Seawater Sulfate Research Articles

Testing the global significance of the sulfur isotope record of the ca. 2.0 Ga Zaonega Formation: A micro-scale S isotope investigation

The Paleoproterozoic metasedimentary rocks of the Zaonega Formation (Onega Basin, NW Russia) are important archives of inferred global environmental change following the initial oxygenation of the Earth’s atmosphere and oceans. However, the geochemical signals preserved in these exceptionally organic-and pyrite-rich metasedimentary rocks and their environmental meaning remain contested. In particular, the Zaonega Formation’s unusually high pyrite sulfur isotope ratios (δ34S) have been explained by either global or local forcings acting on sulfur cycling processes. We tested former interpretations of the Zaonega Formation’s sedimentary pyrite record by integrating bulk and micro-scale δ34S analysis to discriminate the isotopic signatures of different generations of pyrite and determine the underlying mechanisms contributing to δ34S variability. We show that the prolonged genesis of pyrite occurred via multiple stages and included precipitation from early diagenetic fluids, organic matter pyritization, and late-stage alteration fluids. Our results demonstrate that early-stage pyrite typically carries more variable and lower δ34S values than late-stage pyrite. Although the early pyrite captures pore water S isotope signatures least evolved from the seawater, their contribution to the bulk δ34S results can be dwarfed by the greater volume of late-stage coarse pyrite. Consequently, determining the sequence of pyrite precipitation and δ34S characteristics of individual generations in any given sample are fundamental to interpreting bulk δ34S records. Our micro-scale results suggest that previous estimates based on bulk pyrite data (ca. 6 to 18‰) should not be related to the original seawater sulfate’s isotopic composition. These results demonstrate that a thorough understanding of the geological context and mechanisms associated with S-cycling, and pyrite formation is necessary to interpret bulk δ34S records accurately.

An authigenic response to Ediacaran surface oxidation: Remarkable micron-scale isotopic heterogeneity revealed by SIMS

The Ediacaran Shuram excursion (SE) records a global decrease in carbonate carbon isotope (δ13Ccarb) values from +6‰ down to ca. –10‰, representing the largest δ13Ccarb negative anomaly in Earth history. While the SE is widely recorded in the upper Doushantuo Formation of South China, it shows highly variable δ13Ccarb profiles among correlative sections. This inconsistent expression of the SE challenges the conventional view of a homogeneous marine dissolved inorganic carbon (DIC) reservoir. A potential process that could explain δ13Ccarb variability is local mineralization of isotopically distinct authigenic carbonates near the sediment–water interface during early diagenesis. However, a direct test of such authigenic carbonates is still limited. Here, following a recent study on the SE in an intra-shelf environment, we revisited an outer-shelf section, identified and analyzed μm-scale, syn-depositional authigenic calcite cements via integrated cathodoluminescence (CL), micro-X-ray fluorescence (μXRF), scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and secondary ion mass spectrometry (SIMS). Our new SIMS results reveal remarkable micron-scale heterogeneity of δ13Ccarb in authigenic calcite cements, including extremely negative values down to –37.5‰ (VPDB). We interpret these calcite cements as methane-derived authigenic calcite (MDAC) resulting from microbial sulfate reduction (MSR) and anaerobic oxidation of methane (AOM) during early diagenesis. Based on the new results, we propose that the heterogeneous SE in South China — manifest on micrometer, centimeter, and basinal scales — was modulated by methane oxidation under variable local redox and water depth conditions. The SE, therefore, was coupled with different degrees of methane oxidation in individual basins, and globally triggered by enhanced seawater sulfate during an atmospheric oxygenation event. In light of this study, the potential role of redox variability in methane oxidation during the SE may have been underestimated. Our study demonstrates that integrated SIMS-SEM analysis can distinguish different generations of isotopically distinct carbonates otherwise undetected by conventional analysis, and is thus an effective approach to assess the origin and diagenetic history of δ13Ccarb anomalies in the sedimentary record.

Geological and geochemical constraints on the genesis of the Xiqianluzi Pb–Zn polymetallic deposit in Beishan, Gansu Province, NW China

