Minerales y Minas de Madrid. Comunidad de Madrid & Mundiprensa, Madrid,
Spain. 271 pp.

GONZÁLEZ DEL TÁNAGO, J., BELLIDO, F. & GARCÍA CACHO, L. 1986.

Mineralogía y evolución de las pegmatitas graníticas de La Cabrera (Sistema
Central Español) Boletin. Instituto Geológioco y Minero de España 97, 103-121.

GONZÁLEZ LAGUNA, R., LOZANO, R. & CASQUET, C. 2000. Efectos de la

alteración hidrotermal en los minerales accesorios del granito de La Cabrera
(Sistema Central Español). Estudio al microscopio electrónico de barrido (SEM +
EDS). Boletin Sociedad Española de Mineralogía 23, 135-151.

8
 Kamphaugite-(Y).

HOEFS, J. 1980. Stable Isotope Geochemistry. Springer Verlag, Berlin, Germany.

HOGARTH, D.D. 1972. The Evans-Lou Pegmatite, Quebec: A unique Yttrium-Niobium-

Bismuth-Vanadium Mineral Assemblage. Mineralogical Record 3, 69-79.

JAROSEWITH, E. & LA BOATNER, L.A. 1991. Rare-Earth Element Reference Samples

for electron microprobe analysis. Geostandars Newsletters 15, 397-398.

JAROSEWITH, E., NELEN., J.A. & NORBERG, J.A. 1980. Reference samples for
electron microprobe analysis. Geostandars Newsletters 4, 43-47.

KEITH, M.L. & WEBER, J.N. 1964. Isotopic composition and environmental
classification of selected limestones and fossils. Geochimica et Cosmochimica
Acta 28, 1787-1816.

KIM, S.T. & O´NEIL, J.R. 1997. Equilibrium and nonequilibrium oxygen isotope
effects in synthetic carbonates. Geochimica et Cosmochimica Acta 61, 3461-
3475.

KYSER, T.K. 1986. Stable isotope variations in the mantle. In Stable Isotopes in High
Temperature Geological Processes (J.W. Valley, H.P. Taylor, Jr, & H.R. O`Neil,
eds.). Reviews in Mineralogy 16, 141-164.

LOZANO, R. 2003. Petrología de los rellenos cálcicos hidrotermales de las cavidades

miarolíticas del plutón de La Cabrera (Madrid). Ph.D. thesis, Universidad
Complutense, Madrid, Spain.

MCCREA, J.M. 1950. On the isotopic chemistry of carbonates and a paleotemperature

scale. Journal of Chemical Phyisics 18, 849-857.

MÖLLER, P. 1989. REE(Y), Nb, and Ta Enrichment in Pegmatites and Carbonatite-

Alkalic Rock Complexes. In Lanthanides, Tantalum and Niobium. Procedings of a
workshop in Berlin (P. Möller, P. Černý. & F. Saupé, F., eds.), 103-144.

9
 Kamphaugite-(Y).

O´NEIL, J.R., CLAYTON, R.N. & MAYEDA, T.K. 1969. Oxygen isotope
fractionation in divalent metal carbonates. Journal of Chemical physics 51,
5547-5558.

ORLANDI, P. 1997. Zibaldone di mineralogia italiana. Revista Mineralogica Italiana

11, 179-185.

PÉREZ DEL VILLAR, L., PELAYO, M., CÓZAR, J. S., DE LA CRUZ, B.,
PARDILLO, J., REYES, E., CABALLERO, E., DELGADO, A., NUÑEZ, R.,
IVANOVICH, M. & HASLER, S.E. 1997. Mineralogical and geochemical
evidence of the migration/retention processes of U and Th in fracture fillings
from the El Berrocal granitic site (Spain). Journal of Contaminat Hydrology 26,
45-60.

PÉREZ SOBA, C., VILLASECA, C. & GONZÁLEZ DEL TÁNAGO, J. 2003. Zircon
chemistry in Hercynian granites and granulites: some petrogenetical relationship.
Actas IV Congreso Ibérico de Geoquímica, Coimbra, 78-80.

PETERSEN, O.V., GAULT, R.A. & JAHN, S.J. 2001. Kamphaugit-(Y) von der
Rössing-Mine In Namibia, Zauberwelt edler Steine und Kristalle (S. Jahn, O.
Medenbach, G. Nidermayr & G. Schneider, eds.). Bode Verlang GmbH,
Germany.

