Significant Mass-independent Fractionation Research Articles

Isotope-Based Characterization of Soil Elemental Mercury Emissions from Historical Mercury Mining Areas: Driving Pathways and Relative Contributions.

Photo-, microbial, and abiotic dark reduction of soil mercury (Hg) may all lead to elemental mercury (Hg(0)) emissions. Utilizing lab incubations, isotope signatures of Hg(0) emitted from mining soils were characterized to quantify the interplay and contributions of various Hg reduction pathways, which have been scarcely studied. At 15 °C, microbial reduced Hg(0) showed a negative mass-dependent fractionation (MDF) (δ202Hg = -0.30 ± 0.08‰, 1SD) and near-zero mass-independent fractionation (MIF) (Δ199Hg = 0.01 ± 0.04‰, 1SD), closely resembling dark reduced Hg(0) (δ202Hg = -0.18 ± 0.05‰, Δ199Hg = -0.01 ± 0.03‰, 1SD). In comparison, photoreduced Hg(0) exhibited significant MDF and MIF (δ202Hg = -0.55 ± 0.05‰, Δ199Hg = -0.20 ± 0.07‰, 1SD). In the dark, Hg isotopic signatures remained constant over the temperature range of 15-35 °C. Nonetheless, light exposure and temperature changes together altered Hg(0) MIF signatures significantly. Isotope mixing models along with Hg(0) emission flux data highlighted photo- and microbial reduction contributing 79-88 and 12-21%, respectively, of the total Hg(0) emissions from mining soils, with negligible abiotic dark reduction. Microorganisms are the key driver of soil Hg(0) emissions by first dissolving HgS and then promoting ionic Hg formation, followed by facilitating the photo- and microbial reduction of organically bound Hg. These insights deepen our understanding of the biogeochemical processes that influence Hg(0) releases from surface soils.

A newly recognised mafic sill-hosted Ni-sulfide deposit emplaced during the 2.4 Ga Widgiemooltha dike swarm event, Eastern Goldfields, Western Australia

AbstractThe Cathedrals Ni-Cu prospect, located at the western margin of the Eastern Goldfields of the Yilgarn Craton, is hosted within a mafic intrusion interpreted as a sill complex. U-Pb dating of apatite from the sill yielded a crystallisation age of 2336 ± 64 Ma, inferring an association of sill emplacement and Ni mineralisation related to emplacement of the c. 2400 Ma Widgiemooltha dike swarm. The sill is typically differentiated into a lower olivine orthocumulate layer overlain by a dolerite unit containing xenoliths of partially assimilated granitoids in its upper portion. The latter is interpreted to be the result of stoping and melting of the granitic hanging wall, thereby creating a gravitationally stable buoyant melt layer beneath the top contact. Ni-Cu-Fe sulfides are increasingly abundant towards the base of the sill, ranging from globular disseminated sulfides to net-textured and massive sulfides at the basal contact. The presence and orientation of sulfide globule-bubble pairs indicates a primary near-horizontal orientation. Massive sulfides commonly exhibit a loop texture with pyrrhotite grains surrounded by pentlandite and chalcopyrite. Despite the variety of sulfide textures, sulfur isotopes have a homogeneous mantle-like signature without significant mass independent fractionation. Mineral chemistries that indicate sulfide prospectivity in larger intrusions do not work as effectively in this small sill, therefore new indicators may need to be developed to explore for similar deposits. To date, there are no other known magmatic deposits of this age in Australia. Sills of this age may be more prospective than previously recognised.

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.

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.

Determination of the Isotopic Composition of Aqueous Mercury in a Paddy Ecosystem Using Diffusive Gradients in Thin Films.

