Mass-independent 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.

Variation in the relationship between odd isotopes of tin in mass-independent fractionation induced by the magnetic isotope effect

Experimental results are presented showing the variation in the relationship between odd isotopes of tin (Sn) in mass-independent fractionation caused by the magnetic isotope effect (MIE), which has previously only been observed for mercury. These results are consistent with the trend predicted from the difference between the magnitudes of nuclear magnetic moments of odd isotopes with a nuclear spin. However, the correlation between odd isotopes in fractionation induced by the MIE for the reaction system used in this study (solvent extraction using a crown ether) was different from that reported for the photochemical reaction of methyltin. This difference between the two reaction systems is consistent with a theoretical prediction that the correlation between odd isotopes in fractionation induced by the MIE is controlled by the relationship between the spin conversion time and radical lifetime. The characteristic changes in the correlation between odd isotopes in fractionation induced by the MIE observed for Sn in this study provide a guideline for quantitatively determining fractionation patterns caused by the MIE for elements that have multiple isotopes with a nuclear spin. These results improve our understanding of the potential impact of the MIE on mass-independent fractionation observed in natural samples, such as meteorites, and analytical artifacts of high-precision isotope analysis for heavy elements.

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.

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.

Legacy Mercury Re-emission and Subsurface Migration at Contaminated Sites Constrained by Hg Isotopes and Chemical Speciation.

The re-emission and subsurface migration of legacy mercury (Hg) are not well understood due to limited knowledge of the driving processes. To investigate these processes at a decommissioned chlor-alkali plant, we used mercury stable isotopes and chemical speciation analysis. The isotopic composition of volatilized Hg(0) was lighter compared to the bulk total Hg (THg) pool in salt-sludge and adjacent surface soil with mean ε202HgHg(0)-THg values of -3.29 and -2.35‰, respectively. Hg(0) exhibited dichotomous directions (E199HgHg(0)-THg = 0.17 and -0.16‰) of mass-independent fractionation (MIF) depending on the substrate from which it was emitted. We suggest that the positive MIF enrichment during Hg(0) re-emission from salt-sludge was overall controlled by the photoreduction of Hg(II) primarily ligated by Cl- and/or the evaporation of liquid Hg(0). In contrast, O-bonded Hg(II) species were more important in the adjacent surface soils. The migration of Hg from salt-sludge to subsurface soil associated with selective Hg(II) partitioning and speciation transformation resulted in deep soils depleted in heavy isotopes (δ202Hg = -2.5‰) and slightly enriched in odd isotopes (Δ199Hg = 0.1‰). When tracing sources using Hg isotopes, it is important to exercise caution, particularly when dealing with mobilized Hg, as this fraction represents only a small portion of the sources.

Lithospheric mantle as a metal storage reservoir for orogenic gold deposits in active continental margins: Evidence from Hg isotopes

The subcontinental lithospheric mantle (SCLM) is now suggested by many workers to play a role in the formation of orogenic gold deposits in active continental margins, given that the gold and volatiles may be introduced into the SCLM during plate subduction. The giant Cretaceous Jiaodong gold province within the North China block occurs in a convergent margin setting where there is no terrane accretion, thus eliminating from consideration the commonly accepted metal and fluid source reservoir for orogenic gold—the metamorphosed upper crust of an active orogenic belt. Thus, the auriferous fluids were released below the high-grade Archean cratonic rocks from either enriched SCLM or directly from the subducted oceanic slab. Mercury (Hg) isotopes allow fingerprinting of isotopically distinct reservoirs, discriminating between the two possibilities. We present Hg isotope data for a set of pyrite grains, native gold, and lamprophyres from six main gold districts in the Jiaodong gold province. These samples dominantly yielded near-zero Δ199Hg (0‰ ± 0.1‰), within uncertainty of the mantle Δ199Hg value. The results provide novel evidence that the SCLM predominantly controlled the Hg budget of the Jiaodong gold deposits, implying that the SCLM acted as a buffer for the crustal mass-independent fractionation Hg signatures and a storage reservoir for gold and volatiles. Consequently, during slab subduction, gold and volatiles were recycled and stored within the SCLM and were later released from the mantle during uplift and relaxation of compressional tectonics.

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.

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.

Optimization of a pre-concentration method for the analysis of mercury isotopes in low-concentration foliar samples.

