Pyrite Sulfur Isotope Research Articles

The genesis of intersection-type uranium deposits in south China: Insights from zircon and pitchblende U-Pb geochronology and pyrite sulfur isotopes of the Egongtang uranium deposit, southern Jiangxi

Intersection-type uranium deposits refer to the uranium deposits that are located at the intersection of mafic dykes and silicified faults and are an important type of granite-related uranium deposits in South China. However, the genesis of these deposits still remain poorly understood. The Egongtang uranium deposit is a typical intersection-type uranium deposit in the Huangsha uranium ore district (southern Jiangxi) that bears a number of NWW-trending mafic dykes, thus providing an excellent opportunity to study the genesis of intersection-type uranium deposits. In this study, the mineralization age and genesis of this deposit were constrained using in situ zircon and pitchblende U-Pb geochronology, whole-rock geochemistry, and pyrite sulfur isotope data. The zircon U-Pb dating constrains the crystallization ages of 240.4 ± 1.3 Ma and 160.7 ± 1.6 Ma for granites in the Huangsha ore district. The samples (including altered and unaltered) of the granites are characterized by variable whole-rock U contents of 5.8–14.1 ppm and Th/U ratios of 2.4–7.7, which favor the crystallization of uraninite in the granites and suggest U leaching from the granites during alteration. In situ U-Pb dating on pitchblende from the Egongtang uranium deposit yielded a lower intercept age of 89.8 ± 1.1 Ma, indicating that the uranium mineralization took place at the Late Cretaceous. Pyrite associated with pitchblende has δ34S values ranging from 1.6‰ to 3.8‰, suggesting a magmatic source. This study indicates that granites in this area might have represented the source of uranium for the Egongtang deposit, and that the uranium mineralization was probably related to the Late Cretaceous crustal extension in South China.

Primary productivity recovery and shallow-water oxygenation during the Sturtian deglaciation in South China

The Cryogenian Period (ca. 720–635 Ma) marks a key node in Earth's history, characterized by two global glaciations when the paleo-tropical regions were covered by glaciers, namely the Sturtian and Marinoan Snowball Earth events. Within the Cryogenian, the evolution of primary producers persisted, evidenced by the worldwide discovery of diverse microfossils and the proliferation of algae in the interglacial oceans. The Cryogenian radiation of algae facilitated the emergence and evolution of early eumetazoan animals. However, the paleoredox reconstruction of the interglacial Cryogenian presents more challenges. The open oceans were predominantly and permanently ferruginous throughout the Cryogenian Period, and persistently euxinic conditions developed in restricted basins, such as the Nanhua Basin. Some of the studies suggested a possible fully‑oxygenated interval in the aftermath of the Sturtian glaciation. Therefore, a knowledge gap lies between the biological prosperity and severe habitability in the interglacial oceans. In order to fill this gap, we report a newly discovered interglacial deposition – the Datangpo Formation – of shallow water depth from the Guitouwan section, Shennongjia area, South China. A combination of iron speciation, total organic matter (TOC), and pyrite sulfur isotopes (δ34Spy) analyses are conducted, along with numerical simulations, for reconstructions of paleoredox conditions and paleoproductivity level. Additionally, we collected Fe chemistry, TOC, and pyrite sulfur data from multiple successions of the Datangpo Formation in South China to reconstruct the paleoredox landscape. The spatial TOC comparison suggests that the interglacial interval is marked by a TOC increase at the base, and the Guitouwan succession represents the early deposition during the wake of Sturtian deglaciation. Fe speciation suggests locally (dys)oxic-ferruginous condition in the Shennongjia area, while the δ34Spy systematics indicate a transition from ferruginous to euxinic condition and a sharp increase in primary productivity during the Sturtian deglaciation. With respect to the high δ34Spy values, the observed discrepancy suggests that the iron proxy might be inapplicable during fast environmental changes, especially during the deglaciation episodes. The comparison of Fe chemistry and pyrite sulfur isotopes between different water-depth settings informs a redox-stratified ocean in the Nanhua Basin. The newly discovered interglacial deposition fills the blank in understanding the shallow-water oxygenation in the Sturtian glacial aftermath, recording the transition from (dys)oxic-ferruginous to ferruginous-euxinic and from low to high productivity levels. These findings shed new light on the interpretation of Fe chemistry and δ34Spy in the geological past, and provide a novel perspective on investigating productivity levels.

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.