Measuring the isotopic composition of Hg in natural waters is challenging due to the ultratrace level of aqueous Hg (ng L-1). At least 5 ng of Hg mass is required for Hg isotopic analysis. Given the low Hg concentration in natural waters, a large volume of water (>10 L) is typically needed. The conventional grab sampling method is time-consuming, laborious, and prone to contamination during transportation and preconcentration steps. In this study, a DGT (diffusive gradients in thin films) method based on aminopropyl and mercaptopropyl bi-functionalized SBA-15 nanoparticles was developed and extended to determine the concentration and isotopic composition of aqueous Hg for the first time. The results of laboratory analysis showed that Hg adsorption by DGT induces ∼ -0.2‰ mass-dependent fractionation (MDF) and little mass-independent fractionation (MIF). The magnitude of MDF exhibits a dependence on the diffusion-layer thickness of DGT. Since Hg-MDF can occur in a broad range of environmental processes, monitoring the δ202Hg of aqueous Hg using the DGT method should be performed with caution. Field results show consistent MIF signatures (Δ199Hg) between the DGT and conventional grab sampling method. The developed DGT method serves as a passive sampling method that effectively characterizes the MIF of Hg in waters to understand the biogeochemical cycle of Hg at contaminated sites.

Mercury isotope variation during organic matter maturation to petroleum

Although both sedimentary rocks and petroleum generally contain detectable levels of Hg, the characteristics of Hg isotope fractionation and its transformation from biomass to sedimentary rocks to petroleum have not been sufficiently investigated to date. Here, we report Hg contents and isotope compositions in source rocks and crude oils from the Paleogene of the Bohai Bay Basin and in source rocks from the Permian and Jurassic of the Sichuan Basin in China. Our analysis made use of an improved crude oil Hg pre-concentration system involving pyrolytic cracking and KMnO4/H2SO4 Hg trapping to analyze Hg fractionation during organic matter maturation to petroleum. Positive mass-independent fractionation (MIF) signatures of Hg isotopes were detected in the source rocks, with Δ199Hg ranging between −0.04‰ and + 0.48‰ (mean + 0.12 ± 0.12‰), which is significantly different from the negative Δ199Hg of terrestrial non-source rocks. Positive Hg-MIF signatures were detected in the crude oil, with Δ199Hg ranging between +0.04‰ and + 0.21‰ (mean + 0.13 ± 0.06‰). We propose a model of Hg isotopic fractionation related to organic matter history. From organic matter to source rock, Hg system variations are attributed to endogenic (i.e., photoreduction) and exogenic processes (i.e., terrestrial, magmatic and hydrothermal Hg inputs). From source rock to petroleum, Hg is mobilized during hydrocarbon migration, a process that occurs with MDF but without significant MIF.

A comprehensive evaluation of sulfur isotopic analysis (δ34S and δ33S) using multi-collector ICP-MS with characterization of reference materials of geological and biological origin

Sulfur isotope ratios are often used as biogeochemical tracers to gain understanding of abiotic and biological processes involved in the sulfur cycle in both modern and ancient environments. There is however a lack of matrix-matched well-characterized isotopic reference materials that are essential for controlling the accuracy and precision. This study therefore focused on expanding and complementing the currently available sulfur isotope ratio data by providing the bulk sulfur isotopic composition, as determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS), for a comprehensive set of commercially and/or readily available biological and geological reference materials. A total 7 isotopic reference materials and 41 elemental reference materials were studied. These reference materials include standards of terrestrial and marine animal origin, terrestrial plant origin, human origin, and geological origin. Different sample preparation protocols, including digestion and subsequent chromatographic isolation of S, were evaluated and the optimum approach selected for each matrix type. For achieving enhanced robustness, the sample preparation and sulfur isotope ratio measurements were done at two different laboratories for selected reference materials, while at one of the laboratories the measurements were additionally performed using two different MC-ICP-MS instruments. Determined δ34SVCDT and δ33SVCDT values compared well between the different laboratories, as well as between the different generation MC-ICP-MS instruments, and for standards that were previously characterized, our data are similar to literature values. The δ34SVCDT ranges determined for the different categories of the reference materials – terrestrial animal origin: +2 to +9‰, marine animal origin: +15 to +20‰, human origin: +6 to +10‰, terrestrial plant origin: −20 to +7‰, and geological origin: −12 to +21‰ – fit the expected values based on previous studies of similar types of matrices well. No significant mass-independent fractionation is observed when considering the expanded uncertainties for Δ33SV-CDT.

