S，C，O，H，and Pb isotopic studies for the Shuiyindong Carlin-type gold deposit，Southwest Guizhou，China：constraints for ore genesis

Qin-Ping Tan·Yong Xia·Zhuo-Jun Xie·Jun Yan·Dongtian Wei

S，C，O，H，and Pb isotopic studies for the Shuiyindong Carlin-type gold deposit，Southwest Guizhou，China：constraints for ore genesis

Qin-Ping Tan1，2·Yong Xia1·Zhuo-Jun Xie1，2·Jun Yan1，2·Dongtian Wei1，2

The Shuiyindong gold deposit is one of the most famous and largest Carlin-type gold deposits in China and is located in southwest Guizhou，in the eastern part of the Huijiabao anticline.The Shuiyindong's gold mineralization occurred in bioclastic limestone of the Permian Longtan Formation.Sulfur，carbon，hydrogen，oxygen，and lead isotopic compositions are reported in this paper.The properties and sources of ore-forming fluid have been discussed and a metallogenic model for the Shuiyindong gold deposit has been proposed.The δ34S values of stibnite，realgar，orpiment，pyrite from orebodies，and pyrite from quartz veins are similar to or slightly higher than the δ34S values of mantle sulfur.It is suggested that the sulfur of hydrothermal sulfides was likely of magmatic origin with minor heavy sulfur contributed from the country rocks.The measured δD values and calculated δ18OH2O values of inclusion fluid in quartz plotted within or below a magmatic hydrothermal fluid field far from the meteoric water line.This indicates that the ore-forming fluid for the main-stage gold mineralization could have been derived mainly from a magmatic source and mixed with a small amount of meteoric water.The carbon and oxygen isotopic compositions of calcites in the δ18O vs.δ13C diagram suggest that the CO2in ore-forming fluid was derived from dissolution of bioclastic limestone and oxidation of sedimentary organic carbon in limestone.However，the δ13C values of ore-related calcites，which contain intergrown realgar and/or orpiment，are similar to those of mantle carbon.Although no igneous intrusive rock has been observed in the vicinity of the gold deposits，the possibility of mantle fluid integrated into the ore-forming fluid cannot be eliminated based on the δ13C values of ore-related calcites.The lead isotopes of sulfides are distributed near the growth curves of upper crust and orogenic belt in the plumbotectonic diagram.Their calculated Δγ and Δβ values plotted within the magmatism field of crust-mantle subduction zone in the Δγ-Δβ diagram.This suggests that the lead of sulfides has an intimate connection with magmatism.Our S，H，O，C，and Pb isotopic studies for the Shuiyindong Carlin-type gold deposit in Guizhou manifest a concordant possibility that the ore-forming fluid was mainly derived from magmatic fluid with minor contribution from the surrounding strata.With the integration of comprehensive geology and isotopic geochemistry，we have proposed a magmatic hydrothermal model for the origin of the Shuiyindong gold deposit.

Carlin-type·Shuiyindong gold deposit· Stable isotopes·Lead isotopes·Metallogenesis

1 Introduction

Fig.1 A Regional geological sketch map of southwestern Guizhou（modified after Su et al.2009a；Zhang et al.2003）showing the distribution of major Carlin-type gold，antimony，and mercury deposits.B Geological plan map of the Shuiyindong area in the Huijiabao anticline

Southwestern Guizhou，which borders Yunnan Province and the Guangxi Zhuang Autonomous Region，is an important area where many Carlin-type gold deposits and other mineral resources are distributed（Fig.1A）.Carlintype gold deposits are those that share similarities with deposits in Nevada，specifically the Carlin mine，along the North American craton margin（Arehart 1996；Cline and Hofstra 2000；Cline et al.2005；Peters et al.2007；Muntean et al.2011）.The Shuiyindong gold deposit is one of the largest stratabound Carlin-type gold deposits in China with high Au grades（Zhang et al.2004a，b；2005；Su et al.2008；2009a，b；2012）.It is located approximately 20 km northwest of Zhenfeng County Town in Guizhou，China（Fig.1A）and lies on the eastern part of the Huijiabao anticline with gold orebodies hosted in bioclastic limestone of the Permian Longtan Formation（Fig.1B）.

Many investigations have been carried out on the Shuiyindonggolddeposit，thoughitsmetallogenesis remains equivocal.S and Pb isotopes of hydrothermal sulfides were previously analyzed to trace metal sources（Su 2002；Xia 2005；Liu et al.2006；Xia et al.2009；Chen et al.2010；Wang et al.2010；Zhang et al.2010；Wang et al.2013a，b；Chen et al.2014）.However，those S and Pb isotopic compositions of the Au-bearing pyrite，obtained by using conventional S and Pb isotopic analytical methods，could not be appropriated for tracing sources of sulfur andmetals in this case.This is because the Au-bearing pyrite typically is compositionally zoned，with low As content in the diagenetic core，and high content of As and Au in the hydrothermal rim，based on microscopic observations and electron microprobe analyses（Xia et al.2009；Zhang et al. 2010；Su et al.2012）.Therefore，the S and Pb isotopic compositions of different zones of the Au-bearing pyrite could be quite different（Su et al.2012）.Oxygen and hydrogen isotopic compositions for fluid inclusion water extracted from hydrothermal minerals from the Shuiyindong by crushing or thermal decrepitation have been reported（Su 2002；Hofstra et al.2005；Chen et al.2010；Wang et al.2010）.C—O isotopes of calcite veins and bioclastic limestone were previously analyzed for tracing sources of carbon and oxygen（Chen et al.2010；Wang et al.2010）.This paper presents new studies on the S，C，H，O，and Pb isotopes for the Shuiyindong deposit with the purpose of tracing the source of metals，and further to summarize a metallogenic model.With the integration of comprehensive geology and isotopic geochemistry，we have proposed a magmatic hydrothermal model for the origin of the Shuiyindong gold deposit.

2 Regional geologic setting

Southwestern Guizhou is located in the southwestern margin oftheYangtzeCraton，whichiscomposedofProterozoiclowgrade metamorphic rocks overlain by Cambrian to Triassic thickcarbonateandshalesequences（Suetal.2009a；Guetal. 2012；Wang et al.2013a）.Permian and Triassic strata comprisethedominantexposedbedrockinthearea.Triassicstrata are distributed much more widely than the Permian rocks which are seen in cores of a few anticlines（Fig.1A）.Across the area from northwest to southeast，the sedimentary environment gradually changed from a continental and shallowwater platform to the deep-water Youjiang Basin（Su et al. 2009a），whichwasformedintheDevonianduetotheopening of the Paleo-Tethys Ocean（Liu et al.2002）.