Deciphering ore-forming fluid evolution processes of the Yuerya gold deposit, eastern Hebei, China: Insights from pyrite texture, trace element and sulfur isotope compositions

The Yuerya gold deposit, a representative gold deposit associated with Mesozoic granites in the eastern Hebei region, is located in the eastern Hebei-western Liaoning gold ore-concentrated area, the northern margin of the North China Plate. The orebody is mainly preserved in the Yanshanian granite and its contact zone with the carbonate rocks of the Gaoyuzhuang Formation, and the main ore mineral is pyrite. Based on the pyrite texture, geochemical characteristics of the in-situ trace element analysis, and sulfur isotope, the pyrite in the mining area is classified into five generations (Py1, Py2, Py3, Py4a, and Py4b). Five generations of pyrite all have an average Te/Se ratio > 1, and their average Co/Ni ratios are 1087.27, 43.97, 4.17, 12.62, and 4.99, respectively, indicating that the ore-forming fluid predominantly originates from magmatic-hydrothermal. In-situ sulfur isotopic analysis using LA–MC–ICP–MS shows that the δ34S values of the five generations of pyrites ranged from 0.3 ‰ to 9.6 ‰; the mean values are 3.8 ‰ (Py1, n = 4), 4.2 ‰ (Py2, n = 10), 2.6 ‰ (Py3, n = 18), 4.0 ‰ (Py4a, n = 20) and 4.6 ‰ (Py4b, n = 29), respectively. Approximately 32 % of the results exceed 5.0 ‰, surpassing the values indicative of a magmatic-hydrothermal source. Thermodynamic simulations reveal that the fluctuations in the oxidation state of the ore-forming fluid is not the predominant cause of δ34S enrichment in the pyrite. Our studies suggest that sulfur is primarily derived from mantle-crust mixtures, with some contributions from the wallrock of the Gaoyuzhuang Formation. The results from LA–ICP–MS trace element analysis of pyrites reveal a significant enrichment of As-Bi-Te-Tl alongside Au in the ore-forming fluid. Additionally, the results of ore-forming elements in three typical cross sections of different wallrocks in the mining area also show that Au, Ag, As, and Pb are closely related. Therefore, it is considered that the over-enrichment of As could be an important factor leading to the precipitation of Au. Pyrite undergoes expansion of the mineral lattice parameters or lattice dislocation due to the substitution of S with As, creating space for the growth of solid-solution Au. Subsequently, some of the solid-solution Au within pyrite is liberated through internal oscillations, forming the visible gold particles.

Enrichment of cobalt at Baijian skarn Fe-Co deposit in the Handan-Xingtai region, North China Craton: Insights from mineral trace elements and pyrite sulfur isotopes

Cobalt (Co) in skarn deposits generally occurs as discrete Co minerals, or dispersed in sulfides. Recent studies have shown that magnetite from Baijian Fe-Co deposit (North China Craton) contains significant amounts of Co, but the mechanism for its enrichment was unclear. In this study, we present in situ mineral trace element and pyrite sulfur isotopic data from Baijian deposit (reserves of 112 Mt Fe at an average grade of 48.5 %): our results show that Co is mainly hosted in cobaltite, magnetite, and pyrite. Magnetite contains 47.6 ppm Co on average, accounting for most of the Co resource in the deposit. Elevated Co concentrations correspond to elevated levels of both Ti + V and Al + Mn, indicating the influence of elevated temperature. Pyrite grains from different lithologies in the deposit have variable Co contents, with those from the related diorite intrusion having the highest (averaging 9264 ppm Co). Sulfur isotopes of pyrite from the magnetite ores range from 16.6 to 19.4 ‰, similar to those from the Cixian Formation limestone and dolemite, which suggests that the sulfur was mainly derived from evaporites in those strata. Pyrite in magnetite-bearing skarn exhibits core-rim zoning, with the core having higher δ34SV-CDT values than the rim, which has values similar to those of pyrite in the diorite. A comparison of our results with other skarn Fe deposits shows that magnetite tends to have a higher Co concentration with increasing δ34SV-CDT values, suggesting that oxygen fugacity has an important influence on Co enrichment in magnetite.

Mesozoic orogenic gold metallogenesis at the Bangong–Nujiang suture belt, central Tibet: Constraints from pyrite textures, composition and sulfur isotope of the Shangxu gold deposit