The Mercury Isotopic Composition of Earth's Mantle and the Use of Mass Independently Fractionated Hg to Test for Recycled Crust

AbstractThe element mercury (Hg) can develop large mass‐independent fractionation (MIF) (Δ199Hg) due to photo‐chemical reactions at Earth's surface. This results in globally negative Δ199Hg for terrestrial sub‐aerially‐derived materials and positive Δ199Hg for sub‐aqueously‐derived marine sediments. The mantle composition least affected by crustal recycling is estimated from high‐3He/4He lavas from Samoa and Iceland, providing an average of Δ199Hg = 0.00 ± 0.10, Δ201Hg = −0.02 ± 0.0.09, δ202Hg = −1.7 ± 1.2; 2SD, N = 11. By comparison, a HIMU‐type lava from Tubuai exhibits positive Δ199Hg, consistent with altered oceanic crust in its mantle source. A Samoan (EM2) lava has negative Δ199Hg reflecting incorporation of continental crust materials into its source. Three Pitcairn lavas exhibit positive Δ199Hg which correlate with 87Sr/86Sr, consistent with variable proportions of continental (low Δ199Hg and high 87Sr/86Sr) and oceanic (high Δ199Hg and low 87Sr/86Sr) crustal material in their mantle sources. These observations indicate that MIF signatures offer a powerful tool for examining atmosphere‐deep Earth interactions.

Multiple sulfur isotopes constraints on origin and evolution of the Neoarchean and Paleoproterozoic Cu-Au systems from the Carajás Domain, Amazonian Craton, Brazil

Multiple sulfur isotopes in sulfides were measured by in situ Secondary Ion Mass Spectrometry in order to constrain sulfur sources and pathways, as well as explore atmosphere–ore genesis implications on the metallogeny of the Neoarchean and Paleoproterozoic Cu-Au systems of the Carajás Domain, southeast Amazonian Craton, Brazil. All of the investigated Neoarchean (2.70–2.57 Ga; i.e., Salobo, Igarapé Bahia, Castanha and Sequeirinho) and Paleoproterozoic IOCG (ca 1.88 Ga; i.e., Alvo 118 and Sossego) deposits show Δ33S < 0‰ (-0.17‰ to + 0.02‰). The Paleoproterozoic Cu-Au(W-Sn-Bi) Breves deposit reveals Δ33S > 0‰ (+0.08‰ to + 0.27‰), implying that sulfur underwent mass-independent fractionation (MIF). In addition, three distinct δ34S ranges are defined: −3.07‰ to + 3.01‰ and + 2.17‰ to + 4.68‰ for the Neoarchean and Paleoproterozoic IOCG deposits, respectively, and −0.46‰ to + 3.81‰ for the Paleoproterozoic Breves deposit.In the Neoarchean IOCG deposits, sulfur is most likely of mantle/magmatic origin. However, a subtle but detectable MIF-S signature reflects the inheritance of a minor sulfur component transported to the atmosphere, experienced photolytic reactions and returned to the hydrosphere. The interaction between highly saline, hot, and deep-seated metalliferous fluids with the host rocks, including sulfate-bearing volcanic rocks that underwent seafloor alteration, may account for the small negative Δ33S values in the IOCG deposits. The similarity between the negative Δ33S signatures of the Neoarchean and the Paleoproterozoic IOCG deposits (i.e., Sossego and Alvo 118) suggest that the MIF signatures recorded by the latter most likely reflect inheritance of Neoarchean sulfur with MIF signatures acquired by large scale fluid-rock interaction triggered by the ca 1.88 Ga A-type granitic magmatism.The positive Δ33S values of sulfides from the Paleoproterozoic Breves deposit, in contrast, were probably generated by reduced sulfur species sourced from crustal sources (e.g., Archean pyrite-bearing sedimentary units) in addition to magmatic sulfur related to ca. 1.88 Ga A-type granite emplacement.

