Mass-independent Isotope Fractionation Research Articles

Continuous-Flow Stable Sulfur Isotope Analysis of Organic and Inorganic Compounds by EA-MC-ICPMS.

Elemental analysis (EA) coupled to isotope ratio mass spectrometry (IRMS) is a well-established method to derive stable isotope ratios of sulfur (34S/32S). Conversion of sulfur to SO2 by EA and measurement of SO2 isotopologues by IRMS represents the simplest and most versatile method to accomplish isotope measurement of sulfur even in bulk samples. Yet, interferences by oxygen isotopes in SO2 often impair the precision and trueness of measured results. In the current study, we coupled EA to multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) to establish a method that avoids such interferences due to direct measurement of S+ ions. In addition, measurement of the 33S/32S isotope ratios is possible, thus representing the first bulk method that is suitable to study mass-independent isotope fractionation (MIF). Analytical precision (σ) of available Ag2S and BaSO4 reference materials (RMs) was, on average, 0.2 mUr for δ33S and δ34S, never exceeding 0.3 mUr within this study (1 mUr = 1‰ = 0.001). Measured δ34S values of reference materials agreed within ±0.2 mUr of officially reported values. Measurement of wood samples yielded good precision (0.2 mUr) for sulfur amounts as low as 3.5 μg, but precision deteriorated for samples at lower sulfur contents due to poor peak shape. Finally, we explored cross-calibration of organic liquids separated via gas chromatography (GC) against solid RMs combusted via EA that avoids challenging offline conversion of RMs. Results indicate good precision (≤0.08 mUr) and acceptable trueness (≤0.34 mUr) for determination of δ34S, demonstrating the future potential of such an approach.

Sedimentary and stratigraphic architecture of the Duitschland and Rooihoogte formations (Palaeoproterozoic, South Africa): implications for tempo of the Great Oxidation Event

Abstract Determining the tempo and causality of key palaeoclimate events recorded in sedimentary strata depends on high-resolution numerical ages and well-constrained stratigraphic correlations at regional and global scale. This requirement is not necessarily met in Precambrian strata due to poorer age resolution, limited preservation, and secondary overprints. A good example includes the Palaeoproterozoic Rooihoogte and Duitschland formations in South Africa, which document the disappearance of mass-independent fractionation of sulphur isotopes (MIF-S) and contain glacial diamictites at their base. They are thus key records of Earth’s surface oxygenation during the Great Oxidation Event (GOE). However, previous studies have either correlated these units, resulting in a unidirectional oxidation trend; or have regarded them as successive strata, causing an interpretation of oscillating oxidation. This study uses extensive outcrop and new core material to investigate correlation between these two units, and to establish depositional models. Results show that key stratigraphic markers can be traced around the entire Kaapvaal craton both in outcrop and the subsurface. In particular, the basal Bevets breccia and the top Duitschland breccia are here re-interpreted as two separate units that are present at the base and top of both formations, supporting correlation of the formations. Consequently, the base of both formations records a major craton-wide event of uplift and karstification, leading to carbonate dissolution and chert brecciation. Erosion of older rocks from across the craton also delivered material for the basal glacial diamictite. The majority of mixed siliciclastic-carbonate sediments were deposited on a storm- and/or delta-influenced shelf. Depositional packages in both formations reflect post-glacial relative sea level rise, followed by progradation of a deltaic, storm or shoreline depositional system. There is a relatively short-lived depositional hiatus to overlying shales of the Timeball Hill Formation. Both Rooihoogte and Duitschland formations thus record only a single glacial event at their base, and a unidirectional trend of oxidation.