Pyrite is a good carrier to provide gold within a hydrothermal mineralization system. Under prograde metamorphism, recrystallization of sedimentary and diagenetic pyrite and transformation of pyrite into pyrrhotite in a metamorphic terrane lead to the release of trace elements from the pyrite carrier into an upward migrating liquid phase carrier. In this case study, we report the in situ trace element and δ34S compositions of the pyrite from four different stages, which chronologically comprise sedimentary Py1, diagenetic Py2, metamorphic Py3a, Py3b and hydrothermal Py4a, Py4b, Py5, and the dominant sulfides from the hydrothermal stage at Shangxu, an Early Cretaceous turbidite-hosted orogenic gold deposit in the middle Bangong–Nujiang suture belt (BNSB) in central Tibet, in order to decipher the ore-forming material source and the metallogenesis of the Mesozoic orogenic gold mineralization in the BNSB. Concentrations of trace elements, i.e., Au, Co, Cu, Zn, Mo, Ag, Sb, Te, Hg, Tl, Pb and Bi, that are easy to dissolve during pyrite recrystallization, show a general progressive decline from Py1 to Py4b (excepting in Py3b and Py4a, which have a sudden rise in trace element composition) and a plunge in Py5, indicating that Py1 and Py2 supply the parent source minerals for mineralization, and that the main ore-forming stage are contemporary with the deposition of Py3b and Py4a, ending up with the precipitation of Py5. The δ34S values of pyrite narrow from −46.7 ‰–19.3 ‰ (Py1, Py2), through −7.6 ‰–0.2 ‰ (Py3a, Py3b), to − 3.6 ‰–5.7 ‰ (Py4a, Py4b) and −7.7 ‰–5.6 ‰ (Cp, Gn), indicating that a probable coeval seawater sulfate sulfur source for Py1 and Py2 (by bacterial sulfate reduction), and an inherited sulfur source from Py1 and Py2 for Py3 and Py4. We highlight that contributions from the magmatic materials to the hydrothermal gold mineralization are limited at Shangxu, and the widely distributed Lower–Middle Jurassic pyrite-rich turbidite of the Mugagangri Group is a highly potential primary source rock for the regional gold mineralization.

Extreme shifts in pyrite sulfur isotope compositions reveal the path to bonanza gold

Pyrite is the most common sulfide mineral in hydrothermal ore-forming systems. The ubiquity and abundance of pyrite, combined with its ability to record and preserve a history of fluid evolution in crustal environments, make it an ideal mineral for studying the genesis of hydrothermal ore deposits, including those that host critical metals. However, with the exception of boiling, few studies have been able to directly link changes in pyrite chemistry to the processes responsible for bonanza-style gold mineralization. Here, we report the results of high-resolution secondary-ion mass spectrometry and electron microprobe analyses conducted on pyrite from the Brucejack epithermal gold deposit, British Columbia. Our δ34S and trace element results reveal that the Brucejack hydrothermal system experienced abrupt fluctuations in fluid chemistry, which preceded and ultimately coincided with the onset of ultra-high-grade mineralization. We argue that these fluctuations, which include the occurrence of extraordinarily negative δ34S values (e.g., -36.1‰) in zones of auriferous, arsenian pyrite, followed by sharp increases of δ34S values in syn-electrum zones of nonarsenian pyrite, were caused by vigorous, fault valve-induced episodic boiling (flashing) and subsequent inundation of the hydrothermal system by seawater. We conclude that the influx of seawater was the essential step to forming bonanza-grade electrum mineralization by triggering, through the addition of cationic flocculants and cooling, the aggregation of colloidal gold suspensions. Moreover, our study demonstrates the efficacy of employing high-resolution, in situ analytical techniques to map out individual ore-forming events in a hydrothermal system.

Local depositional and diagenetic conditions control the positive δ34S excursion during the Ordovician-Silurian transition: Evidence from the Wufeng-Longmaxi formations in Sichuan Basin

The Ordovician-Silurian (OS) transition was characterized by significant changes in global climate, marine redox conditions, and biological evolution, which include global seawater euxinia, the onset of the Hirnantian glaciation, and large-scale extinctions. During this time, the marine sulfur cycle was disrupted, and the pyrite sulfur isotope (δ34Spy) showed a large positive excursion. This excursion is closely tied to the Hirnantian glaciation, with δ34Spy increasing at the start of and decreasing at the end of the glaciation. Although it is thought that variations in marine sulfate concentration and primary productivity are responsible for the positive excursion in δ34Spy, contemporary marine sediment δ34Spy data suggest that sedimentary processes can also lead to significant fluctuations in δ34Spy. To assess the impact of local changes in sedimentary conditions on this positive δ34Spy excursion event, we conducted detailed depositional and geochemical analyses of sedimentary pyrite found in black shales from the Wufeng-Longmaxi formations in the Weiyuan area of the Sichuan Basin, China. These sedimentary pyrites include three types: framboidal, euhedral, and laminated pyrite. Bulk sample sulfur isotope analyses revealed that δ34Spy values vary from −16.2‰ to 15.8‰ (mean = −3.8‰, n = 22). In situ analyses of δ34Spy show that different pyrite crystals exhibit a range of intragranular δ34Spy values that are likely indicators of diagenesis. Variations in bulk sample δ34Spy are strongly and negatively correlated with the proportion of framboidal pyrite, i.e., lower levels of framboidal pyrite content resulted in a higher bulk sample δ34Spy value, suggesting diagenetic alteration controls on δ34Spy. In addition, the δ34Spy excursion in the Wufeng-Longmaxi formations also appears to be compatible with lithological changes related to sedimentation rate. The δ34Spy values from the Guanyinqiao Bed, which consists of calcareous shales, are higher than those from black shales with a relatively low sedimentation rate. Our results suggest that the positive δ34Spy excursion during the OS transition during the Hirnantian glaciation is controlled not only by diagenetic alterations but also by local sedimentation rate.