Simultaneous Compound-Specific Analysis of δ33S and δ34S in Organic Compounds by GC-MC-ICPMS Using Medium- and Low-Mass-Resolution Modes.

Compound-specific isotope analysis of sulfur (δ34S-CSIA) in organic compounds was established in the last decade employing gas chromatography connected to multiple-collector inductively coupled plasma mass spectrometry (GC-MC-ICPMS). However, δ33S-CSIA has not yet been reported so far. In this study, we present a method for the simultaneous determination of δ33S and δ34S in organic compounds by GC-MC-ICPMS applying medium- and also low-mass-resolution modes. The method was validated using the international isotope reference materials IAEA-S-1, IAEA-S-2, and IAEA-S-3. Overall analytical uncertainty including normalization and reproducibility for δ33S and δ34S was usually better than ±0.2 mUr (σ) for analytes containing at least 100 pmol of S. Further, it is demonstrated that, despite small isobaric interferences, results obtained at low mass resolution are indistinguishable from medium mass resolution offering the benefit of increased sensitivity and versatility of this method. Additionally, the method was applied for the δ33S and δ34S isotope analysis of industrially produced organic compounds to investigate potential mass-independent fractionation (MIF). The relation between δ34S and δ33S in these compounds followed a mass-dependent fractionation trend (MDF; Δ33S ≤ ±0.2 mUr). Degradation of dimethyl disulfide by direct photolysis caused a small but significant MIF (Δ33S = 0.55 ± 0.04 mUr, n = 3), demonstrating sufficient sensitivity of the method for these types of studies.

Multiple sulfur isotope fractionation in hydrothermal systems in the presence of radical ions and molecular sulfur

This study is aimed to evaluate the role played by the sulfur radical ions (S3− and S2−) and molecular sulfur (S0) on sulfur isotope fractionation and to investigate if these species may leave an isotope fingerprint in hydrothermal systems. For this purpose, we combined (i) experiments using a hydrothermal reactor with aqueous S3−(S2−)-S0-sulfate-sulfide fluids and pyrite across a wide range of temperatures (300–450 °C), pressures (300–800 bars), fluid acidity (4 < pH < 8) and with elevated total sulfur concentrations (0.1–1.0 mol/kg fluid) favorable for formation of those polymeric sulfur species, (ii) precise quadruple S isotope analyses of the different S-bearing aqueous species in sampled fluids and in-situ precipitated pyrite, and (iii) thermodynamic modeling of sulfur aqueous speciation and solubility. Our results quantitatively confirm both equilibrium and kinetic SO4-H2S and pyrite-H2S mass dependent fractionation (MDF) factors previously established using extensive experimental and natural data from more dilute fluids in which polymeric sulfur species are negligible. MDF signatures of S0 measured in the sampled fluids of this study reveal different S0-forming pathways such as (i) breakdown on cooling of S3− (and S2−) and other chain-like S0 polymers only stable at high temperature and being isotopically identical to H2S; (ii) cyclooctasulfur (S80, liquid or solid) precipitating by recombination of sulfate and sulfide and/or by exchange with polysulfide dianions (Sn2−) on cooling and being slightly 34S-enriched compared to H2S (by ∼2‰ of δ34S); and iii) a different type of S0 resulting from thiosulfate irreversible breakdown and being highly 34S-depleted (by ∼12‰) relative to H2S. Our data do not show any significant mass independent fractionation (MIF) of 33S and 36S, with Δ33S and Δ36S values of any S aqueous species and pyrite being within ±0.1‰ and ±1.0‰, respectively. Therefore, under the investigated experimental conditions, the radical S3− ion is unlikely to generate significant MIF in the hydrothermal fluid phase and in pyrite and native sulfur precipitated therefrom. Our study supports the existing interpretations of small Δ33S and Δ36S variations between sulfide/sulfate-bearing fluid and pyrite as MDF in terms of reaction kinetics, different reaction pathways, and mass conservation effects such as mixing of S reservoirs or Rayleigh distillation. Our data extend, across a wider range of sulfur concentration and chemical speciation, the existing multiple S isotopes models that exploit such variations as a complement to the traditional δ34S tracer to monitor the approach to equilibrium and evolution of hydrothermal fluids.

