Zn Isotopic Signature Research Articles

Zn Isotope Tracing Unveils Primary Anthropogenic Zn Sources in Glacial Cryoconite of the High Asian Mountains

AbstractZinc (Zn) exerts a significant influence on the global environment, terrestrial ecosystems, and human health. The application of Zn isotopes (δ66Zn) has been suggested as a potent tool for tracing environmental contamination. However, studies focusing on Zn isotope tracing within the cryosphere areas are notably limited. Here we present the first data set on Zn isotopes in glacial cryoconite, based on observations over a large regional scale in High Asian Mountains (including Tibetan Plateau (TP) and its surroundings of western China). The results showed that glacial cryoconite had a general heavy Zn isotopic signature in various TP locations, with δ66Zn values ranging from −0.22‰ to +0.87‰. Employing the MixSIAR model, the overall Zn contribution source to the cryoconite was mineral dust (36%) > coal burning (33%) > non‐exhaust traffic emissions (22%) > industrial smelting (10%). We ascertained that anthropogenic sources account for the primary contribution (about 60%–73%) of Zn inputs in all glacial locations, with coal burning emerging as the foremost anthropogenic contributor (mean 33%). Anthropogenic Zn in various TP locations was primarily derived from Zn emissions resulting from coal combustion, though it is also predominantly influenced by industrial smelting source in cryoconite of the Tianshan Mountains. Our results aligned with coal combustion data from the energy inventory of western China, suggesting that regional coal burning likely represents the foremost source of atmospheric Zn pollutant emission and deposition in the High Asia mountain glaciers.

Fe, Zn, and Mg stable isotope systematics of acapulcoite lodranite clan meteorites

AbstractThe processes of planetary accretion and differentiation, whereby an unsorted mass of primitive solar system material evolves into a body composed of a silicate mantle and metallic core, remain poorly understood. Mass‐dependent variations of the isotope ratios of non‐traditional stable isotope systems in meteorites are known to record events in the nebula and planetary evolution processes. Partial melting and melt separation, evaporation and condensation, diffusion, and thermal equilibration between minerals at the parent body (PB) scale can be recorded in the isotopic signatures of meteorites. In this context, the acapulcoite–lodranite meteorite clan (ALC), which represents the products of thermal metamorphism and low‐degree partial melting of a primitive asteroid, is an attractive target to study the processes of early planetary differentiation. Here, we present a comprehensive data set of mass‐dependent Fe, Zn, and Mg isotope ratio variations in bulk ALC species, their separated silicate and metal phases, and in handpicked mineral fractions. These non‐traditional stable isotope ratios are governed by mass‐dependent isotope fractionation and provide a state‐of‐the‐art perspective on the evolution of the ALC PB, which is complementary to interpretations based on the petrology, trace element composition, and isotope geochemistry of the ALC. None of the isotopic signatures of ALC species show convincing co‐variation with the oxygen isotope ratios, which are considered to record nebular processes occurring prior to the PB formation. Iron isotopic compositions of ALC metal and silicate phases broadly fall on the isotherms within the temperature ranges predicted by pyroxene thermometry. The isotope ratios of Mg in ALC meteorites and their silicate minerals are within the range of chondritic meteorites, with only accessory spinel group minerals having significantly different compositions. Overall, the Mg and Fe isotopic signatures of the ALC species analyzed are in line with their formation as products of high‐degree thermal metamorphism and low‐degree partial melting of primitive precursors. The δ66/64Zn values of the ALC meteorites demonstrate a range of ~3.5‰ and the Zn is overall isotopically heavier than in chondrites. The superchondritic Zn isotopic signatures have possibly resulted from evaporative Zn losses, as observed for other meteorite parent bodies. This is unlikely to be the result of PB differentiation processes, as the Zn isotope ratio data show no covariation with the proxies of partial melting, such as the mass fractions of the platinum group and rare earth elements.

Balancing the oceanic Zn isotope budget: The key role of deep-sea pelagic sediments

Abstract Oxygenated deep-sea pelagic sediments with Fe-Mn–oxide particles represent a key oceanic oxic sink for transition metals in the modern ocean. However, the isotopic composition of authigenic Zn in the pelagic zone remains poorly constrained, which hampers our understanding of the global budget of Zn isotopes. Here, we analyzed the Zn isotopic compositions of two deep-sea pelagic sediment columns collected from the Pacific Ocean. The results show that authigenic Zn in deep-sea sediments is primarily hosted by the Fe-Mn (oxyhydr)oxides. The light Zn isotopic signatures (δ66Zn: −0.02‰ to 0.34‰, n = 42; computed as the per mille deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard) observed in deep-sea sediments are completely different from the previously assumed values of ~1.0‰ based on the Zn isotopic compositions of Fe-Mn crusts and nodules. Based on this observation (Zn flux of deep-sea sediments = 5.3 × 108 mol yr–1), we propose a new, balanced global budget for Zn isotopes.