Controls on pyrite sulfur isotopes during early diagenesis in marine sediments of the South China Sea

Understanding the controls on the sulfur isotope compositions of syndepositional pyrite (δ34Spy) during early diagenesis is critical for environmental reconstructions, especially for the reconstruction of the marine sulfur cycle. Commonly, δ34Spy values increase with depth in marine sediments; this phenomenon has been extensively studied, fostering the reconstruction of both global and regional depositional environments. However, more recently a decrease of δ34Spy values with depth has been increasingly observed, but the corresponding controls on sulfur stable isotopes remain poorly constrained. This study investigated a gravity core collected from the northern continental slope of the South China Sea. Morphology, content, and δ34S values of pyrite, concentration and sulfur isotopic composition of porewater sulfate (δ34SSO4), carbon, nitrogen, and sulfur contents, and grain sizes of terrigenous sediments were analyzed and AMS14C dating of planktonic foraminifera was conducted. The δ34Spy values were found to decrease with depth from −16.8‰ to −42.8‰, indicating low sulfur isotope fractionation (<38‰) during microbial sulfate reduction in the uppermost sediments and a larger fractionation (>64‰) at greater depth. Significant contributions of relatively 34S-enriched pyrite formed at shallow depth leads to overall δ34Spy variations >26‰, whereby low δ34Spy values coincide with higher sedimentation rates and higher organic matter supply. This study highlights the potential significance for relatively 34S-enriched, shallow-depth pyrite for δ34Spy records, which may affect the reconstruction of depositional conditions and the global sulfur cycle.

Constraining reducing conditions in the Prague Basin during the late Silurian Lau/Kozlowskii extinction event

The Silurian was marked by repeated extinctions, carbon cycle volatility and significant intervals of climatic change. The most notable of these events were the Ludfordian Lau/Kozlowskii extinction and the associated Mid-Ludfordian Lau C isotope excursion, both of which have been linked to a period of global cooling and expanded reducing conditions in the global ocean. We present new data that characterize the marine palaeoredox conditions of the Prague Basin, a peri-Gondwanan terrane. We use I/Ca ratios to assess the local redox conditions in a shallow water carbonate succession and Fe speciation and redox-sensitive trace element concentrations to assess the local redox conditions of a deeper water sequence. Consistently low I/Ca values in the shallow water section suggest either persistent local low-oxygen conditions or possibly diagenetic overprinting. Fe speciation data suggest that the bottom water redox conditions in the deeper shelf setting were consistently anoxic with possible intermittent euxinia. Concentrations of redox-sensitive trace elements consistently higher than upper continental crust values also indicate persistent reducing conditions in the deeper part of the basin. These local redox proxy data from the Prague Basin, including trends in new pyrite S isotope ( δ 34 S pyr ) data, are consistent with previous findings of the expansion of anoxic and/or euxinic oceanic conditions. These data, derived from a mid-palaeolatitude marine setting, fill an important gap in our current global dataset for this interval of the late Silurian. Supplementary material: All the geochemical data reported and discussed herein are available in the Supplemental Data Tables at https://doi.org/10.6084/m9.figshare.c.7008107 Thematic collection: This article is part of the Chemical Evolution of the Mid-Paleozoic Earth System and Biotic Response collection available at: https://www.lyellcollection.org/topic/collections/chemical-evolution-of-the-mid-paleozoic-earth-system

Holocene climate regulates multiple sulfur isotope compositions of pyrite in the East China sea via sedimentation rate