Mercury and in situ sulfur isotopes as constraints on the metal and sulfur sources for the world’s largest Sb deposit at Xikuangshan, southern China

It has been well established that metal and sulfur sources in mineral deposits can be very difficult to identify, especially for ore deposits hosted in sedimentary rocks. Using the world’s largest Sb deposit at Xikuangshan in southern China as a case study, this study combined Hg isotopes and in situ sulfur isotope measurements to constrain the sources of Sb and sulfur. A variation of 1.1‰ in δ202Hg (0.04 to 1.15‰) was observed in stibnite ore samples, suggesting that mass-dependent fractionation of Hg isotopes occurred during the formation of the deposit. Significant mass-independent fractionation of Hg isotopes, with △199Hg ranging from − 0.03 to − 0.17‰, was also observed in the ore samples, suggesting that Hg transported by the ore fluids was inherited from Proterozoic basement metamorphic rocks as these rocks show similar △199Hg signatures (− 0.03 to 0.07‰). In situ sulfur isotope measurements yielded δ34S values that cluster in the range of + 6.8 to + 10.2‰, providing evidence that sulfur contained in ore fluids may also have been dominantly derived from underlying Proterozoic basement metamorphic rocks (δ34S = +5.6 to + 11.5‰). Using the new results from Hg and S isotopes, we proposed that deep-circulated meteoric water mobilized Sb, Hg, and S from the Proterozoic metamorphic basement, ascended along deep faults, and subsequently deposited Sb at favorable structural zones as a result of boiling of the hydrothermal fluids, generating the world-class Xikuangshan Sb deposit. This study also highlights the combined use of Hg-S isotopes as a novel method to provide new and additional insights into the source regions of ore materials for sedimentary-hosted Sb deposits.

On apparent mass-independent fractionation (MIF) signatures from phase partitioning at equilibrium

ABSTRACTThe chance of apparent isotope anomalies either in closed systems at equilibrium or during Rayleigh processes is investigated. The term ‘apparent’ is chosen to highlight that only mass-dependent fractionation (MDF) processes are considered. A goal is finding analytical expressions that could be used for dealing with the complexity of real systems. For example, the formula for calculating the isotopic fractionation in systems with any desired number of phases involved is identified. Terrestrial samples could exhibit artificially low MIF signatures because Δ is not invariant with the choice of the reference material. An alternative parameter Δ* only depending on β is therefore introduced. The potential transfer of sample points in a three-isotope plot to parallel lines during reversible processes is also investigated. Larger apparent anomalies are expected in systems lacking an infinite reservoir and for large enrichment factors. Pyrite is stable beyond the conditions for a reducing environment and MIF signatures from Archaean sediments could be compatible with reversible processes involving oxidised species. Isotope anomalies in pyrite from the Dresser Formation, Australia, are compatible with post-depositional incorporation of 2–5% sulphur of atmospheric origin. Overall, observed delta values could mainly be related to changes in the local absolute isotope abundances.

Mercury isotopic signatures of tailings from artisanal and small-scale gold mining (ASGM) in southwestern Ecuador

Artisanal and small-scale gold mining (ASGM) is currently one of the largest anthropogenic sources of mercury (Hg) to the atmosphere and a significant source to downstream terrestrial aquatic systems. Given the potential toxicity of Hg when it is released to aquatic ecosystems, both scientific and regulatory communities have interest in the development of tools and methods for understanding the fate and transport of Hg in the environment. Although Hg isotopes are applied extensively to trace other anthropogenic point sources of Hg in aquatic ecosystems, few studies have used isotopic analyses to investigate the downstream impacts of ASGM. Furthermore, these studies are currently limited by relatively sparse Hg isotopic analyses on ASGM materials. In this study, ASGM samples from Portovelo-Zaruma (Ecuador), representing various stages of the processing of low-grade gold-bearing ores, were analyzed for Hg concentrations and stable isotope ratios. These data were used to assess the isotopic variability of the ASGM endmember and confirm the results of prior isotopic analyses of ASGM materials and downstream sediments from Portovelo-Zaruma. While the Hg concentrations of the ASGM samples varied significantly, isotopic analyses revealed a limited range of signatures that was characterized by relatively heavy mass-dependent fractionation (MDF) with little to no significant mass-independent fractionation (MIF). The signatures of ASGM samples analyzed in this study matched well with previously reported ASGM samples from Portovelo-Zaruma as well as downstream sediments (for up to 120 km). Furthermore, the overall Hg isotopic compositions of potential ASGM endmembers are distinct from typical compositions observed in freshwater ecosystems (e.g., from soil erosion, atmospheric deposition), allowing Hg isotopes to be a powerful tool in tracing downstream Hg contamination from ASGM.

