Sulfur Isotope Analysis Research Articles

Origin of the Miaoling Gold Deposit, Xiong’ershan District, China: Findings Based on the Trace Element Characteristics and Sulfur Isotope Compositions of Pyrite

The Xiong’ershan district is situated on the southern margin of the North China Craton (NCC) and located within the Qinling–Dabieshan Orogen’s orogenic zone. It is adjacent to the XiaoQinling mining district and exhibits very favorable geological conditions for mineralization, as the district contains numerous gold deposits, positioning it as one of the key gold-producing areas of China. The Miaoling gold deposit is a hydrothermal deposit and is controlled by the Mesozoic nearly NS-trending fault. The ore bodies are hosted in the Mesoproterozoic Xiong’er Group of the Changcheng System of volcanic rocks, with reserves reaching large-scale levels. Pyrite is the main gold-bearing mineral and can be classified into four generations: early-stage fine- to medium-grained euhedral to subhedral cubic pyrite (Py1); medium- to coarse-grained euhedral to subhedral cubic granular pyrite in quartz veins (Py2a); fine-grained subhedral to anhedral disseminated pyrite in altered rocks (Py2b); and late-stage anhedral granular and fine-veinlet pyrite in later quartz veins (Py3). Through in situ trace element analysis of the pyrite using LA-ICP-MS, a positive correlation between Au and As was observed during the main mineralization stage; gold mainly exists as a solid solution within the pyrite lattice, and the ablation signal curve reflecting the intensity of trace element signals showed that gold also occurs as micron-scale mineral inclusions. The trace element content suggested a gradual increase in oxygen fugacity from Stage 1 to Stage 2, followed by a decrease from Stage 2 to Stage 3. The Co/Ni values in the pyrite (0.56 to 62.02, with an average of 12.34) exhibited characteristics of magmatic hydrothermal pyrite. The in situ sulfur isotope analysis of the pyrite using LA-MC-ICP-MS showed δ34S values of 4.24‰ for Stage 1, −6.63‰ to −13.79‰ for Stage 2, and −4.31‰ to −5.15‰ for Stage 3. Considering sulfur isotope fractionation, the δ34S value of the hydrothermal fluid during the main mineralization stage was calculated to be between 0.31‰ and 2.68‰.

The cobalt and nickel enrichment in base metal sulfides from the Xiarihamu Cu-Ni-Co deposit, China: Constrained by in-situ mineral geochemistry of sulfides

Rapidly growing demand for cobalt and nickel in rechargeable battery industry promotes research on metallogenic theory of magmatic Cu-Ni-Co sulfide deposits. Xiarihamu Cu-Ni-Co deposit, one of the lately discovered Co-rich magmatic sulfide deposits in China, is typical of distribution in orogenic belts, rather than in divergent tectonic settings as many deposits of the same type. In-situ elemental and sulfur isotopic analyses of base metal sulfides (BMS; pyrrhotite, pentlandite, and chalcopyrite) from Xiarihamu were conducted in this study. The strongly negative correlation between Fe and Co + Ni reveals the major occurrence of Co and Ni as isomorphism states in pentlandite and pyrrhotite. The δ34S values of pentlandite and pyrrhotite generally increase with Co contents and Co/Ni ratios, indicating that the Co enrichment within BMS accompanied with enhanced contamination of crustal sulfur. Zinc, Cd, Sb, and Te are significantly and preferentially fractionated into intermediate sulfide solution (ISS) from which chalcopyrite exsolved. The Se contents and Se/S ratios of pentlandite and pyrrhotite in lherzolite/harzburgite are much higher than those of BMS from gabbro, which has systematically higher δ34S values. Combined with the partially overlapped Sb/Se and As/Se ratios of BMS from lherzolite and gabbro, as well as similar calculated R factors of ore-hosting peridotite and gabbro, it is proposed that the studied Xiarihamu gabbro was crystallized from a separate pulse of Co-Ni-enriched, Se-depleted and intensively contaminated mafic parent magma, rather than evolved from ultramafic magma through crystallization fractionation. The lack of olivine and spinel in gabbro also promoted more Co and Ni into sulfide liquid. Based on Se/Te ratios, the pentlandite and pyrrhotite from drill core XH1E01S was originated from sulfide liquid, which suffered higher degree of crystallization fractionation of monosulfide solution (MSS). While pentlandite and pyrrhotite that crystallized from less evolved parent sulfide liquid bear less cobalt, such as those collected from drill core XH1109. This study strengthens the potential importance of crustal contamination and crystallization fractionation of MSS from sulfide liquid during Co enrichment within BMS (pentlandite and pyrrhotite).

A Machine-Learning Approach to Biosignature Exploration on Early Earth and Mars Using Sulfur Isotope and Trace Element Data in Pyrite.