Marine authigenic pyrite sulfur isotope (δ34Spyr) is one of the most important proxies for reconstructing remarkable changes of Earth's surface in deep time. Recent observations of unexpectedly large δ34Spyr variations in Quaternary sediments complicate the application of this isotopic proxy, and a mechanistic understanding of such variabilities is needed. In this study, we measured multiple sulfur isotopic compositions of pyrite in well dated sediments spanning the last 7500 years from the East China Sea (ECS) inner shelf to study the mechanism how Holocene climate controls pyrite sulfur isotopic compositions. We found that variabilities of pyrite multiple sulfur isotopes, δ34Spyr and Δ33Spyr (ranging from −38.3‰ to 2.3‰ and from −0.01‰ to 0.21‰, respectively) are significantly correlated with large fluctuations of sedimentation rates (0.03–2.09 cm/yr). In tandem with box model calculations and compiled data, the large δ34Spyr variations up to 40‰ are primarily ascribed to fluctuated anaerobic oxidation of methane coupled sulfate reduction (AOM-SR). Further analyses suggest that heightened distillation of interstitial sulfate, likely propelled by high methane flux coupled with increased sedimentation rates, can produce such negatively correlated δ34Spyr-Δ33Spyr pattern and large variations in δ34Spyr. Possible changes in isotope fractionation factors caused by varied cell-specific sulfate reduction rates result in a maximum δ34Spyr variation of <20‰ and therefore play a minor role in the large variation in δ34Spyr (>40‰). The major and minor isotopic compositions of pyrite align with sulfide produced through pure sulfate reduction, indicating little evidence of additional oxidative sulfur cycling. Sedimentation rates in the ECS are controlled by the East Asian winter monsoon that influences the sediment transport capacity from longshore currents on a multicentennial timescale, and also by the coupled East Asian summer monsoon that affects the sediment availability from the Yangtze River on a millennial timescale. Holocene climate changes alter sediment supplies at the ECS and therefore play a vital role in controlling multiple sulfur isotope compositions of sedimentary pyrite in this region. This study has the potential to provide new insights into δ34S excursions in seawater sulfate that occurred during periods of notable acceleration in sedimentation rates throughout the geological history.

Paleo-marine redox environment fluctuation during the early Cambrian: Insight from iron isotope in the Tarim Basin, China

The Ediacaran to Cambrian period is generally considered to be the vital transition in the history of marine redox environment and life evolution on earth. The ocean oxygenation levels during this transition period are still debated. Since iron is widely involved in biogeochemical cycles and undergoes redox cycling both in the seawater and sediments, it has become a significant proxy to reconstruct paleo-marine environment. In order to constrain the paleo-marine redox state in the early Cambrian, the iron isotope composition of bulk rock (δ56FeT) is interpreted combining with iron-speciation, redox sensitive elements and pyrite sulfur isotope (δ34Spy) of Yuertusi Formation in Tarim Block. The δ56FeT values varies from −0.39 ‰ to 0.48 ‰, with an average of 0.07 ‰, mainly controlled by pyrite mineral facies in this study. Based on the mechanism of pyrite generation in different redox condition, it is proposed that the marine environment of the lower Cambrian in the Tarim basin is dominated by anoxic with intermittent euxinic state. The dynamic evolution of redox environment can be divided into three intervals. The gradual decrease of δ56Fe in Interval I indicates the paleo-marine environment changed from anoxic ferruginous to euxinic, and the paleo-marine sulfate reservoir decreased to a limited level, which might be attributed to abundant burial of organic matter and pyrite. For Interval II, δ56Fe values first increase to evident positive because of partial oxidization then decreased to that of seawater (about 0 ‰) due to complete oxidization. In Interval III, the continuous decrease of δ56Fe values infers a sustaining oxidization. In summary, the paleo-marine environment of the lower Cambrian Yuertusi Formation evolved from anoxic ferruginous to euxinic and then oxidized continuous. Iron isotope statistics from geological historical periods indicate that seawater was relatively oxidized after the NOE event but did not reach the oxidation levels of present-day seawater.

Deconvolving microbial and environmental controls on marine sedimentary pyrite sulfur isotope ratios.

Reconstructions of past environmental conditions and biological activity are often based on bulk stable isotope proxies, which are inherently open to multiple interpretations. This is particularly true of the sulfur isotopic composition of sedimentary pyrite (δ34Spyr), which is used to reconstruct ocean-atmosphere oxidation state and track the evolution of several microbial metabolic pathways. We present a microanalytical approach to deconvolving the multiple signals that influence δ34Spyr, yielding both the unambiguous determination of microbial isotopic fractionation (εmic) and new information about depositional conditions. We applied this approach to recent glacial-interglacial sediments, which feature over 70‰ variations in bulk δ34Spyr across these environmental transitions. Despite profound environmental change, εmic remained essentially invariant throughout this interval and the observed range in δ34Spyr was instead driven by climate-induced variations in sedimentation.

