Multiple Sulfur Isotope Data Research Articles

Evaluating the multiple sulfur isotope signature of Eoarchean rocks from the Isua Supracrustal Belt (Southwest-Greenland) by MC-ICP-MS: Volcanic nutrient sources for early life.

On the anoxic Archean Earth, prior to the onset of oxidative weathering, electron acceptors were relatively scarce, perhaps limiting microbial productivity. An important metabolite may have been sulfate produced during the photolysis of volcanogenic SO2 gas. Multiple sulfur isotope data can be used to track this sulfur source, and indeed this record indicates SO2 photolysis dating back to at least 3.7 Ga, that is, as far back as proposed evidence of life on Earth. However, measurements of multiple sulfur isotopes in some key strata from that time can be challenging due to low sulfur concentrations. Some studies have overcome this challenge with NanoSIMS or optimized gas-source mass spectrometry techniques, but those instruments are not readily accessible. Here, we applied an aqua regia leaching protocol to extract small amounts of sulfur from whole rocks for analyses of multiple sulfur isotopes by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Measurements of standards and replicates demonstrate good precision and accuracy. We applied this technique to meta-sedimentary rocks with putative biosignatures from the Eoarchean Isua Supracrustal Belt (ISB, >3.7 Ga) and found positive ∆33S (1.40-1.80‰) in four meta-turbidites and negative ∆33S (-0.80‰ and -0.66‰) in two meta-carbonates. Two meta-basalts do not display significant mass-independent fractionation (MIF, -0.01‰ and 0.16‰). Insitu Re-Os dating on a molybdenite vein hosted in the meta-turbidites identifies an early ca. 3.7 Ga hydrothermal phase, and insitu Rb-Sr dating of micas in the meta-carbonates suggests metamorphism affected the rocks at ca. 2.2 and 1.7 Ga. We discuss alteration mechanisms and conclude that there is most likely a primary MIF-bearing phase in these meta-sediments. Our new method is therefore a useful addition to the geochemical toolbox, and it confirms that organisms at that time, if present, may indeed have been fed by volcanic nutrients.

Sulfur isotope evidence from peridotite enclaves in southern West Greenland for recycling of surface material into Eoarchean depleted mantle domains

Eoarchean peridotite enclaves found in southern West Greenland's Itsaq Gneiss Complex (IGC) represent an important and valuable record of Earth's early geodynamic history. However, the origins of these rocks and the processes acting on them in the Eoarchean remain a subject of debate. Some researchers have proposed that these peridotites represent the oldest preserved pieces of Earth's mantle, while others have suggested that they represent ultramafic cumulates. Similarly, the geodynamic context in which they formed and were emplaced is subject to multiple interpretations. Some researchers argue that only vertical tectonic processes operated in the Eoarchean and others contend that these peridotites were embedded in the crust by horizontal tectonic processes. We present multiple sulfur isotope data from IGC peridotite enclaves, offering new insights into these rocks' origins and tectonic processes in the early Earth. Generally small but significant nonzero Δ33S values of 0.04 to 0.21‰ were detected in the studied peridotites. Peridotites with almost no petrographic signs of metasomatic alteration have on average slightly higher Δ33S values, whereas peridotites with clear petrographic and geochemical signatures of melt metasomatism were found to have slightly lower Δ33S values. These Δ33S values point to incorporation of surface-derived material of Archean age or older. Correlations between Δ33S values and previously published major and trace element data support the view that these peridotites were subject to hydrous melt depletion of incompatible elements, followed by variable melt re-enrichment. Notably, a distinct correlation also exists between previously published Hf isotope data and Δ33S values, indicating a depleted mantle source for melt percolating through the peridotites in the Eoarchean. The sulfur isotope data demonstrate that these processes included the introduction of surface-derived sulfur, pointing to an early onset of crustal recycling. These findings point to the existence of depleted mantle domains in the Hadean and suggest that crustal recycling processes operated during the Eoarchean or earlier.

