δ34S Values Research Articles

Geology and Geochronology of Magmatic–Hydrothermal Breccia Pipes in the Yixingzhai Gold Deposit: Implications for Ore Genesis and Regional Exploration

Magmatic–hydrothermal breccia pipes are widespread in numerous major porphyry and epithermal gold deposits globally, representing significant repositories of metal resources and serving as potential indicators for exploration targeting. More than ten breccia pipes occur in the Central Taihangshan District (CTD) of the North China Craton. Some of these breccia pipes host gold mineralization and are proposed to be related to the adjacent lode gold mineralization. However, the lack of detailed geological constraints make this hypothesis ambiguous. To address this, the present study conducted comprehensive field observations, drill core logging, an in situ sulfur isotope analysis of pyrite, and the 40Ar/39Ar dating of adularia along a 1400 m section of the Tietangdong breccia pipe at Yixingzhai. Three distinct breccia facies were identified at Tietangdong, exhibiting variable proportions across the entire section, including a massive skarn breccia; polymictic, skarn matrix-supported breccia; and polymictic, intrusive rock cement chaotic breccia. Furthermore, adularia 40Ar/39Ar dating indicates a syn-/post-gold mineralization age of 136 ± 1.5 Ma, coinciding with the age of post-breccia felsite dike. The deepest sampled pyrite displays δ34S values of ~2.7‰, strongly indicating a magmatic–hydrothermal signature. These results, when combined with the geological, geochronological, and isotopic studies on the adjacent lode gold mineralization, further suggest a close genetic relationship between the breccia pipes and the lode Au mineralization, paving the way for their utilization as effective indicators for gold targeting within the CTD.

Insights into fluid evolution and Re enrichment by mineral micro-analysis and fluid inclusion constraints: Evidence from the Maronia Cu-Mo ± Re ± Au porphyry system in NE Greece

Porphyry-epithermal veins hosting Re-rich molybdenite and rheniite (ReS2) from the Maronia Cu-Mo ± Re ± Au porphyry in Thrace, NE Greece, provide new insights into the hydrothermal processes causing extreme Re enrichment. Quartz trace element chemistry (Al/Ti, Ge/Ti), Ti-in-quartz thermometry, and cathodoluminescence imaging reveal multiple quartz generations in consecutive hydrothermal quartz-sulfide veins associated with potassic, sericitic, and argillic alteration. Fluid inclusions in different quartz generations indicate that phase separation and fluid cooling are the main ore-forming processes in the porphyry stage (~ 500 – 350 °C), whereas mixing of a vapor-rich fluid with metalliferous (e.g., Pb, Zn, Au) meteoric water forms the epithermal veins (~ 280 °C). These processes are recorded by trace element ratios in pyrite that are sensitive to changes in fluid temperature (Se/Te), fluid salinity (As/Sb, Co/As), and mixing between fluids of magmatic and meteoric origin (Se/Ge). Highly variable intra-grain δ34S values in pyrite record S isotope fractionation during SO2 disproportionation and phase separation, emphasizing the importance of in situ δ34S analysis to unravel ore-forming processes. High δ34S (~ 4.5‰) values of sulfides are indicative of low SO42−/H2S fluid ratios buffered by the local host rocks and mixing of the magma-derived fluid with meteoric water. The formation of Re-rich molybdenite (~ 6600 ppm) is favored by cooling and reduction of a magma-derived, high-temperature (~400 °C), oxidized, and Re-rich fluid triggering efficient Re precipitation in early veins in the potassic alteration zone. The systematic temporal fluid evolution therefore reveals that coeval cooling and reduction of oxidized Re-rich fluids cause extreme Re enrichment at the Maronia porphyry system.

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Geochemical and mineralogical features as indicators of sulfate-methane transition zones in shallow gas-bearing offshore sediments from Zhoushan

Subsurface shallow gas, primarily composed of biogenic methane (>95%), is highly-enriched in global offshore sediments. The redox conditions of methane-rich pore fluid play a crucial role in shaping the geochemical signatures associated with the anaerobic oxidation of methane (AOM) and vertical displacement of sulfate-methane transition zones (SMTZs) within deep sedimentary records. However, long-period, and continuous records of AOM and SMTZs in shallow gas-bearing offshore sediments are sparse. Here, we employed a comprehensive analyses of iron sulfide, elemental, and stable isotopies on a 63-m drilled sediment core (JC-1) from offshore Zhoushan. Four different layers U1–U4 were identified in 11.5–24 mbsf, 24−42 mbsf, 42−51 mbsf, and 51−63 mbsf, respectively, as revealed by the lithofacies and sedimentary structures. By comparing the pyrite contents, total sulfur to total organic carbon ratios, and δ34S-chromium-reducible sulfur values, the commonly seen organoclastic sulfate reduction occurred in U1 and U2, whereas significant AOM activities were found in U1 and U4. Further, the peaks of total sulfur to total organic carbon ratios, sulfur contents, and multiple positive δ34S-chromium-reducible sulfur values indicated the presence of AOM in SMTZs at 18.3, 52, and 59 mbsf. These intervals were featured by a sub-oxic or anoxic condition with strong methane seepages, evident from the scarcity of metals and the enrichment of Mo/Al and U/Al ratios. The presence of multiple SMTZs was consistent with the pore-water data of the adjacent YS4 and YS7 cores. In light of these findings, it is prudent to exercise caution when utilizing geochemical indicators, such as trace element proxies and the δ34S values of sulfide minerals, to comprehend the progression of fluctuating depositional settings in reaction to sea-level fluctuations and shallow gas reservoirs. This study provides a new perspective to better understand the evolution of unsteady depositional environments in response to sea-level changes and shallow gas reservoirs.

