In-situ analysis and genetic investigation of Li-bearing minerals in McDermitt clay-type lithium deposit,Nevada,USA

Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.

Trace elements in magmatic and hydrothermal quartz:Implications on the genesis of the Xingluokeng Tungsten Deposit,South China

The Xingluokeng deposit is the largest gran-ite-related tungsten deposit within the Wuyi metallogenic belt in South China.The Xingluokeng intrusion primarily consists of porphyritic biotite granite,biotite granite,andfine-grained granite.The deposit is represented by veinlet-disseminated mineralization with K-feldspathization and biotitization,alongside quartz-vein mineralization with gre-isenization and sericitization.This study investigates in-situ analyses of quartz compositions from both the intrusion and hydrothermal veinlets and veins.Trace element correlations indicate that trivalent Al^(3+)and Fe^(3+)replace Si^(4+)within the quartz lattice,with monovalent cations(such as Li^(+),Na^(+),and K^(+))primarily serving as charge compensators.Low Ge/Al ratios(<0.013)of quartz from granites suggest a mag-matic origin.The low Al/Ti and Ge/Ti ratios,accompanied by high Ti contents in quartz,suggest that the porphyritic biotite granite and biotite granite are characterized by rela-tively low levels of differentiation and high crystallization temperatures.In contrast,thefine-grained granite exhibits a higher degree of fractionation,lower crystallization tem-peratures,and a closer association with tungsten miner-alization.Ti contents in quartz from quartz veins indicate Qz-Ⅰformed at temperatures above 400°C,while Qz-Ⅱto Qz-Ⅴformed at temperatures below 350°C.Variations in different generations of quartz,as indicated by Al content and(Al+Fe)/(Li+Na+K)ratio,suggest that Qz-Ⅰprecipi-tated from a less acidicfluid with a stable pH,whereas Qz-Ⅱto Qz-Ⅴoriginated from a more acidicfluid with notable pH variations.Consequently,alkaline alteration and acidic alteration supplied the essential Ca and Fe for the precipita-tion of scheelite and wolframite,respectively,highlighting a critical mechanism in tungsten mineralization at the Xin-gluokeng deposit.

Theoretical study of kinetic isotope effects for vacancy diffusion of impurity in solids

Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.

Depositional Environment and Lithofacies Analyses of Eocene Lacustrine Shale in the Bohai Bay Basin:Insights from Mineralogy and Elemental Geochemistry

The effect of various depositional parameters including paleoclimate,paleosalinity and provenance,on the depositional mechanism of lacustrine shale is very important in reconstructing the depositional environment.The classification of shale lithofacies and the interpretation of shale depositional environment are key features used in shale oil and gas exploration and development activity.The lower 3rd member of the Eocene Shahejie Formation(Es_(3)^(x)shale)was selected for this study,as one of the main prospective intervals for shale oil exploration and development in the intracratonic Bohai Bay Basin.Mineralogically,it is composed of quartz(avg.9.6%),calcite(avg.58.5%),dolomite(avg.7%),pyrite(avg.3.3%)and clay minerals(avg.20%).An advanced methodology(thin-section petrography,total organic carbon and total organic sulfur contents analysis,X-ray diffraction(XRD),X-ray fluorescence(XRF),field-emission scanning electron microscopy(FE-SEM))was adopted to establish shale lithofacies and to interpret the depositional environment in the lacustrine basin.Six different types of lithofacies were recognized,based on mineral composition,total organic carbon(TOC)content and sedimentary structures.Various inorganic geochemical proxies(Rb/Sr,Ca/(Ca+Fe),Ti/Al,Al/Ca,Al/Ti,Zr/Rb)have been used to interpret and screen variations in depositional environmental parameters during the deposition of the Es_(3)^(x)shale.The experimental results indicate that the environment during the deposition of the Es_(3)^(x)shale was warm and humid with heightened salinities,moderate to limited detrital input,higher paleohydrodynamic settings and strong oxygen deficient(reducing)conditions.A comprehensive depositional model of the lacustrine shale was developed.The interpretations deduced from this research work are expected to not only expand the knowledge of shale lithofacies classification for lacustrine fine-grained rocks,but can also offer a theoretical foundation for lacustrine shale oil exploration and development.