Reconciling discrepant minor sulfur isotope records of the Great Oxidation Event

Understanding the timing and trajectory of atmospheric oxygenation remains fundamental to deciphering its causes and consequences. Given its origin in oxygen-free photochemistry, mass-independent sulfur isotope fractionation (S-MIF) is widely accepted as a geochemical fingerprint of an anoxic atmosphere. Nevertheless, S-MIF recycling through oxidative sulfide weathering—commonly termed the crustal memory effect (CME)—potentially decouples the multiple sulfur isotope (MSI) record from coeval atmospheric chemistry. Herein, however, after accounting for unrecognised temporal and spatial biases within the Archaean–early-Palaeoproterozoic MSI record, we demonstrate that the global expression of the CME is barely resolvable; thereby validating S-MIF as a tracer of contemporaneous atmospheric chemistry during Earth’s incipient oxygenation. Next, utilising statistical approaches, supported by new MSI data, we show that the reconciliation of adjacent, yet seemingly discrepant, South African MSI records requires that the rare instances of post-2.3-billion-year-old S-MIF are stratigraphically restricted. Accepting others’ primary photochemical interpretation, our approach demands that these implied atmospheric dynamics were ephemeral, operating on sub-hundred-thousand-year timescales. Importantly, these apparent atmospheric relapses were fundamentally different from older putative oxygenation episodes, implicating an intermediate, and potentially uniquely feedback-sensitive, Earth system state in the wake of the Great Oxidation Event.

Evidence from gas-rich ultramafic xenoliths for Superplume-derived recycled volatiles in the East African sub-continental mantle

Volatile-rich fluids are believed to play a key role in the metasomatic enrichment of the East African sub-continental lithospheric mantle (SCLM), but limited data is available on key volatile tracers such as CO2 and N2. We report new CO2 and N2 isotope and relative abundance data in exceptionally gas-rich mantle peridotite and pyroxenite xenoliths from nine localities throughout the eastern branch of the East African Rift System (EARS). Importantly for our study, the xenolith localities straddle the transition between continental and oceanic lithosphere. In addition, we report major and trace element contents together with oxygen isotopes on host crystals and bulk multiple sulfur isotope data on select pyroxene crystals from the same xenolith suite. These new data are interpreted alongside previously published He, Ne and Ar isotope and relative abundance data.Pyroxenite xenoliths formed from the infiltration and crystallization of mafic melts in the lithospheric mantle. This was followed by fluids fracturing through the pyroxenites leaving gas-rich fluid inclusions. The elemental and isotope systematics of the fluid inclusion-hosted volatile species (He, Ar, N, CO2) within the mantle xenoliths are consistent with the enrichment of the EARS SCLM by CO2-rich mantle fluids from subducted carbonate-rich material. Such CO2 enrichments (CO2/3He > 7 × 109, δ13C ~0‰) are also associated with positive δ15N values (as high as +3.4‰), reinforcing the link between the metasomatic fluids and subduction of hydrothermally altered oceanic crust. Recycled signatures are also consistent with oxygen and sulfur isotope compositions of host crystals, which are distinct from compositions typical for the depleted upper MORB-source mantle.The occurrence of recycled volatile signatures in the EARS SCLM is widespread and must therefore be associated with a large-scale mantle process currently supplying material to EARS magmas. Notably, mantle xenoliths with high 3He/4He from the Ethiopian Rift are also associated with δ15N and δ13C values similar to the composition of sediments. This suggest that recycled materials have been entrained within the deep-seated African Superplume, which supplies the EARS with both primordial and recycled volatiles.

SO2 disproportionation impacting hydrothermal sulfur cycling: Insights from multiple sulfur isotopes for hydrothermal fluids from the Tonga-Kermadec intraoceanic arc and the NE Lau Basin