Relationship between Pb-Zn and Au mineralization in the Laoyachao deposit, South China: Constraints from geology and S-Pb-He-Ar isotopes

Both Pb-Zn and Au mineralization can simultaneously occur at the deposit, camp or regional scale, but their spatial-temporal and genetic relationships have received less attention so far. Here we present detailed field investigations and S-Pb-He-Ar isotope data for the Laoyachao deposit, South China, to interpret the intrinsic associations between Pb-Zn and Au mineralization. Both Pb-Zn and Au ores in the studied area are distributed independently but spatially associated with the same granodiorite. Field and microscopic observations, together with previous dating, show that the Au mineralization postdated the Pb-Zn mineralization. The relatively restricted range and lower δ34S values for the Au ores (−0.72 to +0.94 ‰) and the Pb-Zn ores (−1.98 to +2.36 ‰) indicate that both metal mineralization types are attributed to a homogeneous magmatic sulfur source. Lead isotope compositions for the ores and the feldspars from the granodiorites define a well-defined linear array, with the Au ores displaying less radiogenic Pb. In addition, the Pb-Zn ores exhibit lower 3He/4He and 40Ar/36Ar ratios (0.01–0.26 Ra, 298–313) than the Au ores (0.16–2.93 Ra, 341–382). All evidence demonstrated that, besides the granodiorite end-member, an end-member with high-radiogenic Pb and lower 3He/4He values participated in the early Pb-Zn mineralization, in contrast, the other end-member with less radiogenic Pb and higher 3He/4He values was involved in the late Au mineralization. Considering that both Pb-Zn and Au mineralization in the studied deposit are spatially, temporally and genetically related to the same granodiorite, the Pb-Zn mineralization associated with granodiorite can provide an indicator for gold exploration.

Mineralogical and geochemical studies on the Qianjiadian deposit, Songliao Basin, NE China: Insights into multiple metallogenic processes in the sandstone-type uranium deposit

Sandstone-type uranium deposits usually exhibit a range of metallogenic mechanisms. To gain insights into the nature, genetic relationships, and mineralization mechanisms of uranium and associated minerals, representative samples from the Qianjiadian uranium deposit in the Songliao Basin were investigated through detailed mineralogical, elemental geochemical, and in-situ sulfur isotopic analyses. The results provided invaluable information on the various stages of uranium mineralization. During the early diagenetic stage, uranium mineralization occurred in the local organic matter (OM)-enriched sites (TOC = 0.70 ∼ 2.05 %) in the Yaojia Formation. The paragenetic relationship revealed that uranium was firstly precipitated as pitchblende along with the biogenetic framboidal pyrite (δ34S values ranging from −44.1 ‰ to −1.8 ‰) through bacterial sulfate reduction (BSR) process. Simultaneously, organic acids generated through biodegradation of OM caused an acidic fluid condition and subsequent dissolution of feldspars, resulting in the production of kaolinite intergrowth with pitchblende. During the late diagenetic stage, the ore-forming fluid turned alkaline, leading to the conversion of pitchblende into coffinite, with elevated elements such as Si, P, Ca, Zr, and Y in the altered phase. In addition to the contribution of OM and sulfate-reducing bacteria (SRB), pyrite was confirmed as a reducing agent manifested by its replacement by uranium minerals and the Fe-oxide produced along the boundaries. The diagenetic uranium enrichment is mainly hosted in the gray sandstone that experienced reduced alteration of deep hydrocarbons, resulting in pervasive kaolinization and promotion of reduction potential. A significant amount of uranium was fixed by adsorption, as evidenced by the rare observation of independent uranium minerals, but the higher whole-rock U content (U = 133.5 ∼ 394.0 ppm) and the detection of U signal in micro-XRF analysis and EPMA data (U content in representative kaolinite ranges from bld to 0.74 wt%). Overall, the formation of sandstone-type uranium deposits is a long-term and multi-stage process. The early enriched uranium during synsedimentary-diagenetic stages is non-negligible and can even result in an appreciable amount of mineralization, further serving as an important source for the subsequent secondary enrichment.