Spatiotemporal and multi-isotope assessment of metal sedimentation in the Great Lakes

This study investigates spatiotemporal dynamics in metal sedimentation in the North American Great Lakes and their underlying biogeochemical controls. Bulk geochemical and isotope analyses of n = 72 surface and core sediment samples show that metal (Cu, Zn, Pb) concentrations and their isotopic compositions vary spatially across oligotrophic to mesotrophic settings, with intra-lake heterogeneity being similar or higher than inter-lake (basin-scale) variability. Concentrations of Cu, Zn, and Pb in sediments from Lake Huron and Lake Erie vary from 5 to 73 mg/kg, 18–580 mg/kg, and 5–168 mg/kg, respectively, but metal enrichment factors were small (<2) across the surface- and core sediments. The isotopic signatures of surface sediment Cu (δ65Cu between −1.19‰ and +0.96‰), Zn (δ66Zn between −0.09‰ and +0.41‰) and Pb (206/207Pb from 1.200 to 1.263) indicate predominantly lithogenic metal sourcing. In addition, temporal trends in sediment cores from Lake Huron and Lake Erie show uniform metal concentrations, minor enrichment, and Zn and Pb isotopic signatures suggestive of negligible in-lake biogeochemical fractionation. In contrast, Cu isotopic signatures and correlation to chlorophyll and macronutrient levels suggest more differentiation from source variability and/or redox-dependent fractionation, likely related to biological scavenging. Our results are used to derive baseline metal sedimentation fluxes and will help optimize water quality management and strategies for reducing metal loads and enrichment in the Great Lakes and beyond.

Assessment of particulate Zn and Pb sources in the Orne watershed (Northeast France) using geochemical tools.

The Orne River, a tributary of the Moselle River, was highly impacted by industrial activities for more than one century. Land use along the Orne River is highly contrasted, with local specificity from its source to its junction with the Moselle River. The intense industrial activity left behind tons of steelmaking wastes (SMW) on the land surface and within the Orne riverbed. To assess the sources of particulate Zn and Pb transported as suspended sediment in the Orne River, different sets of samples from likely Zn- and Pb-bearing particle sources within the Orne watershed were collected. Three sets of samples were taken from potential sources representing detrital, urban, and inherited industrial particles. Mineralogy, element contents, and Zn and Pb isotope compositions were obtained to characterize and reveal the fingerprint of each set of samples. Soil samples were collected on distinct geomorphological areas characterized by different soil types and land uses. They all display detrital minerals assigned to the geological background. Urban dusts and steelmaking residues display specific mineral phases (sulfates and iron oxides, respectively). Element compositions present strong discrepancies between the distinct sets of samples. SMWs are particularly enriched in Fe, Zn, and Pb. Concerning isotopic composition, SMWs exhibit δ66Zn values ranging from - 0.67 to 1.66‰. Urban samples display δ66Zn values between - 0.11 and 0.13‰, and soils present δ66Zn values between - 0.24 and 0.47‰. The 206Pb/204Pb ratio was estimated to range from 17.550 to 18.807 for soils, from 17.973 to 18.219 for urban samples, and from 18.313 to 18.826 for SMWs. For each of the three sets of samples (soils, urban, industrial), variations of geochemical fingerprint were observed. For soils, the relatively large variations of Zn and Pb isotopic compositions were attributed to distinct land use and the contribution of atmospheric deposition. For industrial samples, the variations were more intense and may be attributed either to distinct industrial processes in the production of pig iron or to distinct furnace-flume treatment modes. The three sets of samples (urban, industrial, and detrital) could be distinguished based on Zn and Pb contents and isotopes. Finally, this study not only highlighted the sources that released particulate Zn and Pb into the Orne River system, it also demonstrated that urban particles are well defined in terms of Zn and Pb isotopic signatures, and those isotopic signatures could be extrapolated to other case studies.

Zinc, carbon, and oxygen isotopic variations associated with the Marinoan deglaciation