Atmospheric oxygenation at the onset of Earth’s Great Oxidation forced enhanced marine anoxia

Abstract Capturing the loss of mass-independent sulphur isotope fractionation (MIF-S), the correlative South African Duitschland and Rooihoogte formations are widely held to bear the isotopic fingerprint of the first atmospheric oxygenation at the onset of the so-called Great Oxidation Event (GOE). Surprisingly, however, while the multiple sulphur isotope systematics of these formations remain central to our understanding of the GOE, until now, comparatively little work has been done to elucidate the repercussions within the marine realm. Here we present chemostratigraphic records from four drill cores covering a large area of the Transvaal Basin, transcending these crucial units and continuing into the overlying Timeball Hill Formation (TBH), that document the immediate, yet counterintuitive, marine response to atmospheric oxygenation. Specifically, irrespective of the interpretative framework employed, our basin-wide redox-sensitive trace element data document an environmental change from oxic/suboxic conditions within the lower and middle parts of the Duitschland and Rooihoogte formations to suboxic/anoxic conditions within their upper reaches. Interestingly, in concert with a ~35‰ negative δ34S excursion that implicates increased sulphate availability and bacterial sulphate reduction, δ98/95Mo3134+0.25 values increase by ~1.0 to 1.5‰. Combining these observations with increased Fe/Mn ratios, elevated total sulphur and carbon contents and a trend towards lower δ13Corg values imply a shift toward less oxygenated conditions across the Transvaal Basin. The combined observations in the mentioned parameters expose a geobiological feedback-driven causality between the earliest oxygenation of the atmosphere and decreased redox potentials of medium to deep marine environments, at least within the Transvaal Basin.

Comet 81P/Wild 2 dust impactors of Stardust turnip-like tracks analogous to cluster IDPs

We measured oxygen isotope ratios of 16 silicate fragments from seven aerogel tracks (turnip-like type B tracks 77, 149, 172, 191, and 220; carrot-like type A tracks 22 and 175) of the comet 81P/Wild 2 collector from NASA’s Stardust mission using secondary ion mass spectrometry. Thirteen were prepared by ultramicrotomy; three from track 220 were prepared by sputtering resin blocks using a SIMS Kohler beam, a new procedure aiming to mine as many cometary particles encased in aerogel/resin as possible. Combining new and literature results, we recognized that most silicate fragments of individual type B tracks have diverse mineralogy but consistent mass-independent fractionation of oxygen isotopes (Δ17O = δ17O − 0.52 × δ18O). These observations suggest that their impactors are loosely bound aggregates of unequilibrated materials originating mainly from similar protoplanetary disk regions, resembling the cluster IDP U2-20-GCA. Furthermore, silicate fragments from type A track 22 have almost identical mineralogy and Δ17O values, confirming that its impactor is a single chondrule-like fragment. The terminal particle of type A track 175 is pure forsterite with Δ17O of ∼ –23 ‰.Six iron-rich fragments of this study have positive oxygen isotope ratios (Δ17O∼ +2 ‰) and ordinary chondrite chondrule-like olivine compositions. Together with five similar fragments in the literature, a unique population (Mg# ≤ 86) of Wild 2 fragments that resemble chondrules from the inner solar system (O-E-R) chondrites or the outer solar system CH-CB chondrites was identified. The remaining 16O-poor Wild 2 fragments are Mg# ≥ 79 silicates with Δ17O ∼ –2 ‰ and a small amount of Mg# ≤ 79 silicates with Δ17O ∼ 0 ‰, which are most consistent with CR chondrite chondrules. Thus, we conclude that in addition to the possible major source of CR chondrite chondrule-like materials, the inner solar system or CH-CB chondrule-like materials are a minor component of comet Wild 2, like the cluster IDP U2-20-GCA.

