Mass-independent Fractionation Of Sulfur Isotopes Research Articles

Age of Granulites of the Cheremshanskaya Unit (Sharyzhalgai Uplift, Siberian Craton, Russia): New Data

The present paper presents new U–Pb and Sm–Nd age data obtained for granulites of the Cheremshanskaya Unit enclosing metamorphosed volcano-sedimentary sulfide ores, in which sulfur isotope mass-independent fractionation (MIF–S) was established. Zircons from orthotectites that cut hosted paragranulites yielded aconcordant U–Pb age of 1866.8 ± 7.6 Ma, reflecting the final stage of granulite metamorphism. The model age (ТND (DM)) of ~3.0 Ga obtained for graphite–sulfide–cordierite (±Bt) and garnet–biotite–orthopyroxene paragneisses indicates that the protolith of sedimentary rocks was formed in the Mesoarchaean. As evidenced from various sources, the Sm–Nd isotopic characteristics of orthotectites differ from those of paragneisses.

Xenon isotopes in Archean and Proterozoic insoluble organic matter: A robust indicator of syngenecity?

Insoluble organic materials (kerogens) isolated from ancient sedimentary rocks provide unique insights into the evolution of early life. However, establishing whether these kerogens are indeed syngenetic with the deposition of associated sedimentary host rocks, or contain contribution from episodes of secondary deposition, is not straightforward. Novel geochemical criterions are therefore required to test the syngenetic origin of Archean organic materials. On the one hand, the occurrence of mass-independent fractionation of sulphur isotopes (MIF-S) provides a tool to test the Archean origin of ancient sedimentary rocks. Determining the isotope composition of sulphur within kerogens whilst limiting the contribution from associated minerals (e.g., nano-pyrites) is however challenging. On the other hand, the Xe isotope composition of the Archean atmosphere has been shown to present enrichments in the light isotopes relative to its modern composition, together with a mono-isotopic deficit in 129Xe. Given that the isotopic composition of atmospheric Xe evolved through time by mass dependent fractionation (MDF) until ~2.5 to 2.0 Ga, the degree of MDF of Xe isotopes trapped in kerogens could provide a time stamp for the last chemical equilibration between organic matter and the atmosphere. However, the extent to which geological processes could affect the signature of Xe trapped in ancient kerogen remains unclear. In this contribution, we present new Ar, Kr and Xe isotopic data for four kerogens isolated from 3.4 to 1.8 Gy-old cherts and confirm that Xe isotopes from the Archean atmosphere can be retained within kerogens. However, new Xe-derived model ages are lower than expected from the ages of host rocks, indicating that initially trapped Xe components were at least partially lost and/or mixed together with some Xe carried out by younger generations of organic materials, therefore complicating the Xe-based dating method. Whilst non-null Δ33S values and 129Xe deficits relative to modern atmosphere constitute reliable imprints from the Archean atmosphere, using Xe isotopes to provide information on the syngenetic origin of ancient organic matter appears to be a promising – but not unequivocal – tool that calls for further analytical development.

Sources of Sulfur for Sulfide Mineralization in the Archean Rocks of the Sharyzhalgai Uplift of the Siberian Craton Basement (from Multi-Isotope Data)

Abstract —We present results of study of sulfide ore occurrence in highly metamorphosed (granulite facies) Archean rocks of the Siberian craton basement. The host rocks and ore minerals are briefly described, and new data on the multiple sulfur isotope (δ33S, δ34S, Δ33S) composition of sulfides are presented. Application of high-resolution analytical methods enabling the assessment of the sulfur isotope behavior in situ made it possible to reveal mass-independent fractionation of sulfur isotopes in the rock samples. The isotopic composition of sulfur in the sulfides indicates its inflow from several sources, including the ancient Archean atmosphere, where primary sulfur has passed through a cycle of fractionation. Despite the high-gradient metamorphism, the subsequent ultrametamorphic and post-ultrametamorphic transformations accompanied by a change in the primary mineral composition of rocks and by chemogenic fractionation of sulfur, the signature of the sedimentary source of sulfur in sulfide ores has been well preserved. Analysis of the chemical composition of rocks and ore minerals and of sulfur isotopes has led to the conclusion that the studied rocks are metamorphosed Late Archean analogs of black shales and the sulfide mineralization is of stratiform pyrite type.

