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Session 7

Understanding ore systems though

precise geochronology, isotope tracing
and microgeochemistry

Chapter 7-1 7-1

Origin of titanomagnetite-ilmenite mineralization,

Arsentyev gabbro-syenite massif, Transbaikalia, Russia
Roza Badmatsyrenova, Dmitriy Orsoev
Geological Institute SD RAS, Ulan-Ude, Russia

Abstract. The study of endogenic titanomagnetite-ilmenite ores are and have the geochemical signature of alkaline basalts.
of interest as they present a number of petrologic problems. One Two intrusive phases, each of them being followed by for-
such problem is determining their genetic connection with alkali-
mation of dike complexes, form the Arsentyev massif
mafic and mafic complexes and associated phosphorus enrichment.
The Arsentyev gabbro-syenite massif is representative of these sys- (Fig. 1b). The first phase consists of a stratified series py-
tems and provides an ideal situation in which a detailed study al- roxenites, olivine and kersutite gabbros, gabbros, an-
lows further understanding of interrelated magmatic and ore-for- orthosites and syenite. The second phase includes the
mation processes. It is shown that an oxide-ore liquid separated rocks of the syenite series.
from a parental silicate melt during early stages of subalkaline ma-
The titanomagnetite-ilmenite mineralization is con-
fic magma crystallization.
fined to the stratified gabbro-anorthosite series. This min-
Keywords. Liquid immiscibility, geochemistry, ore mineralization eralization is subdivided into syngenetic and epigenetic
by morphological features and degree of localization. The
widespread syngenetic mineralization is represented by
1 Introduction disseminated and net-textured ores while the restricted
epigenetic mineralization is represented by massive ores.
Titanomagnetite-ilmenite ores sourced from various de- As a rule, disseminated ores are confined to apatite-free
posits are considered as a premier source of commercial and apatite ore gabbros and pyroxenites with 10 to 25
iron and vanadium. Select deposits additionally contain vol.% ore minerals. Ore gabbros are advanced among most
significant titanium enrichment providing a mineral differentiated intrusive region, where they alternate with
source for titanium production. Currently ores from large leucogabbro (up to anorthosite) and gabbro.
tonnage, high grade deposits are now mined from The thickness of orebodies are highly variable but pre-
Bushveld (the South Africa Republic), Lac-Tio (Canada), vail as ventricular and vein ore. The massive ores are usu-
Panzhihuan (China), Kachkanar (Russia). Ore occurrences ally contained within area associated with disseminated
are known in the Urals, Kareliya, East Sayan, Transbaikalia, and net-textured ores and are related to protomagmatic
and Far East. The Arsentyev gabbro-syenite massif with fracturing. The contact between ore bodies with host
titanomagnetite-ilmenite mineralization is representative gabbroids are tectonic as a rule.
of this association. Understanding iron ore deposit genesis
is problematic, with particular difficulties in rectifying
magmatic titanomagnetite-ilmenite deposits formation, yet
a comprehensive understanding is essential for exploration.
Therefore, studies identifying genetic processes occupies a
special place in the analysis of ore genesis in magmatic sys-
tems. In addition to fundamental understanding, the study
of already known of ore complexes is necessary for devel-
opment of prospecting criteria and interpretations of re-
sults, which may form the basis for rating production
feasability of titanomagnetite-ilmenate ores.

2 Geological setting and structure

The Arsentyev massif is located at the central part of the

Monostoy ridge west of the Arsentyevka village (Fig. 1a).
The massif outcrops over a 20 km2 area.
The Arsentyev massif is defined by intrusions of sy-
enite-pyroxenite-gabbro with a high titanium ultrama-
fic-mafic association (Badmatsyrenova et al. 2004). These
intrusions are related to rift-like structures of various ages

726 Roza Badmatsyrenova Dmitriy Orsoev

3 Mineral composition and geochemistry ing ore much more exceeds (up to 1.57 wt.%) contents in
ore gabbro and gabbro (0.08 wt.%). Mg concentrates in
The disseminated ores are divided into titanomagnetite- lamella of ilmenite in massive ores are 7.94 wt.%. The
ilmenie ore and apatite-titanomagnetite-ilmenite ore with aluminium in magnetite in massive ores contains up to
apatite contents of 10-15 wt.%. Apatite-titanomagnetite- 1.73 wt.%. The maximum contents Al in rocks are 0.11
ilmenite ores have a subordinate value. Magnetite and il- wt.%. Ilmenite is aluminum-poor (0.06 wt.% Al2O3). Dis-
menite are the main ore minerals. They are intimately solution structures in massive ores are present with Al2O3
associated, forming xenomorphic aggregates interstial to up to 5.55 wt.%. Aluminium in titanomagnetite is associ-
silicate minerals and always crystallizing after the sili- ated with spinel intergrowths.
cates. The grains size varies from 0.04 to 3 mm. They also Amphibole (TiO2 up to 6 wt.%) is identified as an ac-
occur as small inclusions in pyroxene, kersutite and pla- cessory mineral in ores. Large kersutite crystals are dis-
gioclase but in insignificant amounts. The separate grains tinctly brown colour and pleochroic suggesting greater
of magnetite and ilmenite display variable degrees of iso- Fe and Ti content. Analyzed amphibole have the high con-
morphism depending on their quantitative ratio. Both tents Al2O3, Ti and alkalis in comparison with gabbro from
homogeneous magnetite having roughly a pure iron other units.
composition and titaniferous magnetite with dissolution Biotite in massive ore is FeO deficient with proportionaly
structures are observed. Ilmenite also has variable com- more MgO, TiO2, Na2O than in dissiminated ores.
position based on the concentration of Fe3 +. Clinopyroxene composition directly correlates to pla-
In addition to ore minerals and apatite, the ores con- gioclase composition. The most magnesian pyroxene (MgO
tain varying amounts of olivine, pyroxene and plagio- 14.56 wt.%) is associated with the most basic plagioclase
clase. Amphibole and biotite are also present. Sulphides (An40). The pyroxene Mg# changes from 80 to 74 %.
and spinel are present but economically insignificant com- Fayalite olivine is enriched with increasing ore abun-
pared to the apatite-titanomagnetite-ilmenite ores. The dances. Nickel contents correlate with the olivine.
apatite-bearing ores have significantly more sulphides and Apatite is often the only mineral in mafic rocks that
spinel compared to the massive and disseminated iron- yield information about volatile composition. Fluorapa-
titanium ores. tite is found in gabbros and ores of the Arsentyev massif.
The mineral composition of massive ores is rather re- The fluorine contents in ores (1 to 2 wt.%) is noticeably
stricted. The ore is dominated (70-90 vol.%) by aggre- less than in gabbro (2 to 3.5 wt.%). High fluorine and
gates of magnetite, titanomagnetite and ilmenite. Mag- phosphorus concentrations in connection with increased
netite is the dominant ore mineral with a half to a third alkalinity of the primary basalt magma facilitates vola-
as much ilmenite. The grains of ore minerals are larger, tile immiscibility and support ore cluster formation. REE
up to 5 mm, in massive ores compared with disseminated concentrations in apatite from gabbro have typical for
ore minerals. Separate, fine-grained pyrite, pyrrhotite, basalt distribution: the relative concentration of lan-
chalcopyrite, marcasite and pentlandite are present in the thanides increases from HREE to LREE, the degree of di-
ores at insignificant amounts. The constant presence of vision is marginal (La/Yb = 21-36), and a negative Eu-
apatite at insignificant amounts and increased contents ropium anomoly is evident. Conversely, apatite from ores
of spinel (up 10-30%) are characteristic of the massive does not have a negative Europium anomoly. The new
ores. Kersutite is also present. data does not contradict immiscibility of titanomagnetite-
Titanomagnetite from the massive ore contains 6.48 ilmenite ores and apatite formation.
wt.% TiO2 and is seen as thin intergrowths of magnetite, The geochemical data suggest an iron-bearing silicate
ilmenite, spinel and ulvspinel(?). Trellised or reticulated melt of large anion trivalent iron complexes (Fe2O42 -)
titanomagnetite from ore gabbros contain appreciablly formed after oxidation by interaction with alkaline oxide
less TiO2 (0.18-0.91 wt.%). Finally, titanomagnetite from components and water. The predominance of oxidic iron
host gabbros contains only TiO2 (0.06-0.08 wt.%). in magnetite points to an oxidizing environment. It is prob-
The concentration of TiO2 in ilmenite forming lamel- able that the formation of anion complexes Fe2O42- in-
lar inclusion in titanomagnetite found in disseminated stead of cation of bivalent iron facilitates initiation of
ore is 48.68 wt.% while concentration of TiO2 in massive immiscibility in the melt system resulting in an ore-form-
ore is 53.31 wt.%. Spinel in disseminated ores contain 0.1 ing and a silicate liquid.
to 0.3 wt.% TiO2, whereas spinel from massive ores form-
ing tear-shaped structures of immiscibility in magnetite 4 Conclusions
contains TiO2 up 4.94 wt.% and in ilmenite in massive
ore contains 0.96 wt.% TiO2. Manganese concentration Microprobe analysis shows that magnetite, ilmenite, am-
in ilmenite is 0.52 to 1.57 wt.%. Mn in magnetite is 0.07 phibole and biotite of the massive ores are significantly
to 0.19 wt.%. The magnesium contents in magnetite-bear- richer in TiO2, Al2O3, MgO and Na2O than the minerals

Chapter 7-1 Origin of titanomagnetite-ilmenite mineralization, Arsentyev gabbro-syenite massif, Transbaikalia, Russia 727

Conditions favorable for phosphorus induced liquid

immiscibility can be expected in silicate-salt melts
(Krigman, Krot 1991), or immiscibility may be induced
by another component, possibly ferrous iron complexes.
For example, it is possible to form gabbroid complexes
associated with apatite-ilmenite and titanomagnetite
mineralization, which, in opinion of some researchers
(McBirney, Nakamura 1974, Marakushev 1987), is con-
nected to immiscibility decomposition of the parental melt
into a salic and a femic melt, where the latter represent-
ing an ore magma with the contents P2O5 7 to 8%.
Two genetic ore types in the Arsentyev massif are al-
located: the first type, massive titanomagnetite-ilmenite
ores, are of immiscibility genesis while the second type,
of the disseminated ores. The massive ores are character- ore gabbro, formed in result of crystallization differen-
ized by high V (1400 to 1600 ppm), Zn (200 to 500 ppm), tiation of a basalt magma.
and Cr (21 to 36 ppm) concentrations and low concen-
trations of Sr (60 to 210 ppm), Co (73 to 112 ppm) and Acknowledgements
P2O5 (0.06 to 0.21 ppm) compared to the disseminated
ores that have very high concentrations of the main com- This work was supported by the Russian Foundation for
ponents (TiO2, Fe2O3 and FeO). Variations in ore compo- Basic Research (grant No 05-05-97246), Russia President
sitions are illustrated on the ratio plots of petrogenic and grant for leading science school No Sh-2284.2003.5, Rus-
trace elements. A later independent formation of the mas- sian Science Support Foundation.
sive ores is indicated by significantly lower values of Cr/
V and Ni/Co ratios than in the disseminated ores if using References
these ratios as indicators of ore formation stages. Using
Badmatsyrenova RA, Orsoev DA (2004) Computer simulation of
classification based on chemical composition, the ores of titanomagnetite-ilmenite mineralization formation, Arsentyev
the Arsentyev massif belong to the iron-titanium-vana- massif, Transbaikalia, Russia. In: Proc. of the Interim IAGOD Con-
dium type. ference, Vladivostok, Russia, 1-20 September, 2004, pp. 407-410
The study of distribution of noble metals has shown Krigman LD, Krot TV (1991) Stable phosphate-aluminosilicate liq-
that the ores have platinum enrichment: Pt contents of uation in magmetic melts Geokhimia. 11: 1548-1561 (in Russian)
Marakushev AA (1987) Geology and mineralogy of the anorthosite
massive ores are up to 6.3 ppb and Ag contents up to 2.8 associations. Vladivostok, p.17 (in Russian)
ppm while Pt contents of disseminated one are < 2 ppb McBirney A.K., Nakamura Y (1974) Ann. Report Director geophys.
and Ag 1 ppm. Lab. Washington, 348 pp

Chapter 7-2 7-2

Direct dating of ore minerals: A feasibility study of

the Pb-Pb isotope step-leaching technique
K. Bassano, J. Hergt, R. Maas, J. Woodhead
pmd*CRC, School of Earth Sciences, The University of Melbourne, Australia

Abstract. Pb-Pb step-leaching (PbSL) is a digestion technique based quired into the circumstances in which this technique may/
on sequential acid treatment of a mineral resulting in the selective may not be reliably applied.
recovery of radiogenic and common Pb components from the crystal
lattice, making single-phase Pb-Pb dating possible. Developed origi-
nally by R. Frei and colleagues at Bern, the technique was recently 2 Discussion
applied to Proterozoic garnets to test the reliability of PbSL as a
dating tool in multiply deformed terranes (Tonelli 2002). In this study the technique has been applied to well-con-
This study builds on previous observations and tests the reli- strained samples from a number of Australian ore de-
ability of PbSL in directly dating ore minerals such as sulfides (chal-
posits, including the analysis of chalcopyrite and magne-
copyrite, pyrite, pyrrhotite/pentlandite) and oxides (magnetite),
thereby obtaining the timing of mineralisation from a phase that is tite from Broken Hill (BHT), Mt Isa, Ernest Henry (IOCG)
unambiguously linked to the ore-forming process. This is based on and Osborne (IOCG). Magnetite and pentlandite/pyrrho-
the often surprisingly high U contents (relative to what might be tite from the Merensky Reef in the Bushveld Complex have
anticipated), yielding rather higher than expected initial U/Pb ra- also been studied.
tios in several types of low-Pb sulfides. The technique is applied to Studies of chalcopyrite from Copper Blow (Broken Hill)
well-constrained samples from a number of predominately Austra-
lian mineral deposits covering a range of mineralization types.
yielded promising results. Lead isotope ratios obtained,
particularly in the second leach step, indicate the pres-
Keywords. Pb-Pb, step-leaching, ore minerals, direct dating ence of radiogenic Pb with 206Pb/204Pb ratios ranging up
to ~57. As chalcopyrite at Copper Blow occurs with
torbernite (U-rich), typical grains were interrogated us-
1 Introduction ing the SEM to confirm that the Pb compositions reflect
those of the chalcopyrite and not inclusions. Results for
The mechanism of Pb isotope unmixing in step-leaching magnetite from the same deposit display greater spread
was examined by Frei et al. (1997) who proposed two main in the 206Pb/204Pb (~23 to 183). The age estimates obtained
processes; the surface/crystallographic site dependent hy- from these co-genetic minerals are the same (magnetite:
drolysis of metal cations, and the progressive remobilisation 109489Ma; MSWD=250; chalcopyrite: 1071210;
of radiogenic Pb from the leached gel-like structure. Dif- MSWD=213), to within error, although the uncertainties
ferent rates of these processes during progressive leaching are quite large. Unlike the 206Pb/204Pb and 207Pb/204Pb ra-
results in an effective separation of common and radio- tios of these samples, 208Pb/204Pb displays very little varia-
genic Pb, producing generally linear unmixing arrays with tion, retaining values typical of common lead (~37 to 38).
age significance in the 206Pb/204Pb vs 207Pb/204Pb diagram. This indicates that the mineralising fluid from which these
Benefits of PbSL over bulk U-Pb and Pb-Pb techniques phases grew carried U but not Th into the system.
include the ability to: Both chalcopyrite and magnetite were also analysed
from the Osborne deposit. The chalcopyrite displays ra-
detect sub-microscopic U-rich inclusions using the diogenic values (206Pb/204Pb ~20 to 48) that generate an
distinct variations in 208Pb/206Pb (i.e. time-integrated age estimate of 1252190Ma.
Th/U) between host mineral and inclusions such as Preliminary studies at Ernest Henry indicate the
zircon or monazite samples are also highly radiogenic. Chalcopyrite shows a
date a wide range of minerals with low-U; minerals large spread in 206Pb/204Pb (~18 to 257) generating an age
generally thought to be unfavourable for conventional estimate of 159017Ma (MSWD=1). The variation in
U/Pb dating 206Pb/204Pb ratios displayed by the associated magnetite

obtain single-mineral isochron ages without the need is even greater (~214 to 965) although the scatter is con-
for analysing associated minerals to produce isotopic siderable. These data yield a poorly constrained age of
dispersion on isochrons 1044450Ma because, although the range in ratios is con-
siderable, gaps in the array contribute to the large errors
Although previous authors (eg Collerson et al. 2002) obtained as the isochrons become dominated by one or two
have obtained age estimates on (mixed) ore minerals us- points. Further analyses of these samples with varied leach-
ing PbSL prior to this study, further investigation is re- ing protocols produced consistently scattered data sets.

730 K. Bassano J. Hergt R. Maas J. Woodhead

In order to determine if the technique is producing as that determined in the step-leaching experiments of
the correct age estimates, three samples from the silicates (where Si-O bonds are broken during hydrolysis
Merensky Reef in the Bushveld Complex, South Africa reactions). The assessment of trace element mobility is
(two magnetites and one mixed pyrrhotite /pentlandite conducted via analysis of the leachates from different leach
sulfide) where analysed. Samples from this orthomagmatic steps, and comparisons between these and data for bulk-
deposit were selected due to the generally widely excepted separates. Finally, the extent to which variations in the
age of the Bushveld Complex ore system. The resulting initial Pb isotope composition within samples has influ-
leach steps from each of these samples displayed little or enced the scatter in isochrons will be explored. This in-
practically no spread in 206Pb/204Pb and 207Pb/204Pb. The volves the analysis of numerous separate aliquots of ma-
majority of the age estimates generated from this data terial to check for levels of heterogeneity in their Pb iso-
fall within error of the known age of the Merensky Reef, tope compositions.
however the uncertainties are large, most likely due to
the minor data spread. Acknowledgements

3 Evaluation of the leaching process The authors would like to thank the many members of
the pmd*CRC who have provided us with the well-con-
ICPMS trace element analyses of the study samples have strained materials required for this study.
been undertaken in order to examine possible causes for
the apparently variable success of this technique. First, References
the U and Pb contents of bulk-separates will clearly in-
fluence how much radiogenic ingrowth can occur rela- Collerson KD, Kamber BS, Schoenberg R (2002) Applications of ac-
tive to the common Pb component, and hence how great curate, high-precision Pb isotope ratio measurements by multi-
the spread in the Pb isotope ratios may be during step- collector ICP-MS. Chem Geol 188: 65-83
leaching. How this varies between particular ore deposit Frei R, Villa IM, Nagler ThF, Kramers JD, Przybylowicz WJ, Prozesky
types is a central question of this study. Another impor- VM, Hofmann BA, Kamber BS (1997) Single mineral dating by
the Pb-Pb step leaching method: Assessing the mechanisms.
tant question is to determine the factors that control the Geochim Cosmochim Acta 61: 393-414
retention or mobility of different elements (particularly Tonelli M (2002) An evaluation of Pb step leaching geochronology
Pb, but also how this behaves relative to other trace ele- as applied to high-grade metamorphic terranes. PhD Thesis,
ments). The acid leaching mechanism cannot be the same University of Melbourne (unpubl)

Chapter 7-3 7-3

Rutiles in eclogite from the Sulu UHPM Terrane:

A preliminary study
Chen Zhenyu, Chen Yuchuan, Wang Denghong, Xu Jue, Zhou Jianxiong
Institute of Mineral Resources, Chinese Academy of Geological Science, Beijing, 100037, China

Abstract. In recent years more than 40 rutile-bearing eclogite ore bodies 2 Petrography of rutile and titanium minerals in
have been discovered among the thousands of eclogite bodies in eclogite
the Sulu Utra-High Pressure Metamorphic (UHPM) terrene. Rock- and
ore-cores obtained by the Chinese Continental Scientific Drilling
(CCSD) Project revealed the presence of several hundred meters of The rutile ore bodies mainly occur in massive eclogites,
rutile-bearing eclogites. This paper presents a preliminary petro- as strips and lenses. Rutile-bearing eclogites have at least
graphic, trace element, and Pb isotope study of rutile ores in eclogite. three different occurrences: (1) xenoliths in ultra-mafic
Rutiles occur as inclusions, intergranular infillings, remnant replace- serpentines, e.g. in Xugou and Jiangzhuang; (2) lenses in
ments, and hydrothermal infillings in the host rocks. The ore minerals
marbles e.g. in Yanmachang and Banzhuang; (3) meta-
define four stages of rutile mineralization and metamorphic evolu-
tion in the eclogites. Electron microprobe (EMP) trace element analysis morphosed intrusive complex rocks in Donghai. The
of three rutile specimens show that different occurrences of eclogite eclogites show variable mineral assemblages and chemi-
also have different trace element compositions in rutile. These com- cal compositions, and indicate diverse origins for their
positional differences may reflect different source rocks for the protoliths (Zhang et al. 2004). The observation and docu-
eclogites. Peak metamorphic temperatures were calculated using the mentation of both the rock- and ore-cores obtained by
Zr geothermometer in rutile. The Pb isotopic compositions of rutile
obtained by step-fuse analysis of single grains of rutile did not fall on
CCSD reveal that the major titanium mineral phases of
one growth line, but show similar variation between different samples. economic interest are rutile and titano-magnetite. The
This implies that the Pb isotopic compositions of rutile may have been most important ore-bearing rock types are normal rutile
disturbed during its growth. This variation could be used to trace the eclogite, quartz eclogite associated with phengite-rutile
growth history of the rutile, and further to trace the process of conti- eclogite and kyanite-rutile eclogite. The modal content
nental subduction- exhumation.
of rutile in eclogite is 2%~5% (vol.) and is as high as
Keywords. Rutile, eclogite, petrography, trace elements, Pb isotope, 8%~10% (vol.) (Xu et al. 2004).
Sulu UHPM terrene Detailed petrographic investigation reveals that rutile
in eclogite mostly occurs in four types: (1) as inclusions
in garnets, omphacites or zircons, which may have crys-
1 Introduction tallized during prograde metamorphism (coesite or its
pseudomorph can be found coexisting with rutile in the
The Sulu ultra-high pressure metamorphic (UHPM) terrene same garnet, omphacite or zircon host); (2) as intergranu-
is the product of the Triassic collision involving the north lar infilling grains between garnets and omphacites. In
China and Yangtze cratons. There are thousands of eclogite
bodies of different size and occurrence in the UHPM belt
in the Sulu terrene, and more than 40 rutile-bearing eclogite
ore bodies have been recently discovered. The total reserves
of rutile ore amount to several million tons (Huang J P., et
al. 2003). The main hole of the Chinese Continental Scien-
tific Drilling (CCSD) project is located at Maobei, Donghai,
in the southern part of the Sulu UHPM terrene (a simpli-
fied geological map is showed in Fig. 1). Drilling to 5100m
at this locality has recently completed. Rock- and ore-cores
obtained by the CCSD revealed rutile-bearing eclogites
amounting to several hundred meters (Xu et al. 2004).
The rutile deposit in the Sulu UHPM terrene is a typi-
cal eclogite-type rutile deposit. To assess the relationship
between UHPM and the mineralization of rutile in
eclogite, we have conducted a preliminary study on the
rutile from the main hole of the CCSD. In this study we
focus on the different rutile occurrences, petrography,
trace element composition and Pb isotopic composition.

732 Chen Zhenyu Chen Yuchuan Wang Denghong Xu Jue Zhou Jianxiong

this stage, metamorphism reached its peak conditions,

and rutile crystallized simultaneously with eclogite-face
minerals such as garnets and omphacites. This is the main
crystallization stage of rutile; (3) as replacement remnant,
at the amphibolite-face retrograde metamorphism stage.
Garnets and omphacites are altered to hornblende and
plagioclase. Rutlie is also partly altered to ilmenite or
titanite; (4) as hydrothermal infilling forms. Rutile fills in
the cleavages and cracks as veins, strings or megacrysts.
This rutile occurrence may have crystallized at the content of these elements, averaging 615ppm, 324ppm,
greenschist-facies metamorphic stage. At this time, hy- 3457ppm and 3333ppm for Cr, Nb, Fe and V respectively.
drothermal fluids extracted components of mineraliza- In the Nb-Cr diagram defined by Zack, et al. (2004b),
tion from wall rocks and deposited them in cleavages and protoliths of these three eclogites all plot in the mafic
cracks in the rocks. On the other hand, the early rutile rocks field. Temperature calculated from Zr content
phase is partly or totally altered to ilmenite or titanite. As in rutile showed that the peak temperature of meta-
for the above-mentioned four occurrences, the second one morphism for these eclogites was 550~575o for Qing-
is the most abundant, and accounts for about 90% of the longshan, 565~615 o for Banzhuang and ~716 o for
gross rutile ore reserves. Rutile and titano-magnetite that Machang. These temperature values are comparable with
were altered to ilmenite and titanite during retrogressive those calculated by the cation-exchange geothermometer
metamorphism led to a drop in grade of the titanium of host minerals.
4 Pb isotopic composition of rutile
3 Trace elements in rutile
To obtain the U-Pb age of rutile in eclogite from the Sulu
Rutile has long been considered to be an important car- UHPM terrene, we selected three rutile specimens for U-
rier of high field strength elements (HFSE; Zr, Nb, Mo, Pb isotope analysis by the step-fuse method. Unfortunately,
Sn, Sb, Hf, Ta, W). It also plays a key role in subduction we could not obtain a correct age because of the very low
zones by retaining HFSE in the restite/residuum during content of radiogenic Pb isotopes in rutile. But, to our
dehydration and melting reactions. Recent studies by surprise, the Pb isotopic compositions (206Pb/204Pb, 207Pb/
Zack et al. (2002, 2004a, 2004b) show that the trace ele- 204Pb, 208Pb/204Pb) obtained from a series of step-fuse

ments in rutile can give us more information than just analyses of a single grain from its shell to its core can not
the dominant control of HFSE in eclogite. For example, be plotted on one growth line. This means that Pb isoto-
the Nb, Cr content in rutile can be used to distinguish pic ratios can not be attributed to in-situ Pb growth. Franz
different protoliths of rutile-bearing eclogites. Addition- et al. (2001) found a similar phenomenon when they tried
ally, the Zr content in rutile is temperature dependent to determine the U-Pb age of a rutile specimen in an
and can be used as a geothermometer in rutile. In this eclogite-facies quartz vein within a metabasalt in South
study, we used a JXA-8800R electron microprobe to de- Dabieshan. In their case, one 4-cm-long single crystal was
termine the trace element composition of rutiles in divided into 3 small fragments, and each fragment was
eclogites from Machang, Qinglongshan and Banzhuang. analyzed. The isotopic variability among these fragments
The Machang and Qinglongshan samples occur in meta- was too large to be attributable to in situ Pb growth, and
morphosed intrusive complex rocks, and the Banzhuang patterns on the 206Pb/204Pb-207Pb/204Pb and 206Pb/204Pb-
samples occur as lenses in marbles. Particular operating 208Pb/204Pb are incompatible with secondary addition or

conditions were used to obtain low detection limit (20kV, removal of Pb (Franz et al. 2001) . The rutile in the quartz
100nA and 100~300s counting time, which resulted in a vein may have been crystallized in the retrograde fluid,
detection limit of elements of interest in the 20~30ppm so they considered the initial Pb composition of this speci-
range). Analytical results (Table 1) show that rutiles in men to be isotopically heterogeneous, which implies that
eclogite from Machang have the lowest content of Cr and the Pb in the fluid is isotoptically variable during rutile
Nb, averaging ~89ppm and mostly below the detection crystallization. In our case, the Pb isotopic compositions
limit. However, these rutiles also have the highest Fe and of these three specimens have shown abrupt variations
V content, averaging 5390ppm and 3853ppm respectively. at a certain middle step and at the final step of fuse analysis
Rutiles in eclogite from Banzhuang show the highest Cr in a similar way. This implies that these three rutile speci-
and Nb content, averaging ~1574ppm and ~385ppm re- mens have similar Pb growth history. The two abrupt
spectively; but they also show the lowest Fe and V con- variations indicate that Pb isotopic compositions of rutile
tent, averaging 2602ppm and 2114ppm respectively. were disturbed twice during its crystallization. These dis-
Rutiles in eclogite from Qinglongshan have moderate turbances may reflect the variation of geologic settings

Chapter 7-3 Rutiles in eclogite from the Sulu UHPM Terrane: A preliminary study 733

during rutile growth, which can be used to infer conti- Acknowledgements

nental subduction-exhumation processes. This suggests
to us that the variation of Pb isotopic composition in rutile This study is supported by the Major State Basic Research
by step-fuse analysis may be used to trace the growth Development Program (2003CB716501). We thank Parham
history of the rutile, and further to trace the process of Gardner for her critical reviews, which improved this pa-
continental subduction- exhumation. Although this is a per significantly.
preliminary discussion and needs further study and more
evidence to support it, this approach has shown great References
potential in the study of the geodynamics of subduction
zones. Franz L, Romer RL, Klemd R, Schmid R, Oberhansli R, Wagner T, Dong
S (2001) Eclogite-facies quartz veins within metabasites of the Dabie
Shan (eastern China): Pressuretemperature-time- deformation path,
5 Conclusions composition of the fluid phase and fluid flow during exhumation of
high-pressure rocks. Contrib Mineral Petrol 141: 322-346
The rutile deposit in the Sulu terrene is genetically re- Huang JP, Ma DS, Liu C, Wang CL (2003) Character and origin of
lated to the UHPM. Rutile is mainly mineralized during rutile deposit in eclogite in Xiaojiao, Xinyi, Jiangsu province.
eclogite-facies metamorphism. The alteration by retro- Geoscience 17: 435-443
gressive metamorphism leads to a drop in grade of the Xu J, Chen YC, Wang DH, Yu JJ, Li CJ, Fu XJ, Chen ZY (2004) Titanium
mineralization in the ultrahigh-pressure metamorphic rocks
titanium mineralization.
from Chinese Continental Scientific Drilling 100~2000m main
EMP was used to obtain trace element composition hole. Acta Petrologica Sinica 20: 119-126
of different occurrences of rutile in eclogites. These analy- Yang JJ, Jahn BM. (2000) Deep subduction of mantle-derived garnet
ses show variations in Nb, Cr, Fe and V content between peridotites from the Su-Lu UHP metamorphic terrane in China.
each occurrence, which may be used to infer the protolith J. metamorphic Geol., 18: 167-180
of these eclogites. Temperatures calculated from the Zr Zack T, von Eynatten H, Kronz A (2004b) Rutile geochemistry and
its potential use in quantitative provenance studies. Sediment
geothermometer in rutile are comparable with the re-
Geol. 171: 37-58
sults from other methods. This implies that the Zr Zack, T, Kronz, A, Foley S., River T (2002) Trace element abundances
geothermometer in rutile is a feasible and effective in rutiles from eclogites and associated garnet mica schists. Chem.
method for calculating peak metamorphic temperatures. Geol. 184: 97-122
Pb isotopic compositions obtained from step-fuse Zack, T, Moraes, R, Kronz A (2004a) Temperature dependence of Zr
analysis of single grains of rutile may be potential trac- in rutile: empirical calibration of a rutile thermometer. Contr.
Min. Petrol. 148: 471- 488
ers of rutile growth history. If so, this analytical tech-
Zhang ZM, Xu ZQ, Liu FL, Shen K, Yang JS, Li TF, Chen SZ (2004)
nique could play an important role in furthering the un- Geochemistry of eclogites from the main hole (100~2050m) of
derstanding of continental subduction- exhumation pro- the Chinese Continental Scientific Drilling Project. Acta
cesses. Petrologica Sinica 20: 27-42

Chapter 7-4 7-4

A non-magmatic component in fluids of South

American Fe oxide-Cu-Au deposits inferred from
37Cl, 87Sr/86Sri and Cl/Br
M. Chiaradia1, D. Banks, R. Cliff
School of Earth Sciences, University of Leeds, Leeds LS2 9JT, U.K.
Present address: Department of Mineralogy, University of Geneva, 1205-Geneva, Switzerland
R. Marschik
Department of Earth and Environmental Sciences, Ludwig-Maximilians University, 80333-Mnchen, Germany
A. de Haller
Department of Mineralogy, University of Geneva, 1205-Geneva, Switzerland

Abstract. The magmatic versus basinal brine origin of the hypersa- range between 3 and 7 (Magenheim et al. 1995) whereas
line fluids associated with iron oxide-copper-gold (IOCG) deposits crustal chlorine has 37Cl values around 0 (Eggenkamp
is controversial. In this study we present and discuss the first stable
et al. 1995). In principle, therefore, chlorine isotopes are
chlorine and strontium isotope data, combined with Cl/Br ratios, of
inclusion fluids of South American IOCG deposits. The isotopic and able to discriminate between heavy mantle- and light
elemental signatures of South American IOCG deposits suggest ei- crust-derived chlorine. Additionally, since IOCG depos-
ther mixing of juvenile magmatic fluids with up to several tens wt.% its constitute an end-member of a continuum with mag-
of crustal brines or magmatic fluids leaching up to few wt.% of netite-apatite (Kiruna-type) deposits (Hitzman 2000),
combined investigations of these two mineralization types
Keywords. Iron oxide Cu-Au deposit, chlorine isotope, strontium iso- increase our understanding of the origin of their hyper-
tope, fluid inclusion, Andes saline fluids resulting in improved exploration strategies.

2 Ore deposits investigated, samples and

1 Introduction techniques

Iron oxide-copper-gold (IOCG) deposits represent a hy- The investigated deposits belong to the Carajs Mineral
drothermal mineralization style characterized by abun- Province (CMP), Brazil, and to the Peruvian and Chilean
dant magnetite and/or hematite, variable amounts of Cu- Andes (Fig. 1). The CMP consists of a Late Archean vol-
sulfides, pyrite, gold and REE, and intense and volumi- cano-sedimentary sequence deposited upon high-grade
nous sodic calcic and potassic alteration (Hitzman et tonalitic and trondhjemitic gneisses of the southern part
al. 1992). These deposits form at shallow to mid-crustal of the Central Brazilian Shield. The region is subsequently
levels within cratonic or continental margin settings intruded by 2.56-2.76 Ga alkaline and calc-alkaline gran-
(Hitzman et al. 1992), and although they usually occur ites and by 1.8-1.9 Ga anorogenic granites (Machado et
within magmatic rocks, they are not always clearly re- al. 1991). Either a continental rift (Olszewski et al. 1986)
lated to igneous activity. The most controversial aspect or a subduction-related arc (Dardenne et al. 1988)
of IOCG deposits is the origin of their hypersaline fluids geodynamic setting is suggested. Investigated CMP min-
as either (i) fluids exsolved from magmas (e.g., Pollard eralization includes the Archean to Early Proterozoic
2002), or (ii) basinal brines heated by nearby intrusions Sossego and Gameleira deposits.
(e.g., Barton and Johnson 1996). The Cretaceous IOCG deposits of Candelaria (Chile),
We report the first stable chlorine and strontium iso- and Raul-Condestable (Peru) and the magnetite-apatite
tope data, as well as Cl/Br ratios, for inclusion fluids of deposit of El Romeral (Chile) occur in the Andean Cor-
four IOCG deposits and one magnetite-apatite deposit dillera of Peru and Chile in extensional to transpressional
from South America. Chlorine is the dominant metal arc settings (e.g. Sillitoe 2003).
ligand in IOCG hypersaline fluids and behaves conserva- Geological, mineralogical, and stable isotope data (mostly
tively during fluid-rock interaction. Therefore, chlorine O, S) indicate dominantly magmatic fluids formed Gameleira
isotopic compositions, combined with strontium isotopes (Lindenmayer et al. 2001) and El Romeral, whereas mixed
and Cl/Br ratios, may provide tighter constraints, com- magmatic and non-magmatic fluids characterize Sossego
pared to O and S stable isotope data, on the origin of (Marschik et al. 2003) Candelaria (Marschik and Fontbot
IOGC fluids. The mean mantle 37Cl value is 4.7 with a 2001) and Raul-Condestable (de Haller et al. 2002).

736 M. Chiaradia D. Banks R. Cliff R. Marschik A. de Haller

The trend defined by the magmatic fluids of Gameleira

and El Romeral integrated with data from the magmatic
Selected fragments of quartz representing the primary fluids of the Capitan and SW-England plutons (Banks et
ore stages at Raul-Condestable, Candelaria, Gameleira, and al. 2000: Figure 2) is shifted to high Cl/Br values suggest-
Sossego, apatite from El Romeral, as well as two calcites ing that chlorine is a mixture between mantle and halite-
from the late ore stage at Sossego were sampled and derived chlorine, probably resulting from variable mag-
crushed. The inclusion fluids were analyzed for stable matic interaction with evaporites. A non-magmatic com-
chlorine and strontium isotope compositions by thermal ponent at El Romeral is supported by the significantly
ionization mass spectrometry (TIMS) and for Cl- and Br- more radiogenic strontium isotopic composition (87Sr/
concentrations by ion chromatography at the School of 86Sr = 0.7065) of the fluid compared to that of the associ-
Earth Sciences (University of Leeds, U.K.). ated magmatic rocks (87Sr/86Sri ~ 0.703-0.704). The Sr iso-
tope data addtionally suggest evaporite assimilation by
3 Sources of chlorine and strontium in inclusion high-temperature exsolved magmatic fluids rather than
fluids evaporite assimilation by the magma itself is responsible
for the observed Cl and Sr isotope systematics of the in-
Chlorine isotope compositions and Cl/Br ratios of hydro- clusion fluid at El Romeral.
thermal fluids of South American IOCG and magnetite- We have calculated that assimilation of 2 to 9 wt.%
apatite deposits plot along two distinct arrays (Figure 2), halite by a mantle-derived magmatic fluid could cause
allowing discrimination between magmatic fluid-domi- the shift to the near 0 37Cl values and high Cl/Br ra-
nated deposits (Gameleira and El Romeral) and deposits tios observed in the Gameleira, El Romeral and Capitan
with mixed magmatic and non-magmatic fluids (Sossego, pluton fluids. The existence of evaporites in the host se-
Candelaria, Raul) consistent with previous geochemical quences of El Romeral (Chile) and Capitan pluton
studies. We interpret the two trends defined by fluids of (Mexico) yields geological support to the above scenario.
the magmatic fluid-dominated (Gameleira, El Romeral) However, there is no evidence for evaporites in the CMP.
and mixed fluid (Candelaria, Raul-Condestable, Sossego) As a result a fluid souce with ~0 37Cl and high Cl/Br
deposits as the result of mixing between a common ratios such as a hypersaline crustal brine may explain the
mantle-derived magmatic fluid and two distinct crustal data of Gameleira.
sources of chlorine both with near 0 37Cl values but The other IOCG deposits investigated (Sossego,
with different Cl/Br values (Fig. 2). Candelaria, Raul-Condestable) define a linear array in the

Chapter 7-4 A non-magmatic component in fluids of South American Fe oxide-Cu-Au deposits inferred from 37Cl, 87Sr/86Sri and Cl/Br 737

Cl/Br-37Cl space that may result from mixing of the of crustal brine (4-30 wt.%). The significant contribution
mantle-derived magmatic-hydrothermal fluid with a of crustal brines in these deposits is suggested by Cl and
crustal brine characterized by Cl/Br ratios significantly Sr isotope data as well as by Cl/Br ratios. The results are
lower than evaporites but higher than seawater (Figure 2). consistent with mixed magmatic and non-magmatic hy-
The fact that all these IOCG deposits plot along a com- drothermal fluid signatures inferred from other isotope
mon mixing line (despite the large compositional field of systems (oxygen, sulfur). Chlorine isotope data combined
crustal brines) is intriguing and appears to indicate that with Cl/Br ratios and strontium isotope compositions
the mantle-derived magmatic fluid has interacted with a suggest a measurable contribution of crustal brines and/
crustal brine characterized by virtually identical Cl/Br or evaporites to the ore fluids in IOCG and magnetite-
ratios despite the different ages and geographic locations apatite deposits of South America. This conclusion may
of the deposits. The presence of a non-magmatic fluid help to refine strategies for IOCG deposit exploration in
component in these IOCG deposits is again supported by South America.
strontium isotope compositions of the inclusion fluids,
which are significantly more radiogenic ( 87Sr/ 86Sr i Acknowledgements
= 0.7053-0.7056 at Candelaria and 0.7051-0.7062 at Raul-
Condestable) than those of the associated magmatic rocks We thank Rolf Romer (GFZ, Potsdam) and Holly Stein,
(87Sr/86Sri = 0.7031 at Candelaria and 0.7042 at Raul- Aaron Zimmerman, and Parham Gardner (AIRIE Pro-
Condestable). In addition, at Candelaria-Punta del Cobre gram, Colorado State University, U.S.A.) for their com-
chalcopyrite, secondary biotite, ore-related calcite and ments that helped to improve an earlier version of the
anhydrite also have 87Sr/86Sri (0.7043-0.7063) higher than manuscript.
the magmatic rocks (R. Marschik, unpublished data). Cal-
culated chlorine contributions from the crustal brine range References
between 50 and 95% assuming 37 Cl mantle = 4.7
(Magenheim et al., 1995) and a 37Clbrine = -0.4. How- Banks DA, Green R, Cliff RA, Yardley BWD (2000) Chlorine isotopes
ever, due to the ten- to hundred-fold higher chlorine con- in fluid inclusions: determination of the origins of salinity in
magmatic fluids. Geochim Cosmochim Acta 64: 1785-1789
tent of crustal brines compared to (non-boiled) magmatic Barton MD, Johnson DA (1996) Evaporitic-source model for igneous-
fluids, these figures correspond to 4 and 30 wt.% crustal related Fe oxide-(REE-Cu-Au-U) mineralization. Geology 24:259-262
brine contribution. Dardenne MA, Ferreira Filho CF, Meirelles MR (1988) The role of
The above calculations are highly sensitive to assump- shoshonitic and calc-alkaline suites in the tectonic evolution of
tions about Cl and Br concentrations in brines and mag- the Carajs district, Brazil. J South Amer Earth Sci 1: 363-372
de Haller A, Ziga Alvarado J, Corfu F, Fontbot L (2002) The iron
matic fluids, to the poorly constrained 37Cl composition
oxide-Cu-Au deposit of Raul-Condestable, Mala, Lima, Peru. In:
of the mantle-derived magmatic fluid and crustal brines, Sociedad Geologica del Peru (ed) Conf Abst Vol XI Congr Peruano
and to the relatively large analytical uncertainty of 37Cl Geol, Lima: p. 80
values (0.2), yet they clearly indicate the presence of Eastoe CJ, Long A, Land LS, Kyle JR (2001) Stable chlorine isotopes
a measurable non-magmatic, crustal Cl (and Sr) compo- in halite and brine from the Gulf Coast Basin: brine genesis and
nent in fluids of IOCG deposits. evolution. Chem Geol 176: 343-360
Eggenkamp HGM, Kreulen R, van Groos FK (1995) Chlorine stable
isotope fractionation in evaporites Geochim Cosmochim Acta
4 Conclusions 59: 5169-5175
Hitzman MW (2000) Iron oxide-Cu-Au deposits: what, where, when,
Chlorine and strontium isotope data combined with Cl/ and why? In: Porter TM (ed) Hydrothermal iron oxide-copper-
Br ratios indicate that ore fluids in the investigated IOCG gold and related deposits: a global perspective, vol 1. PGC Pub-
lishing, Adelaide, Australia, p 9-25
and magnetite-apatite deposits result from variable mix- Hitzman MW, Oreskes N, Einaudi MT (1992) Geological character-
ing of mantle-derived magmatic-hydrothermal fluids with istics and tectonic setting of Proterozoic iron oxide (Cu-U-Au-
crustal brines or evaporites. The Gameleira IOCG deposit REE) deposits. Precamb Res 58: 241-287
and the El Romeral magnetite-apatite deposit formed by Johnson LH, Burgess R, Turner G, Milledge HJ, Harris JW (2000)
magmatic-hydrothermal fluids leaching evaporites from Noble gas and halogen geochemistry of mantle fluids: compari-
son of African and Canadian diamonds. Geochim Cosmochim
the host sequence or by mixing with crustal brines char-
Acta 64: 717-732
acterized by high Cl/BR ratios. Fluids of these deposits Lindenmayer ZG, Pimentel MM, Ronchi LH, Althoff FJ, Laux JH,
preserve a pristine magmatic O and S isotope signatures, Arajo JC, Fleck A, Bortowski DC, Nowatzki AC (2001) Geologia
yet minimal interactions with evaporites (e.g., 2-9 wt.%) do depsito de Cu-Au do Gameleira, Serra dos Carajs, Par. In:
are sufficient to produce the observed evaporite-type Cl Jost H, Brod JA, Queiroz ET (eds) Caracterizao de depsitos
and Sr isotope signatures as well as Cl/Br ratios. auriferous brasileiros. ADIMB-DNPM, Braslia, p. 79-139
Machado N, Lindenmayer Z, Krogh TE, Lindenmayer D (1991) U-Pb
In contrast, the IOCG deposits of Candelaria, Raul- geochronology of Archean magmatism and basement reactiva-
Condestable and Sossego formed by the mixing of mag- tion in the Carajs area, Amazon shield, Brazil. Precambrian Res
matic-hydrothermal fluids with up to a few tens percent 49: 239-354

738 M. Chiaradia D. Banks R. Cliff R. Marschik A. de Haller

Magenheim AJ, Spivack AJ, Michael PJ, Gieskes JM (1995) Chlorine Olszewski WJ, Wirth KR, Gibbs AK, Gaudette HE (1989) The age,
stable isotope composition of the oceanic crust: implications for origin and tectonics of the Gro-Par Group and associated rocks,
Earths distribution of chlorine. Earth Planet Sci Lett 131: 427-432 Serra dos Carajs, Brazil. Precambrian Res 42: 229-254
Marschik R, Fontbot L (2001) The Candelaria-Punta del Cobre iron Pollard PJ (2002) Evidence of a magmatic fluid and metal source for
oxide Cu-Au(-Zn-Ag) deposits, Chile. Econ Geol 96: 1799-1826 Fe-oxide Cu-Au mineralisation. In: Porter TM (ed) Hydrother-
Marschik R, Spangenberg JE, Leveille RA, de Almeida AJ (2003) The mal iron oxide copper-gold and related deposits A global per-
Sossego iron oxide-Cu-Au deposit, Carajs, Brazil. In: Eliopoulos spective v 1. PGC Publishing, Linden Park, Australia: 27-41
D et al (eds) Mineral Exploration and Sustainable Development Sillitoe RH (2003) Iron oxide-copper-gold deposits: An Andean View.
v 1. Millpress, Rotterdam, p. 331-334 Mineral Deposita 38: 787-812

Chapter 7-5 7-5

Origin of hydrothermal ore-forming processes in the

Dapingzhang polymetallic copper deposit in the
Lanping- Simao Basin, Yunnan Province
Dai Baozhang, Jiang Shaoyong
State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing, 210093,
Liao Qilin
Jiangsu Geological Survey Institute, Nanjing, 210018, China

Abstract. The newly discovered Dapingzhang polymetallic copper 2 Rb-Sr isochron age
deposit in the Lanping-Simao Basin is hosted in volcanic rocks. The
orebodies include an upper stratiform and lentiform massive sul-
Determining the age of mineralization is essential for
fide orebody, and a lower vein type and disseminated sulfide
orebody. The Rb-Sr isotopes of quartz fluid-inclusions in the vein understanding any deposit. In this study, mineralization
type orebody yield an isochron age of 118 12 Ma. Fluid-inclusion was dated using Rb-Sr analysis of fluid inclusions. The
analysis shows that the ore-forming fluid is of low to middle salin- Rb-Sr isotopic compositions of fluid inclusions in 8 se-
ity (2.0-8.0 wt%NaCl), and of low to middle temperature (90~200oC). lected quartz samples were analyzed. The data were then
The 34S values of pyrite and chalcopyrite minerals in this deposit
plotted using the ISOPLOT program with ( 87 Rb)
concentrate at about 0. Our modeling and water/rock ratio cal-
culations using available hydrogen-oxygen isotope data suggests 1.42x1011/a. The input error was 87Rb/86Sr = 0.5%. The 6
an evolved meteoric water origin for the ore-forming fluids, instead samples from the vein type and disseminated sulfide
of mixture of seawater and magmatic fluids. The Pb isotope com- orebody yield an isochron age of 118 12Ma, MSWD =
position indicates radiogenic Pb sources, and suggests Pb from sedi- 0.46. Previous isotope dating (Zhong et al. 2000) shows
mentary rocks and mantle-derived volcanic rocks in the basin both that the age of the host rock is 500~530 Ma. The ages of a
contribute to this deposit. In conclusion, the Dapingzhang deposit
shares many similar geochemical characteristics with vein type cop-
variety of intrusions in this area are between 300 Ma and
per deposits in the Lanping-Simao Basin. These data support the 150 Ma, which indicate that the Dapingzhang deposit
conclusion that the Dapingzhang polymetallic copper deposit is a formed after these local intrusions.
hydrothermal deposit formed during Yanshanian period, not a mas- Two samples from the massive orebody evidently de-
sive sulfide deposit of submarine-exhalative-sedimentary origin as part from the isochron and show higher 87Sr/86Sr values
proposed by previous researchers.
(Fig. 1). This could be caused by increased contribution
Keywords. Isotope geochemistry, quartz fluid inclusion, Rb-Sr isoch- from materials with higher 87Sr/86Sr values (e.g., sediments
ron age, Yanshanian period, hydrothermal deposit in the basin). This could be because the massive orebody
is relatively shallower than the vein type deposits. The
limited sample number in this case (2) prevents the pos-
1 Introduction sibility of obtaining an age for the massive orebody. Some

The Dapingzhang polymetallic copper deposit is an im-

portant recent discovery in Lanping-Simao Basin. It is
composed of an upper stratiform and lentiform massive
sulfide orebody, and a lower vein type and dissiminated
sulfide orebody. Previous researchers have identified it
as a massive sulfide deposit with submarine- exhalative-
sedimentary origin (Li 2000; Li et al. 2000; Li and Zhuang
2000; Li and Zhang 2001; Zhong et al. 2000). In this paper,
new results of fluid inclusion, sulfur isotope and miner-
alization age are taken into account. The data lead to a
different perspective on ore-forming process, which is also
consistent with previous data. The Dapingzahng deposit
was formed by extensive interaction between meteoric
water (or brine) and host rocks. This is similar to the
oreforming process identified in the vein type deposits
in Lanping-Simao Basin.

740 Dai Baozhang Jiang Shaoyong Liao Qilin

direct dating methods such as Re-Os isotope analysis of concentrate at about 0, implying that sulfur in this de-
metal sulfides (Jiang et al., 2000) should be adopted in posit is mainly mantle-derived. Sulfur with such charac-
further research. The reliable age of 120 Ma for the vein teristics can either come directly from volcano exhalative,
type and disseminated sulfide orebody indicates that this or can be leached from volcanic rocks. For the
deposit mainly formed in Yanshanian period. Dapingzhang deposit, the latter is more reasonable.

3 Fluid inclusions 4.2 Hydrogen-oxygen isotopes

In this study, quartz and calcite minerals from variety of To determine the origin and evolution of the ore-form-
samples were carefully selected for fluid inclusion analysis ing fluid, available hydrogen and oxygen isotope data (Li
in order to acquire information about the composition and Zhuang 2000; Zhong et al. 2000) are compiled (18OH2O
of ore-forming fluids. The results show that the range of values of -2.5 to +2.9, and D values of 84 to 59
homogeneous temperatures is 90~200 o C (mainly for the ore-forming fluids) and further analyzed. The cal-
from130oC to 160oC), and the salinity of the ore-form- culation of water/rock interaction is taken in this study
ing fluid varies from 2.0 to 8.0 wt%NaCl. These results with the D and 18OH2O values of meteoric water are -
are relatively lower in temperature and salinity than pre- 120 and -16 (Liu et al., 2000) and the D and 18OH2O
vious data; however this could be due to the fact that values of volcanic rocks are -65 and 8 (Shen 1997).
these samples originate from shallower depths than those Figure 4 shows that the available hydrogen and oxygen
from previous studies. data are consistent with the two evolution curves at 150oC
As shown in Figure 2, the ore-forming fluid of Daping-
zhang deposit is similar to that of the vein type deposit
series in Lanping-Simao Basin composed by Jinman,
Shuixie and Bailongchang.
On the other hand, temperature of ore-forming flu-
ids in massive sulfide deposits mainly ranges from 200oC
to 350 o C, which is much higher than that of the
Dapingzhang deposit.

4 Isotope research

4.1 Sulfur isotopes

Chalcopyrites and pyrites from variety of samples were

selected in this study for sulfur isotope analysis. Both the
results in this study and previous studies (Li et al. 2000;
Zhong et al. 2000) indicate that 34S values of all sulfides

Chapter 7-5 Origin of hydrothermal ore-forming processes in the Dapingzhang polymetallic copper deposit in the Lanping- Simao Basin, Yunnan Province 741

2. The ore-forming fluid is similar to that of the vein type

deposit series, with low to middle salinity and low to
middle temperature. Hydrogen-oxygen isotope data
indicate an evolved meteoric water origin for the fluid.
3. Sulfur and lead isotope data imply that the host vol-
canic rocks are the main source for sulfur and ore-
forming metals.
4. It is most likely that mineralization of the Dapingzhang
deposit is similar to that of the vein type deposit se-
ries in Lanping-Simao Basin. The Dapingzhang
polymetallic copper deposit is a hydrothermal deposit.

Jiang S, Yang J, Zhao K (2000) Re-Os isotope tracer and dating meth-
ods in ore deposits research. Journal of Nanjing University (Natu-
ral Sciences) 36(6): 669~677
Li F (2000) Volcanic-exhalative-sedimentary ore- forming model of
Dapingzhang Cu-polymetal deposit, western Yunnan. Bulletin of
and 250oC, respectively. Thus, it is most likely that the ore- Mineralogy, Petrology and Geochemistry 19(4): 296~297
forming fluid is extensively evolved meteoric water. Li F, Zhang F (2001) Volcanic-exhalative- sedimentary genesis of
Dapingzhang Cu-polymetal deposit, western Yunnan. Geology
4.3 Lead isotopes and Prospecting 37(4): 5~8
Li F, Zhuang F (2000) Fluid inclusion characteristics and its
metallogenic significance of the Dapingzhang Cu-polymetal de-
Available lead isotope data are plotted onto the Zartman posit in Simao, western Yunnan. Geotectonica et Metallogenia
Pb isotope diagram. Lead in this deposit is relatively rich 24(3): 237~243
in radiogenic Pb. Fig. 5 shows that host-rock samples lay Li F, Zhuang F, Yang H (2000) Fluid inclusions analysis of
on the orogen curve, while orebody samples lie between Dapingzhang Cu-polymetal deposit, western Yunnan. Acta
the orogen curve and the mantle curve, implying some Petrologica Sinica 16(4): 581~586
Liu J-J, Li C-Y, Pan J-Y (2000) Isotopic Geochemistry of copper de-
contribution from a magmatic source. It is likely that host posits in sandstone and shale of Lanping-Simao basin, western
rocks supply most of the ore-forming metal to both the Yunnan. Mineral Deposits 19(3): 223~234
vein type deposit series and the Dapingzhang copper Ohmoto H, Skinner BJ (1983) The Kuroko and related volcaogenic
polymetallic deposit. massive sulfide deposit. Economic Geology (Monograph) (5): 604
Shen W (1997) Textbook on isotopic geology. Atomic energy pub-
5 Conclusions lishing house, Beijing.
Wu N (2003) Geochemistry of the vein-type copper deposits in
Lanping-Simao Basin, Yunnan Province, China. Paper for masters
Combining the new results in this study and the available degree of Department of Earth Sciences, Nanjing University
data of previous researchers, we acquire some essential Wu N (2003) Lead and sulfur isotope geochemistry and the ore
perspectives on the Dapingzhang copper polymetallic sources of the vein-type copper deposits in Lanping-Simao Ba-
deposit: sin, Yunnan Province. Acta Petrologica Sinica 19(4): 799~807
Zhong H, Hu R-Z, Ye Z-J (1999) Isotopic chronology of the spilite-
ceratophyre formation in Dapingzhang, Yunnan Province and its
1. The fluid-inclusion Rb-Sr isotopes of quartz in the
geologic significance. Science in China (D) 29(5): 407~412
vein-type orebody yield an isochron age of 118 12 Zhong H, Hu R-Z, Ye Z-J (2000) Sulfur, lead, hydrogen and oxygen
Ma. This indicates that the orebody was formed in late isotopic geochemistry of the Dapingzhang copper- polymetallic
Yanshanian period. deposit, Yunnan Province. Geochemica 29(2): 136~142

Chapter 7-6 7-6

Stable isotope geochemistry of the gold-sulfide

mineralized zone of the Kottapalle block of the
Ramagiri greenstone belt, Dharwar Craton, South India
M. Deb, K. Bheemalingeswara
Department of Geology, University of Delhi, Delhi 110007, India

Abstract. The Neo-Archean Ramagiri-Penakacherla belt is located Light and dark phyllites
in the eastern Dharwar craton of South India. It hosts auriferous Greenstones with chert layers
quartz bodies in altered mafic and felsic volcanic rocks, intimately
Quartz-chlorite schists
interlayered and co-folded with carbon phyllites. The sequence is
metamorphosed to low greenschist facies. Pervasive quartz-car- Quartzite
bonate alteration is a conspicuous feature in the gold-sulfide min- Banded Iron Formation
eralized zone of the Kottapalle block of this greenstone belt. Hornblende schist
The carbonate compositions spread along the dolomite-anker- Metagabbro
ite or calcite-ankerite join. The host volcanics are of tholeiitic ba-
Granitic rocks, massive and banded
salt, andesitic and dacitic compositions representing a probable
island-arc setting. The majority of carbonaceous samples fall in
the range of 20 and 28 per mil 13Corg (PDB), suggesting a The light grey phyllite consists essentially of carbon-
biogenic derivation of the reduced carbon and a sedimentary ori- ate and chlorite, with minor amounts of sericite and
gin of the strata. Carbonate 13C (PDB) have median values of -2.4 quartz. The dark grey phyllite on the other hand has chlo-
per mil and mean of 4.0 per mil. 34S (CDT) values of pyrite and rite as the dominant phase over carbonates. Auriferous
pyrrhotite cluster around +2 per mil. Primary fluid inclusions, rich
in CO 2 with subordinate CH 4 , as observed in preliminary
quartz bodies of different types and generations occur
microthermometric studies, demonstrate the pervasive presence in this part of the sequence (shown in italics above) in
of a CO2-rich hydrothermal fluid responsible for the extensive car- the form of reefs, pods and veinlets along the pervasive
bonation of the auriferous host rocks. foliation.
Absence of any sedimentary carbonate strata in the sequence, In the Kottapalle block of the Ramagiri ore zone (Fig. 1)
and the stable-isotope data support the role of mantle-derived
the altered volcanics are intimately interlayered and co-
fluids in producing the quartz-carbonate alteration. The 13C val-
ues of carbonates indicate that the hydrothermal fluid did not folded with carbon phyllite. In the auriferous zone these
have any significant interaction with the reduced carbon in the rocks contain sulfide minerals such as, pyrite, chalcopy-
ore zone. The sulphur isotope data points to the mantle-source of rite, pyrrhotite, sphalerite and minor arsenopyrite..The
sulphur in the ore-bearing hydrotherms. metamorphic mineral assemblage indicates that the grade
of metamorphism has attained low green schist facies.
Keywords. Shear gold, quartz-carbonate alteration, Dharwar cra-
ton, stable-isotope geochemistry Pervasive quartz-carbonate alteration is a conspicu-
ous geological feature noted in the gold-sulfide miner-
alized zone in the Kottapalle block. It has affected both
1 Introduction the felsic and mafic volcanic units of the greenstone belt.
The carbonates co-exist as grains, bands and patches with
The Ramagiri-Penakacherla belt is one of a series of au- the carbonaceous matter in the carbon phyllites. Thus,
riferous greenstone belts in the eastern Dharwar craton carbon, either as graphitic carbon or as carbonate is in-
of South India. This belt, considered to be of Neo-Archean variably associated with the Au-sulfide mineralization.
age (2746+ 64 Ma; Zachariah et al. 1995) is located in the This first stable isotope study in this belt was con-
Anantapur district of Andhra Pradesh. The belt forms a ducted to ascertain the source of carbon and sulfur in
Y-shaped outcrop of prominently mafic volcanic rocks, the ore-host rock association. This work would also pro-
which are surrounded on all sides by the Peninsular vide useful insight into the oregenetic process and envi-
Gneiss. The litho-units present in the area (Ghosh et al. ronment of ore emplacement. Towards this end, three
1970) are: bore holes drilled by the Geological Survey of India in
the Kottapalle block (cf. Fig. 1) were logged and sampled
Dolerite dyke systematically and subjected to XRD, XRF, CHNS (el-
Ultrabasic rocks emental), EPMA analyses and stable isotope mass spec-
Pyroclastics trometry.