Positive Δ199Hg anomalies in Mesozoic porphyry Mo deposits of Northeastern China and their implications to the metallogeny of arc-related hydrothermal systems at convergent margins

Mercury (Hg) isotopes display unique mass-independent isotope fractionation (MIF, reported as Δ199Hg), which is primarily generated via Hg photochemical processes in the land-ocean-atmosphere system. Magmatic and hydrothermal processes do not trigger MIF of Hg isotopes, therefore, Hg-MIF signals detected in deep reservoirs (mantle and crust) are theoretically sourced from recycled surface materials. Here, we observed positive Δ199Hg signals (0.10 ± 0.07‰, SD) in Mesozoic porphyry Mo deposits of NE China. These values correspond to the recently reported Δ199Hg signature of Mesozoic epithermal AuAg systems in NE China (Δ199Hg: 0.11 ± 0.07‰, SD), suggesting that both mineral systems receive large amounts of Hg from subducted marine materials, given that marine Hg has positive Δ199Hg composition. Our study thus provides novel geochemical evidence on the linkage between oceanic plate subduction and metallogeny of various hydrothermal systems at convergent margins. Subduction contributes large amounts of volatiles to arc magmas, which then release metal-rich magmatic-hydrothermal fluids of the porphyry to epithermal ore deposit spectrum.

Increased Contribution of Circumpolar Deep Water Upwelling to Methylmercury in the Upper Ocean around Antarctica: Evidence from Mercury Isotopes in the Ornithogenic Sediments.

Upwelling plays a pivotal role in supplying methylmercury (MeHg) to the upper oceans, contributing to the bioaccumulation of MeHg in the marine food web. However, the influence of the upwelling of Circumpolar Deep Water (CDW), the most voluminous water mass in the Southern Ocean, on the MeHg cycle in the surrounding oceans and marine biota of Antarctica remains unclear. Here, we study the mercury (Hg) isotopes in an ornithogenic sedimentary profile strongly influenced by penguin activity on Ross Island, Antarctica. Results indicate that penguin guano is the primary source of Hg in the sediments, and the mass-independent isotope fractionation of Hg (represented by Δ199Hg) can provide insights on the source of marine MeHg accumulated by penguin. The Δ199Hg in the sediments shows a significant decrease at ∼1550 CE, which is primarily attributed to the enhanced upwelling of CDW that brought more MeHg with lower Δ199Hg from the deeper seawater to the upper ocean. We estimate that the contribution of MeHg from the deeper seawater may reach more than 38% in order to explain the decline in Δ199Hg at ∼1550 CE. Moreover, we found that the intensified upwelling may have increased the MeHg exposure for marine organisms, highlighting the importance of CDW upwelling on the MeHg cycle in Antarctic coastal ecosystems.

Atmospheric ozone destruction and the end-Permian crisis: Evidence from multiple sulfur isotopes

The end-Permian mass extinction (EPME) is considered the largest biotic crisis of the Phanerozoic. To explain the worldwide destruction and mutation of land plants, previous work has emphasized the role of enhanced UV irradiation linked to volcanism-induced disruption of the ozone shield. However, direct evidence for a link between volcanic SO2 emission and stratospheric ozone deterioration is missing. Previous bulk analysis (i.e., SF6 method) found no Mass-Independent Fractionation of sulfur isotopes (MIF-S, noted Δ33S). However, possible grain scale sulfur isotope anomaly can be easily overlooked during bulk analysis. To detect possible sulfur isotope anomaly in grain scale, we applied in-situ multiple sulfur isotope analysis of the sulfide using secondary ion mass spectrometry (SIMS). We found a marked positive shift (higher than +0.30‰ and up to +0.94‰) just before the end-Permian extinction in the Meishan section. Modelling shows that these positive Δ33S anomalies cannot be explained by Mass Dependent Fractionation (MDF) processes alone, rather by UV-induced photolysis of volcanic SO2. The formation and preservation of MIF-S anomalies in the atmosphere and subsequent transport to the oceans require intense and prolonged irradiation of the Earth's surface with solar UV, thus fingerprinting severe disruption of the atmospheric ozone balance at the onset of Earth's largest mass extinction.