Regional structural deformation formed during the Yanshanian Orogeny（Li and Li 2007）.The deformation features narrow anticlines，and gentle and wide synclines（Su et al.2009a）.Regional magmatic rocks are mainly the Emeishan flood basalt which was distributed on the top of the Middle—Upper Permian unconformable contact and the alkaline ultramafic bodies that were intruded into the Permian to Triassic strata（Fig.1A）.The flood basalts are highly variable in thickness and，generally，do not extend into the area of the gold deposits.Geochronological studies have shown that alkaline ultramafic rocks were emplaced between 102 and 85 Ma（Su 2002；Liu et al.2010），corresponding to the late stage of the Yanshanian Orogeny（Zeng et al.1995）.

Orebodies of the Carlin-type gold deposits in southwestern Guizhou are hosted in Permian and Triassic sedimentary rocks of both shallow-and deep-water facies.Two styles of orebody geometry have been recognized.Stratabound orebody is hosted in Permian bioclastic limestone in the core part of the anticline（e.g.，the Zimudang and Shuiyindong deposits）.Fault-controlled orebody formation occurred mainly along reverse faults on the flanks of the anticline，with host rocks of Middle or Lower Triassic siltstone and silty mudstone（e.g.，the Lannigou and Yata deposits）.In addition，there is a kind of lower Au grade orebody which is hosted in silicified，brecciated argillite and limestone in the unconformable contact between the limestone of the Middle Permian Maokou Formation and the argillite of the Upper Permian Longtan Formation.

Due to a lack of minerals suitable for direct isotopic dating，the timing of gold mineralization for Carlin-type gold deposits in China is still controversial.Hu et al.（2002）concluded that the Carlin-type gold deposits in Guizhou were formed between 140 and 75 Ma，corresponding to the late stage of the Yanshanian Orogeny（about 140—65 Ma），which is an important tectonic event in southeastern China（Zeng et al.1995）.

3 Geology of the Shuiyindong gold deposit

Sedimentary rocks in the Shuiyindong deposit include Middle and Upper Permian and Lower Triassic bioclastic limestone，siltstone，and argillite.The Middle Permian Maokou Formation，which consists of massive bioclastic limestone，is overlain in the deposit by the Upper Permian Longtan，Changxing，and Dalong formations，and the Lower Triassic Yelang Formation.The Upper Permian Longtan Formation consists of argillite with interlayered bioclastic limestone.It is about 300 m thick in the Shuiyindong district and has been divided into three stratigraphic units（Liu 2001）.The first unit consists of argillite.The second unit consists of silty argillite intercalated with bioclastic limestone and coal seams.The third unit includes calcareous siltstone，sandstone，argillite，and bioclastic limestone.Gold mineralization preferentially occurred in the bioclastic limestone and calcareous siltstone of the first and second units of the Longtan Formation in the core of the E-W-trending eastern part of the Huijiabao anticline，with limbs cut by reverse faults F101 and F105，respectively（Fig.1B）.A series of nearly S—N-trending normal faults cut those reverse faults（Su et al. 2012），and commonly controlled mercury-thallium mineralization，such as in the Lanmuchang Tl deposit（Zhang et al.2000；Wang et al.2005）.No felsic intrusive rocks have been observed in the vicinity of the Shuiyindong Carlin-type deposit.

Wall-rock alteration types observed in the Shuiyindong deposit include decarbonation，silicification，sulfidation，and dolomitization（Hu et al.2002；Su 2002；Zhang et al. 2003；Xia 2005；Peters et al.2007），similar to those in Carlin-type gold deposits in Nevada，USA （Cline and Hofstra 2000；Cline et al.2005）.Sulfides observed in the Shuiyindongdepositincludemajorarsenianpyrite，arsenopyrite，and marcasite；and minor orpiment，realgar，and stibnite.Gangue minerals include quartz，dolomite，calcite，clay minerals，and minor fluorite.Arsenian pyrite formedearlierthanarsenopyriteintheparagenetic sequence because arsenopyrite occurs as overgrowth on arsenian pyrite（Su et al.2012）.Arsenian pyrite also forms rims on framboidal pyrite cores of diagenetic origin（Fig.2B）.Small amounts of gold-bearing arsenian pyrite and arsenopyrite are enclosed within Fe-poor dolomite，whereas a large amount of gold-bearing arsenian pyrite and arsenopyrite is concentrated in jasperoid quartz grains，where the dolomite was partially or completely dissolved（Fig.2A）.Stibnite，realgar，and orpiment commonly occur with the late-stage quartz—calcite veins in the unconformable contact and in reverse faults（Fig.2G—I）.

The mineralization in the Shuiyindong deposit involved at least four paragenetic stages（Fig.3）based on the textures，crosscutting relationships and mineral assemblages of the ores（Su et al.2012）.Stage 1 consists of disseminated cubic and framboidal pyrite，euhedral ferroan calcite，and dolomite，largely of diagenetic origin.Stage 2 is dominated by milky quartz veins with lesser amounts of jasperoid quartz in the host rocks.Stage 3 consists of iron sulfides，invisible and visible gold，jasperoid quartz，dolomite，and kaolinite.Stages 2 and 3 are considered to be the main stages for ore formation.Stage 4 is dominated by stibnite，orpiment，and realgar along with dolomite and calcite veins in the unconformity contact and in the reverse faults that cut the anticline.

4 Sampling and analytical methods

4.1 Sampling

Six samples were collected from the orebodies，which are dark grey primary ores with wide disseminated pyrite.The arsenian pyrites hosted in these six samples are all compositionally homogenous and of hydrothermal origin based on microscope observations and electron microprobe analysis（Fig.2A）.Ores that contain typical compositionally zoned pyrite grains were excluded in this study（Fig.2B）.Three samples of unmineralized argillite with disseminated pyrite were collected（Fig.2E）.4—5 kg of powder（200-mesh）of the ore or argillite samples were slowly washed in water and the pyrite hosted in these samples commonly precipitated at the bottom of the water. The precipitated pyrite was collected and the wash process was repeated until the purity of the pyrite was more than 90%based on microscope observation.1—2 g of pyrite grains from each sample were separated using this method. Eight samples of stratiform or nodular pyrite grains were separated from the argillite of the Longtan Formation（Fig.2D，E）.Three samples of hydrothermal pyrite grains were separated from pyrite-bearing quartz or calcite veins（Fig.2F）.Quartz veins containing intergrown stibnite or realgar or As-rich pyrite（Fig.2H，J）and quartz veins cementing ores（Fig.2J）suggested that these quartz veins are ore-related.Sixty-nine samples of hydrothermal calcite vein and eight samples of mineralized and unmineralized bioclastic limestone of the Longtan Formation were collected from eight drill holes along a profile（Fig.2K，J）. Stibnite，realgar，and orpiment grains were also collected（Fig.2G—I，L）.Arsenian pyrite，orpiment，realgar，and stibnite were analyzed for S isotope and arsenian pyrite and realgar were analyzed for Pb isotope；calcites were analyzed for C and O isotopes；and quartz veins were analyzed for inclusion fluid H isotope and quartz O isotope.