We propose a novel approach to identify the origin of pyrite grains and distinguish biologically influenced sedimentary pyrite using combined in situ sulfur isotope (δ34S) and trace element (TE) analyses. To classify and predict the origin of individual pyrite grains, we applied multiple machine-learning algorithms to coupled δ34S and TE data from pyrite grains formed from diverse sedimentary, hydrothermal, and metasomatic processes across geologic time. Our unsupervised classification algorithm, K-means++ cluster analysis, yielded six classes based on the formation environment of the pyrite: sedimentary, low temperature hydrothermal, medium temperature, polymetallic hydrothermal, high temperature, and large euhedral. We tested three supervised models (random forest [RF], Naïve Bayes, k-nearest neighbors), and RF outperformed the others in predicting pyrite formation type, achieving a precision (area under the ROC curve) of 0.979 ± 0.005 and an overall average class accuracy of 0.878 ± 0.005. Moreover, we found that coupling TE and δ34S data significantly improved the performance of the RF model compared with using either TE or δ34S data alone. Our data provide a novel framework for exploring sedimentary rocks that have undergone multiple hydrothermal, magmatic, and metamorphic alterations. Most significant, however, is the demonstrated potential for distinguishing between biogenic and abiotic pyrite in samples from early Earth. This approach could also be applied to the search for potential biosignatures in samples returned from Mars.

Gold Mineralization at the Syenite-Hosted Anwangshan Gold Deposit, Western Qinling Orogen, Central China

The Anwangshan gold deposit is located in the northwestern part of the Fengtai Basin, Western Qinling Orogen (WQO). The gold ore is hosted within quartz syenite and its contact zone. The U–Pb weighted mean age of the quartz syenite is 231 ± 1.8 Ma. It is characterized by high potassium (K2O = 10.13%, K2O/Na2O > 1) and high magnesium (Mg# = 55.31 to 72.78) content, enriched in large ion lithophile elements (Th, U, and Ba) and light rare earth elements (LREE), with a typical “TNT” (Ti, Nb, and Ta) deficiency. The geochemical features and Hf isotope compositions (εHf(t) = −6.68 to +2.25) suggest that the quartz syenite would form from partial melting of an enriched lithospheric mantle under an extensional setting. Three generations of gold mineralization have been identified, including the quartz–sericite–pyrite (Py1) stage I, the quartz–pyrite (Py2)–polymetallic sulfide–early calcite stage II, and the epidote–late calcite stage III. In situ sulfur isotope analysis of pyrite shows that Py1 (δ34S = −1.1 to +3.8‰) possesses mantle sulfur characteristics. However, Py2 has totally different δ34S (+5.1 to +6.7‰), which lies between the typical orogenic gold deposits in the WQO (δ34S = +8 to +12‰) and mantle sulfur. This suggests a mixed source of metamorphosed sediments and magmatic sulfur during stage II gold mineralization. The fluid inclusions in auriferous quartz have three different types, including the liquid-rich phase type, pure (gas or liquid)-phase type, and daughter-minerals-bearing phase type. Multiple-stage fluid inclusions indicate that the ore fluids are medium-temperature (concentrated at 220 to 270 °C), medium-salinity (7.85 to 13.80% NaCleq) CO2–H2O–NaCl systems. The salinity is quite different from typical orogenic gold deposits in WQO and worldwide, and this is more likely to be a mixture of magmatic and metamorphic fluids as well. In summary, the quartz syenite should have not only a spatio-temporal but also a genetical relationship with the Anwangshan gold deposit. It could provide most of the gold and ore fluids at the first stage, with metamorphic fluids and/or gold joining in during the later stages.

The Role of Hydrocarbons in the Genesis of Mississippi-Valley-Type (MVT) Zn–Pb Deposits: Insights from In Situ Sulfur Isotopes of Sphalerite from the Southwestern Margin of the Yangtze Block, SW China

The coexistence of numerous Mississippi-Valley-type (MVT) Zn–Pb deposits and (paleo) oil/gas reservoirs in the world suggests a close genetic relationship between mineralization and hydrocarbon accumulation. Xuequ–Shandouya middle MVT Zn–Pb deposits are mainly hosted in the Lower Cambrian Maidiping Member siliceous dolostone on the southwestern margin of the Yangtze Block, accompanied by large amount of bitumen in the orebodies. Therefore, this type of Zn–Pb deposit is a natural laboratory for studying the relationship between the mineralization and the accumulation of paleo-oil/gas reservoirs. The deposit is characterized by spheroidal and concentric banded sphalerite. In situ sulfur isotope studies are carried out to determine the sulfur sources, sulfate reduction mechanisms, and role of hydrocarbons in the zinc–lead mineralization process. According to the mineral paragenesis and relative temporal relationship, two mineralization stages (1 and 2) are identified. An in situ sulfur isotope analysis of spheroidal and concentric banded sphalerite particles from Stage 2 shows that there are the two following types of sulfur isotopes in the sphalerite: one with relatively invariable δ34S values in the core (+8.31 to +9.30‰), and the other with a gradual increase from the core margin (core) to the rim (+0.39 to +16.18‰). These two types reflect that they may have formed in different times, with first type forming in the early period of Stage 2, while the second type was formed in the late period of Stage 2. The sulfur isotopic data suggest the sulfur source of evaporated sulfate minerals and multiple formation mechanisms for reduced sulfur (H2S). In the early period of Stage 2 mineralization, the sulfate reduction mechanism is mainly a mixture of bacterial sulfate reduction (BSR) and/or thermochemical sulfate reduction (TSR), while a very small amount may come from the thermal decomposition of organic compounds (DOCs). In the late period of Stage 2, TSR is dominant, and the gradual increase in the δ34S value may be related to Rayleigh fractionation. The oil/gasreservoir not only acts as a reducing agent to provide the required hydrogen sulfide for zinc–lead mineralization through TSR or BSR, but also provides reduced sulfur for mineralization through the thermal decomposition of organic compounds directly.