Hydrothermal systems located at intra-oceanic volcanic arcs and in back-arc basins reveal a complex sulfur cycling. Here we present multiple sulfur isotope data for dissolved sulfide and sulfate in hydrothermal fluids from vent sites at the southern Kermadec and the northern Tonga island arcs and the NE Lau Basin.δ34S values for H2S range from −7.4 to +4.6‰ for hydrothermal fluids from arc volcanoes and from +0.2 to +4.5‰ for those located in the NE Lau Basin. Ranges for Δ33S values are −0.010 to +0.033‰ and −0.016 to +0.011‰, respectively. SO42− in fluids from hydrothermal vents at Macauley caldera, the Brothers volcanic cones, and Niua North show ranges in δ34S and Δ33S from +16.7 to +24.7‰ and +0.013 to +0.049‰. The multiple sulfur isotope data suggest a contribution to the hydrothermal sulfur budget from the disproportionation of magmatic SO2 for most hydrothermal vent sites from the Kermadec arc, whereas H2S at the NE Lau Basin vent sites is thought to result mainly from two-component mixing between host rock-derived sulfur and seawater sulfate with an additional local contribution from SO2 disproportionation. Data from Brothers NW Caldera suggest isotope exchange between H2S and SO42−, whereas lowering of fluid acidity by dissolution of mineral phases occurs at the Brothers Lower Cone. δ34S values between −8.5 and +3.1‰ and Δ33S values between +0.009 and +0.036‰ for elemental sulfur indicate changing redox conditions and/or a decrease of magmatic SO2 in the hydrothermal fluids at Macauley, Haungaroa, Brothers Lower Cone, Niua North and Niuatahi.We conclude that acid sulfate venting in particular shows the highest variability in sulfur isotopic composition of hydrothermal sulfur, irrespective of whether located at an intra-oceanic arc or in a back-arc basin. Sulfur isotope heterogeneity is due to variable contributions from SO2 disproportionation and host rock compositions.

Sulfur Isotope Evidence for a Geochemical Zonation of the Samoan Mantle Plume

AbstractBasalts from the Samoan volcanoes sample contributions from all of the classical mantle endmembers, including extreme EM II and high 3He/4He components, as well as dilute contributions from the HIMU, EM I, and DM components. Here, we present multiple sulfur isotope data on sulfide extracted from subaerial and submarine whole rocks (N = 16) associated with several Samoan volcanoes—Vailulu‘u, Malumalu, Malutut, Upolu, Savai‘i, and Tutuila—that sample the full range of geochemical heterogeneity at Samoa and upon exhaustive compilation of S‐isotope data for Samoan lavas, allow for an assessment of the S‐isotope compositions associated with the different mantle components sampled by the Samoan hotspot. We observe variable S concentrations (10–1,000 ppm) and δ34S values (−0.29‰ ± 0.30 to +4.84‰ ± 0.30, 2σ). The observed variable S concentrations are likely due to sulfide segregation and degassing processes. The range in δ34S reflects mixing between the mantle origin and recycled components, and isotope fractionations associated with degassing. The majority of samples reveal Δ33S within uncertainty of Δ33S = 0‰ ± 0.008. Important exceptions to this observation include: (a) a negative Δ33S (−0.018‰ ± 0.008, 2σ) from a rejuvenated basalt on Upolu island (associated with a diluted EM I component) and (b) previously documented small (but resolvable) Δ33S values (up to +0.027 ± 0.016) associated with the Vai Trend (associated with a diluted HIMU component). The variability we observed in Δ33S is interpreted to reflect contributions of sulfur of different origins and likely multiple crustal protoliths. Δ36S versus Δ33S relationships suggest all recycled S is of post‐Archean origin.

Atmospheric sulfur is recycled to the crystalline continental crust during supercontinent formation

The sulfur cycle across the lithosphere and the role of this volatile element in the metasomatism of the mantle at ancient cratonic boundaries are poorly constrained. We address these knowledge gaps by tracking the journey of sulfur in the assembly of a Proterozoic supercontinent using mass independent isotope fractionation (MIF-S) as an indelible tracer. MIF-S is a signature that was imparted to supracrustal sulfur reservoirs before the ~2.4 Ga Great Oxidation Event. The spatial representation of multiple sulfur isotope data indicates that successive Proterozoic granitoid suites preserve Δ33S up to +0.8‰ in areas adjacent to Archean cratons. These results indicate that suturing of cratons began with devolatilisation of slab-derived sediments deep in the lithosphere. This process transferred atmospheric sulfur to a mantle source reservoir, which was tapped intermittently for over 300 million years of magmatism. Our work tracks pathways and storage of sulfur in the lithosphere at craton margins.