PLATA, A. 1994 Composición isotópica de las precipitaciones y aguas subterráneas de la

Península Ibérica. Centro de Estudios y Experimentación de Obras Públicas
(CEDEX), Madrid, Spain.

RAADE, G. & BRASTAD, K. 1993. Kamphaugite-(Y), a new hydrous Ca-(Y,REE)-

carbonate mineral. European Journal of Mineralogy 5, 679-683.

RAADE, G., SÆBØ, P.C., AUSTRHEIM, H. & KRISTIANSEN, R. 1993. Kuliokite-(Y)

and its alteration products kainosite-(Y) and kamphaugite-(Y) from granite
pegmatite Nørdal, Norway. European Journal of Mineralogy 5, 691-698.

10
 Kamphaugite-(Y).

REYES, E., PEREZ DEL VILLAR, L., DELGADO, A., CORTEZZI, G., NÚÑEZ, R.,
PELAYO, M. & COZAR, J.S. 1998. Carbonation processes at the El Berrocal
natural analogue granitic system (Spain): Inferences from mineralogical and stable
isotope studies. Chemical Geology 150, 293-315.

ROMANEK, C. S., GROSSMAN, E.L. & MORSE, J.W. 1992. Carbon isotopic
fractionation in synthetic aragonite and calcite: Effects of temperature and
precipitation rate. Geochimica et Cosmochimica Acta 56, 419-430.

RØMMING, C., KOCHARIAN, A.K., & RAADE, G. 1993. The crystal structure of
kamphaugite-(Y). European Journal of Mineralogy 5, 685-690.

SALOMONS, W. & MOOK, W.G. 1986. Isotope geochemistry of carbonate in the

weathering zone. In Handbook of Environmental Isotope Geochemistry 2. The
Terrestrial Environment (P. Fritz & J.Ch. Fontes, eds.). Elsevier, 239-268.

TALMA, A.S. & NETTERBERG, F. 1983. Stable isotope abundances in calcretes. In

Residual Deposits: Surface Related Weathering Processes and Materials (R.C.
Wilson, ed). Blackwell, 221-233.

TAYLOR, S.R. & MCLENNAN, S.M. 1985. The continental crust. Its composition and
evolution. Blackwell Sci. Pub., Oxford. U.K.

TORNOS, F., DELGADO, A., CASQUET, C. & GALINDO, C. 2000. 300 Million years
of episodic hydrothermal activity: stable isotope evidence from hydrothermal rocks
of the Eastern Iberian Central System. Mineralium Deposita 35, 551-569.

VILLASECA, C., & HERREROS, V. 2000. A sustained felsic magmatic system: the
Hercynian granitic batholith of the Spanish Central System. Transactions of the
Royal Society of Edinburgh: Earth Sci. 91, 207-219.

11
 Kamphaugite-(Y).

VILLASECA, C., BARBERO, L., HUERTAS, M.J., ANDONAEGUI, P. &, BELLIDO,

F. 1993. A Cross-section Through Hercynian Granites of Central Iberian Zone.
Excursion Guide. Servicio de Publicaciones, C.S.I.C, Madrid, Spain.

VOLOSHIN, A.V., PAKHMOVSKIY, Y.A., MEN´SHIKOV, Y.P., POVARENNYKH,

A.S., MATVIYENKO, A.S. & YAKUBOVICH, O.V. 1983. Hingganite -Yb a
new mineral species from the amazonitic pegmatites of the Kola peninsula. Doklay
Academy Sciences Nauk SSSR 270, 1188-1192 (in Russian).

WALLWORK, K., KOLITSCH, U., PRING, A., & NASDALA, L. 2002.

Decrespignyite-(Y), a new copper yttrium rare earth carbonate chloride hydrate
from Paratoo, South Australia. Mineralogical Magazine 66, 181-188

WIEDEMANN, H.G. & BAYER, G. 1987. Notes of the thermal decomposition of

dolomite. Thermochimica Acta 121, 479-485.

Figure captions

Fig. 1. DTA and TG curves of the La Cabrera kamphaugite-(Y)

Fig.2. Backscattered electron image of an equatorial section radial aggregate of

kamphaugite-(Y). The whiter zones are richer in REE relative to Y.

Fig. 3. Chondrite normalized REE patterns for world available data of kampahugite-(Y)
Data chondrite values, Taylor & McLennan (1985). La Cabrera, this work, triangles;
Hørtekollen (Raade & Brastad 1993), stars; Rössing (Petersen et al. 2001), circles;
Szarvaskő granite (Fehér et al. 2003), squares.