Atmospheric SO2 oxidation by NO2 plays no role in the mass independent sulfur isotope fractionation of urban aerosols

Modern anthropogenic aerosols usually exhibit low but significant Δ33S signatures (−0.6 to 0.5‰) whose origin still remains unclear. While isotope fractionation factors associated with the oxidation of SO2 by O2+TMI (Transition Metal Ion), H2O2 or OH cannot lead to such extreme Δ33S-values, an increasing number of studies points to the significant role of NO2 as a contributing oxidant, especially in the urban environment.To address the possible relation between atmospheric NO2 and observed Δ33S-values in aerosols, we carried out laboratory experiments oxidizing SO2 by NO2 at temperatures ranging between −7 and 52 °C. Our results show that at temperatures ≥10 °C SO2 oxidation by NO2 is characterized by 1) a 34α-value whose temperature dependence (0.2437/T+0.0457) is distinct from those related to oxidation by O2+TMI, H2O2 and OH oxidation pathways and 2) 33β (0.514 ± 0.0003) and 36β (1.90 ± 0.002) values that are closer to the mass dependent values (0.515 and 1.89 respectively) than those reported for the other oxidation pathways. This implies that the NO2 oxidation pathway cannot explain the extreme Δ33S-values measured in urban aerosols.Our data show that if atmospheric SO2 oxidation by NO2 is neglected, both the O2+TMI and OH oxidation pathways would be overestimated in urban areas. Finally, we conclude that another oxidation reaction is responsible for the high Δ33S-values measured in urban aerosol samples.

The fluid evolution of the Nimbus Ag-Zn-(Au) deposit: An interplay between mantle plume and microbial activity

The Nimbus Ag-Zn-(Au) volcanic-hosted massive sulfide (VHMS) deposit represents an exceptional orebody in the Yilgarn Craton of Western Australia. It is located in a zone of juvenile crust running N-S through the Eastern Goldfields Superterrane. However, unlike most other VHMS occurrences associated with the 2690–2680 Ma rift sequence (Teutonic Bore, Jaguar, Bentley, Erayinia), it is hosted by the ca. 2705 Ma plume-related stratigraphy, which is more typically associated with komatiite-hosted nickel-sulfide mineralization. The Nimbus deposit displays hybrid VHMS-epithermal characteristics resulting from low temperature and shallow water conditions, which developed a quartz-carbonate-sericite dominated alteration assemblage in the dacite host rocks. Sulfide mineralization comprises pyrite, sphalerite, galena, arsenopyrite, Ag-Sb-Pb-Bi sulfosalts, and rare chalcopyrite. In this study, we applied a combination of in-situ analytical techniques to monitor the evolving sulfur isotope signature of the mineralizing fluids, and propose that the Nimbus VHMS deposit developed as a result of a bimodal fluid history. In the first stage, the hydrothermal system – powered by plume-related magmatism – deposited a series of barren pyrite lenses with colloform textures. Their variable but consistently negative mass-independent sulfur isotope fractionation signature (Δ33S = −0.81%) reflects the interaction between mantle-derived magmatic fluids and Archean seawater. The ubiquitous presence of carbon-rich porous textures and the remnants of carbonaceous “nests” in colloform pyrite also indicate a significant contribution of microbial sulfate reducers during the incipient stages of sulfide precipitation. The gradual formation of colloform lenses eventually sealed the hydrothermal system establishing a physical barrier that limited the interaction with seawater. This process promoted the onset of higher temperature and pressure conditions required to form the high-grade Zn-Ag mineralization, sourcing sulfur and fluids largely from a magmatic reservoir (Δ33S = +0.09%). Whereas the identification of a predominantly magmatic sulfur source is supported by sulfur isotope signatures, the recognition of a magmatic origin of the fluid may only be inferred indirectly. It is consistent with the observed quartz-sericite alteration style and the proposed mechanism of sulfide deposition via decompression, which does not require any interaction with seawater. The trace element distribution of the ore-related sulfides also supports a closed hydrothermal system developed through multiple fluid pulses. Indeed, this ore-forming scenario is commonly favored by high confining pressures, which at Nimbus were established following the deposition of the colloform pyrite lenses that progressively sealed the hydrothermal system creating the favorable conditions for mineralization.