In-Situ Geochemical and Rb–Sr Dating Analysis of Sulfides from a Gold Deposit Offshore of Northern Sanshandao, Jiaodong Peninsula, North China: Implications for Gold Mineralization

The gold deposit offshore of Northern Sanshandao is an ultra-large-scale gold deposit discovered in the Jiaodong ore area in recent years. This deposit is a fractured-zone altered-rock-type gold deposit; however, its ore genesis and precise mineralization processes are still highly controversial. Based on petrographical observation, the trace elements, sulfur isotopes, and rubidium–strontium isotopes of the gold-bearing pyrite were analyzed using LA-MC-ICP-MS to obtain the source of the ore-forming fluids and ore genesis. The results show that Au has a good positive correlation with Ag, As, and Cu. It is speculated that the As in the pyrite of the gold deposit offshore of Northern Sanshandao is in the form of As−, replacing S− and entering the pyrite, causing its lattice defects, and thus promoting the entry of Au+ into the gold-bearing pyrite. The Co/Ni ratios mainly range between 0.1 and 10, indicating that the mineralization process has experienced different forms of hydrothermal evolution and the mixing of different fluids. The results of the in-situ sulfur isotope analysis show that pyrite δ34S in the mineralization period is characterized by a high sulfur value. The authors of this study believe that the initial sulfur isotope composition has mantle-derived components. The large-scale, deep cutting, and high degree of fragmentation in the Sanshandao fault zone are conducive to the interaction between fluids and rocks, as well as the mixing and addition of seawater, resulting in the characteristic high δ34S value. The Sr isotopic compositions indicate a crust–mantle mixing attribute of the mineralized material source. The Rb–Sr isochron age of the pyrite is 118.5 ± 0.65 Ma, which represents the age of gold mineralization. According to the characteristics of the trace elements and sulfur isotopes, it is inferred that the gold deposit minerals offshore of Northern Sanshandao originated from deep magmatic-hydrothermal reservoirs, and the mixing of seawater and Au–As-rich hydrothermal fluids was the formation mechanism of huge amounts of gold precipitation.

Genesis of the Mahour Base Metal Deposit, Iran: Constraints from Fluid Inclusions and Sulfur Isotopes

The Mahour base metal deposit is located northeast of Badroud in the middle of the Urumieh–Dokhtar magmatic arc in the Isfahan province of Iran. The main host rocks to the ores are Eocene volcanic and volcaniclastic rocks. Hypogene ore minerals constituting the main ore body are galena, sphalerite, pyrite, and chalcopyrite. In addition to gangue quartz, a variety of supergene minerals comprising gypsum, goethite, hematite, “limonite”, malachite, azurite, covellite, and chalcocite are also present; gangue minerals are quartz, barite, calcite, sericite, and chlorite. Silicification, intermediate argillic, and propylitic are the main wall-rock alteration types. The presence of fluid inclusions with different vapor/liquid ratios in quartz and sphalerite could indicate a boiling process. The primary liquid-rich fluid inclusions suggest that the homogenization temperature was between 107 and 298 °C from fluids with salinities from 1.5 to 13.7 wt.% NaCl equiv. These data suggest that the ore-forming fluids were magmatic with a contribution from meteoric waters. The δ34S values of sulfides range from 1.9 to 3.4‰, those of barite range from 12.1 to 13.2‰, and those of gypsum range from 4.3 to 5.6‰. These data suggest that sulfur was mostly of magmatic origin with a minor contribution from sedimentary rocks. Our data suggest that the boiling of fluids formed an intermediate-sulfidation style of epithermal mineralization for the Mahour deposit.

Origin and evolution of a porphyry-skarn-stratabound system: constraints from geology, magmatic-hydrothermal zircon U–Pb and molybdenite Re–Os geochronology, and in situ S isotopes of the Dongguashan Cu(–Au) deposit, eastern China