744 M. Deb K. Bheemalingeswara

volcanics have turned into fine grained chlorite-sericite

schists, the only distinction being the fine grained quartzo-
feldspathic matrix in the felsic compositions. These schists
have been described as light and dark phyllites in field
Carbonate grains in three samples of metabasalt and
felsic volcanics were investigated through XRD, CL and
EPMA (JEOL JXA 8600 superprobe) analyses. All carbon-
ate grains analysed contain manganese as a minor com-
ponent, with MnO content ranging from nil to 0.9 wt.%.
Their compositional characteristics, in terms of the three
major components, CaO, MgO and FeO, are presented in
Figure 2. Coarse quartz-carbonate veins and lenses oc-
cur in contact with finely schistose carbonaceous and car-
bonate interlayerings in sericite-quartz schists (RG49/11).
Compositions of carbonates in them showed the predomi-
nance of ankerite over dolomite molecule along the do-
lomite-ankerite join. Coarse brownish carbonates in lenses
and bands in another section (RG47/1) within sericite-
2 Results chlorite-quartz schist showed a trend of increasing dolo-
mitic and calcitic molecules. This section showed excel-
2.1 Petrology and geochemistry lent microstructural relationships, with the schistosity
transected by tightly folded late quartz veinlets. In yet
Based on discriminant diagrams, using their major and another section (RG47/18) brownish pre- to syntectonic
trace element abundances, the mafic and felsic volcanics carbonate-quartz-sulfide lenses show compositions along
in the host sequences were found to be of tholeiitic ba- the calcite-ankerite join. In this section, two types of car-
salt, andesite and dacite compositions. In tectonic dis- bonates are observed. The late carbonates, identified un-
criminant diagrams, the Kottapalle metabasalts plot in der CL, are clearly more calcitic. They are located along
the IAB field, suggesting the possibility of subduction- the grain boundaries of earlier carbonate grains. Fe-rich
related volcanism in an island arc setting in the Archean carbonates, as noted in this study, are typically related to
Dharwar craton (cf. Zachariah et al. 1997). The volcanic gold mineralization in greenstone belts the world over.
rocks have been so severely altered and metamorphosed Total carbon content of 48 analyzed samples from the
that the two main protoliths, tholeiitic basalt and dacite, ore zone rocks ranged from 7.3 to 0.27 wt.%, with a mean
can hardly be distinguished petrographically. Both the of 3.11 wt.% (std. dev. 1sigma = 1.67%). Corg content mea-

Chapter 7-6 Stable isotope geochemistry of the gold-sulfide mineralized zone of the Kottapalle block of the Ramagiri greenstone belt, Dharwar craton 745

18O (SMOW) per mil of 21 carbonates from Kottapalle

ore zone (Fig. 4) show spread of 13C values from 0 to -
9.2 per mil with a mean of 4.0 and a median of 2.4 per
mil. 18O values range from 26.0 to 12.5 per mil. One
pure calcite from a late veinlet had an unusual composi-
tion of -9.2 per mil 13C and -11.2 18O. While only one
sample showed sea water-derived carbonate 13C value
near zero, the majority clustered between 1.5 and 2.7
per mil. A few values were spread between 3.9 and - 6.2
per mil while 2 samples gave values around 9 per mil.
Limited sulfur isotope analyses of 8 monomineralic py-
rite and 1 pyrrhotite separates gave a range of 34S (CDT)
between +2.8 and -1.7 per mil, with the majority cluster-
ing around +2 per mil (Fig. 5).

3 Discussion and conclusion

For shear- or fault-controlled Archean epigenetic gold-

quartz deposits, controversy prevails regarding the source
of the ore components and fluids. There are two end-mem-
ber genetic hypotheses - one metamorphic and the other
magmatic - which continue to compete. Since most depos-
its of this type show pervasive carbonate alteration and sul-
fide association, determination of the source of carbon and
sured in 15 samples ranged from 5.8 wt.% to nil, while sulfur in the ore zone can lend significant support to either
Ccarb, estimated as the difference between Ctotal and Corg of the two hypotheses. Extensive quartz-carbonate alter-
in 15 samples, ranged between 5.9 wt.% to nil. ation of the host volcanics, absence of any sedimentary car-
bonate strata in the sequence and presence of primary fluid
2.2 Stable isotope composition inclusions rich in CO2 with subordinate CH4, as observed
in preliminary microthermometric studies, demonstrate the
Twenty one analyses of 13Corg in three carbonaceous pervasive presence of a CO2-rich hydrothermal fluid. This
samples (Fig. 3) ranged between 14.2 and 32.4 per type of fluid is necessary for carbonation of the aurifer-
mil (PDB), with the majority of samples falling in the range ous host rocks in the Kottapalle block of the Ramagiri
of 20 and 28 per mil. These values suggest a biogenic greenstone belt. The variation in the composition of the
source for the carbon, and thus, a sedimentary origin for carbonates, noted above, may be attributed to episodic
the carbonaceous strata. Values heavier than 20 per mil fluctuations in the temperature and composition of the
probably reflect partial equilibration with co-existing car- fluids in the structural conduits (cf. Mumin et al. 1996).
bonates or thermal maturation to heavier values by lib- The median 13C of -2.4 per mil composition of the car-
eration of CH4. 13CCarb-graphite of 11.6 and 13.8 per mil in bonates is too negative to have been derived from meta-
co-existing carbonate and reduced carbon suggest an morphically remobilized CO2 from sea water-derived car-
equilibration temperature of about 300 to 225oC (cf. bonate. This median value of ore zone carbonates and
Oberthr et al. 1996). A plot of 13C (PDB) per mil against their spread upto -6.2 per mil conforms closely to the range

746 M. Deb K. Bheemalingeswara

of -2.0 to -6.0 recorded by Groves et al. (1988) for fault- cilities at Gttingen. Thanks are also due to Dr. Andreas
controlled regional carbonation involving CO2 of mag- Hoppe, Director, Landesamt fur Bodenforschung, Wies-
matic or mantle origin. The median value is also close to baden, for help in generating the XRF data. This study
the -3.1 1.3 per mil 13C value of undoubted magmati- was supported by a research grant (ESS/CA/A5-11/95)
cally-derived carbonates found in association with mo- from the Department of Science & Technology, Govt. of
lybdenite mineralization in a granodiorite intrusion in India, to the first author.
Canada (Burrows et al. 1986). Direct involvement of mantle
fluids in the ore-bearing hydrotherm is envisaged instead References
of reworking of mantle-derived carbonates into metamor-
phic fluids, as an alternative process of ore formation. Burrows DR, Wood PC, Spooner ETC (1986) Carbon isotope evidence
This is supported by the limited variation in the 13C val- for a magmatic origin for Archean gold-quartz vein ore depos-
its. Nature 321 851-854
ues of carbonates and the near-zero (+2 per mil) mantle Ghosh DB, Sastry BBK, Rao AJ, Rahim AA (1970) Ore environment
signature in the associated sulfides. Absence of strongly and ore genesis in Ramagiri Gold Field, Andhra Pradesh, India.
negative (> -10 per mil) 13C values in the carbonates Econ. Geol. 65 801-814
also imply that the hydrothermal fluid did not have any Groves DI, Golding SD, Rock NMS, Barley ME, McNaughton NJ (1988)
significant interaction with reduced carbon. Archean carbon reservoirs and their relevance to the fluid source
for gold deposits. Nature 331: 254-257
Mumin AH, Fleet ME, Longstaffe FJ (1996) Evolution of hydrother-
Acknowledgements mal fluids in the Ashanti gold belt, Ghana: stable isotope geochem-
istry of carbonates, graphite and quartz. Econ. Geol. 91: 135-148
This study was made possible by the kind permission Oberthr T, Schmidt Mumm A, Vetter U, Simon K, Amanor, JA
granted by the Deputy Director General (Southern Re- (1996) Gold mineralization in the Ashanti belt of Ghana: ge-
netic constraints of the stable isotope geochemistry. Econ. Geol.
gion), Geological Survey of India for the logging and col- 91: 289-301
lection of bore hole samples. The help received in the field Zachariah JK, Hanson GN, Rajamani V (1995) Postcrystallisation
from senior geologist, K.N.Reddy is gratefully acknowl- disturbance in the neodymium and lead isotope systems of
edged. The EPMA, CL, XRD and Mass spectrometry were metabasalts from the Ramagiri schist belt, southern India.
carried out during a revisit of the first author (MD) to Geochimica et Cosmochimica Acta 59: 3189-3203
Zachariah JK, Rajamani V, Hanson, GN (1997) Petrogenesis and
the Geochemisches Institut, Gttingen, Germany with an source characteristics of metatholeiites from the Archean
Alexander von Humboldt Foundation fellowship. He is Ramagiri schist belt, eastern part of Dharwar craton, India.
grateful to Prof. J.Hoefs for extending all laboratory fa- Contrib. Mineral. Petrol. 129: pp. 87-104

Chapter 7-7 7-7

Isotope systematics of ore-bearing granites and host

rocks of the Orlovka-Spokoinoe mining district,
eastern Transbaikalia, Russia
A. Dolgopolova, R. Seltmann, C. Stanley
Natural History Museum, Dept. Mineralogy, CERCAMS, Cromwell Road, London SW7 5BD, UK
D. Weiss
Imperial College, London, Prince Consort Road, London SW7 2BP, UK
B. Kober
Institute of Environmental Geochemistry, Im Neuenheimer Feld 234, D-69120 Heidelberg, Germany
W. Siebel
Dept. of Earth Sciences, Eberhard-Karls-University, Wilhelmstr. 56, D-72074 Tbingen, Germany

Abstract. Pb, Rb and Sr isotope data are reported for the Khangilay, mantle interaction in the development of granitoid
Orlovka and Spokoinoe granite massifs and their host rocks in the magmatism, the genetic relationship between the three
Orlovka-Spokoinoe mining district, Eastern Transbaikalia, Russia. Pb
massifs and similarities and differences among them may
isotope analyses indicate a common Pb source for all three granite
massifs reflecting a homogenous source melt from which all mag- be identified. Rb-Sr isotopes provide additional insights into
matic members evolved. Pb isotope systematics identify two pos- the age of granites from the Orlovka-Spokoinoe mining site.
sible scenarios for the source of Li-F granites: 1) a crust-mantle source
where a mixture of MORB and continental-derived material were
brought together in an orogenic environment; and 2) a type II en-
riched mantle source where subducted continental material could
have been strongly implicated in volcanic suites. New Rb-Sr isotope
age data yield a 143.84.2 Ma age for barren granites of the Orlovka
and Khangilay massifs.

Keywords. Pb Rb Sr isotope systematics, ore-bearing granite, East-

ern Transbaikalia

1 Introduction

The rare-metal granite-related Orlovka tantalum deposit

and the Spokoinoe tungsten vein quartz-greisen deposit
are located in Eastern Transbaikalia 140 km and 148 km SE
of Chita, respectively. Both deposits are hosted by the
Khangilay granite pluton and are believed to be its satel-
lites (Fig. 1) (Badanina et al. 2004; Beskin et al. 1994;
Kovalenko et al. 1999; Syritso et al. 2001). In recent years,
the evolution of rare-metal granites, their formational stages,
and their relation to intraplate magmatism have been stud-
ied. Specifically, Rb-Sr and Sm-Nd isotopic systems were
used to reveal the source(s) of rare-metal granite melts from
the study area, and the results indicate that sources were
likely to be either crustal, mantle or combined crustal-mantle
(Kostitsyn 2001; Kovalenko et al. 1999, 2002, 2003; Yarmolyuk
et al. 2001, 2003). Our study uses Pb isotopes for the gran-
ites of the Orlovka, Spokoinoe, and Khangilay massifs and
their host rocks with the goal to study the evolutionary
trends and features of the Khangilay pluton and the Orlovka
and Spokoinoe deposits (barren versus mineralized gran-
ites, ores, host rocks). By examining fluid-rock and crust-

748 A. Dolgopolova R. Seltmann C. Stanley D. Weiss B. Kober W. Siebel

2 Geological setting

The Orlovka-Spokoinoe mining district belongs to the

Central Asian Orogenic Belt (CAOB) (Jahn et al. 2000) or
Transbaikal-Mongolian orogenic collage where multiple
oroclinally bent magmatic arcs separated by accretion-
ary complexes and ophiolitic sutures are located between
the major cratons. Rare-metal Li-F enriched granites and
pegmatites are widespread as products of continental
crustal growth and associated intraplate magmatism. The
Khangilay pluton is located in the central portion of the
Paleozoic Aginskaya microplate, which is made up of pre-
dominantly sandstone and shales (Beskin et al. 1994; Syritso
et al. 2001). The granitoids of the pluton cut Proterozoic to
Carboniferous shales and volcanics, a Triassic terrigenous
and volcano-sedimentary sequence, and gabbro-diorite,
granodiorite, and lamprophyre bodies (Kovalenko et al.
1999). The microplate was intruded by granite plutons, the
largest of which is 24 km by 22 km in dimension at a depth
of 500-2500 m based on gravimetric data.
It is exposed at the surface as three separate granitic
(Khangilay, Spokoinoe and Orlovka) massifs. The
Khangilay granite massif is composed of biotite granite
and biotite-muscovite granites. The Orlovka satellite is a
highly differentiated Ta-(Nb-Sn-) bearing intrusion of
lithionite-amazonite-albite granite. The Spokoinoe body is
a muscovite-albite granite with W (Sn, Be) mineralization.
To assess magmahost-rock interactions of the Khan-
gilay-Orlovka intrusions within the regional geochemical ore-bearing rocks. The high Pb concentrations, up to 190
framework, greisenized Spokoinoe granites and a repre- ppm, found in ore-bearing amazonite granites minimize
sentative suite of host rocks (volcanics, hornfelses, meta- the effects of fluid-wall rock interaction and associated
sediments, gabbro-diorite) were included in the study. perturbation to Pb systematics. The amazonite granites
are characterized by the lowest rate of radiogenic Pb ac-
3 Results and discussion cumulation because of their very low 238U/204Pb (average
= 1.3). The calculated initial values for these least sensi-
The mixing diagram (Fig. 2) shows a strong relationship tive ore-bearing granites are very similar and their aver-
between the barren parental granites of the Khangilay ages are: 206Pb/204Pb = 18.41 0.02; 207Pb/204Pb = 15.56
pluton and the ore-bearing granites of the Orlovka and 0.006; and 208Pb/204Pb = 38.3 0.03 (Dolgopolova et al.
Spokoinoe massifs. They all plot within a single linear 2004). Pb isotope compositions were also determined in
array. Despite a wide range of Pb isotope compositions two separate grains of K-feldspar from the ore-bearing
within each granite body, they do not differ significantly amazonite granite of the Orlovka Ta-Nb deposit. Pb iso-
among all three granite massifs (Dolgopolova et al. 2004). tope analyses and U-Pb isotope dilution measurements
It hints at fractionation from a homogenous (or homog- were carried out for blue-green cores and white feldspar
enized) source melt with uniform initial 206Pb/204Pb and rims. Differences between core and rim Pb isotopic com-
207Pb/204Pb ratios. The overall data trend demonstrates a
positions are negligible within the limits of statistical sig-
simple mixing of the uniform Pb composition with dif- nificance. The averages of measured initial Pb isotope
ferent radiogenic components in the rocks and a strong compositions of feldspars are shown in Table 1.
relation of the barren parental rocks to the ore-bearing The average values of initial Pb isotope composition
rocks. Lead isotope signatures of the host rocks are more of ore-bearing granites were calculated previously to as-
scattered than those of the granite rocks and are off the sess sources of the granitic magmas and were in the range
granites mixing line. of: 206Pb/204Pb = 18.49 0.05; 207Pb/204Pb = 15.57 0.01
The Orlovka ore-bearing amazonite granites, with the and 208Pb/204Pb = 38.23 0.06 (Dolgopolova et al. 2004).
highest Pb concentration, were used to identify the ini- Our new data on Pb isotope compositions of K-feldspar
tial Pb isotopic signature subsequently transferred to the (Table 1) show very good agreement with the calculated

Chapter 7-7 Isotope systematics of ore-bearing granites and host rocks of the Orlovka-Spokoinoe mining district, eastern Transbaikalia, Russia 749

0.0012 (Fig. 4). The data for barren biotite-muscovite gran-

ites are in excellent agreement with published data of the
Orlovka-Spokoinoe granites, where the determined age
of granites was 142.9 1.8 Ma at initial 87Sr/86Sr of 0.706
5 (Kovalenko et al. 1999).

5 Regional evidence for the proposed model

initial Pb isotopic composition of the Orlovka granite Evidence from Sr, Nd and O isotope investigations
pluton. (Kovalenko et al. 1999, 2002, 2003; Yarmolyuk et al. 2003)
Pb isotope systematics show the presence of a mantle is consistent with our lead isotope data reaffirming the
signature transferred during the formation of the stud- two possible common sources for granitic magmas of the
ied granites (Figure 3). A mantle-derived component is Orlovka-Spokoinoe mining district. However, there is no
in a transitional field between mid-ocean ridge basalt unequivocal data implicating either a mixed upper crust-
(MORB) and type II enriched mantle (EM II) (Zartman mantle source or a type II enriched mantle source.
and Doe 1981) but closer to the latter. There is a mixture Regional studies of Transbaikalian granitoids incor-
of different epochs presented on Figure 3. The mantle ar- porating geochemical, geophysical and geodynamic data
rays indicate present-day mantle Pb isotopes while gran- indicate both crustal and mantle inputs triggering gra-
ite data reflects frozen Jurassic Pb isotope compositions. nitic melt generation of all petrochemical series (Jahn et
If the mantle arrays are traced back to a Jurassic age with al. 2000; Kovalenko et al. 1996; Litvinovsky et al. 2002).
less radiogenic EM II and MORB sources than the plot- The isotopic heterogeneity of these granites was prede-
ted arrays, they would slightly shift to the lower left part termined by the isotopic heterogeneity of their sources
of the plot and indicate EM II input. (Kovalenko et al. 1996). Blocks of consolidated pre-
Therefore, Pb isotopic data suggest two possible sources Riphean crust were overthrust during the accretionary
contributed to the formation of the studied granites: 1) a collision of the foldbelts onto the younger crustal com-
crust-mantle source where a mixture of MORB and up- plexes of within-block oceanic basins contributing to an
per crustal-derived material were brought together in an anomalous crustal thickness. The Riphean-aged crust in
orogenic environment; and 2) type II enriched mantle Caledonian structures most likely reflects the same aver-
source where subducted continental material could have age composition of a mixed source (basites + pelites) of
been strongly implicated in several island-arc volcanic the granitoid magmas; the source formed at 450-500 Ma.
suites and the corresponding isotopic signatures, thus The isotopic evolution of this source resulted in Nd(T) ~
reflecting a strong similarity of EM II with upper conti- 0 of the mixed source by 100-200 Ma. Some of the young
nental crust or continentally derived sediment. (~120 Ma) granites show evidence of assimilation of pre-
Riphean crust (Kovalenko et al. 1996). Some metaluminous
4 New Rb-Sr age data and peralkaline syenite-granite suites and closely associ-
ated comendites of Transbaikalia constrain A-type grani-
Seven samples of barren and ore-bearing granites of toid magma generation emplaced at ca. 280 Ma as a re-
Khangilay and Orlovka massifs were analyzed for Rb and sult of fractional crystallization of syenite magmas. Al-
Sr isotope compositions. Analyses of four samples from kali-rich silicic magma formed at an estimated depth of
the barren granites yield a whole rock isochron age of 50-60 km far exceeding the normal crust thickness. The
143.8 4.2 Ma with an initial 87Sr/86Sr ratio of 0.7065 Sr-Nd isotope data advocate the main role of mantle-de-

750 A. Dolgopolova R. Seltmann C. Stanley D. Weiss B. Kober W. Siebel

rived material in the source region from which the al- 6 Conclusions
kali-rich syenitic and granitic magmas were produced
(Litvinovsky et al. 2002). Also, widespread Transbaikalian Pb isotope data of crustal rocks and ore deposits of the
alkali monzodiorite-syenite series are explained by frac- Orlovka-Spokoinoe mining district complement the exist-
tional crystallization from tephritic magma intrusions at ing Nd and Rb-Sr data for this region. Our results indicate
ca. 130 Ma. In contrast to calc-alkaline granite batholiths that the three granite massifs have uniform Pb isotope com-
generated during continental crustal growths, subalkaline positions and show a strong genetic relationship between
granites of Transbaikalia are often accompanied by ba- the barren biotite-muscovite granites of Khangilay and the
salt-trachyte-pantellerite-alkaline granite associations Spokoinoe and Orlovka ore-bearing granites suggesting a
marking rift structures of intraplate hotspots (Kovalenko common source for the three massifs. Pb isotope data also
et al. 1996). The related Li-F and alkaline granites repre- confirm that the Khangilay pluton can be considered as the
sent A-type granites with high heat production. Sr, Nd parental intrusion for its hosted mineralized apical intru-
and O isotope investigations of late OligoceneHolocene sions. Pb isotope systematics outline two possible scenarios
volcanics from the adjacent area of the Southern Baikal for the source of granitic melts: a mixed upper crust-mantle
region (Yarmolyuk et al., 2003) show that the isotopic sig- source, and a type II enriched mantle source.
nature of the magma source is a mixture of moderately New Rb-Sr isotope data confirms the age of 143.84.2
depleted mantle and enriched mantle reservoirs of types Ma for biotite and biotite-muscovite granites of the
I and II enriched mantle (EM I and EM II). EM II source Khangilay and Orlovka massifs.
has been reported to be one of the mantle sources con-
tributing to the formation of Early Mesozoic rocks of the Acknowledgements
Mongolia-Transbaikalia magmatic area and has been listed
among mantle sources for the CAOB as a whole (Kovalenko The authors would like to thank Russian colleagues who
et al. 2002). The published data on Sr and Nd isotopes for participated in the INTAS 97-0721 project for inspiring
the Orlovka massif with the values of initial 87Sr/86Sr of discussions, assistance in field sampling and analytical
0.706 0.005 and Nd = 0.1 (Kovalenko et al. 1999) also support. Continuous assistance of the EMMA laboratory
favor EM II mantle input. Data hints at the possibility at the Natural History Museum London and of Barry Coles
that an EM II source controlled intraplate activity in East- (Imperial College London) with the analytical part of the
ern Transbaikalia during late Mesozoic times including project is acknowledged. This is a contribution to the IGCP
formation of the Orlovka and Spokoinoe deposits. Project #473 GIS Metallogeny of Central Asia.

Chapter 7-8 7-8

Syn-metamorphic dates for tourmaline formation

around Mount Isa, north-west Queensland, Australia
Robert J. Duncan, Andy R. Wilde
pmd*CRC, School of Geoscience, Monash University, Melbourne, VIC 3800, Australia
Roland Mass, Katherine Bassano
pmd*CRC, School of Earth Sciences, Melbourne University, Melbourne, VIC 3010, Australia

Abstract. Pb stepwise leaching of tourmaline from the Palaeoprotero-

zoic Western Fold Belt of the Mount Isa Inlier yield dates of 155917
Ma, 157752 Ma and 148090 Ma. Structural, petrological and tex-
tural data suggest that 155917 Ma is the best estimate for peak
metamorphism in the area. Estimates of Pb closure temperature
and comparison with peak metamorphic temperatures indicate that
this age represents tourmaline crystallisation. These dates repre-
sent syn-metamorphic fluid flow and indicate metal mobility dur-
ing the Isan Orogeny. A result of this event is regional-scale silicifi-
cation that has the same relative timing as extensive silica deposi-
tion in the rocks that now host the Cu orebodies at Mount Isa.

Keywords. Mount Isa, metamorphism, tourmaline, hydrothermal fluid

flow, Pb stepwise leaching

1 Introduction
and Page 1995; Hand and Rubatto 2002), but their rela-
To further constrain the timing of the Isan Orogeny in tionship to metamorphic reactions and structural features
the Western Fold Belt of the Mount Isa Inlier we applied is ambiguous (e.g. Roberts and Finger 1997). Published
the Pb step-leaching (PbSL) technique to tourmaline. PbSL Ar-Ar biotite dates (Perkins et al. 1999) are likely to rep-
involves sequential acid leaching of low-U minerals to resent cooling ages past the closure temperature. Table 1
generate Pb-Pb isochrons for old (>400 Ma) rocks (Frei summarises the current age estimates of peak metamor-
and Kamber 1995). The tourmaline samples dated here phism on single mineral phases.
can be demonstrated to have formed under, or close to,
peak metamorphic conditions using structural, petro- 3 Tourmaline occurrence, petrography and
graphical and geochemical evidence. geochemistry
As tourmaline is generally considered metasomatic in
origin, this work not only allows an improved understand- Tourmaline-rich lithologies are abundant in areas around
ing of the timing of peak metamorphism, but also new Mount Isa. Tourmaline is especially prevalent in the East-
insights into the nature of fluid flow associated with com- ern Creek Volcanics (ECV) west of the Mount Isa fault. In
pressional deformation. The timing and nature of this this area it occurs in quartz-K feldspar-mica-apatite
hydrothermal event has potential implications for the Cu pegmatites around the contact of the Sybella Batholith
mineralisation at Mount Isa. and apparently stratabound, but not stratiform,
tourmalinites (representative of extensive silicification).
2 Previous work Minor tourmaline occurrences have been identified in
the ECV to the east of Mount Isa. The three samples se-
The polydeformed mid- to late Proterozoic Mount Isa In- lected for dating are from within a 25 km radius of Mount
lier in north-west Queensland was tectonically active be- Isa and are in close proximity to small mineral occur-
tween 1900 and 1500 Ma (Blake and Stewart 1992). The rences (Fig. 1).
most intense period of deformation is considered to be Tourmaline has been identified as an accessory phase
largely synchronous with peak high temperature-low pres- in the silica dolomite alteration halo to the Cu orebodies
sure metamorphism that resulted from crustal shorten- at Mount Isa (Mathias and Clark 1975). The silicification
ing during the Isan Orogeny from 1590 to 1500 Ma at the mine is considered to have occurred prior to Cu
(Connors and Page 1995; ODea et al. 1997). mineralisation, synchronous with D2 or D3 deformation
Previous attempts to date peak metamorphism have (Swager 1985; Wilde et al. this volume) during the peak
focused on U-Pb analysis of zircon and monazite (Connors of deformation. The orebody tourmaline is dravitic in

752 Robert J. Duncan Andy R. Wilde Roland Mass Katherine Bassano

composition and is concentrated in the Paroo Fault in structures. Tourmaline in the pegmatite selvages defines a
the footwall of the Cu orebodies (W. Perkins and J. Knights steeply plunging mineral lineation (L2) and pseudomor-
pers. comm. 2004). phs cordierite poikiloblasts in the wall rock (Fig. 2b). Pri-
Tourmaline from close to the King Cu deposit is mary fluid inclusions within tourmaline from this sample
stratabound, but not stratiform within quartzite and contain up to 436 ppm U (Duncan and Wilde 2004).
psammopelitic units of the Myally subgroup. Tourmaline At Andersons Lode (a small U deposit hosted by the
growth overprints the S2 fabric, defined by biotite and ECV) a quartz-fibrous tourmaline vein is deformed by
sillimanite, and is deformed by D3 NNW-trending shear D3 shearing. Host rock tourmaline is overprinted by a bi-
zones and NNW gently plunging meso-scale folds (Fig. 2a). otite-chlorite metamorphic matrix (Fig. 2c). These rela-
The sample consists of zoned glomerocrysts and coarse- tionships suggest that tourmaline crystallisation was early
grained strained quartz, along with minor amounts of to syn-metamorphic and pre-D3 in timing. Parageneti-
titanite, sphalerite and Fe-Ti oxides. cally associated with the quartz-tourmaline vein are mi-
Adjacent to the Eldorado U deposit (hosted by the ECV) nor amounts of pyrite and chalcopyrite.
is a quartz-tourmaline-K feldspar-mica pegmatite. The peg- Electron-microprobe analyses demonstrate the tran-
matite is parallel to the S2 fabric and is boudinaged by D3 sitional Fe-Mg composition of all the tourmaline samples.
Tourmaline from Andersons Lode is schorlitic, whilst
samples from Eldorado and King are dravitic. Trace ele-
ment analysis by laser ablation ICP-MS reveals that the
tourmalines are relatively enriched in light rare earth el-
ements with variable Eu and Ce anomalies, indicative of
crystallisation from a metamorphic fluid (cf. Jiang et al.

4 Pb stepwise leaching

PbSL was carried out at the University of Melbourne. The

main advantage of PbSL over bulk U-Pb dating is the abil-
ity to chemically separate Pb from U-rich and U-poor
domains within the samples, thus generating Pb isotopic
dispersion from a single mineral separate. 208Pb/206Pb sys-
tematics can be used to recognise, and discard if neces-
sary, results from leach steps dominated by unequilibrated
impurities with distinct Th/U ratios, such as zircon and
Tourmaline concentrates (200 to 400 m) were pro-
duced by conventional dense medium separation and
purified by hand-picking. After removal of surficial Pb
contamination with distilled water, samples weighing 80
to 100 mg were sequentially leached with 1.5 N HCl-2N
HBr mix, 1N and 8N

Chapter 7-8 Syn-metamorphic dates for tourmaline formation around Mount Isa, north-west Queensland, Australia 753

HBr, 7N and 15N HNO3 and 48% HF on a hot plate at Pb-Pb isochrons parameters and ages were calculated
~100oC for periods of five minutes to 120 hours. Pb from using ISOPLOT (Ludwig 2003). External 2sigma m
each leach step was extracted using a single pass over 0.1 (0.03%) or internal (2sigmam) errors (whichever is
ml columns of EICHROMTM Sr resin following the method greater) and error correlations derived from these un-
of Thriault and Davies (1999). Pb isotopic ratios were certainties were used as input errors for the isochron cal-
determined by multi-collector ICP-MS (Woodhead 2002). culations. No blank corrections were applied.
Tourmaline from Andersons Lode yielded five leach
steps, with a range in 206Pb/204Pb of 17.2 to 72.9. A regres-
sion of all five leach steps identifies some scatter (MSWD
77), but a relatively precise Pb-Pb isochron age of 155917
Ma (Fig. 3a).
Seven leach steps derived from the tourmaline at
Eldorado gave a range in 206Pb/204Pb from 19.9 to 67.2,
regression of all the data indicates a excessive amount of
scatter (MSWD >6000). Inspection of the 208Pb/206Pb data
shows that three leach steps are affected by Pb from Th-
rich micro-inclusions. Omission of these points results
in a four-point age of 157752 Ma (MSWD 46; Fig. 3b).
The five leach spectra of the tourmaline from King
yield the narrowest range in 206Pb/204Pb (16.4 to 35.3).
After the removal of one step with anomalously high 208Pb/
Pb (i.e., Pb derived from Th-rich inclusions), this short
data array produce an imprecise age of 148890 Ma
(MSWD 16; Fig. 3c).

5 Interpretation of ages

Estimates of Pb closure temperatures in tourmaline for

compositions similar to these samples were calculated
according to the method outlined by Dahl (1997) and range
from 580 oC to 630 oC. The Andersons Lode area is
characterised by low to mid-greenschist facies rocks, so
the 1557 Ma date reflects tourmaline formation. Around
Eldorado peak metamorphic temperatures are estimated
at 540oC to 640oC (Rubenach 1992) and at King tempera-
tures of ~600oC are likely to have been encountered dur-
ing peak metamorphism (Connors 1992). At these two
locations the ages and associated large errors may repre-
sent a period of elevated heat flow, when the ambient geo-
thermal gradient was above the Pb closure temperature
and Pb could diffuse easily. The may explain the range of
U-Pb zircon dates (Table 1; 1565 to 1480 Ma from one
sample in Connors and Page (1995)).
Comparing age data derived from Pb-Pb dating of tour-
malines with other metamorphic dates it is clear that be-
tween ~1575 and ~1530 Ma the Western Fold Belt around
Mount Isa was undergoing high-temperature/low-pressure
peak metamorphism. This metamorphic window reflects
the prolonged duration of tectonic shortening during the
Isan Orogeny. It appears that regional tourmalinisation re-
sulted from prolonged hydrothermal activity related to this
compressional deformation. The best estimate of peak meta-
morphism is now ca. 155717 Ma.
The occurrence of tourmaline with small Cu and U
deposits and paragenetic relationships with minor

754 Robert J. Duncan Andy R. Wilde Roland Mass Katherine Bassano

sulphides suggests that during hydrothermal fluid move- Hand M, Rubatto D (2002) The scale of the thermal problem in the
ment driven by metamorphism, metals of economic in- Mt. Isa Inlier. In: Preiss VP (ed) Geoscience 2002: Expanding
Horizons. Abstracts of the 16th Australian Geological Conven-
terest were mobile. The regional spatial and temporal as-
tion, Adelaide, SA, Australia 67: 173
sociation of tourmalinisation with silicification indicates Jiang SY, Yu JM, Lu JJ (2004) Trace and rare-earth element geochem-
that the silica-rich halo around the Cu orebodies may have istry in tourmaline and cassiterite from the Yunlong tin deposit,
formed at a similar time. Yunnan, China: implications for migmatic-hydrothermal fluid
evolution and ore genesis. Chem Geol 209: 193-213
Ludwig KR (2003) Users Manual for Isoplot 3.00: A geochronologi-
Acknowledgements cal toolkit for Microsoft Excel. Berkeley Geochronology Center
Spec Publ 4, California, p 70
The PbSL routines are based largely on unpublished ex- Mathias BV, Clark GJ (1975) Mount Isa copper and silver-lead-zinc
periments by M Tonelli, J Hergt and J Woodhead (Univ. ore bodies; Isa and Hilton mines. In: Knight CL (ed) Economic
of Melbourne). The work reported is part the pmd*CRC Geology of Australia and Papua New Guinea. Aust Inst Mining
with support from Xstrata Copper. Thanks to R. Romer Metall, pp 351-371
ODea MG, Lister GS, MacCready T, Betts PG, Oliver NHS, Pound KS,
for reviewing this abstract. Huang W, Valenta RK (1997) Geodynamic evolution of the Prot-
erozoic Mount Isa terrain. In: Burg JP, Ford M (eds) Orogeny
References through time. Geol Soc Spec Publ 121: 99-122
Perkins C, Heinrich CA, Wyborn LAI (1999) 40Ar/39Ar geochronol-
Blake DH, Stewart AJ (1992) Stratigraphic and tectonic framework, ogy of copper mineralization and regional alteration, Mount Isa,
Mount Isa Inlier. In: Stewart AJ, Blake DH (eds) Detailed studies Australia Econ Geol 94: 23-36
of the Mount Isa Inlier. Aust Geol Surv Organ Bull 243: pp 1-11 Roberts MP, Finger F (1997) Do U-Pb zircon ages from granulites
Connors KA (1992) Tectonothermal evolution of the Mount Novit reflect peak metamorphic conditions? Geology 25: 319-322
Ranges, Mount Isa Inlier, Australia. PhD Thesis, Monash University Rubenach MJ (1992) Proterozoic low-pressure/high-temperature meta-
Connors KA, Page RW (1995) Relationships between magmatism, morphism and an anticlockwise P-T-t path for the Hazeldene area,
metamorphism and deformation in the western Mount Isa In- Mount Isa Inlier, Queensland, Australia. J Meta Geol 10: 333-346
lier, Australia. Precambr Res 71: 131-153 Swager CP (1985) Syndeformational carbonate-replacement model for
Dahl PS (1997) A crystal-chemical basis for Pb retention and fission- the copper mineralization at Mount Isa, Northwest Queensland; a
track annealing systematics in U-bearing minerals, with implica- microstructural study. Econ Geol 80: 107-125
tion for geochronology. Earth Planet Sci Lett 150: 277-290 Thriault RJ, Davies WJ (1999) Rapid extraction of Sr and Pb by ion-
Duncan RJ, Wilde AR (2004) Tourmaline at Mount Isa, Australia: a specific chromatography for thermal ionisation mass spectrom-
tracer of metal-rich hydrothermal fluid flow. In: Muhling J et etry analysis. In Radiogenic age and isotopic studies, report 12,
al. (eds) SEG 2004: Predictive Mineral Discovery Under Cover, Geol Surv Can Current Research 1999-F: 9-12
Perth, Western Australia; Extended Abstracts, Centre for Glo- Wilde AR, Gregory MJ, Duncan RJ, Gessner K, Khn M, Jones P (2005)
bal Metallogeny, The University of Western Australia Publica- Geochemical process model for the Mt Isa Cu-Co-Ag deposits,
tion 33: 413 this volume
Frei R, Kamber BS (1995) Single mineral Pb-Pb dating. Earth Planet Woodhead JD (2002) A simple method for obtaining highly accu-
Sci Lett 129: 261-268 rate Pb isotope data by MC-ICP-MS. J Anal Atom Spec 17: 1-6

Chapter 7-9 7-9

Potassic alteration and veining and the age of copper

emplacement at Mount Isa, Australia
Melissa J. Gregory, Andy R. Wilde, Bruce F. Schaefer, Reid R. Keays
pmd*CRC, School of Geoscience, Monash University, Melbourne, VIC 3800, Australia

Abstract. Preliminary 187Re/188Os dating of whole rocks and sulphide 2.2 Urquhart Shale
separates from the Mount Isa copper orebody has generated an
isochron age of 1367 80 Ma (MSWD = 49; n = 6). This age is ap-
Biotite is a common phase in metasedimentary rocks of
proximately 150 myr younger than published biotite 40Ar/39Ar ages
previously assumed to date the copper-forming event at ca. 1523 the Mount Isa Group, including the Urquhart Shale. It
Ma. These older ages are from rocks in which biotite is likely to be defines the peak metamorphic foliation, and ranges in
metamorphic rather than hydrothermal in origin. Unambiguous composition from Fe-rich to more magnesian phlogopite,
potassic alteration related to copper formation is characterised by depending on the host rock composition.
biotite replacement of metabasalt (brownstones) and potassium
Biotite is rare in the intense silica-dolomite alteration
feldspar replacement of meta-tuffs. Previous 40Ar/39Ar dating of bi-
otite from brownstone yields 1352 Ma to 1385 Ma ages, while 87Rb/ associated with economic copper mineralisation, but dis-
Sr dating of potassium feldspar altered tuffs gives 1323 Ma. Mus- tinctive biotite-magnetite-stilpnomelane bearing rocks
covite from the Buck Quartz Fault, considered a conduit for copper occur in close proximity to Pb-Zn ore (Fig. 1). Swager et
mineralising fluids, yields an 40Ar/39Ar age of 1324 Ma. We suggest al. (1987) interpret these zones to be the result of the in-
that these ages more accurately reflect the age of copper emplace- teraction of the copper mineralising fluid with pre-exist-
ment, whereas the older 40Ar/39Ar ages more likely relate to cool-
ing from peak metamorphism.
ing iron-rich metasomatic rocks in the Urquhart Shale.
Conversely, Waring (1990) suggests that these zones were
Keywords. Mount Isa, Re-Os, potassic alteration the result of greenschist facies metamorphism. He notes
that the biotite-magnetite-stilpnomelane assemblage is
cut by dolomite veins considered to be contemporaneous
1 Introduction with copper emplacement.

The Mount Isa copper deposit contains over 13 million 3 Absolute age of metamorphism
tonnes of copper at 3.3 wt.%, and is hosted within the
Proterozoic Urquhart Shale (Perkins 1990). Textural evi- The absolute age of the peak (maximum temperature and
dence suggests that chalcopyrite-pyrrhotite mineralisation pressure) of regional metamorphism is poorly con-
occurred late in the tectonic history of the Mount Isa In- strained. Biotite from the Eastern Creek Volcanics 14.5
lier (Perkins 1984; Swager 1985; Valenta 1994; Waring km east of the mine, gave 40Ar/39Ar ages of 1534 4 Ma
1990). The absolute age of copper mineralisation, how- and 1524 3 to 1554 2 Ma (Perkins et al. 1999). These
ever, is poorly defined. In this paper we discuss the avail- ages were interpreted to reflect hydrothermal activity at
able radiometric data and their significance. Most pub- the end of regional metamorphism at 1534 Ma. This date
lished data are from potassic phases, such as biotite, mus- is consistent with the SHRIMP U-Pb zircon ages of 1532
covite and potassium feldspar so it is necessary to review 7 Ma by Connors and Page (1995) and the whole rock
87Rb/86Sr ages of 1544 12 Ma from Page and Bell (1986).
evidence for the relationship of such phases to copper
deposition. U/Pb monazite dating by Hand and Rubatto (2002)
suggests that peak metamorphism is older at ca. 1575 Ma.
2 Metamorphic biotite This older age is supported by new metamorphic tour-
maline dates of 1559 17 Ma and 1577 52 Ma using Pb-
2.1 Eastern Creek Volcanics Pb step leaching (Duncan et al. this volume).

The Eastern Creek Volcanics below and to the east of the 4 Potassic alteration
Mount Isa copper deposit have undergone lower
greenschist facies metamorphism. Stable assemblages in 4.1 Urquhart Shale
the metabasalts include chlorite, albite, actinolite, epidote,
calcite, titanomagnetite, magnetite, sphene and biotite. There are over 60 potassium-rich layers within the
Biotite and chlorite define a metamorphic foliation in Urquhart Shale throughout the Mount Isa mine sequence
some areas. (Croxford 1964). These layers are typically less than 5 cm

756 Melissa J. Gregory Andy R. Wilde Bruce F. Schaefer Reid R. Keays

thick, and characterised by an unusual pale gray colour. sected the Eastern Creek Volcanics below the Mount Isa
Croxford (1964) interpreted these layers as tuffs, based copper deposit (e.g. Hannan et al. 1993).
on the rare presence of glass shards. The tuffs consist of This biotite-rich alteration parallels the Paroo Fault
microcline (after adularia), quartz, rutile, hematite, sericite (Fig. 1) and is thicker (up to 70m) where copper
and carbonate. Perkins (1997), however, found that only mineralisation overlies the fault. In thin section, the bi-
the tuffs in the mine area were potassium-rich, suggest- otite-dominated rocks have a groundmass of chlorite, al-
ing a hydrothermal origin for potassium. bite and ilmenite that is overprinted by a fine network of
biotite veinlets. Undeformed biotite also pseudomorphs
4.2 Eastern Creek Volcanics weakly foliated chlorite.

Detailed logging of drillcore at the northern end of the 4.3 Potassium feldspar veining
Mount Isa copper deposit (mine section 38,000 mN) has
defined a zone of potassium-rich alteration within the Away from biotite-rich zones, potassium-rich veins are
Eastern Creek Volcanics, below copper mineralisation in observed in the metabasalts of the Eastern Creek Volcanics.
the Urquhart Shale (Fig. 1). This zone, which is dominated These veins are dominated by potassium feldspar, cal-
by biotite, has previously been called brownstone and has cite, quartz and chalcopyrite and are commonly 2 to 5
been reported in many deep drillholes that have inter- mm thick. Typically the veins are zoned with potassium
feldspar lining the metabasalt contact and calcite with
lesser quartz in the core. Chalcopyrite is intergrown with
the potassium feldspar. The vein boundaries are sharp
and cross cut the peak metamorphic foliation found within
the metabasalts.

5 Absolute age of ore formation

Preliminary 187Re/188Os isotopic analyses of whole rocks

and sulphide separates from the Mount Isa copper orebody
define an imprecise isochron age of 1367 80 Ma (Fig. 2).
87Rb/86Sr dating of potassic altered tuff horizons from

the mine area define isochron ages from 1341 21 Ma to

1474 202 Ma (Farquharson and Richards 1975; Page

Chapter 7-9 Potassic alteration and veining and the age of copper emplacement at Mount Isa, Australia 757

flow along the fault, as suggested by Hannan et al. (1993)

and Heinrich et al. (1995).
Chalcopyrite-bearing potassium feldspar veins overprint
the metamorphic foliation and therefore have the same rela-
tive timing as the biotite-rich alteration and the copper ore.
The presence of both biotite-rich alteration below the Paroo
Fault and potassium feldspar-rich veins demonstrates the
presence of a potassium and copper-rich fluid. This fluid
post-dates regional metamorphism and is spatially associ-
ated with the Mount Isa copper deposit.
A number of isotopic dating techniques suggest that
the peak of metamorphism at Mount Isa occurred prior
to 1532 Ma and possibly prior to 1575 Ma. Emplacement
of the Mount Isa copper deposit, based on numerous stud-
ies, clearly postdates the metamorphic peak. The abso-
lute age of copper emplacement however, and particu-
larly the gap between the conclusion of metamorphism
and ore formation has been poorly defined.
Our re-evaluation of published 40Ar/39Ar and 87Rb/86Sr
data on potassic hydrothermal alteration, together with
1981). A significantly more precise age is achieved by com- our preliminary 187Re/188Os dating of sulphide ore sug-
bining the two data sets (as all samples are from the same gest that copper mineralisation was emplaced between
lithology and area) to give an age of 1323 12 Ma (Gre- 1300 Ma and 1400 Ma, at least 130 million years after the
gory et al. 2004). A radiogenic initial ratio of 0.7418 metamorphic peak.
0.0061 suggests isotopic resetting may have occurred at An alternative interpretation may be that the terrain
this time (Farquharson and Richards 1975; Gregory et al. remained above the closure temperature for these sys-
2004; Page 1981). tems for several hundred million years after the peak of
Perkins et al. (1999) reported numerous 40Ar/39Ar dates metamorphism.
for biotite and muscovite from the Urquhart Shale and We suggest that the ca. 1523 Ma age of Perkins et al.
the Eastern Creek Volcanics (Table 1). Biotite and phlo- (1999), previously assumed to be the date of copper ore
gopite from stilpnomelane-magnetite zones gave 40Ar/39Ar formation, instead dates cooling from the metamorphic
ages of 1523 3 Ma and 1516 3 Ma, from which 1523 peak. The maximum temperature of ore formation is sug-
Ma was interpreted as the most likely date of copper ore gested to be between 300 and 350C (Heinrich et al. 1989;
deposition (Perkins et al. 1999). Heinrich et al. 1995), and may not have exceeded the Ar
Perkins et al. (1999) also dated biotite separates from closure temperature range of the metamorphic biotite.
brownstones within the Eastern Creek Volcanics adjacent Therefore, there is significantly more evidence to sup-
to the copper deposit. 40Ar/39Ar dating of these separates port a ca. 1350 Ma age for copper mineralisation com-
gave distinct plateau ages at 1352 3 Ma and 1385 3 pared with the previously accepted ca. 1523 Ma age. This
Ma, which was interpreted as the age of late stage fluid has implications for the genetic models proposed for the
flow. formation of the Mount Isa copper deposit.
Muscovite from the Buck Quartz Fault, interpreted to
be the inflow zone for the copper bearing fluids (Waring Acknowledgements
1990), gave an 40Ar/39Ar age of 1324 2 Ma, also inter-
preted as due to minor late stage fluid flow (Perkins et al. Work reported here was conducted as part of the
1999). pmd*CRC with support from Xstrata Copper.

6 Discussion and conclusions References

Biotite and phlogopite are virtually absent from intensely Connors KA, Page RW (1995) Relationships between magmatism,
altered and mineralised rocks which form the Mount Isa metamorphism and deformation in the western Mount Isa In-
lier, Australia. Precambr Res 71:131-153
copper deposit but there is a close spatial relationship Croxford NJW (1964) Origin and significance of volcanic potash-
between biotite-rich alteration below the Paroo Fault and rich rocks from Mount Isa. Inst. Min. & Met. Tr. 74:33-43
copper mineralisation above the fault. The biotite over- Duncan RJ, Wilde AR, Maas R, Bassano K (2005) Syn-metamorphic
prints the metamorphic foliation and the spatial relation- dates for tourmaline formation around Mount Isa, North-west
ships and timing supports the idea of hydrothermal fluid Queensland, Australia, this volume

758 Melissa J. Gregory Andy R. Wilde Bruce F. Schaefer Reid R. Keays

Farquharson RB, Richards JR (1975) Isotopic remobilization in the Page RW, Bell TH (1986) Isotopic and structural responses of gran-
Mount Isa tuff beds. Chem Geol 16:73-88 ite to successive deformation and metamorphism. Journal of
Gregory MJ, Wilde AR, Keays RR, Schaefer BF (2004) Preliminary Re- Geology 94:365-379
Os dating of the Mount Isa copper ores, Northwest Queensland. Perkins C, Heinrich CA, Wyborn LAI (1999) 40Ar/39Ar geochronol-
Barnicoat AC, Korsch RJ (eds) Predictive Mineral Discovery Co- ogy of copper mineralization and regional alteration, Mount Isa,
operative Research Centre Extended Abstracts, Geoscience Aus- Australia. Econ Geol 94:23-36
tralia Record 2004/09, pp 79 Perkins WG (1984) Mount Isa silica dolomite and copper orebodies;
Hand M, Rubatto D (2002) The scale of the thermal problem in the the result of a syntectonic hydrothermal alteration system. Econ
Mt Isa Inlier. In: Preiss VP (ed) Geoscience 2002: Expanding Ho- Geol 79:601-637
rizons, 16th Australian Geological Convention, Adelaide, South Perkins WG (1990) Mount Isa copper orebodies. In: Hughes FE (ed)
Australia, pp 173 Geology of the mineral deposits of Australia and Papua New
Hannan KW, Golding SD, Herbert HK, Krouse HR (1993) Contrast- Guinea. Aust Inst Mining Metall, pp 935-941
ing alteration assemblages in metabasites from Mount Isa, Perkins WG (1997) Mount Isa lead-zinc orebodies; replacement lodes
Queensland; implications for copper ore genesis. Econ Geol in a zoned syndeformational copper-lead-zinc system? Ore Geol
88:1135-1175 Rev 12:61-111
Heinrich CA, Andrew AS, Wilkins RWT, Patterson DJ (1989) A fluid Swager CP (1985) Syndeformational carbonate-replacement model for
inclusion and stable isotope study of synmetamorphic copper the copper mineralization at Mount Isa, Northwest Queensland; a
ore formation at Mount Isa, Australia. Econ Geol 84:529-550 microstructural study. Econ Geol 80:107-125
Heinrich CA, Bain JHC, Mernagh TP, Wyborn LAI, Andrew AS, War- Swager CP, Perkins WG, Knights JG (1987) Stratabound phyllosilicate
ing CL (1995) Fluid and mass transfer during metabasalt alter- zones associated with syntectonic copper orebodies at Mt. Isa,
ation and copper mineralization at Mount Isa, Australia. Econ Queensland. Aust J Earth Sci 34:463-476
Geol 90:705-730 Valenta R (1994) Syntectonic discordant copper mineralization in
Page RW (1981) Depositional ages of the stratiform base metal de- the Hilton Mine, Mount Isa. Econ Geol 89:1031-1052
posits at Mount Isa and McArthur River, Australia, based on U-Pb Waring CL (1990) The Genesis of the Mount Isa Copper Orebodies.
zircon dating of concordant tuff horizons. Econ Geol 76:648-658 PhD, Monash University

Chapter 7-10 7-10

Contact metamorphism at the manganese deposits of

the Noda-Tamagawa Mine, northeast Japan: Insight
from oxygen isotope data of manganese minerals
Ken-ichiro Hayashi
Doctoral Program in Earth Evolution Sciences, Graduate School of Life and Environmental Sciences, University of Tsukuba,
Tsukuba 305-8572, Japan

Abstract. Manganese ores of the Noda-Tamagawa mine are meta- morphism by the granodiorite. Sillimanite, andalusite, and
morphosed equivalents of bedded-type sedimentary manganese cordierite are present in some pelitic hornfels near the
deposits. The ore lenses are typically zoned with a central
manganese ore bodies.
pyrochroite-hausmannite zone, outer tephroite zone, and outermost
rhodonite zone closest to the wall rock chert. The 18O (VSMOW) As a result of the thermal metamorphism, a distinct
values of 65 tephroite, 32 rhodonite and eight quartz samples from zoning of manganese minerals developed in each ore lens,
the manganese ores and chert are in the ranges of 9.920.0, 11.7 on a scale of 2 to 5 m. Pyrochroite (Mn(OH) 2) and
20.3 and 23.023.9, respectively. The overall order of 18O-en- hausmannite (Mn3O4) typically occupy the central part
richment corresponds to the order of equilibrium fractionation
of the ore lens (0 to 1 m in thickness), surrounded by a
among these minerals. However, the temperatures calculated from
quartz-rhodonite and rhodonite-tephroite pairs from neighboring tephroite (Mn2SiO4) ore, and an outer rhodonite (MnSiO3)
ore zones do not give temperatures consistent with those estimated ore.
from the mineral assemblages in the wall rocks. These data suggest The major Mn-bearing minerals in the Noda-
that equilibrium was not established among neighboring mineral Tamagawa mine can be represented in the MnO-SiO2-
pairs, H2O, and CO2 during metamorphism. The fluid/rock ratios Al2O3 system. The principal zoning sequence in the ore
during metamorphism were very low (<< 1).
lenses of the Noda-Tamagawa mine corresponds to a trend
Keywords. Manganese deposit, oxygen isotope, contact metamor- of decreasing MnO content (and increasing SiO2 content)
phism, metamorphic fluid toward the wall rocks. Bulk chemical compositions of the
manganese ores change along the MnO-SiO2 join from
near the MnO apex for pyrochroite-hausmannite ore in
1 Introduction the central part of the bed to rhodonite near the wall rock.

Manganese ores of the Noda-Tamagawa mine are highly 3 Oxygen isotope study
metamorphosed and folded. This metamorphism makes
it difficult to obtain information on the primary features Mineral grains were hand picked from thick sections of
of the deposits, such as the original mineralogy, chemi- ~0.5 mm under a binocular microscope. Since most ore
cal composition, and environment of deposition. Despite samples of this study are monomineralic in nature, the
these difficulties, the deposit is interpreted to be the meta- purities of mineral separates were better than 95 %.
morphosed equivalent of bedded-type sedimentary man- Extraction of oxygen from quartz, rhodonite and
ganese deposits. The main objective of this study is to tephroite was carried out using a CO2-laser and BrF5 by a
elucidate the origin and metamorphic history of the man- fluorination method similar to that described by Hayashi
ganese ores at Noda-Tamagawa using the 18O relation- et al. (2001). The reproducibility of the 18O values was
ships among various metamorphic Mn-bearing silicate better than 0.2 .
minerals. These data constrain the temperatures of meta-
morphism, fluid/rock ratios, and composition of the meta- 4 Results and discussion
morphic fluids.
The 18O values of quartz samples from 3 localities of the
2 Geology of the Noda-Tamagawa mine mine have a narrow range from 23.0 to 23.9 . Quartz
from thin quartz layers in rhodonite ore has essentially
The manganese deposits of the Noda-Tamagawa mine are the same 18O value as quartz in the wall rock chert. Thirty-
situated in the northeastern part of a roof pendant of the two samples of rhodonite from rhodonite ore have 18O
granodiorite body. The roof pendant is ca. 8 km (N-S) x values that range from 11.7 to 20.3 ; 65 samples of
12 km (E-W) in area, and is comprised of the Jurassic tephroite from tephroite ore and have values from 9.9 to
Formation. In the vicinity of the Noda-Tamagawa mine, 20.1 . The order of 18O enrichment is generally quartz
these rocks have been hornfelsed due to the thermal meta- > rhodonite > tephroite, which corresponds to the ex-

760 Ken-ichiro Hayashi

Isotopic equilibrium temperatures were calculated for

mineral pairs in the neighboring zones within individual
ore lenses (Fig. 1). Except for one very high temperature,
three quartz-rhodonite and four rhodonite-tephroite pairs
give temperatures between 545C and 145C. These tem-
peratures are much lower than the estimated metamor-
phic temperatures and suggest that the minerals did not
equilibrate at peak temperature. The presence of silliman-
ite, although it is rare in the pelitic hornfelses near the
manganese ore bodies suggests that the peak metamor-
phic temperature was near the stability limits for an-
dalusite and sillimanite (ca. 600C at P= 2kb).
The 18O values for H2O and CO2 in equilibrium with
quartz, rhodonite and tephroite at the calculated tempera-
tures are variable, 7.6 to 18.4 for H2O and 16.7 to 33.6
for CO2. These data suggest that the equilibrium was
not established among neighboring mineral pairs, H2O,
and CO2 during the metamorphism. At high fluid/rock
ratios, isotopic equilibrium between the neighboring (but
non-coexisting) minerals would be expected. Therefore,
our data suggest that the fluid/rock ratios during meta-
morphism were very low (<< 1) or that fluids with differ-
ent isotopic compositions were present. A comparison of
18O values between the manganese silicate minerals of
pected order of enrichment for isotopic equilibrium be- this study and calc-silicate minerals from skarn deposits
tween minerals. Reversals in the order of 18O enrichment provides constraints on the nature of metamorphism and
(i.e., nonequilibrium relationships) was observed for some the origin of the isotopic composition of the Mn-miner-
rhodonite and tephroite pairs that were collected from als. As the skarn minerals were probably equilibrated with
zones separated by a distance of less than 1 m. magmatic or meteoric water (e.g. El Rhazi and Hayashi
The 18O values for the series of samples from ore stope 2002), the relatively narrow range of 18O values of the
L13S78 do not show a symmetrical pattern from the wall skarn minerals was probably controlled by the 18O val-
rocks toward the center of the ore lens. In general, the ues of skarn-forming water. In contrast, the wide range
18O values of both rhodonite and tephroite are higher in of 18O values for the manganese minerals in this study
the footwall of the ore zone than those in the hanging suggests that their isotopic compositions mainly reflect
wall. the precursor minerals. The contribution of 18O-depleted
Because the manganese ores in the Noda-Tamagawa fluids during metamorphism was not important.
mine are generally monomineralic on a hand specimen
scale, truly coexisting mineral pairs are difficult to ob- References
tain. However, if the Mn-silicates and oxides were both
formed from MnCO3 and SiO2 (i.e., the most probable El Rhazi M, Hayashi K (2002) Mineralogy, geochemistry, and age
primary mineral assemblage of the Mn ores before constraints on the Beni Bou Ifrour skarn type magnetite deposit,
northeastern Morocco. Resource Geology 52: 25-39
metamorphism) in conditions accompanying a large Hayashi K, Maruyama T, Satoh H (2001) Precipitation of gold in a
amount of metamorphic fluid, isotopic equilibrium may low-sulfidation epithermal gold deposit: insights from a submil-
be expected among minerals in samples up to a few meters limeter-scale oxygen isotope analysis of vein quarts. Economic
apart. Geology, 96: 211-216

Chapter 7-11 7-11

Isotopic geochemistry of Mesozoic igneous rocks and

mineralization of Shanmen silver deposit in Yi-Su Basin,
Jilin Province
Huang Wenbin
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, and Chinese Geological Library,
Beijing 100083, China
Shen Haoche
JIlin University, Changchun Jilin, 130021, China
Fen Lin
Research Institute, China Water Northeastern Investigation Design and Research Co. Ltd., Changchun, 130021, China

Abstract. The present study focuses on isotopic geochemistry of the magmatic rocks comprise about 70% of the igneous rocks.
Mesozoic igneous rocks and the Shanmen silver deposit in Yi-Su basin. The petrochemical composition of neutral and acidic ig-
Petrochemistry, isotopic geochemistry and isotopic geochronology are
neous rocks shows that the younger rocks are relatively
used to explore the relationship between regional magmatic activity
and the formation of the ore deposit. In this study, we explore the iso- richer in Si and alkali elements. As rocks get older, Na2O
topic geochemistry in the deposit and the surrounding igneous rocks content, and especially K2O content gradually rise. With
by studying Rb, Sr, Pb, S, H and D isotopes. This helps us to discern the the evolution of magma from neutral to the acidic-alkali,
source of the economic minerals and the metallogenetic mechanism the petrochemical composition of the rocks shows a range
responsible for the formation of the Shanmen silver deposit.
in SiO2 content from 51.0% to 78.9%. Alkalinity ranges
Keywords. Igneous rock, isotopic geochemistry, silver deposit, source from Na2O>K2O to K2O<Na2O. Initial 87Sr/86Sr ratios vary
of ore material from 0.74 to 0.70. These geochemical characteristics in-
dicate that the netural and acidic magma was derived from
1 Introduction the deep earth.