The Xiqianluzi Pb–Zn polymetallic deposit is located in the southeast of the southern Beishan belt, whereas the ore‐forming metal sources are still unclear. Its Pb–Zn ore bodies mainly occur in the Changcheng system Qianluzigou Group metamorphic clastic rocks, showing zonation of Cu–Zn–Pb metals from deep to surface. The ore structures are mainly banded, massive and veined, which have the characteristics of syngenetic sedimentation. Au mineralization in silty slate is obviously controlled by WNW–ESE‐trending faults, and occurs as veined or lenticular type. The Pb, Zn, Cu, and Au are mainly enriched in quartz or siliceous veins. The biotite granodiorites are enriched in Si, Na, Rb, Ba and K, with A/CNK values less than 1.1, and depleted in Nb, P, Ti. They belong to calc‐alkalic series and weak peraluminous I‐type granite, formed in a post‐collision extensional environment and characterized by crust–mantle mixed source. The sulphide minerals in the Pb–Zn ores have δ34S values in the range of 17.7‰–21.0‰ with average of 19.2‰, reflecting seawater sulphate origin of sulphur. The sulphur of Pb–Zn ores was likely transformed from S6+ to S2− by thermochemical sulphate reduction. The Pb isotopic compositions of sulphide minerals in the Pb–Zn ores have 206Pb/204Pb ratios of 16.837–17.001, 207Pb/204Pb ratios of 15.437–15.557, and 208Pb/204Pb ratios of 36.377–36.889. In contrast, sulphide minerals in Au ores have δ34S values (5.4‰–7.6‰, with average of 6.5‰) lower than those of sulphide minerals in the Pb–Zn ores. The δ34S values of sulphide minerals in the Au ores are consistent with those of sulphide minerals in the Late Permian–Middle Triassic magmatic hydrothermal gold deposits in the southern Beishan belt, which imply a magmatic source for sulphur. Sulphide minerals in the Au ores have higher lead isotopic ratios, including 206Pb/204Pb of 18.249–18.325, 207Pb/204Pb of 15.583–15.598, and 208Pb/204Pb of 38.023–38.366, compared to those in the Pb–Zn ores. Geological and isotopic features indicate that the Xiqianluzi Pb–Zn polymetallic deposit comprises two mineralization types; namely, its Pb–Zn ores can be considered as Mesoproterozoic sedimentary exhalative type, while its Au ores are magmatic origin. These show that Au mineralization was closely related to the magmatic hydrothermal activities, and thus Au ores can be classified as Late Permian–Early Triassic magmatic hydrothermal Au mineralization.

Low marine sulfate levels during the initiation of the Cryogenian Marinoan glaciation

The microbial sulfate reduction plays a significant role in regulating marine organic matter degradation. Thus the variation of ancient marine sulfate levels is closely coupled with the changes in global organic carbon burials and Earth’s surface redox evolution in geological time. It is widely assumed that seawater sulfate concentration was deficient during the anoxic Cryogenian Marinoan glaciation (ca.650–635 Ma) which represents the most extreme icehouse condition in Earth’s history. However, such a low seawater sulfate level has not been explicitly confirmed. To address this, here we carried out pyrite content and sulfur isotope (δ34Spy) analysis of the Cryogenian non-glacial (the Datangpo Formation) and the Marinoan glacial successions (the Nantuo Formation) in South China. The Datangpo and Nantuo Formation show relatively high values of δ34Spy, ranging from +19.9 ‰ to +32.9 ‰, and low values of pyrite content (mean = 0.72 wt%). These pyrites are dominated by euhedral crystals with a rare occurrence of framboids, indicating an early diagenetic origin, i.e., pyrite formed in sediments with sulfate supplied from seawater. Using and a one-dimensional diffusion–advection-reaction (DAR) model, we calculate marine sulfate levels. The modeling results show that the seawater sulfate concentration is <1 mM during the transition from the top Datangpo to the basal Nantuo Formation, suggesting a shrink of the marine sulfate reservoir at the onset of Marinoan glaciation. We propose that the low marine sulfate concentration was resulted from a decrease in continental chemical weathering. This study provides a quantitative constraint on marine sulfate levels during the Cryogenian snowball Earth event, and it may shed new light on our understanding of the marine biogeochemical changes in the Neoproterozoic.

Oxygen isotope insights into the Archean ocean and atmosphere

Accurately reconstructing the temperature of the ocean through time carries implications for Earth's climate and early habitability. Attempts to build these reconstructions using oxygen isotope records have led to three end-member interpretations. Namely, that the observed enrichment over time in 18O relative to 16O in ancient chemical sediments reflects a change in sea-surface temperatures (SST), a change in the 18O composition of the contemporaneous water, or that the primary signal has been subsequently overprinted. These questions become most salient in the Archean, where estimates of the isotopic composition of the ocean span ∼20‰, with a correspondingly wide range in estimated SSTs. Here, we introduce barite (BaSO4) as a robust new proxy for the oxygen isotope composition of the Archean ocean. We compile new and existing triple oxygen isotope and sulfur isotope data from the Fig Tree Group barite deposits in the Barberton Greenstone Belt, South Africa, with the goal of identifying the primary sources of sulfate to the Archean ocean. Using a simple Monte Carlo approach, we then constrain the possible isotopic composition of contemporaneous seawater. Our results suggest that microbial sulfur cycling played a limited role in setting the isotopic composition of Archean seawater sulfate. Additionally, it is likely that a significant flux of sulfate to the marine reservoir was atmospherically derived and carried a significant positive triple oxygen isotope signal. Importantly, our results support an Archean ocean with a somewhat enriched oxygen isotope composition (∼0-5‰), with the exact composition dependent on the relative contribution from each sulfate production pathway. This result points either to the decreased significance of low-temperature weathering and/or to elevated SSTs in the early Archean.