4.2 Analytical methods

4.2.1 S isotopic analysis

Sulfur isotopic analysis of sulfides was conducted using an elemental analyzer（EA）and an isotope ratio mass spectrometer（IRMS）at the State Key Laboratory of Environmental Geochemistry，Institute of Geochemistry，Chinese Academy of Sciences（IGCAS）.The analytical method was described by Gao et al.（2013）：200 to 300 μg of sulfide powders（200-mesh）were weighed and wrapped in tin capsules.The samples fell into the EA reactor via an automatic injector and burned instantly（1030°C），and the S in sulfides was oxidized to form SO2through addition of oxygen.The SO2was then purged into a separation column（held at 90°C）using helium，and then the SO2in the separation column was separated and guided into IRMA for δ34S analysis.The sulfur isotope compositions are reported with respect to Vienna-Canyon Diablo Troilite（V-CDT）. The analytical procedure was monitored by measurements of reference materials：GBW04414（-0.07±0.13‰），GBW04415（+22.15±0.14‰），and NBS-123（+17.09 ±0.31‰）（Yang et al.，2010）.Reproducibility of this method was generally better than±0.2‰for a 2σ standard deviation.

4.2.2 H-O isotopic analyses

Fig.2 A Back-scattered electron（BSE）image of gold-bearing arsenian pyrite with homogenous structure in orebodies.B BSE image of pyrite showing typically compositional zones.C BSE image of disseminated pyrite in unmineralized argillite.D Photograph of nodular pyrite. E Photograph of stratiform pyrite.F Photograph of pyrite-bearing calcite vein.G Photograph of orpiment-bearing calcite vein.H Photograph of realgar-bearing quartz vein.I Photograph of stibnite-bearing quartz vein.J Photograph of quartz cemented breccia ore.K Photograph of calcite cemented limestone breccia.L Photograph of realgar-and orpiment-bearing calcite vein in ore

Fig.3 Paragenetic sequence of the Shuiyindong deposit（modified after Su et al.2012）

Oxygen and hydrogen isotopic compositions of inclusion fluids in quartz were determined using Thermo Finnigan MAT-253 Isotopic Mass Spectrometer at the Beijing Research Institute of Uranium Geology，China National Nuclear Corporation.For hydrogen isotope analysis，the fluid-inclusion water was extracted from 1-to 5-g quartz samples（40-mesh）through thermal decrepitation of fluid inclusionsinquartzgrainswhichwereheatedto approximately 600°C in an induction furnace.Gaseous hydrogen was converted from the extracted H2O which passed over and reacted with heated zinc grains at 400°C in a vacuum tube（Friedman 1953）.For oxygen isotope analysis，quartz separates were ground to 200 mesh size and degassed at 250°C for about 2 h in Ni reaction vessels（Clayton and Mayeda 1963）.Oxygen was produced by reacting 5—10 mg of quartz samples with BrF5and converted to CO2with a platinum-coated carbon rod.Hydrogen and oxygen isotopic ratios were measured in dual-inlet mode on a Thermo Finnigan MAT 253 mass spectrometer. Oxygen and hydrogen isotopic compositions are expressed relativetoViennaStandardMeanOceanWater（VSMOW），with analytical deviations of±1.0‰for δD and±0.1‰ for δ18O.The δ18O values of ore-forming fluid were calculated from the δ18O values of quartz by using isotope fractionation factors（Clayton et al.1972）.

4.2.3 C-O isotopic analyses

Carbon and oxygen isotopes of calcites were measured by using a Thermo Finnigan MAT-253 Isotopic Mass Spectrometer at the State Key Laboratory of Environmental Geochemistry，IGCAS.Calcite powder（60—100 μg）reacted with phosphoric acid in a sealed vessel at 80°C to release CO2gas for analysis in the mass spectrometer.The stable carbon and oxygen isotopic ratios are reported in the delta notation as the permil（‰）deviation relative to the Vienna Pee Dee Belemnite（PDB）standard.However，δ18O values listed in Table 3 are relative to standard mean ocean water（SMOW）.They were calculated by using the equation：δ18OSMOW=1.03091δ18OPDB+30.91（Coplen et al.1983）.Laboratory standards were calibrated relative totheinternationalstandardNBS-19withδ13-CPDB=1.95‰andδ18OPDB=-2.2‰.Analytical uncertainties，monitored by analyzing the China national reference standards marble（GBW04406），are no greater than±0.05‰for carbon and±0.1‰for oxygen.

4.2.4 Pb isotopic analysis

Lead isotopic analysis of sulfides was performed at the Wuhan Institute of Geology and Mineral Resources，China Geological Survey.The chemical separation of Pb followed the procedure described by Cheng and Cheng（2014）.The analytical procedure involved dissolution of samples using HF and HClO4in crucibles，followed by basic anion exchange resin to purify Pb.Lead isotope ratios were tested using a thermal ionization MAT-262 mass spectrometer with Si gel as the transmitter agent under the static mode.Measured isotopic ratios were corrected for a mass fractionation by replicate measurements of reference sample SRM 981.Finally，the results were compared to the international standard sample NBS-981（Cheng and Cheng 2014）.