The Yi-Su basin is located in the fold zone of the TianShan- 2.2 Genesis of igneous rocks
Xinan orogenic belt, where two deep parallel faults known
as the Yi-Su fracture zones, are oriented 45~50E and ex- 2.2.1 Mantlederived (M-Type) igneous rocks
tend to the base of the lithosphere. The strata from the
Paleozoic group to the Cenozoic group lie along the side Mantle-derived igneous rocks occur sparsely in this re-
of the basin. Metamorphosed igneous rocks that have gion, with the exception of large scaleHimalayan alkali
experienced alteration and compressional deformation, basalts which are found along the Yi-Su deep fault. The
87Sr/86Sr ratio determined for olivine inclusions in basalt
outcrop around the outer edge of the basin. Many eco-
nomic deposits have been discovered in this region, in- is 0.738. Because the geologic age of these basalts is rela-
cluding iron, copper, gold, silver, and coal, fluorite depos- tively young, the 87Rb content is fairly low. The half-life of
87Rb is 48.8 b.y.. We suggest that the 0.738 may represent
its. These deposits are controlled by fractures and show
an intimate relationship with Mesozoic igneous rocks. the initial 87Sr/86Sr ratio in the basalt. This indicates that
The Shanmen silver deposit is located in the Yi-Su ba- the basaltic magma was derived from the upper mantle.
sin. In this paper, we present a detailed study of isotopic
geochemistry of the Mesozoic igneous rocks and the sliver 2.2.2 Mantle-crust mixed (MC-type) igneous rocks
ore in order to determine the relationship between mag-
matic activity and mineralization. The rocks derived from both mantle and crustal materi-
als are controlled by a basement rift, which lies in the
2 Isotopic geochemistry and formation of igneous topographically lower region of the basin. Most of the
rocks neutral-acidic and acidic igneous rocks occur in this lo-
cality. The initial 87Sr/86Sr ratio in these rocks ranges from
2.1 Petrochemistry 0.705 to 0.710. The 18O value in the quartz varies from
7.8 to 8.5. The Rb/Sr ratio ranges from 0.6 to 0.4.
A variety of igneous rocks from the Herynian to Hima- SiO2 content varies form 57% to 72%, whereas Na2O>K2O,
layan can be found in the Yi-Su basin.Neutral and acidic Al2O3/Na2O+CaO+K2O = 1, and f (%) varies from 0.1

762 Huang Wenbin Shen Haoche Fen Lin

to 0.4. These characteristics can be used to identify igne- consisting of monzogranite, biotite granite, and quartz
ous rocks derived from both crustal and mantle material diorite (Fig. 1). The Indosin Kaodaozi diorite, Wuolong
in the relative deeper earth. hornblende pyroxenite and Yanshanian granites display
a close relationship with the silver deposit. The Kandaozi
2.2.3 Crustal-derived (C-Type) igneous rocks pluton, which controls the distribution of the main ore
body, is located near the upper section of the silver de-
Crustal-derived igneous rocks are mainly located in the posit, and overlaps the Huangyintun group. The Wuolong
folded region of the basin, and are controlled by regional pluton, which forms the base of the ore body, lies on the
fracture zones and folds. In this locality, the crust is thick. eastern edge of the Kaodaozi pluton. It has a skewed con-
The initial 87Sr/86Sr ratio of these igneous rocks ranges from tact with the main fracture, and forms the wall rock for
0.716 to 0.720. The 18O value in the quartz is l0, and the the deposit. The silver deposit is 10 km long, 1~2 km wide,
Rb/Sr ratio is high. The rocks are rich in Si and K, and poor and is distinctly controlled by NE-NNE factures. These
in Ca. SiO2 content varies from 74% to 98% K2O>Na2O, f fractures divide the deposit into 5 ore blocks from south
(%) varies from 0.4~0.7. These characteristics can be used to north: the Zhangjiatun block, the Longwang block, the
to identify rocks derived from crustal materials. Wuolon block, the Gudong block and the Yingpan block.
The Wuolong block contains the majority of the ore re-
3 Isotopic and geochemical features of the silver serves, which occur in marbles and meta-siltstones from
deposit the middle-upper Huangyingtun group. The ore miner-
als are mainly silver (50%), galena, sphalerite, secondly
3.1 Regional geology pyrite and chalcopyrite.

The Shanmen silver deposit is located along the western 3.2 Petrography and petrochemistry of the mine region
margin in the Jihei fold system of the TianShan-Xinan oro-
genic belts. The main strata are the Cambrian-Ordovician The Kaodaozi pluton is the host rock for the main ore body.
Baoan group and the Middle Ordovician Huangyingtun It consists mainly of diorite, with lesser quartz diorite and
group. The latter has undergone silicification, sericitization quartz monzonite. The petrochemical composition is as
and carbonatization. Igneous rocks outcrop in the up- follows: K2O/Na2O<1, Al/K+Na+2Ca<1, [Fe2O3+FeO+1/
lifted area, which intrudes along deep fractures, mainly 2(MgO+Ca)] is 11.65, (Si+Na+K)/Fe2++Fe3++Mg) is 6.03,
(Cao+Na2O+K2O/(Al2O3+CaO+Na2O) is 1.70, and the co-
efficient of consolidation is 24.37. The main accessory min-
erals are titanite, apatite and barringerite.
The geochemistry of the rock is as follows: the 207Pb/
204Pb ratios vary from 15.56 to 15.64, the 206Pb/204Pb ra-

tios from 18.32 to 18.35, the 208Pb/204Pb ratios from 38.24

to 38.47, respectively. The initial 87Sr/86Sr ratio is 0.70544.
The Eu values range from 0.92 to 1.02. The LRee/HRee is
5.93. Therefore, we suggest the Kaodaozi diorite is likely
derived from the mantle-crust melting. Whole rock U-
Th-Pb dating, measured by MS, produces an age of 193.3
Ma. Pb-Pb dating of zircon in the quartz diorite produces
an age of 187.8 Ma.
The Wuolong pluton forms the base of the ore body,
and is the wall rock for the deposit. It consists mainly of
adamellite, with lesser granite and moyite. The petro-
chemical composition is as follows: K2O/Na2O>1, Al/
K+Na+2Ca>1, SiO2 content is 73.4%. The main accessory
minerals are zircon, apatite and magnetite.
The geochemistry of the rock is as follows: the 207Pb/
204Pb ratios vary from 15.58 to 15.61, the 206Pb/204Pb ratios

from 18.56 to 18.61, the 208Pb/204Pb ratios from 38.71 to 38.85,

respectively. The initial 87Sr/86Sr ratio is 0.7158. The Eu
value is 0.45. Therefore, we suggest the Wuolong pluton is
likely derived from mantle-crust melting. U-Th-Pb dating
for zircon, measured by MS, produces an age of 150Ma.
Whole rock K-Ar dating produces an age of 158 Ma.

Chapter 7-11 Isotopic geochemistry of Mesozoic igneous rocks and mineralization of Shanmen silver deposit in Yi-Su Basin, Jilin Province 763

3.3 Isotopic and geochemical evidence of genesis of the come from the modern mantle or the crust, in order to
Shanmen silver deposit discern the source of minerals for the younger deposits
(Y. W. Cheng, 1983). Fig. 2, Fig. 3 illustrate that Pb isotopic
A histogram is plotted for the 22 ore samples. The results composition of the galena is between the Pb composi-
show that the 208Pb/204Pb ratio shows normal distribu- tion of the tholeiite found at mid-oceanic ridges (repre-
tion with a single population except one. This indicates senting the upper mantle), and the Pb composition of is-
that Pb isotopes come from a distinct parental material, land-arc magmas found along the western coast of the
and that the source of mineralization is separate. Pacific Ocean. The results reveal that the mineral mate-
The model age, computed by a Doe single-stage model rial is derived from the deep earth, and formed from a
using Pb isotopes, is a negative age. This reveals that Pb magma composed of mixed upper mantle and crust. We
isotopic values within the ore zone are similar to isotopic compare the Pb isotopic composition in the galena in the
values expected from Pb derived from the upper mantle Shanmen deposit with the Phanerozoic metal deposits in
The model age computed by the Stacey two-stage formula China. The Pb isotopic composition in the metal depos-
is 180 Ma. This model age, which represents the age of its, which are related to the Mesozoic lava or granodior-
the formation of the silver deposit, is close to the age of ite in China is as follows (Cheng 1984): the Pb composi-
formation of Kaodaozi and Wuolong plutons. Moreover, tion is steady, The 207Pb/204Pb ratios vary from 15.3 to
the Pb isotopic composition in the ore is the same as the 15.6, and the 206Pb/204Pb ratios >17.5. In the Shanmen sil-
Pb isotopic composition of the two plutons, but differs ver deposit, the 206Pb/204Pb ratios vary from 18.017 to
from the stratum of Hangyintong group. Therefore, the 18.149, whereas the 207Pb/204Pb ratios vary from 15.418 to
source of Pb isotopes in the ore has an intimate relation- 15.525. Therefore, we suggest the minaeralization may be
ship with magmatic activity. related to the intrusion of the granodiorite.
The Pb isotopic composition in galena ore may be com- We measured the 34S values in galena, sphalerite and
pared with Pb isotopic composition in the rocks which pyrite in the ore bodies, wall rocks, and local strata.
(Table 1). The 34S data is as follows: the variation of the
34S values is narrow, the 34S values are low in the ore
bodies and the wall rocks, This is similar to the 34S val-
ues in meteorites. The 34S values are negative in the stra-
tum. The average 34S values in pyrite are -1.37. This is
within the range of 34S values in meteorites. These re-
sults indicate that the mineral material is derived from
the deep earth.
The 34S values from different ore bodies show a nor-
mal distribution. Most of them cluster around -2.0. The
34S values in the ore minerals are as follows: 34S (FeS) >
34S(ZnS) > 34S(PbS). This agrees with the equilibrium
conditions for sulfur isotopes in hydrothermal systems.
Therefore, these minerals are paragenetic. Thermometry
of sphalerite galena shows that the metallogenic temper-
ature was between 160 to 300oC.

764 Huang Wenbin Shen Haoche Fen Lin

The 18OH2O values in quartz show that mineralized References

fluids consisted of magmatic water in the early stages,
and meteoric waters mixed with magmatic waters dur- Amstrong BL, Hales WH (1977) Rb-Sr and K-Ar geochemistry of
ing the later stages. The D values range from -92% to - Mesozoic grantic rock and their isotopic composition. Ball, Geol.
Soc. Am 88
106%. Thereby, we suggest the silver deposit was formed Cheng YW, Zhu BQ (1984) The feature of isotopic composition of
in the same hydrothermal system. ore lead and genesis. Geochemica 3: 35-45
Hu X, Xu C, Niu S (1990) Evolution of the early Paleozoic continen-
4 Conclusions tal margin in northern margin of the North China Platform.
Beijing: Peking University Publishing House, 6-34
Li L, Zheng YF, Zhou JB (2001) Dynamic model for isotope Pb evo-
The genesis of the igneous rocks in the study region falls
lution in the Continental Crust of China. Acta Petrologica Sinica
into two groups: crustal-derived igneous rocks, and 1:63-67
mantle-crustal mixed igneous rocks. These two groups Liang YH, Zheng, XS, Zhang S (1996) The discussion on the
of igneous rocks have distinct differences in petrochem- relation between the magmatite and the silver deposit and
istry, mineral assemblage, and geologic environment of exploration of the mechanism of the formation of the silver
formation. deposit in Sipin. Songliao Journal (Nature Science Edition) 1:
On the basis of detailed study of geology and isotopic Liu, JQ (1987) Geochronology Study of Cenozoicin Lava in North
geochemistry of Rb, Sr, Pb, S, H, and O in both ore and wall East China. Acta Petrologica Sinica 4: 21-31
rock, we suggest the silver deposit is a mesothermal ore Taylor SR, Mclennan SM (1985) The continental crust: Its compo-
deposit, and the mineral material is derived form the mixed sition and evolution. Oxford: Blackwell, 67-96.
upper mantle and crust. The metallogenesis of Shanmen Wang FK (1994) Analysis on metallogenetic conditions of the
Shanmen Silver Deposit in Sipin, Jilin Povice. Jilin Geology 3:
silver deposit has an intimate relationship with magamatic
activity. The origin of mineral material and mineralizing Wang FK (1997) A new understanding of the Mesozoic intrusive
fluids is complex. Magmatic activity is the metallogenetic rock genesis and relationship with metallogeny in the Shanmen
mechanism of formation for this silver deposit. Silver Deposit, Sipin Area. Jilin Geology 3: 9-26

Chapter 7-12 7-12

Platinum group elements as useful genetic tracers for the

origin of polymetallic Ni-Mo-PGE-Au sulfide ores in Lower
Cambrian black shales, Yangtze Platform, South China
S.-Y. Jiang, Y.-Q. Chen, H.-F. Ling, J.-H. Yang, H.-Z. Feng
State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing, China

Abstract. The polymetallic Ni-Mo-PGE-Au sulfide ores occur in the extreme enrichments of a large spectrum of metals, such
Lowermost Cambrian Niutitang Formation of a thick black shale as Mo, Ni, Se, Re, Os, As, Hg, Sb, Ag, Au, Pt, and Pd, with
sequence in Yangtze Platform of South China. The origin for this
up to 106 to 109 fold enrichment relative to seawater val-
special type of sulfide ore has been hotly debated. Three genetic
models have been proposed: (1) extraterrestrial impact origin (Fan ues. Although this belt extends over 1600 km, economi-
et al. 1984); (2) submarine hydrothermal exhalative origin (Coveney cally minable ores occur mostly within the provinces of
et al., 1992; Lott et al. 1999; Steiner et al. 2001); (3) seawater scav- Guizhou and Hunan, with the most famous deposits be-
enging origin (Mao et al. 2002). In this paper, we discuss the origin ing Huangjiawan near Zuuyi (Guizhou province) and
for this special type of sulfide ore based on platinum group ele-
Dayong near Zhangjiajie (Hunan province).
ment geochemistry. We suggest that the chondrite-normalized PGE
patterns of the sulfide ores show some distinctive difference from Steiner et al. (2001) suggested that the linear trend of
the seawater pattern and may indicate a submarine hydrothermal the Ni-Mo sulfide ore occurrence in South China may re-
input for the metal enrichments in the sulfide ore. We defined a late to structural controls by a major deep fault zone in
new parameter, namely Pt anomaly (Pt/Pt*), and found that the Pt the transitional area between the Neoproterozoic back
anomaly in the polymetallic Ni-Mo-PGE-Au sulfide ores is similar to arc basin and the platform. Lott et al. (1999) found foot-
those ancient and modern sea-floor massive sulfide deposits. Other
platinum group element pairs, such as Pt/Pd, Ir/Pd, and Au/Pd ra-
wall hydrothermal quartz-sulfide stockworks for the sul-
tios of the Ni-Mo sulfide ores also share some similarity with those fide deposit, which may represent submarine hydrother-
of ancient and modern submarine massive sulfide deposits. In con- mal venting systems. Mao et al. (2002) reported a Re-Os
clusion, we support the submarine hydrothermal exhalative origin age for the Ni-Mo sulfide ores of 541 16 Ma. Chen et al.
for the sulfide ores, and suggest that this is a new type of sedi- (2003) also obtained a similar age using the Pb-Pb dating
ment-hosted submarine hydrothermal exhalative sulfide deposits.
technique for the host black shales (531 24 Ma).
Keywords. PGE, sulfide ore, black shale, Lower Cambrian, South China The major ore minerals are vaesite, bravoite, jordisite,
and MOCs; and minor ore minerals include arsenopy-
rite, chalcopyrite, covellite, sphalerite, millerite,
1 Introduction polydymite, gersdorffite, sulvanite, pentlandite, tennantite,
tiemannite, violarite, and native gold. Gangue components
The polymetallic Ni-Mo-PGE-Au sulfide ores occur in the consist of organic debris, siliceous rock, carbonate, clay,
Lowermost Cambrian Niutitang Formation of a thick black and phosphorite.
shale sequence on the Yangtze Platform of South China,
which extend over 1600 kilometers length along a NE 3 Platinum group element geochemistry
trending belt. Although this type of polymetallic Ni-Mo-
PGE-Au mineralization has been known for more than The Platinum group element and their chondrite-normal-
30 years, its origin has long been debated (Fan et al. 1984; ized patterns are very useful indicators for the origin of
Coveney et al. 1992; Horan et al. 1994; Lott et al. 1999; ore deposits including those within black shales and sub-
Steiner et al. 2001; Mao et al. 2002; Coveney 2003; Lehmann marine hydrothermal exhalative massive sulfide depos-
et al. 2003). Our study in recent years suggest that the its (e.g., Coveney et al. 1992; Pasava 1993; Pan and Xie
occurrence of PGE and other metal anomalies and min- 2001; Pasava et al. 2004).
eralizations in black shales may belong to a special class
of sedimentary-exhalative sulfide deposits that can po- 3.1 The Ir anomaly
tentially provide economically significant PGE and other
metal resources in the future. The polymetallic Ni-Mo-PGE-Au sulfide ores in South
China were first reported by Fan et al. (1973) and were
2 Geological setting regarded as an entirely new type of sulfide ore, which
contains up to several percent of Ni, Mo, As, together with
In South China, the polymetallic enrichment bed in the substantial amounts of PGE and Au. In 1984, Fan et al.
Lowermost Cambrian Niutitang Formation accounts for (1984) found high Ir values for these polymetallic Ni-Mo-

766 S.-Y. Jiang Y.-Q. Chen H.-F. Ling J.-H. Yang H.-Z. Feng

PGE-Au sulfide ores, and consequently they suggested a (0.1-3.3) and the ancient massive sulfide ores (0.4-1.0), al-
meteorite impact model for the origin of these ores. How- though the range in these deposits seems to be smaller. The
ever, this model was doubted and discarded by Conveney Fe-Mn crusts, which scavenged PGEs from seawater, also
et al. (1992) who found that the Ir contents are actually show large Pt/Pd ratios ranging from 6 to 272, whereas Au/
relatively low (<0.02-2 ppb, average 1.7 ppb) compared Pd ratios show even larger variations.
with other PGEs (up to 700 ppb Pt and 1255 ppb Pd). Hence, we suggest that a simple comparison of these
Hence, Conveney et al. (1992) concluded that an extrater- noble metal ratios to those of seawater is by no means an
restrial source seems unlikely for the Chinese polymetallic adequate way to prove or disprove their derivation. In-
Ni-Mo-PGE-Au sulfide ores. stead, we suggest that the correlations between the noble
metal ratio pairs are more useful to differentiate hydro-
3.2 The Pt anomaly (Pt/Pt*) thermal origin from seawater origin. The comparison of
Chinese Ni-Mo sulfide ores with submarine hydrother-
Jiang et al. (2003) proposed a new PGE parameter of Pt mal exhalative sulfide ores and Fe-Mn nodules and crusts
anomaly (Pt/Pt*), which can be used as a sensitive ge- in Pt/Pd vs Pt/Pt*, Pt/Pd vs. Ir/Pd, Au/Ir vs. Au/Pd dia-
netic tracer. By analogy with the Eu anomaly in chon- grams demonstrate the similarity between the Chinese
drite-normalized REE patterns, a Pt anomaly can be de- Ni-Mo sulfide ores with Kuroko VMS-type sulfide ores
fined using the following equation: and modern sea-floor metalliferous sediments and sul-
fides, but a distinct contrast to Fe-Mn nodules and crusts.
Taken together, we suggest that the Chinese Ni-Mo ores
are likely to have a similar hydrothermal origin to mod-
ern and ancient sea-floor massive sulfide deposits.
where the PtN, RhN, and PdN are the chondrite-normalized
values of the samples. The Pt/Pt* values are generally larger 4 Conclusions
than 1 (positive Pt anamaly) for most crustal sources. In
contrast, the mantle-derived sources display negative Pt The ore genesis for the Chinese polymetallic Ni-Mo-PGE-
anomaly with Pt/Pt* close to or less than 1. We found that Au ores within the Lowermost Cambrian Niutitang For-
the Pt/Pt* values for the host rocks of phosphorites, sili- mation has been hotly debated. The increasing amount of
ceous shales, and black shales in South China are signifi- data from field geology, fluid inclusions, geochemistry (trace,
cantly larger than 1, but the Pt/Pt* values for the Ni-Mo rare earth elements, and platinum group elements), and
sulfide ores are close to 1, overlapping the values for Kuroko isotopes support a formation of these deposits via subma-
VMS-type sulfide ores. This similarity may imply a similar rine hydrothermal venting systems, in an anoxic environ-
submarine hydrothermal origin for the Chinese Ni-Mo sul- ment where abundant organic matter promotes extreme
fide ores. This hypothesis supports other studies that favor enrichment of redox-sensitive metals. According to our
a hydrothermal origin for the Chinese polymetallic Ni-Mo- systematic PGE investigation, we propose a genetic model
PGE-Au sulfide ores (Murowchick et al. 1994; Li and Gao for the submarine hydrothermal ore-forming process, and
1996; Lott et al. 1999; Steiner et al. 2001). suggest this is a new type of sediment-host Sedex deposits.

3.3 Platinum group element ratios Acknowledgements

The Platinum group element ratios are diagonastic tools This research was supported by China National Science
to trace ore genesis. Lehmann et al. (2003) suggested that Foundation grants (40221301, 40372059, 40172041). Profs.
the Chinese Ni-Mo sulfide ores have Pt/Pd and Au/Pd ra- Zhu Maoyan, Zhang Junming, and Wu Xianhe are thanked
tios around 1, quite close to seawater ratios (Pt/Pd= 0.8, for their very helpful assistance in field work and for criti-
Au/Pd=0.3), but are different from the Serra Pelada Au- cal discussion. This is a contribution to the Sino-German
Pd-Pt deposit of northern Brazil and the Rammelsberg joint project of Biological and Geological Processes of the
deposit of Germany (Au>Pd>Pt). Cambrian Explosion.
However, we found that the Pt/Pd ratios of magmatic
Ni-Cu sulfide deposits are also commonly close to 1 (Barnes References
et al. 1985; Brugmann et al. 1989). In fact, the Pt/Pd ratio for
the Chinese Ni-Mo ores and their host rocks, as well as for Barnes SJ, Naldrett AJ, Gorton MP (1985) The origin of fractionation
many modern and ancient sea-floor massive-sulfide deposits of platinium-group elements in terrestrial magmas. Chem Geol
53: 303-323
and Fe-Mn crusts show a relative large variation. We found Brugmann GB, Naldrett AJ, MacDonald AJ (1989) Magma mixing
that the Pt/Pd ratios of the Chinese Ni-Mo sulfide ores (0.3- and constitutional zone refining in the Lac des Iles Complex,
20) are similar to their host rocks (0.5-14), and are also Ontario: Genesis of platinum-group element mineralization. Econ
comparable to the modern sea-floor metalliferous sediments Geol 84: 1557-1573

Chapter 7-12 Platinum group elements as useful genetic tracers for the origin of polymetallic Ni-Mo-PGE-Au sulfide ores in Lower Cambrian black shales 767

Chen Y-Q, Jiang S-Y, Ling H-F, Feng H-Z, Yang J-H, Chen J-H (2003) calated Ni-Mo polymetallic sulfide bed from the Lower Cambrian
Pb-Pb isotope dating of black shales from the Lower Cambrian Niutitang Formation, South China. Progr Nat Sci 13: 788-794
Niutitang Formation, Guizhou Province, South China. Progr Nat Lehmann B, Mao J, Li S, Zhang G, Zeng M (2003) Re-Os dating of
Sci 13: 771-776 polymetallic Ni-Mo-PGE -Au mineralization in Lower Cambrian
Coveney RM Jr (2003) Re-Os dating of polymetallic Ni-Mo-PGE-Au black shales of South China and its geological significance-A re-
mineralization in Lower Cambrian black shales of South China and ply. Econ Geol 98(3): 663-665
its geological significance-A discussion. Econ Geol 98(3): 661-662 Li S, Gao Z (1996) Siliceous rocks of hydrothermal origin in the Lower
Coveney RM Jr, Murowchick JB, Grauch RI, Michael D, Glascock D, Cambrian black rock series of South China. Acta Mineral Sinica
Denison JD (1992) Gold and platinum in shales with evidence 16: 416-422
against extraterrestrial sources of metals. Chem Geol 99: Lott DA, Coveney RM Jr, Murowchick JB (1999) Sedimentary exhalative
101-114 nickel-molybdenum ores in South China. Econ Geol 94: 1051-1066
Fan D, Yang R, Huang Z (1984) The Lower Cambrian black shales Mao J, Lehmann B, Du A, Zhang G, Ma D, Wang Y, Zeng M, and Kerrich
series and the iridium anomaly in south China. Development in R (2002) Re-Os dating of polymetallic Ni-Mo-PGE-Au mineral-
Geoscience, Inter Geol Congr, 27th, Moscow, 1984, Beijing, Sci- ization in Lower Cambrian black shales of South China and its
ence Press, 215-224 geologic significance. Econ Geol 97: 1051-1061
Fan D, Yang X, Wang Y, Chen N (1973) Petrological and geochemical Murowchick JB, Coveney RM Jr, Grauch RI, Eldridge CS, and Shelton
characteristics of a nickel-molybdenum-multe-element-bearing KL (1994) Cyclic variations of sulfur isotopes in Cambrian
Lower Cambrian black shale from a certain district in south stratabound Ni-Mo-(PGE-Au) ores of southern China. Geochim
China. Geochim 3:143-163 Cosmochim Acta 58: 1813-1823
Horan MF, Morgan JW, Grauch RI, Coveney RM Jr, Murowchick JB, Pasava J (1993) Anoxic sediments- an important environment for
Hul-bert LJ (1994) Rhenium and osmium isotopes in black shales PGE: An overview. Ore Geol Rev 8: 425-445
and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Steiner M, Willis E, Erdtmann BD, Zhao YL, and Yang RD (2001) Sub-
Hunan and Guizhou Provinces, China. Geochim Cosmochim Acta marine-hydrothermal exhalative ore layers in black shales from
58: 257-265 South China and associated fossils- insights into a Lower Cam-
Jiang S-Y, Yang J-H, Ling H-F, Feng H-Z, Chen Y-Q, Chen J-H (2003) brian facies and bio-evolution. Palaeogeo Palaeoclim Palaeoeco
Re-Os isotopes and PGE geochemistry of black shales and inter- 169: 165-191

Chapter 7-13 7-13

Chemical and mineralogical characteristics of tourmaline

in pegmatites from Vavdos, Chalkidiki peninsula, N Greece
M.D. Laskou
Department of Geology and Geoenvironment, Section of Mineralogy and Petrology, Athens University, Greece

Abstract. Pegmatite veins crosscutting dunites and serpentinites The Vavdos ophiolitic complex forms an elongate fault-
of the ophiolitic complex of the Vavdos (Gioldaki and Loukoviti), bounded body within the Circum-Rhodope Belt. It is one
northern Greece contain tourmalines with a wide variation in
of several similar complexes of Middle to Upper Juras-
size and composition. Pegmatite veins mainly consist of quartz
crystals, microcline, albite, perthitised-feldspars. The accessory sic age, extending in NW-SE direction, from north-east
minerals include mostly coarse to medium grained zoned tour- of Thessaloniki to Sithonia (Kockel et al. 1977; Musallam
maline, and lesser amounts of sericite (only occasionally biotite). and Jung, 1986). It consists of dunite, websterite, olivine
There are also trace amounts of some rare earth element miner- clinopyroxenite, gabbroic rocks and serpentinite. It also
als, such as morazite, xenotime and minerals of the bastnaesite
hosts a major deposit of cryptocrystalline magnesite
group (epigenetic products of monazite). The pegmatite veins host
also fine-grained tourmalile, which shows an orientation parallel (Dabitzias 1980).
to the schistosity of the rock. They are composed of quartz, low-T Pegmatites crosscutting the ultramafic sequence of the
albite and K-feldspars. Hydroxy apatite, chlorite, Nb-bearing REE Vavdos ophiolite complex contain tourmaline dispersed
minerals (koragoite), garnet, zircon and talc are also present in throughout the whole tourmaline mass (Kassoli-Four-
lesser amounts. naraki 1990).
Keywords. Tourmaline, quartz, pegmatites, Chalkidiki Greece
The present study focuses on two particular occur-
rences of tourmaline within the unit. These occurrences
have coarse, medium and also fine-grained tourmaline
1 Introduction hosted in pegmatite. The description of the mineral as-
semblages and their composition are given.
Pegmatites occur in veins crosscutting dunites and ser-
pentinites of the ophiolitic complex of Vavdos in the west- 2 Analytical methods
ern part of the Chalkidiki peninsula, N. Greece (Fig. 1).
The phase mineral analyses were carried out using SEM
JEOL JSM-5600 combined with an Oxford Link ISIS Se-
ries 300 EDX (University of Athens). ZAF corrections were
applied using SEMQuant software. Accelerating volt-
age and beam current were kept at 20.0 kV and 0.5 nA,

3 Mineralogical characteristics

Pegmatites from the area of Vavdos (Gioldaki and

Loukoviti) have a thickness ranging from 0.5 to 3m, and
are characterized by a medium- to coarse-grained tex-
ture (Fig. 2). The coarse and medium grained pegmatite
veins mainly consist of quartz crystals, microcline, albite,
and perthitised-feldspars. The accessory minerals include
coarse-grained, medium to fine-grained and the mostly
zoned tourmaline, plus small quantities of sericite and
rarely biotite. Lesser amounts of rare earth element min-
erals are also present (morazite, xenotime and minerals
of the bastnaesite group, which are epigenetic products
of monazite). Tourmaline occurs in sub to euhedral crys-
tals. Optical zoning in coarse-grained tourmaline is well
pronounced, with core color ranging from greenish-blue
to brown, while rims range from green brown to olive-

770 M.D. Laskou

Hydroxyapatite, chlorite, Nb-bearing REE minerals

(koragoite), garnet, zircon and talc are present in lesser
Tourmaline is visible in hand specimens and in thin
section, and is identified as green grains with fine brown
rims. The fine-grained tourmaline associated with quartz
and microcline occurs along shear zones within the host
pegmatite, which seem to have formed by re-crystalliza-
tion during a subsequent event

4 Mineral chemistry

Tourmalines from the area of Vavdos show wide compo-

sitional variation, in particular in the SiO 2 (33.94-
38.93wt%), Al2O3 (34.55-39.92wt%), FeO (3.78-12.29wt%),
TiO2 (0.00-3.33wt%), NaO (0.00-1.51wt%), MgO (0.00-
6.14wt%) and MnO (0.00-1.8wt%).
The range of the FeO/(FeO+MgO+MnO) and Fe/
(Fe+Mg) ratios are generally comparable to those given
in granitic systems (Deer et al. 1986). The majority of tour-
maline cores fall in the schorl field. Tourmaline rims are
depleted in FeO and enriched in Al203 in Table 2 only.
All tourmaline cores data are plotted in two areas: the
field 2 [Li-poor granitoids and their associated pegmatites
and aplites] and the field 3 [Fe3+-rich quartz-tourmaline
rocks (hydrothermally altered granites)] (Fig. 5).
green. Tourmaline of medium size exhibits green-pale
cores and olive-green rims. The textural association of 5 Concluding remarks
tourmaline and quartz (Fig. 2) indicate that these two
minerals are genetically related. Although much more research is required to establish the
Fine grained tourmalines in pegmatite veins occur origin of the Vavdos tourmalines, their textural, mineral-
in crystals with a wide range in grain size, from ogical and chemical characteristics suggest a multistage
250-500 m to 1000-1500 m. (Fig. 3). These pegmatites genesis. Changes in the chemical composition of tour-
are composed of quartz, low-T albite, K-feldspars malines and associated minerals are probably the result
and tourmaline. of epigenetic processes.

Chapter 7-13 Chemical and mineralogical characteristics of tourmaline in pegmatites from Vavdos, Chalkidiki peninsula, N Greece 771

772 M.D. Laskou

Dabitzias S (1980) Petrology and genesis of the Vavdos cryptocrys-
talline magnesite deposits, Chalkidiki Peninsula, Northern
Greece. Econ Geol 75:1138-1151
Deer WA, Howie RA, Zussman J (1986) Rock-forming minerals:
volum 1B, Disilicates and ring silicates: London, Longman Sci-
entific and Technical, 629p
Henry DJ, Guidotti CV (1985) Tourmaline as a petrogenetic indica-
tor mineral: an example from the staurolite-grade metapelites of
NW Maine. Am. Mineral. 70, 1-15.
Kassoli-Fournaraki A (1990) Chemical varuations in tourmalines
from pegmatite occurrences in Chalkidiki Peninsula, Northern
Greece. Scheiz Mineral Petrogr Mitt 70: 55-65
Kockel F, Mollat H, Walther HW (1977) Erlauterung zur geologischen
Karte der Chalkidiki und angrenzender Gibiete 1:100000,
Nordgriechenland. 119 S, Hanover
Mussalam K, Jung D (1986) Petrology and geotectonic significance
of salic rocks preceding ophiolites in the eastern Vardar Zone,
Greece. Tscher Min Petr Mitt 35:217-242

Chapter 7-14 7-14

Geochemical characteristics of He-Ar and Pb isotopes

in the Dajiangping pyrite deposit, western
Guangdong, South China
Kuang Li, Kai Hu, Shaoyong Jiang, Shiming Song
State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing, 210093, China

Abstract. He-Ar isotopes were measured from fluid inclusions in six 2 Sampling and analytical methods
samples of the Dajiangping pyrite orebody III and orebody IV., The
He/4He values range from 0.13 to 2.55Ra, and the 40Ar/36Ar values
He and Ar isotope were measured in fluid inclusions from
range from 348 to 443. These data indicate that mantle-derived flu-
ids contributed to the ore-forming fluids. This study suggests that six pyrites in the Dajiangping Deposit. These samples were
the hot fluids from the deep mantle intruded into the ore body collected from orebody III, orebody IV, CK36 core and
along a thrust fault, and hydrothermed the orebody. This caused wall rock. The samples were dispersed to 0.1~0.2mm grain
differentiation of the orebody resulting in the formation of the size, through dressing by both magnetic separation and
banded orebody III and the massive orebody IV. Pb isotopes from
heavy-liquid separation, then the pyrites were selected
the ore and wall rocks were also measured in this study. 206Pb/204Pb
values range from 18.075 to 18.292, 207Pb/204Pb values range from by stereomicroscope.
15.654 to 15.737, and 208Pb/204Pb values range from 38.401 to 38.781. The He and Ar isotope compositions were analyzed in
These ratios indicate that orebody III is very similar to the wall rock, the Open Laboratory for Isotope Geology at the Institute
whereas orebody IV has lower Pb/Pb ratios than wall rock. The data of Mineral Deposits at the Chinese Academy of Geologi-
support the interpretation that mantle fluid intruded into the en- cal Sciences. All samples were cleaned for 20 min in ul-
trapping Pre-Sinian basement migmatite, causing lower Pb isotope
ratios in orebody IV.
tra-sonic bath using acetone and then dried. The samples
were heated under vacuum at 120oC for 24 h to remove
Keywords. He-Ar isotope, Pb isotope, Crust fluid, Mantle fluid, Thrust absorbed atmospheric gases. They were crushed to ex-
fault tract inclusion-trapped noble gases. The released gases
were purified four times through two titanium sponge
pumps, a Zr-Al pump and an active-carbon cooling trap
1 Introduction filled with liquid nitrogen.
Active gases were frozen and completely absorbed.
The Dajiangping pyrite deposit lies in the northeastern Then comparatively pure He and Ne were introduced into
part of the of Yunkai ridge, south China. It is a unique the analyzing system. He and Ne were purified further to
ultra-large pyrite deposit in the south of Sinian (period) remove traces of impure gases such as H2. and Ar using a
layer (Chen and Chen 1998). The ore genesis model for titanium sublimation pump filled with liquid nitrogen.
the Dajiangping deposit has long been in dispute, and He isotopes were analyzed by mass spectrometer. Finally
the major debate focuses on whether the orebodies formed Ar was released at -78oC and Ar isotopes were then ana-
during hydrothermal sedimentation reform, by a vapour- lyzed. The instrument used in this study is an MI 120l IG
liquid superimposition event (Zhang et al. 1992, 1993, noble gas mass spectrometer. The 3He values were mea-
1994), or whether formation was the product of sured by an electronic multiplier detector. 4He was mea-
hydrothemal sedimentation (Chang and Chang 1998). sured by a Faraday cup. The resolutions are 1200 for the
Noble gases, especially helium and argon have distinct electronic multiplier detector, and 760 for the Faraday cup.
isotopic compositions in the crust and mantle. Due to The standard gas air is atmospheric air with a 3He/4He
this characteristic, He and Ar isotopes have been widely ratio of l.4x10-6.
applied in tracing the origins and water-rock interactions
of contemporary crustal fluids. Recently, these isotope 3 He-Ar isotope analysis and discussion
systematics have also been successfully applied to the study
of the origin of ancient ore-forming fluids and mineral- The results of helium and argon isotope data are given in
ization (Turner and Stuart 1992; Turner et al 1993; Burnard table 1. As shown in table 1, the fluid inclusions from py-
et al. 1994; Hu 1997; Zhao et al. 2002; Sun and Wang 2003; rite have 3He/4He ratios of 0.18~3.55x10-6(0.13~2.55Ra).
Zheng et al. 2003). In this note, we report He and Ar iso- The values of 40Ar/36Ar ratios show slight variation be-
topic data for the Dajiangping ore deposit first time, and tween 348~443, which is higher than Air-saturated waters
discuss the origin and evolution of the hydrothermal fluid. Ar/36Ar ratios of 295.5.

774 Kuang Li Kai Hu Shaoyong Jiang Shiming Song

Three possible noble gas sources exist in hydrother-

mal fluids (Burnard et al. 1999): (1)Air-saturated water
(ASW), including meteoric water and seawater. This is
characterized by atmospheric He and Ar isotopic com-
positions, i.e. 3He/4He=1.4 106 = 1Ra, 40Ar/36Ar=295.5.
(2) Radiogenic He and Ar accumulated in the crust. In
this source, the 3He/4He ratio varies from 0.01 to 0.05 Ra,
and the 40Ar/36Ar ratio usually higher than 295.5. (3)
Mantle-derived volatiles. These are characterized by high
He with a well-defined 3He/4He ratio of 69 Ra. The 40Ar/
36Ar ratio varies widely, and are usually higher than 400.

By comparing the isotopic composition of the sample to

the isotopic compositions of the three possible sources
of noble gases, we can determine the origin of the noble
gases in hydrothermal fluids.
As shown in the plot of 3He/4He vs. 40Ar/36Ar ratios
(Fig. 1), the data fall among three sources district, which
indicates that the hydrothermal fluid did not originate
from the single source, and instead may be a product of
crust-mantle mixture. There are two orebody IV samples,
two orebody IV samples, one CK36 drill core sample
(depth 133 m), and one wall sample of all the six samples. Dajiangping pyrite deposit was located on the thrust
We find that the ore-forming fluids of orebody IV fall in slip fault of a nappe structure in the western Guang-
between mantle-derived fluids and ASW. In contrast, the dong. The deposit was controlled by both a large over-
others lie lower on the graph; the CK-36 and DP-11 even turned fold; which has an axial plane to the south-
lie between ASW and crust fluids. east; and a secondary rotational fault. We can find
We can make use of the 3He/4He ratios to Figure out out the tectonic characteristics from Figure 2. It is con-
the mantle fluids (Rm) ratio and the crustal fluids (Rc) jectured that after the orebodies underwent the hydro-
ratio of the ore-forming fluids. By following formula[13], themal sedimentaion event, thrust faults formed by in-
we can Figure out the helium from mantle fluids: tensive crustal tectonic movement, which pushed the
Sinian layer onto limestone of Devonian and Carbonif-
Helium from mantle fluids = [(RRc)/(RmRc)] (1) erous.
Then mantle fluids rose with the intensive tectonic
The Rm, Rc and R represent the 3He/4He ratios of movement. Finally the hydrotherm from deep mantle
mantle fluids, crust fluids and the samples. Rm=6~9 Ra, fluids entered into, and transformed the orebodies
Rc=0.01~0.05 Ra. According to formula (1), the six along the fault. Therefore, the characteristics of noble
samples helium content from mantle fluids declines from gas isotope signature changed systematically during for-
orebody IV, orebody to wall rock, indicating that the de- mation, as shown in Figure 1. At the same time the
gree of mantle fluids participating in the ore-forming hydrotherm transformed the shape of orebodies, and
processes was decreasing. The reason for this may be that caused differentiation resulting in the formation of the
the ore deposits formation passed through a few differ- banded pyrite ore (orebody III) and the massive pyrite
ent stages. Zhu and Meng (1999) found that the ore (orebody IV).

Chapter 7-14 Geochemical characteristics of He-Ar and Pb isotopes in the Dajiangping pyrite deposit, western Guangdong, South China 775

4 Pb isotope geochemical characteristics

Lead isotopes are a powerful tool to trace the origin of

metal deposits. We also measured lead isotope of 11
samples including orebody III, orebody IV, and wall rock.
The data in Figure 3 also incorporate Pb isotope data of
Yunkai ridge area magmatic rock and basement migmatite ment rocks, and eventually formed the mixing hydrotherm.
in Pre-Sinian period, as well as other Pb isotope data from Then, the fluid burst out of sea floor from growth faults
pyrites. The lead isotope data from the pyrites differs from and formed stratiform deposits in the reducing environ-
the lead isotope data from the magmatic rocks. This in- ment. The formation of the thrust fault was initiated by
dicates that the ore deposit must not be the product of teconic movement at the spot of ore deposits. Later, the deep
igneous magmatism. It also shows that the lead isotope mantle hydrotherm entered into, and reformed the
compositions of minerals and wall rocks are mainly con- orebodies. Though no new element was added in, the
sistent. hydrotherm changed the orebody shape and differentiated
Although the lead isotope compositions of the two ore the deposit into two distinct members: the banded orebody
types partially overlap, the massive orebody has lower III and the massive orebody IV.
Pb isotopic values than the banded orebody. It is possible
that the lead from mantle fluid had been added to the Acknowledgements
orebody. Therefore, the Pb isotope characteristics of the
Dajiangping pyrite deposit strengthen our conclusion that This work was supported by the Youth Excellent-Group
the orebody IV was formed by late mantle fluid, which Program No.40221301 and No.40172035 in the National
migrated along a thrust fault and altered the original shape Science Foundation of China.
of the orebody.
5 Conclusions
Burnard PG, Hu RZ, Turner G (1999) Mantle, crustal and atmosphere
The ore-forming fluid of pyrites in Dajiangping orebodies noble gases in Ailaoshan, yun-nan Province, China. Geochimica
et Cosmochimica Acta, 63,pp. 1595-1604
mainly consists of air-saturated water (seawater), which
Burnard PG, Stuart F, Turner G (1994) C-He-Ar variations with in a
leached lithospheric ore-forming material. The original dunite nodule as a function of fluid inclusion morphology. Earth
R/Ra ratio of Helium Isotope was less than 1, but after Planet Sci.Lett,128: 243-258
the deposit was altered by the late mantle fluid, the R/Ra Chen D, Chen Q (1998) Characteristics of the hydrothermal sedi-
ratio rose by about 50 points. mentation of the Dajiangping super-large pyrite deposit in Yunfu,
Guangdong. Geochimica 27: 12-19
We conclude that in the Sinian layer, the air-saturated
Chen DF (1998) Pb and Nd Isotopes of the dajiangping Pyrite de-
water (seawater) was cyclically heated in the growth faults, posit, Guangdong Province, and its metallic ore source. Mineral
absorbed by the ore-forming matter of the crustal base- deposits: 215-222

776 Kuang Li Kai Hu Shaoyong Jiang Shiming Song

Hu R (1997) Geochemistry of He, Ar isotopes in ore forming fluids. Zhang B, Zhang Q, Pan J (1994) Trace element characteristics and
Bulletin of Mineralogy, Petrology and Geochemistry 16: 120-124 their geological significance of Dajiangping pyrite deposit, west-
Li X, Mao J (2004) Helium and Argon Isotope Systematics in Fluid ern Guangdong. Geology and Prospecting 30: 66-71
Inclusion of the Gold Deposits along the Daduhe River, Sichuan Zhang Q, Zhang B, Cao Y (1993) Preliminary discussion on sulfur
Province, Southwestern China. Acta Geologica Sinica 78: 203-210 and lead isotope compositions of the Dajiangping pyrite deposit
Sun X, Wang M (2003) He-Ar isotopic systematics of fluid inclusions in western Guangdong province. Acta Geologica Sinica, 67(3), pp.
in pyrites from PGE-polymetallic deposits in lower Cambrian 232-242
black rock series, southern China. Geological Journal of China Zhang Q, Zhang B, Pan J (1992) Silicalite characteristics and rare-
Universities 9: 661-666 earth element model of Dajiangping pyrite deposit in western
Turner G, Burnard PB, Ford JL (1993) Tracing fluid sources and in- Guangdong province. Chinese Science Bulletin 37: 1588-1592
teraction. Phil Trans R Soc Lond A 344: 127-140 Zhao K, Jiang S, Xiao H (2002) Origin of ore-forming fluids of the
Turner G, Stuart F (1992) Helium/heatratios and deposition tem- Dachang Sn-polymetallic ore deposit: Evidence from helium iso-
peratures of sulfides from the ocean floor. Nature 357: 581~583 topes. Chinese Science Bulletin 47: 1041-1045
Zeng Z, Qin YS (2003) He, Ne and Ar isotope compositions of fluid Zu D, Meng X (1999) Primary study on the western Guangdong nappe
inclusions in massive sulfides from the Jade hydrothermal field, structure in the hercynian and indo-Chinese epoch. Journal of
Okinawa Trough. Acta Oceanolog 25: 36-42 geomechanics 5: 51-58

Chapter 7-15 7-15

Precise Re-Os dating of molybdenite from the east

Qinling molybdenum belt in central China and its
geodynamic implications
Yong-Feng Li, Jing-Wen Mao, Feng-Jun Bai, Bao-Jian Guo
Faculty of Geosciences and Resources, China University of Geosciences, Beijing 100083, China
Zhi-Guang Wang
Bureau of Geology and Mineral Resources for Nonferrous Metals, Henan Province, 107 Zhongyuandong Road, Zhengzhou
450052, Henan, China

Abstract. Located in central China on the southern margin of the phyry Mo (Fe) deposit and Leimengou porphyry Mo de-
North China craton, the East Qinling molybdenum belt is one of posit. These results, combined with the results of previ-
the important large molybdenum belts in China. This study pro-
ous work in the Mo belt, provide further insight into the
vides reliable Re-Os isotopic dating results for the metallogenetic
epoch of four deposits by inductively coupled plasma mass spec- geodynamic setting for the formation of these ore de-
trometry (ICP-MS), with analytical errors of Re and Os between 0.11- posits.
0.4% (2sigma). The results show that the Re-Os model ages are
141.82.1Ma for the Nannihu deposit, 145.4 2.0 to 144.5 2.2 Ma 2 Geological setting
(averaging 145.0 2.2 Ma) for the Sandaozhuang deposit, 145.82.1
to 143.82.1 Ma (averaging 144.8 2.1 Ma) for the Shangfanggou
deposit, and 133.11.9 to 131.62.0 Ma (averaging 132.42.0 Ma) Located on the southern margin of the North China cra-
for the Leimengou deposit. According to these ages, combined with ton, The East Qinling belt is used to be a part of the North
the results of previous work in the molybdenum belt, it is suggested China craton (Fig. 1). Recently, it has also been described
that the age of the molybdenite deposits in the East Qinling mo- as a component part of the northern margin of the Qinling
lybdenum belt is mainly ~140 Ma. These deposits are the product orogen because of its involvement in the Qinling
of transformation from the N-S to the nearly E-W tectonic regime
in eastern China. Except for the Huanglongpu Mo deposit, which
intracontinental orogenic movement during the Meso-
originated at ~220 Ma, the deposits appear to have geodynamically Cenozoic, accompanied by intense magmatic activities
formed in the extensional stage of the post-collisional orogeny be- dominated by acid magma (Jurassic to Cretaceous), as
tween the North China craton and the Yangtze craton. the Wuzhangshan batholith, the Haoping, Heyu and
Huashan batholiths. Concomitantly with the intrusion of
Keywords. Mo deposit, Re-Os dating, geodynamics, East Qinling, China
the above-mentioned large granite bodies, a number of
small, hypabyssal to near-surface granite porphyries (such
1 lntroduction

The East Qinling molybdenum belt contains the most

important large molybdenum deposits in China. This belt
is the second largest molybdenum belt in the world sub-
sequent to the Climax-Henderson porphyry molybdenum
belt. The molybdenum deposits occur along a tectonic
lineament of trending nearly east-west. They are mostly
concentrated in a region extending from the Jinduicheng-
Huanglongpu area, south to the Shaanxi, eastward to the
Nannihu area in Luanchuan County and the Leimengou
area in Songxian County, western Henan. There are a to-
tal of more than 30 superlarge, large and intermediate
molybdenum polymetallic ore deposits in the belt, which
contribute 52 percent of the total identified Mo reserves
in China (Zhang et al. 2001). Stein et al. (1997) have re-
ported the Re-Os ages for the Jinduicheng-Huanglongpu
area. This study provides the reliable Re-Os isotopic dat-
ing results for the other two clusters, including four large
deposits: the Nannihu porphyry Mo (W) deposit,
Sandaozhuang skarn Mo (W) deposit, Shangfanggou por-

778 Yong-Feng Li Jing-Wen Mao Feng-Jun Bai Bao-Jian Guo Zhi-Guang Wang

as the Leimengou granite porphyry) and their genetically For many years the mineralization ages in this area were
related cryptoexplosive breccias, were emplaced. They indirectly estimated by using the ages of mineralization-
form a NW-trending tectonomagmtic belt in the region related granites, alteration minerals or by dating acces-
and provide the source of ore materials for molybdenum sory minerals and nearby plutonic rocks. The develop-
polymetallic mineralization. The Qinling molybdenum belt ment of new dating techniques, such as Re-Os dating of
may be approximately divided into three molybdenum clus- molybdenite, has allowed for direct dating of mineraliza-
ters. The first cluster is found in the Jinduicheng- tion., In the past several years, Re-Os analyses of molyb-
Huanglongpu area (Huang et al. 1984), and can be described denite from the East Qinling belt have been performed
as a mineralization cluster. The second cluster, is located in by Huang et al. (1994, 1996) and Stein et al. (1997). These
the Nannihu-Sandaozhuang area about 75 km ESE of the data are summarized in Table 1.
Jinduicheng-Huanglongpu area, and consists of porphyry
skarn-type Mo-W mineralization,. The third cluster is lo- 4 Samples and analytical methods
cated in the Leimengou area, and includes the Leimengou
porphyry type Mo deposit and the Huangshuian Mo-Pb A total of eight ore samples were collected from the East
deposit, which occurs in carbonatite veins. Qinling Mo deposits for Re-Os dating in this study. One
According to the geological characteristics, ore ele- of them came from the Nannihu deposit, three from the
ment assemblage, ore genesis, mode of occurrence and Sandaozhuang deposit, two from the Shangfanggou de-
metallogenic mechanisms of the ore deposits, the posit, and two from the Leimengou deposit. The samples
molybdenum deposits in the Qinling belt may be classi- were carefully identified under the binocular microscope
fied into three distinctly different groups; porphyry and then molybdenite separates were picked out by hand.
type, skarn-porphyry type and hydrothermal carbonate The separates were fresh, non-oxidized and pollution-free.
vein type. Samples were sealed in tubes and dissolved, following the
Carius tube digestion technique (Mao et al. 2003b). The
3 Previous dating Re and Os isotopic compositions were determined by us-
ing the ICP-MS (VG PQ-EXCELL). In this study, the aver-
In the East Qinling molybdenum belt, there have been age blanks for the Carius tube procedure as described
numerous attempts to date molybdenum mineralization. above are ca.10 pg for Re and ca.1 pg for Os.

Chapter 7-15 Precise Re-Os dating of molybdenite from the east Qinling molybdenum belt in central China and its geodynamic implications 779

5 Results County, Jiudian of Ruyang County and other areas (Wang

et al. 1997). Magmatism intensified, and the magma evolved
Common Os was not detected in the eight samples of successively from the alkaline through subalkaline to calc-
molybdenite Table2.shows the isotopic components of the alkaline compositions. This suggests a change in the char-
samples. The decay constant used for 187Re of 1.66610- acter of the magamitic activity during that period. The
11 -1
yr , which has an uncertainty of about 1.02%. The re- fact that more than 80% of Mesozoic intrusive rocks oc-
sults show that the Re-Os model ages are 141.82.1 Ma curred in the Early Cretaceous indicates that the transition
for the Nannihu deposit, 145.4 2.0 to 144.5 2.2 Ma (av- of the tectonic regime began at the turn of the Jurassic-
eraging 145.0 2.2 Ma) for the Sandaozhuang deposit, Cretaceous. The Re-Os isotope model ages obtained in this
145.82.1 to 143.82.1 Ma (averaging 144.8 2.1 Ma) for study are between 145.82.1 and 131.62.0Ma. It can be
the Shangfanggou deposit, and 133.11.9 to 131.62.0 Ma concluded that the East Qinling metallogenic molybdenum
(averaging 132.42.0 Ma) for the Leimengou deposit. belts originated during this great transition of the tectonic
regime in eastern China. This time period belongs to the
6 Metallogenic environment and geodynamical second phase of large-scale metallogenesis in East China
setting during the Mesozoic (Mao et al. 2000; 2003b).