In Situ Rb‐Sr Dates of Muscovite and Sulfur Isotope of Pyrite from the Yangshan Gold Deposit in Western Qinling, China

AbstractLocated along the southern part of the West Qinling orogenic belt, the Yangshan gold deposit is one of the largest in China. The major gold ores of Yangshan are disseminated in metasedimentary host rocks with minor native gold amounts in stibnite‐gold quartz veins. Pyrite and arsenopyrite are the major Au‐bearing minerals. Hydrothermal muscovite from gold‐bearing quartz veins was dated using the in situ Rb‐Sr method to determine the formation age of the Yangshan gold deposit. The Rb‐Sr isochron date of the muscovite yielded 210.1 ± 5.6 Ma (MSWD = 1.2). This date is near the lower end of the period of the mineralized granitic dykes (210.49–213.10 Ma). Two stages of gold enriching process are recognized in the gold‐bearing pyrite: the first is incorporated with the Co, Cu, As, Ni enrichment; and the second is accompanied by Bi, Co, Ni, Pb, Cu, Sb concentration. The in‐situ sulfur isotopic values of pyrites show a restricted Δ34s range of –1.43 ‰ to 2.86 ‰ with a mean value of 0.43 ‰. Trace‐element mapping and in‐situ sulfur isotopic analysis of pyrite suggest that the sulfur deposits are likely derived from a magmatic source and likely assimilated by sulfur from the sedimentary bedrock. Thus, magmatism plays a critical role in the formation of the Yangshan gold deposit.

Geochemistry of sulfide in mafic enclaves from Gushan granite: Implications for the role of contemporaneous mafic magma in the genesis of the large-scale Jiaodong gold province, eastern China

Studies have revealed the key role of deep-seated, ore-forming fluids and metals in the generation of the Early Cretaceous large-scale gold deposits in the Jiaodong gold province of eastern China. However, how the ore-forming materials were transported to shallow crustal levels remains unclear. Here, we investigate trace elements and sulfur isotopes of pyrite within mafic microgranular enclaves (MMEs) of Gushan granite to evaluate the role of the syn-mineralization of mafic enclaves in the transportation of ore-forming materials. Zircon U-Pb and molybdenite Re-Os dating indicate that the magmatic-hydrothermal event in the potassic-altered Gushan granite occurred at ca. 120 Ma, which is contemporaneous with the Jiaodong gold mineralization. The texture and geochemical compositions of pyrite indicate that pyrite grains hosted by Gushan MMEs are of deuteric hydrothermal origin and precipitated during or shortly after magma mixing. The distribution of elements (i.e., Co, Cu, Ni, Zn, As, Ag, Au, Pb, and Bi) and the sulfur isotope (4.14‰−8.8‰) data for pyrites from Gushan MMEs are quite identical to those of the Xiejia diorite intrusion (DI) and other ores from the Jiaodong gold province, which indicates a common source of these pyrites. The common origin of the pyrites, combined with evidence from previous work, suggest that the ore-forming fluids and materials originated from the metasomatized lithospheric mantle, which was the repository of water, sulfur, and volatiles from the subducted Paleo-Pacific plate, rather than by direct release from the subducted sediments of the Paleo-Pacific plate. Our results collectively show that the arc-like mafic magmas derived from the metasomatized lithospheric mantle at ca. 120 Ma were the intermediary that transported the gold and other ore-forming components from the deep mantle to the shallow crustal levels where gold and ore-related material were injected into the Weideshan granitic suite during magma mixing. Thus, the Weideshan granitic suite may have played a critical role by continuously transferring gold to the shallow crustal faults where it precipitated. Therefore, future research or deep-drilling exploration programs in the area should emphasize the Weideshan granitic suite rather than the Xiejia DI.

In Situ Trace Element and Sulfur Isotope Composition of Pyrite from the Beiwagou Pb-Zn Deposit, Liaodong Peninsula, Northeast China: Implications for Ore Genesis