5 Analytical results and discussions

5.1 Sulfur isotope

Sulfur isotopic compositions of sulfide minerals from the Shuiyindong deposit are given in Table 1 and plotted in Fig.4.Previous studies have shown that δ34S values of sulfide minerals are not always equal to those of the hydrothermal fluid from which sulfides precipitated and are instead controlled by physical and chemical conditions，namely total sulfur composition，temperature，oxygen fugacity，pH，and ionic strength（Ohmoto 1972）.The oreforming fluid of the Shuiyindong deposit is a low salinity，mildly acidic，low oxygen fugacity，and highly reduced fluid with low-intermediate homogenization temperatures（Hu et al.2002；Su 2002；Su et al.2009a；Wang et al. 2013a；Peng et al.2014）.No gypsum and barite have been found closely coexisting with sulfide minerals in the main mineralization stage in the Shuiyindong gold deposit.In this case，sulfides precipitating from hydrothermal solutions would have δ34S values similar to the（Ohmoto and Goldhaber 1997）.Therefore，thvalues of orpiment and realgar can be taken to represent the bulk sulfur isotopic composition of the ore-forming fluid for the Shuiyindong gold deposit.

The δ34S values vary from-4.88 to 1.76‰ with an average of-1.53‰for stibnite，from 2.48 to 3.04‰withan average of 2.67‰for orpiment，from 1.50 to 6.24‰with an average of 3.60‰ for realgar，from-25.73 to 17.92‰with an average of-6.48‰for pyrite hosted in unmineralized argillite，from-0.64 to 6.79‰ with an average of 3.02‰ for pyrite hosted in orebodies，from 1.09 to 5.92‰ with an average of 3.92‰ for stratiform and nodular pyrite，and from 3.97 to 4.30‰ with an average of 4.08‰ for pyrite hosted in quartz veins.The range of δ34S values for most sulfides is very narrow with the exception the pyrite hosted in unmineralized argillite. The δ34S values of the pyrite hosted in unmineralized argillite ranging from-25.73 to 17.92‰ suggests that thesepyritesamplescouldcontaindiageneticor hydrothermal pyrites or that their mixtures and their δ34S values have no specific clear geological significance.The steady decrease of δ34S values for sulfides from realgar（average 3.60‰），orpiment（average 2.67‰），and stibnite（average-1.53‰）is generally consistent with the relative fractionation factors for these minerals（Ohmoto 1972；Ohmoto and Goldhaber 1997）.

Table 1 Sulfur isotopic compositions of sulfides from the Shuiyindong deposit

There are three distinct reservoirs of δ34S（Rollinson 1993）：（1）mantle-derived sulfur with δ34S value of 0±3‰（Chaussidon et al.1989），（2）seawater sulfur with δ34S value of+20‰today，though this value has varied in the past，and（3）strongly reduced（sedimentary）sulfur with large negative δ34S values.The δ34S values of stibnite，realgar，orpiment，pyrite from orebodies，and pyrite from quartz or calcite veins are in a narrow range and are similar or slightly higher than those of mantle-derived sulfur.This suggests that the sulfur of hydrothermal sulfides was likely of magmatic origin with minor heavy sulfur contributed from the country rocks，though no igneous rocks are observed in the vicinity of the deposits.The δ34S values of stratiform or nodular pyrites hosted in the argillite of the Longtan Formation are also similar to the values of magmatic sulfur.The sulfur isotopic compositions of these pyritesmayrepresentmixturesofdiageneticand hydrothermal pyrites and have no specific clear geological significance.

Fig.4 Histogram of sulfur isotopic compositions of sulfides from the Shuiyindong gold deposit

5.2 Hydrogen and oxygen isotopes

The analytical and calculated hydrogen and oxygen isotopic compositions are presented in Table 2 in order to discuss possible sources of the hydrothermal fluid.The analyzed hydrogen isotopic compositions，varying from -112.5 to-73.5‰，of inclusion waters from ore-related quartz veins are used to represent those of ore-stage solutions.Using the homogenization temperature of 200°C obtained through previous studies of the Shuiyindong deposit（Su 2002；Xia 2005；Su et al.2009a；Chen et al. 2010；Wang et al.2013a；Peng et al.2014），the δ18O values of the hydrothermal fluid，which is isotopically equilibrated with the quartz vein，were calculated by applying the quartz—water fractionation equation of Clayton et al.（1972）based on measured δ18O values of quartz veins from the Shuiyindong deposit.The δ18O values of the quartz（δ18-OQtz）ranged from 12.5 to 21.3‰，and the calculated δ18O values of the inclusion water（δ18OH2O）varied from 0.79 to 9.59‰.

In order to explore the properties of ore-forming fluids，all data were plotted into a diagram of hydrogen versus oxygen isotopes.The measured δD values of the fluid（from-112.5 to-73.5‰）and the calculated δ18OH2O values（from 0.79 to 9.59‰）plotted within or below the magmatic water field but far away from the meteoric water line（Fig.5）.This indicates that the ore-stage mineralization fluids could have derived from a magmatic source mixing with variably exchanged meteoric water.

5.3 Carbon and oxygen isotopes

Carbon and oxygen isotopic compositions of the mineralizedandunmineralizedbioclasticlimestoneand hydrothermal calcites from the Shuiyindong Carlin-type gold deposit are given in Table 3 and plotted in Fig.6.The carbon and oxygen values of the bioclastic limestone mostly plotted within or near the field of marine carbonates in Fig.6，with the exception of two low δ13C values that could have been affected by organic matter in the rocks.Those of calcites mainly plotted between the field of marine carbonates and the field of granite but with some points falling within these two fields（Fig.6）.There are horizontal and inclined arrays of plotted points for carbon and oxygen isotopes of calcite veins.The horizontal array might indicate that the CO2in the ore-forming fluid was derived from dissolution of bioclastic limestone.The inclined array might suggest that the CO2in ore-forming fluid was derived from oxidation of sedimentary organic carbon in limestone（Hu et al.2002）.Some calcite veins containing intergrown realgar and/or orpiment are clearly ore-related based on petrographic observations（Su et al.2009b）.They have strongly negative δ13C values ranging from-9.34 to -3.21‰（Table 3）and are similar to those of the mantle varying from-3 to-8‰with a mean of about-6‰，determined from the isotopic study of carbonatites，kimberlites，and diamonds（Rollinson 1993）.Although no igneous intrusive rocks were observed at the vicinity of thegold deposits，the possibility of mantle fluid contributing to the ore-forming fluid cannot be eliminated based on the similarity between the δ13C value of the mantle and those of ore-related calcites in the Shuiyindong deposit.