The North China craton had been in a stage of steady Acknowledgements

development from the Cambrian until the Early Triassic.
The isotopic age data suggest the following: the Yangtze This study was supported by the National Natural Sci-
craton collided and converged with the North China cra- ence Foundation of China (grant 40434011) and the State
ton at about 218 to 238 Ma (Li et al. 1989), This was fol- Development and Planning Program for Basic Researches
lowed by an intracontinental orogeny, which ended in the in Key Areas of China (grant 1999043211).
Jurassic (Chen and Fu 1992). During the late Jurassic and
early Cretaceous, the regional tectonic regime in the whole References
of eastern China began to change. The main stress field
began to shift from N-S to nearly E-W, signaling the be- Chen Y, Fu S (1992) Mineralization of gold deposits in Henan, China.
Beijing: Seismological Press: 1-146 (in Chinese)
ginning of the Pacific tectonic evolution stage (Ren 1991).
Huang D, Du A, Wu C, Liu L, Sun Y, Zhou X, (1996) Metallochronology
During this stage the southern margin of the North China of Mo(-Cu) deposits in the North China plateform: Re-Os age of
craton, including the East Qinling area, transformed into molybdenite and its geological significance. Mineral Deposits 15:
the extensional tectonic environment. The Indosinian- 365-373
Yanshanian magmatic activity corroborates the features Huang D, Wu C, Du A, He H (1994) Re-Os isotope ages of molybde-
num deposits and in East Qinling their geological significance.
of the tectonic evolution in this period.
Mineral Deposits 13; 221-230 (in Chinese with English abstract)
First, in the Middle-Late Jurassic mafic magma rose and Li S, Hart SR, Zheng S (1989) The collision time of North China plate
intruded along tenso-shear steep-dipping fractures, form- and South China plate: evidence from Sm-Nd ages. Scientia
ing diabase dikes or dike swarms in the area. Later, wide- Sinica(B):19: 312-319 (in Chinese)
spread acid magmatic activity formed large granite Li Y, Mao J, Guo B (2004) Re-Os dating of molybdenite from the
Nannihu Mo(W) orefield in the east Qinling and Its Geodynamic
batholiths and numerous granite porphyry stocks and dikes.
significance. Acta Geologica Sinica 78: 463-470
During the Early Cretaceous, large amounts of intermedi- Mao J, Wang Z (2000) A preliminary study on time limits and
ate-acid magma were erupted along the Sanmenxia-Lushan geodynamic setting of large-scale metallogeny in East China.
deep fault, forming volcanic basins at Tianhu of Songxian Mineral Deposits 19:289-296 (in Chinese with English abstract)

780 Yong-Feng Li Jing-Wen Mao Feng-Jun Bai Bao-Jian Guo Zhi-Guang Wang

Mao J, Yang J, Qu W, Du A, Wang Z, Han C (2003b) Re-Os age of Cu- Stein HJ, Markey RJ, Morgan JW, Du A, Sun Y (1997) Highly precise
Ni ores from the Huangshandong Cu-Ni sulfide deposit in the and accurate Re-Os ages for molybdenite from the east Qinling
east Tianshan Mountains and its implication for geodynamic molybdenum belt, Shaannxi Province, China. Economic Geology
process. Acta Geol Sinica 77: 220-226. 92:827-835
Mao J, Zhang Z, Yu J, Wang Y, Niu B (2003a) The geodynamics setting Wang Z, Cui B, Xu M (1997) The tectonic evolution and mineraliza-
of Mesozoic large-scale mineralization in North China: the rev- tion in the south margin of North China block. Beijing: Metal-
elation from accurate timing of metal deposits. Science in China lurgical Industry Press. pp1-296 (in Chinese)
(series D) 33:289-299 Zhang Z, Zhu B, Chang X, Qiang L, Wen M (2001) Petrogenetic
Ren J (1991) A discussion on the basic features of the lithosphere metallogenetic background and time space relationship of the
tectonics in Chinese continents. Regional Geology of China 2: East Qinling molybdenum ore belt, China. Geological journal of
289-293 (in Chinese with English abstract) China University 7(3):307-315(in Chinese with English abstract)

Chapter 7-16 7-16

Studies on the genesis of adjacent Changkeng gold-

and Fuwang silver-deposits, Guangdong Province, China
Hua-Ying Liang, Ping Xia, Xiu-Zhang Wang
Laboratory of Marginal Sea Geology, Guangzhou Institute of Geochemistry and South China Sea Institute of Oceanol-
ogy, Chinese Academy of Sciences, 510640 Guangzhou, China
Heng-Xiang Yu
Guilin Institute of Technology, Guilin 541004, China

Abstract. The Changkeng Au- and Fuwang Ag-deposits represent gold deposit is hosted in brecciated siliceous rocks on the
an economically significant and distinct member of the AuAg de- top of rocks of the Zimenqiao Group bioclastic limestone
posit association in China. The two deposits are immediately adja-
and is characterized by disseminated mineralization. Ore
cent, but the Au- and Ag-orebodies separated from each other.
Changkeng is hosted in brecciated cherts and jasperoidal quartz minerals in the gold deposit include disseminated anhedral
and is characterized by disseminated ore minerals. Fuwang, hosted pyrite, native gold, stibnite, realgar, and orpiment. Gangue
in the Lower Carboniferous Zimenqiao group bioclastic limestone, minerals include quartz, illite, dickite, calcite, less fluorite,
has vein and veinlet mineralization associated with alteration com- and barite (Du et al. 1993). The silver content in the gold
prised of quartz, carbonate, sericite, and sulfides. The Changkeng
orebodies is low (generally <11 ppm).
gold and Fuwang silver deposits overlap in homogenous tempera-
ture and salinity of fluid inclusions. The DH2O, 18OH2O, 13CCO2 and The Fuwang silver deposit is hosted in Early Carbon-
He/4He values of the fluid inclusions suggest the ore fluids of the iferous Zimenqiao bioclastic limestone along the contact
Changkeng Au-ore come from the meteoric water and the ore flu- fault zones between the limestone and the overlying
ids of the Fuwang Ag-ore are derived from mixing of magmatic Changkeng gold-hosting siliceous rocks. The Fuwang sil-
water and meteoric water. The Changkeng gold- and the Fuwang ver is characterized by vein and veinlet mineralization
silver deposits show different Pb isotope signatures, suggesting dif-
ferent sources of ore-forming material. Rb-Sr isochron age (68 6
with zones of silicification. The main sulphide minerals
Ma) and 40Ar-39Ar age (64.3 0.1 Ma) of the ore-related quartz veins are sphalerite and galena, with lesser pyrite and rare ar-
from the Ag-deposit indicate that the Fuwang deposit formed dur- senopyrite, chalcopyrite, and bornite. The deposit is poor
ing the Cenozoic Himalayan tectono-magmatic event. The adjacent in gold (< 0.2 ppm). The crosscutting relationship indi-
Changkeng and Fuwang deposits could, however, represent a single cates that the gold deposit is older than the silver deposit.
evolved hydrothermal system. The deposits are alternatively the
product of the superposition of two different geological events. Our
work indicates that the Pacific Coastal Volcanic Belt in the South
China Fold Belt has greater potential for Himalayan precious metal
mineralization than previous realized.

Keywords. Himalayan, gold, silver, Guangdong, ore genesis

1 Geological setting

The adjacent Changkeng gold- and Fuwang silver-deposits

are located along the southwestern rim of the Shanshui
basin (Fig. 1). Sedimentary rocks in the region range from
Proterozoic to Cenozoic.(Bureau of Geology and Mineral
Resource of Guangdong Province 1985; Du et al. 1993).
Eocene volcanic and sedimentary rocks are widespread
(Tang 1987) and a small Tertiary volcanic rocks hosted-
silver deposit was discovered (Fig. 1).
The adjacent Changkeng gold- and Fuwang silver- de-
posits differ in their geologic characteristics, stratigraphic
position, and metal contents, but are both located at the
same locality (Fig. 1), The Changkeng gold orebodies are
present in the upper part of the stratigraphic section (Du
et al. 1993). The Fuwang silver orebodies are located in the
lower parts of the stratigraphic section. The gold and silver
ore bodies are separated from each other. The Changkeng

782 Hua-Ying Liang Ping Xia Xiu-Zhang Wang Heng-Xiang Yu

2 Genesis of the gold-hosting siliceous rocks 3.2 Pb Isotopes of the adjacent Changkeng gold- and
Fuwang silver- deposits
Genesis of the gold-hosting siliceous rocks has been de-
bated extensively. Du et al. (1993) argues that the gold- The adjacent Changkeng gold- and Fuwang silver- de-
hosting siliceous rocks are jasperoid quartz formed from posits show different lead isotopic signatures. The
limestone. However, Xia et al. (1996) suggest that these Changkeng gold deposit has Pb isotope ratios (206Pb/204Pb:
rocks are syngenetic chert. Gold-hosting silicious rocks 18.580-19.251, 207Pb/204Pb: 15.672-15.801, 208Pb/204Pb:
consist of thin-bedded and laminated, massive, and brec- 38.700-39.104) similar to those (206Pb/204Pb: 18.578-19.433,
ciated black material. Some radiolaria, which suggest an 207Pb/204Pb: 15.640-15.775, 208Pb/204Pb: 38.925-39.920) of

age of between Carboniferous and Permian, are present its host rocks and different from those (206Pb/204Pb: 18.820-
in some of the laminated and massive siliceous material. 18.891, 207Pb/204Pb: 15.848-15.914, 208Pb/204Pb: 39.579-
This suggests that some parts of the gold-hosting sili- 39.786) of the Fuwang silver deposit. The Pb in the gold
ceous laminated and massive material is radiolarian chert. deposit is derived from the local sources. The Pb isotope
The limestone-siltstone contacts are common sites of deep composition of the Fuwang silver deposit is similar to
burial diagenetic silicification. Some of the massive zones those of the Neoproterozoic metamorphic basement of
contain framboidal pyrite, and therefore may have formed the western Guangdong region (Zhang et al. 1993), sug-
by diagenetic processes as diagenetic chert. The Chang- gesting that the Pb of the Fuwang silver deposit is de-
keng gold ore is hosted mainly in the breccia. Thus, the rived from the Neoproterozoic metamorphic basement.
gold-bearing breccias imply that the gold was introduced
40Ar/39Ar age and Rb-Sr isochron age of mineralized
after the diagenetic silicification. The gold-hosting rocks, 3.3
therefore, formed by multistage silicification that at least quartz veins
includes syngenetic-, diagenetic-, and hydrothermal- si-
licification. The hydrothermal silicification is related to The mineralized quartz sample from the Fuwang silver
gold deposition. The syngenetic silicification and the di- deposit yields 40Ar/39Ar a plateau age of 64.3 0.1 Ma
agenetic silicification have high background abundances and isochron age of 64.0 0.1 Ma with an initial 40Ar/36
of gold and may indicate that a pre-existing enriched of ratio of 294.5 0.4. The Rb and Sr isotopic data obtained
gold in the stratigraphic section contributed to the Chang- from six samples define an Rb-Sr isochron, with an age
keng gold deposit, similar to processes suggested for the of 68 6 Ma, MSWD = 4.14. Quartz 40Ar/39Ar age s and
Meikle and neighboring Carlin-type deposits of Nevada Rb-Sr isochron age are concordant within error, and cor-
(Emsbo et al. 2003). respond to the Himalayan tectono-magmatic event (Hi-
malayan is a period <90 Ma; Wang and Mo 1995).
3 Geochemical studies of the adjacent Changkeng
gold and Fuwang silver deposits 4 Origin of Changkeng gold and Fuwang silver
3.1 Geochemistry of the ore-forming fluid
The Changkeng gold deposit is hosted in siliceous rocks
The gold and silver deposits overlap in homogenization and limestone and shows similar mineralization and min-
temperature, in the ranging 210 80 C and 230 50 C, eral associations to many Carlin-type deposits (Hofstra
respectively. Salinities of the fluid inclusion from the gold and Cline 2000; Hu et al. 2002; Peters et al. 2002).
and silver deposits are also overlap, ranging from 1.6 Age evidence suggests that the Fuwang silver deposit
- 7.3 wt % and 1.6 - 2.6 wt % equiv. NaCl, respectively. bear a genetic relation to the Himalayan magmatic event
The adjacent Changkeng gold- and Fuwang silver- de- in the Shanshui Basin. Given the close temporal and broad
posits are different in DH2O, 18OH2O, 13CCO2 and 3He/4He spatial association of the silver deposit with Early Ter-
isotope composition (Guo et al. 1996; Sun et al. 1999). The tiary magmatism, the D, O, C, and He isotope data are
DH2O, 18OH2O, 13CCO2 and 3He/4He values of the fluid in- consistent with ore fluids that consisted of a mixture of
clusions from the Changkeng gold deposit range from 80 deeply sourced magmatic and local meteoric water.
to -30 , -7.8 to 3.0 , -16.6 to -17.0 and 0.0100 to The most plausible explanation is to ascribe these com-
0.0054 Ra, respectively. The DH2O, 18OH2O, 13C CO2 and bined mineralized ages and isotopic results for the Fuwang
3He/4He values of fluid inclusions from the Fuwang silver silver deposit to the Himalayan tectono-magmatic event. The
deposit range from 59 to -45 , -0.9 to 4.1 , -6.7 to 0.6 presence of disseminated gold in brecciated siliceous rocks
and 0.5930 to 0.8357 Ra, respectively. The DH2O, 18OH2O, along with epigenetic quartz, orpiment, realgar, and stibnite,
13CCO2 and 3He/4He values of the fluid inclusions suggest together with meteoric D, O, C, and He isotopic values and
the ore fluids of the Changkeng gold ore come from the fluid inclusion salinity and temperature data that overlap those
meteoric water and the ore fluids of the Fuwang silver ore from Fuwang silver deposit, suggests that the gold was de-
come from mixing of magmatic water and meteoric water. posited by an epigenetic meteoric hydrothermal system.

Chapter 7-16 Studies on the genesis of adjacent Changkeng gold- and Fuwang silver-deposits, Guangdong Province, China 783

The adjacent Changkeng gold- and Fuwang silver-de- Emsbo P, Hofstra AH, Lauha EA, Griffin GL, Hutchinson RW (2003)
posits could represent a single evolved hydrothermal sys- Origin of high-grade gold ore, source of ore fluid components,
and genesis of the Meikle and Neighboring Carlin-type depos-
tem where the ore fluids deposited gold at first in the brec-
its, Northern Carlin trend, Nevada, Econ Geol 98: 1069-1105
ciated silicification, and then mixed with the magmatic water Guo XS, Du JE (1996) Study on the fluid inclusions and geochemis-
and deposited silver in the fracture zone in the limestone. try of the Changkeng Gold-Silver deposit. Min Res Geol 10: 187-
Alternatively, the second ore genetic model is that the adja- 193. (in Chinese with English abstract)
cent Changkeng gold- and Fuwang silver-deposits may have Hofstra A H, Cline JS (2000) Characteristics and models for Carlin-
type gold deposits, Rev Econ Geol 13: 163-220.
resulted from the superposition of different geological
Hu RZ, Su WC, Bi XW, Tu GZ, Hofstra AH (2002) Geology and
events. Given the close proximity of the two deposits and geochemistry of Carlin-type gold deposits in China. Miner Depos
the overlap of fluid inclusions salinities and temperatures, 37: 378-392
the adjacent Changkeng gold and Fuwang silver deposits Peters SG, Huang JZ, Jing CG (2002) Introduction to and classifica-
were most likely formed by the first model. tion of sedimentary rock-hosted Gold deposits in P.R. China. In:
Early Tertiary isotopic ages from the Fuwang silver de- Peters S.G. (ed), Geology, geochemistry, and geophysics of sedi-
mentary rock-hosted gold deposits in P. R. China. Open-File Rep
posit and the nearby Xiqiaoshan Tertiary volcanic rock- 02-131, versi 1.0: 1-60
hosted silver deposit suggest that the South China Fold Sun XM, Norman DI, Sun K, Chen BH (1999) Characteristics and
Belt underwent a Himalayan event of precious metal min- source of ore-forming fluids of Changkeng Gold-Silver deposits
eralization. in middle Guangdong province, evidences from N2-Ar-He. Scie
China (Series D) 29: 240-246 (in Chinese)
Tu GZ (2000) The super-large deposits in China. Vol. 1. Scie China
Acknowledgements Press, Beijing, pp. 3-9 (in Chinese)
Wang HZ, Mo XX (1995) An outline of the tectonic evolution of China.
The work was supported by the the NSFC (No.49872035, Episodes 8: 6-16
40472049), and the important project of CAS (No. KZCXZ- Xia P, Zhang H, Wang XZ, Chen JP (1996) Geology-geochemistry and
SW-117 and No. GIGCX-03-04). genesis of chert from Changkeng Au-Ag deposit, west Guangdong
province, China. Geochemica 25: 129-139 (In Chinese with En-
References glish abstract)
Zhang Q, Zhang BG, Pang JY, Cao YB, Hong DH (1993) The isotope
Bureau of Geology and Mineral Resource of Guangdong province signature and source rocks of Chadong Silver-Gold deposit. Min-
(1985) Regional geology of Guangdong province. Geol Pub House, eral Deposits 12: 349-355 (in Chinese with English abstract)
Beijing, China, 1-350 (in Chinese) Zhang WH, Lu WJ, Jiao YQ, Li ST (2000) Composition and source
Du JE, Ma CH, Zhang GH (1993) Mineralization characteristics of study of ore-forming fluid in the Changkeng gold-silver depos-
the Changkeng gold-silver deposit, Guangdong province. Guang- its, Guangdong province, China. Acta Petrol Sinica 16: 521-527
dong Geology 8: 1-8. (in Chinese with English abstract) (in Chinese with English abstract)

Chapter 7-17 7-17

Fluid inclusion and stable isotope geochemistry of the

Ernest Henry Fe oxide-Cu-Au deposit, Queensland, Australia
Geordie Mark1, Patrick J. Williams, Nick H.S. Oliver
School of Earth Sciences, James Cook University, Townsville 4811, Australia
1 Current address: School of Geosciences, Monash University, Melbourne 3168, Australia

Chris Ryan
CSIRO Exploration and Mining, School of Geosciences, Monash University, Melbourne 3168, Australia
Terry Mernagh
Geoscience Australia, GPO Box 378, Canberra 2601, Australia

Abstract. Ernest Henry is an iron oxide-copper-gold deposit charac- fluid inclusions to be small and difficult to work with.
terized by magnetite>>hematite, chalcopyrite as the only significant New stable isotope data augment earlier work by
hypogene copper mineral. It occurs within a large, zoned, medium to
Twyerould (1997) and include the first reported D data
high temperature alteration system. Pre- to synmineralization quartz
contains three broad populations of fluid inclusions. Type 1 (L-V- for the deposit.
HnS) inclusions decrepitate or homogenise at 200-500 C, have
salinities of 32-55 wt% NaClequiv, display chemical variations that 2 Geological context
parallel the paragenetic sequence of alteration, and have variable
Br/Cl mostly less than magmatic brines. Type 2 (L-V) inclusions
Ernest Henry is the largest of several magnetite bearing
homogenise at temperatures of 120-350C have salinities up to 20
wt% NaClequiv and inferred to contain CaCl2. Type 3 L-rich CO2 in- IOCG deposits in the Cloncurry mining district, which
clusions were entrapped at 130-370MPa. dD and dO of pre- to encompasses the eastern part of the Proterozoic Mount
synmineralisation fluids are estimated to have been -23 to -66 and Isa inlier in northwest Queensland, along with its exten-
8 to 11 per mil respectively. dS in main ore pyrite and chalcopyrite sions beneath shallow cover in the surrounding area (Wil-
is -1.6 to +5.4 per mil. The data are compatible with a substantial liams and Pollard 2003). Late Palaeoproterozoic
magmatic contribution to Ernest Henry fluids but also suggest the
system was complex and involved fluids and other components
supracrustal rocks and early ca 1.74 and 1.66 Ga intru-
with different sources. Ernest Henry is distinguished from the giant sions were deformed and metamorphosed at greenschist
Olympic Dam deposit by evidence for high temperature/salinity to amphibolite facies between 1.58 and 1.50 Ga and ex-
fluids and for no major involvement of surficial waters during min- tensively intruded by granitoids from 1.55 to around 1.50
eralization. Ga (Page and Sun, 1998; Williams and Pollard, 2003). The
Ernest Henry deposit is hosted in a sequence of meta-
Keywords. Ernest Henry, copper, gold, fluid inclusions, stable isotopes
morphosed, predominantly intermediate volcanic rocks
and is spatially-associated with bodies of ca 1.66 Ga di-
1 Introduction orite. U-Pb dating of titanite from pre-ore alteration as-
semblages suggests that the Ernest Henry hydrothermal
The sources of ore fluids and mechanisms of mineraliza- system was broadly contemporaneous with the later (1.55-
tion in iron oxide-copper-gold (IOCG) deposits are poorly- 1.50) granitoids, examples of which are present within 15
understood and could differ amongst the geologically km of the ore deposit (Mark et al. in press). Proterozoic
diverse members of the group (e.g. Barton and Johnson basement near Ernest Henry is obscured by Mesozoic to
2004). Ernest Henry is the largest known magnetite-domi- recent cover. However, extensive drilling around the de-
nated IOCG deposit in Australia (Mark et al., in press; cf. posit has demonstrated there is a very large volume of
Williams and Pollard 2003). In contrast to the giant he- altered rocks that extends for at least several kilometres
matite-rich Olympic Dam deposit in South Australia, it is in all directions near the current erosion level (Mark et
characterized by complex high temperature alteration al. in press).
zoning and has chalcopyrite as the only significant cop-
per mineral (Mark et al. in press; cf. Reeve et al. 1990). 3 Paragenesis of alteration and mineralization
This paper reports on fluid inclusion and stable isotope
studies that were undertaken to characterize Ernest Henry Twyerould (1997) and Mark et al. (in press) documented
ore fluids. It is the first fluid inclusion study to have been the time-space evolution of the Ernest Henry hydrother-
attempted at the deposit where such work is challenging mal system. Distal stage 1 alteration produced secondary
because of the low abundance of quartz compared to most albitic plagioclase and calc-silicates and was similar to
other hydrothermal deposits and a general tendency for regional-scale sodic-calcic metasomatism elsewhere in the

786 Geordie Mark Patrick J. Williams Nick H.S. Oliver Chris Ryan Terry Mernagh

district (De Jong and Williams 1994). It is preserved with

variable overprints by younger alteration at distances of
1-3 km from the orebody. Stage 2 formed a potassic-iron-
(manganese) association represented predominantly by
biotite, magnetite, K feldspar, almandine-spessartine gar-
net and quartz rich veins. Stage 2 alteration is preserved
around the periphery of the mine and along NE-trend-
ing structures extending away from it. Stage 3 potassic
alteration was pervasive in the immediate vicinity of the
orebody where the rocks were replaced by hematite-
stained and variably barian K-feldspar. Stage 3 altered
rocks were selectively affected by Stage 4 which formed a
SE-plunging breccia lens up to 300m thick in which mag-
netite, sulphides and a very complex association of other
minerals form the matrix to K-feldspar-dominated clasts.
Stage 5 calcite-dominated veins are predominantly local-
ized near the footwall contact of the ore lens.

4 Sampling and methods

Samples were obtained from drill cores where the geo-

logical context and paragenetic setting was well known
from detailed logging undertaken as part of general geo-
logical description of the deposit and the surrounding
altered rocks (Mark et al. in press). The fluid inclusion
study focussed on interpreted primary inclusions hosted
by quartz from paragenetic stages 2, 3 and 4 (i.e. pre- to
synmineralization). The inclusions were investigated by
conventional and electron microscopy, subjected to
microthermometric experiments, and selected examples
were analyzed by Laser Raman spectrometry and proton
induced X-ray excitation (PIXE) analysis (cf. Ryan et al.
2001). Hand-picked separates were prepared of minerals
from stages 1-5 and analyzed using conventional meth-
ods as appropriate for D in biotite and amphibole (n=10,
SUERRC, East Kilbride, Scotland), 13C and 18O in car-
bonates (n=36, Monash University), 18O in silicates and
magnetite (n=42, Monash University) and 34 S in
sulphides (n= 32, University of Tasmania).

5 Fluid inclusion types and geochemistry

Quartz-hosted fluid inclusions from stages 2 to 4 can be

classified into three broad groups (Fig. 1). Type 1 (L-V-
HnS) inclusions contain liquid, a small H2O vapour
bubble (<10% of total volume) and a halite solid at room
temperature. Most have additional solids in a variety of
assemblages containing one or more of ferropyrosmalite,
sylvite, Fe-chloride, magnetite, hematite, calcite and
kutnahorite (CaMn(CO3)2). Brown ice forms on freezing
and low first melting temperatures indicate the presence
of Ca and other divalent metals. A small proportion of
Type 1 inclusions decrepitate without homogenising on and 520C (65% > 300C). Salinities estimated from ha-
heating while the remainder homogenise by halite or lite dissolution temperatures are 32-55 wt% NaClequiv. Type
ferropyrosmalite dissolution at temperatures between 200 2 (L-V) inclusions occur in both primary and secondary

Chapter 7-17 Fluid inclusion and stable isotope geochemistry of the Ernest Henry Fe oxide-Cu-Au deposit, Queensland, Australia 787

settings (i.e. some of them represent the youngest fluid carbonates either involving an external fluid with higher
type). At room temperature they contain liquid and an 18O of 13-16 per mil that had equilibrated with such rocks
H2O vapour bubble which occupies up to 25% of the vol- or from their presence in the protoliths of the highly de-
ume of the inclusion. They homogenise at temperatures formed rocks in the footwall of the deposit where the car-
of 120-350C. Type 2 inclusions form brown ice on freez- bonate veining is localized.
ing and are deduced to be CaCl2-bearing. Salinities range Mean 13C values (per mil) in calcite are; Stage 1, -2.4;
up to 20 wt% NaClequiv. Type 3 inclusions are dominated Stage 2, -4.2; Stage 3, -3.5; Stage 4 -3.0; Stage 5, -2.1. 34S
by CO2 and are liquid-rich (>90%) at room temperature. ranged from - 0.5 to +5.4 per mil (mean 2.2) in ore stage
Some contain a small proportion of liquid H2O and/or a chalcopyrite and from -1.6 to +4.8 (mean 1.6) in ore stage
nahcolite (NaHCO3) solid. Their densities suggest entrap- pyrite. The two common sulphide minerals are not pre-
ment at pressures of 130-370 MPa during stages 2 to 4. served in isotopic equilibrium.
PIXE studies were undertaken on populations of single
fluid inclusions from stages 2, 3 and 4 (total analyses = 7 Discussion
40). The results are quantitative at an accuracy of around
50% for Cl, K, Ca, Mn, Fe, Cu, Zn, As, Br, Rb, Sr, Ba and The pre- to synmineralization (Stages 2-4) mineral
Pb. Accuracy for many interelement ratios is far better parageneses at Ernest Henry that distinguish the system
than this as the main sources of error have similar effects from from regionally sodic-calcic altered rocks are de-
on all elements. Analytical detection limits were mostly duced to have formed in a hydrothermal system domi-
in the range 30-300 ppm. Type 1 inclusions display sys- nated by compositionally complex fluids. Type 3 (high
tematic stage to stage variation. All are distinguished by density CO2) inclusions may have formed by unmixing
high Mn:Fe ratios (mostly > 1) compared to complex brine from aqueous brine phase. The Type 1 and 2 inclusions
inclusions from other Cloncurry Fe oxide Cu-Au depos- imply that at least two fundamentally different types of
its such as Osborne, Starra and Eloise (Williams et al. 1999; aqueous brine were present echoing the situation that
2001). Stage 3 (K feldspar-related) Type 1 inclusions have has been found in other Cloncurry district Cu-Au de-
lower (Mn+Fe)/K than those from stages 2 and 4 (mag- posits (e.g. Williams et al. 2001). High salinity brines are
netite/biotite/garnet-related). With the exception of one most likely to have cotransported Cu and Au in the sys-
outlying result, Br/Cl ratios in Type 1 inclusions are less tem though ore-stage Type 1 inclusions studied by PIXE
than 0.0013 and in some cases in which Br was undetec- have much lower Cu concentrations than were found at
ted must be less than 0.0005. Cu was only detected in Type the much smaller Starra Au-Cu deposit (Williams et al.
1 inclusions at concentrations of 30-200ppm. Analyses of 2001). They do however high concentrations of Zn, Pb
the eight analyzed ore stage Type 1 inclusions have pre- and Ba compared both to premineralization Type 1 in-
viously been reported by Mark et al. (2005). These are clusions and the relatively Cu-rich brines from Starra.
distinguished by the highest K/Ca ratios and absolute This suggests ore deposition was associated with the in-
concentrations of Ba (mean 2.8 wt%), Zn (mean 4800 flux of a distinct mineralizing brine and although the
ppm), As (mean 590 ppm), and Pb (mean 2300 ppm) but studied Type 1 inclusions could indicate that the ore was
all had estimated Cu below 120 ppm. deposited by efficient Cu precipitation from a very large
mass of fluid a more plausible explanation maybe that
6 Stable isotope results the analyzed inclusions represent a spent fluid after
chalcopyrite precipitation (cf. Mark et al. 2005). Assum-
D values are -80 to -88 per mil in three stage 1 amphib- ing that fluid Br/Cl ratios would have been essentially
oles, -85 and -91 per mil in two stage 2 biotites, - 69 to -95 insensitive to fluid-rock interactions, then the variable
in four stage 4 biotites, and -72 in a stage 5 amphibole. measured values in Type 1 inclusions imply they derived
Allowing for the likely fractionations this suggests that their salinity from more than one source and including
the fluids in the Ernest Henry system had D of -23 to - a component with Br/Cl similar to evaporitic halite. The
66 per mil Mean 18O values (per mil) are: Stage 1, am- rocks near Ernest Henry have evidently undergone ex-
phibole = 5.8, calcite = 15.7; Stage 2, biotite = 6.4, calcite tensive fluid-rock interactions at elevated temperatures.
= 12.5, K feldspar = 11.3, magnetite = 4.6, quartz = 10.7; The O-H stable isotopic data are consistent with sub-
Stage 3, biotite = 5.7, calcite = 12.5, K feldspar = 9.0, mag- stantial magmatic contributions of these elements dur-
netite = quartz = 11.8; Stage 4, biotite = 6.2, calcite = 12.6, ing the main presyn mineralization stages but given that
K feldspar = 10.1, magnetite = 3.1, quartz = 11.7; Stage 5, immediate host rocks are igneous, cannot be taken to
amphibole = 10.5, calcite = 14.9. In conjunction with data demonstrate an exclusively magmatic fluid source. Com-
from Twyerould (1997) these results suggest that fluid 18O pared to Olympic Dam, Ernest Henry seems to have
remained in the range 8-11 per mil in the time period formed from relatively high temperature and salinity flu-
represented by stages 1-4. The data for carbonate-rich stage ids without a significant contribution from surfice wa-
5 are consistent with an influence from metamorphosed ters (cf. Oreskes and Einaudi 1992).

788 Geordie Mark Patrick J. Williams Nick H.S. Oliver Chris Ryan Terry Mernagh

Acknowledgements Oreskes N, Einaudi MT (1992) Origin of hydrothermal fluids at Olym-

pic Dam: preliminary results from fluid inclusions and stable iso-
topes: Economic Geology 87: 64-90
This research was supported by the Australian Research
Page RW, Sun S-S (1998) Aspects of geochronology and crustal evo-
Council, Ernest Henry Mining and MIM Exploration. The lution in the Eastern Fold Belt, Mt Isa Inlier: Australian Journal
project was planned and executed in collaboration with of Earth Sciences 45: 343-361
Richard Crookes and Rick Valenta. Reeve JS, Cross KC, Smith RN, Oreskes N (1990) Olympic Dam cop-
per-uranium-gold-silver deposit: Australasian Institute of Min-
ing and Metallurgy Monograph 14:1009-1035
References Ryan CG, McInnes BM, Williams PJ, Guoyi Dong, Tin Tin Win, Yeats
CJ (2001) Imaging fluid inclusion content using the new CSIRO-
Barton MD, Johnson DA (2004) Footprints of Fe-oxide(-Cu-Au) sys- GEMOC nuclear microprobe: Instruments and Methods in Phys-
tems. SEG 2004: Predictive Mineral Discovery Under Cover. Cen- ics Research B 181: 570-577
tre for Global Metallogeny, The University of Western Austra- Twyerould SC (1997) The geology and genesis of the Ernest Henry
lia, Special Publication 33: 112-116 Fe-Cu-Au deposit, NW Queensland, Australia: Unpublished PhD
De Jong G, Williams PJ (1995) Giant metasomatic system formed thesis, University of Oregon. 494pp
during exhumation of mid crustal Proterozoic rocks in the vi- Williams PJ, Dong Guoyi, Pollard PJ, Perring C, Ryan CG Mernagh
cinity of the Cloncurry Fault, NW Queensland: Australian Jour- TP (1999) Fluid inclusion geochemistry of Cloncurry (Fe)-Cu-
nal of Earth Sciences 42: 281-290 Au deposits: In: Stanley CJ et al. (eds) Mineral Deposits: Processes
Mark G, Oliver NHS, Williams PJ (in press) Mineralogical and to Processing. Balkema, Rotterdam, pp 111-114
chemical evolution of the Ernest Henry Fe oxide-Cu-Au ore Williams PJ, Guoyi Dong, Ryan CG, Pollard PJ, Rotherham, JF,
system, Cloncurry district, northwest Queensland, Australia: Mernagh TP, Chapman LH (2001) Geochemistry of high salinity
Mineralium Deposita fluid inclusions from the Starra (Fe)-Cu-Au deposit, Cloncurry
Mark G, Wilde AR, Oliver NHS, Williams PJ (2005) Predicting al- district, Queensland: Economic Geology 96: 875-883
teration patterns in the outflow zones of hydrothermal ore sys- Williams PJ, Pollard PJ (2003) Australian Proterozoic iron oxide-Cu-
tems: a case study using the spent fluids from the Ernest Henry Au deposits: An overview with new metallogenic and explora-
Fe-oxide-Cu-Au deposit: Journal of Geochemical Exploration tion data from the Cloncurry district, northwest Queensland.
85: 3146 Exploration and Mining Geology 10: 191-213

Chapter 7-18 7-18

The Re-Os age for molybdenite from the Variscan

Strzegom-Sobtka massif, SW Poland
Stanislaw Z. Mikulski
Department of Economic Geology, Polish Geological Institute, 4 Rakowiecka St., 00-975 Warsaw, Poland
Holly J. Stein
AIRIE Program, Department of Geosciences, Colorado State University, Fort Collins, CO 80523-1482 USA
Norges Geologiske Underskelse, Leiv Eirikssons vei 39, 7491 Trondheim, Norway

Abstract. Molybdenites from quartz veins in a late Variscan granite for the SSG range from 0.703 to 0.707 (Kennan et al. 1999).
from the Fore-Sudetic block in southwest Poland yield ages of 309 However, for some of petrographic variants this ratio is
to 304 Ma with the Re-Os method. The ages of the molybdenites
as high as 0.708-0.709 probably due to crustal contami-
reflect post-magmatic hydrothermal activity associated with
leucogranite porphyry (aplogranite) related to regional uplift and nation (Pin et al. 1989). The Strzegom-Sobtka granites
shear deformation during Westphalian time within this part of the are calcic to calc-alkaline in character (Oberc-Dziedzic
Saxothuringian zone of the European Variscan belt. et al. 1999). Using the Pearce et al. (1984) classification
scheme, the SSG are within the late orogenic to syn-colli-
Keywords. Molybdenite, Re-Os, Strzegom-Sobtka granites, Fore-
sional granite groups.
Sudetic block, SW Poland, Bohemian Massif
Numerous faults divide the SSGM into an elevated
western part and downthrown middle and eastern parts.
1 Introduction The SSGM contains three petrographic varieties
(Majerowicz 1972; Maciejewski and Morawski 1975;
Re-Os dating of molybdenite has been successfully em- Puziewicz 1985, 1990):
ployed to date magmatic and metamorphic pulses within
orogenic cycles (Bingen and Stein 2003; Requia et al. 2003). 1. equigranular to porphyritic monzonite granite
Magmatism associated with deformation and hydrother- (Kostrza type, western SSGM),
mal activity in regional scale shear zones has also been 2. equigranular biotite granodiorite (Chwalkw type,
dated using molybdenite geochronology (Stein et al., in central and eastern SSGM),
press). In northern Sweden, over 100 m.y. of Svecofennian 3. equigranular two-mica monzonite granite (eastern
orogenic history is recorded in molybdenite, both within SSGM).
magmatic and metamorphic assemblages, and low Re
concentrations are attributed to molybdenite derived by
local biotite breakdown (Stein, in press).
In the northeastern part of the Bohemian massif that
constitutes the Saxothuringian zone of the European
Variscan belt, exposed crystalline rocks in the Western
Sudetes continue under the Cenozoic cover across the
Sudetic Marginal fault into the Fore-Sudetic block to the
Odra Fault Zone, which defines the northeastern bound-
ary of the massif. During the Carboniferous and early
Permian, a major post-orogenic episode of granitic
magmatism and coeval volcanism occurred. Most of the
granites in this region are generally late to post-tectonic
I-type and S-type intrusions with a span of Rb-Sr ages
from ~330 to 280 Ma (Pin et al. 1989; Duthou et al 1991;
Oberc-Dziedzic et al. 1996; Kennan et al. 1999).

2 The Strzegom-Sobtka granitoid Massif

The Strzegom-Sobtka granites (SSG) are classified as I-

type granites, based on their generally low A/CNK (com-
monly less than 1.1). The 87Sr/86Sr initial ratios determined

790 Stanislaw Z. Mikulski Holly J. Stein

3 Molybdenite mineralization from the Paszowice


In the NW part of the Strzegom-Sobtka granitoid mas-

sif (SSGM), numerous occurrences of molybdenite min-
eralization have been documented (Pendias and
Walenczak 1956; Salacinski 1978). Among other locali-
ties, Mo mineralization is found in the abandoned
aplogranite quarry near the Paszowice village (Fig. 1).
Here, mineralization occurs in a system of gray quartz
veinlets up to 2 cm thick that cut fine-grained leucogranite
porphyry (aplogranite). The veins are oriented at 290-
300 and dip steeply to the NE. The ore veinlets are cut by
massive but barren milky quartz veinlets striking 240.
Molybdenite is a major sulfide present in veinlets form-
ing either monomineral concentrations or may occur in
paragenetic association with other sulfides (chalcopyrite,
pyrite) native bismuth, or rarely with oxides such as wol-
framite and cassiterite (Pendias and Walenczak 1956;
Salacinski 1973). The ore mineralization is accompanied
by feldspathization, albitization, silicification, sericitization
and chloritization. The deposit has a moderate to high
temperature hydrothermal origin based on ore paragen-
esis (Salacinski 1978). According to fluid inclusion stud-
ies of sulfide-bearing quartz veinlets the deposit has been
classified as mesothermal based on temperatures and
pressures of 361-236C and ~0.9 MPa, respectively (Ilnicki
1998). Ore-bearing quartz veinlets have also been found
in three oriented prospecting holes drilled in 1957 in the
surrounding area (Chilinska, unpublished). The average
content of Mo is 0.34 wt% and of Cu 0.13 wt%. Existing
data from these boreholes and from the surface geochemi-
cal prospecting led to the classification of the mineral-
ization as Mo-Cu stockwork type (Kanasiewicz and
The granite intrusion has two phases. A younger phase Mikulski 1989). Two zones of quartz vein Mo-Cu miner-
is represented by Kostrza-type granite and leucogranite alization are now identified, extending to 100 m below
from the Paszowice quarry. Rb-Sr ages for two-mica gran- the surface (Fig. 2). They occupy shear zones oriented NW-
ite from the SSGM provide an age of ca. 330-325 Ma ( SW and dipping 70-80 NE. The shear zones range from
22 Ma), whereas some of monzogranites have a reported about 2 to 5 m in thickness.
age of ca. 290 Ma (Pin et al. 1989). Based on Rb-Sr whole-
rock isochron ages, Kennan et al. (1999) suggest that post- 4 Sample description for Re-Os data
tectonic Carboniferous granites in the Western Sudetes,
including some of the Strzegom-Sobtka massif, were Two molybdenite samples for Re-Os dating were collected
emplaced over a short time interval at ~328 Ma and de- from the lowest level in the central part of the quarry
rived from a source with similar 87Sr/86Sr initial ratios. within the Strzegom-Sobtka granitoid massif. Molyb-
The present U/Pb dating of monazite and xenotime from denite in quartz veins represents the main stage of min-
two-mica granites of SSGM yielded ages of 309.1 0.8 eralization. Euhedral molybdenite was selected from fine-
Ma and 306.4 0.8 Ma, respectively and indicate for the crystalline gray quartz veins (up to 2 cm thick) cutting
younger emplacement of the two-mica granites during fine-grained leucogranite porphyry (aplogranite). Some
the late Westphalian (Turniak and Brcker 2002). The crystals form rosette aggregates 3-5 mm in diameter. The
relation of the leucogranite porphyry (aplogranite) from length of single molybdenite flakes is usually <1 mm with
the Paszowice quarry to the entire SSGM is not well un- a width of ~0.1 mm. Larger molybdenite crystals are
derstood (Pendias and Walenczak 1956; Majerowicz curved and overgrown by chalcopyrite or pyrite, or they
1972). may contain fine-grained chalcopyrite and pyrite grains

Chapter 7-18 The Re-Os age for molybdenite from the Variscan Strzegom-Sobtka massif, SW Poland 791

uplift of the Variscan orogen. The unidirectional NW-SE

strike of the ore veinlets at the Paszowice quarry and the
vein-hosted Mo zones recognized by boreholes are simi-
lar to the direction of the Marginal Sudetic fault, which
was also active during the Upper Carboniferous
(Zelazniewicz et al. 1997).
Mo mineralization of similar type and age (307 3
Ma) has been reported from the southern margin of the
Variscan orogen (Langthaler et al. 2004) and similarly,
but slightly younger Re-Os ages from Sardinia are also
latest Variscan (289 1 Ma; Boni et al. 2003). In Sardinia,
at least two ages of leucogranites are recognized, with
only the younger one displaying Mo mineralization and
the older (~310-300 Ma) being barren (Boni et al. 2003).
The molybdenite Re-Os ages from the SSGM also coin-
cide with a sharp increase in the rate of uplift in the Mas-
sif Central (310-305 Ma; Bouchot et al. 2000) that consitute
intergrown within molybdenite crystal cleavage, indicat- the western part of European Variscides.
ing an intimate temporal relationship. Albite crystals may
be found within quartz veinlets, but more commonly al- Acknowledgements
bite together with chlorite (after biotite) is found mar-
ginal to the quartz veins. The analytical work was supported by the National Com-
mittee Scientific Research, Grant 5 T12B 001 22. Special
5 Methods and results thanks goes to Dr. S. Ilnicki for providing one of molyb-
denite samples.
Re-Os dating of molybdenite is described in Stein et al.
(2001). We present the results of high precision Re-Os age References
determinations for two molybdenite samples using pro-
cedures and techniques outlined in Markey et al. (2003). Bingen B, Stein HJ (2003) Molybdenite Re-Os dating of biotite dehy-
A mixed double Os spike was used (185Re, 188Os-190Os). dration melting in the Rogaland high-temperature granulites, S
Norway. Earth and Planet Scientific Letter 208: 181-195
The samples have low Re contents, all < 1 ppm, and the Boni M, Stein HJ, Zimmerman A, Villa IM (2003) Re-Os age for mo-
resulting ages range from 309 to 304 Ma. A replicate of lybdenite from SW Sardinia (Italy): A comparison with Ar/Ar
sample #3, is provided in MDID-315. Sample weights dating of Variscan granitoids. In: Eliopoulos et al (eds), Mineral
ranged from 41 to 73 mg. Exploration and Sustainable Development: pp 247-250. Millpress,
Bouchot V, Milesi JP Ledru P (2000) Crustal scale hydrothermal
6 Discussion Paleofield and related Au, Sb, W orogenic deposits at 310-305 Ma
(Massif Central). SGA News 10: 6-10
Re-Os dating of molybdenites from the Paszowice quarry Duthou JL, Couturie JP Mierzejewski MP, Pin C (1991) Next dating
from the western part of the Strzegom-Sobtka granitoids of granite sample from the Karkonosze Mountains using Rb-Sr
massif yields ages from 309 to 304 Ma. Their markedly total rock isochrones method. Przeglad Geologiczny 39:75-79
Ilnicki S (1998) Conditions of hydrothermal alterations in aplite from
low Re concentrations (<1 ppm) are consistent with a Paszowice (Strzegom-Sobtka massif). Mineralogia Polonica 29:
derivation related to metamorphic processes (Stein, in 29-42
press). The Mo mineralization clearly postdates emplace- Kanasiewicz J, Mikulski SZ (1989) On the occurrence possibility of
ment of leucogranite porphyry (aplogranite), but is con- the molybdenium deposit of Cu-Mo formation on the Strzegom
sidered as either (1) related to post-magmatic processes granites massif. Przeglad Geologiczny 37: 129-133
Kennan PS, Dziedzic H, Lorenc MW Mierzejewski MP (1999) A re-
associated with the emplacement of evolved and Mo-spe-
view of Rb-Sr isotope patterns in the Carbo-niferous granitoids
cialized leucogranite magma (Kanasiewicz and Mikulski of the Sudetes in Poland. Geologia Sudetica 32: 49-53
1989), or (2) related to metamorphic processes and the Kural S, Morawski T (1968) Strzegom-Sobtka granitic massif.
development of shear zones. Field relationships permit Biuletyn Instytutu Geologicznego 227: 33-85
an interpretation whereby the Paszowice leucogranite and Langthaler KJ, Raith JG, Cornell DH, Stein HJ, Melcher F (2004)
Molybdenum mineralization at Alpeiner Scharte, Tyrol (Austria):
mineralized quartz veins were emplaced during shear
results of in-situ U-Pb zircon and Re-Os molybdenite dating.
deformation in late Variscan time. Re-Os dating of mo- Mineralogy and Petrology 82: 33-64
lybdenite provides an age for this deformation of about Maciejewski S, Morawski T (1975) Petrographic diversity of gran-
310-305 Ma. Thus, the Mo mineralization formed during ites of the Strzegom massif. Kwartalnik Geologiczny 19: 47-65

792 Stanislaw Z. Mikulski Holly J. Stein

Majerowicz A (1972) The Strzegom-Sobtka granite massif. Geologia Salacinski R (1973) Ore mineralization in granite at Paszowice. Acta
Sudetica 6: 7-96 Geologica Polonica 23: 587-596
Markey R, Hannah JL, Morgan JW, Stein HJ (2003) A double spike Salacinski R (1978) Ore mineralization and its origin in the grani-
for osmium analysis of highly radiogenic samples. Chemical toids of the Strzegom massif. Biuletyn Instytutu Geologicznego
Geology 200: 395-406 308: 41-90
Oberc-Dziedzic T, Zelazniewicz A, Cwojdzinski S (1999) Granitoids Smoliar MI, Walker RJ, Morgan JW (1996) Re-Os ages of group II1,
of the Odra Fault Zone: late- to post-orogenic Variscan intru- IIIA, IVA and IVB iron meteorites. Science 271: 117-133
sions, SW Poland. Geologia Sudetica 32: 55-71 Stein HJ, Hannah JL, Zimmerman A, Markey R, Sarkar SC, Pal AB,
Pearce JA, Harris NB, Tindle AG (1984) Trace Element Discrimina- in press, A 2.5 Ga porphyry Cu-Mo-Au deposit at Malanjkhand,
tion Diagrams for the Tectonic Interpretation of Granitic rocks. central India: implications for Late Archean continental assem-
Journal Petrology 25: 956983 bly. Precambrian Research.
Pendias H, Walenczak Z (1956) Signs of mineralization in the NW part Stein HJ, in press, Low-rhenium molybdenite by metamorphism:
of Strzegom Massif. Biuletyn Instytutu Geologicznego 227: 209-228 recognition, sampling, genesis, economics, and regional impli-
Pin C, Puziewicz J, Duthou JL (1989) Ages and origins of a compos- cations based on examples from northern Sweden. Lithos.
ite granitic massif in the Variscan belt: a Rb-Sr study of the Stein HJ, Markey RJ, Morgan JW, Hannah JL, Scherstn A (2001)
Strzegom-Sobtka Massif. Neues Jahrbuch Mineralogische The remarkable Re-Os chronometer in molybdenite: how and
Abhandlungen 160: 71-82 why it works. Terra Nova 13: 479-486
Puziewicz J (1985) Origin of chemical, structural and textural varia- Turniak K, Brcker M (2002) Age of the two-mica granite from the
tions in aplites from Strzegom granite (Poland). Neues Jahrbuch Strzegom Massif: new data from U/Pb monazite and xeno-
Mineralogische Abhandlungen 153: 19-31 time study. Mineralogical Society of Poland Special Papers 20:
Puziewicz, J., 1990. Strzegom-Sobotka granitic massif (SW Poland). Sum- 211-213
mary of recent studies. Archiwum Mineralogiczne 45: 135-154 Zelazniewicz A, Cwojdzinski S, England P, Zientara P (1997) Varis-
Requia K, Stein HJ, Fontbot L, Chiaradia M (2003) Re-Os and Pb-Pb cides in the Sudetes and the reworked Cadomian orogen: evi-
geochronology of the Archean Salobo iron oxide copper-gold dence from the GB-2A seismic reflection profiling in southwest-
deposit, Northern Brazil. Mineralium Deposita 38: 727-738 ern Poland. Geological Quarterly 41 (3): 289-308

Chapter 7-19 7-19

Re-Os ages for auriferous sulfides from the gold

deposits in the Kaczawa Mountains (SW Poland)
Stanislaw Z. Mikulski
Department of Economic Geology, Polish Geological Institute, 4 Rakowiecka St., 00-975 Warsaw, Poland
Richard J. Markey1, Holly J. Stein1, 2
AIRIE Program, Department of Geosciences, Colorado State University, Fort Collins, CO 80523-1482 USA
2 Norges Geologiske Underskelse, Leiv Eirikssons vei 39, 7491 Trondheim, Norway

Abstract. A Re-Os six-point isochron age of 317 17 Ma has been 2 Geological setting
obtained for auriferous sulfides from sheeted quartz-veins repre-
senting the first stage of ore precipitation at the Radzimowice Au-
In the northwestern part of the Bohemian Massif, i.e., the
As-Cu deposit. The age uncertainty is dominated by the fact that
sulfides contain very little common Os. Extremely low Re concen- Western Sudetes that constitute the eastern fragment of
trations for gold-bearing sulfides from another gold district, Klecza- the Saxothuringian Zone of the European Variscides, sev-
Radomice, permitted dating of only one Co-arsenopyrite sample eral abandoned small and medium size gold-bearing ar-
G-4 from Klecza analyzed as a Low Level Highly Radiogenic (LLHR) senic-polymetallic deposits are found (Manecki 1965;
sample. A precise age of 316.6 0.4 Ma was obtained. Re-Os ages
Paulo and Salamon 1974; Mikulski 2001). Among them,
indicate gold mineralization in Late Namurian time associated with
post-collisional extension and regional uplift in a continental arc there is still a high potential for exploration in vein de-
setting. Opening of deep-seated structures, marked also by the pres- posits in Radzimowice and the Klecza-Radomice gold ore
ence of lamprophyre dykes, may have allowed for the migration of district (KROD) in the Kaczawa Mountains. In these de-
post-magmatic mineralizing fluids from various magmatic sources posits the major gold, silver, and arsenic production came
at about 317 Ma. from the sheeted quartz-sulfide veins, and vein arrays in
Keywords. Gold, Re-Os, low level and highly radiogenic sulfides (LLHR),
folded flysch-like sediments deformed and metamor-
Kaczawa Mountains, SW Poland, Bohemian Massif phosed to lower greenschist facies during Upper Devo-
nian-Lower Carboniferous. At the Radzimowice and
Klecza deposits the most important ore minerals are re-
1 Introduction fractory gold-bearing Co-arsenopyrite and pyrite. This
stage of mineralization underwent strong cataclasis and
The Re-Os method has been successfully applied to mo- was later overprinted by base metal sulfides and non-re-
lybdenite and can be similarly applied to other sulfides fractory gold associated with quartz and carbonates. The
with much lower concentrations of Re and Os, provided Radzimowice auriferous ore mineralization is considered
the Re/Os ratio is very high. These sulfides have been transitional between a porphyry and epithermal type
named LLHR (low level highly radiogenic), as their Os around the Upper Carboniferous composite Zelezniak
isotopic composition mimics molybdenite (Stein et al. porphyry intrusion of subalkaline to alkaline igneous
2000). LLHR sulfides are samples whose 187Os dominates rocks formed in a post-collisional arc setting (Mikulski
the total Os. They are common in some hydrothermal 2005). The genesis of gold mineralization at the Klecza-
environments, and may be particularly common in small Radomice ore district was commonly assumed to be a
crustally-derived deposits (Stein et al. 2000). The first hydrothermal type connected with Variscan Karkonosze-
Re-Os isotopic ages for LLHR sulfides closely associated Jizera granites. Recently auriferous mineralization is clas-
with Au mineralization were reported from Bendigo, Aus- sified as orogenic type (Mikulski 2003).
tralia (Arne et al. 2001). Recently, the giant Muruntau Au
deposit was successfully dated using LLHR samples of 3 Sample description for Re-Os data
arsenopyrite (Morelli et al. 2004). Analysis of samples
with extremely low-level Os contents is dominated by The auriferous sulfide samples for Re-Os dating were col-
Os contributions from procedural blanks (Markey et al. lected from the old mining wastes and underground work-
2003). Subtraction of blank contributions in such cases ings of the Luis shaft in the northern part of the
may result in significant adjustments to the 187Os/188Os Radzimowice Au-As-Cu deposit and from the old mining
ratio, with a commensurate increase in the uncertain- wastes of the Klecza Northern Ore Field of the KROD.
ties of both the isotopic composition and the concentra- Auriferous sulfide mineralization occurs as massive or
tion of Os in the samples. semi-massive ores in quartz veins that have been brecci-

794 Stanislaw Z. Mikulski Richard J. Markey Holly J. Stein

ated and cemented by a younger generation of quartz-

carbonate and base metal sulfides with non-refractory
gold. For Re-Os measurements we selected medium-, and
fine-grained (0.5 to 3 mm) euhedral Co-arsenopyrite,
pyrite and chalcopyrite non-fractured crystals. Arsenopy-
rite crystals from Radzimowice display compositional
variability in their As contents (34.8 to 37.4 at.%) and high
admixtures of cobalt (up to 6.4 at.%) and refractory gold.
Refractory gold (ca. 70 ppm) appears as sub-microscopic
inclusions within Co-bearing arsenopyrite and is less
abundant in pyrite. Arsenopyrite from Klecza has arsenic
contents between 31.5 and 33.4 at.% and a cobalt admix-
ture from 0.1 to 0.9 at.%.