Chain formation as a mechanism for mass-independent fractionation of sulfur isotopes in the Archean atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this ‘mass-independent’ fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negativeΔ33S values and positiveΔ36S values in elemental sulfur—just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive Δ33S and negative Δ36S. Positive Δ33S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

Globally asynchronous sulphur isotope signals require re-definition of the Great Oxidation Event

The Great Oxidation Event (GOE) has been defined as the time interval when sufficient atmospheric oxygen accumulated to prevent the generation and preservation of mass-independent fractionation of sulphur isotopes (MIF-S) in sedimentary rocks. Existing correlations suggest that the GOE was rapid and globally synchronous. Here we apply sulphur isotope analysis of diagenetic sulphides combined with U-Pb and Re-Os geochronology to document the sulphur cycle evolution in Western Australia spanning the GOE. Our data indicate that, from ~2.45 Gyr to beyond 2.31 Gyr, MIF-S was preserved in sulphides punctuated by several episodes of MIF-S disappearance. These results establish the MIF-S record as asynchronous between South Africa, North America and Australia, argue for regional-scale modulation of MIF-S memory effects due to oxidative weathering after the onset of the GOE, and suggest that the current paradigm of placing the GOE at 2.33–2.32 Ga based on the last occurrence of MIF-S in South Africa should be re-evaluated.

Synsedimentary fault control on the deposition of the Duitschland Formation (South Africa): Implications for depositional settings, Paleoproterozoic stratigraphic correlations, and the GOE

The Paleoproterozoic Great Oxidation Event (GOE) marks the first significant oxidation of atmosphere and surface environments, and is causally associated with the global disappearance of mass-independent sulfur isotope fractionation (MIF-S). However, fundamental sedimentary aspects of successions recording this event (e.g. depositional environment, tectonic setting and stratigraphic correlation) are poorly constrained and often debated, restricting full understanding of causes and effects related to the GOE. In South Africa, MIF-S disappears across the ‘mid-Duitschland unconformity’ (MDU) in the Duitschland Formation (Transvaal Supergroup). New sedimentological observations of the lower Duitschland Formation have identified up to 5 times thicker and more diverse chert-pebble conglomerates than previously documented. New facies observed include lenticular conglomerates which incise cross-bedded dolomites, and imbricated conglomerates. The overlying MDU is angular in nature, recording an ∼15° N dip of the lower Duitschland strata; elsewhere it possesses a disconformable geometry. A new depositional model is proposed where shallow-marine carbonate (ramp) deposition interfaced with wave-influenced Gilbert-type fan deltas in an isolated depocentre produced during synsedimentary faulting. There is no evidence that the MDU formed due to direct glaciation as proposed previously. However, glacio-eustatic changes may have had an influence. This study supports the lithostratigraphic correlation of the Duitschland and Rooihoogte formations. This interpretation challenges the idea that they are separate lithostratigraphic units that record oscillations in MIF-S; this apparent oscillation in MIF-S is a stratigraphic artefact. The correlation proposed in this study implies a unique MIF-S signal and has important consequences for differentiating true spatiotemporal oscillations in MIF-S chemistry from artificial variations caused by unresolved stratigraphic relations.

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8–3.2 billion years ago (Ga)) and Neoarchaean (2.8–2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2–2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of ~30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (−1.31 to −0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases ~3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

Sedimentary sulfur isotopes and Neoarchean ocean oxygenation.