The geothermal gradient shapes microbial diversity and processes in natural-gas-bearing sedimentary aquifers

Abstract. Deep subsurface microorganisms constitute over 80 % of Earth's prokaryotic biomass and play an important role in global biogeochemical cycles. Geochemical processes driven by geothermal heating are key factors influencing their biomass and activities, yet their full breadth remains uncaptured. Here, we investigated the microbial community composition and metabolism in microbial-natural-gas-bearing aquifers at temperatures ranging from 38 to 81 °C, situated above nonmicrobial-gas- and oil-bearing sediments at temperatures exceeding 90 °C. Cultivation-based and molecular gene analyses, including radiotracer measurements, of formation water indicated variations in predominant methanogenic pathways across different temperature regimes of upper aquifers: high potential for hydrogenotrophic–methylotrophic, hydrogenotrophic, and acetoclastic methanogenesis at temperatures of 38, 51–65, and 73–81 °C, respectively. The potential for acetoclastic methanogenesis correlated with elevated acetate concentrations with increasing depth, possibly due to the decomposition of sedimentary organic matter. In addition to acetoclastic methanogenesis, in aquifers at temperatures as high as or higher than 65 °C, acetate is potentially utilized by microorganisms responsible for the dissimilatory reduction of sulfur compounds other than sulfate because of their high relative abundance at greater depths. The stable sulfur isotopic analysis of sulfur compounds in water and oil samples suggested that hydrogen sulfide, generated through the thermal decomposition of sulfur compounds in oil, migrates upward and is subsequently oxidized with iron oxides present in sediments, yielding elemental sulfur and thiosulfate. These compounds are consumed by sulfur-reducing microorganisms, possibly reflecting elevated microbial populations in aquifers at temperatures as high as or higher than 73 °C. These findings reveal previously overlooked geothermal-heat-driven geochemical and microbiological processes involved in carbon and sulfur cycling in the deep sedimentary biosphere.

Online Isotope Analysis of Sulfur in Proteins via Capillary Electrophoresis Coupled With Multicollector ICP-MS (CE/MC-ICP-MS): A Proof of Concept Study.

Isotope ratio analysis of sulfur in biological samples using inductively coupled plasma-mass spectrometry (ICP-MS) has gained significant interest for applications in quantitative proteomics. Advancements like coupling separation techniques with multicollector ICP-MS (MC-ICP-MS) enhance the throughput of species-specific sulfur isotope ratio measurements, fostering new avenues for studying sulfur metabolism in complex biological matrices. This proof-of-concept study investigates the feasibility of online CE/MC-ICP-MS for directly analyzing sulfur isotope ratios in proteins (albumin). Leveraging our previous work on the applicability of CE/ICP-MS for quantifying sulfur-containing biological molecules, we explore its potential for sulfur isotope analysis. Our results demonstrate that direct analysis of sulfur isotopes in albumin protein using online capillary electrophoresis MC-ICP-MS (CE/MC-ICP-MS) eliminates the need for laborious pretreatment steps, while yielding isotope ratios comparable to the reference values. Although initial precision can be improved through further system optimization and protein injection techniques, this approach paves the way for future analysis of mixtures of various biological compounds in, for example, clinical diagnosis studies.

Decoding organic compounds in lava tube sulfates to understand potential biomarkers in the Martian subsurface

Exploring molecular biomarkers in lava tube speleothems offers insights into environmental dynamics, biogeochemical processes, and subsurface life, with implications for astrobiology, particularly in Martian analog environments. Despite extensive biomarker research in marine and terrestrial settings, lava tube studies are limited. This study employed molecular, isotope and mineralogical characterization to analyze sulfate speleothems from six lava tubes of Lanzarote (Canary Islands), considered analog for the Moon and Mars. The combination of mass spectrometry, thermogravimetry, and mineralogical techniques, revealed geological processes, biomarkers and their biological sources. The identified minerals were primarily calcium and sodium sulfates. Sulfur isotope analyses indicated volcanic and oceanic origins, while carbon isotope composition and pyrolysis analyses suggested influences from vegetation and microbial activity. Lipidic profiles highlighted branched and n-alkanes, as well as palmitic and stearic acid methyl esters, suggesting microbial origins. These findings contribute to understanding geological and environmental dynamics in lava tubes and recognizing potential biosignatures on Earth and other planets.