Table 2 Measured hydrogen isotopes of inclusion fluids from quartz separates，measured oxygen isotope of quartz separates，and calculated oxygen isotopes of hydrothermal fluids isotopically equilibrated with the host quartz separates from the Shuiyindong deposit

Fig.5 A diagram of measured δD values versus calculated δ18O values of inclusion water in quartz veins from the Shuiyindong gold deposit.The field of magmatic water is taken from Taylor（1974）.The meteoric water line is from Epstein et al.（1965，1970）.The metamorphic water field combines the values of Taylor（1974）and Sheppard（1981）.H and O isotope composition of local meteoric water and the dashed arrows showing meteoric water/rock exchange are from Hofstra et al.（2005）

5.4 Lead isotope

The analyzed lead isotopic compositions of pyrite and realgar from the Shuiyindong deposit are listed in Table 4. Combining206Pb/204Pb and207Pb/204Pb values of pyrite，realgar，and arsenopyrite（Chen et al.2014），the compositions are plotted in a plumbotectonic diagram（Zartman and Haines 1988）to characterize the tectonic environment of the source region of ore-forming materials（Fig.7A）.The data of all samples plotted close to the upper crust and the orogenic Pb evolutionary curves in Fig.7A.Although the plumbotectonic diagram（Fig.7A）provides an important tracer for the source of metallogenic components，the validity of employing this technique for genetic interpretations is imperfect（Zhu 1998）.The implication of orogenic belt lead is indefinite and might be a mixture of crustmantle lead from the subduction zone，submarine hot-water process lead，sedimentation lead，and metamorphism lead（Zhu 1998）.In order to address this uncertainty，here weintegrate the results using a Δγ-Δβ diagram to understand the metallogenic evolution（Fig.7B）.The detailed calculation steps of this method have been explained by Zhu（1998）.The calculated Δγ and Δβ mainly plotted within the magmatism field of crust-mantle subduction zone（3a）in Fig.7B.This suggests that the lead of these sulfides could be mainly sourced from magma.

Table 3 Carbon and oxygen isotopic compositions of calcites and whole rocks from the Shuiyindong deposit

5.5 Model for the formation of the Shuiyindong gold deposit

Previous studies proposed various genetic models for Carlin-type deposits in Nevada.There are three types of models with respect to ore-forming fluid sources：magmatic fluid（Radtke et al.1980；Ressel et al.2000；Kesleret al.2005；Ressel and Henry 2006；Muntean et al.2011），metamorphic fluid（Groves et al.1998；Cline and Hofstra 2000；Large et al.2011），and deeply or shallowly circulated meteoric waters（Ilchik and Barton 1997；Emsbo and Hofstra 2003；Emsbo et al.2003）.Our studies on S，C，H，O，and Pb isotopic geochemistry for the Shuiyindong Carlin-type gold deposit in Guizhou show that the oreforming fluid could be mainly derived from magmatic fluid with minor contribution from the surrounding strata.

Fig.6 A diagram of carbon versus oxygen isotopes of calcites and bioclastic limestones from the Shuiyindong gold deposit. Abbreviation：MC marine carbonates，Sedim Org sedimentary organic matter，CMX carbonatite and mantle xenoliths，BUR basic and ultrabasic rocks，Gran granite，Dis Carb carbonate dissolution，Dec decarbonation，Decbx decarboxylation of organic matter，Oxid Org oxidation of organic matter，MT mixing trend.The frameworks are modified after Hu et al.（2002）

Table 4 Lead isotopic compositions of arsenian pyrite and realgar samples from the Shuiyindong deposit

Magmatic rocks outcropped in Southwestern Guizhou include mainly the Emeishan flood basalt which is distributed on the top of the Middle to Upper Permian unconformable contact and the alkaline ultramafic bodies that intruded into Permian to Triassic units（Fig.1A）. Geochronological studies have shown that the alkaline ultramafic rocks were formed in a period from 102 to 85 Ma（Su 2002；Liu et al.2010），corresponding to the late stage of the Yanshanian Orogeny（about 140—65 Ma）（Ashley et al.1991；Hu et al.2002），an important tectonic event in southeastern China（Zeng et al.1995）.Hu et al.（2002）has concluded that the Carlin-type gold deposits in Guizhou were formed between 140 and 75 Ma.The Carlintype gold mineralization might have a genetic relationship withthealkalineultramaficmagmaticactivityinSouthwestern Guizhou（Xia 2005）.Based on comprehensive geological and isotopic geochemical studies，a new metallogenic model for the Shuiyindong gold deposit is described below for demonstrating close temporal and spatial links between the gold mineralization and the magmatism.

Fig.7 A Evolution diagram（frameworks adapted from Zartman and Haines（1988））of207Pb/204Pb vs.206Pb/204Pb for sulfides from the Shuiyindong gold deposit.B Genetic classification diagram（frameworks adapted from Zhu（1998））of calculated Δγ vs.Δβ using lead isotopes of sulfides from the Shuiyindong gold deposit，1 mantle，2 upper crust，3 crust-mantle subduction zone（3a，magmatism；3b，sedimentation），4 chemical sedimentation，5 submarine hotwater sedimentation，6 middle-deep metamorphism，7 deep metamorphism lower crust，8 orogenic belt，9 ancient shale upper crust，10 retrograde metamorphism.Δβ=［β/ βM（t）-1］×1000；Δγ=［γ/ γM（t）-1］×1000；β=207Pb/204Pb；γ=208Pb/204Pb；βM（t）=15.33；γM（t）=37.47

The Youjiang Basin，which is located tectonically in the southwest margin of the Yangtze craton，is located geographically at the conjunction of the Yunnan，Guizhou，and Guangxi provinces in southwest China（Gu et al.2012）.It was developed on the Paleozoic basement and has experienced three distinct tectonic settings including the rift basin on a passive continental margin from the Early Devonian to Early Permian，the back-arc rift basin from the Late Permian to Middle Triassic，and the foreland basin in the Late Triassic（Zeng et al.1995；Liu et al.2002）.The rifting of the southwestern margin of the Yangtze craton，related to the formation of Paleo-Tethys Ocean，led to the deposition of a thick sequence of carbonate and siliciclastic rocks in the Youjiang Basin from the Devonian to the Triassic（Zeng et al.1995；Liu et al.2002；Gu et al.2012）. The evolution of the Youjiang Basin ended because of Late Indosinian to Early Yanshanian tectonic movement（Hu et al.2002；Liu et al.2002）.