Assessing bulk carbonates as archives for seawater sulfur isotopic composition using shallow water cores from the South China Sea

The sulfur isotopic composition (δ34S) of Carbonate Associated Sulfate (CAS) is widely used to track changes in the isotopic composition of ancient seawater sulfate which signify the global sulfur cycle, Earth's surface redox evolution, and biological activity. However, our understanding of to what extent the isotopic composition of CAS records ambient seawater sulfate is primarily deduced from modern calcifying species. A few studies have examined modern bulk carbonate sediments which are important analogs for sedimentary carbonate rocks in the geologic record. To evaluate the fidelity of bulk carbonate sediments in recording ambient seawater δ34S values, we extracted CAS component and provided δ34SCAS results of five modern corals from the Hainan Island and 74 core-top unlithified carbonate sediments from the Nansha Islands in the South China Sea. Modern coral samples show a uniform δ34SCAS range from 21.5‰ to 21.7‰ close to previously published δ34S values for modern coral and seawater in other open oceans, consistent with globally homogeneous seawater δ34S compositions (i.e., δ34Ssw = 21.2 ± 0.2‰). The δ34SCAS values of core-top carbonate sediments vary within a narrow range from 21.1‰ to 22.1‰, which is fractionated from the overlying seawater by 0.4‰ ± 0.2‰. We suggest that these irregularly positive but small S-isotope fractionations (<1‰) are potentially due to the varying proportions of various calcifying organism granules with species-dependent sulfur isotopic fractionation. Overall, our data indicate that the CAS of bulk carbonate sediments from the open ocean settings is a reliable archive of seawater δ34S composition, provided the isotopic compositions have not been altered by post-depositional diagenesis.

Multiple Sulfur Isotope Compositions in Mesoarchean Sulfide Deposits of the Karelian Craton: Implications for Determining the Sulfur Source, Biogeochemical Processes, and Deposit Genesis

Abstract —In the present paper we demonstrate that most sulfides of the studied deposits of the Archean Sumozero–Kenozero greenstone belt within the Karelian Craton on the Fennoscandian Shield have nonzero Δ33S values. This indicates that proportions of seawater sulfate and elemental sulfur in Mesoarchean, included into the ores and resulting from UV photolysis, are different. Our results show that systematics of sulfur isotopes of sulfides generally reflects the mixing of mass-independently fractionated sulfur reservoirs with positive and negative Δ33S values. Pyrite is depleted in 34S isotope, which was interpreted as evidence for microbial sulfate reduction. Variations in the positive Δ33S anomalies of the Leksa deposit and the general tendency for Δ33S sulfide content to increase with stratigraphic levels in certain boreholes most likely reflect the change in temperature and the fluid mixing throughout the life of the hydrothermal system. The presence of sulfides with strongly negative Δ33S anomalies suggests that atmospheric sulfur and seawater sulfate, rather than volcanic sulfur, were the prevailing source for mineral systems of the studied deposits. The presented data require the Mesoarchean seawater to contain sulfates at least locally.

Early diagenetic constraints on Permian seawater chemistry from the Capitan Reef

The Capitan Reef Complex in West Texas is famous for its high prevalence of early marine cements, unusual for a Phanerozoic platform, leading some to suggest that Precambrian styles of carbonate sedimentation enjoyed a Permian encore. Here, we use patterns of stable Ca, Mg, C and S isotopes to better understand the environmental driver(s) of the enigmatic cementation. We find that calcite that is the most enriched in 44Ca has δ34S values that approach the inferred composition of Permian seawater sulfate. Microbial sulfate reduction in pore fluids must have been spatially and temporally coincident with recrystallization of primary carbonate phases, such that substantial 34S-enriched sulfate was incorporated into diagenetic calcite under relatively closed-system conditions. Moreover, the magnitude of 34S-enrichment of carbonates relative to seawater was strongly influenced by local diagenetic conditions, with fluid-buffered early marine cements, shelf, reef, and upper slope preserving more seawater-like S isotope ratios than the more sediment-buffered lower slope. Some samples are far more 34S-enriched relative to seawater than those from modern sites in similar depositional environments, possibly responding to specific combinations of sedimentary parameters (e.g., grain size, porosity, organic matter rain rate). Additionally, the sulfate concentration in the Delaware Basin might have been slightly lower than modern levels, leading to more extensive isotopic evolution of sulfate in pore waters during carbonate recrystallization. Based on the data and a numerical model of carbonate recrystallization, we suggest that one driver of the extensive seafloor cement precipitation in the Capitan Reef Complex was a Permian water column [Ca2+]:[SO42−] ratio somewhere between 1 and modern seawater.