Foraging behavior and sea ice-dependent factors affecting the bioaccumulation of mercury in Antarctic coastal waters

To elucidate the potential risks of the toxic pollutant mercury (Hg) in polar waters, the study of accumulated Hg in fish is compelling for understanding the cycling and fate of Hg on a regional scale in Antarctica. Herein, the Hg isotopic compositions of Antarctic cod Notothenia coriiceps were assessed in skeletal muscle, liver, and heart tissues to distinguish the differences in Hg accumulation in isolated coastal environments of the eastern (Chinese Zhongshan Station, ZSS) and the antipode western Antarctica (Chinese Great Wall Station, GWS), which are separated by over 4000 km. Differences in odd mass-independent isotope fractionation (odd-MIF) and mass-dependent fractionation (MDF) across fish tissues were reflection of the specific accumulation of methylmercury (MeHg) and inorganic Hg (iHg) with different isotopic fingerprints. Internal metabolism including hepatic detoxification and processes related to heart may also contribute to MDF. Regional heterogeneity in iHg end-members further provided evidence that bioaccumulated Hg origins can be largely influenced by polar water circumstances and foraging behavior. Sea ice was hypothesized to play critical roles in both the release of Hg with negative odd-MIF derived from photoreduction of Hg2+ on its surface and the impediment of photochemical transformation of Hg in water layers. Overall, the multitissue isotopic compositions in local fish species and prime drivers of the heterogeneous Hg cycling and bioaccumulation patterns presented here enable a comprehensive understanding of Hg biogeochemical cycling in polar coastal waters.

Mercury Isotope Fractionation during Dark Abiotic Reduction of Hg(II) by Dissolved, Surface-Bound, and Structural Fe(II).

Stable mercury (Hg) isotope ratios are an emerging tracer for biogeochemical transformations in environmental systems, but their application requires knowledge of isotopic enrichment factors for individual processes. We investigated Hg isotope fractionation during dark, abiotic reduction of Hg(II) by dissolved iron(Fe)(II), magnetite, and Fe(II) sorbed to boehmite or goethite by analyzing both the reactants and products of laboratory experiments. For homogeneous reduction of Hg(II) by dissolved Fe(II) in continuously purged reactors, the results followed a Rayleigh distillation model with enrichment factors of -2.20 ± 0.16‰ (ε202Hg) and 0.21 ± 0.02‰ (E199Hg). In closed system experiments, allowing reequilibration, the initial kinetic fractionation was overprinted by isotope exchange and followed a linear equilibrium model with -2.44 ± 0.17‰ (ε202Hg) and 0.34 ± 0.02‰ (E199Hg). Heterogeneous Hg(II) reduction by magnetite caused a smaller isotopic fractionation (-1.38 ± 0.07 and 0.13 ± 0.01‰), whereas the extent of isotopic fractionation of the sorbed Fe(II) experiments was similar to the kinetic homogeneous case. Small mass-independent fractionation of even-mass Hg isotopes with 0.02 ± 0.003‰ (E200Hg) and ≈ -0.02 ± 0.01‰ (E204Hg) was consistent with theoretical predictions for the nuclear volume effect. This study contributes significantly to the database of Hg isotope enrichment factors for specific processes. Our findings show that Hg(II) reduction by dissolved Fe(II) in open systems results in a kinetic MDF with a larger ε compared to other abiotic reduction pathways, and combining MDF with the observed MIF allows the distinction from photochemical or microbial Hg(II) reduction pathways.

Mercury Sources and Fate in a Large Brackish Ecosystem (the Baltic Sea) Depicted by Stable Isotopes.