Sulfur isotope and metal variations in sulfides in the BIF-hosted orogenic Cuiabá gold deposit, Brazil: Implications for the hydrothermal fluid evolution

Textural, chemical and multiple sulfur isotope analyses of sulfides from the Archean world-class Cuiabá orogenic Au deposit, Quadrilátero Ferrífero district, Brazil, were conducted to track distinct trace element signatures from syngenetic to epigenetic-hydrothermal pyrite types in different host units, and to deduce the nature and source of the mineralizing fluids. Gold mineralization in Cuiabá is hosted in greenschist facies volcanic and sedimentary host rocks belonging to the Archean Rio das Velhas Supergroup, especially in association with quartz veins and sulfide minerals. The BIF-hosted Fonte Grande Sul orebody is controlled by quartz veins and disseminated gold-bearing pyrite, pyrrhotite and arsenopyrite in the wall rocks. Five pyrite types are classified based on textural relations as spongy, syngenetic (Py1), porous early-(Py2), smooth main-(Py3) and smooth isolated and overgrown late-stage (Py4 and Py5) types variably present in metamorphosed carbonaceous pelites, BIF and andesite. Besides pyrite, pyrrhotite and arsenopyrite are also defined according to textural and paragenetic differences, and they display significant trace element contents. Trace element abundance maps and LA-ICP-MS analyses display trace element incorporations in Py1 (present only in carbonaceous pelite), Py2 and Py3 (in all host rocks), and Py4 and Py5 (only in BIF). Py1 yields high As, Co, Ni, Pb and Ag concentrations, whereas Py2 (formed by agglomeration of Py1) maintains high trace element concentrations with slightly less of those elements. Trace element incorporation in Py3 is similar to Py1 in carbonaceous pelite. Early-stage Py2 and main-stage Py3 in BIF and andesite have increased Co and Ni, but have less Au and As. Late-stage Py4 is characterized by lower trace element concentrations, whereas Py5 is further enriched in As, Bi, Co, Ni and Pb. The hydrothermal alteration is divided into early-, main- and late-stage, which correlate to the sulfide hydrothermal evolution. The study shows that carbonaceous pelite is pre-enriched in Co, Ni and Pb, whereas certain elements like Ag, Au, Bi and As are only hydrothermally concentrated either during the early, main or late stage in BIF and andesite. This geochemical pattern supports a syngenetic versus hydrothermal origin of distinct elements, including some trace elements now in the ore zones. Multiple sulfur isotope data suggest that mineralizing fluids at the Cuiabá gold deposit reflect a complex mixing of sulfur evolved from three possible sources: seawater, mantle, and reduced elemental sulfur. Spongy, syngenetic Py1 yields Δ33S values ranging from −2.28 to −0.25‰, separated into two ranges, the first from −2.28 to −1.97‰, and the second from −0.96 to −0.25‰. The first range suggests Py1 in the carbonaceous pelite was deposited in a seawater environment. These pyrites probably mixed with later mantle sulfur carrying a near-zero Δ33S signature, which is indicated by the second Δ33S range, or could have mixed with fluids sourced from sedimentary rocks at depth carrying a positive Δ33S signature. The second scenario is more common in sedimentary and diagenetic pyrites. An unequivocal contrast is shown by early-, main- and late-stage pyrite types (Py2, Py3, Py4 and Py5) in carbonaceous pelite, BIF and andesite, which present a continuous process of crustal assimilation values towards increasingly positive δ34S and Δ33S values. This confirms evidence for a sedimentary-derived sulfur source as also indicated by fluid inclusion data of the andesite-hosted orebody at the Cuiabá deposit.

Anomalous sulfur isotopes trace volatile pathways in magmatic arcs

The cycle of sulfur, an important volatile in Earth9s crust, is the driver of many significant processes such as biological evolution, climate change, and the formation of ore deposits. This study investigates the ancient cycle of volatiles by tracing the indelible signal of anomalous sulfur isotopes, expressed as Δ 33 S ≠ 0, to illuminate the pathway of sulfur recycling through magmatic arcs. We selected the ca. 2.0 Ga Glenburgh gold deposit in the Glenburgh magmatic arc of Western Australia as a natural laboratory for this study. High-precision multiple sulfur isotope analyses of samples from the Glenburgh gold deposit and surrounding granitoid rocks yield the largest known sulfur isotope anomalies (Δ 33 S up to +0.82‰) in rocks <2.33 Ga globally. These data indicate that sulfur, and possibly gold, originated from multiple geochemical reservoirs in sedimentary rocks subducted beneath the magmatic arc, one of which is >2.33 Ga. Multiple sulfur isotope data are able to clarify a process that is cryptic to most other currently available data sets, showing that the cycling of volatiles and metals in arc settings occurs on very large scales, from the atmosphere-hydrosphere through to the lithosphere during crustal generation.