4 Methods and results

Re and 187Os concentrations in selected sulfides were de-

termined at AIRIE, Colorado State University, using pro-
cedures and techniques outlined in Stein et al. (2000) and
Markey et al. (2003). Analyses of auriferous Co-arsenopy-
rites from the Radzimowice Au-As-Cu deposit yield Re
concentrations of 0.13-3.5 ppb with total Os in the very
low ppt range (Table 1). Nearly all analyzed auriferous
sulfide samples from the KROD were characterized by
extremely low Re concentrations (near blank level), so
age information based on those samples, with the excep-
tion of one, is not possible. Co-arsenopyrite sample G-4 187Os/188Os initial ratio (187Re/188Os > 105). A four-point
from Klecza analyzed as a LLHR sample gave an age isochron based on auriferous Co-arsenopyrites yields a
316.6 0.4 Ma assuming an initial 187Os/188Os ratio of 0.2 Re-Os age of 314 31 Ma (initial ratio = 0.8 2.2, MSWD
(Table 1). The LLHR arsenopyrite from Radzimowice with = 2.1). However, the large uncertainties for two Co-arse-
the highest Re content (run LL-99) yields a Re-Os model nopyrite analyses (LL-28, 29) resulting from extremely
age of 317 Ma that is fairly insensitive to the assumed low Os contents, precludes a precise age. We note that there

Chapter 7-19 Re-Os ages for auriferous sulfides from the gold deposits in the Kaczawa Mountains (SW Poland) 795

magmatic event was restricted to the Late Namurian

(weighted mean 206Pb/238U at 316.7 1.2 Ma; Muszynski
et al. 2002). The Re-Os age of ca. 317 Ma for arsenopyrite
sample LL-99 in the context of SHRIMP ages from ZI sup-
port an association between post-orogenic felsic
magmatism and auriferous Co-arsenopyrite mineraliza-
tion. This is further supported by the six point 317 17
Ma Re-Os isochron age. The spatial association of quartz-
sulfide veins with lamprophyre dykes implicates them in
the ore-forming process, and suggests they are also of
similar age. Genesis of the gold mineralization in Klecza,
like other Au deposits and occurrences in the KROD, is
suggested to be of orogenic type (Mikulski 2003). The
KROD deposit is located in the Intra Sudetic Fault zone
that separates two different terranes (Aleksandrowski et
al. 1997). At KROD there is no evidence for a direct mag-
is general agreement between model ages for these matic origin for hydrothermal fluids responsible for the
samples when an Os initial ratio of 0.2 is used. We sup- gold mineralization, despite the widely held belief that
port our arsenopyrite analyses by additional analyses of mineralization is related to the Karkonosze-Jizera gran-
a pyrite and chalcopyrite sample from the Radzimowice ites located ca. 10 km to the south. Re-Os data for aurifer-
deposit. These sulfides also contained low to very low ppt ous Co-arsenopyrite from Klecza (316.6 0.4 Ma), the
level Re and Os (Table 1). Collectively, all sulfide analyses first stage of refractory gold mineralization, may be slightly
from Radzimowice provide a six-point isochron with a younger than the porphyritic granites of the Karkonosze-
Re-Os age of 317 17 Ma (Fig. 2). The six-point isochron Jzera pluton dated at 325-330 Ma by the Rb-Sr method
has a reduced uncertainty compared to the four-point iso- (Duthou et al. 1991) or date at 320 2 Ma by 40Ar/39Ar on
chron based only on Co-arsenopyrite samples. The still biotite (Marheine et al. 2002). Au mineralization is most
relatively large uncertainty is due to the very low Os con- likely associated with lamprophyre dykes dated at 314
centrations of most of the samples (<5 ppt total Os in all 6 Ma 40Ar/39Ar (Marheine et al. 2002) or with aplitic gran-
cases but one). Within uncertainty, the Re-Os isochron ites date at 310 5 Ma by Rb-Sr (Duthou et al. 1991).
age overlaps with a much more precise model age of 316.6 Summarizing, our Re-Os results indicate that one of
0.4 Ma for Co-arsenopyrite sample G-4 (run MDID- the major Late Namurian post-orogenic extension epi-
350) from the Klecza deposit. sodes and regional uplift in the Kaczawa Mountains took
place ca. 317 Ma. Deep-seated structures allowed miner-
5 Discussion alizing fluids, mostly likely associated with magmatic
sources, to migrate upwards, forming auriferous sulfide
According to 40Ar/39Ar data presented by Marheine et al. mineralization. The age of auriferous mineralization (ca.
(2002), in the Western Sudetes, host rock schists of Or- 317 Ma) recognized in the Kaczawa Mountains is not co-
dovician-Lower Carboniferous represent shaly flysch-type eval with gold events described from the Central Bohe-
sediments that were recrystallized during regional up- mian province (ca. 338 Ma; Bouchot et al. 2001; or at 344
lift-related greenschist metamorphism in the Visan at 2.8 Ma by Re-Os method on molybdenite by Zachari
344-333 Ma and the upper limit of the Variscan et al. 2001) and Massif Central (310-305 Ma; Bouchot et
tectonometamorphic and magmatic activity was dated al. 2000).
at 314-312 Ma (Namurian / Westphalian boundary). Re-
Os data suggest that refractory gold- sulfide mineraliza- Acknowledgements
tion in the Kaczawa Mountains postdates regional meta-
morphism of host rocks and orogenic deformation. Re- The analytical work was supported by NCSR, Grant no. 5
fractory gold mineralization is related to Late-Namurian T12B 001 22.
tectonometamorphic and magmatic processes. At the
Radzimowice Au-As-Cu deposit, the schist unit was in- References
truded by the Zelezniak Intrusion (ZI) (Mikulski 2005).
Gold-bearing sulfide veins cut dacite porphyries and post- Aleksandrowski P, Kryza R, Mazur S, Zaba J (1997) Kinematics data
date lamprophyre dykes, but are spatially associated with on major Variscan strike-slip faults and shear zones in Sudetes.
Geol Magazine 134: 727-739
the dykes. SHRIMP ages for zircons from the fine-grained Arne DC, Bierlein FP, Morgan JW, Stein HJ (2001) Re-Os dating of
rhyolite are similar to zircon ages from the medium- sulfides associated with gold mineralization in Victoria, Austra-
grained microgranites of ZI, and indicate that the main lia. Economic Geology 96: 1455-1459

796 Stanislaw Z. Mikulski Richard J. Markey Holly J. Stein

Bouchot V, Faure M, Feybesse JL, Correira P, Zachari J (2001) Mikulski SZ (2003) Orogenic quartz-sulfide-gold veins from the
Variscan orogenic Au district related to a regional Visean detach- Klecza-Radomice ore district in the Kaczawa Mountains (West-
ment in the Central Bohemian province. In: Eliopoulos et al (eds) ern Sudetes) NE part of Bohemian Massif. In: Eliopoulos et al
Mineral Exploration and Sustainable Development. Millpress, pp (eds), Mineral Exploration and Sustainable Development,
747-750 Millpress, pp 787-790
Bouchot V, Milesi JP Ledru P (2000) Crustal scale hydro-thermal Mikulski SZ (2005) Geological, mineralogical and geochemical char-
Palaeofield and related Au, Sb, W orogenic deposits at 310-305 acteristics of the Radzimowice Au-As-Cu deposit from the Kaczawa
Ma (Massif Central). SGA News 10: 6-10 Mts. (Western Sudetes, Poland) - an example of the transition of
Duthou JL, Couturie JP, Mierzejewski MP, Pin C (1991) Rb/Sr whole porphyry and epithermal style. Mineralium Deposita 39: 904-920
rock samples isochrones method of the age determination of the Morelli, R, Creaser, RA, Seltmann, R (2004) The age of gold mineral-
Karkonosze granite (in Polish). Przeglad Geologiczny 32: 75-79 ization at the Muruntau Au deposit, Uzbekistan, from Re-Os ar-
Manecki A (1965) Petrographic-mineralogical studies of the senopyrite geochronology. Geological Society America Abstracts
polymetallic veins from Wojcieszow vicinities (Lower Silesia). with Programs 36 (5): 444
Prace Mineralogiczne PAN, 47 (2): pp 65 Muszynski A, Machowiak K, Kryza R, Armstrong R (2002) SHRIMP
Marheine D, Kachlik V, Maluski H, Patocka F, Zelazniewicz A (2002) U-Pb zircon geochronology of the Zelezniak rhyolite intrusion,
The 40Ar/39Ar ages from the West Sudetes (NE Bohemian Mas- Sudetes preliminary results. Mineral Society of Poland Spe-
sif): constraints on the Variscan polyphase tectonothermal de- cial Papers 19: 156-158
velopment. In: Winchester JA, Pharaoh TC, Verniers J (eds) Paulo A, Salamon W (1974) Contribution to the knowledge of the
Palaeozoic Amalgamation of Central Europe. Geological Society Stara Gora deposit. Kwartalnik Geol 18: 266-276
of London Special Publication 201: 133-155 Stein HJ, Morgan JW, Scheresten A (2000) Re-Os of low level highly
Markey R, Hannah JL, Morgan JW, Stein HJ (2003) A double spike radiogenic (LLHR) sulfides: The Harnas gold deposit, southwest
for osmium analysis of highly radiogenic samples. Chemical Sweden, records continental-scale tectonic events. Economic Ge-
Geology 200: 395-406 ology 95: 1657-1671
Mikulski SZ (2001) Late-Hercynian gold-bearing arsenic-polymetallic Zachari J, Pertold Z, Pudilov M, Zk K, Pertoldov J, Stein H,
mineralization in Saxothuringian zone in the Polish Sudetes, NE Markey R (2001) Geology and genesis of Variscan porphyry-style
Bohemian Massif. In: Piestrzynski et al (eds), Mineral Deposits gold mineralization, Petrckova hora deposit, Bohemian Massif,
at the Beginning of the 21st century. Balkema, pp 787-790 Czech Republic. Mineralium Deposita 36: 517-541

Chapter 7-20 7-20

Dating of gold occurrences in the Sayan-Baikal Fold

Belt, Southern Siberia, Russia
A.G. Mironov
Geological Institute of SB RAS, Sakhyanova 6a, Ulan-Ude, 670047, Russia
H. Stein, A. Zimmerman
AIRIE Program, Department of Geosciences, Colorado State University, Fort Collins, CO 80512-1482 USA
S.M. Zhmodik
Institute of Geology UIGGM SB RAS, Koptyuga 3, Novosibirsk, 630090, Russia

Abstract. The complex geologic history of the Tain gold-porphyry massif hosting gold mineralization is shaped like two at-
deposit in the Sayan-Baikal Fold Belt (South Siberia) makes direct tached lenses. The inner massif is composed of the grey
age determinations problematic. Timing of porphyry gold mineral-
mid- to fine-grained diorites and quartz diorites (grano-
ization, magmatism, and hydrothermal alteration are constrained
to an interval of 670-280 Ma based on dating of the host grano- diorites) that are variably altered and deformed. The mar-
diorites, altered rocks, and ores by the Rb-Sr, Ar-Ar, and Re-Os tech- ginal areas of the massif are variably enriched in yet to
niques, respectively. identified carbonaceous matter. The carbonaceous mat-
ter is commonly encountered as fine dust in quartz, along
Keywords. Sayan-Baikal Fold Belt, gold-porphyry deposit, dating, Ar-
zone planes, or as dust-like spotted disseminations in pla-
Ar, Rb-Sr, Re-Os techniques
gioclase. The carbonaceous matter is also observed in the
cross-cutting microfractures, occasionally associated with
1 Introduction epidote-clinozoisite. The granulated aggregates of albite
replacing calcic plagioclase are also pigmented by dust-
The gold-bearing Sayan-Baikal Fold Belt is known for its like carbonaceous matter (Mironov et al. 2001).
important ore reserves. Both quartz lode deposits (Pio- The beresitized rocks and beresites (mineral associa-
neer, Granite, Dynamite, Irokinda, etc.) and gold-sulfide tion of quartz, sericite, pyrite, and calcite) are the domi-
polymetallic deposits, along with sub-economic ore oc- nant rock type in the massif. They are greenish-grey fine-
currences (Zun-Kholba, Zun-Ospin, etc.), are located in and medium-grained rocks composed of sericitized pla-
the Belt (Mironov and Zhmodik 1999). Only recently, new gioclase, quartz, sericite, calcite, chlorite, sulfides (pyr-
types of gold mineralization such as those at Tain, rhotite predominates), leucoxene, apatite, and zircon.
Konevinskoye, and Kharalginskoye have been discovered. Quartz is characterized by two varieties, i.e., pressed, frac-
The Tain deposit is of particular significance as it ap- tured grains (quartz 1) and almost undeformed aggre-
pears genetically different from previously studied de- gates (quartz 2). Sulfides are represented by impregna-
posits in the region and has unique geolocial features. tions (0.1-1.5mm) of pyrrhotite. Pyrite is associated with
The Tain gold deposit lies in the central Ospin-Kitoi quartz 2, iron hydroxides, and calcite or chlorite. The low
massif of ultrabasic rocks comprising the ophiolitic Ilchir SiO2 concentrations, higher concentrations of MgO and
plate. Regionally, the Gargan Craton consists of Archean- CaO and dominantly more Na2O than K2O are character-
Proterozoic volcanogenic-sedimentary strata, ophiolite se- istic of beresitized rocks.
quences of the Neo-Proterozoic age, and granitoids of the In the southern part of the massif, accompanying and
Sumsunur (PZ1-2) and Samsal (PZ2-3) sequences. The hosting gold mineralization are medium to dark grey, vari-
Ospin-Kitoi ultrabasic massif is defined by the conver- ably grain-sized, porphyritic plagiogranites. They have an
gence of ophiolite outcrops from north to south in the irregularly grained texture of quartz and plagioclase ag-
eastern Gargan Craton. The massif is suggested to be a gregates 0.2-5mm in size and porphyry-like quartz impreg-
single unit later dissected by erosion associated with up- nations with traces of deformational cataclasite. Muscovite
lift of the Gargan Craton and preserved along its periph- is developed along fractures in plagioclase and locally
ery (Belichenko et al. 1988). intense alteration results in completely replaced plagio-
clase. Calcite (up to 1-2 wt.%), sulfides (to 3-5 wt.%),
2 Gold deposit description sericite, biotite, sphene, rutile, apatite, and carbonaceous
matter (0.1-0.5 wt.%). The carbonaceous matter gives the
The Tain deposit is localized in 300 m by 700 m grano- dark grey colour to the rock and is best developed on al-
diorites and plagiogranites stocks that crosscut local tered plagioclase, infilling of microfractures in quartz grains,
serpentinites and serpentinized harzburgites (Fig. 1). The and along fractures intersecting mineral aggregates.

798 A.G. Mironov H. Stein A. Zimmerman S.M. Zhmodik

quartz muscovite granitoids. The vein-like bodies are up

to 0.6 m thick in the quarry walls, hardly accessible, and
dominantly studied from rockfall in talus piles.
In contrast to the quartz veins, this type of ore is char-
acterized by lighter colored quartz without carbonaceous
matter, high precious metal contents between 150 to 200
ppm Au and 300 to 450 ppm Ag, and a peculiar paragen-
esis of gold and sulfide minerals. Hexagonal pyrrhotite is
the dominant sulfide mineral comprising 95-98 vol.% of
ore minerals. Chalcopyrite (0.1-3 vol.%) occurs as thread
veinlets and impregnations at the contact between mas-
sive pyrrhotite ores and quartz-muscovite aggregates.
Pyrite, cobaltite, sphalerite, galena, kustelite, and native
gold occur in subordinate amounts. Cobaltite (CoAsS) is
always seen as impregnations of small (0.01-0.09mm) crys-
tals in pyrrhotite. The important peculiarity of this ore
type is the partitioning of Au and Ag into kustelite rather
than other Au and Ag minerals. Kustelite forms isometric
grains 0.01-0.06mm in size that localize at the contact of
pyrrhotite with chalcopyrite and quartz.
Ores of veined-impregnated type are found within the
Geochemically all the varieties of the stock granitoids dark grey carbonatized, muscovitized and cataclased por-
have low Th and U concentrations, moderate Ba and Sr phyry-like plagiogranites. The ore consists of quartz vein-
concentrations with Sr prevailing in the unaltered or lets 0.5-3 cm thick and a few meters long with impregna-
weakly altered rocks, and sharp increase of Ba concen- tions (0.1-5 mm) of pyrrhotite and chalcopyrite (0.5-5
trations in muscovitized and dyke formations. The pre- vol.%) and noticably subordinate pyrite, sphalerite and
cious metal contents significantly vary, reaching maxi- galena. The plagiogranite host rocks are five to thirty
mum in the muscovitized and carbonatized rocks. meters thick and 100s of meters long zones made of
Three types of orebodies: (1) quartz-veined low sulfide quartz-sericite-muscotite rocks with variable amounts of
bodies, (2) quartz-muscovite-pyrrhotite ores and (3) vein- calcite, sulfides, and carbonaceous matter. Mineralogical
let-impregnated ores are identified at the Tain deposit. analysis of this ore type identify native gold, silver, ar-
gentite, and Ag-bearing bornite. Gold is present as two
Quartz veined low sulfide bodies occur as 0.3 to 1.5 m distinctly different morphologies. The first is represented
thick bodies observable for 230 m along strike. The quartz by middle and large native gold particles (0.1-0.3 mm and
veins are characterized by the carbonaceous matter-in- 0.7-1.0 mm, respectively) of bright yellow color and
duced dark gray color and intensive boudinage structures cloddy-laminar shape with high purity (915-965). The
with a clear tectonic orientation. Quartz grains within second variety is composed by small and middle (0.01-
the boudins elongate by unidirectional fracturing and 0.3 mm) gold particles of low purity (429-323) and
dislocation with equigranular grains showing pressure- kustelite.
induced dissolution-reprecipitation. In some locations Molybdenite is found as flakes and little nests in both
brittle deformation is seen as cataclasis and brecciation dark grey quartz and beresite ores. In the veinlets of dark
of host granitoids.. Muscovite, chlorite, biotite, amphib- grey quartz, molybdenite is found together with gold and,
ole and iron hydroxides (1-3 wt.%) are locally developed in beresite ore, it is found as dry veinlets along frac-
in microfractures. tures.
The Tain gold deposit has a number of features that
The major ore minerals (0.1-10 wt.%) occur as nest-like are atypical of East Sayan hydrothermal deposits. The
features (1-8cm across) of pyrite, pyrrhotite, galena, veinlet-impregnated type of ore mineralization in por-
sphalerite and chalcopyrite. These minerals also occur as phyry-like granitoids are dominant here unlike the Pio-
fine impregnations. Rare ore minerals hessite, wehrlite, neer, Barun-Kholba, Granite, and other lode deposits. The
argentite, native gold and silver are associated with net- presence of carbonaceous material, predominance of pyr-
like features as well. rhotite among sulfides, that of kustelite among gold min-
erals, and of methane in the gas phase are peculular as
Quartz-muscovite-pyrrhotite ores are differientiated by well. In our view, it is interpreted that the Tain deposit
high sulfide contents, mainly pyrrhotite, comprising up formed in different conditions and due to the magmatism
to 70% of the total rock, hosted in light grey and white of another type.

Chapter 7-20 Dating of gold occurrences in the Sayan-Baikal Fold Belt, Southern Siberia, Russia 799

The granitoids of the Tain stock belong to the granitoids TN-1 was taken from a single molybdenite bleb in an
of the island arc type based on geochemical data. Although 0.8 cm vein of dark gray quartz, of the variety associated
variable in absolute composition, the stocks generally with Au mineralization. Although the rock is quite weath-
corresponds to the island arc granites according to the ered and Fe stained, the vein and molybdenite are mod-
main indices (for example, Nb-Y, Rb-(Nb+Y) ratios) in erately fresh. The rock appears to be a fine-grained grani-
discrimination plots. Predominance of Sr and Ba and low toid that is highly altered, including silicification and a
contents of U and Th are typical of unaltered varieties. vuggy nature due to leaching of mm scale feldspar. This
Ba, Cu, and Zn concentrations increase in the beresitized molybdenite-bearing vein yielded a Re-Os age of about
and carbonatized granodiorites and granites. The maxi- 550 Ma, but additional molybdenite separates will be taken
mum contents of Ba (1100-1600 ppm) have been found and dated to confirm this result.
in the carbonatized dykes of granite-porphyries. Co and TN-2 is also a fine-grained granitoid with mm scale
Ni predominance as well as low concentrations of U (1.3- euhedral crystals of feldspar with diffuse margins due to
3.2 ppm) and Th (0.4-3.9 ppm) are also characteristic of silicification. The rock is also sericitized. Fe-oxide stain-
the granite porphyries. Analyzed rare earth elements form ing is locally prevalent. Molybdenite occurs in abundance
a trend similar to the REE trend of granitiods from the along a surface that appears to be the margin of an ir-
Amur-Alyaska island arc system. Some decrease of their regular, not planar, vein. The Re-Os age is about 860 Ma,
contents is observed in ores at their enrichment in quartz but additional mineral separates are necessary to affirm
and pyrrhotite. geologic accuracy of this somewhat weathered occurrence.
The massif rocks are intensly tectonized by subhorizonal Thus, the gold mineralization in the massif has the
faulting. Small, spotted occurences of plagiogranites, di- age that is close to the island arc and island arc type grani-
orites and dacite-porphyries are known in other areas of toid formation (800-600 Ma). The Tain gold deposit con-
the ophiolite cover (Ekhe-Shigns, Borto-Gol rivers, etc.). tains the mineralization formed by reducing fluids and
All this testifies to the fact that the Tain stock granitoids has obvious features typical of gold porphyry deposits.
and analogous rocks formed in the island arc stage suf- Its specific features are caused by granitoid emplacement
fered deformation during the subsequent collision and in an area of ultrabasites and black shales that are en-
obduction. In contrast, the granitoids of the Sumsunur riched in carbonaceous matter of both biogenic and
and other younger sequences (PZ2-3) are clearly syn- and mantle nature. It is likely the earliest gold mineralization
postcollisional. in the region in the massif of island arc granitoids that
were subsequently subjected to obduction within the
3 Dating results ophiolite cover and accompaning turbidite and craton
terranes (Bogatikov and Tsvetkov 1988).
The study of absolute age in rocks and ores of the Tain
deposit shows significant variations in obtained data. A Acknowledgements
Rb-Sr isochron indicates 67019 Ma and 87Sr/86Sr
=0.71200.0010 on the altered porphyry-like granites and The work has been carried out with the grant support of
muscovite. Two Ar-Ar ages of 4359 Ma (samples Th330 the leading research schools No -2208.2003.5 and RFBR
and Th331) and 2804.1 Ma (Th329) were obtained grant 03-05-65162.
from amphiboles taken from the Tain massif diorite. Those
ages are likely to indicate the later metamorphism and References
hydrothermal alteration of rocks.
The question arises which process is associated with Belichenko VG, Butov YuP, Dobretsov NL (1988) Geology and meta-
and/or reponsible for gold mineralization. The answer morphism of the East Sayan. Novosibirsk, Nauka.
may be obtained from Re-Os data on molybdenite asso- Bogatikov OA, Tsvetkov AA (1988) Magmatic evolution of island arcs.
ciated with gold mineralization. A sample of molybden- Moscow, Nauka.
Mironov AG, Zhmodik SM (1999) Gold deposits of the Urik-Kitoi
ite as a rosette-like inclusion in a veinlet (6mm thick) of
metallogenic zone (East Sayan, Russia). Geology of ore deposits.
dark grey quartz (TN-1) and a sample of molybdenite V. 41, N1, 54-69
from a dry veinlet (molybdenite powdery coating on Mironov AG, Zhmodik SM, Ochirov YuCh, Borovikov AA, Popov VD
the fracture surface 0.5-1.5mm thick) (sample TN-2) were (2001) The Tain gold deposit (East Sayan, Russia) is rare type of
selected. gold-porphyry formation. Geology of ore deposits. N5, 395413

Chapter 7-21 7-21

Jurassic magmatism and Au-Ag mineralization

in the Deseado Massif (Patagonia Argentina):
Lead and sulfur isotopic studies
P. Moreira, R.R. Fernndez, I.A. Schalamuk, R.O. Etcheverry
Instituto de Recursos Minerales (INREMI), Universidad Nacional de La Plata, CICBA, Argentina
A.P. Rolando
Par-Iso Laboratory, Instituto de Geociencias, Universidade Federal do Par, Belm, Brazil

Abstract. Lead isotope analyses of volcanic rocks and hydrothermal the low sulfidation epithermal type of deposits. The last
minerals and sulfide isotope analyses of sulfurs from Au-Ag La prospect, currently under exploration, is located in the cen-
Josefina prospect (Deseado Massif geological province, Argentina)
tral part of the DM and the mineralization is represented
are reported. Lead isotope ratios for sphalerite and pyrite have mean
values of 18.48, 15.69 and 38.61 for 206Pb/204Pb, 207Pb/204Pb and by Au-Ag bearing vein systems (up to 300 g Au/t).
208Pb/204Pb, respectively, and are similar to Pb isotope ratios for the The objective of this paper is to present the lead and
Jurassic volcanic rocks of Bajo Pobre and Chon Aike Formations. sulfur isotopic data from samples of hydrothermal sul-
34S values of sphalerite, pyrite and galena cluster between 1.3 fides and volcanic rocks obtained at the La Josefina pros-
and 3.8 , suggesting that the sulfur at La Josefina was primarily
of magmatic origin. These results are interpreted to indicate that
the Jurassic volcanic rocks are closely related with low sulfidation There are few isotopic studies of the DM, only two lead
Au-Ag occurrences. isotope data for the Jurassic volcanic rocks are indicated
by Kay and Gorring (1999) and five lead isotope mea-
Keywords. Pb isotopes, S isotopes, epithermal deposits, Jurassic vol- surements on galena from several ore deposits of the DM
canism, Patagonia Argentina were showed by Schalamuk et al. (1997). Theses analyses
show isotopic values between 18.48-18.72, 15.73-15.95 and
1 Introduction 38.70-39.53 for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb,
The Deseado Massif (DM) is located in the southern Isotope sulfur ratios carried out in samples from Au-
Argentinean Patagonia (Fig. 1). In this region, the most Ag epitermal prospects (Cerro Vanguardia, Manantial
important unit is a volcanic complex of upper to middle Espejo, El Dorado-Monserrat and Cerro Len) in the DM,
Jurassic age with bimodal features marked by andesitic were reported by Echavarra (1997), Schalamuk et al.
and rhyolitic magmas that conform the Bajo Pobre and (1998) and Jovic et al. (2004). The 34S values range be-
Chon Aike Formations, respectively. These units crop out tween 2.8 and 4.2 , indicating a magmatic source for
over more than half the area of a wide plateau. The the sulfur.
geochemical analyses of the Jurassic volcanism show a
calc-alkaline magmatism with a volcanic arc affinity. 2 La Josefina geology
These volcanic rocks are related to the early history of
the Gondwana break-up and were deposited in the back- The La Josefina prospect (Fig. 1) includes lower Paleo-
arc Patagonian Andes during a long period (187 to 144 zoic low grade metamorphic muscovitic schists,
My) of extension (Riley et al. 2000). The geotectonic en- metavolcanic and calk-silicate rocks with minor mag-
vironment of Patagonia in the Jurassic times was charac- netitic levels and tourmalinites of La Modesta Forma-
terized by very slow subduction in the Pacific margin of tion (Moreira et al. 2005).
Gondwana (Ramos 1988). Pankhurst et al. (2000) support The Bajo Pobre and Chon Aike Formations represent
the idea that the volcanic rocks were probably generated the Jurassic volcanic rocks. The Bajo Pobre Formation,
by a variety of mechanism, among which the melting of mainly andesitic-dacitic rocks, include porphyritic and
pre-existing continental crust was a dominant process. aphanitic flows partially self-brecciated, porphyries, sills
These volcanic rocks host the Au-Ag veins of Cerro that intrude the low angle dip schist of the La Modesta
Vanguardia, the principal ore deposit currently in produc- Formation, and ring-dikes surrounding rhyolitic domes.
tion, and also host the Ag-ore shoot worked in the Marta The Chon Aike Formation cover approximately a 60 % of
Mine, as well as some other important prospects like the area. The lower member outcrop on the west part,
Manantial Espejo, Huevos Verdes-Cerro Saavedra-El Pluma, and consists of crystal-rich quartz-feldspar-biotite welded
El Dorado-Monserrat, Cerro Negro and La Josefina. Most ignimbrite with some flatten pumice-rich levels that was
of these prospects (Schalamuk et al. 1997) correspond to dated at 153.2 3.6 My (K/Ar on biotite; Arribas et al.

802 P. Moreira R.R. Fernndez I.A. Schalamuk R.O. Etcheverry A.P. Rolando

1996). On the eastern part dominate a welded pumice- 4 Samples and results
rich, crystal-poor welded ignimbrite whose lower levels
carrying 5-20 cm crystal-rich-ignimbrite lithic fragments, 4.1 Samples
whereas in the upper levels these lithics are smaller and
sporadic. A rhyolitic dome-complex outcrops on 10 km2 The samples collected for the lead isotopic study of the
in the north-northwest of the area and some smaller rhy- La Josefina prospect consisted in intermediate-acid Ju-
olitic domes extend to the northwest, both with slowly rassic volcanic rock from Bajo Pobre and Chon Aike For-
propylitic, pyritic and argillic patch of hydrothermal al- mation (feldspar separates) and hydrothermal minerals
teration. These domes intruded the Paleozoic metamor- from veins (pyrite and sphalerite). The isotopic Pb com-
phic rocks (La Modesta Formation). position were determinate on 13 samples in the Par-Iso
Paleogene and neogene basaltic flows cover the Juras- Laboratory, Instituto de Geociencias, Universidade Fed-
sic volcanic rocks. eral do Par, Belm, Brazil.
Seven sulfide paragenetic samples, including separates
3 La Josefina Au-Ag epithermal ocurrences of pyrite (3), sphalerite (3), and galena (1), were analyzed
for their sulfur isotope composition. Analyses were car-
The mineralization at the La Josefina prospect consists ried out at the Stable Isotopic Service from Salamanca
of system of low sulphidation epithermal veins and vein- University (Spain). The results are given as 34S val-
lets filled mainly by quartz and chalcedony with minor ues relative to the CDT standard.
adularia, barite and platy calcite. The primary assemblages
are composed by native gold, electrum, specularite and 4.2 Results
pyrite, arsenopyrite, galena with freibergite inclusions,
sphalerite, chalcopyrite and bornite and a supergenic as- The analyses of Pb in samples from La Josefina prospect
sociation consist in limonites, chalcocite-covelite, cerusite- are summarized in the Table 1 and plotted in the Zartman
anglesite and malachite. and Doe (1981) diagrams (Fig. 2).
These occurrences are distributed in a curved belt about The volcanic Jurassic samples have an average ratios
N-S 12 km long and between 500 and 1200 m wide. The of 206Pb/204Pb= 18.44, 207Pb/204Pb= 15.65 and 208Pb/204Pb=
age of the mineralization is not well constrained; a Rb-Sr 38.50 and the elongate trends in the general cluster indi-
errorchron gave an age of 156 2 My (Fernndez et al. cate mainly an orogenic model fit, suggesting variable
1999). The veins are spatially associated with superficial mixing of lead from different sources, mainly model up-
epithermal occurrences, like hydrothermal eruption brec- per crust and to a lesser extent model mantle and lower
cias, silica sinter terraces, geyserites, carbonate stroma- crust reservoirs.
tolitic deposits, and steam heated blankets, mainly to the The Pb isotopic compositions of pyrite and sphalerite
north of the prospect. from La Josefina are near 206Pb/204Pb= 18.48, 207Pb/204Pb=

Chapter 7-21 Jurassic magmatism and Au-Ag mineralization in the Deseado Massif (Patagonia Argentina): Lead and sulfur isotopic studies 803

Lead isotopes obtained from galena samples by

Schalamuk et al. (1997) although have slightly higher val-
ues, do not show significant differences from the samples
studied here. The 34S results in La Josefina are similar to
those in several ore deposits in the DM.
Based on these features, there is a genetic link between
the DM low sulfidation epithermal deposits and the bi-
modal magmatism of the Bajo Pobre and Chon Aike For-
15.69 and 208Pb/204Pb= 38.61. The lead isotope composi- mation.
tion of these sulfides are in general slightly more radio-
genic than the volcanic host rocks. Acknowledgements
The analyses of 34S are summarized in the Table 2.
Sulfur samples in La Josefina show 34Smineral values be- The authors are grateful to the Agencia Nacional de
tween 1.3 and 3.8 . The 34S high value for sphalerite Promocin Cientfica y Tecnolgica (FONCyT) and the
(13.1 ) demonstrate an overall increase. This could be Santa Cruz state mining company (FOMICRUZ S.E.) for
explained by changes of the hydrothermal fluid pH pro- the support and close cooperation during this research.
duced by the interaction with the volcanic rocks.
5 Conclusions
Arribas Jr A, Schalamuk I, de Barrio R, Fernndez R, Itaya T (1996)
The 34S values of pyrite, sphalerite and galena indi- Edades Radimtricas de Mineralizaciones Epitermales Aurferas
del Macizo del Deseado, Provincia de Santa Cruz, Argentina. In:
cate that their sulfur was derived from a magmatic XXXIX Congresso Brasileiro de Geologa, pp 254-257
sulfur source with scarce supergene activity. Pb isotope Echavarra LE (1997) Estudio geolgico-minero del rea El Dorado-
ratios of pyrite and sphalerite, are most similar to those Monserrat, Departamento Magallanes, provincia de Santa Cruz.
of the volcanic rocks and suggest that they are the likely Tesis Doctoral Facultad de Ciencias Naturales y Museo,
source. Universidad Nacional de La Plata. Unpublished
Fernndez R, Echeveste H, Tassinari C, Schalamuk I (1999) Rb-Sr
The correspondence of both sets of values with the
age of the La Josefina ephitermal mineralization and its relation
orogenic growth curve of Zartman and Doe (1981) sug- with host volcanic rocks. Macizo del Deseado, Santa Cruz Prov-
gests further that varied sources contributed to the lead ince, Argentina. In: 2 Simposio Sudamericano de Geologa
of the magma. Isotpica, pp 462-465

804 P. Moreira R.R. Fernndez I.A. Schalamuk R.O. Etcheverry A.P. Rolando

Jovic SM, Guido D, Tiberi P, Schalamuk I (2004) Cerro Leon, una varia- Ramos V. (1988) Late Proterizoic-Early Paleozoic of South America.
cin del modelo epitermal de baja sulfuracin del Macizo del Dese- A collisional history. Episodes, 11:168-175
ado. In: VII Congreso de Mineraloga y Metalogenia, pp 225-230 Riley T, Leat P, Pankhurst R, Harris C (2000) Origin of large volume
Kay SM, Gorring ML (1999) Evolution of the Patagonian Mantle: rhyolitic volcanism in Antartic Peninsula and Patagonia by crustal
evidence from isotopic studies of Tertiary to recent plateau lavas. melting. J Petrol 42: 1043-1065
II South American Symposium on Isotope Geology, pp 556-565 Schalamuk I, Echeveste H, Etcheverry RO, Ametrano S (1998)
Moreira P, Gonzlez P, Fernndez R, Echeveste H, Schalamuk I, Metalognesis del yacimiento Manantial Espejo,Macizo del
Etcheverry R (2005) El basamento de bajo grado de las Estancias Deseado, provincia de Santa Cruz. In: Academia Nacional de
La Modesta y La Josefina, Macizo del Deseado, Provincia de Santa Ciencias Exactas, Fsicas y Naturales, Anales 50: 217-236
Cruz. Revista de la Asociacin Geolgica Argentina 60-1 Schalamuk I, Zubia M, Genini A, Fernndez R (1997) Jurassic
Pankhurst RJ, Riley TR, Fanning CM, Kelley SR (2000) Episodic si- epithermal Au-Ag deposits of Patagonia, Argentina. Ore Geol Rev
licic volcanism in Patagonia and the Antarctic Peninsula: chro- 12: 173-186
nology of magmatism associated with the break-up of Gondwana. Zartman RE, Doe BR (1981) Plumbotectonic-the model. Tectonophys
J Petrol 41: 605-625 75: 135-162

Chapter 7-22 7-22

Re-Os ages for molybdenite from the Tepeoba

breccia-centered Cu-Mo-Au deposit, western Turkey:
Brecciation-triggered mineralization
Hiroyasu Murakami
Institute for Geo-resources and Environment, Geological Survey of Japan, AIST, 1-1-1 Higashi, Tsukuba 305-8567, Japan
Yasushi Watanabe
Institute for Geo-resources and Environment, Geological Survey of Japan, AIST, 1-1-1 Higashi, Tsukuba 305-8567, Japan
Holly Stein
AIRIE Program, Department of Geosciences, Colorado State University, Fort Collins, CO 80523-1482 USA, and
Norges Geologiske Underskelse, Leiv Erikssons vei 39, 7491 Trondheim, Norway

Abstract. The Tepeoba breccia-centered Cu-Mo-Au deposit is asso- sions was emplaced into these basement rocks during the
ciated with the Miocene Eybek granodiorite complex in western Oligocene and Early Miocene period. A ~24 Ma rapidly
Turkey. The ages for molybdenite samples in the hydrothermal brec-
exhumed high-grade metamorphic core complex in the
cia and two molybdenite samples in veins surrounding breccia, one
in metasedimentary rocks and one in the granodiorite, were dated Kazda mountain range was uplifted from ~14 km to ~7
by the Re-Os method using a double Os spike. Re-Os ages of mo- km along a thick shear zone (Okay and Satir 2000). The
lybdenite are 25.03 0.14 and 25.11 0.14 Ma for the veins and Eybek granodiorite is situated on eastern margin of the
25.62 0.09 Ma for the breccia-hosted sample. These results indi- Edremit graben bounded by ENE-WSW trending high-
cate that the hydrothermal breccia in the Tepeoba deposit formed
angle normal faults. The granodiorite is a typical calc-
prior to the vein formation. We conclude, based on the Re-Os ages,
that hydrothermal activity at Tepeoba lasted at least half a million alkaline, I-type, magnetite-series. Granite body with S-
years. type and ilmenite-series signatures occurs locally along
the margin of the granodiorite body (Fig. 1B). A two-com-
Keywords. Re-Os, 188Os-190Os double spike, hydrothermal breccia, Cu- ponent mixing pattern of strontium isotope values sug-
Mo-Au deposit, Turkey gests the granite formed by mixing between the grano-
diorite and the host meta-sedimentary rocks. Early to
1 Introduction Middle Miocene volcanic and sedimentary rocks overlie
the basement rocks.
Re-Os dating of molybdenite (MoS2) is an effective tool
for directly dating mineralization. Notably, molybdenite 3 Tepeoba breccia-centered Cu-Mo-Au deposit
posses the unique property of accommodating Re at the
ppm level, while incorporating essentially no initial (com- The Tepeoba deposit was discovered in 2002, by diamond
mon) Os, thus providing a suitable single mineral chro- drilling conducted by the General Directorate of Mineral
nometer utilizing the 187Re-187Os method (Stein et al. 2001). Research and Exploration of Turkey. A drill hole shows
The 188Os-190Os double spike may be essential for young the upper 100 m with an average grade of 0.5 % Cu and
or low Re molybdenites (Markey et al. 2003). This method ~1 g/t Au, with the upper 53 m at 1 % Cu, and 0.05 % Mo.
can precisely determine and correct for common Os and The deposit occurs along and above the south granite body,
mass fractionation. The method thus provides a precise located at the southern margin of the Miocene Eybek gra-
mineralization age associated with formation of molyb- nodiorite complex. This deposit is hosted by metamor-
denite even in young samples with low Re contents. phic and sedimentary rocks of Permo-Triassic age, meta-
In this study, we report three Re-Os ages of molyb- morphosed to andalusite-biotite schist due to the con-
denite, dated by the double Os spike method, in the tact metamorphism by the granodiorite. The deposit con-
Tepeoba Cu-Mo-Au deposit in western Turkey. We dis- sists of semicylindrical hydrothermal breccia 200 m wide,
cuss duration of mineralization and the spatial and tem- and extends for 800 m southwards with a maximum thick-
poral evolution of the Tepeoba hydrothermal system. ness of 100 m (Fig. 1B). This hydrothermal breccia in-
cludes fragments of surrounding rocks (e.g., andalusite-
2 Geologic background biotite schist and granite) except granodiorite in a ma-
trix mainly of phlogopite. The ratio of granite fragments
Western Turkey is comprised of Permo-Triassic metamor- to andalusite-biotite schist fragments is greater nearer to
phic and sedimentary rocks (Fig. 1A). A series of intru- the granite. The breccia ore is composed of chalcopyrite

806 Hiroyasu Murakami Yasushi Watanabe Holly Stein

and phlogopite with accessory molybdenite, pyrite, cal- Au mineralization is related to the granodiorite intrusion
cite, quartz, tourmaline, sphalerite, and electrum. In the and subsequent brecciation (Murakami et al. 2004).
hydrothermal breccia, post-brecciation hydrothermal ac-
tivity is limited to thin quartz veining. 4 Samples and analytical procedures of Re-Os
It has been proposed that the Tepeoba deposit has been dating
tilted almost 90 with its top to the south due to Miocene
normal faulting, resulting in full exposure of hydrother- The three molybdenite samples used for Re-Os dating are
mal alteration zones associated with the granodiorite- (A) molybdenite cementing a matrix of a granite-frag-
granite complex on the present surface (Murakami et al, ment rich hydrothermal breccia, with phlogopite, quartz
2004). We suggest that alteration and mineralization at and chalcopyrite, (B) molybdenite in a hydrothermal cal-
Tepeoba resemble types seen at porphyry-style Cu-Mo cite-quartz vein in andalusite-biotite schist, and (C) mo-
deposits. The alteration sequence in order of increasing lybdenite in a vein containing chlorite (after igneous bi-
proximity to mineralized breccia is a propylitic zone, otite) found along cracks in the granodiorite (Fig. 1B).
muscovite zone, and K-silicate zone. The propylitic and Molybdenite was extracted from these samples in a
muscovite zones are characterized by the presence of small targeted, occurrence-specific manner using a diamond-
amounts of chlorite and pyrite, and the presence of mus- tipped, slow-speed drill (Stein et al. 2003). Chemical pro-
covite partly replacing biotite and quartz-calcite-molyb- cedures follow Markey et al. (2003). Isotopic compositions
denite veins, respectively. These alteration zones surround were determined using NTIMS on two NBS spectrom-
the breccia dominated by K-silicate alteration, depicted eters at AIRIE. Age is calculated by applying the equation
by phlogopite with disseminated chalcopyrite and mo- 187
Os=187Re (et-1), where is the decay constant for 187Re
lybdenite. K-Ar ages for phlogopite in the matrix of the and t is the age. The 187Re decay constant used is 1.666
mineralized breccia are 23.8 1.2 and 23.8 1.4 Ma (here- 10-11 yr-1 with an uncertainty of 0.31%. During this study,
after, all ages are shown with two sigma uncertainty), and blanks were Re = 4.77 0.04 pg, total Os = 4.09 0.02 pg,
K-Ar ages for muscovite surrounding the breccia are 22.8 and 187Os/188Os = 0.229 0.002 pg.
1.4, and 24.6 1.4 Ma. Ages of the intrusions have also
been dated by K-Ar. Biotite in the granodiorite is dated at 5 Relationship between granodiorite and
20.3 1.0 and 21.4 1.2 Ma. K-feldspar in the granite is hydrothermal alteration
older at 34.72.0 Ma. Integration of stable isotope data,
together with geologic relations and fluid inclusion data Re-Os and K-Ar ages for hydrothermal minerals, grano-
indicate that boiling, high-salinity fluids were responsible diorite and granite from the Tepeoba Cu-Mo-Au deposit
for the K-silicate and muscovite alteration and Cu-Mo- are summarized in Figure 2.

Chapter 7-22 Re-Os ages for molybdenite from the Tepeoba breccia-centered Cu-Mo-Au deposit, western Turkey: Brecciation-triggered mineralization 807

Re-Os ages for molybdenites yield a time-span from

25.62 0.09 to 25.03 0.14 Ma, a period > 0.5 m.y., slightly
longer than 0.3 m.y. estimates for the Far Southeast por-
phyry deposit (Arriibas et al. 1995) and 0.16 m.y. for the
Batu Hijau porphyry deposit (Garwin 2002). Recent Re-
Os dating indicates that some porphyry Cu-Mo deposits
have longer mineralization periods (e.g. Los Pelambres,
El Teniente, Stein et al. 2004a). Dilles et al. (2004) inter-
preted extended mineralization at Butte to overprint of
multiple mineralization events.
There is no syn- or post-hydrothermal activity except
a single stage of mineralized breccia at the Tepeoba de-
posit with a lack of significant veining in the hydrother-
mal breccia body. Molybdenite of ca. 25.03 Ma also coex-
ists with low-temperature assemblages compare to those
in the breccia. These occurrences suggest that the 0.5
m.y.mineralization period of Tepeoba is more likely to
represent an extended mineralization event such as pro
and retro-grade alteration in skarn type deposit, rather
Re-Os dates are consistently older than all K-Ar dates. than possible multiple mineralization events.
The Re-Os system has been shown to remain closed at the We have determined formation pressure for the gra-
scale of the molybdenite phase even through high-grade nodiorite using plagioclase-hornblende geobarometry.
ductile deformation and metamorphism of a porphyry sys- The crystallization pressure is estimated at ~2 kbar. Ac-
tem (Stein et al. 2004b). On the contrary, the temperatures cording to geobarometry, if rock density is 2.7 g/cm3, depth
where minerals begin to lose radiogenic argon are of 300 of crystallization of the Eybek granodiorite is considered
50 C, 350 50 C, and the interval ranging from 400 to to be ~7.5 km, which is consistent with depth estimates
470C, for biotite, muscovite, and phlogopite, respectively for surrounding metasedimentary rocks (Okay and Satir
(Dodson and McClelland-Brown 1985). Additionally, K-Ar 2000). Such a deeper depth relative to many other por-
dates in a contact metamorphic aureole generally reflect phyry copper deposits (ca. 1-4 km) may utilize a more
cooling ages for the associated intrusion. A pluton showing static regime for skarn formation (e.g. controlled by dif-
a close temporal and spatial association with the Eybek gra- fusion rate rather than infiltration), and to limit hydro-
nodiorite has a Rb-Sr age of 25 0.4 Ma (Yilmaz and Karacik thermal activity accompanying mineralization in the vi-
2001 and references therein), which is close to the Re-Os cinity of hydrothermal source without disturbance such
molybdenite ages. Therefore, K-Ar ages for biotite in the as meteoric water circulation. This may be supported by
granodiorite should correspond to final cooling of the gra- the presence of small-scale skarn type Cu-Fe deposits
nodiorite, and that of hydrothermal minerals rejuvenated which are sporadically distributed in and around the
due to contact metamorphism. Eybek granodiorite at almost the same depth as the
During cooling of the granodiorite, contact metamor- Tepeoba deposit.
phism may cause continuous loss of radiogenic argon from Although a period of hydrothermal activity at the
hydrothermal minerals, because the youngest age of gra- Tepeoba deposit related to the granodiorite and subse-
nodiorite is accord with that of hydrothermal muscovite. quent brecciation is consistent with the time interval for
The K-Ar age of the hydrothermal phlogopites is some- common porphyry-style deposits, there is a huge differ-
what older than that of muscovite, which is consistent ence in the scale between these types. This is interpreted
with the observation that phlogopite commonly retains that volume and scale of mineralization of intrusion-re-
its radiogenic argon better than muscovite at higher tem- lated style should be controlled by number of cycles of
perature (Dodson and McClelland-Brown 1985). hydrothermal alteration linked to magmatic fluid derived
from intramineral intrusion (e.g., giant Cu-Mo porphyry
6 Style of Tepeoba mineralization relative to deposits in Chilean Andes).
porphyry copper
For porphyry-style Cu deposits, hydrothermal breccia gen-
erally forms at the close of major hydrothermal activity, We are grateful to Dr R Sari and Mr S Kkefe of the
although there are exceptions (e.g. Sillitoe 1985). Based on General Directorate of Mineral Research and Exploration
Re-Os dating results, mineralized hydrothermal breccia at of Turkey for helping a field survey and providing geo-
the Tepeoba deposit formed prior to the vein formation. logic data of the Tepeoba deposit.

808 Hiroyasu Murakami Yasushi Watanabe Holly Stein

References Okay A, Satir M (2000) Coeval plutonism and metamorphism in a

latest Oligocene metamorphic core complex in northwest Tur-
Arribas AJr, Hedenquist JW, Itaya T, Okada T, Concepcin RA, Garcia, key. Geol Mag 137: 495-516
JSJr (1995) Contemporaneous formation of adjacent porphyry Sillitoe RH (1985) Ore-Related Breccias in Volcanoplutonic Arcs. Econ
and epithermal Cu-Au deposits over 300 ka in northern Luzon, Geol 80: 1467-1514
Philippines. Geology 23: 337-340. Stein HJ, Cannell J, Cooke D, Sillitoe R, Perell J (2004a) Metallifer-
Dilles JH, Stein H.J, Martin MW (2004) Re-Os and U-Pb ages for the ous moments inside the lifespan of porphyry-style Cu-Au-Mo
duration of the giant Butte, Montana, porphyry Cu-Mo and Cor- deposits: (electronic, session 12a) IAVCEI General Assembly,
dilleran base metal lode ore deposit. IAVCEI general assembly Pucn, Chile
Pucn, Chile Stein HJ, Hannah JL, Zimmerman A, Markey R, Sarkar SC, Pal AB
Dodson MH, McClelland-Brown E (1985) Isotopic and paleomag- (2004b) A 2.5 Ga porphyry Cu-Mo-Au deposit at Malanjkhand,
netic evidence for rates of cooling, uplift and erosion. Geol Soc central India: implications for Late Archean continental assem-
Mem 10: 315-325 bly. Precambr Res 134: 189-226
Garwin S (2002) The Geologic Setting of Intrusion-Related Hydro- Stein HJ, Markey, RJ, Morgan JW, Hannah JL, Scherstn, A (2001)
thermal Systems near the Batu Hijau Porphyry Copper-Gold De- The remarkable Re-Os chronometer in molybdenite: how and
posit, Sumbawa, Indonesia, Global Exploration 2002: Integrated why it works. Terra Nova 13: 479-486
Methods for Discovery, Colorado, USA. Soc Econ Geol 9: 333-366 Stein HJ, Scherstn, A, Hannah, JL, Markey R (2003) Sub-grain scale
Markey R, Hannah JL, Morgan1 JW, Stein HJ (2003) A double spike decoupling of Re and 187Os and assessment of laser ablation ICP-
for osmium analysis of highly radiogenic samples. Chemi Geol MS spot dating in molybdenite. Geochim Cosmochim Acta 67:
200: 395-406 3673-3686
Murakami H, Watanabe Y, Sari R, Kkefe S (2004) Newly discovered Yilmaz Y, Karacik Z (2001) Geology of the northern side of the Gulf
Tepeoba breccia-centered Cu-Mo-Au deposit in western Turkey: of Edrem it and its tectonic significance for the development of
(electronic, session 1c) IAVCEI general assembly Pucn, Chile the Aegean grabens. Geodin Acta 14: 31-43

Chapter 7-23 7-23

U-Pb SHRIMP dating of zircon from quartz veins

at the Yangshan gold deposit: Evidence for multiple
magmatic-hydrothermal events
Qi Jinzhong, Li Li, Yuan Shisong, Liu Zhijie
Gold Geological Institute of China Armed Police Force, Langfang 065000, China

Abstract. The Yangshan gold deposit is a fine-grained disseminated ing fine-grained disseminated gold ore. The quartz vein-
gold deposit located in south Gansu province. The metallogenic age lets (often 1 to 2 cm wide) occur in the contact zone be-
was determined by cathodoluminescence imaging and U-Pb SHRIMP
tween the plagiogranite dikes and the Devonian phyllite.
techniques. Zircons associated with quartz veins containing fine-
grained disseminated gold ore have typical magmatic features in- The samples consist mainly of quartz (95 wt.%) with sub-
cluding pillar idiomorphism, rhythmic zoning, and Th/U ratio of 0.5 ordinate sericite and clay minerals (4 wt.%), minor arse-
to 1.5. Average 206Pb/238U ages of 197.6 1.7 Ma, 126.93.2 Ma, and nopyrite and pyrite (1 wt.%), and rare electrum.
51.21.3 Ma define three primary zircon populations. The former age Representative zircon grains from the samples were
correlates to K-Ar ages (189.47.2 Ma mean) for plagiogranite dikes,
selected under microscope. The grains together with a
while the later two ages suggest buried Cretaceous and Tertiary
intrusives in or near the ore field. The Yangshan gold deposit is ge- slice of standard zircon SL13 and grains of standard zir-
netically related to the three magmatic-hydrothermal events. con TEM from Australia State University were mounted
in epoxy, ground, and polished to expose the interior.
Keywords. Disseminated gold, zircon, quartz vein, SHRIMP dating, Cathodoluminescence (CL) images were made on the zir-
Gansu cons prior to analyses at the electronic probe laboratory
of Institute of Mineral Deposits, CAGS. U, Th, Pb isotopic
1 Introduction compositions of zircons were analyzed on a SHRIMP II
at the ion probe center of Geological Institute, CAGS.
The recently discovered found Yangshan gold deposit, lo- Analyses followed the established methods of Composton
cated in south Gansu province, China, is a large deposit et al (1992) and Williams et al (1998). Programs SQUID
containing fine-grained disseminated gold. Four discov- 1.02 and ISOPLOT were utilized for data processing. Re-
ered ore blocks occur in metamorphosed Devonian sand- ported uncertainties for U/Pb ratios are at the 1 level.
stone, phyllite and limestone. The ore belt is primarily Common Pb is corrected from measured 204Pb. Weighted
controlled by the Anchanghe- Guanyinba fault as well as mean ages are quoted at the 95% confidence level.
small secondary faults. Locally, plagiogranite dikes lie along
the fault, and gold mineralization is concentrated in the con- 3 Result of SHRIMP dating
tact zone between the dikes and the Devonian phyllite. The
orebodies, roughly sigmoidal in plane and tabular in pro- Fourteen analyses were made on zircon grains from
file, are hosted in pyritized, arsenopyritized, sericitized and sample YM representing fine-grained disseminated ore.
argillized phyllite and plagiogranite. Late-stage pyrite-quartz Three age groups are defined and shown in the U-Pb
veinlets crosscut the orebodies. Native gold, mainly elec- concordia diagram (Fig. 1). The first group consists of
trum, is found as microscopic to sub-microscopic (<3m) three analyses giving 206Pb/238U ages of 195.4 to 200.9 Ma.
inclusions in pyrite and arsenopyrite. These zircons are prismatic with concentric zoning (Fig. 3)
Previous K-Ar and 39Ar-40Ar dating of the deposit give suggesting a magmatic genesis (Yang 2002; Wu 2002). The
early Jurassic ages for the plagiogranite dikes, which were second group consists of six analyses yielding 206Pb/238U
spatially associated with the mineralization (Qi 2003). In ages between 121.8 and 137.0 Ma with a 128.25.5 Ma
order to refine the metallogenic age of the Yangshan gold mean. These oscillatory zoned zircons are also prismatic
deposit, zircons from quartz veinlets are analyzed using (Fig. 3) and regarded as magmatic. The third group con-
cathodoluminescence images (CL) combined with sists of four analyses giving 206Pb/238U ages between 48.1
SHRIMP U-Pb dating. and 51.7 Ma (50.03.0 Ma mean). These zircons are also
prismatic with clear oscillatory zoning and are interpreted
2 Sample description and experimental method as magmatic (Fig. 3). The remaining analyses are scat-
tered in the diagram.
Sample YM is from 305# gold vein in the Caopingliang Zircon samples YM-13 and YM-15 are short prisms
adit while sample AB from 314# gold vein in the Anba with concentric zoning yielding 206Pb/238U ages of 106922
adit. Both samples are from pyrite-quartz veinlets host- Ma and 80917 Ma, respectively. They likely represent

810 Qi Jinzhong Li Li Yuan Shisong Liu Zhijie

4 Geological significance of the SHRIMP age and


With high U-Pb isotope closure temperature of 700 to

750C (Harrison et al. 1987; Tilton et al. 1991) and a strong
resistence to thermal disturbance (Meger et al. 1997), zir-
con is widely used to constrain the timing of geological
events. Although it has been proposed that hydrother-
mal zircon may form at lower temperatures (Corfu et al.
1984; Claoue-long et al. 1990), published ages of hydro-
thermal zircons from quartz veins in some gold depos-
its are very close to the ages of their host rocks, so whether
hydrothermal zircon do exist in quartz veins is suspi-
cious (Luo et al. 2000). The relatively low temperature of
the hydrothermal fluid (150 to 250oC, Qi et al. 2003) at
Yangshan could hardly result in the formation of hydro-
thermal zircon. Furthermore, among the 30 analyses, only
3 zircons have Th/U ratios close to or less than 0.1, indi-
cating that typical metamorphic zircons are not well-de-
veloped in the district (Gebauer et al, 1985; Yang J S et al.
2002). Therefore, zircons from the quartz veins in the dis-
trict should be the ones captured during hydrothermal
activity. The zircons may be captured from intrusives (in-
cluding intrusives in the source area and those near the
path of the hydrothermal fluid flow) and those captured
from strata (mainly from older rocks that supplied source
material to the Devonian strata).
Three analyses on zircons from sample YM constitute
the first group age, giving the 206Pb/238U ages between 195.4
and 200.9 Ma. Having short prism form with concentric
zoning and Th/U ratios of 0.44 to 0.87, these are regarded
as Jurassic igneous zircons. As the age is consistent with the
whole rock K-Ar ages of five plagiogranite samples in the
gold field (171 to 209 Ma, Qi et al. 2003), these zircons may
be captured from the plagiogranite dikes. Furthermore, the
age coincides with the 39Ar-40Ar plateau age of 195.401.05
Ma of the quartz veinlet (Qi et al. 2003), suggesting that the
intrusion of the plagiogranite dikes is responsible for hy-
captured zircons from late Proterozoic intrusives. Analy- drothermal activity in the district.
sis on zircon YM-12 gives an 206Pb/238U age of 37511 Ma Cretaceous and Tertiary zircon groups were detected
and might be captured from the Devonian strata. in samples YM and AB. Analyses revealed eleven Creta-
16 zircons from sample AB representing the quartz ceous zircons yielding an average 206Pb/ 238U age of
veinlet of fine-grained disseminated ore were analyzed. 126.93.2 Ma and twelve Tertiary zircons give an average
206Pb/238U age of 51.21.3 Ma. These zircons are prismatic
These zircons are small and their common lead concen-
trations are slightly high. One analysis with significantly with concentric oscillatory zoning and dominant Th/U
high common lead content was rejected. Two age groups ratios between 0.5 and 1.5 indicating their magmatic gen-
were obtained as shown in the U-Pb concordia diagram esis. These zircons could not be captured from the nearby
(Fig. 2). The first group consists of five analyses giving strata as no Cretaceous or younger strata is found in the
206Pb/238U ages between 121.4 and 130.2 Ma (125.34.9 district. Furthermore, no intrusives other than the Juras-
Ma mean). These zircons are interpreted to be magmatic sic plagiogranite are found related to the ore belt sug-
from their prismatic morphology and oscillatory zoning gesting these zircons are captured from buried Cretaceous
(Fig. 4). The second group consists of eight analyses which and Tertiary intrusives. Consequently, after the intrusion
yield 206Pb/238U ages of 49.8 to 55.3 Ma (51.71.6 Ma in of plagiogranite dikes, two major magmatic events oc-
average). These concentrically zoned zircons are also curred in early Cretaceous and in early Tertiary, with a
primsatic (Fig. 4) and regarded as magmatic zircons. later ore fluid capturing the zircons from the intrusives.

Chapter 7-23 U-Pb SHRIMP dating of zircon from quartz veins at the Yangshan gold deposit: Evidence for multiple magmatic-hydrothermal events 811

Therefore, the gold field was influenced by three mag- the continental-continental collision of the penetrating In-
matic and associated hydrothermal events. dian plate and Eurasian plate. The gold mineralization at
Comparing Yangshan magmatic-hydrothermal events Yangshan may be directly linked to multiple, localized mag-
with the magmatic events in western Qinling, we can see matic-hydrothermal events in the district and major mag-
that the early Jurassic hydrothermal epoch coincides with matic-tectonic events in the region.
one fastigium of felsic intrusions in western Qinling (190Ma
to 220Ma, Zhang et al. 1994), while the early Cretaceous 5 Conclusion
hydrothermal epoch corresponds to another fastigium of
granite activities in western Qinling (120Ma to 150Ma, Du 1. Zircons from quartz veinlets associated with ore are
et al. 1998). These two epochs were also considered to be dominantly prismatic with concentric oscillatory zon-
the fastigiums of gold mineralization in China (Zhai et al. ing and Th/U ratios of 0.5 to 1.5 indicating a magmatic
2002; Mao et al. 2002). The early Tertiary magmatic-hydro- genesis.
thermal epoch is consistent with the major metallogenic 2. The magmatic zircons with 206Pb/238U ages of 195.4 to
age of gold deposits in southwestern China (Chen et al. 2001), 200.9 Ma in quartz veinlet sample YM are captured
and the magmatic-hydrothermal activity may be linked to from the early Jurassic plagiogranite intrusives.

812 Qi Jinzhong Li Li Yuan Shisong Liu Zhijie

3. The two zircon groups with average 206Pb/238U ages of Luo ZK, Miao LC, Guan K (2000) Discussion on the metallogenetic
126.93.2 Ma and 51.21.3 Ma in quartz veinlets are cap- epoch of gold deposit on north fringe of North China platform,
Gold Geology 6: 70-75 (in Chinese with English abstract)
tured from buried Cretaceous and Tertiary intrusives,
Mao JW, Qiu YM, Goldfarb RJ, Zhang Z, Garwin S, Fengshou R
respectively. The early Jurassic, early Cretaceous, and (2002) Geology, distribution, and classification of gold depos-
early Tertiary magmatic-hydrothermal events affected its in the western Qinling belt, central China, Mineralium De-
Yangshan gold field and the deposit was genetically re- posita 37:352-377
lated to the three magmatic-hydrothermal events. Mezger K, Krogstad E J (1997) Interpretation of discordant U-Pb
zircon ages: An evaluation. J. Metamorphic Geol. 15:127-140
Qi JZ, Yuan SS, Li L, Sun B, Guo JH (2003) Geological and geochemi-
References cal study of yangshan gold deposit, gansu province. Mineral De-
posits. 22:24-31 (in Chinese with English abstract)
Chen YC, Wang DH (2001) Study of Himalayan endogenic mineral- Tilton GR, Schreyer W, Schertl HP (1991) Pb-Sr-Nd isotopic behav-
ization. Bejing: Seismic Publishing House. 1-138 (in Chinese with ior of deeply subducted crustal rocks from the Dora Maira mas-
English abstract) sif, Western Alps, Italy-II: what is the age of the ultra-high pres-
Claoue-long J, King RW, Kerrich R (1990) Archean hydrothermal zir- sure metamorphism? Contrib. Mineral. Petrol, 108:22-33
con in the Abitibi greenstone belt: constrains on the timing of Williams I S. (1998) U-Th-Pb Geochronology by Ion Microprobe, in
gold mineralization. Earth Planet Sci. Letters 98:109-128. McKibben MA, Shanks III WC and Ridley WI (eds), Applications
Composton W, Williams IS, Kirschvink JL, Zhang Z, Ma G (1992) Zir- of microanalytical techniques to understanding mineraling pro-
con U-Pb ages for the Early Cambrian time scale. Journal of the cesses. Reviews in Economic Geology 7:1-35.
Geological Society London 149:171-184. Wu CL, Jone W, Yang JS, Li HB (2002) margin of Qilian mountains:
Corfu F, Ayres LD (1984) U-Pb age and genetic significance of het- evidence from zircon SHRIMP age of the Aolaoshan granite, Acta
erogeneous zircon populations in rocks from the Favourable Lake Geologica Sinica, 76(1): 118-125
area, Northwestern Ontario. Contrib Mineral Petrol 88: 86-101 Yang JS, Xu ZQ, Wu CL, Liu FL, Shi RD, Wooden J, Maruyama S (2002)
Du ZT, Wu GG (1998) Study on tectonic systems and gold SHRIMP U-Pb dating on coesite bearing zircon: Evidence for
metallogenic tectono-dynamics in the region of west Qinling. Indosinian ultrahigh-pressure metamorphism in Su-Lu, East
Bejing: Geological Publishing House. 1-145 (in Chinese with En- China, Acta Geologica Sinica, 76(3): 354-372 (in Chinese with
glish abstract) English abstract)
Gebauer D, Lappin MA, Grunenfelder M (1985) The age and origin Zhai YS, Miao LC, Xiang YC, Deng J, Wang JP (2002) Preliminary
of same Norwegian eclogite: A U-Pb zircon and REE study. discussion on ore-forming system in greenstone belt-type of
Chemical Geology 52: 227-248 north China Craton. Earth Science-Journal of China University
Harrison TM, Aleinkoff JN, Compston W (1987) Observation and of Geosciences. 27: 522-529 (in Chinese with English abstract).
controls on the occurrence of inherited zircon in concord-type Zhang BR, Gao S, Luo TC (1994) Lithosphere structure of Qinba area
granitoids, New Hampshire. Geochem Cosmochim Acta5 1: and metallogenic geochemistry. Wuhan: Publishing House of China
2549-2568 University of Geosciences. 1-446 (in Chinese with English abstract)

Chapter 7-24 7-24

34S, 18O)
87Sr/86Sr, 3He/4He, REE and stable isotope (

constraints on the hydrothermal fluid evolution of
the PACMANUS system, Manus Basin
Stephen Roberts
School of Ocean and Earth Science, Southampton Oceanography Centre, University of Southampton, Southampton, SO14
Wolfgang Bach
Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA
Adrian Boyce
Scottish Universities Environmental Research Centre, Scottish Enterprise Technology Park, Rankine Avenue, East Kilbride,
G70 0QF, UK
Ray Burgess
Department of Earth Sciences, University of Manchester, Manchester, M13 9PL, UK

Abstract. 34S, 87Sr/86Sr, 18O, REE and 3He/4He analyses of anhydrite The 87Sr/86Sr and 34S data for anhydrite from Snowcap
from the PACMANUS hydrothermal system suggest a complex inter- (Site 1188) and Roman Ruins (Site 1189) suggest contrast-
play between hydrothermal fluid, magmatic fluid, and seawater dur-
ing fluid evolution and flow regimes.
ing alteration and mineralization. These new data significantly ex-
pand the subsurface data on seafloor hydrothermal systems and may The rare-earth element (REE) contents of anhydrite
begin to explain the earliest processes of multistage mineralization from PACMANUS show extreme variability, in terms of
and alteration history that typify ancient massive sulfide systems. both absolute concentrations (e.g., 0.0828.3 ppm Nd) and
pattern shape (LaN/SmN=0.083.78, SmN/YbN=0.4823.1,
Keywords. Hydrothermal vents, sulfides, anhydrite, isotopes

1 Introduction

Ocean Drilling Program Leg 193 investigated two sites of

hydrothermal activity along the crest of the Pual Ridge
in the eastern Manus Basin. A site of low-temperature
diffuse venting, Snowcap (Site 1188), and a high-temper-
ature black smoker site, Roman Ruins (Site 1189), were
drilled to depths of 386 and 206 meters below sea floor,
respectively (Binns et al. 2002; Roberts et al. 2003; Bach et
al. 2003; Vanko et al. 2004). Although the two sites are
<1000 m apart, the geochemical signatures of anhydrite
recovered at both sites are very different. Measured an-
hydrite 87Sr/86Sr ratios vary between 0.7050 and 0.7086;
the most radiogenic values occur just beneath the vari-
ably altered dacitic cap at both sites (Fig. 1).
At Snowcap (Site 1188) there is a clear trend downhole
to less radiogenic 87Sr/86Sr values, from 0.7086 beneath
the dacite cap to values of 0.7060 at ~100 mbsf, and these
low values are broadly maintained to the base of the hole.
The measured anhydrite 34S values vary between
18.1 and 22.5. For Snowcap, most of the values are
less than 21.0 and trend significantly toward lower val-
ues downhole. In contrast, anhydrite 34S values at Ro-
man Ruins are mostly equal to or greater than the seawa-
ter value and show no obvious downhole trends.