Diet in high mediaeval Florence through stable isotope analysis of carbon, nitrogen and sulphur

In this paper, we aim to reconstruct the dietary habits of supposedly lower rank nobles or middle-class High Middle Ages individuals recovered from the cloister arcade of San Pier Scheraggio within the Uffizi Museum complex in Florence, Italy. Notably, the High Middle Ages was a period of cultural and social changes, which is partly reflected in the dietary habits, as suggested by historical sources. Here we apply stable carbon, nitrogen, and sulphur isotope analysis on humans (n = 34) and animals (n = 13) from San Pier Scheraggio to directly investigate food consumption in this peculiar assemblage. The diet of human individuals was based on terrestrial C3 sources without clear contribution of marine fish (δ13C mean and 1SD: −19.5 ± 0.7 ‰; δ15N mean and 1SD: 9.6 ± 0.4 ‰; δ34S values are mean and 1SD: 7.6 ± 1.2 ‰). The comparison with animal and human samples from other Italian Middle Ages contexts shows that the overall diet of the population buried at San Pier Scheraggio is in line with that of other mediaeval communities in Italy, although with a generally higher contribution of terrestrial animal products. Our data seem to suggest that at the site there was no dietary differentiation concerning age at death or biological sex of the individuals. Some differences, however, can be outlined, for example, in the contribution of C4 crops. In addition to this, we identify two individuals as possible non-locals.

Genesis of Yongping copper deposit in the Qin-Hang Metallogenic Belt, SE China: Insights from sulfide geochemistry and sulfur isotopic data

Yongping copper deposit is a large-scale polymetallic mine that contains 1.6 Mt of proven Cu metal reserves with an average grade of 0.74 % and contributes significantly to China’s production of copper. This deposit is situated in the eastern part of the Qin-Hang Metallogenic Belt (Jiangxi province, SE China) at the contact zone between the Yangtze Cu–Mo metallogenic belt and the Jiangxi W–Sn–REE metallogenic belt. The thick stratiform and lenticular-shaped orebodies are hosted in the Carboniferous Yejiawan Formation, consisting of sandstone, limestone, mudstone, and chert-rich clastic rocks. Dominant metal-bearing minerals are chalcopyrite and pyrite with a minor amount of sphalerite, tetrahedrite, galena, molybdenite, pyrrhotite, magnetite, hematite, and scheelite. Although intensive research has been done on its geological setting, geochemical characteristics, and geodynamic evolution over the past thirty years, the origin and depositional environments have remained controversial. In the current research, in situ trace element geochemistry and sulfur isotope analyses, coupled with microscopic investigation, were conducted on sulfide minerals using the LA-ICP-MS technique. The results display that Yongping pyrite rich in Co, As, Ni, Zn, Cu, and Te and deplete in other trace elements. Sphalerite rich in Fe, Mn, Cu, and Cd, followed by In, Co and Ga. The calculation results of formula T(°C) = (Fe/Zn + 0.2953)/(0.0013) reveal that sphalerite was formed in medium–high temperature conditions (262 °C–377 °C). The δ34SV-CDT values of studied sulfides (pyrite, chalcopyrite, sphalerite, and tetrahedrite) varied from −1.52 ‰ to 5.13 ‰ with an average of 2.36 ‰, which are highly consistent with those recorded from porphyritic biotite granite stock of Shizitou (from 2.20 ‰ to 4.5 ‰), suggesting a dominantly magmatic origin. Collectively, trace element compositions of analyzed sphalerite and pyrite from the Yongping area exhibit characteristics of typical skarn deposits. Combined with previous studies, we can conclude that the Yongping Cu deposit is a skarn deposit that was most likely formed by contact metasomatism after the intrusion of the Jurassic Huoshaogang-Shizitou granitic stock into the Carboniferous Yejiawan Formation.

The Xilaokou carbonate-sulfide vein type gold deposit: A distinct mineralization in the giant Jiaodong gold province, North China

The Xilaokou gold deposit with ca. 50 t of gold reserve @ 2.7 g/t represents a novel type (carbonate-sulfide vein type) of gold mineralization within the Jiaodong gold province. However, its mineralization age and metallogenic mechanism remain poorly constrained, hindering a comprehensive understanding of the ore-forming processes in the Jiaodong gold province. In this study, we employ syn-ore stage hydrothermal monazite in situ U-Pb geochronology to determine the ore-forming age of the Xilaokou gold deposit. Additionally, we conduct in situ LA-(MC)-ICP-MS elemental mapping and sulfur isotope analysis in ore-related pyrite to unravel the sulfur source(s) and provide new insights into the ore-forming processes of the Xilaokou gold deposit. Our findings reveal the following key points: (1) U-Pb dating of hydrothermal monazite in Au-bearing pyrite yields an ore-forming age of119.9 ± 3.0 Ma. This age is consistent with the mineralization ages (around 120 ± 5 Ma) of other gold deposits in the region, including Liaoshang-, Jiaojia-, and Linglong-type deposits. (2) Gold in pyrite primarily occurs as micro-grains (5–20 μm) within pyrite fissures associated with sphalerite and galena. (3) Elemental mapping and sulfur isotope analysis indicate that major Au mineralization is linked to elevated concentrations of As, Sb, and Tl, along with heavy sulfur isotope values (δ34S∼24.7 ‰). (4) Early-stage Au mineralization is characterized by enrichment of As, Cu, and Bi, with normal sulfur isotopic composition (δ34S∼8 ‰). We propose that the carbonate-sulfide vein type gold deposits represented by the Liaoshang and Xilaokou gold deposits in the Jiaodong gold province are genetically linked to quartz-sulfide vein and disseminated type deposits. The major ore-forming stage involved the addition of S and Au from a metamorphic massif at slightly lower temperatures. These findings highlight a new exploration direction within the North China Craton. In summary, the Xilaokou gold deposit provides valuable insights into gold mineralization processes in Jiaodong, emphasizing the importance of considering diverse deposit types and their genetic relationships in the region.