In-situ pyrite trace element and sulfur isotope characteristics and metallogenic implications of the Qixiashan Pb-Zn-Ag polymetallic deposit, Eastern China

The Qixiashan Pb-Zn-Ag deposit (2.6 Mt at 13.4% Pb + Zn and 3.9 Kt at 236.5 g/t Ag) in the Middle-Lower Yangtze River Valley Metallogenic Belt (MLYRB) is the largest Pb-Zn-Ag polymetallic deposit in Eastern China. The stratabound orebodies are hosted in the Carboniferous carbonate units. Whether this deposit and other sediment-hosted deposits in MLYRB are associated with Late Mesozoic magmatism or Carboniferous sedimentary exhalative events is still disputed, due to the poor constraints on their ore-material source and metallogenic processes. In-situ pre-/syn-ore pyrite S-isotopic and trace-element data from Qixiashan favor a seawater sulfate origin over a magmatic-hydrothermal one. Framboidal pyrite (Py1) is likely diagenetic, as evidenced by its low Co/Ni ratio (<1), size (∼4 μm), and negative δ34S values (−27.4 to −2.2‰) caused by bacterial sulfate reduction (BSR). Pre-ore colloform (Py2) and massive (Py3) pyrites have high Mn concentrations, whereas syn-ore pyrites (Py4 and Py5) have elevated Pb, Zn and Cu grades. The low Co/Ni values of the pre-/syn-ore pyrites indicate that both the Fe and base metals are of non-magmatic diagenetic origin. Sulfur isotope fractionation in the fluid may have reached equilibrium in the Pb-Zn-Ag metallogenic stage. Equilibrium fractionation calculation suggests that the positive shift of δ34S values from Py2 to Py5 (10.2 to + 22.2‰) is primarily caused by thermochemical sulphate reduction (TSR). Pre-ore pyrites were likely formed in early carboniferous diagenesis, and then enclosed by epigenetic pyrites. Iron in the syn-ore pyrites was most likely recycled from sediments or pre-ore pyrites via dissolution-leaching or replacement processes. During the Qixiashan Pb-Zn-Ag mineralization, the magmatic-hydrothermal fluid is unlikely a major base metal source.

Marine anoxia as a trigger for the largest Phanerozoic positive carbon isotope excursion: Evidence from carbonate barium isotope record

The mid-Ludfordian Lau carbon isotope excursion (Lau CIE) represents the largest positive carbon isotope excursion in the Phanerozoic (∼9‰), coincident with the biodiversity loss of many marine animal clades. Two main explanations for the Lau CIE are enhanced organic carbon burial via increased marine productivity and preservation-driven expansion of anoxia. While these two explanations are not mutually exclusive, the main driver of Lau CIE is yet to be constrained. Here, we resolve this longstanding debate using barium isotopes (δ138Ba) of marine carbonates deposited across the Lau CIE. Our δ138Ba data from the Kosov section (Czech Republic) record a large negative excursion in correlation to the positive shift in δ13Ccarb. We suggest that the observed negative shift in δ138Ba to values as low as −0.33‰ can be best interpreted as upwelling of isotopically light Ba from deeper waters due to pelagic barite dissolution under euxinic conditions. This hypothesis is consistent with results from barium concentration data as well as the results from the sulfate mass balance modeling that indicates a contraction in the seawater sulfate reservoir, with seawater sulfate concentrations decreasing from several mM ranges before the Lau CIE to less than 100 μM during Lau CIE. Taken together, evidence for a strong negative correlation between δ138Ba and δ13Ccarb suggests that shallow water anoxia, rather than enhanced marine productivity, was a primary driver of the Lau CIE that resulted in a notable decrease in the size of seawater sulfate reservoir.

Microbial Hydrocarbon Degradation in Guaymas Basin-Exploring the Roles and Potential Interactions of Fungi and Sulfate-Reducing Bacteria.

Hydrocarbons are degraded by specialized types of bacteria, archaea, and fungi. Their occurrence in marine hydrocarbon seeps and sediments prompted a study of their role and their potential interactions, using the hydrocarbon-rich hydrothermal sediments of Guaymas Basin in the Gulf of California as a model system. This sedimented vent site is characterized by localized hydrothermal circulation that introduces seawater sulfate into methane- and hydrocarbon-rich sediments, and thus selects for diverse hydrocarbon-degrading communities of which methane, alkane- and aromatics-oxidizing sulfate-reducing bacteria and archaea have been especially well-studied. Current molecular and cultivation surveys are detecting diverse fungi in Guaymas Basin hydrothermal sediments, and draw attention to possible fungal-bacterial interactions. In this Hypothesis and Theory article, we report on background, recent results and outcomes, and underlying hypotheses that guide current experiments on this topic in the Edgcomb and Teske labs in 2021, and that we will revisit during our ongoing investigations of bacterial, archaeal, and fungal communities in the deep sedimentary subsurface of Guaymas Basin.