814 Stephen Roberts Wolfgang Bach Adrian Boyce Ray Burgess

Eu/Eu*=0.596.1). The range of REE patterns in anhy- the sulfate concentration is increased because of mag-
drite includes enrichments in the middle and heavy REEs matic SO2 disproportionation and dissociation, it would
and variable Eu anomalies (Fig. 2a,b). The REE patterns predict a lower fluid pH. This is consistent with the domi-
of anhydrite from hole 1188 differ markedly from those nance of pyrophyllite at Snowcap and secondary feld-
of anhydrite recovered during ODP Leg 158 from the TAG spar at Roman Ruins.
hydrothermal system at the Mid-Atlantic Ridge, which Furthermore, Bach et al. (2003) have suggested that
display uniform LREE-enriched patterns, in contrast the the range of REE patterns in the anhydrites from Snowcap
1189 data are more comparable. reflects the waxing and waning input of magmatic
The anhydrite and sulfides from both sites show volatiles (HF, SO2) and variable complexation of REEs in
variable 3He/4He ratios with R/Ra in the range 0.29-6.91 the fluids. Taken together, these observations strongly
(R/Ra Seawater = 1.05) (Fig. 3). The data show cor- suggest a magmatic contribution to the hydrothermal
relations with depth, 34S and 87Sr/86Sr data. Oxygen system drilled at Snowcap. In contrast, Roman Ruins data
isotope data for the anhydrite are relatively uniform, are characterized by 87Sr/86Sr ratios of ~0.7065, with sig-
18O varies between 8 and 10, and show no downhole nificant intrasample variation, and 34S ratios that are at
correlation. seawater or slightly elevated values. The 87Sr/86Sr and S
isotope data show no systematic downhole trends and
2 Discussion are very similar to data reported for anhydrites recov-
ered during the TAG drilling, ODP Leg 158 and are con-
The Snowcap data are consistent with higher sulfate con- sistent with the mixing of a low-sulfate hydrothermal fluid
centrations of the hydrothermal end-member fluid. If and seawater.

34S, 18O) constraints on the hydrothermal fluid evolution of the PACMANUS system, Manus Basin
Chapter 7-24 87Sr/86Sr, 3He/4He, REE and stable isotope ( 815

Overall, the data suggest a complex interplay among

hydrothermal fluid, magmatic fluid, and seawater dur-
ing alteration and mineralization of the PACMANUS

Bach W, Roberts S, Vanko DA, Binns RA, Yeats CJ, Craddock PR,
Humphris SE (2003) Controls of fluid chemistry and complex-
ation on rare earth element contents of anhydrite from the
PACMANUS subseafloor hydrothermal system, Manus Basin,
Papua New Guinea. Mineralium Depos, 38: 916-935
Binns RA, Barriga FJAS, Miller DJ (2002) Proc. ODP, Init. Repts., 193
[CD-ROM]. Available from: Ocean Drilling Program, Texas A&M
University, College Station TX 77845-9547, USA
Roberts S, Bach W, Binns RA, Vanko DA, Yeats CJ, Teagle DAH,
Blacklock K, Blusztajn J.S, Boyce AJ, Cooper MJ, Holland N,
McDonald B (2003) Contrasting evolution of hydrothermal flu-
ids in the PACMANUS system, Manus Basin: The Sr and S iso-
tope evidence. Geology 31: 805-808
Vanko DA, Bach W, Roberts S, Yeats CJ, Scott SD (2004) Fluid inclu-
sion evidence for subsurface phase separation and variable fluid
mixing regimes beneath the deep-sea PACMANUS hydrother-
mal filed, Manus Basin back arc rift, Papua New Guinea. J Geophys
Res 109: B03201-03214

Chapter 7-25 7-25

U-Pb dating of micro-inclusions: The age of the

Ehrenfriedersdorf tin deposit (Erzgebirge, Germany)
R.L. Romer, R. Thomas
GeoForschungsZentrum Potsdam, Telegrafenberg, D-14473 Potsdam, Germany

Abstract. Multiple reworking of ore deposits may disturb geochrono- Romer 1992; Romer and Soler 1995) and for hydrother-
logic systems and eventually render incorrect ages for ore deposi- mal vein deposits may involve gangue minerals such as
tion or different stages of ore formation. Micro-inclusions may
white mica or quartz (e.g. Franzke et al. 1996; Romer and
beprotected from later disturbances by their host mineral and, thus,
yield reliable age information. Major problems in dating micro-in- Linnemann 2004), and (iii) by dating fluid inclusions in
clusions include their genetic connection with various stages of economically interesting minerals or associated gangue
ore formation and technical aspects, such as loss of daughter iso- minerals (e.g. Glodny 1997; Pettke and Diamond 2000).
topes by -recoil and the initial isotopic composition of the daugh- In this paper, we demonstrate that U-Pb dating of micro-
ter element. The problem of daughter-loss from a high- micro-
inclusions is technically possible and yields accurate re-
inclusion ( = 238U/204Pb)by -recoil can be avoided by analyzing
the inclusion together with its low- host. The philosophy behind sults as long as precautions are taken (i) to avoid micro-
the presented analytical approach is to trade radiogenic composi- minerals along grain-boundaries and fractures and (ii)
tion of the daughter element (i.e., high 206Pb/204Pb, 207Pb/204Pb, and to sample in a way that compensates for recoil-related
Pb/204Pb) against closed-system behavior. This approach is dem- open-system behavior in the U-Pb system.
onstrated for <10 microns small uraninite inclusions in darkmica
from Ehrenfriederdorf, Erzgebirge, Saxony. Our data demonstrate
that micro-inclusions may yield precise and accurate age data for
2 Advantages and disadvantages of the use of
early ore forming processes. micro-inclusions in mineral dating
Keywords. Micro-inclusions, U-Pb dating, Ehrenfriederdorf, tin deposits Dating micro-inclusions entirely enclosed in other min-
erals has the advantage that the host prevents interaction
of the micro-inclusion with later fluids. The host-min-
1 Introduction eral represents a container that makes the geochronologic
system of the inclusion behave as a closed system even
Precise and accurate dating of many kinds of ore depos- for inclusions (e.g., uraninite) that are known to react
its is problematic because later hydrothermal and tectonic readily with fluids. The host mineral, however, should
overprint (resulting in the repeated redistribution of ele- neither react with the inclusion nor incorporate those ele-
ments or the introduction of various metals at different ments that define the geochronologic system of the inclu-
time) may disturb geochronometers that are genetically sion. Otherwise there may be exchange of the geochrono-
and texturally related to early stages of deposit forma- logically relevant element between host and inclusion. The
tion. For instance, U deposits in the Aue-Niederschlema major problem in the use of micro-inclusions for dating
district (Erzgebirge, Saxony) yield ages of c. 280-270 Ma, originates from ambiguities in the genetic connection be-
190 Ma, 120 Ma, 80 Ma, and 30 Ma (Frster 1996), the tween inclusion and host and the representativity of the
oldest age related with the introduction of U into the de- inclusion.
posit, the younger ages reflecting redistribution of U in
conjunction with multiple tectonic reactivation of the 3 Requirements on micro-inclusions to be suitable
Gera-Jachymov zone, along which numerous U deposits for dating
Many of the ambiguities and complexities arising from There are basically three requirements that must be ful-
the redistribution of the ore metals during multiple over- filled for micro-inclusions to become potentially attrac-
print and alteration can be avoided by (i) dating the eco- tive for dating attempts: (i) closed system, (ii) strong
nomically interesting minerals, which is possible for min- daughter-to-parent (D/P) fractionation, and (iii) high P
erals of the columbite-tantalitetapiolite series (e.g. Romer contents.
and Wright 1992; Romer and Smeds 1996), molybdenite
(e.g. Stein et al. 1998, 2001; Stein and Bingen 2002), and i. Closed system behavior requires that neither the P nor
U-minerals (e.g. Ludwig and Simmons 1991; Frster 1996), the D element is lost from the inclusion. Major pro-
(ii) by dating minerals that have formed cogenetically with cesses for possible daughter loss include diffusion and
the economically interesting minerals, which for skarn recoil, both of which are more likely to become more
ores may involve titanite, vesuvianite, and garnet (e.g., important for smaller grain size. Loss by diffusion de-

818 R.L. Romer R. Thomas

pends not only on temperature, the diffusion constant typically is displaced by some 20 to 30 nm (e.g., Matzke
of the considered element, the cooling history of the 1982). At the contact between a high- phase and a
sample, and the distance to the grain surface, but also low- phase, the loss of daughter isotopes from the
on the transport of the lost ions away from the grain high- phase is more important than the addition of
surface. If a host that does not accept ions lost from daughter isotopes. Thus, the high- phase eventually
the inclusion, these ions will concentrate at the con- shows a deficit in daughter isotopes and the low-
tact between the two minerals and prevent additional phase shows an excess (cf. Ludwig 1978; Mattinson et
loss from the inclusion. An example for an inclusion al. 1996; Romer 2001, 2003). This effect becomes more
that remained a closed system to high temperature important, the smaller the high- phase (cf. Romer
has been presented by Khn et al. (2000). They showed 2003). Because of -recoil, isolated small high- in-
that biotite in Sveconorwegian granulite-facies gar- clusions are beyond doubt open systems showing a
net recorded this older event rather than the Caledo- daughter deficit. The same inclusion and its immedi-
nian eclogite facies overprint. -recoil refers to the ate host in combination, however, may represent a
displacement of the daughter isotope due to the emis- closed system as the daughter isotopes lost from the
sion of an -particle (Fig. 1). The daughter nucleus inclusion are collected in the host. This behavior is
shown in Figure 1. Note that the isolated inclusion
would fall below the concordia and the separated host
would fall above the concordia.
ii. High P/D values result with time in highly radiogenic
D-element compositions, which makes uncertainties
about the initial composition of D irrelevant for the
age calculation and allows to constrain the slope of an
isochron more closely, i.e., to deduce more precise ages.
High P/D are restricted to element-pairs of contrasting
geochemical behavior, such as Rb-Sr, U-Pb, and Th-Pb
and to mineral phases that strongly prefer P over D.
iii. Analytical uncertainties originating from counting sta-
tistics depend on signal intensity. To obtain small un-
certainties, the signal has to be strong, i.e., many ions
have to be available for counting. For small inclusions
to yield high signal intensities, the content of D has to
be high, which is a function of time and P. Thus, for an
optimal analytical result, P has to be high.

Only few phases fulfill above three requirements. For

the U-Th-Pb systems, minerals that have high P/D and
high P contents include xenotime, monazite, and uraninite;
for the Rb-Sr system, the requirements may be fulfilled
by micas and Rb-rich phases. To obtain a closed system,
the inclusions should be analyzed together with their host.
Thus, the host should yield very low or no contributions
of P and D to the bulk sample.

4 High- inclusions (monazite, xenotime, and


Because of alpha-recoil, micro-inclusions are notoriously

open systems. Separating inclusions results in too young
apparent 206Pb/238U ages as there is a deficit in radio-
genic Pb. Drilling the inclusions together with a rim of
their host directly from thin sections solves the prob-
lem. (i) Recoiled daughter isotopes are collected by the
host. (ii) U-rich and Th-rich minerals are readily recog-
nized by their pleochroitic haloes (Fig. 2) and can be iden-

Chapter 7-25 U-Pb dating of micro-inclusions: The age of the Ehrenfriedersdorf tin deposit (Erzgebirge, Germany) 819

the granite is closely related with the formation of the Sn

tified by micro-Raman. For sampling, special care should deposits in the marginal greisen and skarns (Thomas et al.
be taken to collect only inclusions that are entirely en- 2003). The radioactive elements U and Th are predomi-
closed in the host. Outcropping inclusions always show nantly hosted in tiny crystals of zircon, uraninite, mona-
a deficit in radiogenic Pb. (iii) The radius of pleochroitic zite, and less common xenotime that are readily recognized
haloes is more than 100 times larger than the distance as they show distinctive pleochroitic haloes in mica
of recoil displacement of U-daughters. Thus, drilling (Fig. 2). The small crystal size of the radioactive miner-
samples that include the entire pleochroitic halo must als and the distinctive pleochroitic haloes are typical for
yield closed systems. In thoroughly altered or multiply most late Variscan granites of the Ehrenfriedersdorf-Geyer
overprinted rocks, inclusions that are protected by their district.
host mineral from interaction with late fluids may rep- We analyzed three uraninite inclusions that gave
resent the only datable minerals from the early evolu- concordant data (filled symbols, Fig. 3). The best age
tion of the altered rock. estimate, obtained from the weighted mean of the
206Pb/238U ages, is 323.93.5 Ma (2sigma). It falls within

5 Uraninite inclusions in mica from the the expectation range for these post-kinematic granites,
Ehrenfriederdorf tin deposit which is defined by 40Ar/39Ar ages of intruded meta-
morphic rocks and the age of tectonically comparable
Extensive high-temperature Sn-mineralizations that form granites from Fichtelgebirge, Oberpfalz, and the Bavar-
skarns, pegmatites, greisen, and pneumatolyitc- hydro- ian Forrest (e.g., Werner and Lippolt 2000; Siebel et al.
thermal vein deposits are closely associated with Late 2003). The age also agrees well with chemical ages ob-
Variscan granites in the Ehrenfriedersdorf-Geyer area (cf. tained on uraninite, monazite, and xenotime from nu-
Oelsner 1952). The granite is dominated by quartz, al- merous geochemically corresponding granites of the
kali-feldspar, plagioclase (<An12), and up to 5 vol-% mica. Erzgebirge (Frster et al. 1999). Thus, our data demon-
Accessory minerals include topaz, cassiterite, zircon, strate that complete dissolution of inclusion and host
monazite, xenotime, uraninite, apatite, tourmaline, and yields concordant data that give accurate age constraints.
Sn-rich pyrrhotite. Melt inclusions in topaz prove that this Data from samples with incompletely dissolved mona-
mineral is magmatic and did not form during pneuma- zite and xenotime (open symbols, Fig. 3) show an excess
tolytic or hydrothermal overprinting. High Sn contents (up of radiogenic Pb that represents Pb implanted by -re-
to 800 ppm) in melt inclusions in quartz demonstrate that coil into the host.

820 R.L. Romer R. Thomas

References Pettke T, Diamond LW (2000) Rb-Sr Dating of Sphalerite based on fl

uid inclusion-host mineral isochrons: A clarifi -cation of why it
Frster B (1996) U/Pb Datierung an Pechblenden der U-Lagersttte works. Econ Geol 91: 951-956
Aue-Niederschlema (Erzgebirge). Dissertation, Universitt Romer RL (1992) Vesuvianite a new tool for the U-Pb dating of
Giessen Frster H-J, Tischendorf G, Trumbull RB, Gottesmann B skarn ore deposits. Mineral Petrol 46: 331-341
(1999) Late-collisional granites in the Variscan Erzgebirge, Ger- Romer RL (2001) Isotopically heterogeneous initial Pb and continu-
many. J Petrol 40: 1613-1645 ous 222Rn loss in fossils: The U-Pb systematics of Brachiosaurus
Franzke HJ, Ahrend H, Kurz S, Wemmer K (1996) K-Ar Datierungen von brancai. Geochim Cosmochim Acta 65: 4201-4213
Illiten aus Kataklasiten der Flossbergstrung im sdstlichen Thrin- Romer RL (2003) Alpha-recoil in U-Pb geochronology: effective
ger Wald und ihre geologische Interpretation. Z geol Wiss 24:441-456 sample size matters. Contrib Mineral Petrol 145: 481-491
Glodny J (1997) Der Einflu von Deformation und fl uidinduzierter Romer RL, Linnemann U (2004) U-Pb dating the Schlottwitz ag-
Diaphthorese auf radioaktive Zerfallssysteme in Kristallingestei- ate-amethyst vein (Erzgebirge, Saxony). Eur J Mineral 16
nen. Dissertation, Universitt Mnster Khn A, Glodny J, Iden K, (Beiheft 1): 116
Austrheim H (2000) retention of Precambrian Rb/Sr phlogopite Romer RL, Smeds S-A (1996) U-Pb columbite ages of pegmatites
ages through Caledonian eclogite facies metamorphism, Bergen from Sveconorwegian terranes in southwestern Sweden.
Arc Complex, WNorway. Lithos 51: 305-330 Precambr Res 76: 15-30
Ludwig KR (1978) Uranium-Daughter Migration and U/Pb Isotope Romer RL, Soler A (1995) U-Pb age and lead isotopic characteriza-
Apparent Ages of Uranium Ores, Shirley, Basin, Wyoming. Econ Geol tion of Au-bearing skarn related to the Andorra granite (central
73: 29-49 Pyrenees, Spain). Mineral Deposita 30: 374-383
Ludwig KR, Simmons KR (1991) U-Pb dating of uranium ores in Romer RL, Wright JE (1992) U-Pb dating of columbites: a geochro-
collapse-breccia pipes, Grand Canyon region. In: Pagel M, Leroy nologic tool to date magmatism, metamorphism, nand ore de-
JL (eds) Source, transport and deposition of metals. A.A. Balkema, posits. Geochim Cosmochim Acta 56: 2137-2142
Rotterdam, pp 405-408 Siebel W, Chen F, Satir M (2003) Late-Variscan magmatism revis-
Mattinson JM, Gaubard CM, Parkinson DL, McLelland WC (1996) ited: new implications form Pb-evaporation zircon ages on the
U-Pb reverse discordance in zircons: the role of fi ne-scale oscil- emplacement of redwitzites and granites in NE Bavaria. Int J Earth
latory zoning and sub-microscopic transport of Pb. Am Geophys Sci 92: 36-53
Union Geophys Monogr 95: 355-370 Stein HJ, Bingen B (2002) 1.05-1.01 Ga Svenconorwegian metamor-
Matzke H (1982) Radiation damage in crystalline insulators, oxides phism and deformation of the supracrustal sequence at Saesvatn,
and ceramic nuclear fuels. Rad Effects 64: 3-33 South Norway: Re-Os dating of Cu-Mo Mineral occurances. In:
Nasdala L,Wenzel M,Vavra G, Irmer G,Wenzel T, Kober B (2001) Metamic- Blundell DJ, Neubauer F, von Quadt A (eds) The timing and loca-
tisation of natural zircon: Accumulation versus thermal annealing of tion of major ore deposits in an evolving orogen. Geol Soc Lon-
radioactivity-induced damage. Contrib Mineral Petrol 141: 125-144 don Spec Publ 204: 319-335
Oelsner O (1952) Die pegmatitisch-pneumatolytischen Lagersttten Stein HJ, Markey RJ, Morgan JW, Hannah JL, Schersten A (2001) The
des Erzgebirges mit Ausnahme der Kontaktlagersttten. Freib remakable Re-Os chronometer in molybdenite: how and why it
Forschh 9: 80 pp works. Terra Nova 13: 479-486

Chapter 7-26 7-26

U-Pb data of Au-Pd-Pt-bearing quartz-hematite veins,

Quadriltero Ferrfero, Minas Gerais, Brazil
R.L. Romer, V. Lders
GeoForschungsZentrum Potsdam, Telegrafenberg, 14473 Potsdam, Germany
D.A. Banks
School of Earth Sciences, University of Leeds, Leeds, LS2 9JT, UK
J. Schneider
Inst. Geowissenschaften und Lithosphrenforschung, Universitt Gieen, 35390 Gieen, Germany

Abstract. Fluid inclusions hosted in specular hematite from aurifer- 2 Results

ous (jacutinga) and barren veins in the Quadriltero Ferrfero ei-
ther contain fluid inclusions assemblages of high-temperature
Fluid inclusions have been studied in specular hematite
aqueouscarbonic and multiphase high-salinity, high-temperature
aqueous inclusions or multiphase aqueous fluid inclusions show- from two auriferous jacutinga-style mineralization and
ing narrow ranges of salinity and homogenization temperatures. two barren hematite veins using infrared microscopy.
Fluid inclusions in quartz and hematite are characterized by uni- Hematite from barren veins of the Fbrica and Crrego
form Na/K ratios and considerable SO4 contents indicating similar do Feijo iron ore mines contain only one compositional
formation conditions and perhaps fluid origin from a common
type of fluid inclusions. These are aqueous inclusions with
source. The formation of specular hematite veins may be related to
retrograde metamorphic fluids being released during the Brazilian a vapour bubble and with more than 90% having one or
orogenic cycle (600-700 Ma). The Pb isotopic characteristics of all more solid phases. Hematite-hosted fluid inclusions from
jacutinga-type samples is readily reconciliated in a simple model the jacutinga style mineralization of Gongo Soco are simi-
that (i) involves different Palaeoproterozoic or Archaean source lar to those of barren veins. Hematite from jacutinga-style
lithologies for lead and gold and that (ii) possibly reflects contrast- mineralization at Itabira contain two compositional types
ing depths of fluid percolation during the Braziliano orogeny and
(iii) heterogeneous Au distribution in the greenstone source.
of fluid inclusions, (i) aqueous carbonic inclusions, and
(ii) multiphase aqueous inclusions with at least one solid
Keywords. Fluid inclusions, U-Pb, jacutinga, Au-Pd-Pt, Minas Gerais phase. Both types of inclusions occur together in isolated
clusters or as isolated fluid inclusion pairs within indi-
vidual samples.
1 Introduction Two-phase and multiphase aqueous inclusions with
solid phases in specular hematite from jacutinga veins of
Palladian gold mineralization is unusual worldwide and
only Brazilian occurrences are of economic importance.
In the Quadriltero Ferrfero of Minas Gerais, which in-
cludes Paleoproterozoic clastic and chemical sedimentary
sequences (Minas Supergroup) underlain by an Archean
greenstone belt (Riodas Velhas Supergroup) and granite-
gneiss terrains (Fig. 1), the auriferous portions of itabirites
have traditionally been denoted as jacutinga. This peculiar
mineralization occurs as Au-Pd-Pt-bearing quartzspecular
hematite veins crosscutting the metamorphosed host
itabirites. The gold is coarse-grained and commonly black
(ouro preto) due to coatings of Pd-O species and Fe-
oxyhydroxide. A number of jacutinga-style gold deposits
were worked in the 18 th and 19 th centuries in the
Quadriltero Ferrfero. Openpit iron ore mining-opera-
tions have exposed sections of jacutinga mineralization.
Gold is currently an intermittent by-product of iron ore
mining at Gongo Soco (several tens of kg Au per year)
and Itabira, where gold production amounted to about
600 kg Au per year in 2000.

822 R.L. Romer V. Lders D.A. Banks J. Schneider

the Gongo Soco mine as well as from barren veins show 3 U-Pb systematics of hematite and gold
narrow ranges of salinity between 7.211.7 wt.% NaCl
equiv. and homogenization temperatures between 148 and 3.1 Hematite
229C (Fig. 2). Fluid inclusions in specular hematite from
the Itabira area are comparatively more complicated. The The Pb isotope data of the hematite samples scatter widely
ice melting temperatures of multiphase aqueous inclu- in the 206Pb/204Pb 207Pb/204Pb, 206Pb/204Pb208Pb/204Pb,
sions cover a wide range between -26.1 and -10.7C (Fig. 2). and 206Pb/204Pb238U/204Pb diagrams (Fig. 3a-c). The data
The majority of the homogenization temperatures of do not define isochrons. Although the scatter among
multiphase aqueous inclusions range between 317 and samples from individual deposits is smaller than for the
365C (Fig. 2). In contrast, aqueous carbonic inclusions entire data set, there is significant excess scatter, which
have considerably higher total homogenization tempera- may originate from (i) initial isotopic heterogeneity within
tures when compared with multiphase aqueous inclusions single deposits and contrasting Pb composition in differ-
and higher ice melting temperatures (Fig. 2). Crush-leach ent deposits, (ii) addition of isotopically distinct Pb at
analyses on samples of quartz and hematite show that Cl some time after formation of the deposits, and (iii) frac-
and SO4 are the major anions in the fluid inclusions. The tionation between U and Pb (modification of the 238U/
204Pb ratio) during a later event. Furthermore, there may
fluids are dominated by Na and show significant but vari-
able amounts of K and Ca, and lesser amounts of Mg and have been some redistribution of radiogenic Pb between
Li. The low Cl/Br and Na/Br ratios of the analyzed inclu- hematite host and fluid inclusions by recoil. These po-
sions are indicative of halite dissolution and reprecipitation tential non-idealities make the derivation of a precise age
by a halite saturated fluid. During dissolution and impossible. Nonetheless, the Pb isotope systematics of the
reprecipitation, Br is excluded from halite and enriched fluid-free hematite samples imposes several constraints
in the fluid, just as during halite precipitation from sea- on the evolution of the hematite deposits. (1) The data
water. The salinity of the fluid inclusions, however, is be- fall in a triangular area in the 206Pb/204Pb207Pb/204Pb dia-
low halite saturation and indicates dilution after they have gram (shaded area, Fig. 3a), which may reflect a hetero-
gained Br by interaction with halite. The Na/K ratios of geneous source or a poly-stage evolution of the hematite
the analysed fluids fall into the narrow range (mean veins. The steepest 207Pb/206Pb trend corresponds to a
4.52.2). The Na/K ratios in brines are likely to be con- mixing line of Pb that evolved from ca. 2.7 Ga to 1.9-2.0
trolled by equilibrium reactions with alkali feldspars and Ga. Since the sampled jacutingastyle veins are hosted
muscovite. Therefore, the elevated K and Li concentra- by Palaeoproterozoic itabirite-type iron deposits, varia-
tion in the fluids are likely to derive from water-rock in- tions along the 2.7-1.9 Ga trend possibly reflects deriva-
teraction between the ore-forming fluids and granites and/ tion of Pb from an isotopically heterogeneous source dur-
or gneisses of the crystalline basement. ing the Palaeoproterozoic formation of the iron deposits.
(2) In the 206Pb/ 204Pb 238U/ 204Pb isochron diagram
(Fig. 3c), most data scatter about a linear trend, whose
slope corresponds to an age of c. 635 Ma. This age has no
strict geochronological meaning as the requirements for
an isochron (common initial, single stage evolution) are
not met. There are numerous samples that fall above this
Palaeozoic reference line, which either implies that these
samples had a more radiogenic initial Pb isotopic com-
position (dashed line, Fig. 3c) or that they record an older
age. (3) Hematite from each deposit shows a relatively
narrow range in 208Pb/204Pb, but shows distinct differences
between deposits (Fig. 3b). (4) The initial Pb isotopic com-
position of all deposits is characterized by 207Pb/204Pb
values, which implies that the initial Pb of the hematite
deposits was dominantly derived from an old crust.

3.2 Gold

The Pb isotopic composition of gold flitters from jacutinga

veins at Gongo Socco align along the steep trend in the
Pb/204Pb207Pb/204Pb diagram (Fig. 3a) with some
samples being displaced to the right of this trend. In situ
Pb growth (shift to the right) was insignificant for most

Chapter 7-26 U-Pb data of Au-Pd-Pt-bearing quartz-hematite veins, Quadriltero Ferrfero, Minas Gerais, Brazil 823

samples. The Pb from the gold samples is distinctive by

its higher 207Pb/204Pb and lower 208Pb/204Pb values (at com-
parable 206Pb/204Pb) than the hematite samples (Figs. 3a
and 3b), the itabirites, or the wall-rocks. This implies that
trace Pb in gold may have been derived from a different
source than the iron. Hematite from the barren deposit
Crrego do Feijo is in its 208Pb/204Pb signature closest to
the host-rocks and the itabirite deposits, whereas hema-
tite from the Au-bearing jacutinga-style veins have 208Pb/
Pb values that are closer to the signature of Au.

4 Discussion

Specular hematite ores from barren veins and Au-Pd-Pt-

bearing jacutingastyle mineralization at Gongo Soco
were deposited from fluids that show narrow ranges of
salinity and homogenization temperatures. This may be
due to similar formation conditions or fluid origin from
a common source, although the barren veins do not con-
tain Au, Pd, and Pd. Crush-leach analyses demonstrate Cl
and SO4 to be the major anions in the ore-forming fluids.
The high sulfate concentrations of the analyzed fluids may
also be derived by leaching of evaporites (gypsum). The
formation of schistose high-grade specular hematite veins
at Itabira can be related to acid Cl-SO4-CO2 retrograde
metamorphism fluids that interacted intensively with crys-
talline rocks. The absence of CO2 in hematite-hosted in-
clusions from veins in the low-strain domain may be at-
tributed to carbonate precipitation or conversion of CO2
to bicarbonate due to cooling during fluid migration from
the highto low-strain domain. A Brasiliano age can be
derived from the 238U/204Pb206Pb/204Pb diagram (Fig. 3c)
where specular hematite samples from the Itabira dis-
trict and fluid inclusions therein fairly plot on or close to
the reference line for 635 Ma. The least radiogenic Pb iso-
topic composition from the investigated region was mea-
sured on galena from stratiform gold deposits in the Ar-
chaean Rio das Velhas Supergroup. Starting from such a
composition and lasting until the Transamazonian orog-
eny in situ Pb growth would yield values that fall on the
red array in Fig. 3. Samples with low values would have
evolved less from their starting composition, whereas
samples with high values would have evolved to more
radiogenic composition. There may be a lithologic con-
trol on the values, which higher values in more evolved
felsic units than in mafic units. Depending on source re-
gions for the itabirite-type iron deposits in the
Palaeoproterozoic clastic-chemical sediments of the Minas
Supergroup, different deposits may have a constrasting
Pb isotopic composition. Undisturbed in situ Pb growth
in itabitirite-type iron deposits until the present would
result in Pb isotopic compositions that fall between the
1.83 Ga reference line of Olivo et al. (1996) and the Ar-
chaean-to-Transamazonian Pb trend (Fig. 3). As the Pb
isotopic composition of most samples falls to the right of

824 R.L. Romer V. Lders D.A. Banks J. Schneider

the 1.83 Ga reference line, lead evolution to highly radio- neous Na/K ratios in hematite-hosted fluid inclusions. A
genic compositions occurred mainly after the Braziliano felsic Archean basement, however, could not provide Au
orogeny (see also Fig. 3c). The scatter of the data in the and Pd. Instead, these two elements may be derived from
206Pb/204Pb vs. 238U/204Pb diagram either may reflect sev- the Archaean supracrustal rocks that include voluminous
eral events, most prominantly a Braziliano and a units of mafic volcanic rocks. Since the Pb contents in
Transamazonian event (Fig. 3c) or it may reflect that the felsic rocks are much higher than in mafic and ultrama-
initial Pb isotopic compositions of some deposits was fic rocks, the Pb isotopic composition reflects the signa-
highly radiogenic at the time of the Braziliano orogeny ture of the felsic basement rather than the mafic units.
(dashed line in Fig. 3c). Thus, the fluid that transported Au and Pb into the
The Pb isotopic composition of trace Pb in gold gen- jacutingastyle veins may carry the Pb isotopic signa-
erally has lower 208Pb/204Pb values than the hematite ture of a source rock that does not correspond to the
samples. Furthermore, this trace Pb plots above the 1.83 source of Au and Pd. This explanation allows the fluid to
Ga reference line and above the hematite field (Fig. 3). acquire its Pb isotopic signature either in the felsic base-
The contrasting Pb isotopic composition between hema- ment below the greenstone unit or in the Palaeoprotero-
tite and gold in the jacutinga-style veins possibly sug- zoic clastic sediments between the Archaean basement
gests that hematite incorporated significant amount of and the units hosting the itabirite-type iron deposits. The
locally derived material and that the veins in part even occurrence of Au (and Pd), however, is controlled by the
may contain hematite grains originating from the older distribution of Au-bearing mafic to ultramafic
wallrock. The relation of the trace Pb from gold is com- supracrustal rocks in the Archaean basement. Thus, there
patible with a derivation from an Archaean source rock may be a spatial correspondance between stratiform Ar-
that is characterized by high 238U/204Pb values and rela- chaean and jacutinga-type Braziliano gold deposits. Au
tively low 232Th/204Pb values. In this context, Archaean in both deposits would have been mobilized from the
source does not only refer to the Archaean basement, but same source rocks.
also to its cover of Palaeoproterozoic clastic sediments The formation of the jacutingastyle veins during the
that were derived from the Archaean basement. The rela- Brazilian orogenic cycle explains both the homogeneous
tion of the trace Pb from gold is incompatible with a deri- nature of the fluids with respect to dissolved major com-
vation from the same source as the Pb in the itabirites or ponents, e.g., Na/K, Cl/Br ratios, high-SO4 content, and
from the itabirites itself. If the Archaean felsic basement the heterogeneous character of the fluids with respect to
is the source of the trace Pb in gold, the same source could CO2 content and trace (Au, Pd, Pb, and U) constituents,
also be the source of U, which eventually gave rise to ra- as differences in proportions of major components re-
diogenic Pb isotopic compositions in hematite. This source flect contrasting evolution histories of the fluid in terms
may also have had controlling influence on the homoge- of unmixing and cooling.

Chapter 7-27 7-27

Constraints on the source and evolution of mineralising

fluids in the Norrbotten Fe oxide-Cu-Au province, Sweden
Martin Smith
School of the Environment, University of Brighton, Brighton, BN2 4GJ, U.K.
Sarah A. Gleeson
University of Alberta, Edmonton T6G 2E, Canada

Abstract. Norrbotten County, Sweden, is well known for the iron ox- tion and from a range of Cu-(Au) deposits and prospects
ide-apatite deposits of the Kiruna and Malmberget areas. These are using a bulk crush leach technique to analyse for cation,
spatially associated with iron oxide Cu ( Au) deposits and a ge-
anion, and chlorine isotope composition within the in-
netic link between the two has been suggested as a part of the
IOCG spectrum of deposits. Here, we report the results of a fluid clusion fluids.
inclusion microthermometry and bulk crush leach halogen and
chlorine stable isotope study, carried out to test that hypothesis. 2 Sample sites
Quartz veins from late stage veins from Fe oxide-apatite deposits
and Cu-(Au) deposits contain hypersaline brine inclusions, with a
The geology of the Norrbotten area consists of a Palaeopro-
salinity range of 32 to 38wt. % NaCl eq. in Fe-oxide bodies, and of
38 to 47wt % NaCl eq. in Cu-Au deposits. In Cu-(Au) deposits these terozoic supracrustal sequence overlying Archaean base-
are sometimes accompanied by CO2-rich inclusions. ment, which was deformed and intruded by grantoids dur-
The Cl/Br ratio of the fluid inclusion leachates is consistent with ing the Svecofennian orogeny (1.96-1.85Ga). The Palaeopro-
magmatic fluid compositions, and ranges between 859 and 9597, terozoic sequence within the area studied is broadly sepa-
with no distinction between the Fe-oxide samples and the Cu-minera- rated into the Greenstone Group metabasic rocks, and the
lizing brines. 37Cl(SMOW) values range from 0.99 to 5.63. The data
are far removed from both mantle (37Cl = +4.7) and crustal (37Cl
overlying Porphyry Group, which consists of intermediate
= 0) values and must represent fractionation of the isotopes dur- to acid volcanics and intercalated sediments. Within Fe ox-
ing the mineralizing process. We suggest this fractionation occurred ide-apatite bodies, quartz veins cross-cut both the ore it-
during the formation of Cl-rich mineral phases commonly found as- self, and altered footwall rocks. Samples of this kind were
sociated with the deposits e.g. scapolite, biotite and amphibole. collected from the magnetite-hematite-apatite bodies of the
Kiruna area and from the Valkommen deposit, which forms
Keywords. Fluid inclusions, halogens, IOCG, chlorine isotopes
a part of Malmberget Fe oxide-apatite body.
Samples from Cu-(Au) deposits where collected from
1 Introduction sites hosted in the Greenstone and Porphyry Group
volcanics at Pahtohavare (Lindblom et al. 1996), Kallosalmi
The original classification of iron oxide-copper-gold type and Gruvberget, and from younger deposits associated
deposits by Hitzman et al. (1992) postulated a link be- with the Nautanen Deformation Zone (Fig. 1).
tween Fe oxide-apatite deposits (Kiruna-type) and the
IOCG deposits themselves. Northern Norrbotten County,
Sweden, is well known for the Kirunavaara deposit, and
also hosts several Cu-(Au) deposits (Bergman et al., 2001).
However, magnetite-apatite bodies and epigenetic Cu-Au
bodies formed in the range 1900-1860Ma (Romer et al.,
1994; Billstrom and Martinsson, 2000), but with the Cu-
Au systems potentially post-dating the Fe oxide-apatite
bodies. Younger deposits still (~1800-1750Ma) are asso-
ciated with regional scale shear zones. All these deposits
show similar alteration types and association with regional
sodic alteration (Frietsch, 1997), and have been suggested
to belong to the IOCG group. A knowledge of fluid source
in all three deposit types is therefore of value for
metallogenetic models, and will help to define any com-
mon mineralising processes related to episodic metamor-
phism or magmatism. As a part of the EU-RDF Georange
program we have investigated the fluid sources for quartz
veins from the late stage of Fe oxide-apatite ore forma-

826 Martin Smith Sarah A. Gleeson

3 Techniques deposits and prospects, range from much higher salini-

ties (around 50-60 wt % NaCl eq.) to those comparable
Samples were initially characterised petrographically and with the late stage veins associated with the Fe-oxide bod-
microthermometrically using a Linkam TMS600 heating- ies. Two veins from the Gruvberget body contain lower
freezing stage at the University of Brighton. Samples were salinity, Ca-rich inclusions, which probably represent a
then crushed and hand picked to provide approximately post-ore fluid.
5g of pure quartz for crush leach analysis. Samples were The inclusion assemblage from deposits associated with
electrolytically cleaned prior to crushing, and the leachates the NDZ is more complex, with coexisting Lw+Sh+V,
analysed for Na, Li and K using atomic absorption spec- Lw+Lc+V and Lc+V inclusions. In some instances these
troscopy, for other cations using ICP-MS, and for halo- are preserved along the same secondary fluid inclusion
gens, sulphate and phosphate using ion chromatography trails. Lw+Sh+V inclusions from the Valkommen body,
at the University of Alberta. Chlorine isotope analyses and from some veins at Nautanen show similar salinities
were carried out on the leachates using gas source mass and homogenisation temperatures to those from the Fe-
spectrometry at Environment Canada, Saskatoon. oxide and Cu-Au deposits already discussed. At Nautanen
complex inclusion assemblages are hosted on secondary
4 Results trails. These are indicative of phase separation. Salinities
vary from ~12-18 wt. % NaCl eq. for Lw+Lc+V inclusions
4.1 Microthermometry to ~29wt % NaCl eq. for halite bearing inclusions. Total
homogenisation temperatures for Lw+Lc+V inclusions
Late stage quartz veins cutting Fe-oxide apatite bodies or are typically around 250-300C, whilst partial L-V
their wall rocks contain a consistent fluid population homogenisation for halite bearing inclusions is around
across the area (salinity 30-40 wt. % NaCl eq.; Th=100- 100-120C. At both Nautanen and Ferrum a further as-
150C). Fluids associated with quartz veins from Cu-(Au) semblage of Ca-rich brines is observed similar to those
observed in some veins at Gruvberget. Many of the ob-
servations made here are in agreement with previous work
by Broman and Martinsson (2000).

4.2 Halogen chemistry

Log Br/Cl ratios within leachates from these fluids (Fig. 2)

range from approximately 2.5 to -3.7, with two excep-
tional analyses at 2.3 and 4.4. The majority of analyses
fall in the range 2.8 to 3.5 with no distinction between
Fe-oxide related and Cu-related brines. These data are
compared with a selection of previous data from Yardley
et al. (2000) in Figure 2. They are most comparable to S.W.
England granite related fluids, and are clearly distinct from
fluids associated with the Capitan Pluton, New Mexico
and Columbian Emerald deposits. This is significant as
these are both interpreted as deriving their salinity ei-
ther from magmatic interaction with evaporites, or from
metamorphism of evaporites. Our data are therefore con-
sistent with magmatic sources for mineralising fluids in
Norrbotten, and not with a meta-evaporitic source. The
more Br enriched samples are lower salinity fluids from
the NDZ, and possibly indicate interaction of a magmatic
fluid with the surrounding metasediments.

4.3 Chlorine isotopes

The chorine isotopic composition of leachates from vein

quartz samples from Fe oxide-apatite bodies, and from
epigenetic Cu-Au deposits ranges in 37Cl relative to stan-
dard mean ocean chlorine (SMOC) from -5.63 to -0.99.
These data are compared with previous data from inclu-

Chapter 7-27 Constraints on the source and evolution of mineralising fluids in the Norrbotten Fe oxide-Cu-Au province, Sweden 827

sion fluids, natural porewaters and rocks and minerals and amphibole) results in a passive enrichment of hy-
in Figure 3. Norrbotten inclusion fluids are consistently drothermal fluids in 35Cl. Chlorine isotope analyses of sili-
enriched in 35Cl relative to all previously analysed fluid cate minerals are relatively limited at the present time,
inclusions, most rocks and minerals and most natural but those available from biotites in the Stillwater com-
porewater samples. The only comparable data are from plex (Boudreau et al. 1997), Porphyry Cu related biotites
subduction zone porewaters sampled in the Barbados (Arcuri and Brimhall 2003) show uniformly positive 37Cl
and Nankai accretionary prisms (Ransom et al. 1995). values. Experimental data from. Pan and Dong (2003) show
Luders et al. (2002) showed that submarine hydrother- that Br/Cl ratios of marialitic scapolite closely reflect the
mal fluids could be enriched in 37Cl by extraction of 35Cl halogen composition of co-existing fluids, and hence this
into a vapour phase during boiling, and consequently a process would not be expected to affect the Br/Cl signa-
condensate from a low density fluid or vapour could show ture of hydrothermal fluids.
low 37Cl values.
However, the high salinity of these fluids would seem 5 Discussion and conclusions
to preclude their origin as a condensate. Equally 35Cl en-
riched fluids can be formed by the evapo-concentration The data presented here are consistent with a magmatic
of seawater and precipitation of halite (Eastoe et al. 1998), fluid source for Porphyry and Greenstone Group hosted
but such fluid have not yet been reported with the low Cu-(Au) mineralization in Norrbotten, and for late stage
37Cl values seen here. The most likely explanation for fluids associated with Fe oxide-apatite bodies. The
the Cl isotope data is the preferential extraction of 37Cl microthermometric data do not, however, indicate that
into silicate mineral phases (in this case scapolite, biotite directly comparable fluids were involved in the forma-
tion of the Fe oxide- apatite bodies and the Cu-(Au) min-
eralization. The displacement of 37Cl values to lower val-
ues in the epigenetic Cu-(Au) mineralising fluids may re-
flect extensive water rock interaction and Na-Cl metaso-
matism during this stage of the regions evolution.
Fluids associated with younger, shear zone hosted de-
posits are also potentially magmatic, although the inclu-
sion of several fluid inclusion populations reflects the
modification over an extended period and possibly the
input of metamorphic fluids. Temporal constraints indi-
cate that the highly saline ore fluids present in all depos-
its must have been generated during several magmatic
events, with the additional input of non-magmatic fluids
into the younger, shear zone hosted deposits at Nautanen.
Previous workers have suggested that meta-evaporites
may have played a role in generating the highly saline
brines and regional sodic alteration in Norrbotten
(Frietsch et al. 1997). We find no evidence to support this
idea. Halite typically shows heavy 37Cl values relative to
the fluid from which it precipitates, so halite dissolution
is unlikely to form strongly 37Cl depleted fluids. We have
not yet, however, analysed samples containing a signifi-
cant proportion of the Ca-rich brine, and this may pre-
serve such a signature (Wanhainen et al. 2003).


Arcuri T, Brimhall G (2003) The chloride source for atacamite min-

eralization at the Radomiro Tomic porphyry copper deposit,
Northern Chile. Econ Geol 98:1667-1681
Banks DA, Gleeson SA, Green R (2000) Determination of the origin
of salinity in granite-related fluids: evidence from chlorine iso-
topes in fluid inclusions. J Geochem Expl 69-70: 309-312
Banks DA, Green R, Cliff R, Yardley BWD (2000) Chlorine isotopes
in fluid inclusions: Determination of the origins of salinity in
magmatic fluids. Geochim Cosmochim Acta 64:1785-1789

828 Martin Smith Sarah A. Gleeson

Bergman S, Kbler L, Martinsson O (2001) Description of regional Hitzman MW, Oreskes N, Einaudi MT (1992) Geological character-
geological and geophysical maps of northern Norrbotten county istics and tectonic setting of proterozoic iron-oxide (Cu-U-Au-
(east of the Caledonian orogen). Sver Geol Unders Ba 56. REE) deposits. Precambr Res 58: 241-287
Billstrom K, Martinsson O (2000) Links between epigenetic Cu-Au mine- Lindblom S, Broman C, Martinsson O (1996) Magmatic-hydrother-
ralisations and magmatism/deformation in the Norrbotten county, mal fluids in the Pahtohavare Cu-Au deposit in greenstone at
Sweden. In: LuT research report 2000:06. 2nd GEODE Fennoscandian Kiruna, Sweden. Mineralium Depos 31: 307-318
Shield field workshop on Palaeoproterozoic and Archaen greenstone Luders V, Banks DA, Halbach P (2002) Extreme Cl/Br and 37Cl iso-
belts and VMS districts in the Fennoscandian Shield. tope fractionation in fluids of modern submarine hydrothermal
Boudreau AE, Stewart MA, Spivack AJ (1997) Stable Cl isotopes and systems. Mineralium Depos 37: 765-771
origin of high-Cl magmas of the Stillwater Complex, Montana. Pan Y, Dong P (2003) Bromine in scapolite-group minerals and so-
Geology 25 791-794 dalite: XRF microprobe analysis, exchange experiments, and ap-
Broman C, Martinsson O (2000) Fluid inclusions in epigenetic Fe- plication to skarn deposits. Can Mineral 41: 529-540
Cu-Au ores in northern Norrbotten. In: L..T research report Ransom B, Spivack AJ, Kastner M (1995) Stable Cl isotopes in sub-
2000:06. 2nd GEODE Fennoscandian Shield field workshop on duction-zone pore waters - implications for fluid-rock reactions
Palaeoproterozoic and Archaen greenstone belts and VMS dis- and the cycling of chlorine. Geology 23:715-718
tricts in the Fennoscandian Shield. Romer RL, Martinsson O, Perdahl JA (1994) Geochronology of the
Eastoe CJ, Long A, Kinaith LP (1998) Stable chlorine isotopes in the Kiruna iron ores and hydrothermal alterations. Econ Geol,
Palo Duro Basin, Texas: Evidence for preservation of Permian 89:1249-1261
evporite brines. Geochim Cosmochim Acta 63: 1375-1382 Yardley BWD, Banks DA, Barnicoat AC (2000) The chemistry of
Frietsch R, Tuisku P, Martinsson O, Perdahl JA (1997) Early proterozoic crustal brines: tracking their origins. In: TM Porter (ed) Hydro-
Cu-(Au) and Fe ore deposits associated with regional Na-Cl meta- thermal iron oxide copper-gold and related deposits: A global
somatism in northern Fennoscandia. Ore Geol Rev 12: 1-34 perspective. Austral Min Found, Adelaide, pp. 61-70.

Chapter 7-28 7-28

LA-ICPMS U-Pb dating of titanite: New constraints

on multistage geological evolution of the Norrbotten
mining district, Sweden
Martin Smith, Craig Storey
School of the Environment, University of Brighton, Brighton, BN2 4GJ, U.K.
Teresa Jeffries
Department of Mineralogy, The Natural History Museum, London, SW7 5BD, U.K

Abstract. Established techniques for the laser ablation ICP-MS U- 2 Technique

Pb analysis of zircon have been developed for application to com-
mon Pb bearing phases, including titanite and allanite. A novel
In this study we have extended established U-Pb techniques
common Pb correction procedure has been developed for deriv-
ing mineral ages, and has been tested using well characterised by LA-ICPMS (quadrupole) to titanite and allanite. Titanite
samples. This technique has been applied to samples from the and other common U hosting minerals readily incorporate
mining district of Norrbotten, Sweden, with the aim of constrain- up to ppm levels of (common)Pb into their lattice along-
ing the timing of iron oxide-copper-gold (IOCG) mineralization in side U and Th during crystallisation, making the necessity
relation to the formation of Fe-oxide-apatite deposits and the re-
for common Pb correction paramount. In this study we have
gional geological evolution. Titanites from three of the Fe oxide
apatite deposits studied show complex multistage growth tex- used both a mathematical based 207Pb-correction, and the
tures implying a prolonged metasomatic history. Cores from these far more robust TIMS-style correction. The TIMS-style cor-
samples show ages in the range 2070 to 2000 Ma before present, rection is based upon measurement of the stable 204Pb iso-
indicating that the age of the host supracrustal sequence in tope to assess the amount of common Pb in the analysis.
Norrbotten may be significantly older than previously thought. This requires an independent measurement or estimate of
The rims of these crystals, which show distinct trace element
signatures to the cores, as well as unequivocally metasomatic
the common Pb composition to be corrected for. We have
titanites and allanites from other areas give ages in the range made measurements of common Pb composition by utilising
~1875-1820Ma. These ages probably indicate the time of primary in line gold traps to reduce interferances on the 204Pb peak
mineralization of both the late stages of Fe oxide and Cu-Au types. from mercury stable isotopes. In samples with low analyti-
Younger ages in the range ~1790-1700Ma are interpreted to re- cal signal intensity we combine this approach with a novel
late to subsequent metamorphism of the deposits, and
appraoch based on 3 dimensional U-Pb concrodia.
remobilisation of sulphide mineralization along long lived, regional
scale structures.
3 Sites investigated
Keywords. U-Pb, geochronology, titanite, Norrbotten, Kiruna, IOCG
The geology of the Norrbotten area consists of a
Palaeoproterozoic supracrustal sequence overlying Ar-
1 Introduction chaean basement, which has subsequently been deformed
and intruded by grantoids during the Svecofennian orog-
Northern Norrbotten County, Sweden, is well known as a eny (1.96-1.85Ga). The Palaeoproterozoic sequence within
region of Fe oxide-apatite mineralization, and also hosts the area studied is broadly separated into the Greenstone
a range of copper-gold deposits (Bergman et al. 2001). Group metabasic rocks, and the overlying Porphyry Group,
These deposits have been proposed to be related as a part which consists of intermediate to acid volcanics and inter-
of the iron oxide-copper-gold (IOCG) spectrum of de- calated sediments.
posits. A more detailed understanding of this relation- For the purpose of this study we have examined mate-
ship will be of great use to defining ore genetic and ex- rial from both Fe oxide-apatite and copper deposits
ploration models in terms of both the relationship of Cu- (Bergman et al. 2001) including titanite intergrown with
Au mineralization to Fe oxide mineralization, and the re- magnetite from deformed vesicle fills within the sodically
lationship of both mineralization types to the regional altered footwall trachyandesites at Luossavaara, and
geological evolution. As a part of the EU-RDF Georange titanite hosted in quartz-carbonate veins cutting magne-
program we have investigated this relationship via the tite cemented brecciated metavolcanics in the footwall of
development of a novel U-Pb geochronological technique, the Kirunavaara magnetite-apatite body. Within the
which allows the use of in situ laser ablation ICP-MS for Kiruna area samples were also analysed from Cu-(Au)
analysis of titanite and other common lead-bearing phases deposits and prospects at Rakkurijarvi (Porphyry Group
within polished thick sections. hosted) and Kallosalmi (Greenstone Group hosted). We

830 Martin Smith Craig Storey Teresa Jeffries

have also analysed samples from the Gruvberget Cu de-

posit, developed in the footwall to a magnetite-hematite-
apatite body, again hosted by intermediate metavolcanics.
The third area studied was around Malmberget to the
south of Kiruna. The Malmberget body itself is an Fe oxide-
apatite body exposed in a large fold structure. It is inter-
preted to be a metamorphosed Kiruna type deposit. Samples
where taken from the hanging wall of the Valkommen ore
body. To the east of the Malmberget body both the supra-
crustal sequences and the Svecofennian granitoids are cut
by a regional scale shear system (the Nautanen Deforma-
tion Zone). This hosts the working Cu-(Au) mine at Aitik,
and a historically worked prospect at Nautanen.

4 Results of geochronological studies

A number of samples show complex multistage growth

(Fig. 1). Samples from Luossavaara, Gruvberget, and
Malmberget show core ages in the range 2073-2028 Ma. All
these bodies are Fe-oxide (and sometimes copper) depos-
its hosted in Porphyry group metavolcanics, supposedly of
Svecofennian age. The BSE light rims of most of these

Chapter 7-28 LA-ICPMS U-Pb dating of titanite: New constraints on multistage geological evolution of the Norrbotten mining district, Sweden 831

titanites give ages in the range 1920 to 1826 Ma. LA-ICPMS either metamorphic growth of titanite during this pe-
trace element analyses from corresponding sites in the same riod or metasomatic growth of titanite during hydro-
grains show a clear distinction between core and rim analy- thermal activity. The youngest ages so far encountered
ses (Fig. 2). The younger, rim zones are strongly LREE en- are from the Valkommen body, with titanite at 170820
riched relative to the core zones. These patterns are com- Ma, and apatite at 158412 Ma. The very young age re-
parable to the composition of unequivocally metasomatic corded in apatite from Valkommen is related to the lower
titanites from other deposits. The rim zones are volumetri- closure temperature of apatite relative to either titanite
cally the most significant parts of the crystals. The ages or zircon. We suggest that these ages record subsequent
obtained from these zones are reflected in previous TIMS metamorphism of the deposits in question.
data from Norbotten titanite which analysed bulk crystals. Data from deposits hosted by, or associated with, the
The range of ages from the alteration surrounding Fe-ox- NDZ range from 1826+/-15 Ma to 1756+/-20 Ma. Two
ide and Cu-deposits is previously unreported from the Por- samples from the Nautanen deposit gave ages of 1810+/-
phyry Group and the deposits which it hosts. These data 21 Ma and 1756+/-20 Ma respectively. These data indi-
suggest a minimum age of the Porphyry group of between cate a prolonged history of deformation and fluid flow
~2070-2028 Ma, significantly older than currently thought. along the NDZ, probably involving multiple episodes of
Analyses of titanites from regional alteration (Nunasvaara) ore deposition and remobilisation. The REE patterns of
and the alteration surrounding Fe-oxide and Cu-Au deposits these titanites are LREE depleted; indicating different
hosted by the Porphyry Group range from 1902+/-8 Ma chemical conditions of titanite formation in the NDZ com-
(Nunasvaara) to 1758+/-18 Ma (Tjarrajkka). The data in pared to other Cu-(Au) deposits. This may be related to
the range of 1920-1826 Ma correspond to the time range contrasting fluid chemistry, or may reflect ore-forming
of the Svecofennian metamorphism, and the main in- processes, particularly the co-precipitation of allanite and
trusive activity in the area. Our data are consistent with LREE enriched epidote.