Sulfur isotope and trace element data from ore sulfides in the Noranda district (Abitibi, Canada): implications for volcanogenic massive sulfide deposit genesis

We examine models for volcanogenic massive sulfide (VMS) mineralization in the ~2.7-Ga Noranda camp, Abitibi subprovince, Superior Province, Canada, using a combination of multiple sulfur isotope and trace element data from ore sulfide minerals. The Noranda camp is a well-preserved, VMS deposit-rich area that is thought to represent a collapsed volcanic caldera. Due to its economic value, the camp has been studied extensively, providing a robust geological framework within which to assess the new data presented in this study. We explore previously proposed controls on mineralization within the Noranda camp and, in particular, the exceptional Au-rich Horne and Quemont deposits. We present multiple sulfur isotope and trace element compositional data for sulfide separates representing 25 different VMS deposits and “showings” within the Noranda camp. Multiple sulfur isotope data for this study have δ34SV-CDT values of between −1.9 and +2.5 ‰, and Δ33SV-CDT values of between −0.59 and −0.03 ‰. We interpret the negative Δ33S values to be due to a contribution of sulfur that originated as seawater sulfate to form the ore sulfides of the Noranda camp VMS deposits. The contribution of seawater sulfate increased with the collapse and subsequent evolution of the Noranda caldera, an inference supported by select trace and major element analyses. In particular, higher concentrations of Se occur in samples with Δ33S values closer to 0 ‰, as well as lower Fe/Zn ratios in sphalerite, suggesting lower pressures and temperatures of formation. We also report a relationship between average Au grade and Δ33S values within Au-rich VMS deposits of the Noranda camp, whereby higher gold grades are associated with near-zero Δ33S values. From this, we infer a dominance of igneous sulfur in the gold-rich deposits, either leached from the volcanic pile and/or directly degassed from an associated intrusion.

Multiple sulfur and carbon isotope composition of sediments from the Belingwe Greenstone Belt (Zimbabwe): A biogenic methane regulation on mass independent fractionation of sulfur during the Neoarchean?

To explore the linkage between mass-independent sulfur isotope fractionation (MIF-S) and δ13Corg excursions during the Neoarchean, as well as the contemporary redox state and biogeochemical cycling of carbon and sulfur, we report the results of a detailed carbon and multiple sulfur (δ34S, δ33S, δ36S) isotopic study of the ∼2.7Ga Manjeri and ∼2.65Ga Cheshire formations of the Ngezi Group (Belingwe Greenstone Belt, Zimbabwe).Multiple sulfur isotope data show non-zero Δ33S and Δ36S values for sediments older than 2.4Ga (i.e. prior to the Great Oxidation Event, GOE), indicating MIF-S thought to be associated with low atmospheric oxygen concentration. However, in several 2.7–2.5Ga Neoarchean localities, small-scale variations in MIF-S signal (magnitude) seem to correlate with negative excursion in δ13Corg, possibly reflecting a global connection between the relative reaction rate of different MIF-S source reaction and sulfur exit channels and the biogenic flux of methane into the atmosphere during periods of localized, microbiologically mediated, shallow surface-water oxygenation.The Manjeri Formation black shales studied here display a wide range of δ13Corg between −35.4‰ and −16.2‰ (average of −30.3±6.0‰, 1σ), while the Cheshire Formation shales have δ13Corg between −47.7‰ and −35.1‰ (average −41.3±3‰, 1σ). The δ34S values of sedimentary sulfides from Manjeri Formation vary between −15.15‰ and +2.37‰ (average −1.71±4.76‰, 1σ), showing very small and mostly negative Δ33S values varying from −0.58‰ to 0.87‰ (average 0.02±0.43‰, 1σ). Cheshire Formation black shale sulfide samples measured in this study have δ34S values ranging from −2.11‰ to 2.39‰ (average 0.25±1.08‰, 1σ) and near zero and solely positive Δ33S anomalies between 0.14‰ and 1.17‰ (average 0.56±0.29‰, 1σ). Moreover, Δ36S/Δ33S in the two formations are comparable with a slope of −1.38 (Manjeri Formation) and −1.67 (Cheshire Formation), respectively. This differs from the Archean reference line (i.e. −0.9).The sulfur and carbon isotopic signatures recorded here likely reflect different environmental conditions and/or ecosystems within the sampled Cheshire and Manjeri formations paleofacies. The differences in carbon isotopes in different sedimentological facies are interpreted as recording different metabolic pathways, including photosynthesis, methanogenesis and methanotrophy. Low δ13Corg values in the Cheshire Formation black shales suggest a strong influence of methanotrophy (likely preceded by bacterial methanogenesis), while the large range of Manjeri Formation δ34S may record bacterial sulfate reduction. The C and multiple S isotopic variations recorded here may imply different patterns of C and S fractionation, perhaps dependent on variations in the biogenic egress of methane to the atmosphere.