Study on the occurrence state of indium in sphalerite of Dulong Sn–Zn–In polymetallic deposit,Southwest China

The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.

REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits,Yunnan,China:Implications for the Ore Genesis

The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.

Geology and sulfur isotope geochemistry of Dafulou tin-polymetallic deposit in Dachang orefield, Guangxi, China

No. 22 ore of Dafulou deposit was systematically analyzed for sulfur isotopes. The results show that the δ34S values of sulfide minerals, ranging from 0.154 to +0.218% and with an average value of +0.114 1%, are mostly positive and characterized by rich sulfur(S) content. This suggests that the sulfur of the Dafulou ore deposit is derived from magma and relates to the Longxianggai concealed granite, which points to the important role of magma during mineralization and implyies the product of the active continental margin. By comparison between the Dafulou and the Kengma tin deposit, significant differences exist in the sulfur isotope composition. In the Kengma deposit, the sulfur isotope composition is characterized by the high negative value, which is different from the Dafulou tin-polymetallic deposit. The difference of the enrichment and fractionation of the sulfur isotope is the synthesized result of the metallogenic conditions. It also has the difference in the metallogenic environment and metallogenic characteristics of the deposit in the same ore belt.

Helium, lead and sulfur isotope geochemistry of the Gejiu Sn-polymetallic ore deposit and the s ources of ore-forming materials

Studies on the helium, lead and sulfur isotopic composition were performed of the Gejiu super-large Sn-polymetallic ore deposit. The results indicated that the ore-forming materials came from different sources and the deposit is a product of superimposed mineralization. The deposit is characterized by multi-source and multi-period mineralization, which experienced submarine hydrothermal deposition and Late Yanshanian magmatic hydrothermal mineralization. It is held that the Gejiu super-large Sn-polymetallic ore deposit is a multi-genesis deposit.

Rare earth element(REE) geochemistry of different colored fluorites from the Baoshan Cu–Pb–Zn deposit, Southern Hunan,South China

The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

Trace Elements and Rare Earth Elements of Sulfide Minerals in the Tianqiao Pb-Zn Ore Deposit,Guizhou Province,China

Trace elements and rare earth elements（REE） of the sulfide minerals were determined by inductively-coupled plasma mass spectrometry.The results indicate that V,Cu,Sn,Ga,Cd,In,and Se are concentrated in sphalerite,Sb,As,Ge,and Tl are concentrated in galena,and almost all trace elements in pyrite are low.The Ga and Cd contents in the light-yellow sphalerites are higher than that in the brown and the black sphalerites.The contents of Ge,Tl,In,and Se in brown sphalerites are higher than that in light-yellow sphalerites and black sphalerites.It shows that REE concentrations are higher in pyrite than in sphalerite,and galena.In sphalerites,the REE concentration decreases from light-yellow sphalerites,brown sphalerites,to black sphalerites.The ratios of Ga/In are more than 10, and Co/Ni are less than 1 in the studied sphalerites and pyrites,respectively,indicating that the genesis of the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis associated with hydrothermal genesis.The relationship between LnGa and LnIn in sphalerite,and between LnBi and LnSb in galena,indicates that the Tianqiao Pb-Zn ore deposit might belong to sedimentary-reformed genesis.Based on the chondrite-normalized REE patterns,δEu is a negative anomaly（0.13-0.88）,andδCe does not show obvious anomaly（0.88-1.31）;all the samples have low total REE concentrations（〈3 ppm） and a wide range of light rare earth element/high rare earth element ratios（1.12-12.35）.These results indicate that the ore-forming fluids occur under a reducing environment.Comparison REE compositions and parameters of sphalerites,galenas,pyrites,ores,altered dolostone rocks,strata carbonates,and the pyrite from Lower Carboniferous Datang Formation showed that the ore-forming fluids might come from polycomponent systems,that is,different chronostratigraphic units could make an important contribution to the ore-forming fluids.Combined with the tectonic setting and previous isotopic geochemistry evidence,we conclude that the ore-deposit genesis is hydrothermal,sedimentary reformed,with multisources characteristics of ore-forming fluids.