Deformation and fluid flow history of a fractured basement hydrocarbon reservoir below the Sab'atayn Basin, Habban Field, Yemen

Fractured crystalline basement reservoirs are of increasing economic interest for oil and gas exploration and subsurface fluid storage. The successful characterization of these reservoirs is commonly challenged by their structural heterogeneity, complexity in fracture distribution and flow properties at multiple scales, and the difficulty of imaging fractures in exploration seismic. We analyzed the fracture geometry and fracture diagenetic attributes in two oriented cores from the Habban Field in the Late Jurassic Sab'atayn Basin (Yemen) to evaluate the multi-phase deformation history and fracture flow pathway evolution for (hydrothermal) fluids and hydrocarbons. Analyses included petrographic and fluid inclusion analysis of fracture-filling cements, and stable sulfur isotope analyses of fracture-filling pyrite.The Paleoproterozoic basement consists of amphibolite-facies metamorphic ortho- and paragneiss cut by several phases of Neoproterozoic granitoid intrusions. The investigated lithologies in the drill cores comprise (1) epidote quartzite, (2) amphibolite, (3) monzogranite, (4) meta-arkose, and (5) quartz-feldspar porphyry. These lithologies show an inhomogeneous fracture network that is partially cemented. Ediacaran brittle-ductile deformation (D1) recognized only within a Pan-African monzogranite lead to cataclasis and porosity generating alteration. Late Jurassic – Early Cretaceous extension (D2) related to the break-up of Gondwanaland and the formation of the Sab'atayn Basin is found in all lithologies and likely resulted in pervasive quartz cementation. Late Jurassic fractures parallel to the NW-SE trending long axis of the Sab'atayn Basin are best recognized in a strongly foliated amphibolites. Cenozoic extensional fracturing (D3) reactivated older structures, which probably formed during activity of the Neoproterozoic Najd Fault System and caused multi-phased (pyrite-(saddle) dolomite-calcite) fracture cementations. The sulfur isotope compositions of pyrite with δ34S values ranging between −17.4 and + 26.4‰ vs. V-CDT reflects the variability of the fluid source during sulphide mineral formation from hydrocarbon-rich hydrothermal solutions. Fluid inclusions indicate that cementation reactions occurred in a relatively narrow temperature field between 120 °C and 140 °C, ideal for hydrocarbon maturation. Our results demonstrate the potentially complex charge history of basement reservoirs, involving multiple phases of fracture formation and cementation, and fluid charge episodes.

Oceanic and Sedimentary Microbial Sulfur Cycling Controlled by Local Organic Matter Flux During the Ediacaran Shuram Excursion in the Three Gorges Area, South China.

The increased difference in the sulfur isotopic compositions of sedimentary sulfate (carbonate-associated sulfate: CAS) and sulfide (chromium-reducible sulfur: CRS) during the Ediacaran Shuram excursion is attributed to increased oceanic sulfate concentration in association with the oxidation of the global ocean and atmosphere. However, recent studies on the isotopic composition of pyrites have revealed that CRS in sediments has diverse origins of pyrites. These pyrites are formed either in the water column/shallow sediments, where the system is open with respect to sulfate, or in deep sediments, where the system is closed with respect to sulfate. The δ34S value of sulfate in the open system is equal to that of seawater; on the contrary, the δ34S value of sulfate in the closed system is higher than that of seawater. Therefore, obtaining the isotopic composition of pyrites formed in an open system, which most likely retain microbial sulfur isotope fractionation, is essential to reconstruct the paleo-oceanic sulfur cycle. In this study, we carried out multiple sulfur isotope analyses of CRS and mechanically separated pyrite grains (>100 μm) using a fluorination method, in addition to secondary ion mass spectrometry (SIMS) analyses of insitu δ34S values of pyrite grains in drill core samples of Member 3 of the Ediacaran Doushantuo Formation in the Three Gorges area, South China. The isotope fractionation of microbial sulfate reduction (MSR) in the limestone layers of the upper part of Member 3 was calculated to be 34ε = 55.7‰ and 33λ = 0.5129 from the δ34S and Δ33S' values of medium-sized pyrite grains ranging from 100 to 300 μm and the average δ34S and Δ33S' values of CAS. Model calculations revealed that the influence of sulfur disproportionation on the δ34S values of these medium-sized pyrite grains was insignificant. In contrast, within the dolostone layers of the middle part of Member 3, isotope fractionation was determined to be 34ε = 47.5‰. The 34ε value in the middle part of Member 3 was calculated from the average δ34S values of the rim of medium-sized pyrite grains and the average δ34S values of CAS. This observation revealed an increase in microbial sulfur isotope fractionation during the Shuram excursion at the drill core site. Furthermore, our investigation revealed correlations between δ34SCRS values and CRS concentrations and between CRS and TOC concentrations, implying that organic matter load to sediments controlled the δ34SCRS values rather than oceanic sulfate concentrations. However, these CRS and TOC concentrations are local parameters that can change only at the kilometer scale with local redox conditions and the intensity of primary production. Therefore, the decreasing δ34SCRS values likely resulted from local redox conditions and not from a global increase in the oceanic sulfate concentration.