Abrupt disappearance of mass-independent fractionation of sulfur isotopes (MIF-S) from the geologic record and an apparent ingrowth in seawater sulfate around 2.45 billion years ago (Ga) signal the first large-scale oxygenation of the atmosphere [the Great Oxygenation Event (GOE)]. Pre-GOE O2 production is evident from multiple other terrestrial and marine proxies, but oceanic O2 concentrations remain poorly constrained. Furthermore, current interpretations of S isotope records do not explain a concurrent expansion in the range of both MIF-S-diagnostic for low atmospheric O2-and δ34S beginning at 2.7 Ga. To address these unknowns, we developed a reaction-transport model to analyze the preservation patterns of sulfur isotopes in Archean sedimentary pyrites, one of the most robust and widely distributed proxies for early Earth biogeochemistry. Our modeling, paradoxically, reveals that micromolar levels of O2 in seawater enhance the preservation of large MIF-S signals, whereas concomitant ingrowth of sulfate expands the ranges in pyrite δ34S. The 2.7- to 2.45-Ga expansion in both Δ33S and δ34S ranges thus argues for a widespread and protracted oxygenation of seawater, at least in shallow marine environments. At the micromolar levels predicted, the surface oceans would support a strong flux of O2 to the atmosphere, where O2 sinks balanced these fluxes until the GOE. This microoxic seawater would have provided habitat for early aerobic microorganisms and supported a diversity of new O2-driven biogeochemical cycles in the Neoarchean.

Multiple sulfur isotopes from the Neoarchaean Serra Sul black shale, Carajás mineral province, northern Brazil

In-situ laser ablation and multicollector–inductively coupled plasma–mass spectrometry were combined to analyse for sulfur isotopes in sulfide minerals that occur in the 2.7-billion-year-old black shale of Serra Sul, Carajás mineral province, Brazil. The black shale is part of a banded-iron-formation unit – the Carajás Formation – that hosts world-class iron-ore deposits. An obvious signal of mass-independent fractionation of sulfur isotopes (MIF-S) is not present in the black-shale sulfide minerals. Any significant MIF-S signal, above the analytical error of ∼0.5‰ Δ33S, was likely obscured by endogenic S. This explanation should also apply to the missing MIF-S signal in the clastic rocks of the overlying Águas Claras Formation. The absence of MIF-S in the latter was interpreted to indicate a depositional age younger than 2.45 Ga. However, Palaeoproterozoic hydrothermal pyrite can reconcile the non-MIF-S signature with the Neoarchaean Águas Claras Formation.

Multiple Sulfur Isotope Constraints on Sources and Formation Processes of Sulfate in Beijing PM2.5 Aerosol.

Recently air pollution is seriously threatening the health of millions of people in China. The multiple sulfur isotopic composition of sulfate in PM2.5 samples collected in Beijing is used to better constrain potential sources and formation processes of sulfate aerosol. The Δ33S values of sulfate in PM2.5 show a pronounced seasonality with positive values in spring, summer and autumn and negative values in winter. Positive Δ33S anomalies are interpreted to result from SO2 photolysis with self-shielding, and may reflect air mass transport between the troposphere and the stratosphere. The negative Δ33S signature (-0.300‰ < Δ33S < 0‰) in winter is possibly related to incomplete combustion of coal in residential stoves during the heating season, implying that sulfur dioxide released from residential stoves in more rural areas is an important contributor to atmospheric sulfate. However, negative Δ33S anomalies (-0.664‰ < Δ33S ← 0.300‰) in winter and positive Δ33S anomalies (0.300‰ < Δ33S < 0.480‰) in spring, summer, and autumn suggest sulfur isotopic equilibrium on an annual time frame, which may provide an implication for the absence of mass-independent fractionation of sulfur isotopes (S-MIF) in younger sediments. Results obtained here reveal that reducing the usage of coal and improving the heating system in rural areas will be important for efficiently decreasing the emissions of sulfur in China and beyond.

Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital [Formula: see text] values obtained within this model for 33S and 36S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