Trace Element Geochemistry of Magnetite from the Fe(-Cu) Deposits in the Hami Region, Eastern Tianshan Orogenic Belt, NW China

Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite： Ni–Mn–V–Ti（Factor 1）, Mg–Al–Zn（Factor 2）, and Ga– Co（Factor 3） magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe（–Cu） deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe（–Cu） deposits may be related to felsic magmatism.

Sulfur isotopic composition of the Tianqiao Pb-Zn ore deposit,Northwest Guizhou Province,China:Implications for the source of sulfur in the ore-forming fluids

The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Sichuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in this area. It consists of three main orebodies, whose Pb+Zn reserves are more than 0.2 million ton. This paper analyzes the sulfur isotopic composition of these orebodies. The data show that the ore minerals (galena, sphalerite, pyrite) in these orebodies are enriched in heavy sulfur, with δ34SV-CDT values varying between 8.35‰ and 14.44‰, i.e. the δ34SV-CDT values of pyrite are between 12.81‰ and 14.44‰, the mean value is 13.40‰; the δ34SV-CDT values of sphalerite are range from 10.87‰ to 14.00‰, the mean value is 12.53‰; the δ34SV-CDT values of galena are range from 8.35‰ to 9.83‰, the mean value is 8.84‰, and they have the feature of δ34Spyrite>δ34Ssphalerite>δ34Sgalena, which indicates the sulfur isotope in ore-forming fluids has attained equilibrium. The δ34S V-CDT values of the deposit are close to those of sulfates from carbonate strata of different ages in the ore-field (15‰), which suggests that the sulfur in the ore-forming fluids should be derived from the thermo-chemical sulfate reduction of sulfates from the sedimentary strata.

Distribution and existing state of indium in the Gejiu Tin polymetallic deposit, Yunnan Province, SW China

The Gejiu tin polymetallic deposit, located in the southwest margin of the South China Belt bordering on the Yangtze Block, is hosted in Triassic carbonates. This study shows that there is an indium enrichment in the ores.Indium mainly exists in sphalerite-rich massive sulfide ores with a concentration of 198.3–1570 ppm; the indium concentration in sphalerite ranges from 493.3 up to4781 ppm. The inferred indium reserve in the Gejiu Sn deposit is over 4000 t, indicating that the Gejiu tin deposit is a giant In-bearing Sn-polymetallic deposit, similar to the Dachang and Dulong in southwest China. Sphalerite with a high Fe value(8.05–13.27 wt%) is the predominant indium carrier mineral; meanwhile chalcopyrite plays the secondary indium carrier role. EPMA mapping result shows that indium is likely distributed homogeneously and presented as a substitution for Zn in sphalerite.

Study on the evolution of ore-formation fluids for Au-Sb ore deposits and the mechanism of Au-Sb paragenesis and differentiation in the southwestern part of Guizhou Province, China