Identifying Hg sources to aquatic ecosystems and processes controlling the levels of monomethylmercury (MMHg) is critical for developing efficient policies of Hg emissions reduction. Here we measured Hg concentrations and stable isotopes in sediment, seston, and fishes from the various basins of the Baltic Sea, a large brackish ecosystem presenting extensive gradients in salinity, redox conditions, dissolved organic matter (DOM) composition, and biological activities. We found that Hg mass dependent fractionation (Hg-MDF) values in sediments mostly reflect a mixing between light terrestrial Hg and heavier industrial sources, whereas odd Hg isotope mass independent fractionation (odd Hg-MIF) reveals atmospheric inputs. Seston presents intermediate Hg-MDF and odd Hg-MIF values falling between sediments and fish, but in northern basins, high even Hg-MIF values suggest the preferential accumulation of wet-deposited Hg. Odd Hg-MIF values in fish indicate an overall low extent of MMHg photodegradation due to limited sunlight exposure and penetration but also reveal large spatial differences. The photodegradation extent is lowest in the central basin with recurrent algal blooms due to their shading effect and is highest in the northern, least saline basin with high concentrations of terrestrial DOM. As increased loads of terrestrial DOM are expected in many coastal areas due to global changes, its impact on MMHg photodegradation needs to be better understood and accounted for when predicting future MMHg concentrations in aquatic ecosystems.

A 1500-year record of mercury isotopes in seal feces documents sea ice changes in the Antarctic

Temporal and spatial variations in sea ice coverage at high Northern Hemisphere latitudes have been shown to affect the photodegradation of methylmercury in seawater and the mercury isotope signatures in biological samples, suggesting the potential of mercury isotopes to reconstruct sea ice variability. Here we study the mercury isotopic composition of a 1500-year sediment profile strongly affected by seal activities on the Fildes Peninsula, King George Island, Antarctic Peninsula. The mass independent isotope fractionation of mercury (represented by Δ199Hg) in sediments dominated by seal feces input reflects the Δ199Hg of marine methylmercury before entering the food web, documenting the changes in the degree of photodemethylation. We found much higher Δ199Hg in sediments deposited during a warm period (~700-1000 years ago), suggesting that reduced sea ice promoted greater photodemethylation. Thus, this study demonstrates the modulation of methylmercury photodegradation by sea ice in the Antarctic, and that mercury isotopes can record historical sea ice changes.

Aquatic methylmercury is a significant subsidy for terrestrial songbirds: Evidence from the odd mass-independent fractionation of mercury isotopes

In contrast to aquatic food chains, knowledge of the origins and transfer of mercury (Hg) and methylmercury (MeHg) in terrestrial food chains is relatively limited, especially in songbirds. We collected soil, rice plants, aquatic and terrestrial invertebrates, small wild fish, and resident songbird feathers from an Hg-contaminated rice paddy ecosystem for an analysis of stable Hg isotopes to clarify the sources of Hg and its transfer in songbirds and their prey. Significant mass-dependent fractionation (MDF, δ202Hg), but no mass-independent fractionation (MIF, ∆199Hg) occurred in the trophic transfers in terrestrial food chains. Piscivorous, granivorous, and frugivorous songbirds and aquatic invertebrates were all characterized by elevated Δ199Hg values. The estimated MeHg isotopic compositions obtained using linear fitting and a binary mixing model explained both the terrestrial and aquatic origins of MeHg in the terrestrial food chains. We found that MeHg from aquatic habitats is an important subsidy for terrestrial songbirds, even those that feed mainly on seeds, fruits, or cereals. The results show that MIF of the MeHg isotope is a reliable tool to reveal MeHg sources in songbirds. Because the MeHg isotopic compositions was calculated with a binary mixing model or directly estimated from the high proportions of MeHg, compound-specific isotope analysis of Hg would be more useful for the interpretation of the Hg sources, and is highly recommended for future studies.