The sulfur isotopic consequence of seawater sulfate distillation preserved in the Neoproterozoic Sete Lagoas post-glacial carbonate, eastern Brazil

Since the report of tubular structures interpreted as Cloudina from the Neoproterozoic Sete Lagoas Formation (SLF) in the Bambuí basin of eastern Brazil, this stratigraphic unit has become a focus of numerous geochemical, palaeomagnetic, geochronological and sequence stratigraphic studies. Geochemical data from the SLF have been used to infer palaeoenvironmental conditions in the Bambuí basin and to study the 13 C enrichment reported in this and overlying units. To further address depositional environments of the SLF, we present high-resolution δ 13 C and δ 34 S data from the SLF in the Januária and Sete Lagoas regions. We report the presence of superheavy pyrite with δ 34 S value greater than carbonate-associated sulfate (CAS) and observe a decrease in CAS abundance coupled with a δ 34 S change from c. +20 to near +50‰. These data are interpreted as evidence for distillation of sulfate through CAS and pyrite removal from the epeiric Bambuí basin. These changes are qualitatively consistent with quantitative simulations of isotopic distillation over a period of c. 10 myr of a seawater sulfate reservoir comparable with modern concentration. Considering that Neoproterozoic seawater sulfate concentrations were probably much lower than in modern oceans, the distillation time interval was probably much shorter than 10 myr. Supplementary material : MATLAB/Octave code to replicate Figs 11, 12 and 13 is available at https://doi.org/10.6084/m9.figshare.c.5845089 Thematic collection: This article is part of the Sulfur in the Earth system collection available at: https://www.lyellcollection.org/cc/sulfur-in-the-earth-system

Diagenetic barite-calcite-pyrite nodules in the Silurian Longmaxi Formation of the Yangtze Block, South China: A plausible record of sulfate-methane transition zone movements in ancient marine sediments

The sulfate-methane transition zone (SMTZ) serves as an important geochemical transition especially during early diagenesis. Organoclastic sulfate reduction (OSR), sulfate-driven anaerobic oxidation of methane (SD-AOM), fermentation, and methanogenesis, the dominant diagenetic processes near the SMTZ, play key roles in marine sulfur and carbon cycling. However, the paleo-SMTZ has rarely been identified in the geologic record because of equivocal evidence. The presence of barite-calcite-pyrite assemblages (abundant nodules and pyritic laminae) concentrated over a 1-m thick interval of the Silurian Longmaxi Formation, Yangtze Block, South China, provide a unique opportunity to investigate possible vertical movements of the paleo-SMTZ in ancient sediments. The inferred paleo-SMTZ comprises nodules made up of barite (BaSO4), calcium carbonate (CaCO3), and pyrite (FeS2), and pyritic laminae. Strong 34S enrichment of barite (50 to 62.1‰ VCDT) and modestly 13C-depleted calcite (−11.4‰ to −5.3 VPDB) of the nodules associated with positive δ34S values of pyritic laminae (4 to 6.2‰ VCDT) suggest precipitation of these minerals sourced by mixed carbon and sulfur sources close to and/or within the paleo-SMTZ. Nodules from center to edge display mineral zonation that may reflect the effects of depth fluctuations of the paleo-SMTZ. Initial (stage 1) barite mineralization in nodule centers appears to have occurred within the base of the sulfate reduction zone (SRZ). By the time if stage 2 mineralization, the stratigraphic locus of precipitation had migrated closer to highly alkaline SMTZ resulting in barite dissolution and calcium carbonate precipitation. Higher proportions of calcium carbonate exhibiting some enrichment of 12C associated with cubic pyrite crystals in nodule centers are consistent with the occurrence of SD-AOM within the SMTZ. Stage 3 acicular barite mineralization along nodule edges likely took place near at the base of SRZ immediately above the SMTZ, whereas the replacement of barite by calcite during stage 4 mineralization occurred again within the SMTZ. Vertical movement of paleo-SMTZs suggested by the occurrences of barite-calcite-pyrite assemblages in the Longmaxi Formation across Yangtze Block, are likely the consequence of the complex interplay of varying sedimentation rate, organic matter quality, methane flux, and perhaps seawater sulfate concentration.