During the Yanshanian period，this region was in an extensional state with the injection of alkaline ultrabasic magma（Liu et al.2010）and the reactivation of syn-sedimentary faults.The alkaline ultramafic dykes intruding along deep lithospheric fault zones and fractures indicate that they were derived in an extensional tectonic settingthat allowed decompression melting of the asthenosphere（Liu et al.2010）.Upwelling asthenosphere possibly impinged on lithospheric mantle，generating magmas that released hydrous，S-and Au-bearing fluids（Muntean et al. 2011）.The rising fluids with elevated H2S concentrations underwent phase changes and mixed with meteoric water（Muntean et al.2011）.The fluids dissolved and sulphidized carbonate wall rocks，leading to deposition of gold-bearing pyrite in a few kilometers of the surface（Su et al.2009a；Muntean et al.2011；Tan et al.2015）.

At that time，relevant for the Shuiyindong gold deposit，the Huijiabao short-axis anticline was conducive to gathering gold-bearing fluids into the anticline core along the unconformable contact at the bottom of the Longtan Formation（Tan et al.2015）.The deposition of a thick sequence of Devonian to Triassic carbonate and siliciclastic rocks in the Youjiang Basin is a favorable lithologic assemblage for gold precipitation（Xia 2005）.Gold mineralization at the Shuiyindong deposit is preferentially disseminated in bioclastic limestone and calcareous siltstone of the Permian Longtan Formation.Iron of the sulfide minerals in the Shuiyindong deposit was probably derived from dissolution of ferroan carbonate in the host rocks（Tan et al.2015），as has been documented in Carlin-type gold deposits in Nevada by lithogeochemistry of ores（Hofstra et al.1991；Stenger et al.1998；Kesler et al.2003；Yigit and Hofstra 2003）.Sulfidation of ferroan carbonate-rich host rocks by H2S-rich ore-forming fluid containing Au HS（ ）-1or Au（HS）0（Seward 1973；1984）would have effectively extracted gold from ore-forming fluid and transformed primary ferroan carbonate to gold-bearing arsenian pyrite（Su et al.，2012）.Dissolution of carbonate increased permeability，facilitating fluid flow into the country rocks and leading to further sulfidation of ferroan carbonate，and then formed the world-class sediment-hosted Shuiyindong gold deposits in Guizhou，China.

6 Conclusions

The sulfur，carbon，hydrogen，oxygen，and lead isotope analyses were performed and these data were obtained principally to gain information on possible sources of oreforming fluid.Our studies of isotopic geochemistry of the Shuiyindong Carlin-type gold deposit in Guizhou indicate that the ore-forming fluid could have mainly been derived from magmatic fluid with minor contribution from the strata.Through comprehensive geological and isotopic geochemical studies，a new metallogenic model for the Shuiyindong gold deposit has been described.

AcknowledgmentsWe are grateful to the Guizhou Zijin Mining Co.Ltd for granting access to the mine and to Jianzhong Liu，Jie Qi， and Zepeng Wang for geological guidance and discussions during the study.This study is supported financially by project 2014CB440905 under the Major State Basic Research Development Program of China（973 Program）and the 12th Five-Year Plan Project of State Key Laboratory of Ore-deposit Geochemistry，Chinese Academy of Sciences（SKLODG-ZY125-01）.

Arehart GB（1996）Characteristics and origin of sediment-hosted disseminatedgolddeposits：areview.OreGeolRev 11（6）：383—403

Ashley RP，Cunningham CG，Bostick NH，Dean WE，Chou IM（1991）Geology and geochemistry of three sedimentary-rockhosted disseminated gold deposits in Guizhou Province，People's Republic of China.Ore Geol Rev 6（2）：133—151

Chaussidon M，Albare`de F，Sheppard SM （1989）Sulphur isotope variations in the mantle from ion microprobe analyses of microsulphide inclusions.Earth Planet Sci Lett 92（2）：144—156

Chen BJ，Wen CQ，Huo Y，Cao SY，Song FZ，Zhou Y（2010）Study on fluid inclusion of the Shuiyindong gold deposit，southwestern Guizhou.Bull Miner Petrol Geochem 29（1）：45—51（in Chinese with English abstract）

Chen MH，Zhang ZQ，Santosh M，Dang Y，Zhang W（2014）The Carlin-type gold deposits of the‘‘Golden Triangle''of SW China：pb and S isotopic constraints for the ore genesis.J Asian Earth Sci.doi：10.1016/j.jseaes.2014.08.022

Cheng YS，Cheng P（2014）Ore-forming material of Dachang tin deposit in Guangxi，China：lead isotope evidence.Trans Nonferrous Metals Soc China 24（11）：3652—3659

Clayton RN，Mayeda TK（1963）The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis.Geochim Cosmochim Acta 27（1）：43—52

Clayton RN，O'Neil JR，Mayeda TK（1972）Oxygen isotope exchange between quartz and water.J Geophys Res 77（17）：3057—3067

Cline JS，Hofstra AA（2000）Ore-fluid evolution at the Getchell Carlin-typegolddeposit，Nevada，USA.EurJMiner 12（1）：195—212

Cline JS，Hofstra AH，Muntean JL，Tosdal RM，Hickey KA（2005）Carlin-type gold deposits in Nevada：critical geologic characteristics and viable models.Econ Geol，100th Anniv Vol 100：451—484

Coplen TB，Kendall C，Hopple J（1983）Comparison of stable isotope reference samples.Nature 302（17）：236—238

Emsbo P，Hofstra AH（2003）Origin and significance of postore dissolution Collapse breccias cemented with calcite and barite at the Meikle gold deposit，Northern Carlin Trend，Nevada.Econ Geol 98（6）：1243—1252

Emsbo P，Hofstra AH，Lauha EA，Griffin GL，Hutchinson RW（2003）Origin of high-grade gold ore，source of ore fluid components，and genesis of the Meikle and neighboring Carlin-Type deposits，Northern Carlin Trend，Nevada.Econ Geol 98（6）：1069—1105

Epstein S，Sharp RP，Gow AJ（1965）Six-year record of oxygen and hydrogen isotope variations in South Pole firn.J Geophys Res 70（8）：1809—1814

Epstein S，Sharp RP，Gow AJ（1970）Antarctic ice sheet：stable isotope analyses of Byrd station cores and interhemispheric climatic implications.Science 168（3939）：1570—1572

Friedman I（1953）Deuterium content of natural waters and other substances.Geochim Cosmochim Acta 4（1）：89—103

Gao JB，Yang RD，Tao P，Cheng W，Wei HR（2013）Discovery of an abnormally high-δ34S barite deposit and a new understanding of global sulfur isotope variation during geological history.Chin J Geochem 32（3）：321—325