Different circulation history of mercury in aquatic biota from King George Island of the Antarctic

To trace the circulation history of aquatic bioavailable Hg in the Antarctic, the species and isotopic compositions of Hg in sediment, Archaeogastropoda (Agas), Neogastropoda (Ngas), and fish collected from King George Island were studied in detail. Positive mass independent fractionation (MIF) was observed and positively correlated with the percentages of methylmercury (MeHg%) in Agas and Ngas, suggesting an effect of MeHg accumulation during trophic transfer on MIF signatures. However, both the ratios of Δ199Hg/δ202Hg and Δ199Hg/Δ201Hg indicated different circulation histories of Hg in Agas, Ngas, and fish. The microbial methylation in sediment was the primary source of MeHg in Agas and Ngas (Δ199Hg/δ202Hg ∼0, Δ199Hg/Δ201Hg ∼1.00). In contrast, the MeHg in fish (Δ199Hg/δ202Hg = 0.55 ± 0.06, Δ199Hg/Δ201Hg = 1.19 ± 0.17) came from the combined sources of residual MeHg which had sunk from the surface water and microbial-methylated MeHg in sediments, and the bioavailable Hg in the sediments contributed to approximately 44% of the total Hg in fish. Subsequently, the Δ199Hg values of bioavailable MeHg and IHg in sediments were quantitatively calculated, which provided key end-member information for future source apportionment in the Antarctic and other pelagic regions. It was also found that the Hg accumulated in Agas and Ngas had no history of MeHg photo-degradation, indicating that the methylated Hg in benthic zones suffered little photo-degradation and thus presented high bioavailability and environmental risk.

Subsurface deposition of Cu-rich massive sulphide underneath a Palaeoproterozoic seafloor hydrothermal system—the Red Bore prospect, Western Australia

The Proterozoic Bryah and Yerrida basins of Western Australia contain important base and precious metal deposits. Here we present microtextural data, trace element and S isotope analyses of massive sulphide mineralisation hosted in Palaeoproterozoic subvolcanic rocks (dolerite) recently discovered at Red Bore. The small-scale high-grade mineralisation, which extends from the sub-surface to at least 95 m down-hole, is dominated by massive chalcopyrite and contains minor pyrite and Bi-Te-(Se) phases. Massive sulphide mineralisation is surrounded by discontinuous brecciated massive magnetite, and a narrow (< 2 m) alteration halo, which suggests very focussed fluid flow. Laser ablation ICP-MS analyses indicate that chalcopyrite contains up to 10 ppm Au and in excess of 100 ppm Ag. Sulphur isotope analyses of pyrite and chalcopyrite indicate a narrow range of δ34SVCD (− 0.2 to + 4.6 ‰), and no significant mass-independent fractionation (− 0.1 < Δ33S < + 0.05 ‰). Re-Os isotope analyses yield scattered values, which suggests secondary remobilisation. Despite the geographical proximity and the common Cu-Au-Ag association, the mineralisation at Red Bore has significant differences with massive sulphide mineralisation at neighbouring DeGrussa, as well as other massive sulphide deposits around the world. These differences include the geometry, sub-volcanic host rocks, extreme Cu enrichment and narrow δ34S ranges. Although a possible explanation for some of these characteristics is leaching of S and metals from the surrounding volcanic rocks, we favour formation as a result of the release of a magmatic fluid phase along very focussed pathways, and we propose that mixing of this fluid with circulating sea water contributed to sea floor mineralisation similar to neighbouring VHMS deposits. Our data are permissive of a genetic association of Red Bore mineralisation with VHMS deposits nearby, thus suggesting a direct connection between magmatism and mineralising fluids responsible for VHMS deposition at surface. Therefore, the Red Bore mineralisation may represent the magmatic roots of a VHMS system.