Fig. 4. δ13C (V-PDB)/δ18O (V-SMOW) diagram of La Cabrera calcites and

kamphaugite-(Y).

12
 Kamphaugite-(Y).

Note that the isotopic values plot close to the present Meteoric Calcite Line
(MCL). The δ18O value (+24‰ V-SMOW) of the MCL has been calculated using the
equation of Kim and O’Neil (1997) for the system calcite-water, the average
temperature (9.5ºC) and δ18O (-7.6 ‰ V-SMOW) of groundwater at the Iberian Central
System (Plata 1994; Pérez del Villar et al. 1997).

Fig. 5. Temperature and δ18O (V-SMOW) values of mineralising waters.

The curves represent the theoretical temperature of formation of calcites and
kamphaugite-(Y) in equilibrium with meteoric waters of different isotopic values.
Considering superficial temperatures (10 ºC to 20 ºC) and the isotopic range of calcites
(δ18O = +19.1 to +23.2‰ vs. V-SMOW) it possible to obtain an isotopic range for the
origin water coincident or/and including more frequent present rain water and
groundwater (-9.5‰ to -6‰). The Kim and O’Neil (1997) and O’Neil et al.(1969)
equations were used to relate temperature with isotopic fractionation in the systems
calcite-water and strontiantite (kamphaugite-Y) respectively. The dotted line represents
the values of kamphaugite-(Y).

13
 Kamphaugite-(Y)

TABLE 1. EPMA AVAILABLE WORLD DATA OF KAMPHAUGITE-(Y).

La Cabrera Hørtekollen Rössing Szarvaskő
σ(51) σ(5)
SiO2 0.04 0.02 na na na
P2O5 0.12 0.11 na na na
CaO 17.84 1.06 18.40 0.2 15.11 20.07
Y2O3 33.83 2.61 30.50 0.3 27.12 29.72
La2O3 0.05 0.02 na na 0.10
Ce2O3 0.24 0.10 na na 0.93
Pr2O3 0.10 0.07 na na 0.33
Nd2O3 0.51 0.10 1.40 0.3 1.47 2.13
Sm2O3 0.55 0.24 0.80 0.3 2.03 1.55
Eu2O3 0.14 0.11 na na 0.53
Gd2O3 1.98 0.48 na 3.57 3.26
Tb2O3 0.76 0.29 1.60 0.3 0.81 0.63
Dy2O3 3.91 0.93 na 5.58 4.91
Ho2O3 0.64 0.19 2.20 0.4 1.27 0.99
Er2O3 2.24 0.55 1.20 0.1 2.59 2.74
Tm2O3 0.17 0.09 na 0.37 0.50
Yb2O3 1.07 0.24 1.10 0.3 1.07 1.65
Lu2O3 0.70 0.17 na na 0.43
ThO2 0.14 0.10 na na na
UO2 0.15 0.09 na na na
F 0.29 0.10 na 0.81 na
Total 65.41 57.10 61.91 70.47
Total F≡O 65.28 61.57

Hørtekollen: Raade & Brastad (1993); Rössing: Petersen et al. (2001); Szarvaskő: Fehér
et al. (2003). Number of analyses for each calculated standard deviation is given in
brackets. “na” = no analysed. La Cabrera kamphugite-(Y) structural formula based on
2.5 oxygens:
Si<0.01Ca0.90P<0.01Y0.84La<0.01Ce<0.01Pr<0.01Nd0.01Sm0.01Eu<0.01Gd0.03Tb0.01Dy0.06Ho0.01Er0.03Tm<0.01
Yb0.02Lu0.01Th<0.01U<0.01F0.04. Totalising 1.99 cations (ΣREE = 0.20; and Y/Σ(Y+REE) = 0.81)

1
TABLE 2. δ13C AND δ18O VALUES OF KAMPHAUGITE-(Y) AND CALCITE
FROM THE LA CABRERA PLUTON.

Mineral Sample δ13C ‰ δ18O ‰

(PDB) (V-MOW)
Calcite J-2 -16.45 19.13
Calcite CA-M -18.45 19.99
Calcite J-1 -15.78 20.23
Calcite CA-5 -15.96 20.46
Calcite J-5 -15.52 20.54
Calcite CA-L -16.72 20.86
Calcite CV-1 -11.40 21.57
Calcite J-6 -15.65 21.92
Calcite J-3 -17.63 22.39
Calcite J-4 -17.16 23.23
Kamphaugite-(Y) Kam-2 -14.16 24.82
Kamphaugite-(Y) Kam-1 -15.26 25.91