The superposition of Cretaceous mineralization events leading to the formation of the large Baiyinnuoer Pb–Zn deposit in NE China

The Baiyinnuoer Pb–Zn deposit, estimated at 26.57 million metric tonnes (Mt) with grades of 1.77% Pb and 5.21% Zn, is situated in the southern Great Xing'an Range (SGXR) of northeast China. The deposit comprises southern and northern ore belts. The southern belt primarily contains skarn ore bodies (32% of reserves) associated with Triassic granodiorite, while the northern belt is dominated by skarn ore bodies (30% of reserves) related to Triassic diorite porphyry. In addition to Triassic skarn‐type mineralization, the deposit also exhibits Early Cretaceous mineralization. This includes vein‐type occurrences (36% of reserves) within volcanic tuff and syenite porphyry, alongside a small amount of skarn ore bodies (2% of reserves) related to syenite porphyry. LA‐ICP‐MS U–Pb dating of intrusive rocks and garnets was conducted to investigate the timing and genesis of these mineralization events, revealing two distinct stages of skarn‐type mineralization. The first stage, associated with Early Triassic granitoids, dates to 254.6 ± 1.4–241.7 ± 2.7 Ma, while the second stage is closely associated with Early Cretaceous syenite porphyry, constrained to 135.4 ± 1.1–135.2 ± 1.6 Ma. Garnet U–Pb dating in the syenite porphyry‐related skarn yielded an age of 134.9 ± 4.7 Ma; however, due to low U content, reliable dating of garnets associated with Early Triassic granitoid‐related skarn was not feasible. Micro‐thermometry and Laser Raman analyses of fluid inclusions within vein‐type ore bodies highlighted distinct differences between vein‐type mineralization and Early Triassic skarn‐type mineralization. Additionally, in situ sulfur isotope analyses of sphalerite from both Early Triassic and Early Cretaceous ore bodies indicate a magmatic origin for sulfur in both stages. Through comprehensive geological, geochronological, in situ sulfur isotope and fluid inclusion studies, the Baiyinnuoer Pb–Zn deposit is conclusively identified as a large deposit characterized by two distinct periods of mineralization (Early Triassic and Early Cretaceous), akin to several other significant polymetallic deposits in NE China.

Reconstructing Redox Landscape With Coupled Nitrogen‐Sulfur Isotopes: A Case Study From Middle‐Late Triassic Chang 7 Member of the Yanchang Formation in the Ordos Basin (North China)

AbstractEuxinia, a crucial geological condition, usually signifies more severe extinction events attributed to deoxygenation in Earth's history. Despite extensive exploration of various proxies in paleoredox studies, most are primarily utilized to reconstruct atmospheric pO2, the proportion of anoxic water relative to the entire basin, and broader trends in redox states. Few, however, hold the capacity to precisely delineate local euxinia within confined areas. To address this gap and gain insights into the temporal and spatial extent of benthic euxinia, we propose leveraging the synergistic analysis of total nitrogen isotopes (δ15NTN) and pyrite sulfur isotopes (δ34Spy). Our study focuses on the Triassic Chang 7 Member from the Yanchang Formation, Ordos Basin, North China. Through coupling the δ15NTN and δ34Spy systematics on 11 drill cores within the Ordos Basin, we reconstruct the temporal and spatial distribution of the benthic euxinia zone during the Chang‐7 period. Our results suggest strong spatial heterogeneity of benthic redox conditions, with the euxinia boundary shifting from the central lake to the southwestern sections. Moreover, we identify redox‐controlling factors, including organic carbon loading, water depth, and potential water circulation, and evaluate their interplay with benthic euxinia. Furthermore, the discernment of water circulation patterns may provide an innovative approach to restore the paleowind direction. These findings highlight the effectiveness of coupling δ15NTN and δ34Spy in reconstructing the local benthic redox landscape of benthic environments, and enrich our understanding of biogeochemical processes.