The Archean komatiite-hosted, PGE-bearing Ni–Cu sulfide deposit at Vaara, eastern Finland: evidence for assimilation of external sulfur and post-depositional desulfurization

Archean komatiites host important resources of Ni, Cu, Co, and PGE, particularly in Western Australia and Canada. In Finland, several small, low-grade sulfide deposits have been found in komatiites, including the ca. 2.8 Ga Vaara deposit in the Archean Suomussalmi greenstone belt. It occurs in the central part of the serpentinized olivine cumulate zone of a komatiitic extrusive body and is composed of disseminated interstitial sulfides consisting of pyrite, pentlandite, millerite, violarite, and chalcopyrite accompanied by abundant magnetite. Although currently subeconomic, the mineralization is interesting due to the very high chalcophile element contents of the sulfide fraction (38 wt% Ni, 3.4 wt% Cu, 0.7 wt% Co, 22.4 ppm Pd, and 9.5 ppm Pt). The sulfides occur in relatively Cr-poor olivine cumulates suggesting involvement of a chromite-undersaturated magma. The parental magma was an Al-undepleted komatiite with an estimated MgO content of at least 24 wt%. In contrast to the common komatiite types in the eastern Finland greenstone belts, the Vaara rocks are moderately enriched in LREE relative to MREE, suggesting that crustal contamination played an important role in the genesis of the Vaara deposit. Multiple sulfur isotope data reveal considerable mass-independent sulfur isotope fractionation both in country rock sedimentary sulfides (Δ33S ranges from −0.50 to +2.37 ‰) and in the Vaara mineralization (Δ33S ranges from +0.53 to +0.66 ‰), which provides strong evidence for incorporation of crustal sulfur. Extensive replacement of interstitial sulfides by magnetite and the presence of millerite- and violarite-bearing, pyrrhotite-free sulfide assemblages indicate significant post-magmatic, low-temperature hydrothermal oxidation of the primary magmatic pyrrhotite-pentlandite-chalcopyrite assemblages and associated sulfur loss that led to a significant upgrading of the original metal tenors of the Vaara deposit.

Multiple Sulfur Isotope Determination by SIMS: Evaluation of Reference Sulfides for Δ33S with Observations and a Case Study on the Determination of Δ36S

High spatial resolution multiple sulfur isotope studies undertaken by multi‐collector secondary ion mass spectrometry (SIMS) commonly use well‐characterised sulfide reference materials that do not (or are assumed not to) exhibit mass‐independent fractionation in 33S and 36S, taking advantage of the three‐isotope plot to evaluate the extent of such fractionation in unknown targets. As a result, few studies to date have used a mass independently fractionated reference sulfide to demonstrate accuracy of measurement and/or data reduction procedures. This article evaluates two mass independently fractionated sulfides, a pyrite from the 3.7 Ga Isua greenstone belt and a pyrrhotite from a 2.7 Ga gold deposit in Minas Gerais, Brazil, which may be used to provide additional confidence in the obtained multiple sulfur isotope data. Additionally, the article presents a method for measuring quadruple sulfur isotopes by SIMS at a comparable spatial and volume resolution to that typically employed for triple sulfur isotopes. This method has been applied to the Isua pyrite as well as to a sample of 2.5 Ga pyrite from the Campbellrand, Transvaal, South Africa, previously investigated using SIMS for triple sulfur isotopes, illustrating its potential for quadruple sulfur investigations.