Mercury stable isotope compositions in magmatic-affected coal deposits: New insights to mercury sources, migration and enrichment

Mercury (Hg) is commonly present at trace levels in coal deposits. Geological processes, particularly magmatic intrusion and hydrothermal cycling in coal-bearing strata can significantly increase Hg levels in coals. However, the effects of thermal stress, magmatic components, magmatic-hydrothermal fluids, low-temperature hydrothermal fluids on Hg enrichment are confounded in a magmatic-affected coal basin. Here, we demonstrate the use of stable Hg isotopes to understand the controlling factors on Hg enrichment in two well-known Chinese coal deposits affected by magmatic activities: Wulantuga low-temperature hydrothermal-altered coal deposit and Wolonghu magmatic-intruded coal deposit.The Wulantuga No. 6 coal seam is extremely enriched in Hg, varying from 0.37μg/g in middle coal benches to 40–90μg/g in the upper most and lowest coal benches. Approximately 2.5‰ variation in mass dependent fractionation (MDF, −3.07‰ to −0.58‰ in δ202Hg) is observed. δ202Hg vs. 1/[Hg] diagram suggests a mixture of three Hg end-members: original hydrothermal fluids, fractionated hydrothermal fluids and native coal-forming materials. In addition, Wulantuga coals all show positive mass independent fractionation (MIF) of odd isotopes, up to 0.87‰ in Δ199Hg and 0.66‰ in Δ201Hg. The Δ199Hg/Δ201Hg ratios range from 1.3 to 3.3, suggesting that a large fraction of photodegraded methylmercury was likely incorporated into the coal deposit. The magmatic-intruded Wolonghu No. 8 coal seam is only slightly to intermediately enriched in Hg, varying from 0.10μg/g to 0.40μg/g. The coals near the contact sill (≤5cm, −1.81‰ to −1.52‰) have similar δ202Hg as the magmatic sill rocks (−2.05‰ to −1.80‰), both with insignificant MIF values. Coals far from the contact sill (≥15cm) have δ202Hg values varying from −3.40‰ to −1.61‰ and Δ199Hg varying from 0.26‰ to 0.58‰, which are significantly enriched in light and odd Hg isotopes compared to coals near the contact sill. Δ199Hg and Δ201Hg in Wolonghu coals far from the contact sill resemble those of meteoritic waters and seawater in both magnitude and Δ199Hg/Δ201Hg ratio. Our two case studies show significant MDF and MIF of Hg isotopes, which inform on Hg migration and sequestration in the magmatic rocks and coal deposits, and on the roles of meteoric water and hydrothermal fluid circulation.

Mercury anomalies and the timing of biotic recovery following the end-Triassic mass extinction

The end-Triassic mass extinction overlapped with the eruption of the Central Atlantic Magmatic Province (CAMP), and release of CO2 and other volcanic volatiles has been implicated in the extinction. However, the timing of marine biotic recovery versus CAMP eruptions remains uncertain. Here we use Hg concentrations and isotopes as indicators of CAMP volcanism in continental shelf sediments, the primary archive of faunal data. In Triassic–Jurassic strata, Muller Canyon, Nevada, Hg levels rise in the extinction interval, peak before the appearance of the first Jurassic ammonite, remain above background in association with a depauperate fauna, and fall to pre-extinction levels during significant pelagic and benthic faunal recovery. Hg isotopes display no significant mass independent fractionation within the extinction and depauperate intervals, consistent with a volcanic origin for the Hg. The Hg and palaeontological evidence from the same archive indicate that significant biotic recovery did not begin until CAMP eruptions ceased.