Genetic link between the Kangjiawan gold deposit and late Jurassic granitic magmatism, South China: Constraints from in situ calcite U-Pb dating, sulfur isotope and trace elements of pyrite

(Meta)sedimentary rock-hosted gold (Au) deposits are globally important Au resources, of which ore genesis and mineral exploration have been attracted considerable attention. However, the precise dating of Au mineralization of those Au deposits remains challenging due to the absence of suitable dating minerals, thus impeding a comprehensive understanding of their genesis. The Kangjiawan Au deposit, situated in the southern Hunan Province, South China, is one of representative (meta)sedimentary rock-hosted Au deposits. Due to the lack of mineralization age, the genesis of Kangjiawan Au deposit is still a matter of debate. Here we report the data of in situ calcite U-Pb dating, in situ trace elements and sulfur isotope analysis of pyrite, to further constrain the mineralization timing and the sources of ore-forming materials of the Kangjiawan Au deposit. Based on the detailed field investigation and petrographic observations, three mineralization stages have been identified: pyrite (Py1) + quartz (Stage I), gold-bearing pyrite (Py2) + polymetallic sulfides + quartz + calcite (Stage II), and gold-bearing pyrite (Py3) + calcite (Stage III). The results of mineralogical and trace elemental analyses indicate that Au are mainly hosted in Py2 (average 14.19 ppm) and Py3 (average 4.80 ppm), primarily as the form of “invisible gold”. In situ LA-ICP-MS U-Pb dating on calcite intergrowth with the gold-bearing pyrite (Py3) yields a Tera-Wasserburg lower intercept age of 151.7 ± 5.4 Ma. This age is well consistent with the published zircon U-Pb age (158.3 ± 1.2 Ma) of the nearby Shuikoushan granodiorite, the molybdenite Re-Os age (157.8 ± 1.4 Ma) of the Laoyachao skarn Pb-Zn deposit in the Shuikoushan ore field, and the garnet U-Pb age (159.1 ± 1.9 Ma) of the skarn Pb-Zn ore in depth of the Kangjiawan Au deposit. These suggested that the Au mineralization of the Kangjiawan deposit is coeval with the emplacement of the Shuikoushan granodiorite and Laoyachao Pb-Zn mineralization, which are important parts of the large-scale Middle-Late Jurassic Cu-Au-Pb-Zn Metallogenic event of the Qin-Hang Metallogenic Belt, South China. In addition, trace elemental contents, such as relative low Co, Ni, and Se (i.e., <0.01 to 100 ppm), and a narrow δ34S range of −2.94 ‰ ∼ +3.03 ‰ of pyrite, indicate that ore-forming materials were mainly derived from granitic magmas. Integrated with previous studies, it is suggested that the Au mineralization in the Kangjiawan deposit is genetically associated with the late Jurassic granitic magmatism and is probably as the distal products of the deep-seated concealed granitic intrusions and related proximal skarn Pb-Zn ore.

Sulfur isotope analyses using 3× elemental analysis/isotope ratio mass spectrometry: Saving helium and energy while reducing analytical time and costs.

Helium (He) and energy shortages have caused price increases and reduced their availability. Using three combustion reactions per acquisition of carbon and nitrogen isotope ratios saves 50% He and energy during the elemental analysis/isotope ratio mass spectrometry (EA/IRMS). This approach needs to be tested for sulfur isotope (δ34S) analyses. A new method to measure δ34S in three sequential combustion reactions within one EA/IRMS acquisition was developed. The same material or blank samples could be used in the three reactions. After SO2 was used, a N2 purging method was employed to prolong the lifetime of the valves in the EA/IRMS interface. The 3×EA/IRMS was applied to measure δ34S in precious samples, such as Ag2S from acid-volatile and chromium-reducible sulfur extracted with a multiple-port setup. The 3×EA/IRMS-δ34S method was validated with replicate analyses of international reference materials and laboratory standards with a wide range of mineralogical compositions and δ34S values. The method provided a strategic advantage for the δ34S measurements of small precious samples (measured between blanks). The accuracy and precision of the 3×EA/IRMS values effectively matched those obtained using conventional EA/IRMS, with good agreement between the mean ± SD values and the recommended values with their uncertainties. Compared with the conventional EA/IRMS, the proposed method provides accurate and precise δ34S measurements of the sulfate and sulfide samples while saving approximately 50% of He, energy, SO2 reference gas, O2, analysis time, and cost. Notably, 3×EA/IRMS can provide up to three δ34S values unaffected by memory effects.

Atmosphere and biological impact during sulfide formation in the Archean Central-Vozhma sulfide deposit (Karelia)