One possible source of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

Energy transfer mechanism for recombination of two sulfur atoms into a diatomic molecule, S2, is studied theoretically and computationally to determine whether the rate coefficient of this process can be significantly affected by isotopic substitutions, and whether the resultant isotope effect is expected to be mass-dependent or mass-independent. This is one of sulfur polymerization processes thought to be important in the anoxic atmosphere of the Archean Earth and, potentially, relevant to mass-independent fractionation of sulfur isotopes. A simplified theoretical approach is employed, in which all properties of S2 molecule are characterized rather accurately, whereas the process of stabilization of metastable S2∗ by bath gas collisions is described approximately. Properties of individual scattering resonances in S2 are studied in detail, and it is found that most important contributions to the recombination process come from ro-vibrational states formed near the top of centrifugal barrier, and that the number of such states is about 50 (in 32S32S). Absolute value of recombination rate coefficient is computed to be 1.22×10−33cm6/s (for 32S32S at room temperature and atmospheric pressure), close to experimental result. Two distinct isotope effects are identified. One is a classical mass-dependent effect due to translational partition function, which leads to a weak, smooth, and negative mass-dependence of rate coefficient (4% decrease when the mass is raised from 32S32S to 34S34S). Second effect, due to quantized resonances, is two orders of magnitude stronger, but is local. In practice, due to presence of multiple individual resonances, this phenomenon leads to irregular mass-independent variations of rate coefficients in the ranges ±5%. It is also demonstrated that in real molecules this irregular behavior is expected to be somewhat smoother, and the isotope effect is somewhat smaller, due to dependence of stabilization cross section on properties of individual resonances (not described by present model). Thus, additional calculations of stabilization cross sections are needed in order to give quantitative prediction of this mass-independent isotope effect, and to determine its relevance to mass-independent fractionation of sulfur isotopes in the Archean rock record.

The first data on mass-independent fractionation of sulfur isotopes in sulfides from rocks of the eastern part of the Fennoscandian Shield

The first data on the multi-isotope composition of sulfur (32S, 33S, 34S) in samples from the Fennoscandian Shield were obtained by the laser local method. An anomalous concentration of the stable isotope 33S was registered in some samples. Δ33S ranges from–0.45 to +0.24‰, which indicates the mass-independent fractionation of S isotopes and provides evidence for the processes of primarily sedimentary accumulation of sulfides in the Archean oxygen-free atmosphere.

Multiple sulfur isotope signature of early Archean oceanic crust, Isua (SW-Greenland)

The Archean sulfur cycle was different from the present-day cycle, as the emission of volcanogenic sulfurous gases was the dominant process in the anoxic environment of the early Earth.This emitted sulfur exhibits mass-independently fractionated sulfur isotopes (MIF-S), resulting from photochemical reactions in the atmosphere, and it differs substantially from unfractionated sulfur in the mantle.So far, the main focus of multiple sulfur analyses (32S, 33S, 34S and 36S) was placed on the sedimentary part of the Archean sulfur cycle.In order to constrain the magmatic part of the sulfur cycle, we analyzed the sulfur isotopic composition of oceanic crustal rocks from the ca.3.7–3.8Ga Isua Supracrustal Belt (ISB). Differently altered samples were taken from two units:(1) the Undifferentiated Amphibolites (UA) and (2) the younger Amphibolites with Boninitic affinity (AB). The mean values are:δ34SCRS=+0.01±0.65‰ (values range from −0.87 to 1.37‰; CRS=chromium-reducible sulfur),Δ33SCRS=+0.02±0.12‰ (values range from −0.17 to 0.26‰), Δ36SCRS=-0.47±0.06‰ (values range from −0.56 to −0.38‰). Thus, the mean isotope values support the assumption that the sulfur isotopic signature reflects the expected near-zero signature of their mantle origin. However, differences in Δ33SCRS values are discernible and non-zero suggesting that different sources are contributing to the isotopic signature. An influence of alteration is excluded for all samples as different alteration-sensitive geochemical parameters do not show any correlation with the multiple sulfur isotope signatures. Further, it is unlikely that the small magnitudes in Δ33SCRS are generated by microbial mass-dependent processes because of the narrow range of δ34SCRS values. Possible sources contributing an atmospheric MIF-S signature include seawater sulfate (negative Δ33SCRS values) through hydrothermal circulation, the assimilation of ocean floor sediments during the ascent of the melt and/or a mantle source contamination by subducted oceanic slab.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni–Cu–PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni–Cu–platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni–Cu–PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni–Cu–(PGE).

Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates.