Ore-forming processes of the Qixiashan carbonate-hosted Pb-Zn deposit, South China: Constraints from sulfide trace elements and sulfur isotopes

The Middle-Lower Yangtze River Valley Belt (MLYRB) in South China contains many stratabound Fe-Cu-Pb-Zn deposits hosted in Middle-Upper Carboniferous carbonates. The origin and nature of the ore fluids are poorly constrained (syngenetic vs. epigenetic). Trace elements and sulfur isotope compositions of sphalerite and galena from the Qixiashan carbonate-hosted Pb-Zn deposit (Eastern of MLYRB) help to clarify the ore-fluid source and metallogenic processes. Three types of sphalerites have been distinguished (black sphalerite a, zoned sphalerite b and light color sphalerite c). High Fe and Mn contents of the early black sphalerite (Sp-a) were possibly derived from preceding Fe-Mn-rich sulfide layer or sediments from ore-bearing strata via replacement at 274–315 °C. The zoned sphalerite (Sp-b) has a dark Fe-Cu-rich core (321–348 °C) overgrown by a light Fe-Cu-poor rim (285–314 °C). The Sp-b rims are compositionally similar to Sp-a, Therefore, zoned Sp-b possibly represents the transition stage from poor copper (Sp-a) to rich copper (Sp-c) fluids. The light-color late sphalerite (Sp-c) is characterized by Fe-Mn depletion, as well as Ga, Cu, Cd and Sn enrichments. The Ga-rich Sp-c was possibly precipitated by the mixing of Ga-bearing sulfate and metalliferous fluid at 146–255 °C. We considered the Qixiashan Pb-Zn deposit to be of epigenetic origin that has undergone multistage ore-forming processes, in which the ore sulfur (δ34S: –3.7‰ to +7.8‰) was sourced from seawater sulfate (+22‰) via thermochemical sulfate reduction (TSR).

The metallogeny of the Devonian sediment-hosted sulfide deposits, South China: A case study of the Huodehong deposit

The Devonian sedimentary rocks in South China host numerous sulfide deposits (e.g. the Siding and Beishan Pb-Zn sulfide deposits, and the Yingde iron sulfide deposits) that are distinctly characterized by a wide variation of δ34S values in sulfides (−28.7‰ to +42.8‰). Such signature, however, has not been investigated in depth and thus the metallogeny of these deposits remain poorly understood. This paper investigated the Huodehong deposit hosted by sedimentary rocks of the Middle Devonian in the western Yangtze Block, South China. A complex paragenesis has been defined: I) micro-grained pyrite (Py1) associated with organic materials; II) radial and crustiform pyrite (Py2) and marcasite (Mc1) aggregates; III) subhedral-anhedral pyrite (Py3), microcrystal colloform sphalerite (Sp1), and dendritic galena; and IV) coarse-grained euhedral sphalerite (Sp2) occurred as veinlets. The mineralogical evidence shows that the Py1 occurred as syn-sedimentary pyritic stromatolites, which is overprinted by cavity-filling hydrothermal Py2, Py3, Sp1, and Sp2. In situ S isotopes show that the δ34S values of Py1-Py3 and Sp1 range from –22.8‰ to −10.8‰. Such highly depleted heavy sulfur isotopes indicate that the reduced sulfur was mainly derived from bacterially reduced seawater sulfate in an open system. The Sp1 has similar δ34S values to its reworking Py1, implying that part of reduced sulfur was sourced from sedimentary pyrite. Such sedimentary pyrite might act as a geochemical barrier in accelerating sulfate reduction via the hydrolysis of Fe2+ resulting an increase in the H+ concentration and the formation of HSO4−. In addition, the Sp2 has slightly depleted heavy sulfur isotopes (δ34S = −9.3‰ to −1.1‰), implying the late input of heavy sulfur isotopes component. Hence, the highly heterogeneous sulfur isotopes at Huodehong likely resulted from bacterial sulfate reduction coupled with reworking sedimentary pyrite, and subordinate incorporation of 34S-rich sulfur. The reduced sulfur of the Huodehong deposit has multiple sources (i.e. sedimentary pyrite and sulfate-bearing evaporites), and the ore formation has experienced the epigenetic hydrothermal mineralization with mixture of metals from the metamorphic basement rocks. The outcomes will have a great implication for understanding the origin and exploration of the Devonian sulfide deposits in South China.

The Formation of Highly Positive δ34S Values in Late Devonian Mudstones: Microscale Analysis of Pyrite (δ34S) and Barite (δ34S, δ18O) in the Canol Formation (Selwyn Basin, Canada)