Ore deposits (occurrences) of Au, As, Sb, Hg, etc. distributed in Southwest Guizhou constitute the important portion of the low-temperature metallogenic domain covering a large area in Southwest China, with the Carlin-type Au and Sb deposits being the most typical ones. In this paper the Au and Sb ore deposits are taken as the objects of study. Through the petrographic analysis, microthermomitric measurement and Raman spectrophic analysis of fluid inclusions in gangue minerals and research on the S and C isotopic compositions in the gold ore deposits we can reveal the sources of ore-forming materials and ore-forming fluids and the rules of ore fluid evolution. Ore deposits of Au, Sb, etc. are regionally classified as the products of ore fluid evolution, and their ore-forming materials and ore fluids were probably derived mainly from the deep interior of the Earth. Fluid inclusion studies have shown that the temperatures of Au mineralization are within the range of 170-361℃,the salinities are 0.35 wt%-8 wt% NaCl eq.; the temperatures of Sb mineralization are 129.4-214℃ and the salinities are 0.18 wt%- 3.23 wt% NaCl eq.; the ore-forming fluid temperatures and salinities tend to decrease progressively. In the early stage (Au metallogenic stage) the ore-forming fluids contained large amounts of volatile components such as CO2, CH4, N2 and H2S, belonging to the H2O-CO2-NaCl fluid system; in the late stage (Sb metallogenic stage) the ore-forming fluids belong to the Sb-bearing H2O-NaCl system. The primitive ore-forming fluids may have experienced at least two processes of immiscibility: (1) when early ore-bearing hydrothermal solutions passed through rock strata of larger porosity or fault broken zones, CO2, CH4, N2 would escape from them, followed by the release of pressure, resulting in pressure release and boiling of primitive homogenous fluids, thereafter giving rise to their phase separation, thus leading to Au unloading and mineralization; and (2) in the late stage (Sb metallogenic stage ) a large volume of meteoric water was involved in the ore-forming fluids, leading to fluid boiling as a result of their encounter, followed by the drop of fluid temperature. As a result, the dissolubility of Sb decreased so greatly that Sb was enriched and precipitated as ores. Due to differences in physic-chemical conditions between Au and Sb precipitates, Au and Sb were respectively precipitated in different structural positions, thus creating such a phenomenon of Au/Sb paragenesis and differentiation in space.

Characteristics of rare-earth elements (REE),strontium and neodymium isotopes in hydrothermal fluorites from the Bailashui tin deposit in the Furong ore field,southern Hunan Province,China

In this paper the authors present the REE concentrations and Sr and Nd isotopic compositions of fluorites from the Bailashui tin deposit of the Furong ore field,southern Hunan Province. The results showed that the total amount of REE in fluorites is usually low,ranging from 0.705 to 8.785 μg/g with the chondrite-normalized REE dis-tribution patterns similar to those of the Qitianling granites in the study area,characterized by LREE-enrichment patterns with pronounced negative Eu anomalies. The fluorites vary in Sr isotopic composition within the range of 0.7083-0.7091,the values are lower than those of the granites and higher than those of the host carbonate rocks in this area. The εNd(t) values of fluorites vary between -9.4 and +10.3,revealing that both the crust-and mantle-source materials were involved in the ore-forming hydrothermal fluids. Combined with previous studies on this ore deposit,the Bailashui tin deposit is temporally and spatially closely related with granitic magmatism in this area. The hydro-thermal fluorites are the product of fluid/rock interactions between granitic magmatic hydrothermal fluid and marine carbonate rocks. The REE and F in the ore-forming fluid were derived from the granites,whereas Sr in the ore-forming fluid came mainly from the granitic magmatic hydrothermal fluid and marine carbonate rocks,although variations in Sr isotopic composition cannot be explained by a simple mixture of these two end-members. Evidence demonstrated that the ore-forming fluids are of crustal-mantle mixing origin,but that the fluids were probably in-completely homogenized and this may be caused by inhomogeneous mixing of the fluids of different sources.

Re–Os dating of molybdenite and in-situ Pb isotopes of sulfides from the Lamo Zn–Cu deposit in the Dachang tin-polymetallic ore field, Guangxi, China