Toward the Origins of Quadruple Sulfur Isotope Anomalies in Modern Sulfate: A Multitracer Approach and Implications for Paleo- and Planetary Atmospheres

Sulfur isotope mass-independent fractionation signatures (S-MIF) have been widely found in modern sulfate aerosols. Their mechanistic origins and potential implications for atmospheric sulfate formation chemistry are however poorly understood. Of particular importance is that the mystery of modern sulfate S-MIF hinders precise interpretations of S-MIF in geological sediment and meteorite samples. Here, we examine several proposed origins of modern sulfate S-MIF using a multiple-tracer approach. Quadruple sulfur isotopes of sulfate aerosols collected from Guangzhou, a megacity in South China, were measured along with various chemical and isotopic tracers for high-altitude air masses, biomass burning, and mineral dusts in the same samples. Similar to previous studies, we found that negative Δ36S values in modern sulfate aerosols are linked to combustions, and to a larger extent, to high-temperature processes that may involve symmetry-dependent recombination reactions of sulfur. The origins of Δ33S anomalies widely observed in modern sulfate aerosols remain elusive and require further investigation before we can unambiguously use this proxy to quantify sulfur emission and transformation pathways in the modern atmosphere. From a comparative planetology perspective, we highlight that a complete understanding of S-MIF in modern aerosols is crucial for tracking paleo- and planetary atmospheres by multiple sulfur isotope measurements in Phanerozoic sediments and Martian meteorites because their S-MIF magnitudes are similar.

Mass-independent Sn isotope fractionation and radiogenic 115Sn in chondrites and terrestrial rocks

Tin has ten stable isotopes, providing the opportunity to investigate and discriminate nucleosynthetic isotope anomalies from mass-dependent and mass-independent isotope fractionation. Novel protocols for chemical separation (based on TBP-resin) and MC-ICP-MS analyses are reported here for high precision Sn isotope measurements on terrestrial rocks and chondrites. Relative to the Sn reference standard (NIST SRM 3161a), terrestrial basalts and chondrites show isotope patterns that are consistent with mass-dependent and mass-independent isotope fractionation processes as well as with 115Sn radiogenic ingrowth from 115In.Two different mass-independent isotope effects are identified, namely the nuclear volume (or nuclear field shift) and the magnetic isotope effect. The magnetic isotope effect dominates in the two measured ordinary chondrites, while repeated analyses of the carbonaceous chondrite Murchison (CM2) display a pattern consistent with a nuclear volume effect. Terrestrial basalts show patterns that are compatible with a mixture of nuclear volume and magnetic isotope effects. The ultimate origin of the isotope fractionation is unclear but a fractionation induced during sample preparation seems unlikely because different groups of chondrites show distinctly different patterns, hence pointing towards natural geo/cosmochemical processes. Only the carbonaceous chondrite Murchison (CM2) shows a Sn isotope pattern similar to what expected for nucleosynthetic variations. However, this pattern is better reproduced by nuclear volume effects. Thus, after considering mass-independent and mass-dependent effects, we find no evidence of residual nucleosynthetic anomalies, in agreement with observations for most other elements with similar half-mass condensation temperatures.Most chondrites show a deficit in 115Sn/120Sn (typically −150 to −200 ppm) relative to terrestrial samples, with the exception of one ordinary chondrite that displays an excess of about +250 ppm. The 115Sn/120Sn data correlate with In/Sn, being consistent with the β− decay of 115In over the age of the solar system. This represents the first evidence of the 115In-115Sn decay system in natural samples. The radiogenic 115Sn signature of the BSE derives from a suprachondritic In/SnBSE, which reflects preferential partitioning of Sn into the Earth’s core.

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.

Giant Mesozoic gold ores derived from subducted oceanic slab and overlying sediments