Hg isotope analysis in samples from background regions is constrained by the presence of low Hg concentration and therefore requires a pre-concentration method. Existing Hg pre-concentration methods are constrained by long sample processing time and limited sample loading capacity. Using foliar samples as a test case, an optimized Hg pre-concentration method is presented that involves the microwave-assisted digestion of samples for Hg isotope analysis with the addition of a pre-digestion step. Microwave-digested foliar samples and CRMs were transferred to an impinger, reduced with SnCl2, and collected in a 2.25 mL concentrated inverse aqua regia (3:1 HNO3:HCl, v/v). This resulted in an optimal acid concentration in the solution ideal for analysis on MC-ICP-MS. The time for purging with Hg-free N2 was optimized to 30 min and the efficiency of the pre-concentration method was tested using a combination of approaches. Tests performed on pure reagents and matrix of foliar samples spiked with 197Hg radiotracer showed recoveries averaging 99 ± 1.7% and 100 ± 3.0%, respectively. Mercury at concentrations as low as 1.83 ng g-1 was pre-concentrated by digesting aliquots of foliage samples in individual digestion vessels. Recoveries following their pre-concentration averaged 99 ± 6.0%, whereas recoveries of 95 ± 4.7% and 95 ± 2.5% were achieved for NIST SRM 1575a (pine needle) and reagents spiked with NIST SRM 3133, respectively. Analysis using multicollector-ICP-MS showed low fractionation of δ202Hg during sample pre-concentration with no significant mass-independent fractionation. The proposed method is a relatively simple and robust way to prepare Hg samples for Hg isotopic analysis and is suitable even for complex biological matrices.

Enhanced volcanic activity and long-term warmth in the middle Eocene revealed by mercury and osmium isotopes from IODP Expedition 369 Site U1514

Rapid plate reorganization may have influenced global climate during the Eocene; however, its linkage remains poorly constrained, particularly during the middle Eocene. To elucidate this tectonic–climatic relationship, here, we conducted a comprehensive analysis based on high-resolution mercury (Hg) and osmium (Os) abundance and isotope data obtained from the complete Eocene sedimentary sequence of Site U1514, drilled in the Mentelle Basin off southwest Australia. The Hg signals in this sedimentary sequence, which are characterized by significantly high enrichment and insignificant mass-independent fractionation (Δ199Hg) signal, confirm that the middle Eocene (∼45–38 Ma) was a period of persistent, increased volcanism, accompanied by intense tectonic activity. In particular, a remarkable seafloor volcanic eruption persisted for approximately 1.5 million years (∼42.0–40.5 Ma), immediately preceding the Middle Eocene Climate Optimum (MECO). Contemporaneously, the trends toward a slightly more radiogenic seawater 187Os/188Os (Osi) composition denote the prevalence of intensified continental weathering under a warm, humid climate during the middle Eocene, a phenomenon particularly evident during the MECO. Importantly, the Hg and Os records from Site U1514 reveal the occurrence of a multi-million-year warming reversal amid the long-term Eocene cooling trend, which likely contributed to significant CO2 reduction during the late Eocene. These findings significantly enhance our understanding of Eocene climate dynamics, which are fundamentally linked to intensive tectonic-driven volcanic activity and associated continental chemical weathering.

Instrumental mass-independent fractionation accounting for the sensitivity of the double spike proportion effect by MC-ICP-MS: a case study of Zn isotope measurements

Mass-independent fractionation during Zn isotope analysis by MC-ICP-MS is identified, which is responsible for the sensitive DS ratio effect. Using the correction method proposed, the results obtained are consistent with theoretical predictions.

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.

Condensation of fallout glasses in the Hiroshima nuclear fireball resulting in oxygen mass-independent fractionation

A new kind of Hiroshima nuclear fallout, the Hiroshima glasses, was discovered around the Hiroshima Bay. Here, the chemical compositions and the silicon and oxygen triple isotope compositions were analyzed to understand the formation process of these new fallouts. The chemical analysis shows four different families of glasses: the melilitic glasses, the anorthositic glasses, the soda-lime glasses, and the silica glass. The silicon isotopic compositions show wide variations in the glasses, with δ30Si varying between -23.0 ± 1.8 ‰ and -1.5 ± 1.1 ‰. The oxygen isotopic compositions indicate the presence of mass-independent fractionation on ≈38 % of the analyses, reaching a Δ17O of -3.1 ± 0.6 ‰. The chemical and silicon isotopic compositions of the Hiroshima glasses show that these glasses were formed by condensation within the nuclear fireball. Our scenario for the Hiroshima glasses formation, tested by modeling (GGchem code), considers a rapid condensation (1.7–5.5 s) in the nuclear fireball (3200–1000 K) at atmospheric pressure with a gas resulting from a mixing between air, and vaporized water and city materials. Chemical reactions during the Hiroshima glasses condensation are the most probable source for the oxygen mass-independent fractionation. The formation of the Hiroshima glasses by condensation implies that they may be an analog to the first condensates in the solar system: Calcium-Aluminum-rich Inclusions (CAIs), which are found in chondrites. The Hiroshima glasses exhibit similarities with CAIs in their chemical and isotopic compositions (Si and O).

Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation.

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ∼30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ199Hg/Δ201Hg ratio was uniform across experiments (∼1.4), Δ199Hg/δ202Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

Mercury isotope constraints on the timing and pattern of magmatism during the end-Triassic mass extinction

The End-Triassic Mass Extinction (ETME) was broadly coincident with the emplacement of the Central Atlantic Magmatic Province (CAMP). However, the relationship between evolutionary phases of CAMP (i.e. prolonged shallow intrusive pulses and later extrusives) and the ETME is not clear. Here, a high-resolution record of changing magmatic activity is established using mercury (Hg) isotopes through a Triassic-Jurassic sedimentary succession deposited on the northern flank of CAMP. Successive negative and positive mass independent fractionation (MIF) of odd Hg isotopes through the end-Triassic interval in this succession suggest dominantly thermogenic Hg release from intrusive heating of organic-rich sedimentary rocks, followed by mainly volcanogenic input of mantle-sourced Hg. This inferred pattern is also supported by correlations to available CAMP ages. Minimum calculated volumes of thermogenic and volcanogenic Hg needed to drive the observed shifts at the basin-scale are plausible based on likely CAMP Hg release volumes, and biotic turnover in the studied region was unlikely to have occurred before the onset of volcanogenic Hg release.

The multiple sulfur isotope architecture of the Kambalda nickel camp, Western Australia

New data on the multiple sulfur isotope signature of Archean sulfides from country rocks and magmatic mineralization at the Moran deposit (Kambalda, Western Australia) were combined with previously published geochemical data to constrain the various stages of the dynamic evolution of this magmatic system, unveiling new insights into the transport mechanisms of sulfide liquids in komatiite magmas. Sulfides in the Archean magmatic and sedimentary host rocks of the komatiites display a unique mass-independent sulfur isotope signature (Δ33S), which records a photochemical reaction of sulfur in an oxygen-poor atmosphere prior to the Great Oxidation Event.Sedimentary rocks that are thought to be assimilated by komatiite show a distinctly positive Δ33S signature (+ 0.9 to + 2.4‰). Early ore sulfides situated above these sedimentary rocks contain relatively few valuable metals and display an overlapping Δ33S range (+ 0.6 to + 1.0‰). Subsequent but still early ore sulfides are situated above basalt, as the sedimentary rocks were thermo-mechanically eroded by the sulfide melt, displaying more mantle-like signatures (+ 0.2 to + 0.3‰) and valuable metal content - indistinguishable from the main ore deposit. This reflects a progressive dilution of the contaminant signature by the magmatic isotope signature of the komatiite liquid. Calculated volumes of the interaction of silicate melt and sulfide melt to explain the metal tenor of the ore and its Δ33S signature indicate a decoupling between chemical and isotopic signatures. This can be explained by upgrading the sulfide melt with valuable metals simultaneously with the dissolution of sulfur in the komatiite melt.

Mercury isotopic compositions of iron oxide‑copper‑gold (IOCG) hydrothermal systems: Deep Hg cycling in intracontinental settings

Mercury isotopes display unique mass-independent fractionation (MIF), typically expressed as Δ199Hg, which relates to photochemical reactions occurring at Earth's surface. Pronounced Hg-MIF signals have been observed in various hydrothermal systems in both convergent margins and intracontinental settings, highlighting the recycling of Hg from marine or terrestrial reservoirs into shallow continental hydrothermal systems. However, the geochemical fate of Hg in deep continental environments of intracontinental settings remains poorly understood. Iron oxide‑copper‑gold (IOCG) hydrothermal systems typically involve the circulation of fluids from both deep magmatism and continental basins, providing an opportunity to investigate this issue. Here, we present the Hg isotopic compositions of ore minerals from five representative IOCG deposits in the Kangdian region, South China. All the studied ore samples display large mass-dependent fractionation with δ202Hg of −3.23 to 1.06‰, but a relatively narrow range of Δ199Hg of −0.17 to 0.11‰. These isotopic signatures support the hypothesis of binary mixing of Hg from two sources: (1) a magmatic endmember (∼two thirds) derived from the lithospheric mantle with low δ202Hg (−3 to −1‰) and near-zero Δ199Hg, and (2) a crustal source (∼one third) originating from the basement rocks with relatively higher δ202Hg (−1 to 1‰) and negative Δ199Hg (−0.2 to 0‰). Compared to the shallow Pb-Zn-Au-Sb hydrothermal systems which formed in intracontinental basins through the circulation of fluids in the upper crust, the Hg components (and by analogy, the ore metals) in the Kangdian IOCG system are dominated by a lithospheric mantle source. Our study sheds light on deep Hg cycling and confirms the Hg isotope tracer as a tool for revealing metal sources in hydrothermal ore systems.