The Beiwagou Pb-Zn deposit, located in the western part of the Liaodong Peninsula, is a carbonate-hosted stratiform deposit with a Pb + Zn reserve of 0.08 Mt @ 4.14% (Pb + Zn). The orebodies occur as conformable layers and lenses and are strictly controlled by strata (the Paleoproterozoic Gaojiayu and Dashiqiao Formations) and lithology (plagioclase amphibolite and dolomitic marble). Given that previous studies have focused only on the mineralization features and mineralogy of deposits, herein, we report in situ trace element analyses of pyrite using LA-ICP-MS, together with in situ sulfur isotopes of pyrite, to constrain the composition, substitution mechanisms, source of sulfur, and sulfate reduction pathways of pyrite in the Beiwagou deposit. Based on pyrite morphology, texture, and chemistry, four pyrite types were identified: subhedral, porous-to-massive pyrite (Py1) related to chalcopyrite; subhedral, porous crushed pyrite (Py2) associated with fine-grained sphalerite; rounded and porous pyrite (Py3) related to the Zn-rich part of the laminated ore; and anhedral, porous-to-massive pyrite (Py4) associated with pyrrhotite, arsenopyrite, sphalerite, and galena. Py1 is characterized by high As, Ag, Cd, In, Au, Cu, and Zn concentrations and low Te, Bi, and Mo concentrations, whereas Py2 has high concentrations of Co and Ni and low concentrations of other trace elements, such as Cu, Zn, Bi, and Te. Py3 is characterized by elevated As concentrations, low Co, Ni, In, W, Te, and Tl concentrations, and varying Pb concentrations, whereas Py4 has low Ag, Cd, In, Zn, Cu, and Mn concentrations and varying W, Co, Ni, Pb, Sb, and As concentrations. Significant correlations between some elements in each pyrite type suggest substitution mechanisms, such as (Zn2+ + Cu2+ + Mn2+ + Cd2+) ↔ 2Fe2+, Ag+ + (Sb)3+ ↔ 2Fe2+, and (Te+ + Ag+) + Sb3+ ↔ 2Fe2+, and the existence of a negative correlation between Co and Ni implies competition between both elements. The strongly positive δ34S values (12.11‰–23.54‰) are similar to that of seawater sulfates and likely result from thermochemical sulfate reduction (TSR). In conclusion, the Beiwagou Pb-Zn deposit is a typical SEDEX deposit and mineralization likely occurred during diagenesis.

Platinum-group elements (PGE) in the New Afton alkalic Cu-Au porphyry deposit, Canadian Cordillera, I: relationships between PGE, accessory metals and sulfur isotopes in pyrite

The second part of this article can be found here: 10.3389/feart.2023.819109 (DOI). At the late Triassic New Afton alkalic porphyry Cu-Au deposit (British Columbia, Canada), pyrite is a widely distributed minor sulfide phase within hypogene ore where it predates Cu mineralization and hosts significant concentrations of Pd and Pt. Here we characterize pyrite major, minor and trace element composition by EPMA and LA-ICP-MS, and S isotopes (bulk pyrite and in situ SIMS in individual growth zones) to elucidate compositional variations at different stages of pyrite growth with respect to PGE deposition. At least two cycles of zoned Co-Ni-Pd-Pt-Se-As co-enrichment are recorded over two stages of pyrite growth at the New Afton deposit. Concentrations of Co (up to ∼5.5 wt%; highest observed in any reported ore-forming system) and Ni (up to 1 wt%) overlap with pyrite from mafic-ultramafic platinum-group element (PGE) deposits, iron oxide±apatite and iron oxide-copper-gold deposits (IOA-IOCG), and mantle peridotite-associated base metal exhalative deposits. In early hypogene (type I) pyrite, high Pt (up to ∼24 ppm) occurs in crystal cores that have high Co/Ni ratio (&amp;gt;∼7), high Co (&amp;gt;∼ 1 wt%) and are poor in Ni, Se, and As. With progressive growth, early hypogene pyrite rims and late hypogene (type II) cores record an initial Ni-Pd-As-Se (±Co) co-enrichment stage, followed by oscillations in composition (from “barren” to variably Co-Ni-Pd-Pt-As-Se-enriched). Pd in pyrite (up to ∼70 ppm) is inversely correlated to Co/Ni ratio, being enriched when Co/Ni &amp;lt; ∼7 and Ni &amp;gt; ∼1000 ppm. The highest levels of Pd enrichment occur in the most Ni- and Se-enriched growth zones. The transition from early, high Co/Ni (Pt-enriched) to later, low Co/Ni (Pd-enriched) growth zones is accompanied by a decrease in pyrite δ34SVCDT of up to ∼7‰ (4‰ range in single grains) with a total range in composition measured between −5.5‰ and +1.4‰. Subsequent to the shift to lower values, overgrowths of high Co/Ni pyrite formed with values of δ34SVCDT similar to the earliest Co-Pt-rich growth zones. Some combination of fluctuations in temperature and oxygen fugacity related to episodic cooling and hydrothermal recharge involving new pulses of metal-rich magmatic fluids is required to explain the observed metal enrichment patterns and variations in S isotope values. Co-Ni-rich pyrite may be a valuable exploration vector to PGE enrichment in porphyry deposits.