Groves DI，Goldfarb RJ，Gebre-Mariam M，Hagemann SG，Robert F（1998）Orogenic gold deposits：a proposed classification in the context of their crustal distribution and relationship to other gold deposit types.Ore Geol Rev 13（1）：7—27

Gu XX，Zhang YM，Li BH，Dong SY，Xue CJ，Fu SH（2012）Hydrocarbon-and ore-bearing basinal fluids：a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin，South China.Mineralium Deposita 47（6）：663—682

Hofstra AH，Leventhal JS，Northrop HR，Landis GP，Rye RO，Birak DJ，Dahl AR（1991）Genesis of sediment-hosted disseminatedgold deposits by fluid mixing and sulfidization：chemicalreaction-path modeling of ore-depositional processes documented in the Jerritt Canyon district，Nevada.Geology 19（1）：36—40

Hofstra AH，Emsbo P，Christiansen WD，Theodorakos P，Zhang XC，Hu RZ，Su WC，Fu SH（2005）Source of ore fluids in Carlin-type gold deposits，China：implications for genetic models.Springer，pp.533—536

Hu RZ，Su WC，Bi XW，Tu GZ，Hofstra AH（2002）Geology and geochemistry of Carlin-type gold deposits in China.Miner Deposita 37（3—4）：378—392

Ilchik RP，Barton MD（1997）An amagmatic origin of Carlin-type gold deposits.Econ Geol Bull Soc Econ Geol 92（3）：269—288

Kesler SE，Fortuna J，Ye ZJ，Alt JC，Core DP，Zohar P，Borhauer J，Chryssoulis SL（2003）Evaluation of the role of sulfidation in deposition of gold，Screamer section of the Betze-Post Carlintype deposit，Nevada.Econ Geol 98（6）：1137—1157

Kesler SE，Riciputi LC，Ye ZJ（2005）Evidence for a magmatic origin for Carlin-type gold deposits：isotopic composition of sulfur in the Betze-Post-Screamer deposit，Nevada，USA.Mineralium Deposita 40（2）：127—136

Large RR，Bull SW，Maslennikov VV （2011）A carbonaceous sedimentary source-rock model for Carlin-type and orogenic gold deposits.Econ Geol 106（3）：331—358

Li ZX，Li XH（2007）Formation of the 1300-km-wide intracontinental orogen and postorogenic magmatic province in Mesozoic South China：a flat-slab subduction model.Geology 35（2）：179—182

Liu JZ（2001）The geology of the yanshang gold deposit，Zhenfeng county，Guizhou.Guizhou Geol 8（3）：174—178（in Chinese with English abstract）

Liu JM，Ye J，Ying HL，Liu JJ，Zheng MH，Gu XX（2002）Sedimenthosted micro-disseminated gold mineralization constrained by basin paleo-topographic highs in the Youjiang basin，South China.J Asian Earth Sci 20（5）：517—533

Liu JZ，Deng YM，Liu CQ，Xia Y，Zhang XC，Tao Y（2006）Geochemical studies on the inclusion and isotopes of the Shuiyindong gold deposit.Guizhou Geol 23（1）：51—56（in Chinese with English abstract）

Liu S，Su WC，Hu RZ，Feng CX，Gao S，Coulson IM，Wang T，Feng GY，Tao Y，Xia Y（2010）Geochronological and geochemical constraints on the petrogenesis of alkaline ultramafic dykes from southwest Guizhou Province，SW China.Lithos 114（1）：253—264

Muntean JL，Cline JS，Simon AC，Longo AA（2011）Magmatichydrothermal origin of Nevada's Carlin-type gold deposits.Nat Geosci 4（2）：122—127

Ohmoto H（1972）Systematics of sulfur and carbon isotopes in hydrothermal ore deposits.Econ Geol 67（5）：551—578

Ohmoto H，Goldhaber MB （1997）Sulfur and carbon isotopes. Geochemistry of hydrothermal ore deposits，3rd edn.Wiley，New York，pp 517—611

Peng YW，Gu XX，Zhang YM，Liu L，Wu CY，Chen SY（2014）Source and evolution of ore-forming fluid of the Huijiabao gold field，Southwestern Guizhou：evidences from fluid inclusions and stable isotopes.Bull Miner Petrol Geochem 33（5）：666—680（in Chinese with English abstract）

Peters SG，Huang JZ，Li ZP，Jing CG（2007）Sedimentary rock-hosted Au deposits of the Dian—Qian—Gui area，Guizhou，and Yunnan Provinces，and Guangxi District，China.Ore Geol Rev 31（1）：170—204

Radtke AS，Rye RO，Dickson FW（1980）Geology and stable isotope studies of the Carlin gold deposit，Nevada.Econ Geol 75（5）：641—672

Ressel MW，Henry CD（2006）Igneous geology of the Carlin trend，Nevada：development of the eocene plutonic complex and significance for Carlin-type gold deposits.Econ Geol 101（2）：347—383

Ressel MW，Noble DC，Henry CD，Trudel WS（2000）Dike-nested ores of the Beast deposit and the importance of Eocene magmatism in gold mineralization of the Carlin Trend，Nevada. Econ Geol Bull Soc Econ Geol 95（7）：1417—1444

Rollinson，H.R.，1993.Using geochemical data：evaluation，presentation，interpretation.Longman Scientific&Technical，Copublished in the U.S.with J.Wiley&Sons

Seward TM（1973）Thio complexes of gold and the transport of gold in hydrothermal ore solutions.Geochim Cosmochim Acta 37（3）：379—399

Seward TM（1984）The transport and deposition of gold in hydrothermal systems.Gold 82：165—181

Sheppard SM （1981）Stable isotope geochemistry of fluids.Phys Chem Earth 13：419—445

Stenger DP，Kesler SE，Peltonen DR，Tapper CJ（1998）Deposition of gold in Carlin-type deposits：the role of sulfidation and decarbonation at Twin Creeks，Nevada.Econ Geol Bull Soc Econ Geol 93（2）：201—215

Su WC（2002）.The hydrothermal fluid geochemistry of the Carlintype gold deposits in the southwestern Yangtze Craton，China. Unpublished Ph.D Thesis，Institute of Geochemistry，Chinese Academy of Sciences，Guizhou，China（in Chinese with English abstract）

Su WC，Xia B，Zhang HT，Zhang XC，Hu RZ（2008）Visible gold in arsenian pyrite at the Shuiyindong Carlin-type gold deposit，Guizhou，China：implications for the environment and processes of ore formation.Ore Geol Rev 33（3）：667—679