A hundred year record of industrial and urban development in French Alps combining Hg accumulation rates and isotope composition in sediment archives from Lake Luitel

This study reconstructs the history of multiple industrial and urban mercury (Hg) emissions recorded in the sediment archive of Lake Luitel (France) from AD ~1860 to AD 2011. For this purpose, we provide a well constrained short-lived radionuclides continuous age–depth relationship of the sediment sequence (mean accumulation rate of 5.18±0.28mm·yr−1) with Hg accumulation rates (Hg AR), Hg isotopic composition and extensive historical data. Hg AR were stable around 45μg·m−2·y−1 from 1860 to WWI and rose to reach their maximum at the end of WWII (250μgm−2y−1) followed by a gradual decreased to reach about 90μgm−2y−1 in the current period. Normalization to a terrigenous Hg proxy highlighted the dominance of atmospheric Hg inputs to the lake. The combination of Hg AR with isotopic signatures through the use of binary mixing (Δ199Hg vs 1/Hg AR) models and isotopic plots (and comparison to literature data) allowed us to identify the main industrial and urban historical inputs. The major outcome of this study is that the Hg mass independent fractionation (MIF) signature did not enable the identification of particular anthropogenic sources but reflected an integrated pool of industrial and urban emissions which tend to shift to less negative MIF values (mean: −0.15±0.04‰) during their period of maximum emissions. Temporal MIF and Hg AR variations depict the rising Hg emissions from the industrial revolution (1860–1910) to the modern industrial and urban development period (1950–1980). Mass dependent fractionation (MDF) signatures enabled the identification of major contributors in relation to their relative intensities lying between two endmember pools: (i) the combustion activities (smelters, cement factories and urban heating) with more negative δ202Hg values, and (ii) the chemical and electrometallurgical activities (electrochemistry, chlor-alkali) with higher δ202Hg values. Unconformities of MIF and MDF signatures were observed during WWI, WWII and interwar period, and were attributed to drastic and rapid changes in regional industrial activities. Finally, recent laws regarding Hg emissions (1998–2011) prove their efficiency as Hg AR decreased with a return to more negative MIF and MDF signatures such as during the industrial revolution period. Our study highlights that the combination of Hg isotopic data with Hg AR in sediment archives is a useful tool for reconstructing the history of anthropogenic Hg emissions, and has the potential to identifiy their relative contributions.

Sources and fate of mercury pollution in Almadén mining district (Spain): Evidences from mercury isotopic compositions in sediments and lichens

Variations in mercury (Hg) isotopic compositions have been scarcely investigated until now in the Almadén mining district (Spain), which is one of the most impacted Hg areas worldwide. In this work, we explore and compare Hg isotopic signatures in sediments and lichens from Almadén mining district and its surroundings in order to identify and trace Hg aquatic and atmospheric contamination sources. No statistically significant mass independent fractionation was observed in sediments, while negative Δ201Hg values from −0.12 to −0.21‰ (2SD = 0.06‰) were found in lichens. A large range of δ202Hg values were reported in sediments, from −1.86 ± 0.21‰ in La Serena Reservoir sites far away from the pollution sources to δ202Hg values close to zero in sediments directly influenced by Almadén mining district, whereas lichens presented δ202Hg values from −1.95 to −0.40‰ (2SD = 0.15‰). A dilution or mixing trend in Hg isotope signatures versus the distance to the mine was found in sediments along the Valdeazogues River-La Serena Reservoir system and in lichens. This suggests that Hg isotope fingerprints in these samples are providing a direct assessment of Hg inputs and exposure from the mining district, and potential information on diffuse atmospheric contamination and/or geochemical alteration processes in less contaminated sites over the entire hydrosystem. This study confirms the applicability of Hg isotope signatures in lichens and sediments as an effective and complementary tool for tracing aquatic and atmospheric Hg contamination sources and a better constraint of the spatial and temporal fate of Hg released by recent or ancient mining activities.