Orogenic gold deposits account for more than 30 % of the global gold resources. To understand the genesis of orogenic gold deposits and ultimately target new orogenic gold deposits, it is important to determine the origin of gold. However, there has been a continuing debate surrounding gold source reservoirs. The Jiaodong gold province, comprising ore hosted within Mesozoic granitoids that intruded Archean metamorphic rocks, together with other gold occurrences in the North China block, collectively constitute the only Mesozoic world-class gold resource in a Precambrian basement. This geological setting, with young deposits in ancient rocks, offers a great opportunity to better determine the gold source because it allows us to fingerprint the isotopically distinct reservoirs. Specifically, it is possible to determine whether the mass-independent isotopic fractionation sulfur (MIF-S)-bearing Archean supracrustal rocks that form the lower crust are a permissive source. We present multiple sulfur isotope (δ34S and Δ33S) measurements of pyrite grains (n = 161) from 18 gold deposits in the six main districts of the Mesozoic Jiaodong gold province. Gold-associated pyrite grains yield non-MIF-S signatures (Δ33S = 0 ‰), indicating that Archean metasedimentary rocks are not a source reservoir of sulfur and gold. The isotopically heavy S (average δ34S = +9.0 ± 3.7 ‰, 2SD) demonstrates a sulfur contribution from a subducted oceanic slab and, in particular, its overlying sediments while excluding mantle and magmatic sources. The subduction-related metamorphism released appreciable gold and sulfur from the top of the downgoing slab into aqueous-carbonic fluids that ascended into the upper plate along crustal structures traversing a tectonically thinned crust. Here, we demonstrate that these giant Mesozoic orogenic gold deposits sourced gold and sulfur during subduction-related devolatilization reactions.

Rapid timescale for an oxic transition during the Great Oxidation Event and the instability of low atmospheric O2

The Great Oxidation Event (GOE), arguably the most important event to occur on Earth since the origin of life, marks the time when an oxygen-rich atmosphere first appeared. However, it is not known whether the change was abrupt and permanent or fitful and drawn out over tens or hundreds of millions of years. Here, we developed a one-dimensional time-dependent photochemical model to resolve time-dependent behavior of the chemically unstable transitional atmosphere as it responded to changes in biogenic forcing. When forced with step-wise changes in biogenic fluxes, transitions between anoxic and oxic atmospheres take between only 102 and 105 y. Results also suggest that O2 between [Formula: see text] and [Formula: see text] mixing ratio is unstable to plausible atmospheric perturbations. For example, when atmospheres with these O2 concentrations experience fractional variations in the surface CH4 flux comparable to those caused by modern Milankovich cycling, oxygen fluctuates between anoxic ([Formula: see text]) and oxic ([Formula: see text]) mixing ratios. Overall, our simulations are consistent with possible geologic evidence of unstable atmospheric O2, after initial oxygenation, which could occasionally collapse from changes in biospheric or volcanic fluxes. Additionally, modeling favors mid-Proterozoic O2 exceeding [Formula: see text] to [Formula: see text] mixing ratio; otherwise, O2 would periodically fall below [Formula: see text] mixing ratio, which would be inconsistent with post-GOE absence of sulfur isotope mass-independent fractionation.

New insight into the source of metals in Hg deposits at the southwestern margin of the Yangtze Platform, China: Evidence from mercury stable isotope compositions

The genesis of the typical Hg-Au-Sb metallogenic district in the southwestern margin of the Yangtze Craton, Southwestern China, remains controversial. A systematic study of the mercury (Hg) concentrations and Hg isotopic compositions of the Hg deposit at Paiting was conducted to constrain the sources of metals. Mass-independent fractionation (MIF) of Hg isotopes with slight positive Δ199Hg (0.03‰ to 0.22‰) was observed in the Hg ore samples, indicating that Hg transported by the ore fluids was primarily derived from the Cambrian black shale as these rocks show similar Δ199Hg signatures (−0.02‰ to 0.08‰). Based on these newly obtained Hg isotope ratios, we propose that deep hydrothermal fluids promoted the mobilization of Hg in Hg-bearing strata (i.e., Cambrian Niutitang Formation black shale) in the paleo-basin sedimentary strata to form Hg-enriched fluids. The Hg-enriched fluids flowed and permeated from the lower to the upper strata during mineralization and were transported to the platform margin slope facies along faults, followed by Hg precipitation to form Hg deposits. Hg isotope ratios could be a robust tracer to distinguish the metal sources of hydrothermal Hg deposits.