Intrusion-related stratabound deposits within Late Carboniferous carbonate units are an abundant and highly economically significant ore type in eastern China. In such deposits, stratabound mineralization commonly coexists with porphyry and/or skarn mineralization, and the vast majority of reserves (>90 %) are derived from extensive stratabound orebodies, which are easy to exploit and of great interest to geologists. However, it is unclear whether these deposits were formed via the Late Carboniferous seafloor sedimentary exhalation formation or the Early Cretaceous magmatic-hydrothermal processes. Moreover, the fluid and sulfur isotope variations within porphyry-skarn-stratabound systems have not been adequately constrained. We investigated the Dongguashan deposit, one of the largest and most representative stratabound Cu(–Au) deposits in eastern China. Three mineralization types were recognized based on field and petrologic studies: porphyry, skarn, and stratabound. In the stratabound mineralization zone, magmatic and hydrothermal zircons from laminated ores yielded concordant U–Pb ages of 137.3 ± 1.1 and 135.7 ± 1.4 Ma, respectively, while molybdenite samples from vein-like ores yielded Re–Os model ages of 137.8–133.1 Ma (isochron age, 135.9 ± 1.4 Ma). These ages were consistent with the zircon U–Pb age of quartz monzodiorite (137.8 ± 1.7 Ma). A total of 146 in situ S isotope analyses yielded δ34S values (1.9–7.4 ‰) indicating that the sulfur was derived from a magmatic source. Therefore, the Dongguashan deposit resulted from Early Cretaceous magmatism rather than submarine exhalative sedimentary processes. The fluctuations in S isotopes of sulfides across the three mineralization types are attributable to different factors (pH, temperature, and oxygen fugacity) during the evolution of hydrothermal ore-forming fluids. This study demonstrates the importance of geochronology of mineralization and in situ sulfur isotope analysis under robust geological and petrographic frameworks, which can yield information about the ore-forming processes and ore genesis.

Multistage evolution of gold mineralization in the Kibali gold district: Insights from pyrite analyses

The Kibali gold district, located on the Congo Craton, comprises a Neoarchean gold resource exceeding 28.7 Moz. The district is located within a westerly-verging stacked fold-and-thrust belt associated with a compressional tectonic regime active from ca. 2.64–2.60 Ga. Deposits are hosted by a major fault zone that consists of a complex series of smaller thrust faults, shear zones, and folds, which extend over 60 km. Gold deposits are primarily hosted in BIF and clastic sedimentary rocks. The gold and associated sulfides are in veins and disseminated in NE-to NNE-trending ore shoots within the deformed and metamorphosed volcanosedimentary rocks. Pyrite is the dominant sulfide mineral and hosts both solid solution gold and free gold. Because of its strong association with the gold mineralization, our study focusses on unravelling the metallogeny of the area by considering pyrite textural analyses, in situ trace element analyses using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), and S isotopic composition (δ34S) analyses using Secondary Ion Mass Spectrometry (SIMS).Eight distinct pyrite types were identified, including microcrystalline sooty (py-0a), small grains (<40 μm) (py-0b), aggregate recrystallized (py-1), core-rich inclusion (py-2), vein-like (py-3), non-zoned (py-4a), oscillatory As-bands zoned (py-4b), and cubic euhedral (py-5) pyrite. The ore-forming processes occurred over a polyphase evolution. Syn-diagenetic pyrite py-0a in volcaniclastic layers of older basin sediments served as the primary repository of Au (15.6 ppm median) with a near-zero δ34S value. Late diagenetic or early metamorphic pyrite (py-0b) was found in younger basin sediments. Py-1 resulted from solid-state recrystallization of py-0a and py-0b. During the early ore stage, porous py-2 with high Au concentrations (3.1 ppm) and various trace element enrichments precipitated due to fluid-rock interaction. Metal precipitation occurred through sulfidation and carbonation of wall rock with a relatively reduced fluid undergoing 34S-depletion. However, py-3 displayed notable trace element depletion and a complex mineral association. In a second ore stage, py-4a and zoned py-4b deposition occurred, dominated by an over-pressured fluid fracturing brittle rock. Py-4b, rich in Au (5.5 ppm) concentrated in oscillatory zoned As-rich bands, resulted from interactions during pulsed fluid flow. This process involved fluid phase separation, non-equilibrium conditions, 32S-depletion, and precipitation of py-4b with a high δ34S value (6.4 ‰ mean). Subsequently, pyrite (0–4) generations underwent deformation during a later ductile deformation event, leading to the remobilization and concentration of invisible gold into adjacent gold grains within the high-grade shoot plunging NE. This process involved shearing, boudinaging, and folding ore minerals in tightly folded structures. Late-stage py-5 formed under gold-poor fluid conditions or inefficient gold depositional conditions. Brittle fracturing of these grains later provided local sites for remobilized gold. The study contributes insights into the origin and evolution of gold mineralization in the Kibali gold district, supporting a multistage ore-forming fluid system.