832 Martin Smith Craig Storey Teresa Jeffries

5 Discussion and conclusions correlation of Norrbotten stratigraphy with that of the

Skellefte district (Bergman et al. 2001). The timing of Fe
The data presented here are generally in agreement with oxide and Cu-Au deposit formation corresponds to that of
previous data on mineral deposits within the Norrbotten the Svecofennian metamorphism, and the intrusion of the
region. The Kirunavaara and Luossavaara mineralization Haparanda and Perthite-monzonite suite granitoids. A sec-
has previously been dated at 1888+/-6 Ma between 1876+/ ond stage of mineralisation, or metamorphism of previ-
-9 Ma by Billstrom and Martinsson (2000), who reported ously formed deposits occurred in association with the
U-Pb titanite ages for Cu-Au mineralization in the ranges younger stage of metamorphism. This possibly accompa-
1880-1860Ma and 1800-1750Ma. These ages are also in broad nied movements on the Nautanen Deformation Zone.
agreement with our data; however, a number of deposits in
the younger group in their study gave ages in the older group References
in this study. This is likely to represent a difference in the
scale of sampling, and suggests that the age heterogeneity Bergman S, Kbler L, Martinsson O (2001) Description of regional
seen in these deposits is the result of metamorphic geological and geophysical maps of northern Norrbotten county
(east of the Caledonian orogen). Sveriges geologiska underskning
remobilisation of ore in the period 1800-1750Ma. In com-
Ba 56
plex zoned grains we interpret the data from the cores as Billstrom K, Martinsson O (2000) Links between epigenetic Cu-Au
indicating the timing of initial metamorphism (and a mini- mineralisations and magmatism/deformation in the Norrbotten
mum age for magmatism), and data from the rims as indi- county, Sweden. In L.U. T. research report 2000:06. 2nd GEODE Fenno-
cating the timing of metasomatic fluid flow associated with scandian Shield field workshop on Palaeoproterozoic and Archaen
mineralization. greenstone belts and VMS districts in the Fennoscandian Shield
Romer RL (1996) What is the significance of lead isotope data from
Previous constraints on the age of the Porphyry group stilbite, a low temperature natural ion exchanger? The 22nd Nor-
come from U-Pb dating of zircon (Welin 1987; Skild and dic Geological Winter Meeting, Turku, bo, Abstracts, 172
Cliff 1984). Our new data now suggest these ages may rep- Romer RL, Martinsson O, Perdahl JA (1994) Geochronology of the
resent recrystallisation of zircon during a later metamor- Kiruna iron ores and hydrothermal alterations. Economic Geol-
phic/metasomatic event. In summary, the data from titanite ogy 89: 1249-1261
cores suggest that Porphyry and Porphyrite group volcan- Skild T, Cliff RA (1984) Sm-Nd and U-Pb dating of Early
Protoerozoic mafic-felsic volcanism in northernmost Sweden.
ism occurred significantly earlier than previously thought. Precambrian Research 26: 1-1
This has significant implications for the timing of rifting Welin E (1987) The depositional evolution of the Svecofennian
and subduction during the early tectonic evolution of the supracrustal sequence in Finland and Sweden. Precambrian Re-
Fennoscandian shield. It may also have implications for search 35: 95-113

Chapter 7-29 7-29

Metamorphic to magmatic transition captured at the

Myszkw Mo-W deposit, southern Poland
H.J. Stein
AIRIE Program, Department of Geosciences, Colorado State University, USA, and
Norges Geologiske Underskelse, Trondheim, Norway
M. Markowiak, S.Z. Mikulski
Polish Geological Institute, Sosnowiec and Warszawa, Poland

Abstract. Millimetre scale drilling of paragenetic ally-specific sulphide Re contents (hundreds to thousands of ppm) associated
occurrences represented by ten Myszkw molybdenite samples with main stage molybdenites, and are the product of a
provides a temporal framework for this Mo-W deposit, associated
vertically and laterally communicative magmatic-hydro-
with the transcontinental Hamburg-Krakw tectonic zone. With rep-
licates (second mineral separates) for two samples, a total of twelve thermal system that moved from deep to shallow crustal
Re-Os model ages pin high temperature molybdenite-scheelite- levels, over a period of several million years, importantly,
(chalcopyrite) mineralization to a narrow time window, from 300 without venting. With these characteristics in mind, we
1 to 296 1 Ma (2-sigma). Published 40Ar/39Ar ages (305-290 Ma) apply Re-Os dating of molybdenite through the parage-
for potassium feldspar, white mica, and biotite do not precisely pin
netic history of Myszkw to document the timing and
the timing of mineralization, but provide information on the re-
gional cooling history. Alteration is characterized by local metaso- duration for its formation and to improve our understand-
matism of hosting Vendian to Cambrian metamorphic rocks, and ing of this unusual deposit.
spatial patterns for Mo-W-(Cu) mineralization support a relation-
ship between metasomatism and mineralization. Dehydration melt- 2 Geologic setting
ing of middle crust was followed by local intrusion of magmas along
structurally vulnerable zones. Melting of hosting metaclastic se-
quences influenced local metallic assemblages and provided the
The Myszkw deposit is situated along the NE margin
magmatic apophyses and crustal enclaves associated with much of the NW-trending Krakw-Lubliniec tectonic zone, a
of the Myszkw mineralization. Even though local stockwork may segment of the transcontinental Hamburg-Krakw tec-
be found, the overall architecture of the Myszkw deposit does not tonic zone. In southern Poland, the tectonic history of
support a calc-alkaline porphyry-style deposit, and this interpreta- this zone is poorly known but strike-slip movement ap-
tion should be reconsidered. We attribute Myszkw mineralization
pears to be an important component. Mafic to felsic
to unroofing of the Variscan orogen, rapid late Variscan uplift, and
exhumation melting. magmatism with granodiorite prevailing is common
along the 15 km segment of the Krakw-Lubliniec tec-
Keywords. Re-Os, molybdenite, Mo-W deposit, metasomatism, tonic zone that includes the Myszkw Mo-W region.
Myszkw, Poland Magmatic rocks are hosted by intensely folded, predomi-
nantly fine-grained Vendian to Cambrian clastic units
1 Introduction at regional greenschist facies. Upper amphibolite-granu-
lite facies (metasomatic) is locally present in the vicin-
Late Variscan (~300 Ma) Mo-W mineralization at ity of magmatic rocks. A NW-trending granodiorite body
Myszkw has been classified as a calc-alkaline porphyry- with subvolcanic dacite and rhyolite porphyry dikes in-
type deposit situated in a poorly defined belt of mag- truded the metasedimentary rocks, and contact relations
matic rocks in south-central Poland (Podemski et al. 2004; vary from sharp to ill-defined. The overall character of
Markowiak et al. 2001). Features defining of calc-alkaline the Myszkw granodiorite is one of a moderately flat-
porphyry-style mineralization, however, are conspicuously top intrusion extending over tens of kilometres, and dis-
absent, not the least an intrusion centered brittle-planar sected by normal faults (Fig. 1). Interfingering and fo-
stockwork and attendant alteration types. liation parallel magmatic units intersected in drill holes
Re-Os data for molybdenites have provided key infor- in the vicinity of the granodiorite are interpreted as apo-
mation on the timing and genesis of a broad spectrum of physes to the granodiorite body (Podemski et al. 2001).
deposits, in particular, metamorphically-derived depos- Associated alteration is described both as metasomatic
its versus classic Cu-Mo-Au porphyry-style mineraliza- and hydrothermal vein type, with significant K-feldspar,
tion (e.g. Stein, in press). The former tend to be small in silica, sericite, and carbonate. While potassic alteration
size, of erratic but locally high-grade, and display widely is prevalent, secondary biotite, magnetite, and signifi-
dispersed rather than focussed ore zones. They are asso- cant pyrite are conspicuously sparse. Some alteration
ciated with moderate-low ppm to sub-ppm levels of Re. assemblages have been described as greisen-like at
In contrast, true porphyry systems have high to very high Myszkw.

834 H.J. Stein M. Markowiak S.Z. Mikulski

Three periods of mineralization are defined at

Myszkw: Early Skarn (Period I), Main Hydrothermal
(Period II), and Late Post-Ore (Period III). The first two
are molybdenite-bearing. Within Period I, early skarn
consists of magnetite-sulfide mineralization. Within Pe-
riod II, different stages of ore deposition are proposed
(Stage 1, feldspar-molybdenite veins with biotite; Stage 2,
quartz-feldspar pegmatite veins; Stage 3, quartz-molyb-
denite stockwork with scheelite; Stage 4, black quartz veins
with microsulfide; Stage 5, quartz polymetallic veins with-
out molybdenite and late brecciated quartz veins with
sulfide. The Period-Stage classification (lsarz 1985, 1993)
was used for our molybdenite samples (Table 1), and is
summarized in Podemski et al. (2001).

4 Re-Os analytical results

Twelve Re-Os ages representing paragenetically defined

Myszkw molybdenites provide a remarkably narrow age
The Myszkw deposit, outlined by 35 boreholes from range, 300 1 to 296 1 Ma (2-sigma). Re concentra-
1985 to 1993, is estimated to contain 800 million tons of tions are moderate, ranging from an about 40 to 74 ppm.
ore at 0.15% Cu, 0.05% Mo, and 0.04% W and continues The lower value (40 ppm) is an estimate of the true Re
to at least 1250m depth (Podemski et al. 2001). Several concentration as up to 95% dilution of the molybdenite
similar deposits were also discovered in this region. Sig- separate by quartz was unavoidable during drilling of
nificantly, Cu mineralization (chalcopyrite) bears little some samples. Such samples consist of very fine-grained
spatial relation to W and Mo mineralization (scheelite grey streaks of molybdenite in quartz (see footnote,
and molybdenite). And, W and Mo also exhibit differ- Table 1). This does not affect the age calculation, as dilut-
ences. In general, W (and Mo) are associated with mag- ing quartz contains essentially no Re and Os. Four samples
matic rocks, whereas Cu and to some extent Mo, are as- with abundant and coarser crystalline molybdenite sug-
sociated with contact regions between granodiorite and gest that ~70 ppm Re was common to the fluids forming
metaclastic host units. Molybdenite is generally associ- quartz-molybdenite veins.
ated with quartz veins and patches in pink (potassic) gra- Notably, the Re values reported in Podemski et al.
nodiorite, but these ill-defined and scattered veins do not (2001), 0.07 to 0.17% (700 to 1700 ppm), bear no resem-
constitute stockwork in the classical sense. Also, the rich- blance to our Re values determined by isotope dilution. It
est ore body is contained in an enclave of metaclastic host is highly unlikely that both data sets can be correct for a
rock within the upper portion of the granodiorite (Chaffee single deposit.
et al. 1997), rather than exhibiting an intrusion-wide as-
sociation to the granodiorite. Myszkw mineralization and 5 Discussion and conclusions
paragenesis have been described in detail by Piekarski
(1982, 1995) and lsarz (1985, 1993), including vein, peg- The moderate and fairly consistent Re levels (about 40 to
matitic, metasomatic, disseminated, and skarn varieties 75 ppm) for Myszkw molybdenites do not support a sub-
(see Podemski et al. 2001). duction-related porphyry-style origin (Stein et al. 2001).
A better fit would be a moderately local derivation utiliz-
3 Molybdenite samples dated ing a crustal reservoir with fairly consistent Re, rather
than one dependent on batch additions of material from
This Re-Os study utilizes different ore occurrences to de- different reservoirs, mixing, and system wide fluid sepa-
termine the relative timing of ore-forming environments ration (porphyry model). At Myszkw, development of
at Myszkw. Even at the hand-specimen scale, molybdenite local veins, stockwork, and pegmatite likely depended on
was drilled from occurrence-specific sites, a critical step local separation and volatile enhancement of hydrother-
for successful age determinations in complex metamor- mal fluids that were not far-travelled.
phic settings (Stein in press). Replicate ages for two Re-Os ages have a very tight range (300-296 Ma) and
40Ar/39Ar ages (305-290 Ma) overlap the molybdenite age
samples were acquired from new mineral separates ex-
ploiting the same occurrence. This is an indisputable test range but should be interpreted as recording the cooling
for age accuracy. history at the sampled localities for the minerals dated

Chapter 7-29 Metamorphic to magmatic transition captured at the Myszkw Mo-W deposit, southern Poland 835

(potassium feldspar, biotite, white mica). Argon geochro- ronment conducive to classic porphyry-style mineraliza-
nology should not be used to define ages of high temper- tion, as at ~300 Ma the Variscan orogeny is not character-
ature Mo-W-Cu mineralization (Stein et al. 2001). Gen- ized by subduction. We suggest that the Myszkw Mo-W
eral agreement between Re-Os and 40Ar/39Ar ages sug- deposit is the product of exhumation melting associated
gests that the region cooled very quickly, and has not seen with rapid unroofing of the Variscan orogen.
any further thermal activity.
Mineralogy (e.g. lack of abundant chalcopyritee, fluo- Acknowledgements
rite, and Au), lack of an intrusion-centered relationship
for mineralization, lack of correlation between Cu and Re-Os analytical work was carried out by AIRIE gradu-
Mo, the abundance of W, lack of planar-brittle vein styles, ate students A Zimmerman and N Loeppke, and supported
and lack of classic porphyry-style alteration collectively by NSF EAR-0087483. Salary support for HJS was pro-
do not support a Mo-W calc alkaline intrusion-related, vided by Edward Warner.
porphyry model (Podemski et al. 2001).
Re-Os ages and the preserved regional greenschist fa- References
cies character of host rocks with local high temperature
contact metamorphism suggest rapid uplift with struc- Chaffee MA, Eppinger RG, Lasn K, Mlsarz J, Podemski M (1999) A
turally favourable but localized discontinuities serving as geological, alteration, and geochemical model of the Myszkw
focussing sites for intrusion. This was accompanied by porphyry Cu-Mo deposit, southern Poland, in Papunen (ed).
Mineral Deposits, Balkema, Rotterdam, 851-854
local and brief in situ melting and metasomatism. As a Markey RJ, Hannah JL, Morgan JW, Stein HJ (2003) A double spike
result, erratic mineralization of variable grade covers a for osmium analysis of highly radiogenic samples. Chemical
large region. This includes the Myszkw deposit and other Geology 200: 395-406
prospects in the Krakw-Lubliniec tectonic zone. Small Markowiak M, lsarz J, Lasn K, Podemski M, Karwowski L, Chaffee
perturbations in pressure permitted local formation of MA (2001) Palaeozoic porphyry molybdenum-tungsten miner-
alization in the Myszkw area, southern Poland, in Piestrzynski
thick (cm scale) stockwork veins but true and abun-
et al. (eds). Mineral Deposits at the Beginning of the 21st Cen-
dant stockwork never formed system wide as defines clas- tury, Swets & Zeitlinger Publishers Lisse, 445-448
sic Cu-Mo-Au-W porphyry-style mineralization. Further- Piekarski K (1982) Molybdenum schists in the vicinities of Myszkw
more, there is no evidence for a regional tectonic envi- (Eng Sum). Prz Geol 30(7): 335-340

836 H.J. Stein M. Markowiak S.Z. Mikulski

Piekarski K (1995) Geologic setting and ore mineralisation charac- lsarz J (1993) The main paragenetic stages for molybdenum
teristics of the Myszkw area (Poland). Geol Quart 39(1): 31-42 mineralisation in the Palaeozoic rocks of the Myszkw area and
Podemski M (editor), Bua Z, Chaffee MA, Ciela E, Eppinger R, Habryn their importance to the formation of the ore deposits of that area
R, Karwowski L, Lason K, Markiewicz J, Markowiak M, Snee LW, (Eng Sum). Pol Tow Mineral Pr Spec 3: 123-128
lsarz J, Truszel M, Wybraniec S, Zaba J (2001) Palaeozoic por- Stein HJ (in press) Low-rhenium molybdenite by metamorphism in
phyry molybdenum-tungsten deposit in the Myszkw area, south- northern Sweden: recognition, genesis, and global implications.
ern Poland. Polish Geological Institute Special Papers 6: 1-87 Lithos.
lsarz J (1985) Stages and zonality of ore mineralization in Stein HJ, Markey RJ, Morgan JW, Hannah JL, Scherstn A (2001) The
Palaeozoic rocks of the environs of Myszkw. Ann Soc Geol Pol remarkable Re-Os chronometer in molybdenite: how and why it
53(1-4): 267-288 works. Terra Nova 13(6): 479-486

Chapter 7-30 7-30

New K-Ar, 87Sr/86Sr, REE, and XRF data for Tertiary

volcanic rocks in the Sasa-Toranica ore district,
G. Tasev, T. Serafimovski, P. Lazarov
Department of Mineral Deposits, Faculty of Mining and Geology, Goce Delcev 89, 2000 Stip, Macedonina

Abstract. The latest K-Ar, 87Sr/86Sr, and REE data for samples from 3 Results and discussion
Sasa-Toranica ore district are presented. Whole rock XRF analyses
confirm host rock composition as dacites, quartz-latites, trachyande-
The new K-Ar, Sr isotope, REE, and whole rock XRF data
sites and rhyolites. K-Ar absolute ages range from 31 to 14 Ma con-
firming Oligocene-Miocene age as previously determined by rela- from Sasa-Toranica host rocks provide insight into the
tive methods. 87Sr/86Sr ratios (0.70954 to 0.71126) suggest material composition, timing, and sources of volcanic activity in
is sourced from the contact zone between the lower crust and up- the region.
per mantle where contamination of primary melt occured. New REE Dacites in the Luke-Kiselica area occur from the
data including negative Eu anomalies along with previously deter-
Karamanica mountain to the southeast at the Osogovo
mined La/Yb ratios ranging from 13.3 to 43.0 (Serafimovski 1990)
confirm inferred material source. These new data reconfirm previ- mountain (Serafimovski and Alexandrov 1995). The
ous results, provide insight into the Tertiary magmatic history of dacites contain plagioclase (37% An), small amount of
the district, and suggest the exact origin of the material that pro- orthoclase, quartz, biotite and amphibole phenocrysts.
duced the Tertiary magmatic rocks. Their matrix is holocrystaline to hypocrystaline with
glassy domains. Apatite, sphene and zircon were identi-
Keywords. Sasa, Toranica, volcanic rocks, age, origin, contamination,
fied as accessory minerals; while sericite, chlorite, kaolinite,
carbonate and metallic minerals are present as second-
ary minerals.
1 Introduction Quartzlatites are found near the springs of Lucka River
and Kuprina Padina as dykes and at Samar and
Tertiary volcanic rocks in the Osogovo-Besna Kobila (Sasa- Karamanica as dykes and volcanic flows (Samar and
Toranica ore district) area regionally strike NW-SE for Crcorija) over the volcano-sedimentary rocks. They are
100 km on both sides of Macedonia-Bulgaria border. Vol- characterized by a porphyritic coarse grained texture with
canic rocks in the area occur as ~50 m thick elongate sanidine and plagioclase (35-40% An) phenocrysts, with
dykes oriented roughly east-west (260o). From the Osogovo secondary amphibole and augite phenocrysts. Sphene and
Mountain to the Besna Kobila Mountain (Osogovo-Luke- zircon are accessory minerals. These rocks also contain
Karamanica), volcanic rocks are present as pyroclastics metallic secondary minerals.
(Deve Bair), volcanic domes, dykes, necks and veins. Vol- Hialoandesites appear as necks and lava flows over the
canic rocks at the Osogovo-Besna Kobila mountains cut Upper Pliocene sediments at Gradeska Mountain. These
the Paleozoic and Riphean-Cambrian metamorphic and rocks are porphyry-vitrophyric with phenocrysts of pla-
igneous rocks and overlie Upper Eocene sedimentary se- gioclase (37% An), biotite, amphibole and augite; apatite
quences. The volcanics are mainly dacitic tuffs (Deve Bair), and zircon occur as accessory minerals.
dacites, quartzlatites, rhyolites, trachyandezites, andesite- Hypoabyssal and subvolcanic dacites and quartzlatites
latites and occasionally lamprophyre veins (Sasa and dominate the Sasa-Toranica zone (Osogovo). All the
Toranica localities). dacites and quartzlatites in the Sasa-Toranica zone ex-
perienced hydrothermal alteration. Dacites are
2 Methodology holocrystalline with ~ 30% phenocrystals of andesine
(5-16%), quartz (2-3%) and smal amount of orthoclase
After detailed sampling and preparation at the Faculty of and coloured minerals (13-20%), mainly replaced by epi-
Mining and Geology in Stip, samples were sent to the dote, chlorite and carbonates. Hydrothermal alteration
Geological Department, University of Padova, Italy for of andesites result in various new mineral assemblages.
whole rock XRF analysis, Actlabs in Canada for ICP-MS Illitization, seritization and propylitization dominante
and INAA REE analysis, the Geology Department, Royal andesite alteration. Apatite, zircon, sphene and magne-
Holloway University of London, U.K. for TIMS 87Sr/86Sr tite are present as accesory minerals, while pyrite, chal-
ratios, and the Geological Institute in Budapest, Hungary copyrite, sphalerite and galena represent economic min-
for K-Ar dating. eralization.

838 G. Tasev T. Serafimovski P. Lazarov

Quartzlaties are the most common rocks in the zone Lamprophyres occur as small dykes near Sredno Brdo
mentioned above. They occur as elongated dykes a few and Toranica. They are dark grey to brown rocks with a
kilometers in length. These rocks are characterized by fine-grained porphyrtic texture and glassy matrix. Py-
large phenocrysts of sanidine, andezine and femic min- roxene, amphibole and biotite pheocrysts are identified.
erals biotite, amphibole and rarely augite. Sanidine crys- Accessory minerals are apatite, sphene and zircon.
tals are fresh and quite large (up to 5-6 cm). Quartzlatites Data obtained after geochemical analyses were entered
were intensively hydrothermaly altered. into the computer software IGPET 2000 and Microsoft
Transition rocks from quartzlatites to rhyolites are Excel; results are displayed in Table 1.
found at a few locations at Osogovo Mountain. Rocks with Use of IGPET 2000 software facilitated determination
increased SiO2 content occur near the Sekirica Tower close of rock types by the Total Alkali Silica (TAS) classifica-
to the Macedonian-Bulgarian state border. These rocks tion scheme, their classification under the calk-alkaline
were intensly propylitized and hydrothermaly altered. or tholeiitic series of rocks (Fig. 1, 2), and subsequent in-
The volcanic rocks from the Kozja River and Svinja terpretations based on the classifications.
River (Sasa Mine area) are dominantly dacites and Graphical view of those determinations is presented
quartzlatites. The volcanic rocks from this area are intensly in Figure 1.
propylitized and hydrothermaly altered. In addtion to TAS classification indicate that the rocks of interest
previously mentioned secondary minerals, these rocks also mostly plot in the areas that define dacites, trachydacites,
contain ore minerals including pyrite, galena, sphalerite, trachyandesites and rhyolites. All analyzed rocks plot in
sometimes chalcopyrite and occasionally traces of the area of calk-alkali series. Selected samples were ana-
ceruzite, anglezite and malachite.Trachyandesites occur lyzed for rare earth element (REE) concentrations. The
as small bodies at subvolcanic-volcanic levels in the Sasa- analyses were performed at the Active Labs, Canada. REE
Toranica zone and its western borders. They are charac- concentration data for four samples are presented in
terized by porphyry structure (fine grained porphyry) Table 2 and plotted in a chondrite-normalized spider dia-
and crystalized microlitic or microtrachytic matrix. gram in Figure 2.
Phenocrystals of large, around 2 to 3 mm, andezine, From the spider diagram (Fig. 2) it can be seen that
sanidine, biotite, augite and hornblende are present. Apa- the rare earth elements in the Sasa-Toranica ore region
tite, sphene, and zircon occurs as accessory minerals. In have a decreasing trend. Comparing the left and right side
comparison to the quartzlatites, the trachyandesites are of the diagram suggests there is a decrease in heavy rare
characterized by lower SiO2 concentrations. Similar rocks earth elements, HREE with an atomic number higher than
were identified in Pecovska Maala on the Osogovo Moun- 63 (Eu), in comparison with light rare earth elements,
tain on the Bulgarian side of the Bulgaria-Macedonian LREE with an atomic number lower than 63 (Eu). The
border. trend is typical as the product of fractionation of light

Chapter 7-30 New K-Ar, 87Sr/86Sr, REE, and XRF data for Tertiary volcanic rocks in the Sasa-Toranica ore district, Macedonia 839

of feldspars. Eu2+ is compatible in plagioclase and K-feld-

spar, in contrast to the Eu3+ which is incompatible. Thus
the removal of feldspar from a felsic melt by crystal frac-
tionation or the partial melting of a rock in which feld-
spar is retained in the source will result in a negative Eu
anomaly in the melt.
Accordingly, the data for Eu in analyzed samples and
its negative anomaly it can be concluded that Eu has been
removed from the melt as a compatible Eu2+, by the pro-
cesses of crystal fractionation or partial melting.
With the analyses of strontium isotopes (Table 4) was
performed to construct a general model of formation for
rare earth elements and their increase in comparison to rock complexes at the Osogovo Mountain (Sasa-Toranica
the chondritic values. Fractionation occurred as a direct ore field). Strontium isotope analyses of rock samples from
consequence of partial melting, which according to the the volcanic rocks from the Sasa-Toranica ore field re-
angle of the line in the diagram was not of high intensity. sults in strontium ratios that range from 0.70954 up to
Looking at the middle part of the diagram the value 0.71125. The results suggest the magma forming Neogene
of Eu is slightly and negatively displaced from the ideal magmatic complexes at the Osogovo Mountain is a prod-
linear line between Sm and Gd defining a distinct nega- uct of primary magmatic melt originating from the bor-
tive Eu anomaly. A chondrite normalized, geometric mean der zone between upper mantle and continental crust
calculation of the Eu anomaly is shown in Table 3. where mixing and contamination of primary magma oc-
From the table it can be seen that Eu anomaly values curred.
are in range from 0.727669702 up to 0.828905716, and all The new data complies with previous 87Sr/86Sr data for
are less than 1, which implies a negative Eu anomaly Upper Tertiary calk-alkaline complexes formed in the
(Rollinson 1992). Eu anomalies are controled by presence Serb-Macedonian metallogenic province. 87Sr/86Sr ratios

840 G. Tasev T. Serafimovski P. Lazarov

tration distribution of elements show that the magmatic

rocks originated from one magmatic chamber but dur-
ing different time intervals producing different rock types.
K-Ar isotopic age data give Tertiary magmatic ages in
the study area. Results of this study are shown in Table 5.
The range of ages (Oligocene-Miocene) confirms the
age determined by the relative methods.

4 Conclusion

This study of the volcanic rocks in the Sasa-Toranica ore

region identified the distinct and uniform chemical com-
position of these rocks. The rocks are characterized as
dacites, trachydacites, trachyandesites and rhyolites based
on the TAS scheme. New K-Ar ages range from 31.16
1.40 to 14.0 3.0 Ma confirming Oligocene-Miocene ages.
Strontium isotope ratios and REE analyses identify mag-
matic material originated from the contact zone between
the upper mantle and lower continental crust where cer-
tain contamination of primary melts occurred.

Rollinson H (1992) Using Geochemistry Data: evaluation, presenta-
tion, interpretation. pp. 352. Prentice Hall, an imprint of Pearson
Education, Harlow, England.
Serafimovski T (1990) Metallogeny of the Lece-Halkidiki zone. Doc-
toral thesis, Faculty of Mining and Geology, Stip, p. 390 (in
Serafimovski T (1993a) Structural - Metalogenic features of the Lece-
Halkidiki zone: Types of Mineral Deposit and Distribution. Fac-
ulty of Mining and Geology. Stip, Special Issue N. 2, 325 p, Stip.
Serafimovski T, Aleksandrov M (1995) Lead-zinc deposits and oc-
of samples from Kozuf Mountain range from 0.7088 to currences in the Republic of Macedonia. Faculty of Mining and
0.7090 and those for volcanic rocks from the Rogozna Geology, Stip, Special Issue 4, p. 387 (in Macedonian)
range between 0.7074 and 0.7085 (Serafimovski 1990). Serafimovski T, Jelenkovic R, Tasev G (2003) Geodynamic Evolution
Osogovo Tertiary igneous rocks are characterized by and Metallogeny in the Southern Parts of the Balkan Peninsula.
Geodynamics and Ore Deposit Evolution of the Alpine-Balkan-
interesting distributions of Pb, Ba, Sr, Rb, Li, Cs and Be. Carpathian-Dinaride Province. Final GEODE-ABCD Workshop.
Compared to Clark standard values Pb, Ba, Sr and Be are Programme and Abstracts. pp. 50. Seggauberg, Austria.
enriched while Li, Rb and Cs are similar to Clark stan- Serafimovski T, Jelenkovic R, Tasev G, Lazarov P (2003) Mineral
dard values. Also, in magmatic processes it was noticed Deposits Related to Tertiary Magmatism in the Southern Part
trend of increasing Li, Pb, Cs, Be, Rb and Ba concentra- of the Balkan Peninsula. Geologica Macedonica, Volume 17, pp.
19-23, Stip.
tions going from fine-grained porphyry quartzlatites to Tasev G (2003) Polymetalic mineralizations related to the Tertiary
coarse-grained porphyry quartzlatites (Serafimovski magmatism in the Republic of Macedonia. Faculty of Mining and
1993a; Serafimovski et al. 2003). Tendencies in concen- Geology, Stip. Master thesis, p. 176. (in Macedonian)

Chapter 7-31 7-31

Sources of rhenium and osmium enrichment in

fumaroles, sulphide sublimates and volcanic rocks
from the Kudriavy volcano
Svetlana G. Tessalina, Franoise Capmas, Jean-Louis Birck, Claude-Jean Allgre
Laboratoire de Geochimie et Cosmochimie, Institute de Physique du Globe, 4 pl. Jussieu, 75252 Paris, France
Marina A. Yudovskaya, Vadim V. Distler, Ilya V. Chaplygin
Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry (IGEM), RAS, Moscow, Russia

Abstract. Rhenium loss through magma degassing could be partly loor sediments are almost completely subducted beneath
balanced by rhenium enrichment in fumarolic magmatic gases and Kurile Island arc (Von Huene and Scholl 1991). The lower
Re-bearing precipitates, as may be the case for the Kudriavy vol-
part of the sedimentary section consists of the Cretaceous
cano associated with an active subduction zone. The relatively
unradiogenic 187Os/188Os isotope ratios (0.122 up to 0.152) and high chert (120 to 92 Ma) of carbonate composition with abun-
Os contents (averaging 0.6 ppb) of fumarolic gas condensates im- dant siliceous organisms. The radiolarian and diatom ooze
ply that significant Re and Os are remobilised from depleted MORB accumulated during the middle to late Miocene (14 to 5
mantle. Involvement of a Re-rich component is evident from high Ma) represents the upper part of the sedimentary sec-
Re concentrations in high-temperature gas condensates, ranging
tion (Bailey 1993).
from 7 to 200 ppb. Indeed, Re-rich Os-poor components such as
organic-rich subducted sediments and volcanic rocks do not sig- The Kudriavy volcano has been passively degassing at
nificantly shift the isotopic composition of fumarolic products. The 500-940 C, as recorded in fumarole activity for the last
relatively radiogenic composition of the dacite-andesite-basaltic arc 100 years. The unique occurrence of rhenium disulphide
volcanics (187Os/188Os ratio up to 0.58), however, could result from (rheniite ReS2) has been discovered around high-temper-
significant Os (and Re) input from subducted sediments. ature fumaroles on the Kudriavy volcano, together with
Keywords. Re-Os, subduction zone, rheniite, Kurile Islands, Kudriavy
elevated PGE contents.

3 Sample description and analytical methods

1 Introduction
In order to understand mechanisms for rhenium and os-
Subduction zones are major sites of continental crust for- mium enrichment, we undertook integrated studies of
mation and elemental recycling between the mantle and fumarolic gases, sulphide sublimates and volcanic rocks
crust. The great difference between Re contents in de- at Kudriavy. The sulphide sublimates are represented by
gassed subaerially deposited arc volcanics (~0.19 ppt, molybdenite (MoS2), rheniite (ReS2) and Pb-Bi sulphosalt.
Lassiter 2003) and in melt inclusions from undegassed The suite of volcanic rocks ranges from basaltic to dacitic
primary arc volcanics (~2 ppb, Sun et al. 2003) requires in composition. Two fractions of fumarolic gas conden-
Re loss during magma degassing. Substantial Re loss from sates were analysed: = 0.2 mm (Fraction 1) and bulk fu-
arcs can be partly balanced by high Re contents in mag- maroles condensates (Fraction 2). Re and Os concentra-
matic gases and the presence of pure Re sublimates in tions and Os isotopic compositions was determined by
arc systems (Korzhinsky et al. 1994), as reported for the negative thermal ionisation mass spectrometry (NTIMS)
Kudriavy volcano, above an active subduction zone in the on a Finnigan MAT 262 at the IPGP. Analytical procedure
Kurile Islands. The Re-Os systematics should provide has been described previously (Birck et al. 1997).
important information on the source of Re-rich magmatic
volatiles and sulphide precipitates with regard to contri- 4 Re-Os isotope systematics
butions from the mantle, crust, subducting slab, and sea-
water, because of compatible Os and slightly incompat- The Re contents in Kudriavy volcano rocks range from
ible Re behaviour. 3.5 to 17 ppb (Fig. 1) averaging 7 ppb, which is about 20
times higher than the estimated average Re abundance
2 Tectonic setting of the Kudriavy volcano for arc lavas (0.3 ppb) and 3 times higher than for melt
inclusions from primitive arc lavas, southern Pacific (Sun
The Kurile Islands are the result of Pacific plate subduc- et al. 2003). The Os contents (ave. 11 ppt.) are similar to
tion beneath the Eurasian plate. Subducted Pacific plate those of MORB (Roy-Barman and Allgre 1994). The 187Os/
188Os ratios vary from 0.205 in basalt to 0.588 in dacite
comprises oceanic crust (MORB), oceanic lithospheric
mantle and associated sediments. The 400 m-thick seaf- with an average of 0.385. This range of Os isotopic com-

842 Svetlana G. Tessalina Franoise Capmas Jean-Louis Birck Claude-Jean Allgre Marina A. Yudovskaya Vadim V. Distler Ilya V. Chaplygin

position in volcanic rocks could be explained by mixing

of an unradiogenic MORB-type reservoir with more ra-
diogenic components. Our mass balance calculations are
based on the following parameters (Table 1).
The unradiogenic MORB-type component could rep-
resent Os-poor oceanic crust. The Os contribution from
high-Os depleted mantle is limited to 10% in basalts and
almost negligible in felsic volcanic rocks formation. Fluid
saturated sedimentary slab from the subduction zone can
be considered as the more radiogenic end-member. Thus,
the relatively radiogenic Os signatures for Kudriavy vol- (averaging 0.6 ppb) for fumarolic gas condensates imply
canic rocks could be explained by significant Os and Re that a significant part of Re and Os was remobilised from
input (up to 50 %) from slab-derived fluids and melts con- depleted MORB mantle (Table 1). Involvement of a Re-
taminated by more radiogenic (0.29 to 0.64 for 187Os/188Os) rich component is evident from high Re concentrations
organic-rich sediments from the subducting Pacific plate in gas condensates, ranging from 7 to 200 ppb. But this
(Peucker-Ehrenbrink et al. 1995) (Fig. 2) . radiogenic, Re-rich and Os-poor component, possibly
Previous studies of fumarolic gases using H, He and C organic-rich subducted sediments (up to 20%) and vol-
isotopic systematics (Taran et al. 1995; Fischer et al. 1998) canic rocks (up to 20%), does not significantly shift the
showed that the subducted slab and mantle wedge were the Os isotopic composition of fumarolic products.
main sources for fluids in the Kudriavy volcanic system. Rheniite is highly radiogenic due to its high Re content
The Re-Os contents and isotope composition of gas con- (74.5 wt.% Re). Repeated analyses of two rheniite samples
densates vary significantly depending on the method of provide model ages of 7911 yr, which agree with the known
analytical sampling. Fractions = 0.2 mm (Fraction 1) are 100 year period of fumarolic activity. The initial 187Os/188Os
characterised by high Re and Os contents (average values ratio is not well defined (0.320.15), but appears to be higher
are 85 ppb and 0.6 ppb, respectively) and unradiogenic 187Os/ than ratios associated with gas condensates. The Pb-Bi
188Os compositions (0.122 to 0.152). In contrast, bulk con- sulphosalts have much lower Re contents (~250 ppb) and
densates (Fraction 2) are characterised by lower Re and Os relatively unradiogenic osmium isotopic compositions
concentrations (~0.4 ppb Re and 2-37 ppt Os) and slightly (0.125 to 0.176), similar to that of gas condensates.
more radiogenic Os isotope compositions (0.12 to 0.45),
similar to those of the hosting volcanic rocks. This dif- 5 Conditions of Re enrichment
ference can be explained by chemical procedure (incom-
plete digestion of Fraction 2 due to the absorption of Re Experimental work has shown that rhenium can be mo-
and Os complexes by coarse sulphur particles coagulated bilized by high-temperature, saline, and sulphide-poor
during acid decomposition), or by the presence of rocks hydrothermal solutions (Xiong and Wood 1999). Accord-
particles in a Fraction 2. Thus, the data obtained for Frac- ing to these experimental data, Re concentrations at 510C
tion 1 can be considered as representative of bulk gas in 0.5 m KCl solution are about 8 x 10-6moles/kg H2O (~1
condensate composition. The relatively unradiogenic ppm). Thus, Re could be easily remobilised from the host
187Os/188Os ratios (0.122 to 0.152) and high Os contents rocks and sediments by high temperature (700-940C)

Chapter 7-31 Sources of rhenium and osmium enrichment in fumaroles, sulphide sublimates and volcanic rocks from the Kudriavy volcano 843

fumarolic gases with 0.5 mol% of Cl (Taran et al. 1995). Lassiter JC (2003) Rhenium volatility in subaeral lavas: constraints
On the other hand, Re and Os enrichment in fumarolic from subaeral and submarine portions of the HSDP-2 Mauna
Kea drillcore. Earth Planet. Sci. Lett. 214: 311-325
gases could depend on melt-vapor fractionation processes.
Peucker-Ehrenbrink B, Ravizza G, Hofmann AW (1995) The marine
Deposition of Re-bearing sulphide could be induced by 187Os/188Os record of the past 80 million years. Earth Planet Sci
subaerial conditions, which exclude the possibility for Lett 130: 155-167
dissolution of Re-complexes in water. Roy-Barman M, Allgre CJ (1994) 187Os/186Os ratios of mid-ocean
ridge basalts and abyssal peridotites. Geochim Cosmochim Acta
58: 5043-5054
6 Importance for Re resources Stein H, Scherstn A, Hannah J, Markey R (2003) Sub-grain scale
decoupling of Re and 187Os and assessment of laser ablation ICP-
Until now, molybdenite-bearing Cu-porphyry deposits MS spot dating in molybdenite Geochim Cosmochim Acta 67:
have been the primary source of Re. High Re concentra- 3673-3686
tions in molybdenite from Cu-porphyry environments Sun W, Benett VC, Eggins S, Kamenetsky VS, Arculus R (2003) En-
have been attributed to mantle involvement in a subduc- hanced mantle-to-crust rhenium transfer in undegassed arc
magmas. Nature 422: 294-297
tion setting (Stein et al. 2003; Zimmerman et al. 2003) Taran YuA, Hedenquist JW, Korzhinsky MA, Tkachenko SI,
The occurrence of high levels of rhenium in gases and Shmulovich KI (1995) Geochemistry of magmatic gases from
sulphides from the Kudriavy volcano may represent a new Kudriavy volcano, Iturup, Kuril Islands. Geochim Cosmochim
and unexplored resource for Re. The Re resources of Acta 59: 1749-1761
Kudriavy volcano are still under considerations. Von Huene R, Scholl DW (1991) Observations at convergent mar-
gins concerning sediment subduction, subduction erosion, and
the growth of continental crust. Reviews in Geophysics 29: 279-
References 316
Widom E, Kepezhinskas P, Defant M (2003) The nature of metaso-
Bailey JC (1993) Geochemical history of sediments in the northwest- matism in the sub-arc mantle wedge: evidence from Re-Os iso-
ern Pacific Ocean. Geochem. J 27: 71-92 topes in Kamchatka peridotite xenoliths. Chemical Geology 196:
Birk JL, Roy-Barman M, Capmas F (1997) Re-Os isotopic measure- 283-306
ments at the femtomole level in natural samples. Geostandards Xiong Y, Wood SA (1999) Experimental determination of the solu-
newsletter 20: 19-27 bility of ReO2 and the dominant oxidation state of rhenium in
Fischer TP, Giggenbach WF, Sano Y, Williams SN (1998) Fluxes and hydrothermal solutions. Chem Geol 158: 245-256
sources of volatiles discharged from Kudriavy, a subduction zone Zimmerman A, Stein H, Markey R, Fanger L, Heinrich C, von Quadt
volcano, Kurile Islands. Earth Planet Sci Lett 160: 81-96 A, Peytcheva I (2003) Re-Os ages for the Elatsite Cu-Au deposit,
Korzhinsky MA, Tkachenko SI, Shmulovich KI, Taran YA, Steinberg Srednogorie zone, Bulgaria: in Eliopoulos, D.G. et al. (eds), Min-
GS (1994) Discovery of a pure rhenium mineral at Kudriavy Vol- eral Exploration and Sustainable Development, Millpress,
cano. Nature 369: 51-52 Rotterdam: 1253-1256

Chapter 7-32 7-32

Muluozhai REE deposit in Sichuan Province, China:

Stable isotope data and their implications on the
dynamics of mineralization
Shihong Tian, Zengqian Hou, Tiping Ding
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China, and Key Laboratory on
Isotope Geology, Ministry of Land and Resources, Beijing 100037, China
Yuling Xie
Civil & Environmental Engineering School, Beijing University of Science and Technology, Beijing 100083, China
Zhongxin Yuan, Ge Bai, Tianren Zou
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China

Abstract. The Muluozhai REE deposit, located about 60 km to the and is situated at the eastern margin of the Tibetan Pla-
southwest of the Mianning County, Sichuan Province, is the third teau, it is necessary to understand regional metallogenic
largest light REE deposit in Sichuan. The Muluozhai REE deposit is
rules and the collision between the Indian plate and the
tectonically located on the northern Jinpingshan Mountains, a Ceno-
zoic intracontinental orogenic belt in southwestern China. The au- Eurasia plate. In this paper, we present systematic studies
thors analyzed the essential ores from two tunnels for their carbon, on the characteristics of S, C, O, and H isotopes of the
hydrogen, oxygen, and sulfur isotopic compositions of the miner- ores to ascertain the sources of the mineralizing fluids
alizing fluid. The 13CV-PDB values of fluid from fluid inclusions of the and the dynamic process related to the mineralization.
quartz and fluorite vary from - 2.5 to - 9.0 per mil, which show char-
acteristics of mantle-derived carbon. The DV-SMOW values of fluid
from fluid inclusions of the calcite, quartz, fluorite, and bastnaesite 2 Geologic setting and REE mineralization
range from - 63 to - 87 per mil, which are characteristics of mantle-
derived hydrogen. The 34SV-CDT values of barite and galena vary in The Muluozhai REE deposit is tectonically located on the
a narrow range of + 0.1 to + 2.2 per mil and - 8.6 to - 9.3 per mil, northwest margin of the Panxi (Panzhihua-Xichang) rift
respectively, showing the isotopic characteristics of mantle-derived zone at the western side of the Yangtze Platform (Fig. 1).
sulfur. The 13CV-PDB values and the 18OV-SMOW values of calcite range
from - 6.6 to - 6.8 per mil and from + 8.4 to + 9.1 per mil, respec-
According to Luo et al. (1985), the Panxi rift zone formed
tively, which are fallen into the range of the primary carbonatites, on the Yangtze platform starting in the early Paleozoic.
showing the carbon and oxygen in the ores of the Muluozhai ore Deposition continued during the late Paleozoic into the
veins were mainly derived from depths. The stable isotopic data Mesozoic and ended in the early Cenozoic with the be-
suggest a mantle source for the rare earth elements mineralization ginning of the Himalayan Orogeny. The Panxi rift was
and a dynamic process involving mantle materials and tectonics.
bordered by the Ganluo-Xiaojiang Fault to the east and
Keywords. Rare earth element deposit, stable isotopes, mantle source, Qinghe-Chenghai Fault to the west. It extends north-south
mineralization dynamics, Muluozhai in Sichuan Province for over 300 km and reaches a width of about 100 km.
Large amounts of alkali-rich ultramafic, basic, and inter-
mediate-acid rocks with a great deal of REE were intruded
1 Introduction or erupted in the Panxi rift zone and its neighboring ar-
eas. In the region, the Devonian, Permian, Triassic and
The Muluozhai REE deposit (2822 N Lat. and 10150 E Jurassic strata are distributed scatteredly because of the
Long.), located about 60 km to the southwest of the destruction of the developed igneous rocks. The latter
Mianning County, Sichuan Province, is the third largest are distributed extensively in the region and the main
light REE deposit in Sichuan. Along with other REE de- rocks are Indosinian quartz diorite, granite, and
posits in the Panzhihua-Xichang area, it forms one of the Yanshanian alkali-feldspar granite.
three major REE deposit producing regions in China. Al- On the basis of orebody distribution, three kinds of
though known since the 1960s, it has not attracted nearly ores have been identified: (i) massive fluorite-bastnaesite,
as much interest as the Maoniuping and the Daluchao (ii) impregnated, and (iii) banded. The ore minerals are
REE-deposits in the Panxi REE ore belt, and, therefore, mainly bastnaesite, whereas the gangue minerals include
only little research has been performed concerning its fluorite, barite, calcite, feldspar, quartz, mica and aegirine-
geological characteristics, geochemistry, isotopic augite. The textures and structures are allotriomorphic
geochemistry, mineralogy, and fluid inclusions. Because inequigranular, tabular, subhedral, and massive, banded,
it is an important part of the Panxi REE ore-forming belt respectively. The wall-rock alteration is characterized by

846 Shihong Tian Zengqian Hou Tiping Ding Yuling Xie Zhongxin Yuan Ge Bai Tianren Zou

clusions in quartz and fluorite was released by the de-

crepitation method and collected in sample tube at liq-
uid N2 temperature. All SO2, CO2, and H2 were analyzed
using a Finnigan MAT 251 mass spectrometer at the Key
Laboratory on Isotope Geology, Ministry of Land and
Resources. Analytical reproducibility in this study is
0.2 per mil for C, O, and S isotopes, and 2 per mil for H

3.2 Results

Sulfur isotope analyses have been done on 3 barite and 3

galena samples. The 34SV-CDT values vary in a narrow
range of + 0.1 to + 2.2 per mil with an average of + 0.8
per mil for the barite, and - 8.6 to - 9.3 per mil with an
average of - 9.0 per mil for the galena, respectively. Ac-
cording to the theory by Ohmoto (1972), the 34SV-CDT
values of ore-forming fluid in the Muluozhai deposit vary
from - 9.0 to + 0.8. On account of barite more than ga-
lena, the 34SV-CDT values of ore-forming fluid is more than
0 per mil, but less than + 2.2 per mil, which shows the
isotopic characteristics of mantle-derived sulfur (Lu 1986).
Five calcite samples were analyzed for their carbon and
oxygen isotopes. The 13CV-PDB values and the 18OV-SMOW
values range from - 6.6 to - 6.8 per mil with an average of
- 6.7 per mil and from + 8.4 to + 9.1 per mil with an
average of + 8.7 per mil, respectively. These values fall
into the range of primary carbonatites, showing that
carbon and oxygen in the ores of the Muluozhai deposit
were mainly derived from the mantle (Keller and Hoefs
contact metamorphism and hydrothermal alteration, 1995).
which includes sericitization, pyritization, baritization, and Carbon isotope analyses of fluid from fluid inclusions
carbonatization. were made on 2 quartz and 5 fluorite samples. The 13CV-
PDB values range from - 2.5 to - 3.6 per mil for quartz with
3 Stable isotope analysis an average of - 3.1 per mil and - 5.5 to - 9.0 per mil for
fluorite with an average of - 7.1 per mil. Quartz and fluo-
3.1 Experiments rite samples show narrow ranges in 13CV-PDB values, which
are close to the estimated value of mantle carbon (Pineau
Sulfur, carbon, oxygen, and hydrogen isotopes of mineral and Methez 1990).
separates from the Muluozhai deposit have been analyzed. Hydrogen isotope analyses of fluid from fluid inclu-
SO2 was prepared from the samples for sulfur isotope sions have been done on 2 quartz, 5 fluorite, 5 calcite, and
analysis with the method of Robinson and Kusakabe 5 bastnaesite samples. The DV-SMOW values range from -
(1975). For oxygen and carbon isotope analysis, calcite 69 to - 76 per mil for the quartz with an average of - 73
was reacted with phosphoric acid at 25 (McCrea 1950) per mil, - 73 to - 87 per mil for the fluorite with an aver-
to release CO2. The 18OV-PDB values of calcite samples age of - 81 per mil, - 70 to - 82 per mil for the calcite with
were directly obtained from the 18O values of their CO2 an average of - 76, and - 63 to - 86 per mil for the bastnaesite
against the CO2 of PDB. For converting the 18OV-PDB to with an average of - 71 per mil. All minerals show a nar-
18OV-SMOW, the equation by Friedman and ONeil (1977) row range in DV-SMOW values that fall close to the esti-
was used, 18OV-SMOW = 1.03086 18OV-PDB + 30.86. For mated value (-60 to -80 per mil) of mantle hydrogen (Mao
analysis of hydrogen isotopes, the water in fluid inclu- and Li 2004).
sion was released by the decrepitation method. Then, the
water was reacted with Zn at 400 to produce H2 (Coleman 4 Discussion and conclusions
et al. 1982), which was collected in a sample tube with
activated charcoal at liquid N2 temperature. For the analy- REE mineralizations in rift belts are characterized by
sis of carbon isotopes from the fluid, the CO2 in fluid in- multiphase and multistage processes. Mineralizing types

Chapter 7-32 Muluozhai REE deposit in Sichuan Province, China: Stable isotope data and their implications on the dynamics of mineralization 847

vary through time. Correspondingly, geological, miner- Professor Chen Wenming at the Institute of Mineral Re-
alogical, petrological, and geochemical features differ also. sources, CAGS, for their constructive suggestion. We also
For example, in the Liaodong rift belt, REE mineraliza- thank Professor Wan Defang, Senior Engineer Li Jincheng,
tions in pegmatites and migmatites formed during an early Senior Engineer Bai Ruimei, and Engineer Luo Xurong
stage of rift formation, REE-Fe-rich formation of meta- at the Key Laboratory on Isotope Geology, Ministry of
morphism volcano-sedimentary rocks during the mid- Land and Resources, for their performance of analyses.
stage of rift formation, and REE-U-rich aegirine and
aegirine-nepheline syenites are related to the postrift evo- References
lution (Chen 1984). In the Bayan Obo rift belt, Inner
Mongolia, the famous Bayan Obo Fe-Nb-REE ore deposit Bai G, Yuan ZX, Wu CY (1996) Geotectonic setting of the Bayan Obo
formed during the Proterozoic, in the evolved rift (Bai deposit, Inner Mongolia. Acta Geosci Sinica 17 (supl): 1-8 (in
Chinese with English abstract)
1996) and REE-rich hydrothermal vein and skarn depos- Burchfiel BC, Chen, ZL, Liu, YP, Royden LN (1995) Tectonics of the
its formed during the Caledonian and Hercynian. These Longmen Shan and adjacent regions, central China. Intern Geol
late mineralizations reworked the Proterozoic mineral- Rev 37: 661-735
izations (Yuan et al. 1992). The REE mineralizations of Chen RD (1984) A Proterozoic rift basin-Liaodong rift. Liaoding
the Panxi rift belt are also characterized by multiphase Dizhi 2: 125-133 (in Chinese with English abstract)
Coleman ML, Sheppard TJ, Durham JJ, Rouse JE, Moore GR (1982)
and multistage processes.
Reduction of water with zinc for hydrogen isotope analysis. Anal
REE-rich nordmarkites, alkali granites, syenite porphy- Chem 54: 993-995
ries, and albitites. formed during the Hercynian-Indosinian Friedman I, ONeil JR (1977) Compilation of stable isotope frac-
epoch in the developed stage of the Panxi rift, which were tionation fraction factors of geochemical interest. In: Fleischer
mostly associated with alkaline and basic bedded rocks in M (ed) Data of geochemistry. Sixth Edition. Geol Surv Profl Pap
the region. Affected by the collision between the Indian plate US P. 117
Keller J, Hoefs J (1995) Stable isotope characteristics of recent
and the Eurasia plate, the rift closed during the Himalayan natrocarbonatites from Oldoinyo Lengai. In: Bell K (ed)
epoch and changed into an intracontinental orogenic belt, Carbonatites volcanism: Oldoinyo Lengai and Petrogenesis of
i.e. the Jinpingshan Orogen (Fig. 1), which was formed dur- Natrocarbonatites. LAVCEI Proceeding in Volcanology. LAVCEI,
ing Cenozoic and became the eastern margin of the Ti- 113-123
betan Plateau (Burchfiel et al. 1995). Lu CW (1986) Stable Isotopic geochemistry. Chengdu Univ Technol,
Publ House, Chengdu, pp. 40-43 (in Chinese)
The Muluozhai REE deposit is located in the transi- Luo YN (1985) Panzhihua-Xichang paleo-rift zone, Southwest of
tional zone between the Panxi rift and the Longmenshan- Sichuan. In: Zhang YX (ed) Contribution to Panzhihua-Xichang
Jinpingshan orogenic zone, where the Yangtze plate pen- rift, China. Geol Publ House, Beijing, pp. 1-25 (in Chinese with
etrated as a wedge into the crust at Longmenshan, result- English abstract)
ing in a Moho dislocation, thereby inducing partial melt- Mao JW, Li XF (2004) Mantle-derived fluids in relation to ore-form-
ing and oil-forming process. Mineral Deposits 23: 520-532 (in
ing of the mantle materials (Xu et al. 1999). This tectonic
Chinese with English abstract)
environment may have caused intensive faulting and McCrea JM (1950) On the isotope chemistry of carbonates and a
magmatism, possible metamorphic dehydration and up- paleotemperature scale. J Chem Phys 18: 849-857
welling of mantle fluids along the deep faults in the west- Ohmoto H (1972) Systematics of sulfur and carbon isotopes in hy-
ern margin of the Yangtze. The fluids that were respon- drothermal ore deposits. Econ Geol 67: 551-578
Pineau F, Methez EA (1990) Carbon isotopes in xenoliths from the
sible for the formation of the Muluozhai REE deposit have
Hualalai volcano, Hawaii, and the generation of isotopic variabil-
S, C, O, and H isotopes similar to mantle or mantle-de- ity. Geochim Cosmochim Acta 54: 2117-2127
rived rocks. Robinson BW, Kusakabe M (1975) Quantitative preparation of sul-
phur dioxide for 34S/32S analyses from sulphides by combustion
Acknowledgements with cuprous oxide. Anal Chem 47: 1179
Wang DH, Yang JM, Yan SH, Xu J, Chen YC, Pu GP, Luo YN (2001) A
special orogenic-type rare earth element deposit in Maoniuping,
This work was supported by grants from the State Sci- Sichuan, China: Geology and Geochemistry. Resource Geol 15:
ence and Technology Commission (contract No. 177-188
2002CG412610 and G1999043211) and China Natural Sci- Xu ZQ, Yang JS, Jiang M, et al., (1999) Continental subduction and
ences Foundation (Grant No. 40425014). We thank Luo uplifting of the orogenic belts at the margin of the Qinghai-Ti-
bet Plateau. Earth Sci Front 6: 139-150 (in Chinese with English
Yaonan of Sichuan Bureau of Geology and Mineral Re-
sources and Pu Guangping, Yu Bo and other engineers of Yuan ZX, Bai G, Wu CY, Zhang ZQ, Ye XJ (1992) Geological features
the No. 109 Geological Team during our field investiga- and genesis of the Bayan Obo REE ore deposit, Inner Mongolia,
tion. We are grateful to Professor Wang Denghong and China. Appl Geochem 7: 429-442

Chapter 7-33 7-33

Stable isotope composition of the Dalucao rare earth

deposit in western Sichuan
Wan Defang, Tian Sihong
Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China
Luo Mei
Chengdu University of Technology, Chengdu 610059, Sichun China
Jiang Shaoyong
Department of Earth Sciences, Nanjing University, Nanjing 210093, Jiangsu, China

Abstract. Ore-forming solutions and the origin of mineralizing ma- ing, and emplacement of the source rocks under the acti-
terial in the Dalucao rare earth deposit were studied by means of H, vation of mantle plume and tectonic mobilization in the
O, C, and Si isotope analyses. The 13C of the bastnasite range nar-
Himalaya period.
rowly from -8.1 to-8.0, while the D values range from -89
to -79. The quartz 30Si of the orebody is -0.3, and the D and
18O of the quartz-fluid inclusion range from -87 to +6.0, re- 2 Geological survey of Dalucao rare earth deposit
spectively. The D and 18O values of the fluorite-fluid inclusion in
the ore body are -99 to -11.6, respectively. The study shows Dalucao rare earth ore deposit is located in the middle
that the compositions of hydrogen and oxygen isotopes in ore-
part of the Panxi rift belt, which is a famous epicontinen-
forming fluid of Dalucao rare earth deposit lie in the region be-
tween magmatic water and meteoric water. Therefore the ore-form- tal rift in the western border of the Yangtze platform. The
ing fluid was mixed from magmatic and meteoric water. The car- distributive strata of the deposit are mainly Previndean
bon isotopic features suggest that carbon of the bastnasite was system, Vindean-Cambrian system and Jurassic system
from the mantle, carbon of fluorite-fluid inclusions in the ore body (Fig. 1). Previndean strata are mainly composed of Yanbian
was from a mixture carbon source, and carbon of quartz-fluid in- formation strata of Huili group, Vindean-Cambrian strata
clusions was from the mantle.
are consisted of Guanyinyan formation and Dengying
Keywords. Stable isotope composition, quartz-fluid inclusion, fluo- formation, and Jurassic system is made up of Baiguowan
rite-fluid inclusion, rare earth deposit, Dalucao group and Yimen formation.
The deposit is situated in part between Shuenhe
syncline and Xincun syncline, located at intersections
1 Introduction with the Dalucao (F1), Nanmuhe (F7)and Xincun syn-
cline, located at intersections with the Dalucao (F1),
The Dalucao rare earth ore deposit, one of the largest Nanmuhe (F7) and Zhangmenzha (F6) faults. The re-
rare earth ore deposits of China, is located 20 km south- gional structural framework was mainly made up of
west from Dechang county town, Sichuan Province. It cov- SN-striking, NW-striking and NE-striking faults. The
ers an area of about 3 km2. Tectonically, the deposit is ore body is cut through by Dalucao fault (F1), and af-
situated in the middle part of the Panxi rift belt, a fa- fected by the fault.
mous epicontinental rift in the western border of the Outcropping magmatic rocks in the mineral dis-
Yangtze platform. trict include quartz diorites of the Jinning epoch, al-
Rare earth ore bodies of Dalucao rare earth ore de- kali granites of the Indo-Chinese epoch, aegirine-aug-
posit are mainly hosted in the aegirine-augite syenite, ite syenites, and syenites of the Himalaya epoch. The
bordering to quartz diorite, and are related to hydrother- Daluxiang quartz diorite (853Ma) is emplaced into the
mal activations associated with the quart diorite. Geo- Presinian Huili group and is covered by the Jurassic
logical and geochemical features demonstrate that the Baiguowan formation. Rare earth ore bodies are hosted
deposit is a hydrothermal deposit that formed at medium in the 64.9 Ma old aegirine-augite syenite, which is
to low temperature. Based on the C, H, O, and Si isotopes emplaced in Daluxiang quartz diorite. The major ore
and in the context of the regional geology and tectonics body is lens-shaped and shows net-veining and min-
of the Panxi rift, it is further suggested that the source eralization of structural fissures in the aegirine-aug-
rocks of the ore-bearing aegirine-augite syenite are prob- ite syenite. The major mineral assemblage in the ore
ably early-formed alkali-rich rocks of the Hercynian ep- is made up of bastnasite, celestobarite, barytocelestite,
och that are present at depth. The ore-bearing aegirine- aegirine-augite, fluorite, calcite, quartz, mica, minor
augite syenite was mostly formed by remelting, ascend- sulphide, and rare earth titanite.