Sulfur isotopes as biosignatures for Mars and Europa exploration

Sulfur (S) isotopes are used to trace metabolic pathways associated with biological S-cycling in past and present environments on Earth. These pathways (sulfate reduction, sulfur disproportionation and sulfide oxidation) can produce unique S isotope signals that provide insight into biogeochemical S-cycling. The S cycle is also relevant for extraterrestrial environments and processes. On early Mars, sulfur existed in different redox states and was involved in a large range of surface processes (e.g. volcanic, atmospheric, hydrothermal and aqueous brines). Sulfur compounds have also been detected on Europa's icy moon surface, with the S cycle implicated in Europa's surface and ocean geochemistry. Given the well-established utility of S isotopes in providing a record for past life on Earth, S isotopes are a valuable tool for identifying biosignatures on Mars and Europa. Here, we review S isotopes as a biosignature, in light of two recent advances in understanding the S cycle in both Mars and Europa: (1) the measurements of δ 34 S in situ at Gale Crater and quadruple S isotopes (QSI) in Martian meteorites; (2) the identification of a likely exogenous origin of sulfur on Europa's surface. We discuss important considerations for unravelling QSI biosignatures in Martian environments, considering high- and low-sulfur environments, atmospheric mass-independent fractionation of sulfur isotopes (S-MIF) signals and metabolic energy-limited niches. For Europa, we describe the potential for S isotopes to probe biogeochemistry, and identify key knowledge gaps to be addressed to unlock S isotopic tools for future life detection efforts. The resulting picture demonstrates how S isotopes will be a valuable tool for Mars sample return, and how future missions can focus on the search for environments where QSI signatures of microbial S-cycling processes have a greater chance of being preserved. For Europa, the first step will be to account for the S isotope composition of the various S pools, to recognize or rule out non-biologically mediated S isotope values, with a focus on experimental examination of potential S isotope signatures from exogenous sulfur sources. 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

Sulfur mass-independent fractionation during SO2 photolysis in low-temperature/pressure atmospheres

Mass-independent fractionation of sulfur isotopes (MIF-S) has been observed in Archean sedimentary rocks and modern stratospheric sulfate aerosol (SSA). Photolysis of SO2 is known to cause significant MIF-S and could be related to the observed MIF-S. However, previous experiments with SO2 photolysis at room temperature, or at low temperatures and atmospheric pressure, did not quantitatively explain quadruple sulfur isotopic compositions (δ34S, Δ33S, and Δ36S values) of the Archean sedimentary rocks and the modern SSA. Here we describe sulfur isotopic fractionation during SO2 photolysis including isotopic self-shielding at low temperatures (down to 228 K) and low pressures (from 5.9 to 9.8 kPa) where pressure broadening of SO2 becomes negligible. Results indicate that magnitudes of sulfur isotopic fractionation factors (34ε, 33E, and 36E values, where 33E = 33ε – 1000 × [(1 + 34ε/1000)0.515 − 1] and 36E = 36ε − 1000 × [(1 + 36ε/1000)1.90 − 1]) increase with decreasing temperature, with values at 228 K being about four times those at 296 K (34ε of up to +344‰). Meanwhile, 33E/34ε and 36E/33E ratios are roughly independent of temperature over the temperature range (by approximately +0.1 and − 3.1, respectively), although the 33E/34ε ratios slightly increase with decreasing temperature, ranging from ~ + 0.08 to ~ + 0.13. A two-component mixing model involving SO2 oxidation by OH and SO2 photolysis in the stratosphere reproduces δ34S and Δ33S values of modern SSA when the contribution ratio of SO2 photolysis to SO3 production is ~20%. The contribution ratio of ~20% is consistent with a previous estimation by Whitehill et al. (2015). However, Δ33S/δ34S ratios at low temperatures are far from those of Archean sedimentary rocks, calling for an additional mechanism (or mechanisms) to explain Archean MIF-S.