The genesis of acid alteration in the Luohe IOA-type deposit, Eastern China and its constraints on mineralization

Luohe is the largest IOA-type deposit in the Middle and Lower reaches of the Yangtze Metallogenic belt. The iron ore body is hosted in thick volcanic rocks, and widespread acidic alteration (secondary quartzite) developed at shallow depths, providing an excellent opportunity to study the genesis of acidic alteration rocks and the genetic links with the IOA mineralization. In this study, detailed mineralogy, in situ sulfur isotopes, and trace element analyses were performed on pyrite from a shallow drill hole in the Luohe deposit. The results indicate that the formation time of acidic alteration is between magnetite (stage II) and anhydrite-pyrite (stage IV), with pyrite sulfur isotopes ranging from −14 to 4‰, which is significantly different from those in stage IV (7-9‰). The anomaly negative sulfur isotope suggests the existence of SO2 disproportionation reaction, and the δ34S of pyrite increases with depth decrease, ultimately falling within the mantle sulfur range. This indicates that the sulfur origin of acidic alteration pyrite is a single magma sulfur source, which is significantly different from the deep iron mineralization system (magmatic + evaporite). The trace elements Co, Ni, As, Ti, Cu, Sb, Tl in pyrite indicate that the acidic alteration fluid has the characteristics of low temperature, low pH, and is rich in F and Cl. Combined with the sulfur isotope results, it is believed that pyrite in the acidic alteration rock of the Luohe was formed by the mixing of gaseous SO2 and shallow groundwater, which is a part of the Luohe magmatic-hydrothermal mineralization system and an important indication for regional exploration of similar deposits.

Geochronology, pyrite trace elements, and sulfur isotope geochemical characteristics of the Saibagou gold deposit in the eastern part of the northern Qaidam Basin

Introduction: The Saibagou gold deposit, located in the eastern part of the tectonic belt of the northern Qaidam Basin in western China, has its gold ore bodies strictly controlled by the regional fault system. Despite this understanding, there remain controversies surrounding the deposit’s metallogenic epochs, sources of ore-forming materials, and properties of ore-forming fluids. To address these controversy, the metallogenic process of the Saibagou gold deposit can be further determined by analyzing the U-Pb ages of hydrothermal zircons in the gold-bearing quartz veins and investigating the trace element and sulfur isotope compositions of pyrite in the gold deposit.Methods: This study does not focus on the mineral characteristics susceptible to interference by the metallogenic condition in gold ore bodies. Instead, it offers a detailed discussion on stable associated minerals and their indicative markers formed in the process of gold mineralization.Results: The results of this study showed that the metallogenic process of the gold deposit can be categorized into the following stages: 1) quartz–pyrite veins, 2) milky-white quartz—pyrite—native gold veins, 3) hoary quartz—native gold—polymetallic sulfide veins. As indicated by the U-Pb ages of hydrothermal zircons in the gold-bearing quartz veins, the Saibagou gold deposit has two metallogenic ages, namely, 423.91 ± 4.5 Ma (the Silurian) and 470.18 ± 4.92 Ma (the Ordovician).Discussion: The Silurian metallogenic age, predominates and nearly aligns with the expansion of the regional NWW-trending brittle-ductile shear zone, followed by the Ordovician metallogenic age. Data on the trace elements and sulfur isotopes of pyrite, show that the Saibagou gold deposit has similar pyrite compositions in the three metallogenic stages. Gold in the deposit primarily occurs as native gold or minor petzite inclusions and has a very low lattice gold concentration. As indicated by the concentrations of elements such as Co, Ni, and as in the pyrite, as well as the variation range of δ34S values, the ore-forming fluids were derived from low-temperature arsenic-bearing acidic magmas. In addition, the primary ore-forming materials appear to encompass mantle-derived materials from the deep earth.

A metasedimentary origin for gold deposits in the Dian-Qian-Gui “Golden Triangle” of Southwest China

The Dian-Qian-Gui “Golden Triangle” area of Southwest China hosts a large number of Au deposits. However, the sources of the ore-forming fluids are still controversial, hampering the formulation of a sound genetic model and effective ore prospecting. Here we investigate the sources of ore-forming fluids by an integrated study of in-situ sulfur isotope analyses and available trace element (e.g., Co and Ni) data for the pyrite in the “Golden Triangle” area. We find that the ore stage pyrites are featured by low Co/Ni ratios (mostly < 2), which is distinct from pyrite formed in magmatic-hydrothermal systems but resemble typical sedimentary pyrite. In addition, the significant variation (from −7.5 to +20.0‰) in sulfur isotopes (δ34S) of the ore stage pyrite in these deposits also support a sedimentary origin of the ore-forming fluids. Considering the difference in sulfur isotopic compositions of ore-stage pyrite and the sedimentary host rocks, we suggest the metasedimentary basement rocks (>500 Ma) in the area may have supplied most of the sulfur and gold for the ore-forming fluids during the Triassic orogenesis in the Dian-Qian-Gui “Golden Triangle” area of Southwest China.