Sedimentary environment of basal Ediacaran barite growth on Baltica in E. Finnmark, N. Norway, and subsequent dissolution/reprecipitation

Basal Ediacaran barite, which has mass-anomalous depleted 17O, supporting Snowball Earth models, likely grew in shallow-marine settings, but sedimentological constraints lack details. Environmental conditions in the Varanger Palaeovalley during the basal Ediacaran are well preserved in the Nyborg Formation, where barite forms < 15 mm high synsyn-sedimentary crystal fans on Archean basement or thin intervening sediments. Sedimentary evidence suggests crystal fans formed in low-energy, very shallow-marine to subaerial facies. Rare earth element and yttrium signatures in associated carbonates suggest non-saline growth environments. Post-depositional fluid-flow replaced crystal fan barite with silica (now quartz) and redeposited barite as: <1 × 0.2 mm “dispersed” grains in sediments below fans; <5 mm grains replacing calcite filling desiccation cracks; <1 mm grains in basement fissures; <3 µm grains replacing matrix calcite; irregular grains in detrital sheet-silicate + calcite grains. Caledonian dissolution-reprecipitation reworked barite into brittle fractures and stylolites. Barite Δ17O values are amongst the most negative (-0.9 – -1.25 ‰) and δ18O values the lowest recorded (9.9 – 16.9 ‰) anywhere, consistent with a high latitude Baltica at ∼ 635 Ma. δ34S values (17.7 – 24.5 ‰) lie within the known range for basal Ediacaran barite.

Rb–Sr Pyrite Dating and S–Pb Isotopes in the Fang’an Gold Deposit, Wuhe Area, Eastern Anhui Province

The Fang’an gold deposit in the Wuhe area, Anhui Province, is located in the area adjacent to the Bengbu Uplift and Wuhe Platform Depression in the southeastern part of North China. This study aimed to determine the deposit’s mineralization age and the source of its metallogenic materials and mineralization processes through investigations into its geological characteristics, Rb–Sr isotopes, and S–Pb isotopes. The orebodies of the Fang’an gold deposit in the Neoarchean Xigudui Formation primarily exhibit a vein-type structure. The ore-forming process can be divided into four stages: (i) the quartz stage (Py1); (ii) the quartz–pyrite stage (Py2); (iii) the polymetallic sulfide stage (Py3); and (iv) the carbonate stage. Of these, the main mineralization stage is also the main period in which gold mineralization occurs. In situ sulfur isotope results of pyrite (Py1 to Py3) in the first three mineralization stages, suggesting a contribution of sulfur from crust–mantle magmatic fluids. The δ34S values for Py2 (average 5.51‰) are higher than Py1 (average 4.45‰) and showed that the magmatic fluids mixed with meteoric waters. The δ34S values for Py3 (average 5.18‰) are lower than Py2 (average 5.51‰), revealing that it related fluid immiscibility. The lead isotopic compositions of sulfides within the ores possessed 206Pb/204Pb ratios ranging from 16.759 to 16.93, 207Pb/204Pb ratios ranging from 15.311 to 15.402, and 208Pb/204Pb ratios ranging from 37.158 to 37.548. These lead data were plotted close to the Xigudui Formation, relatively distant from the Mesozoic granites, indicating that the Xigudui Formation was the source of lead for the Late Mesozoic ores of the deposit. Taken together, due to the degassing of mantle-derived magma in the shallow parts of the crust, it can be determined that the sources of ore-forming sulfur and lead were crust–mantle magmatic activities in the Wuhe area. Rb–Sr dating of pyrite from Fang’an gold deposit reveals that the mineralization occurred at 126.89 ± 0.58 Ma. Considering the previous research into the dating of magmatic rocks in the Wuhe area, we propose that the genesis of the Fang’an gold deposit is closely associated with magmatic activities in the area at around 130 Ma.

Robust sulfur and oxygen isotope evidence for a highly anoxic paleoenvironment in Late Devonian seawater: Insights from marine anhydrites in the Zaige Formation, South China

A global-scale mass extinction event occurred in the Late Devonian, and its triggering mechanisms have remained a subject of controversy. The key to resolving this controversy lies in elucidating paleoenvironmental characteristics and their coupling relationship with the mass extinction. Marine evaporites serve as sensitive indicators that can be used for reconstructing the geochemical history of ancient oceans. In this study, we present a dual sulfur and oxygen isotopic dataset of marine anhydrites in the Lunatian gypsum deposit (Yunnan, China), and investigate its paleoenvironmental significance within the framework of the Late Devonian mass extinction. These anhydrites originate in arid and hot continental margin seas near convergent plate boundaries, forming as a result of the dehydration of marine gypsums during burial processes. Anhydrites exhibit a conspicuous positive anomaly in δ34S values (23.6–25.1‰, averaging 24.3‰), primarily attributed to bacteria-mediated sulfate reduction. The δ18O values of the Lunatian anhydrites (12.2–15.2‰, averaging 14.0‰) indicate a slightly higher oxygen isotope composition for Late Devonian seawater (8.7–11.7‰, averaging 10.5‰) compared to those of contemporary seawater (9.5–10.1‰). Such an oxygen isotopic characteristic for the Lunatian anhydrites is intricately associated with the chemical processes that occur during the diffusion of sulfides into the upper seawater. The anhydrite-forming evaporating system has a noticeable brine layering where the surface seawater is less dense than the deeper brine, and bacterial processes gradually increase δ34S in the deep brine. When the deep brine and surface seawater rapidly mix, it leads to a significant positive shift in the sulfur isotope composition of the resulting evaporites. Our sulfur and oxygen isotope data from Lunatian anhydrites validate the existence of an exceedingly anoxic marine environment during the Late Devonian, potentially serving as a pivotal factor in the mass extinction event.