The sulfur isotope composition of pyrite in marine sedimentary rocks is often difficult to interpret due to a lack of precise isotopic constraints for coeval sulfate. This study examines pyrite and barite in the Late Devonian Canol Formation (Selwyn Basin, Canada), which provides an archive of δ34S and δ18O values during diagenesis. Scanning electron microscopy (SEM) has been combined with microscale secondary ion mass spectrometry (SIMS) analysis (n = 1,032) of pyrite (δ34S) and barite (δ34S and δ18O) on samples collected from nine stratigraphic sections of the Canol Formation. Two paragenetic stages of pyrite and barite formation have been distinguished, both replaced by barium carbonate and feldspar. The δ34Sbarite and δ18Obarite values from all sections overlap, between +37.1‰ and +67.9‰ (median = +45.7‰) and +8.8‰ and +23.9‰ (median = +20.0‰), respectively. Barite morphologies and isotopic values are consistent with precipitation from diagenetically modified porewater sulfate (sulfate resupply &amp;lt;&amp;lt; sulfate depletion) during early diagenesis. The two pyrite generations (Py-1 and Py-2) preserve distinct textures and end-member isotopic records. There is a large offset from coeval Late Devonian seawater sulfate in the δ34Spyrite values of framboidal pyrite (-29.4‰ to -9.3‰), consistent with dissimilatory microbial sulfate reduction (MSR) during early diagenesis. The Py-2 is in textural equilibrium with barite generation 2 (Brt-2) and records a broad range of more positive δ34SPy-2 values (+9.4‰ to + 44.5‰). The distinctive highly positive δ34Spyrite values developed from sulfate limited conditions around the sulfate methane transition zone (SMTZ). We propose that a combination of factors, including low sulfate concentrations, MSR, and sulfate reduction coupled to anaerobic oxidation of methane (SR-AOM), led to the formation of highly positive δ34Spyrite and δ34Sbarite values in the Canol Formation. The presence of highly positive δ34Spyrite values in other Late Devonian sedimentary units indicate that diagenetic pyrite formation at the SMTZ may be a more general feature of other Lower Paleozoic basins.

Mineralization and Structural Controls of the AB-Bid Carbonate-Hosted Pb-Zn (±Cu) Deposit, Tabas-Posht e Badam Metallogenic Belt, Iran

The Ab-Bid deposit, located in the Tabas-Posht e Badam metallogenic belt (TPMB) in Central Iran, is the largest Pb-Zn (±Cu) deposit in the Behadad-Kuhbanan mining district. Sulfide mineralization in the Ab-Bid deposit formed in Middle Triassic carbonate rocks and contains galena and sphalerite with minor pyrite, chalcopyrite, chalcocite, and barite. Silicification and dolomitization are the main wall-rock alteration styles. Structural and textural observations indicate that the mineralization occurs as fault fills with coarse-textured, brecciated, and replacement sulfides deposited in a bookshelf structure. The Ab-Bid ore minerals precipitated from high temperature (≈180–200 °C) basinal brines within the dolomitized and silicified carbonates. The sulfur isotope values of ore sulfides suggest a predominant thermochemical sulfate reduction (TSR) process, and the sulfur source was probably Triassic-Jurassic seawater sulfate. Given the current evidence, mineralization at Ab-Bid resulted from focusing of heated, over-pressurized brines of modified basinal origin into an active fault system. The association of the sulfide mineralization with intensely altered wall rock represents a typical example of such features in the Mississippi Valley-type (MVT) metallogenic domain of the TPMB. According to the structural data, the critical ore control is a bookshelf structure having mineralized dextral strike-slip faults in the northern part of the Ab-Bid reverse fault, which seems to be part of a sinistral brittle shear zone. Structural relationships also indicate that the strata-bound, fault-controlled Ab-Bid deposit was formed after the Middle Jurassic, and its formation may be related to compressive and deformation stages of the Mid-Cimmerian in the Middle Jurassic to Laramide orogenic cycle in the Late Cretaceous-Tertiary.

Origin of the Devonian carbonate-hosted Banbianjie Ge-Zn deposit, Guizhou Province, South China: Geological, mineralogical and geochemical constraints

This paper investigates the origin of the newly discovered Devonian carbonate-hosted Banbianjie Ge-Zn deposit in South China. This deposit is rich in Ge (>900 t @ 110 ppm Ge) and contains 7.7 Mt of sulfide ores at a mean grade of 5.1 wt% Zn. The mineralization is stratabound or veined and is structurally controlled by the E-W trending Huangsi fault. Sulfide ores are dominated by sphalerite and dolomite with subsidiary pyrite, marcasite, and calcite, and minor galena. The mineralization forms massive, veined, brecciated, and disseminated structures and the hydrothermal minerals present in the deposit have colloform, fibrous, granular, and acicular textures. The hydrothermal dolomite has positive Ce (δCe = 1.13–1.20) and negative Eu (δEu = 0.43–0.68) anomalies that are indicative of formation in a weakly acidic, reduced, and low-temperature environment. The δ13CPDB and δ18OSMOW values of the dolomite range from −0.97‰ to −0.24‰ and +13.89‰ to +21.84‰, respectively, indicating that the dissolution of carbonate wall rocks was involved in the formation of hydrothermal dolomite. Theoretical C-O isotopic calculations further suggest that the hydrothermal dolomite formed as a result of water/rock (W/R) interaction and CO2 degassing. The δ34S values of the sulfides (−11.23‰ to −4.95‰) are markedly lower than those of the Devonian seawater sulfate and sulfate from evaporates in the Devonian strata (+21.9‰ to +25.9‰), suggesting that the reduced sulfur was derived from evaporates within the ore-hosting sedimentary rocks by bacterial sulfate reduction (BSR). The Banbianjie sulfides have an upper crustal Pb isotopic affinity, as demonstrated by their 206Pb/204Pb (18.335–18.343), 207Pb/204Pb (15.725–15.735), and 208Pb/204Pb (38.288–38.326) ratios, suggesting the metals were derived from metamorphosed basement rocks. These data suggest that: i) the Banbianjie deposit formed as a result of a combination of weakly acidic, reduced, and epigenetic low temperature mineralized fluids, trap structures, and favorable lithologies; ii) W/R interaction and CO2 degassing caused the precipitation of hydrothermal dolomite, whereas mixing of metals and S2− was the main formation mechanism of the sulfides; and iii) the Banbianjie Ge-Zn deposit is a typical Mississippi Valley-type (MVT) deposit.