District to Camp Controls on the Genesis of Komatiite-Hosted Nickel Sulfide Deposits, Agnew-Wiluna Greenstone Belt, Western Australia: Insights from the Multiple Sulfur Isotopes

The Agnew-Wiluna greenstone belt of Western Australia is the largest komatiite-hosted nickel sulfide belt in the world and contains two world-class Ni-Cu-(PGE) deposits and a host of smaller deposits. This study focuses on the broader scale geology of this greenstone belt in order to understand the key controls on the genesis of the komatiite-hosted Ni-Cu-(PGE) deposits, with specific focus on camp to district controls. We apply multiple sulfur isotopes to this geologic framework and conclude not only that the addition of crustal sulfur is a prerequisite for ore genesis in komatiite systems, but above all that the sulfur required to generate world-class deposits is most likely derived from barren volcanic massive sulfide lenses, which are spatially and genetically associated with felsic volcanic and volcaniclastic sequences that were emplaced coevally with large komatiitic sills and channelized lava flows. Multiple sulfur isotope data can be utilized in exploration at the deposit to district scales. At the deposit scale, the spatial pattern of mass-independent S isotope values (Δ 33 S) provides crucial insight into the identification of proximal high-grade and high-tenor ores in mineralized systems. In fact, sulfur data reflect the assimilation process that occurred upon komatiite emplacement, whereby hot turbulent magma thermomechanically eroded and assimilated exhalative sulfides spatially located close to vent with negative to near zero Δ 33 S values, whereas less turbulent flows interacted with distal sulfidic shales having Δ 33 S values above 0 per mil. Accordingly, the spatial variation of multiple sulfur isotope values in magmatic sulfides and associated host rocks may be utilized as a vector towards high-grade ores of poorly known systems. At the district scale, rather than ascertaining what controls the distribution of komatiite-hosted Ni-Cu-(PGE) deposits, the appropriate question to ask is what controls the distribution of country rock sulfides, considering that exhalative sulfides may be crucial to ore genesis in komatiite systems. We propose that felsic lava domes unambiguously mark their vents and can be directly mapped or inferred from gravity data. This work provides the first step in identifying district-scale control on komatiite-hosted Ni-Cu-(PGE) deposits. This is the scale that has high impact on exploration for new komatiite-hosted nickel sulfide belts globally.

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

Abstract The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry. Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ34S range between −29.8 and + 10.2‰ and Δ33S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ34SCRS with less negative values between −11.3 and −1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea. Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ34S and Δ33S values for pyrite between −32.8 and −1.1‰ and between −0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ34S and Δ33S values between −26.7 and −2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ34S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro. Although a magmatic SO2 contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.

Multiple sulfur isotope fractionations in biological systems: A case study with sulfate reducers and sulfur disproportionators

Multiple sulfur isotope measurements of sulfur compounds associated with dissimilatory sulfate reduction, elemental sulfur disproportionation and sulfite disproportionation indicate that different types of metabolic processes impart different multiple isotope signatures. An established network for sulfate reduction was used previously to explain the multiple isotope variability. Here, we revisit that treatment and expand it to branching networks representative of biological sulfur disproportionation, in an attempt to understand multiple sulfur isotope fractionations associated with that metabolism. We use this context to interpret experimental data for both sulfate reducers and sulfur compound disproportionators. We explore the types of information about material flow through these metabolic processes that can be extracted by using multiple sulfur isotope data. The different multiple sulfur isotope relationships (Δ³³S′ and λ) allow various metabolic processes to be distinguished from one another, even when δ³⁴S fractionations are similar, providing a tool that can be used to interpret and identify different types of biological sulfur fractionations in the geologic record.