Trace Element and Sulfur Isotope Signatures of Volcanogenic Massive Sulfide (VMS) Mineralization: A Case Study from the Sunnhordland Area in SW Norway

The Sunnhordland area in SW Norway hosts more than 100 known mineral occurrences, mostly of volcanogenic massive sulfide (VMS) and orogeny Au types. The VMS mineralization is hosted by plutonic, volcanic and sedimentary lithologies of the Lower Ordovician ophiolitic complexes. This study presents new trace element and δ34S data from VMS deposits hosted by gabbro and basalt of the Lykling Ophiolite Complex and organic-rich sediments of the Langevåg Group. The Alsvågen gabbro-hosted VMS mineralization exhibits a significant Cu content (1.2 to &gt;10 wt.%), with chalcopyrite and cubanite being the main Cu-bearing minerals. The enrichment of pyrite in Co, Se, and Te and the high Se/As and Se/Tl ratios indicate elevated formation temperatures, while the high Se/S ratio indicates a contribution of magmatic volatiles. The δ34S values of the sulfide phases also support a substantial influx of magmatic sulfur. Chalcopyrite from the Alsvågen VMS mineralization shows significant enrichment in Se, Ag, Zn, Cd and In, while pyrrhotite concentrates Ni and Co. The Lindøya basalt-hosted VMS mineralization consists mainly of pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V, and Tl. The δ34S values of sulfides and the Se/S ratio in pyrite suggest that sulfur was predominantly sourced from the host basalt. The Litlabø sediment-hosted VMS mineralization is also dominated by pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V and Tl. The δ34S values, which range from −19.7 to −15.7 ‰ VCDT, point to the bacterial reduction of marine sulfate as the main source of sulfur. Trace element characteristics of pyrite, especially the Tl, Sb, Se, As, Co and Ni concentrations, together with their mutual ratios, provide a solid basis for distinguishing gabbro-hosted VMS mineralization from basalt- and sediment-hosted types of VMS mineralization in the study area. The distinctive trace element features of pyrite, in conjunction with its sulfur isotope signature, have been identified as a robust tool for the discrimination of gabbro-, basalt- and sediment-hosted VMS mineralization.

Sedimentary Environment and Mineralization of the Black Shale Polymetallic Layer in the Early Cambrian, SW China: Constraints from in situ LA‐ICP‐MS Analysis of Pyrite

AbstractA polymetallic layer is usually developed at the bottom of the early Cambrian black shale in Guizhou Province. The mineral that makes up the polymetallic layer is related to the sedimentary facies. To analyze the differentiation mechanism between polymetallic deposits (Ni‐Mo and V), the Zhijin Gezhongwu profile located in the outer shelf and the Sansui Haishan V deposit located in the lower slope are selected to study the in situ sulfur isotopes and trace elements of pyrite. The results show that δ34S values of pyrite vary widely from −7.8 ‰ to 28 ‰ in the Gezhongwu profile, while the δ34S values are relatively uniform (from 27.8 ‰ to 38.4 ‰) in the Haishan profile. The isotopic S composition is consistent with the transition that occurs in the sedimentary phase from the shelf to the deep sea on the transgressive Yangtze platform; this indicates that the δ34SO42– values in seawater must be differently distributed in depositional environments. The sulfur in the Ni‐Mo layer is produced after the mixing of seawater and hydrothermal fluid, while the V layer mainly originates from seawater. Overall, the Ni‐Mo and V deposits have been differentiated primarily on the basis of the combined effect of continental weathering and hydrothermal fluid.

Gold source and deposition in the Sanakham gold deposit, SW Laos: Constrains from textures, trace element geochemistry and in-situ sulfur isotopes of pyrite