Hydrocarbon seepage in the mid-Cretaceous greenhouse world: A new perspective from southern Tibet

The mid-Cretaceous greenhouse climate was induced by volcanic outgassing and the release of biogenic or thermogenic methane into the ocean-atmosphere system. During this period, major episodes of oceanic anoxic conditions enabled the large scale deposition of marine black shales rich in organic carbon, serving as a source for methane production. Studies on the anaerobic oxidation of methane, the key biogeochemical process at sites where methane is transported toward the seafloor, and its associated authigenic carbonates from mid-Cretaceous strata can contribute to elucidate such extreme climatic conditions. A total of nine layers of authigenic carbonates were recognized in the sequence of mid-Cretaceous inner shelf sedimentary rocks of the Qiangdong section, Gamba area, southern Tibet. In this study, we decipher the mode and causes of carbonate authigenesis by combining field observation, thin section petrography, mineralogy, and carbon and oxygen stable isotope geochemistry. The lowest obtained δ13Ccarb value of −30.5‰ is not low enough to exclude oil compounds as a carbon source, but since other evidence of oil seepage is lacking, methane is the most likely carbon source that was admixed to dissolved inorganic carbon to form authigenic carbonate. Typical seep carbonate phases including 13C depleted matrix micrite, clotted micrite, and banded and botryoidal cement as well as three types of authigenic pyrite comprising framboids, zoned aggregates with radial overgrowths surrounding a framboidal core, and euhedral pyrite crystals indicate the occurrence of methane seepage in the mid-Cretaceous depositional environments. In situ brecciation and subvertical tubular carbonates – the former reflecting rupture caused by local fluid overpressure and the latter interpreted as part of a plumping system – agree with widespread and vigorous seepage. Expanded shallow and deep-water anoxia in combination with low seawater sulfate concentration prior to the oceanic anoxic event 2 (OAE 2) event apparently caused an increased flux of organic matter to the methanogenic zone, stimulating methanogenesis and enabling a higher flux of methane toward the seafloor. In the water column, aerobic oxidation of methane would have enhanced oxygen depletion, thereby contributing to black shale deposition and providing a positive feedback to organic matter preservation and burial. Based on correlation with coeval authigenic carbonate deposits from the Tethyan continental margin, we conclude that organic matter accumulation and sea-level change were the main factors controlling carbonate authigenesis in the mid-Cretaceous.

Understanding the isotopic composition of sedimentary sulfide: A multiple sulfur isotope diagenetic model for Aarhus Bay

Measurement of the multiple sulfur isotopes (³²S/³³S/³⁴S) enables the calibration of microbial biosignatures and provides a unique diagnosis of S-based metabolic processes: sulfate reduction, disproportionation, and sulfide oxidation. All three metabolisms carry distinct geochemical consequences for S cycling in modern systems, and are particularly powerful for paleoenvironmental interpretations if their respective contributions can be separated. To hone those interpretations and to further develop a quantitative context for understanding early diagenetic sulfur cycling, we constructed a multiple S isotope reactive transport model for the sediments of a geochemically well-characterized system (Aarhus Bay, Denmark). The model reconciles pore water and solid phase concentration profiles of the major species associated with Fe/S/C cycling, and uses multiple S isotope systematics to predict the isotope profiles of the major S species, including pore water sulfate, free sulfide and solid phase pyrite. We note that very large fractionations associated with sulfate reduction (³⁴ε_sr = 70‰) are required to reproduce the observed pore water profiles, and we reconcile these fractionations with low temperature theoretical predictions for isotope equilibrium fractionation. The minor sulfur isotope values (noted as Δ³³S) of sulfate increase at shallow depths within the Aarhus Bay core, and decrease when sulfate drops below 10 mM. Values (Δ³³S) for sulfide decrease nearly monotonically towards seawater sulfate values near the zone of sulfate depletion. Pyrite Δ³³S values are nearly uniform downcore (0.170 ± 0.010‰) despite a ∼10‰ enrichment in surface versus deep pyrite δ³⁴S values. Sulfate reduction is the most important process controlling S isotope pore water distributions, with modest contributions from oxidative S cycling. Further, microbial sulfate reduction demonstrates large fractionations typically not expected for shallow, organic rich (TOC ∼ 4%) continental margin systems.