The Dachang tin-polymetallic district, Guangxi,China, is one of the largest tin ore fields in the world. Both cassiterite-sulfide and Zn–Cu skarn mineralization are hosted in the Mid-Upper Devonian carbonate-rich sediments adjacent to the underlying Cretaceous Longxianggai granite(91–97 Ma). The Lamo Zn–Cu deposit is a typical skarn deposit in the district and occurs at the contact zone between the Upper Devonian limestone and the granite.The ore minerals mainly consist of sphalerite, arsenopyrite,pyrrhotite, galena, chalcopyrite, and minor molybdenite.However, the age of mineralization and source of the metals are not well constrained. In this study, we use the molybdenite Re–Os dating method and in-situ Pb isotopes of sulfides from the Lamo deposit for the first time in order to directly determine the age of mineralization and the tracing source of metals. Six molybdenite samples yielded a more accurate Re–Os isochron age of 90.0 ± 1.1 Ma(MSWD = 0.72), which is much younger than the reported garnet Sm–Nd isochron age of 95 ± 11 Ma and quartz fluid inclusions Rb–Sr isochron age of 99 ± 6 Ma. This age is also interpreted as the age of Zn–Cu skarn mineralization in the Dachang district. Further, in this study we found that in-situ Pb isotopes of sulfides from the Lamo deposit and feldspars in the district's biotite granite and granitic porphyry dikes have a narrow range and an overlap of Pb isotopic compositions(^(206) Pb/^(204) Pb =18.417–18.594,^(207) Pb/^(204) Pb = 15.641–15.746, and^(208) Pb/^(204) Pb = 38.791–39.073), suggesting that the metals were mainly sourced from Cretaceous granitic magma.

Sulfur isotopic composition of the Bainiuchang super-large Ag polymetallic deposit,Yunnan Province,China: Implications for the source of sulfur in ore-forming fluids

The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn reserves and a mass of dispersed elements (i.e., In, Cd, Ge, Ga, etc.). Based on systematic studies of sulfur isotopic composition, the authors conclude: The Bainiuchang deposit experienced two epochs of metallogenesis, i.e., the Middle-Cambrian sea-floor exhalative sedimentary metallogenic epoch and the Yanshanian magmatic hydrothermal superimposition metallogenic epoch. In the two metallogenic epochs, the δ34S values of sulfides were all near 0, showing a tendency of being enriched slightly in heavy sulfur. The δ34S values of sulfides in the early metallogenic epoch are within the range of 2‰–5‰ with a peak value range of 2‰–3‰ and an average of 3.0‰, and those of sulfides in the late metallogenic epoch are within the range of 2‰–6‰ with a peak value of 3‰–4‰ and an average of 3.9‰. For the single metallogenic epoch, sulfur in the ore-forming fluids in the early epoch already reached isotopic equilibrium and was derived mainly from underneath the magma chamber or basement metamorphic igneous rocks. Sulfur in the sulfides in the late epoch was derived mainly from magmatic hydrothermal fluids formed in the process of remelting of the basement metamorphic igneous rocks.

Gold and antimony metallogenic relations and ore-forming process of Qinglong Sb(Au) deposit in Youjiang basin, SW China: Sulfide trace elements and sulfur isotopes