The Luang Prabang (Laos) – Loei (Thailand) metallogenetic belt is endowed with major porphyry-skarn, and epithermal gold deposits. The Sanakham gold deposit is a newly discovered hydrothermal vein-type orogenic gold deposits (10.6 t Au @ 3.05 g/t) in the belt, and consist of a series of quartz-sulfide veins that are controlled by secondary structures of the regional NNE-trending brittle-ductile shear zone. Its mineralization can be divided into four stages: (I) quartz–pyrite–arsenopyrite, (II) quartz–pyrite–pyrrhotite–chalcopyrite, (III) quartz–pyrite–base-metal sulfide, and (IV) quartz–carbonate. Three pyrite generations were identified: py1 (stage I) as disseminated euhedral to subhedral coarse grains; py2 (stage II) as subhedral to anhedral fine grains occur around the cataclastic and corrosion textures in py1; py3 (stage III) as subhedral to anhedral fine grains occurred in sulfide veins or veinlets that overprint the existing quartz-sulfides. All three generations of pyrite have low trace-element contents including very low lattice-bound gold (py1: 0.040 ppm; py2: 0.098 ppm; py3: 0.028 ppm) and arsenic (py1: 227 ppm; py2: 133 ppm; py3: 13.3 ppm) contents. Visible gold grains are sited in textures of pyrite grains that relate to brittle cataclastic deformation. Considering the relatively low contents of pyrite in the ores of Sanakham, it is impossible to derive the high-gold grade orebodies through local remobilization of originally lattice-bound gold in pyrite. The py2 might be formed during hydrothermal overprinting and dissolution of py1 led by continuous supply of ore fluids with relatively higher contents of Au, Ag, Cu, Sb, Te, Pb, and Bi. A reduction reaction related to reduced carbon species in wallrock is an assignable cause for gold deposition, even though the fluid-rock interaction and fluid immiscibility processes might be important. The Au- and As-poor pyrites have similar δ34S values (py1: –2.58 to –0.83 ‰; py2: –2.17 ‰ to + 0.25 ‰; py3: –1.24 to –0.60 ‰ ppm) that close to 0 ‰, indicating the sulfur may have been originated from magmatic or mantle sources. Therefore, we propose that the Sankham gold deposit is a member of the orogenic deposit class, but notably characterized by the low concentrations of invisible gold in the relatively As-poor pyrite lattice.

Pyrite Characteristics in Lacustrine Shale and Implications for Organic Matter Enrichment and Shale Oil: A Case Study from the Triassic Yanchang Formation in the Ordos Basin, NW China.

Pyrite is widely distributed in lacustrine shales and has become a research focus in unconventional oil and gas exploration. Pyrite morphology is useful for identifying different types of organic matter and assessing shale oil enrichment in organic-rich shale. Abundant pyrite is developed in the source rocks from the Chang 7 Member of the Yanchang Formation in the Ordos Basin, NW China. However, the relationship between different pyrite types and the differential enrichment of shale oil still needs to be clarified. The organic geochemistry, petrology, and isotopic composition of the Chang 7 Member samples were analyzed. The significance of pyrite types and sulfur isotopic compositions as indicators of depositional environments and shale oil enrichment was emphasized. The Chang 7 shales contain three pyrite morphologies, framboidal pyrite (type A), spherulitic pyrite (type B), and euhedral and anhedral pyrite (type C), and their aggregates. The sulfur isotopic compositions of pyrite (δ34Spy) in Chang 7 shales with different pyrite types exhibited regular patterns. The δ34S values of types A, B, and C pyrites were sequentially positive overall (average values are -2.739, 2.201, and 7.487‰ in sequence), indicating that type A pyrite was formed during the syn-sedimentary to early diagenetic stage and types B and C pyrites were formed during the early to middle diagenetic stage. Types A, B, and C pyrites showed sequentially increasing kerogen type index values and kerogen carbon isotope values (mean values of -31.59, -28.70, and -26.45‰, successively), indicating that the horizons where types A, B, and C pyrites developed correspond to types I, II, and III organic matter, respectively. Strong correlations between the pyrite content and oil components reveal that pyrite indicates shale oil enrichment. Moreover, variations in pyrite type significantly influenced the enrichment behavior of shale oil. Types A and B pyrites contributing to reservoir space showed shale oil enrichment. They promoted saturated hydrocarbon enrichment at >15% pyrite content, whereas type C pyrite did not indicate shale oil enrichment. These findings provide new insights into the differential enrichment of organic matter and shale oil and valuable guidance for the large-scale exploration and development of shale oil resources.

Genesis of Fe–Ti Oxide-Bearing Ultramafic Intrusions in the Duluth Complex, Minnesota, USA