850 Wan Defang Tian Sihong Luo Mei Jiang Shaoyong

3 Geochemistry of stable isotopes The 18O and 30Si of quartz in the ore body are re-
spectively +10.1 and -0.3, the 18OH2O of fluid inclu-
3.1 Signature of silicon and oxygen isotopic compositions sions in quartz is 6.0, and bastnasite 18O is from
+19.2 to +19.3.
We measured the silicon and oxygen isotope composi-
tions of many wall rock and quartz samples from the rare 3.2 Signature of H, O and C isotopic compositions
earth ore body in order to elucidate the origin and the
evolution of ore-forming fluid in the deposit. Table 1 shows Table 2 displays H, O, and C isotope compositions of min-
the Si and O isotope compositions of the deposit. Quartz eral-hosted fluid inclusions in the REE deposit.
18O in quartz diorite has values around 9.1 to 9.3, The quartz D in quartz diorite is -96 and the 13CPDB
and the quartz diorite 18O is +7.1. of its CO2 is -11.9.
It is suggested that the quartz diorite belongs the grani- D and 18OH2O of quartz in the ore body are respec-
toid (Talor 1968). The quartz 30Si in quartz diorite is tively -87 and +6.0, the fluite inclusion 13CPDB of
0.0, hornblende -0.2 and the quartz diorite 30Si quartz in the ore body is -8.4, which show the H, C and
0.1, which is close to the granitoid average. O isotope compositions of the magmatic water.

Chapter 7-33 Stable isotope composition of the Dalucao rare earth deposit in western Sichuan 851

Fluorite D of in the ore body range from -119 to - fluorites in the ore body was from a mixed carbon source,
83, averaging around -99. Its 18OH2O range from - and the fluid inclusion carbon of quartz was from mantle.
13.6 to -9.6, with an average of -11.6, indicating The rare earth partitioning of the bastnasite, the ore and
that the ore-forming fluid is a mixed fluid of the mag- the alkali complex is all Ce>La>Nd, and Ce-rich, showing
matic water and the meteoric water. the mantle features of the metallogenetic material in the rare
The fluid inclusion D of the bastnasite range from - earth deposit. The 134Nd/144Nd of the rare earth deposit range
89 to -79, showing that the ore-forming fluid is a from 0.512297 to 0.512313, indicating that the rare earth
magmatic water. The bastnasite 13CPDB is about -8.0, elements were mainly derived from the upper mantle.
indicating the characteristic of mantle carbon.
4 Conclusions
3.3 Derivation of the metallogenetic material
The rare earth elements of Dalucao deposit are mainly from
In the graph of 18O vs D for ore-forming fluids (Fig. 2), the mantle. Si may also be from a deep magmatic source.
it is evident that the fluid-inclusion water in quartz be- The ore-forming fluid was a mixture fluid of the magmatic
long to magmatic water, and the fluid-inclusion water in water and the meteoric water. The carbon of bastnasite was
fluorite belong to meteoric water, indicating that the ore- deduced from the mantle and the carbon of the ore-form-
forming fluid was a mixed fluid of the magmatic water ing fluid in bastnasites was from a mixture carbon source
and the meteoric water. area. It is further suggested that the source rocks of the ore-
According to the Si isotope compositions of the ore bearing aegirine-augite syenite are probably early-formed
body quartz and whole rock, it can help us infer that the alkali rich rocks in Triassic period or Carboniferous-Per-
Si may be from a deep magmatic source area. mian period. The ore-bearing aegirine-augite syenite was
The carbon isotopic features suggest that carbon of the mostly formed by remelting, ascending and emplacement
bastnasite was from mantle, the fluid inclusion carbon of of the source rocks under the activation of mantle plume

852 Wan Defang Tian Sihong Luo Mei Jiang Shaoyong


Clayton RN, ONeil JR, Mayeda TK (1972) Oxygen isotope exchange

between quartz and water. J Geophys Res 77: 3057-3059
Ding T (1994) Silicon isotope geochemistry. Geol Pub House, Beijing,
Matsuhisa Y, Goldsmith JR, Clayton RN (1979) Oxygen isotopic frac-
tionation in the systemquartz-albite-water. Geochim. Cosmochim
Acta 43: 1131-1140.
ONeil JR, Taylor HP (1967) The oxygen isotope and cation exchange
chemistry of feldspars. Am Mineral 52: 1414-1418
Pu G (2001) REE mineralization evolution in Panxi rift and basic
metallogenic feature in Himalaya age. Study on the endogenetic
minerallization in Hymalaya age, China. China Seismol Press,
Beijing, 104-113 (in Chinese)
Shen W (1987) Geology of stable isotope. Atom Ener Pub House,
Beijing: 123-125 (in Chinese)
Tang L, Yang D, Liu S, Wang Z, Ye X, Chen Z (1985) The double struc-
tural feature of Panxi rift. The collected works of Panxi rift, China.
and tectonic mobilization in the Tertiary-Quaternary pe- Geol Pub House Beijing: 72-84 (in Chinese)
Taylor HP (1968) 18O/16O ratios coexisting minerals in glancophane-
riod. C, H, O, and Si isotope compositions of the deposit bearing metamorphic rock: Bull Geol Soc Am 79: 1727-1756
indicate that Dalucao rare earth deposit was a hydrother- Yuan Z, Shi Z, Bai G, Wu C, Li X (1995) Mouniuping REE deposit,
mal vein type deposit of the rich light rare earth element, Mianning County, Sichuan Province. China Seismol Press, Beijing:
which was formed in the Tertiary-Quaternary period. 103-105 (in Chinese)

Chapter 7-34 7-34

Preliminary study on the Chinese continental

mineralization system
Wang Denghong
Institute of Mineral Resources, CAGS, Beijing, 100037, China
Chen Yuchuan
Chinese Academy of Geological Sciences (CAGS), Beijing, 100037, China

Abstract. China is enriched in mineral resources. How to systemati- deposits located in the present continental crust of China
cally deduce the regularity of mineralization in order to serve for pros- and their genetically related geological factors. All min-
pecting is the main purpose of this paper. The Chinese continental
eral deposits located in the present continental crust of
mineralization system (CCMS) can be referred to as the whole group
of mineral deposits located in the present continent of China and China formed during the history of continent evolution.
their genetically related geological factors. The CCMS consists of 214 The concept of CCMS contrasts with the term Chinese
minerogenic series of 11 geological periods from Early Archean to oceanic mineralization system (COMS), both the CCMS
Cenozoic, including at least 978 patterns of representative mineral and the COMS compose the Chinese Mineralization Sys-
deposits.The CCMS is the final result of mineralization formed through
tem (CMS), while the CMS is part of the global mineral-
the whole evolution history of Chinese continental crust.
ization system (GMS). The global mineralization system
Keywords. Chinese continental mineralization system, minerogenic can be divided into a series of sub-systems geographi-
series, metallogenic prognosis, evolution regularity cally. The GMS can be divided into sub-systems accord-
ing to different classification systems, such as spatial sub-
1 Introduction systems, temporal sub-systems (Mesozoic mineralization
system, Cenozoic mineralization system and so on), and
After a long history of mining (at least 3000 years), espe- genetically sub-systems (magmatic mineralization system,
cially large-scale geological exploration conducted since the sedimentary mineralization system and metamorphic
founding of the Peoples Republic of China (1949), 171 kinds mineralization system). Thus, the CCMS is in fact a com-
of mineral resources have been discovered up to present. plex big system composed of different levels of sub-sys-
Among these, 156 commodities have explored reserves, in- tems, which related to each other structurally, regularly,
cluding 9 types of energy resource, 54 metallic minerals, 90 inevitably and recognizably. By the study of CCMS, the
industrial minerals, plus groundwater, mineral water, and wholly, knowledge about mineralization can be concluded
carbon dioxide gas. The total value of potential reserves systematically and sequentially, instead of individually,
places China third in the world. Various deposits are among fragmentally or randomly. In this paper, we will pay more
the richest in the world, including rare earths, W, Sn, Sb, attention to the CCMS, because its forming history shows
Mo, Bi, Be, coal, magnesite, barite, fluorite, talc, graphite, an important aspect of the continental evolution history
bentonite, fireclay, asbestos, gypsum, wollastonite, diatoma- of China and provides valuable clues and indispensable
ceous earth, and building stone. On the other hand, the coun- examples for the understanding of global mineralization
try is lacking oil, high-grade iron, Cr, Mn, Cu, PGE, potash system. The relationships among different deposits and
salt, and diamond. By now, about 200,000 localities of ore the relationships between mineralization and its geological
deposits or mineral occurrences have been discovered. history and tectonic setting are very important for the
Among these, 20,000 ore deposits have been investigated in study of CCMS.
detail, including 90 super giant deposits (Fig. 1; Chen 1999). The present Chinese continental crust includes rela-
However, little geological work has been done in the vast tive stable regions (paleo-plates or massif) and active belts
western territory of China and for depths greater than 500 (suture zones and/or collision belts). There are three large
m, suggesting a great potential for further discoveries. Ow- landmass or plates and four active belts in China (Fig. 2).
ing to the diversity of geological settings for mineraliza- The three main landmass include: (1) the North China
tion in China, there is great potential for ore prospecting landmass, which were formed after the Lvliang Movement
(Guo, 1987; Chen 1999). (1800 Ma) and includes a basement of Archean and/or
Lower Proterozoic metamorphic rocks; (2) the Tarlimu
2 Concept of Chinese continental mineralization landmass, formed after the Jinning Movement (1000 Ma)
system and related terms and has a basement of pre-Sinian metamorphic rocks;
(3) the Yangtze landmass, also formed after the Jinning
In this paper, we refer the Chinese continental mineral- Movement and its basement consists mainly of Protero-
ization system (CCMS) as the whole group of mineral zoic metamorphic rocks.

854 Wang Denghong Chen Yuchuan

The main active belts include: (1) the Tianshan- Xingan factors related to mineralization. In this paper, we apply
active belt, which consist with a series of fold belts and the terminology of minerogenic series to describe the
micro-plates and formed after the Caledonian- Hercynian CCMS in brief. The concept of CCMS is different from
movement; (2) the Kunlun-Qilianshan- Qinling active belt, that of minerogenic series presented by Cheng et al. (1979,
located between North China and South China and acti- 1983), which groups a series of mineral deposits related
vated at different epochs of Jinning, Caledonian, to each other genetically within a certain setting of geo-
Hercynian, Indo-Chinese, Yanshanian and Himalayan; (3) logical environment and within a certain stage of geo-
the Sichuan-Yunnan-Qinghai-Tibet active belt, which is logical history (Wang et al. 2002). However, because each
the most important active belt of Tethys- Himalayan in minerogenic series bases on the four most important fac-
the southwestern China; and (4) the western circum-Pa- tors (ore-forming age, tectonic setting, geologic event and
cific active belt, mainly overprinted on the Paleozoic and mineral assemblage and/or metal association), it is suit-
pre-Paleozoic tectonic belts in the eastern China and fea- able to apply the nomenclature of minerogenic series to
tured by strong activation of Mesozoic-Cenozoic volcan- construct the framework of CCMS. Generally speaking, we
ism-magmatism in East China, large-scale granitoid in- have divided the CCMS into different sub-systems accord-
trusion in the Nanling Region (Chen et al. 1989), NE-NNE- ing to geological time, and each sub-system consist of sec-
trending movement of blocks and rifting-magmatism in ondly sub-system of mineralization based on geological
the margin area of paleo-landmass. setting of the same geological time. Given a certain geo-
logical setting of a certain geological time, each minerogenic
3 Manifestation of the CCMS series refers to a certain group of metals and/or mineral
resources and/or energy resources related to a certain geo-
Generally speaking, the CCMS is a natural system con- logic process. Thus, minerogenic series is the preferred and
sisting of more than 200 thousand localities of ore de- integrant unit to make up of the CCMS. As a whole, the
posits or mineral occurrences. Obviously, it is difficult to CCMS consists of 214 minerogenic series of 11 geological
reveal the nature and complexity of CCMS by single de- periods from Early Archean to Cenozoic, including at least
posits, deposit types, mineralized belts, host rocks, or other 978 patterns of representative mineral deposits.

Chapter 7-34 Preliminary study on the Chinese continental mineralization system 855

4 Application significance of the CCMS of mineralization evolution can thus be deduced as a piece
of regularity for prospecting in the Sichuan basin and in
Because the CCMS can be build up by basic unit of other similar basins further.
minerogenic series, minerogenic series and their relation- In a broad sense, in a geosynclines environment such
ship with the evolution history of China continental crust as the Northern marginal belt of the North China Plat-
then become the most important aspect of our present form of Proterozoic, the Kunlun- Qilianshan-Qinling belt
research. As to each minerogenic series, all the mineral of Proterozoic-Paleozoic, the Altay tectonic belt of Paleo-
deposits are grouped together genetically rather than ran- zoic ,and the Tethys belt of Mesozoic, mineral deposits
domly. For example, the Triassic sedimento-minerogenic usually change from base metal deposits of VHMS-type
series of salt and coal deposits associated with marine formed at its early stage to rare metal deposits associated
carbonaceous rocks and paralic clastic rocks within the with magmatism at its folding or mountain building stage,
Sichuan basin, which is one of the above 214 minerogenic and to gold deposits controlled by regional structures at
series of the CCMS, consists of a series mineral deposits its late stage of structural adjustment within an actually
including the gypsum deposits (named as Nongle-type) continental setting. Such trend is partly similar to that of
and the celestite deposits (named as Chongqing-type) an Wilson cycle, but each minerogenic series is different
hosted within the Jialingjiang Formation (T12j), includ- from each other because of its unique geological time of
ing the polyhalite deposits (named as Quxian-type) within ore-forming, tectonic environment, special association of
the Jialingjiang Formation and the Leikoupo Formation mineral resources and genetic relationship with other
(T21l), including the halite deposits (named as Weixi-type) geologic process. Thus, the study of CCMS also can pro-
within the Leikoupo Formation, and including the coal vide a new approach for deduction the evolution history
deposits (named as Yongrong-type) within the Xujiahe of the Chinese continent crust.
Formation (T32-3x). The evolution trend of mineral de- In addition, the study of CCMS can contribute to
posits from salt to coal gradually is in accordance with metallogenic prognosis. For instance, the number of
the evolution history of the Sichuan basin changing from minerogenic series become more and more from Archean
oceanic to terrestrial facies at its waning stage. Such trend to Proterozoic to Paleozoic to Mesozoic and to Cenozoic.

856 Wang Denghong Chen Yuchuan

However, the number of Yanshanian minerogenic series 1. Archean sub-systems occurred in nucleus of the Chinese
shows a negative anomaly calculated on the same scale continental crust, dominated by BIF-type deposits,
of geological time, suggesting that there is still a good VHMS-type Fe, Cu, Pb, and Zn deposits, gold, graphite,
potential for prospecting Yanshanian minerogenic series and sillimanite deposits associated with metamorphic
in China. Recently, numerous new deposits of Mesozoic rocks;
age have been discovered both in northwestern China 2. Proterozoic sub-systems occurred in the marginal rift
(such as the Baishan Mo deposit in Xinjiang, dated setting peripheral to the Archean Chinese continental
at 2293Ma by a Re-Os isochron on molybdenite) shield, also dominated by Fe, Cu, Ni, REE, Pb, Zn de-
and in south-eastern China (such as the Taoxikeng wol- posits related to magmatism and sedimentary process
framite deposit in south Jiangxi, the Baolun gold deposit and Au, B, P, magnesite, graphite, andalusite, and sil-
in Hainan). Some important deposits discovered earlier limanite deposits related to metamorphic process, and
have also been proved to be of Mesozoic age by system- featured by massive Cu-Ni deposits related to mafic-
atic dating. For example, the famous rare metal deposit ultramafic rocks;
hosted within the No.3 pegmatite-vein in Keketuohai 3. Paleozoic sub-systems occurred in the main orogenic
mine, North Xinjiang, yields 40Ar/39Ar isochron ages rang- belts around the Proterozoic Chinese continent, fea-
ing from 177.9 Ma to 148 Ma (Wang et al. 2002). This tured by more complex association of elements and/
deposit has been recognized as a Hercynian deposit for or mineral resources than that of Proterozoic and by
nearly a century. typical plate tectonic environment;
4. Mesozoic-Cenozoic sub-systems occurred both around
5 Evolution of the CCMS and within the Paleozoic Chinese continent (Chen and
Wang 2001), featured by porphyry-type copper depos-
In general, the concept of CCMS can also be summa- its, skarn-type Fe-Cu deposits, granite-related W, Sn,
rized as the systematic combination of all the minerogenic Bi, Mo, REE, Rare metal, Pb, Zn, Sb, Ag, Au, Hg depos-
series that formed during the whole evolution history its, placer deposits, industrial mineral deposits formed
of the present continental crust in China. So, the CCMS within weathering crust, energy resources formed
can be divided into Archean, Proterozoic, Paleozoic, Me- within continental basins and so on, with banded iron
sozoic, and Cenozoic sub-systems of mineralization as formation and mafic-ultramafic massive Cu-Ni depos-
follows: its disappearing (Wang et al. 2000).

Chapter 7-35 7-35

Origin and evolution of Sn- and Cu-rich fluids in the

Dajing tin-polymetal deposit - evidence from
LA-ICP-MS analysis of individual fluid inclusions
Wang Lijuan, Wang Yuwang, Wang Jingbin
Beijing Institute of Geology for Mineral Resources, Beijing 100012, and Key Laboratory of Mineral Resources Institute of
Geology and Geophysics, Chinese Academy of Sciences, Beijing, 100029, China
Zhu Heping
Key Laboratory of Mineral Resources Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, 100029,
Gnther Detlef
ETH, Swiss Federal Institute of Technology, 8092 Zrich, Switzerland

Abstract. LA-ICP-MS analysis of the composition of individual fluid the reseach focused on fluids of high temperature and
inclusions indicate that shallow-originated Sn-rich fluids and deep- high salinity (Audeat et al. 1998; Gnther et al. 1998;
originated Cu-rich fluids mix at moderate to low temperature and
Gnther and Heinrich 1999). Because some fluid inclu-
low salinity, eventually resulting in the formation of Cu and Sn min-
eralization in the Dajing deposit. sions in fluorite contain chalcopyrite crystals, we made
LA-ICP-MS analysis of individual fluid inclusions on them
Keywords. Dajing, single inclusion, LA-ICP-MS anslysis, Cu-rich fluids, and take their compositions as representative of the Cu-
Sn-rich fluids rich fluids. Near the Dajing deposit, there is a tin deposit
named Huanggangliang, which belongs to the same tin-
The Dajing tin-polymetal deposit is located at the north- mineralization belt as the Dajing deposit. Both deposits
ern margin of North China Craton (Zhao and Zang 1997; have quite similar geological background (Li et al. 2001;
Wang et al. 2001). Quartz and fluorite are intergrown with Wang et al. 2001). We analyzed the fluid inclusions in
cassiterite and chalcopyrite. Chalcopyrite can be found quartz associated with cassiterite from the Dajing deposit
included in fluorite. Abundant fluid inclusions were found and primary fluid inclusions in fluorite from the
in fluorite. They are large with a gas/liquid ratio of 10%. Huanggangliang deposit with LA-ICP-MS analysis. The
Chalcopyrite crystals can be found in some fluid inclu-
sions. It is deduced that these fluid inclusions with chal-
copyrite crystals are trapped from Cu-rich fluids. Cas-
siterite can be found included in quartz. Fluid inclusions
in quartz are small in size and some are gas inclusions
with high gas/liquid ratios. Microthermometric data show
that the chalcopyrite-bearing fluid inclusions in chlorite have
low to moderate temperature and low to moderate salinity
whereas gas inclusions in quartz have moderate to high
temperature and low salinity. Therefore, it is inferred that
Cu-rich fluids are low to moderate temperature and low to
moderate salinity whereas the Sn-rich fluids are moderate
to high temperature and low salinity. The intergrowth of
Sn and Cu probably resulted from mixing of Cu-rich fluids
and Sn-rich fluids (Wang et al. 2000).
To further ascertain the origin and evolution of the
Sn-rich and Cu-rich fluids in the Dajing deposit, LA-ICP-
MS analyses on individual fluid inclusions with different
temperature, salinity, and occurrence in quartz and fluo-
rite from the Sn-Cu orebodies were carried out at Swiss
Federal Institue of Technology, Switzerland in February,
2004. LA-ICP-MS is the most advanced analysis method
for the composition of single fluid inclusions. Most of

858 Wang Lijuan Wang Yuwang Wang Jingbin Zhu Heping Gnther Detlef

results are quite similar. Therefore, the LA-ICP-MS ana- Cu-rich and Sn-rich fluids, we infer whether other fluid
lytic results of individual fluid inclusions in quartz asso- inclusions with different occurrence, temperature and
ciated with cassiterite from the Dajing deposit were taken salinity in quartz and fluorite belong to Cu-rich or Sn-
as representative of the Sn-rich fluids. rich fluids, and thereby trace the origin and evolution of
Tables 1 and 2 are the LA-ICP-MS analytic results of in- these fluids.
dividual Cu-rich and Sn-rich fluid inclusions, respectively. Cu-rich and Sn-rich fluid inclusions are listed in
Table 1 shows that the Cu-rich fluids have higher Cu Tables 3 and 4, respectively.
contents than Sn, have Sr contents one to several order of Figure 2 shows that both the Cu-rich and the Sn-rich
magnitude higher than Rb, and are relatively richer in fluids have a similar evolutionary trend from high to low
Na than K. Table 2 shows that the Sn-rich fluids have higher temperature and the two kinds of fluids probably mix at
Sn contents than Cu, have Rb contents one to several oder moderate temperature, resulting in mineralization.
of mragnitude higher than Sr, and are relatively richer in The Sr and Rb concentrations in the fluids are impor-
K than Na. Based on the compositions of representative tant indicators for the fluid source. According to Zhao et

Chapter 7-35 Origin and evolution of Sn- and Cu-rich fluids in the Dajing tin-polymetal deposit - evidence from LA-ICP-MS analysis of individual fluid inclusions 859

shallow-originated Sn-rich fluids and the deep-origi-

nated Cu-rich fluids mix at the stage of moderate to low
temperature and low salinity and result in the forma-
tion of Cu and Sn mineralization in the Dajing deposit.
4. To our knowledge, there have been no reports about
LA-ICP-MS analysis on individual fluid inclusions with
such low temperature, low salinity and small size as in
the Dajing deposit. The results demonstrated that the
LA-ICP-MS analysis of individual fluid inclusions has
practical applications in studying ore-forming pro-
cesses in polymetal ore deposits.


Audetat A, Gnther D, Heinrich CA (1998) Formation of a magmatic-

hydrothermal ore deposit: Insights with LA-ICP-MS analysis of
al (1997), Sr is enriched in the early stage of magma dif- fluid inclusions. Science 279: 2091-2094
ferentiation, whereas Rb is enriched in the late stage of Gnther D, Heinrich CA (1999) Enhanced sensitivity in laser abla-
tion-ICP mass spectrometry using helium-argon mixtures as
magma differentiation. Therefore, the ratio of Rb/Sr in- aerosol carrier. J Anal Atom Spectrom 14: 1363-1368
creases with magma differentiation, from an average of Gnther, D Audetat A, Frischknecht R, Heinrich CA (1998) Quanti-
about 0.5 at the early stage to above 10 at the late stage. tative analysis of major, minor and trace elements in fluid inclu-
The Cu-rich fluid in the Dajing deposit are highly en- sions using laser ablation-inductively couple plasma mass spec-
riched in Sr, indicating that the fluids are derived from trometry. J Anal Atom Spectrom 13: 263-270
Li JW, Shimazaki H, Yoshihide S (2001) Skarns and genesis of the
the deep, whereas the Sn-rich fluids are enriched in Rb,
Huanggang Fe-Sn deposit, Inner Mongolia, China Resource Geol
reflecting their derivation from the shallow. 51: 359-376
Based on the analyses, several conclusions can be Wang L, Wang J, Wang Y, Shimazaki H (2001) Ore-forming fluid and
reached: metallization of the Huanggangliang skarn Fe-Sn deposit, Inner
Mongolia. Sci China (Series D) 44: 735-747
1. The Cu-rich fluids have higher Cu contents than Sn, Wang L, Wang Y, Wang J, Jin X, Zhu H (2000) Metallogenetic fluid
study of tin and copper stage from Dajing deposit and its genetic
higher Sr contents than Rb, and are relatively rich in significance. Acta Petrol Sinica 16: 609-615 (in Chinese with En-
Na. The fluids are derived from a deep source and are glish abstract)
mainly trapped in fluorite. Wang YW, Wang JB, Uemoto T, Wang LJ (2001) Geology and miner-
2. The Sn-rich fluids have higher Sn contents than Cu, alization at Dajing tin-polymetallic ore deposit, Inner Mongolia,
higher Rb contents than Sr, and are relatively rich in K. China. Resource Geol 51: 307-320
Zhao Y, Zhang D (1997) Metallogeny and prospective evaluation of
The fluids are shallowly derived and mainly trapped copper-polymetallic deposits in the Da Hinggan Mountains and
in quartz. its adjecent regions Seismo Press, Beijing: 125-144
3. Both the Cu-rich and Sn-rich fluids have an evolution- Zhao Z (1997) The principle of trace elements geochemistry. Sci-
ary trend from high temperature to low temperature. The ence Press 1-153 (in Chinese)

Chapter 7-36 7-36

Lead and zinc-rich fluid inclusions in Broken Hill-type

deposits: Fractionates from sulphide-rich melts or
consequences of exotic fluid infiltration?
Patrick J. Williams, Dong Guoyi
School of Earth Sciences and 1Predictive Mineral Discovery CRC, James Cook University, Townsville 4811, Australia
Bruce Yardley
School of Earth Sciences, University of Leeds, Leeds LS2 9JT, UK
Thomas Ullrich
Geology Department, The Australian National University, 0200 Canberra, Australia
Chris Ryan
CSIRO Exploration and Mining, School of Geosciences, Monash University, Melbourne 3168, Australia
Terry Mernagh
Geoscience Australia, GPO Box 378, Canberra 2601, Australia

Abstract. High salinity fluid inclusions (Th = 200-550 C) from the New South Wales (2 pyroxene granulite) and Cannington
Broken Hill and Cannington Broken Hill-type ore deposits in Aus- in NW Queensland (upper amphibolite). Along with just
tralia have been analysed by PIXE and LA-ICP-MS. They have high
a few other ore deposits worldwide these are referred to
Pb (>1%) and Zn (>1000 ppm) and Pb/Zn ratios much higher than
those of the majority of crustal brines. Laser Raman studies reveal as Broken Hill-type (BHt) deposits which are defined
the presence of methane and PIXE images show that Pb and Zn are more by their high grade metamorphic settings than any
respectively concentrated in a Pb-K-Cl solid, and the liquid phase. consensus on their origin (e.g. Walters, 1998). It has re-
This indicates that the inclusions have very low total sulphur con- cently emerged that very Pb- and Zn-rich aqueous fluid
tents. The Pb/Zn ratios are similar to those of eutectic melts in the
inclusions occur in both large Australian BHt deposits
Gn-Sp-Po system whereas Pb/Fe ratios are variable and lower than
those of such melts. If these brines originated by fractionation from (Williams et al. 1999). In this paper we show that the chem-
synmetamorphic sulphide-rich melts, then they must been greatly istry of these brines is unlike any others previously known
modified prior to entrapment. An alternative origin involving late- and discuss the possible processes by which they may have
to post-metamorphic interaction of externally-derived brines with formed.
pre-existing sulphide accumulations should also be considered. In
either case, the unique brine chemistry would appear to relate to
the large amounts of sulphides in these systems.

Keywords. Lead, zinc, fluid inclusions, Broken Hill-type deposits, PIXE,


1 Introduction

Yardley et al. (2003) used compiled natural brine and fluid

inclusion analyses to show that concentrations of many
metals vary systematically with temperature and salinity.
This was taken to indicate that rock buffering is a power-
ful control on other major chemical influences of solu-
bility, such as pH, fO2 and sulphur abundance. Concen-
trations of elements such as Mn, Fe, Cu, Zn and Pb in
natural fluids can be predicted within about an order of
magnitude for known temperature and salinity and this
can be viewed as a limiting chemical framework for hy-
drothermal ore-forming processes
Large and very distinctive Pb-Zn-Ag ore deposits oc-
cur in partially melted metamorphic rocks at Broken Hill,

862 Patrick J. Williams Dong Guoyi Bruce Yardley Thomas Ullrich Chris Ryan Terry Mernagh

2 Petrography and microthermometry lyzed by LA-ICP-MS owing to a lack of suitable external

standards, and (c) able to image the distribution of ele-
A large variety of fluid inclusions have previously been ments between the phases present in the inclusions at
observed in the Broken Hill ore deposit but this have re- room temperature. Coupled with microthermometric and
ceived little attention in the literature (Wilkins 1977; Spry laser Raman gas phase data, the images throw light on
1978). The current study used rocks displaying evidence the likely abundance and speciation of the critical ele-
of hydrothermal modification during the retrograde meta- ment sulphur which can not be determined at normal
morphic history of the deposits. Sample 147001 from Bro- geological abundance by either microanalytical technique.
ken Hill is a partly recrystallized quartz-rich rock from PIXE analyses give a quantitative estimate of element abun-
Western A lode in which older blue quartz is overprinted dances to an accuracy of circa 50 % though interelement
by late stage white quartz as described by Wilkins (1977). ratios are determined to a much better level of accuracy as
Fluid inclusions, predominantly less than 15 microns in the main sources of error have similar effects on all ele-
diameter are very abundant as secondary trails in the older ments. LA-ICP-MS data are determined as ratios and esti-
quartz and belong to the same fracture association that mation of absolute concentrations depends on an indepen-
formed the white quartz. Sample 42170 from Cannington dent internal standard such as the estimated abundance of
is an example of a quartz vein associated with a form of a component by PIXE or microthermometric salinity esti-
Fe- and Cl-rich hornblende alteration which is very com- mates (Heinrich et al. 2003). PIXE analysis can only be un-
mon in the deposit (Chapman and Williams 1998). Fluid dertaken of shallow inclusions (typically < 20 microns).
inclusions are again abundant in secondary trails (Fig. 1) Attempts to achieve controlled laserablation of shallow
and in this case can be very large (up to circa 100 mi- inclusions were generally unsuccessful and the analyses
crons). obtained by the two techniques were undertaken on dif-
In both samples, the vast majority of inclusions at room ferent groups of inclusions.
temperature are composed of liquid, a small vapour bubble, Pb and Zn data from the three different laboratories
and number of solids. The latter have been investigated by are very consistent (Fig. 2). The average concentrations
microprobe in opened inclusions, in PIXE images and (42170 estimated by PIXE are 3150 ppm Zn, 36500 ppm Pb in
only) by laser Raman probe and were consistently found to 147001 and 4950 ppm Zn, 30300 ppm Pb in 42170 (ex-
include halite, pyrosmalite, and a Pb-K chloride.Some in-
clusions additionally contain sylvite and/or a Mn-rich car-
bonate mineral. Vapour bubbles were investigated by laser
Raman probe in 42170 only and were found to consist of
methane. The inclusions in 147001 homogenise by vapour
bubble disappearance at temperatures between 270 and 410
C and have NaCl equivalent salinities between 30 and 40 wt
%. Those in 42170homogenise by pyrosmalite dissolution
at 400-450 C and have NaCl equivalent salinities between
30 and 40 wt %. In both samples the Pb-K-Cl phase dis-
solves at temperatures 100-200 below those of total

3 Fluid inclusion geochemistry

In situ microanalysis of fluid inclusions is a new and rap-

idly developing field and to date there has been a general
lack of studies comparing results obtained using differ-
ent techniques and in different laboratories. High salin-
ity brine inclusions from Cannington and Broken Hill were
investigated using both proton induced X-ray excitation
(PIXE) analysis (method of Ryan et al. 2001), and laser
ablation inductively coupled plasma mass spectrometry
(LA-ICP-MS) using Excimer laser ablation systems (cf.
Heinrich et al. 2003) at the Australian National Univer-
sity and Leeds University. The PIXE method is (a) rela-
tively insensitive to contamination from the host quartz
and any solid inclusions it contains, (b) able to provide
quantitative data for halogens (Cl, Br) that were not ana-

Chapter 7-36 Lead and zinc-rich fluid inclusions in Broken Hill-type deposits: Fractionates from sulphide-rich melts or consequences of exotic fluid infiltration? 863

cluding one outlying analysis with lower concentrations

- cf. Fig. 2). The PIXE images reveal that Zn is codistributed
with Ca and Br in the liquid phase of the inclusions at
room temperatures. Zn/Pb ratios determined by both tech-
niques are all less than 1 and on average around an order
of magnitude below those of high temperature and high
salinity brines in the data set compiled by Yardley et al.
(2003). This reflects much higher concentrations of Pb in
the Broken Hill and Cannington inclusions than have been
measured in other natural high salinity fluids excepting
a single case where extreme Pb enrichment was deduced
to occurred in a fluid involved in retrograde hydration of
granulites (Svenson et al. 1999). Pb/Ag ratios measured
by LA-ICP-MS are between 640 and 1470 in sample 147001
and between 200 and 800 in sample 42170.
Br/Cl ratios determined by PIXE in sample 42170 are
in the range 0.0003 to 0.0016 which is distinctly lower
than seawater and magmatic brines as measured from
porphyry copper deposits (cf. Kendrick et al. 2003). The
PIXE investigation of sample 147001 was undertaken un-
der conditions of comparatively poor instrumental per-
formance and meaningful data were not obtained for Br
in this case. ity derived from evaporitic halite or its preserved signa-
ture in metamorphic rocks.
4 Discussion Other features of the fluid inclusions are less easily
reconciled with a relationship to sulphide melts. Ther-
The studied fluid inclusions from Broken Hill and mometric results and paragenetic associations with
Cannington have much higher Pb concentrations and Pb/ retrograde hydrous and Cl-bearing silicates suggest the
Zn ratios than fluid inclusions with similar salinities from inclusions were trapped at temperatures several 100s
other geological settings suggesting that they result from below those of the metamorphic peaks in the two sys-
some process which is specific to this sort of ore deposit. tems. At Cannington, metamorphic hornblendes did not
Mavrogenes et al. (2001) have shown that compositions pass through their 40Ar-39Ar blocking temperatures un-
in the FeS-ZnS-PbS-Ag2S system would have been par- til some 40 million years after the partial melting event
tially-molten under peak metamorphic conditions at Bro- recorded in the gneissic host rocks (Pollard et al. 1997;
ken Hill (though it is not clear that this would also have Giles and Nutman 2002). Aqueous fluids present at peak
been the case at Cannington). One possible explanation conditions would have somehow had to have avoided
for the unusual fluid inclusions is that they represent aque- extraction by silicate melts and remained trapped in
ous phases that equilibrated with sulphide melts. If this the system throughout this period to have been preserved
is the case then element abundances in the inclusions in fluid inclusions. Fluids from both locations were
should reflect their activity ratios in the melt. The FeS- evidently strongly undersaturated in Pb and Zn when
ZnS-PbS eutectic as determined by Mavrogenes et al. trapped and must have very low reduced sulphur con-
(2001) has Pb:Fe:Zn (by weight) approximating to 12:2.5:1 tents given the phase distribution of metals at room
(Fig. 3) and all melts below 900 C have low ZnS com- temperature. Large chemical variations are present in-
pared to the other two components. High Pb/Zn ratios cluding those of Pb/Fe (all lower than eutectic melt; Fig. 3)
are therefore to be expected in fluids equilbrated with and Pb/Ag (different in the two samples) suggesting that
FeS-ZnS-PbS melts and the average ratios measured in the fluids were involved in chemical reactions at the time
the fluid inclusions from samples 147001 and 42170 are the inclusions were trapped. An alternative origin involv-
very similar to the ratio of the eutectic composition Fur- ing late- to postmetamorphic interaction of externally-
thermore, Mungall and Brenan (2003) established that Cl derived brines with pre-existing sulphide accumulations
has an affinity for Fe-Cu-Ni-S melts (due to similarities should also be considered. In this case the high Pb/Zn
with sulphur) and predicted that aqueous fluids evolved ratio might reflect the higher solubility of galena com-
from such melts should have low Br/Cl ratios (cf. the fluid pared to sphalerite in high temperature brines (Hemley
inclusions in 42170). This would be also expected to be a et al. 1992). In either case the unique chemistry would
feature of other sulphide melt systems. However, it is not appear to relate to the large concentrations of sulphides
a diagnostic feature as low ratios could also reflect salin- in these systems.

864 Patrick J. Williams Dong Guoyi Bruce Yardley Thomas Ullrich Chris Ryan Terry Mernagh

Acknowledgements Mavrogenes JA, Macintosh JW, Ellis DJ (2001) Partial melting of the
Broken Hill galena-sphalerite ore. Experimental studies in the
system PbS-FeS-ZnS-(Ag2S). Econ Geol 96: 205-210
This work was supported by AMIRA, the ARC and the
Mungall JE, Brenan JM, (2003) Experimental evidence for the
Predictive Mineral Discovery CRC. chalcophile behavior of halogens. Can Mineral 41: 207-220
Pollard PJ, Perkins C (1997) 40Ar/39Ar geochronology of alteration
References and Cu-Au-Co mineralization in the Cloncurry district, Mount
Isa Inlier. AMIRA P438 Cloncurry Base Metals and Gold Final
Chapman LH, Williams PJ (1998) Evolution of pyroxene-pyrox- Report, Section 3, 40pp
enoid-garnet alteration at the Cannington Ag-Pb-Zn deposit, Ryan CG, McInnes, BM, Williams PJ, Guoyi Dong, Tin Tin Win, Yeats CJ
Cloncurry district, Queensland, Australia: Econ Geol 93: 1390- (2001) Imaging fluid inclusion content using the new CSIRO-
1405 GEMOC nuclear microprobe. Instr Meth Physics Res B 181: 570-577
Giles D, Nutman AP (2002) SHRIMP U-Pb monazite dating of 1600- Spry PG (1978) The geochemistry of garnet-rich lithologies associ-
1580 Ma amphibolite facies metamorphism in the southeast- ated with the Broken Hill orebody, N.S.W., Australia. Unpubl MSc
ern Mt Isa Block, Australia. Austr J Earth Sci 49: 455-465 thesis, University of Adelaide, 129pp
Heinrich CA, Pettke T, Halter WE, Aigner-Torres M, Audtat A, Svenson H, Jamtveit B, Yardley B, Engvik AK, Austrheim H, Broman C
Gnther D, Hattendorf B, Bleiner D, Guillong M, Horn I (2003) (1999) Lead and bromine enrichment in eclogite-facies fluids: extreme
Quantitative multi-element analysis of minerals, fluid and melt fractionation during lower-crustal hydration. Geology 27: 467-470
inclusions by laser-ablation inductively-coupled plasma mass- Walters SG (1998) Broken Hill-type deposits. AGSO J Austr Geol
spectrometry: Geochim Cosmochim Acta 67: 3473-3496 Geophys 17: 229-237
Hemley JJ, Cygan GL, Fein JB, Robinson GR, DAngelo WM (1992) Wilkins RWT (1977) Fluid inclusion assemblages of the stratiform Bro-
Hydrothermal ore-forming processes in the light of studies in ken Hill ore deposit, New South Wales, Australia. Science 198: 185-187
rock-buffered systems: I, iron-copper-zinc-lead sulfide solubil- Williams PJ, Dong Guoyi, Prendergast K, Pollard PJ, Ryan CG (1999)
ity relations: Econ Geol 87: 1-22 Metasomatism and metal mobility in Broken Hill-type deposits.
Kendrick MA, Burgess R, Pattrick RAD, Turner G (2001) Fluid in- In: Stanley CJ et al. (eds) Mineral Deposits: Processes to Process-
clusion noble gas and halogen evidence on the origin of Cu- ing. Balkema, Rotterdam, pp 999-1002
porphyry mineralising fluids: Geochim Cosmochim Acta 65: Yardley B, Bennett A, Banks D (2003) Controls on the chemical com-
2651-2668 position of crustal brines. J Geochem Expl 78/79: 133-135

Chapter 7-37 7-37

Isotopic composition and source of lead in the

Jinding Zn-Pb Deposit, Yunnan, China
Zeng Rong, Zhao Shihua, Gao Yongbao, Li Yongqiang
Faculty of Earth Sciences and Territory Resources, Changan University, Xian, Shaanxi 710054, China

Abstract. The Jinding Zn-Pb deposit is the largest Zn-Pb deposit so tributed around the center of dome and tilt in towards
far discovered in China. To study the source of the mineralizing ma- the deep dome. At the top of the dome the orebody is
terials, we analyzed its lead isotopes. We found that the isotopic
thicker. Two stratigraphic systems are present in the
composition of lead in coarse-grained and fine-grained galenite
crystals are very different. The ratio of lead isotopes in fine-grained Jinding area, referred to as the autochthonous system and
galenite is higher, and lead isotopes are distributed over the lead the allochthonous system. The former refers to strata of
development curve of the orogenic belt which is located in the range the Cretaceous Hutousi Formation (K2h) and the Pale-
of upper crustal lead. All these indicate that the lead of fine-grained ocene Yunlong Formation (E1ya-E1yb). The allochthonous
galenite comes mainly from stratigraphy. In contrast, the ratio of
system includes the Lower Cretaceous Jingxing Forma-
lead isotopes in coarse-grained galenite is lower and lead isotopes
are distributed beneath the lead development curve of the oro- tion (K1j), Mid-Jurassic Huakaizuo Formation (J2h), the
genic belt, as well as in the upper mantle and lower crust. Upper Triassic Maichuqing Formation (T3m) and the
Sanhedong Formation (T3s). The Zn-Pb ores are hosted
Keywords. Lead isotope, composition, source, Jinding Pb-Zn deposit, in the sandstones of the Lower Cretaceous Jingxing For-
Yunnan, China mation (K1j) and the Upper Yunlong Formation (E1yb),
which are separated by a thrust-nappe structure (F2).
There are two distinct types of ores at the Jinding de-
1 Previous research posit, breccia-type ores and sandstone-type ores. The tex-
tures associated with the breccia-type ores include meta-
The Jinding Zn-Pb deposit is one of the seventeen giant somatic and solutional texture, concentric zonal texture,
Zn-Pb deposits in the world, with more than 10 million massive structure, brecciated structure and reticular vein
tons of Zn+Pb reserves. It is also the largest Zn-Pb de- structure. These ores are hosted in the Upper Yunlong
posit so far discovered in China. The Jinding Zn-Pb de- Formation (E1yb), east of ore district. The sandstone-type
posit is sediment-hosted, however its genetic origin dif- ores consist mainly of cementation texture and dissemi-
fers from other sediment-hosted Zn-Pb deposits such as nated structure and are hosted in the middle and west of
Mississippi Valley-type (MVT) deposits, Sedimentary the ore district.
exhalative (Sedex) deposits and Sandstone-type (SST)
deposits. The Jinding Zn-Pb deposit may represent a new 3 Isotopic composition and source of lead
type of sediment-hosted deposit. Geologists have been
studying the Jinding Zn-Pb deposit intensively since the To study the source of the mineralizing materials of the
1980s, and during the twenty years of study there have been Jinding Zn-Pb deposit, we choose the homogeneous
many different opinions about the genesis of the lead ores. galenite samples to do comparative study on lead isotopes
Some think the lead in the ores comes mainly from the (Table 1). We find that the composition of lead isotopes
deep mantle, with minor input from the crust (Zhao 1989). from coarse-grained and fine-grained galenite is differ-
Some argue that the lead in the ores is derived from the ent (Fig. 1): Fine-grained galenite 206Pb/204Pb 18.15~18.60,
mantle, but has been hybridized by lead from the crust (Zhou Pb/ 204Pb 15.612~ 15.64, 208Pb/ 204Pb 38.287~ 38.66;
and Zhou 1992). And others consider that the lead in the Coarse- grained galenite 206Pb/204Pb 18.03~19.21, 207Pb/
204Pb 15.252~15.55, 208Pb/204Pb 37.800~38.930. The ratio
ores is derived from the lower crust and is related to the
interaction between lead in the lower crust and in the of lead isotopes in fine-grained galenite is higher, and
sedimentary rocks (Zhang and Shao 2002). lead isotopes are distributed over the lead development
curve of the orogenic belt which is located in the range of
2 Geologic characteristics of the ore zone upper crustal lead. All these indicate that the lead of fine-
grained galenite comes mainly from stratigraphy.
The Jinding Zn-Pb deposit occurs in a Cenozoic dome In contrast, the ratio of lead isotopes in coarse-grained
structure whose center is eroded. There are six ore blocks galenite is lower and lead isotopes are distributed beneath
(Beichang, Paomaping, Jiayashan, Xiponanchang, the lead development curve of the orogenic belt, as well
Baicaoping and Fengzishan) surrounding the dome. The as in the upper mantle and lower crust. The composition
slaty, veined, phacoidal and stratoid orebodies are dis- of lead isotopes in three plagioclases crystals and garnets

866 Zeng Rong Zhao Shihua Gao Yongbao Li Yongqiang

Chapter 7-37 Isotopic composition and source of lead in the Jinding Zn-Pb Deposit, Yunnan, China 867

derived fluids rich in CO2 (jingdin and Chaoyang 1991).

The isotopes of He, Ne, Xe also indicate that there are
mantle components in the Jinding Zn-Pb deposit (Xue
and Chen 2003). These data are consistent with the lead
isotope data from coarse-grained galenite distributed in
the upper mantle. According to the data, we may conclude
that there are at least two metallogenic epochs in the
Jinding Zn-Pb deposit: (1) The epoch of fine-grained
galenite; (2) The epoch of coarse-grained galenite. The
source of the mineralizing materials is different between
the two epochs. The mineralizing materials of fine-grained
galenite come mainly from stratigraphy, while mineral-
izing materials of coarse-grained galenite come mainly
from the upper mantle and lower crust. The study on the
controlling factors of evolution of the Lanping-Simao
basin also indicates that the mineralization of the Jinding
Zn-Pb deposit involves the interaction between crust and
mantle (Yin and Fan 1990). All the data and analyses vali-
date the theory of a multiperiod and multisource origin
for the Jinding Zn-Pb deposit.

Wang J, Li C (1991) REE geochemistry of the Jinding superlarge Pb-
Zn deposit Geochemica 19: 359~365
Xue C, Chen Y (2003) Geology and isotopic of Helium, Neon, Xeon
and Metallogenic age of the Jinding and Baiyangping Ore De-
posits Northwest Yunnan, china. Science in China, Ser. D,
Yin H, Fan W (1990) Deep processes and mantle-crust compound
mineralization in the evolution of the Lanping-Simao Mesozoic-
Cenozoic Diwa Basin in Western Yunnan, China 4: 113~124
derived from the enclosures of the lower crust in alkalic Zhang Q, Shao A (2002) Lead isotopic composition and lead soure
rocks of western Yunnan is: 206Pb/204Pb 18.135~18.187, of polymetallic deposits in the Large Ore Assembly District in
207Pb/204Pb 15.335~15.388, 208Pb/204Pb 37.836~38.899. the Langping Basin. Acta Mineralogica Sinica 22: 147~153
These values are identical to the coarse-grained galenite Zhao X (1989) stable isotope geochemistry of the Jinding lead-zinc
samples whose values are the lowest, so we can conclude ore deposit, Yunnan, Science in the EarthThe Journal of Geol-
ogy University of China 14: 495~501
that coarse-grained galenite come from the lower crust. Zhou W, Zhou Q (1992) A study on the isotopic composition of Pb
The REE geochemical data indicate that the mineralizing and Sinc in the Lanping Pb-Zn Deposit, Yunnan, Geochemica 2:
materials of the Jinding Zn-Pb deposit are mainly mantle- 141~148

Chapter 7-38 7-38

Geology and geochemistry of the Furong Tin Deposit,

Hunan Province, P. R. China
Zhao Kuidong, Jiang Shaoyong, Jiang Yaohui
State Key Laboratory for Mineral Deposits Research, Department of Earth Sciences, Nanjing University, Nanjing, China

Abstract. Recently, a giant tin deposit, the Furong deposit, has been been suggested as one of the domains of the transition
discovered in the Qitianling granitoid, Hunan, South China. The tin from the Paleo-Asian to the Paleo-Pacific tectonic sys-
mineralization occurs as disseminated crystals or veins of cassiter-
tem (Shu and Zhou 2002). The Qitianling granite is el-
ite. The cassiderite is found in narrow envelopes of chlorite alter-
ation within the granite. The Qitianling granite has distinctly differ- lipse shaped and is one of the largest stocks in the Nanling
ent petrology and mineralogy from common S-type tin granites. Granite Belt with a total outcrop area of 520km2. Coutry
The oxygen and hydrogen isotope data indicate a dominant influ- rocks intruded by the Qitianling granite are Permo-Car-
ence of surface-derived meteoric water associated with chlorite al- boniferous carbonates and Permo- Triassic sandy shales.
teration. Variations in 18O of fresh and altered granites are due to
continuous isotopic exchange reaction between hydrothermal flu-
ids and granites at variable water/rock ratios. The sulfur isotope com- 3 Geology of the Furong deposit
positions of sulfides from the tin ores indicate that both the gran-
ite and the strata supported the sulfur for mineralization. The Pb Most of the cassiterite ores occur as veins hosted by al-
isotopic compositions of sulfides are same as those of feldspars from tered granites. There are about 40 cassiterite-bearing veins,
the granite. Thus, Pb in the ores might come from the granite. Frac- in which the No. 19 and the No. 10 veins contain 90% of
tional crystallization of the magma and tin deposition directly from
exsolved magmatic-hydrothermal fluids may not be the major
the tin reserve in the deposit. The main granite alterations
mechanism for the tin mineralization in this deposit. Instead, we are chloritization, phyllic and potassic feldspar alteration,
suggest that interactions between fluids of meteoric origin and the in which chloritization is mostly associated with tin min-
granite may contribute to the release and deposition of tin. eralization. Cassiterite occurs as disseminated mineral-
ization in the altered granites. There are minor skarn-
Keywords. Geochemistry, Furong tin deposit, Qitianling granite, South
type tin orebodies, which forms at the contact between
the granites and the country rocks. Other metallic min-
erals include scheelite, pyrite, chalcopyrite, sphalerite,
1 Introduction arsenopyrite, and rutile. An interesting fact is that cas-
siterite is generally precipitated together with rutile as
The Furong deposit is a newly discovered giant tin de- disseminations in chlorite. Chlorite has been used as a
posit in Hunan Province, P. R. China (Fig. 1). The tin re- useful exploration guide for tin mineralization in the
serve in this deposit has been estimated to be about granites.
600,000 tons (Wei et al. 2002). Tin orebodies mainly oc-
cur as veins in the Qitianling granite, which lies in the 4 Petrology and mineralogy of the Qitianling
middle of the Nanling Granite Belt in South China. Pre- Granite
vious workers mainly focused on the geology of this de-
posit (e.g. Wei et al. 2002; Huang et al. 2003; Wang et al. The Qitianling Granite is complex, with different intru-
2003; Mao et al. 2004). The main objectives of the present sive phases (Zheng and Jia 2001). Tin mineralization
study are to investigate the source of the ore-forming mainly occurs in the Furong phase. Geochemical charac-
materials, and to determine the origin and evolution of teristics of the granite are distinctly different from com-
the hydrothermal fluids and its relationship with the mon S-type tin granites. The Furong phase is composed
Qitianling granite. We review the geology of the deposit of potassic feldspar (40%), plagioclase (24%), quartz (27%),
and present the geochemical and isotopic data of the gran- biotite (7%) and minor amphibole (2%). Accessory miner-
ites and the ores. These data provide important insights als are mainly magnetite, ilmenite, zircon, fluorite, apatite,
into the genetic model of this deposit. monazite, sphene. The granite is metaluminous with a ACNK
ratio (molar ratio of Al2O3/(CaO+K2O+Na2O)) of 0.88~1.05,
2 Regional geology which is different from common strongly peraluminous tin
granites. The granite is alkaline-enriched and shows low
The Qitianling granite and the Furong tin deposit lie in initial 87Sr/86Sr value (0.708), high Nd value (-5.1~-5.8)
the middle of the Nanling granitic magma intrusive belt, and young Nd model ages, which suggests contribution
South China. The belt is an important granitic intrusion of mantle materials in granite genesis. Zircon SHRIMP
and metallic mineralization zone. The Nanling zone has U-Pb dating gave a crystallization age of 157.11.2Ma.

870 Zhao Kuidong Jiang Shaoyong Jiang Yaohui

5 Geochemical studies of the granite and the 5.2 REE geochemistry

REE contents of both fresh and altered granites are ana-
5.1 Mineral chemistry lyzed. Fresh granites show a LREE-enriched and large
negative Eu anomaly REE pattern. Altered granites have
The main rock-forming minerals (amphibole, biotite, pla- a similar REE pattern to fresh granites. It suggested that
gioclase and ore minerals such as cassiterite and rutile) REEs were immobile during hydrothermal alteration of
were analysed for chemical composition by electron mi- granites in this case.
croprobe (Zhao et al., 2004). The biotite is Fe-rich annite, Most sulfides have very low REE contents and show
and has high Ti, Cl and Sn concentrations. The biotite similar REE patterns with granites. Because REEs have
has high Fe3+/(Fe2++Fe3+) ratios and the oxygen fugacity distinctly different ionic radii from those of base metal
calculated by biotite compositions is above Ni-NiO (NNO), elements, it is difficult for REEs to substitute into crystal
and near the Fe2O3-Fe3O4 (MH). The amphiboles are lattices of sulfides. Thus, it may be assumed that a major
ferropargasite and ferro-edenite hornblende. The pres- part of REE content of sulfides comes from fluid inclu-
sure of the granite, estimated by Al-in-hornblende ba- sions in these minerals. REE patterns of sulfides may rep-
rometer, is 3.6 0.9kbar. Amphibole- plagioclase ther- resent those of ore-forming fluids.
mometry and a semiquantitative hornblende thermom- Fluorites coexisting with sulfides have relatively high
eter yield a forming temperature of 750~820C. The chlo- REE contents and show a different REE pattern. Fluorites
rite from the orebody has negligible K2O, Ti2O, F, and Cl, show a HREE-enriched pattern. Marchand et al. (1976)
but shows similar Fe/(Fe+Mg) ratios with amphibole and studied the REE partition between fluorite and a solu-
biotite. Disseminated cassiterite is closely associated with tion of calcium chloride. The REE distribution coefficients
rutile in chlorite alteration veins and envelopes. The ore- strongly favor fluorite, and those for the HREE are greater
forming temperature is estimated to be 290~405C from than those for the LREE.
chlorite geothermometry. The studied cassiterites are
nearly pure SnO2 (>98%). The concentrations of Nb2O5 5.3 H-O isotopes
and Ta2O5 in cassiterite are very low and almost negli-
gible (Nb2O5+Ta2O5<0.1%).These values are distinctly Cassiterites have 18O values from -4.8 to 1. Chlo-
different from cassiterites found in granites or pegmatites, rites from the ores have 18O values from 0.5 to 2.5,
but similar to cassiterite from epithermal or hydrother- and D values from -62 to -68. The estimated oxy-
mal ore deposits. gen isotope compositions of the hydrothermal fluid from

Chapter 7-38 Geology and geochemistry of the Furong Tin Deposit, Hunan Province, P. R. China 871

cassiterites and chlorites vary from -2.0 to +3.8. The Pb diagram (Zartman et al. 1981). This suggests that Pb
values are lower than those of magmatic-hydrothermal is of crustal origin.
fluids, and are higher than those of Mesozoic meteoric
water (-8~-9) in the studied area. Involvement of 6 Conclusions
surface water of meteoric origin during mineralization
of the Qitianliang granite can be ascertained by the oxy- Tin mineralization in the Furong tin deposit is related to
gen and hydrogen isotope data. hydrothermal alteration of the Qitianling granite. The ore-
Oxygen isotopic compositions of fresh and altered forming fluids might be derived from meteoric water. Both
granites have also been measured. The fresh granite far the granite and the strata supported the sulfur for miner-
away from tin mineralization has the highest oxygen iso- alization. Water-rock interaction might have released tin
topic composition (+10.5). The fresh and slightly al- and other metals (e.g. Pb and Ti) from the granite.
tered granites near the tin veins have lower 18O values
from +6.0 to +10.0. The completely chloritized gran- Acknowledgements
ites collected from the tin orebodies have the lowest oxy-
gen isotopic composition (5.4~6.6). The oxygen iso- This work was supported by funding from China National
topic variations of the whole rocks are the result of fluid- Science Foundation (40221301).
rock interactions. The W/R ratios of completely chloritized
granites are estimated to be 0.3~0.5. References

5.4 Sulfur isotopic data Huang GF, Gong SQ, Jiang XW, Tan SX, Li CB, Liu DH (2003) Explo-
ration on the ore-forming regularities of tin deposits in Qitianling
area, southern Hunan. Geological Bulletin of China 22: 445-451
Sulfur isotopic compositions of twelve sulfides were ana- Mao JW, Li XF, Lehmann B, Chen W, Lan XM, Wei SL (2004) 40Ar-
lyzed. The 34S values of sulfides vary from -20.4 to 39
Ar dating of tin ores and related granite and its geodynamic
3.2. The sulfur isotopic compositions were divided into significance for rock and ore formation. Mineral Deposits 22: 164-
two groups in the histogram plot. In one group, the sul- 175
fur isotopic compositions vary from -0.5 to +3.2. Marchand L, Joseph D, Touray JC, Treuil M (1976) Critres danalyse
gochimique des gisements de fluorine bass sur ltude de la
Sulfur in this group might come from the granite. In the
distribution des lanthanides- application au gte de Maine (71-
other group, the sulfur isotopic compositions vary from - Cordesse, France). Mineralium Deposita 11: 357-379
20.4 to -10. Sulfur in this group might come from Shu LS, Zhou XM (2002) Late Mesozoic tectonism of Southeast China.
sulfides in strata. Geological Review 48:249-260
Wang DH, Chen YC, Li HQ, Chen ZH, Yu JJ, Lu YF, Li JY (2003)
Geochemical and geochemical features of the Furong tin deposit
5.5 Lead isotopic data
in Hunan and their significance for mineral prospecting. Geo-
logical Bulletin of China 22: 50-56
Thirteen sulfides from the ores and ten feldspars from the Wei SL, Zeng QW, Xu YM (2002) Characteristics and ore prospects
Qitianling granite were analyzed for Pb isotopic composi- of deposits in the Qitianling area, Hunan. Geology in China 29:
tion. The Pb isotopic composition of both sulfides and 67-75
Zartman RE, Doe BR (1981) Plumbotectonics - the model.
feldspars is relatively homogeneous. 206Pb/204Pb, 207Pb/204Pb
Tectonophysics 75: 135-162
and 208Pb/204Pb ratios of sulfides are 18.615~18.898, Zhao KD, Jiang SY, Jiang YH, Wang RC (2004) Mineral chemistry of
15.726~15.766 and 38.893~39.077, respectively. The Pb iso- the Qitianling granitoid and the Furong tin ore deposit in Hunan
topic ratios of feldspars are 18.682~18.970, 15.747~15.774 Province, South China: Implication for the genesis of granite and
and 39.030~39.183, respectively. The similarity in Pb iso- related tin mineralization. Accepted by European Journal of Min-
topic composition in sulfides and feldspars indicates that
Zheng JJ, Jia BH (2001) Geological characteristics and related tin-
lead in sulfides might come from the Qitianling granite. polymetallic mineralization of the Qitianling granite complex in
The lead isotope data of both sulfides and feldspars were southern Hunan Province. Geology and Mineral Resources of
plotted on the upper crust Pb growth curve in a Zartman South China 4: 50-57


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