In the northwestern margin of the Youjiang basin(NWYB)in SW China,many Carlin-like gold deposits are highly antimony(Sb)-rich,and many vein-type Sb deposits contain much Au.These deposits have similar ages,host rocks,ore-forming temperatures,ore-related alterations and ore mineral assemblages,but the Au and Sb metallogenic relations and their ore-forming process remain enigmatic.Here we investigate the large Qinglong Sb deposit in the NWYB,which has extensive sub-economic Au mineralization,and present a new metallogenic model based on in-situ trace elements(EPMA and LA-ICP-MS)and sulfur isotopes(NanoSIMS and fs-LA-MC-ICPMS)of the ore sulfides.At Qinglong,economic Sb ores contain coarse-grained stibnite,jasperoid quartz and fluorite,whilst the sub-economic Au–Sb ores comprise dominantly veined quartz,arsenian pyrite and fine-grained stibnite.Three generations of ore-related pyrite(Py1,Py2 and Py3)and two generations of stibnite(Stb1 and Stb2)are identified based on their texture,chemistry,and sulfur isotopes.The pre-ore Py1 is characterized by the lower ore element(Au,As,Sb,Cu and Ag)contents(mostly below the LA-ICP-MS detection limit)and Co/Ni ratios(average 0.31)than the ore-stage pyrites(Py2 and Py3),implying a sedimentary/diagenetic origin.The Py2 and Py3 have elevated ore element abundance(maximum As=6500 ppm,Au=22 ppm,Sb=6300 ppm,Cu=951 ppm,Ag=77 ppm)and Co/Ni ratios(average 1.84),and have positive As vs.Au–Sb–Cu–Ag correlations.Early-ore Stb1 has lower As(0.12–0.30 wt.%)than late-ore Stb2(0.91–1.20 wt.%).These features show that the progressive As enrichment in ore sulfides is accompanied by increasing Au,Sb,Cu and Ag with the hydrothermal evolution,thereby making As a good proxy for Au.As-rich,As-poor and As-free zones are identified via NanoSIMS mapping of the Au-bearing pyrite.The As-rich zones in the Qinglong Au-bearing pyrites(Py2 and Py3)and ore stibnites(Stb1 and Stb2)have narrowδ^(34)SH_(2)S ranges(-8.9‰to +4.1‰,average-3.1‰)and-2.9‰to +6.9‰,average + 1.3‰),respectively,indicating that the Au-rich and Sb-rich fluids may have had the same sulfur source.Published in-situ sulfur isotopic data of pyrite As-rich zones from other Carlin-like Au deposits(Shuiyindong,Taipingdong,Nayang,Getang and Lianhuashan)in the NWYB have similar ore-fluidδSH_(2)S values(-4.5‰to +6.7‰,average-0.6‰)to those of Qinglong.Therefore,we infer that the sulfur of both Au and Sb mineralization was derived from the same magmatic-related source(0±5‰)in the NWYB.Moreover,the core of pyrites(Py1)has variable S isotope fractionation(-18.9‰to +18.1‰,mostly +3‰to +12‰),suggesting that the higher-^(34)S H_(2)S was produced by bacterial sulfate reduction(BSR).The hydrothermal pyrite(Py2 and Py3)δ^(34)S values gradually decrease with increasing As concentrations,and ultimately,within the restricted range(-5‰to +5‰)in As-rich zones.This variation implies that the As-rich pyrite was formed through ongoing interactions of the magmatic-hydrothermal fluid with pre-existing sedimentary pyrites,causing the progressive decreasing δ^(34)S values with As content increase,Hence,the fluid/mineral interaction may have generated the observed variation in δ^(34)S and As contents.Overall,comparing the Au and Sb deposits in the NWYB,we favor a magmatic-related source for the Au–Sb–As-rich fluids,but the Au-and Sb-ore fluids were likely evolved at separate stages in the ore-forming system.

The mixing of multi-source fluids in the Wusihe Zn–Pb ore deposit in Sichuan Province, Southwestern China

The Sichuan-Yunnan-Guizhou(SYG)metallogenic province of southwest China is one of the most important Zn-Pb ore zones in China,with^200 Mt ZnPb ores at mean grades of 10 wt.%Zn and 5 wt.%Pb.The source and mechanism of the regional Zn-Pb mineralization remain controversial despite many investigations that have been conducted.The Wusihe Zn-Pb deposit is a representative large-scale Zn-Pb deposit in the northern SYG,which mainly occurs in the Dengying Formation and yields Zn-Pb resources of^3.7 Mt.In this paper,Zn and S isotopes,and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations,the potential sources of ore-forming components,and the possible mineralization mechanisms.Both theδ66Zn andδ34S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies.Such spatial evolution inδ66Zn andδ34S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations.The strong correlations between the Zn-S isotopic compositions and Fe-Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism.However,the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit.It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks,respectively.Therefore,the mixing of two-source fluids with distinct Zn-S isotopic signatures was responsible for the spatial variations of Zn-S isotopic compositions of sphalerite from the Wusihe deposit.The fluids from basement rocks are characterized by relatively lighter Zn(~0.2‰)and S(~5‰)isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn(~0.6‰)and S(~15‰)isotopic compositions.