Relevance. The need of new knowledge about the early stages of the Earth. Sulfur isotope analysis of sulfide minerals is a powerful tool to understand the processes during the Archaean and Paleoproterozoic. Combined with other data, isotope geochemistry provides an insight into sulfur sources of sulfides from ancient sulfide volcanosedimentary deposits; geochemical factors affecting Archaean sulfide volcanosedimentary ore formation; adjust genetic models and determine the degree of influence of bacteria on the mineral formation. Aim. To identify the sources of sulfur during the formation of sulfide deposits via isotope analysis, and to evaluate bacteria affect mineral formation. Objects. They were obtained from the core of boreholes of Mesoarchaean volcanosedimentary sulfide Central-Vozhma deposit, being a part of the Sumozersko-Kenozersky greenstone belt of the Karelian craton. Methods. Mineralogical studies of rock and ore samples were carried out using optical microscopy; scanning electron microscopy and energy dispersive X-ray spectroscopy. The ratios of four stable sulfur isotopes were analyzed in sulfide minerals of the deposit (33S/32S, 34S/32S, 36S/32S). Results. The results obtained demonstrated the polygenic source of sulfur in sulfides. The sulfides have both positive and negative Δ33S values, indicating the presence of atmospheric sulfur formed under UV photolysis during mineral formation. Sulfide minerals include the following components: Seawater sulfate sulfur of photolytic genesis showed a negative anomaly Δ33S (∼ –0.4‰). It was the source of authigenic pyrite. Sulfides crystallized as a result of biological sulfate reduction demonstrated a narrow range of δ34S values (–2.64‰˂0˂+4.27‰). Elemental sulfur of photolytic genesis mobilized from the host sedimentary rocks by hydrothermal fluids. This sulfur, with a positive Δ33S anomaly (up to +1.6‰) took part in the massive sulfide ores formation.

Anomalous cobalt enrichment in pyrite from an altered mafic dike in the Linglong gold deposit, Jiaodong Peninsula, China: Mechanisms and implications

Traditionally, gold deposits in the Jiaodong gold province of China have been regarded as gold-only deposits lacking economic base metals. However, recent studies found some cobalt (Co) enrichment in those deposits. The mechanisms of this Co enrichment remain poorly understood. In this study, we identified a type of pyrite highly enriched in Co (concentrations up to 32800 ppm) at the Linglong gold deposit, Jiaodong gold province. The pyrite was collected from a hydrothermally altered mafic dike contacting with gold ore veins. To decipher the enrichment mechanisms of Co, in-situ textural, elemental and sulfur isotopic analyses were conducted on the pyrite. The pyrite typically exhibits core-mantle-rim textures. The cores (Py-m1) have high Co concentrations (up to 5950 ppm) with homogeneous texture and elemental distribution, which could be the primary pyrite formed by pyritization of the mafic dike. The mantles (Py-m2) have the highest Co concentrations (up to 32800 ppm) and contain abundant mineral inclusions (chalcopyrite, galena, and sphalerite) and pores, showing the formation through coupled dissolution-reprecipitation (CDR) reactions. The rims (Py-m3) have low concentrations of Co (0.14–559 ppm) and show cubic shapes, forming directly from hydrothermal fluids. The δ34S values increase from the cores (4.2 ‰ to 9.1 ‰, mean of 8.0 ‰) to the mantles (8.9 ‰ to 11.9 ‰), but vary between the above two in the rims (4.2 ‰ to 12.2 ‰, mean of 9.0 ‰). The sulfur isotopic compositions of the Py-m are similar to those of pyrite (4.8 ‰ to 9.5 ‰) from the neighboring auriferous quartz-sulfide veins at Linglong in previous study. Combined with the geological and textural features, it is inferred that hydrothermal fluids during gold mineralization extracted abundant Co from the mafic dikes, leading to the primary enrichment of Co in the Py-m1. The Py-m1 was dissolved and re-precipitated during subsequent hydrothermal activities, forming Py-m2 with enhanced re-enrichment of Co. Basically, the Co-rich mafic dike provided the initial enrichment of Co while the gold-bearing hydrothermal fluids contributed to concentrate Co further. Considering the widespread mafic rocks and extensive hydrothermal activities during gold mineralization throughout the Jiaodong gold province, there might be a considerable Co resource formed through the above processes.

Oxygen and sulfur stable isotope ratios of Late Devonian vertebrates trace the relative salinity of their aquatic environments

Late Devonian aquatic environments hosted the fin-to-limb transition in vertebrates. Upper Devonian (ca. 365−360 Ma) strata in Pennsylvania, USA, preserve a diversity of fishes and tetrapods in coastal marine to fluvial depositional environments, making this region ideal for investigating the ecology and evolution of Late Devonian vertebrates. A key unresolved issue has been reconstructing the specific aquatic habitats that hosted various vertebrates during this period. Specifically, the salinity of environments spanning fresh to shallow marine water is difficult to discern from sedimentological and paleontological analyses alone. Here, we analyze rare earth elements and yttrium (REY) as well as stable oxygen and sulfur isotope compositions (δ18O, δ34S) in fossil vertebrate bioapatite from late Famennian (ca. 362−360 Ma) strata of the Catskill and Lock Haven formations in the Appalachian Basin, USA, to determine the relative salinity of their aquatic environments. These results confirm the ecological euryhalinity of several taxa (Bothriolepis sp., tristichopterids, and Holoptychius sp.). Our results are the first demonstrating that some early tetrapod species occupied unequivocally freshwater habitats by late Famennian time (ca. 362−360 Ma). Our study shows that integrating sedimentological and paleontological data with combined oxygen and sulfur isotope analysis allows precise tracing of the relative salinity of vertebrate habitats deep in the past.