Su WC，Heinrich CA，Pettke T，Zhang XC，Hu RZ，Xia B（2009a）Sediment-hostedgolddepositsinGuizhou，China：productsofwallrock sulfidation by deep crustal fluids.Econ Geol 104（1）：73—93

Su WC，Hu RZ，Xia B，Xia Y，Liu YP（2009b）Calcite Sm-Nd isochron age of the Shuiyindong Carlin-type gold deposit，Guizhou，China.Chem Geol 258（3）：269—274

Su WC，Zhang HT，Hu RZ，Ge X，Xia B，Chen YY，Zhu C（2012）Mineralogy and geochemistry of gold-bearing arsenian pyrite from the Shuiyindong Carlin-type gold deposit，Guizhou，China：implications for gold depositional processes.Miner Deposita 47（6）：653—662

Tan Q-P，Xia Y，Xie Z-J，Yan J（2015）Migration paths and precipitation mechanisms of ore-forming fluids at the Shuiyindong Carlin-type gold deposit，Guizhou，China.Ore Geol Rev 69：140—156

Taylor HP（1974）The application of oxygen and hydrogen isotope studies to problems of hydrothermal alteration and ore deposition.Econ Geol 69（6）：843—883

Wang SF，Feng XB，Qiu GL，Wei ZQ，Xiao TF（2005）Mercury emission to atmosphere from Lanmuchang Hg—Tl mining area，southwesternGuizhou，China.AtmosphericEnvironment 39（39）：7459—7473

Wang CH，Wang DH，Liu JZ，Deng YM，Liu CQ，Li JK，Chen FE，Zhang JZ（2010）Characteristics of isotopic geochemistry of Shuiyindong super-large Carlin gold deposit in Guizhou.Earth Sci Front 17（2）：396—403（in Chinese with English abstract）

Wang ZP，Xia Y，Song XY，Liu JZ，Yang CF，Yan BW（2013a）Study on the evolution of ore-formation fluids for Au-Sb ore depositsand the mechanism of Au-Sb paragenesis and differentiation in the southwestern part of Guizhou Province，China.Chin J Geochem 32（1）：56—68

Wang ZP，Xia Y，Song XY，Yan BW，Tan QP（2013b）Sulfur and lead isotopic composition of the Huijiabao Carlin-type gold field and the ore-forming material sources in southwest of Guizhou. Bull Miner Petrol Geochem 32（6）：746—758（in Chinese with English abstract）

Xia Y（2005）.Characteristics and model for Shuiyindong gold deposit in southewestern Guizhou，China.Unpublished Ph.D Thesis，Institute of Geochemistry，Chinese Academy of Sciences，Guizhou，China.（in Chinese with English abstract）

Xia Y，Zhang Y，Su WC，Tao Y，Zhang XC，Liu JZ，Deng YM（2009）Metallogenic model and prognosis of the Shuiying super large Strata-bound Carlin-type gold deposit，Southwesten Guizhou Provence，China.Acta Geologica Sinica 83（10）：1473—1482（in Chinese with English abstract）

Yang XR，Peng JT，Hu RZ，Qi HW，Liu S（2010）Sulfur isotopes characteristics and gensis of Tamu lead and zinc ore deposit，southwest margin of tarim，Xinjiang.Acto Petrologica Sinica 26（10）：3074—3084（in Chinese with English abstract）

Yigit O，Hofstra AH（2003）Lithogeochemistry of Carlin-type gold mineralization in the Gold Bar district，Battle Mountain-Eureka Trend，Nevada.Ore Geol Rev 22（3—4）：201—224

Zartman RE，Haines SM （1988）The plumbotectonic model for Pb isotopic systematics among major terrestrial reservoirs—a case forbi-directionaltransport.GeochimCosmochimActa 52（6）：1327—1339

Zeng YF，Liu WJ，Cheng HD，Zheng RC，Zhang JQ，Li XQ，Jiang TC（1995）Evolution of sedimentation and tectonics of the Youjiang composite basin，South China.Acta Geologica Sinica-English Edition 8（4）：358—371（in Chinese with English abstract）

Zhang Z，Zhang BG，Chen YC，Zhang XM（2000）The Lanmuchang Tl deposit and its environmental geochemistry.Sci China，Ser D Earth Sci 43（1）：50—62

Zhang XC，Spiro B，Halls C，Stanley CJ，Yang KY（2003）Sedimenthosted disseminated gold deposits in Southwest Guizhou，PRC：their geological setting and origin in relation to mineralogical，fluid inclusion，and stable-isotope characteristics.Int Geol Rev 45（5）：407—470

Zhang X-C，Xia Y，Su WC，Liu JZ，Tao Y，Gao ZM，（2004a）.A preliminary study of the location and distribution of gold in the Shuiyindong gold deposit，Guizhou，China.32nd IGC Florence 2004，Abstract Part 1，pp 48

Zhang XC，Su WC，Xia Y，Liu J-Z，Tao Y，Gao ZM（2004b）A discussion on the relationship between the unvisiable gold and the overpressured fluid in the Carlin type gold deposit in Guizhou-A Case study of the Shuiyingdong gold deposit. Guizhou Geology 21（4）：274—275（in Chinese）

Zhang XC，Hofstra AH，Hu RZ，Emsbo P，Su WC，Ridley WI（2005）Geochemistry and δ 34 S of ores and ore stage iron sulfides in Carlin-type gold deposits.Implications for ore genesis.Springer，Dian-Qian-Gui area，China，pp 1107—1110

Zhang Y，Xia Y，Su WC，Tao Y，Zhang XC，Liu JZ，Deng YM（2010）Metallogenic model and prognosis of the Shuiyindong superlargestrata-boundCarlin-typegolddeposit，southwestern Guizhou Province，China.Chin J Geochem 29（2）：157—166

Zhu BQ（1998）Theory and application of isotopic systematic in Earth Science.Science Press，Beijing，pp 1—330（in Chinese）

10.1007/s11631-015-0063-5

31 December 2014/Revised：9 April 2015/Accepted：1 July 2015/Published online：18 July 2015

✉ Yong Xia

xiayong@vip.gyig.ac.cn

Qin-Ping Tan

565310821@qq.com

1State Key Laboratory of Ore Deposit Geochemistry，Institute of Geochemistry，Chinese Academy of Sciences，Guiyang 550002，China

2University of Chinese Academy of Sciences，Beijing 100049，China

©Science Press，Institute of Geochemistry，CAS and Springer-Verlag Berlin Heidelberg 2015