Abstract The Duluth Complex is a large mafic intrusive system located in northeastern Minnesota emplaced as part of the 1.1-Ga Midcontinent Rift. Several Fe–Ti oxide-bearing ultramafic intrusions are hosted along the Western Margin of the Duluth Complex, and are discordant bodies present in a variety of geometries, hosted in multiple rock types, and dominated by peridotite, pyroxenite, and semi-massive to massive Fe–Ti oxide rock types. Their origin has been debated, and here we present geochemical evidence and modeling that supports a purely magmatic origin for the Titac and Longnose Fe–Ti oxide-bearing ultramafic intrusions. Ilmenite and titanomagnetite textures indicate a protracted cooling process, and δ34S values of sulfides reveal little assimilation of the footwall Virginia Formation, a fine-grained pelitic unit that contains sulfide-rich bands. We model the crystallization of a hypothetical parental magma composition to the host intrusion of Longnose using Rhyolite-MELTS and demonstrate that the accumulation of Fe–Ti oxides in the discordant intrusions cannot be explained by density-driven segregation of crystallized Fe–Ti oxides. Instead, we show that the development of silicate liquid immiscibility, occurring by the unmixing of the silicate melt into conjugate Si- and Fe-rich melts, can result in the effective segregation and transportation of the Fe-rich melt. The Fe-rich melt is ~2 orders of magnitude less viscous than the Si-rich melt, allowing the Fe-rich melt to be more effectively segregated and transported in the mush regime (crystallinities &amp;gt;50%). This suggests that viscosity, in addition to density, plays a significant role in forming the discordant Fe–Ti oxide-bearing ultramafic intrusions. We propose a genetic model that could also be responsible for the Fe–Ti oxide-rich layers or bands that are hosted within the igneous stratigraphy of mafic intrusions of the Duluth Complex.

Geochemistry, Mineralization, and Fluid Inclusion Study of the Bayan-Uul Porphyry Au-Cu-(Mo) Deposit, Central Mongolia

The Bayan-Uul porphyry Au-Cu-(Mo) deposit occurs within the Mongol–Okhotsk Orogenic Belt, which is a part of the Central Asian Orogenic Belt. To understand geotectonic, petrogenesis, mineralization, and ore-forming fluid evolution of the Bayan-Uul deposit, we report petrographic and geochemical analyses of host rocks, mineralogy of ores, and fluid inclusion characteristics. Based on petrographic and mineralogical analyses, Cu, Mo, and Au mineralization occurs as disseminated and sulfide-bearing quartz–tourmaline veins hosted within granodiorites, monzodiorites, and diorite porphyry and tourmaline breccia. Four main alteration assemblages are identified: potassic, phyllic, argillic, and quartz–tourmaline alteration. The ore mineralogy of quartz–tourmaline veinlets are classified into A-type veinlets (quartz + tourmaline + chalcopyrite + magnetite + pyrite ± electrum), B-type veinlets (quartz + tourmaline + molybdenum + chalcopyrite + pyrite), and C-type veinlets (quartz + tourmaline + pyrite ± chalcopyrite). Fluid inclusions are found in quartz–tourmaline veinlets consisting mainly of liquid-rich two-phase (L-type), vapor-rich two-phase (V-type), and solid-bearing multi-phase (S-type) inclusions. The homogenization temperatures for the fluid inclusions in A-type, B-type, and C-type veinlets range from 215 to 490°C, 215 to 500 °C, and 160 to 350 °C and their salinity varies from 5.4 to 43.5 wt.%, 16 to 51.1 wt.%, and 3.4 to 24.1 wt.% NaCl equivalent, respectively. Coexistance of (L-type), (V-type), and (S-type) inclusions support fluid boiling. The δ18O values of ore fluids from different mineralizing A-, B-, and C-type veins are 8.7‰, 10.9‰, and 8.4‰, respectively, and the δ34S values of sulfide minerals range from −1.4‰ to 5.3‰, which indicates magmatic origin.

Spatio-temporal fluid evolution of gold deposit in the Jiaodong Peninsula, China: A case study of the giant Xiling deposit

The Xiling gold deposit (>592 t @ 4.02 g/t) in the eastern Zhaoyuan-Laizhou gold belt of the Jiaodong Peninsula, is currently the largest gold deposit and deepest gold mine in China. This study presents microthermometric fluid inclusions data on quartz gangue, as well as trace element and S isotope data on pyrite from different mineralization stages and depths in the Xiling gold deposit to provide new insights into the spatio-temporal evolution of the ore-forming fluid that led to a giant Early Cretaceous gold deposit in the Jiaodong Peninsula. The δ34S values of pyrite range from 7.5 to 15.2 ‰, but vary temporally and spatially, reflecting a changes in physicochemical conditions as the ore-forming fluid migrated to different crustal levels over time, also suggesting Precambrian basement as the principal sulfur source. Trace element analyses of pyrite revealed that ore-forming metals were scavenged from the wall rock and then incorporated into the pyrite. Fluid inclusions data reveal that the ore-forming H2O-CO2-NaCl ± CH4 fluid had a medium to high temperature (283–401 °C), medium-low salinity (1.91–8.00 wt% NaCl equivalent), analogous to most gold deposits in the Jiaodong Peninsula. Intensive interaction between the ore-forming fluid and wall rock changed the physicochemical conditions of fluid, leading to gold precipitation. The study supports the notion of the ore fluid of Jiaodong-type gold deposit having originated from a metasomatized lithospheric mantle.