An approach to coordinated, spatially resolved, insitu carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of δ(13) C, δ(34) S, Δ(33) S, and Δ(36) S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS δ(13) C measurement of organic matter is identified. Small (2-3μm) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-μm domains of kerogen in a single ~0.5cm(3) sample of the ~2.7Ga Tumbiana Formation have δ(13) C=-52.3±0.1‰ and -34.4±0.1‰, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the ~2.6Ga Jeerinah Formation and the ~2.5Ga Mount McRae Shale is systematically (13) C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Δ(33) S and more extreme spatial gradients in Δ(33) S and Δ(36) S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of δ(34) S, Δ(33) S, and Δ(36) S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation (S-MIF) associated with the Mesoarchean continued into the early Neoarchean, and that the connections between methane and sulfur metabolism affected the production and preservation of S-MIF during the first half of the planet's history.

Rovibrational bound states of SO2 isotopologues. II: Total angular momentum J = 11–20

In a two-part series, the rovibrational bound states of SO2 are investigated in comprehensive detail, for all four stable sulfur isotopes 32–34,36S. All low-lying rovibrational energy levels—both permutation-symmetry-allowed and not allowed—are computed, for all values of total angular momentum in the range J=0–20. The calculations have carried out using the ScalIT suite of parallel codes. The present study (Paper II) examines the J=11–20 rovibrational levels, providing symmetry and rovibrational labels for every computed state, relying on a new lambda-doublet splitting technique to make completely unambiguous assignments. Isotope shifts are analyzed, as is the validity of “J-shifting” as a predictor of rotational fine structure. Among other ramifications, this work will facilitate understanding of mass-independent fractionation of sulfur isotopes (S-MIF) observed in the Archean rock record—particularly as this may have arisen from self shielding. S-MIF, in turn is highly relevant in the broader context of understanding the “oxygen revolution”.

The Hietaharju PGE-enriched komatiite-hosted sulfide deposit in the Archean Suomussalmi greenstone belt, eastern Finland

The Hietaharju Ni–Cu–PGE deposit occurs in the Archean Suomussalmi greenstone belt of eastern Finland and is associated with high-Mg basalts and low-Mg komatiitic rocks. It represents a PGE-enriched type among komatiite-related Ni–Cu deposits. The Hietaharju deposit consists of several mineralized lenses in highly altered olivine–pyroxene cumulates (i.e., talc–carbonate–chlorite rocks) and contains disseminated, massive to semi-massive and brecciated sulfides. Post-magmatic processes have not significantly changed the primary magmatic sulfide assemblage (i.e., pyrrhotite–pentlandite–chalcopyrite), but has modified sulfide textures and possibly remobilized and reconcentrated the sulfides. Though the deposit is currently subeconomic, it has high PGE contents in the sulfide fraction, averaging 5.7ppm Pd and 2ppm Pt (average of all ore types), being highest in disseminated sulfides. The parental magma represents an intermediate type between Al-undepleted and Al-depleted komatiites and differs from most other komatiitic rocks in the Tipasjärvi–Kuhmo–Suomussalmi greenstone belt complex, which are normally of the Al-undepleted type. The relatively fractionated nature of the komatiitic basalt parental magma of the Hietaharju deposit is consistent with the low Ni/Cu (<4) and Ni/Co (<18) and high Pd/Ir (<25) ratios of the sulfide fraction, similar to the values in the Paleoproterozoic Raglan belt deposits, Canada. Use of REE for constraining crustal contamination is hampered by the highly altered nature of komatiitic rocks in the Hietaharju area. Sulfides in the country rock metasediments that host the Hietaharju Ni–Cu–PGE deposit show clear mass-independent sulfur isotope fractionation (MIF-S) consistent with their age and published S isotope data from the Suomussalmi belt. In contrast, sulfides of the Hietaharju Ni–Cu–PGE deposit only possess a small degree of MIF-S, providing limited direct evidence for the role of local metasedimentary sulfur in ore formation. Archean base metal sulfide mineralization is among the potential sources of sulfur, however, and, as shown by the epithermal Taivaljärvi Au–Ag–Zn deposit, can have mass-independent sulfur isotope fractionation that is similar in magnitude and sign to that of the Hietaharju Ni–Cu–PGE deposit.