The "Snowball Earths" were cataclysmic events during the late Neoproterozoic's Cryogenian period (720-635 Ma) in which most, if not all, of Earth’s surface was covered in ice. Paleoenvironmental reconstructions of these events utilize isotopic systems, such as Δ17O and barium isotopes of barites. Other isotopic systems, such as zinc (Zn), can reflect seawater composition or environmental conditions (e.g., temperature changes) and biological productivity. We report here a multi-isotopic C, O, and Zn data set for carbonates deposited immediately after the Marinoan glaciation (635 Ma) from the Otavi Group in northern Namibia. In this study, we chemically separated calcite and non-calcitic carbonate phases, finding isotopically distinct carbon and oxygen isotopes. These could reflect changes in the source seawater composition and conditions during carbonate formation. Our key finding is largescale Zn isotopic variations over the oldest parts of the distal foreslope cap carbonate sections. The magnitude of variation is larger than any found throughout post-snowball cap carbonates to date, and in a far shorter sequence. This shows a heretofore undiscovered difficulty for Zn isotopic interpretations. The primary Zn sources are likely to be aeolian or alluvial, associated with the massive deglaciation related run-off from the thawing continent and a greater exposed surface for atmospheric aerosol entrainment. The samples with the lightest Zn isotopic compositions (δ66Zn < 0.3 ‰) potentially reflect hydrothermally sourced Zn dominating the carbonates’ Zn budget. This finding is likely unique to the oldest carbonates, when the meltwater lid was thinnest and surface waters most prone to upwelling of hydrothermally dominated Snowball Earth brine. On the other hand, local variations could be related to bioproductivity affecting the Zn isotopic composition of the seawater. Similarly, fluctuations in sea-level could bring the depositional site below and above a redoxcline, causing isotopic variations. These variations in Zn isotope ratios preclude the estimation of a global Zn isotopic signature, potentially indicating localized resumption of export production.

Transition from tholeiitic to alkali basalts via interaction between decarbonated eclogite-derived melts and peridotite

Intraplate basalts generally show a geochemical continuum from alkali to tholeiitic basalts. However, the genetic link between these two types of rocks has remained controversial. The Early Jurassic Karamay basalts in the West Junggar terrane, southern Central Asian Orogenic Belt (CAOB), erupted to form a small-volume outcrop in the stable continental intraplate region. The basalts are characterized by aphyric textures without any visible phenocrysts. Thus, they are different from the ubiquitous porphyritic-textured intraplate basalts and have a composition close to that of the mantle-derived primary melt. In contrast to chemically and petrographically well-defined alkali and tholeiitic basalts, the Karamay basalts exhibit transitional compositions spanning from alkali (with normative olivine+nepheline and normative olivine+hypersthene) to tholeiitic (with normative quartz+hypersthene), providing an important case to address the geochemical continuum of intraplate basalts. Similar to the alkali basalts in eastern China, the Karamay basalts have isotopic imprints of sedimentary carbonates, i.e., significantly lighter Mg (δ26Mg = −0.54‰ to −0.34‰) and heavier Zn (δ66Zn = 0.36–0.46‰) isotopes than the normal mantle. However, they display initial ((87Sr/86Sr)t ratios of 0.7047–0.7051, positive εNd(t) values (3.3–4.2) and positive anomalies of Nb-Ta-Ti-Zr-Hf, which are not expected in the case of incorporation of recycled carbonates. This contradiction can be reconciled by considering a decarbonation reaction between carbonates (i.e., dolomite and magnesite) and co-existing eclogite in the subducted oceanic slab at pressure >5 GPa, leaving light Mg and heavy Zn isotope signatures in the stagnant eclogite residue in the deep mantle. Combining the geochemical compositions of our samples with the geologic evidence, and considering the previous results of melt-peridotite reaction experiments, we conclude that the Karamay basalts might have originated from the interaction of silica-rich tholeiitic melt derived from the recycled decarbonated eclogite with fertile peridotite during its ascent. Our study highlights that intraplate alkali basalts, especially silica-rich ones (e.g., with SiO2>45 wt.%), can be transformed from tholeiitic melts through reaction with peridotite mantle, and demonstrates that deeply recycled oceanic crust stagnated in mantle can serve as a main source for alkaline lavas.

Zn stable isotope fractionation during adsorption onto todorokite: A molecular perspective from X-ray absorption spectroscopy and density functional theory

Mineral-solution interface reactions control the mobility and fate of trace metals (e.g., Zn) and may drive their associated isotopic fractionation in the natural environment, but understanding the coupling between interfacial reactions and isotopic behavior requires a molecular-level understanding of these processes. In this study, we investigate Zn stable isotope fractionation during adsorption to todorokite as a function of reaction time, pH and Zn concentrations. We show that Zn stable isotope fractionation reaches equilibrium at ∼12 h reaction time at pH 6 and Zn concentrations of 0.05 mM. For Zn concentrations of 0.05 and 0.2 mM, Zn isotopic fractionation between adsorbed and aqueous Zn (Δ66Znadsorbed-aqueous) is approximately −0.1 ± 0.04‰ at pH 3–5, and Δ66Znadsorbed-aqueous gradually increases from −0.1 ± 0.04‰ to 0.05 ± 0.05‰ at higher pH 6–8. Extended X-ray absorption fine structure (EXAFS) spectroscopy shows that Zn adsorbs to the todorokite surface as an outer-sphere octahedral complex with an average ZnO interatomic distance of 2.06 Å at pH 3. In contrast, Zn is predominantly present as a tetrahedral coordinated structure with a shorter average ZnO interatomic distance of ∼2.00–2.05 Å at pH 6 and 8, suggesting the presence of a mixture of octahedral outer-sphere and tetrahedral inner-sphere surface complexes. Density functional theory calculations suggest that outer-sphere surface complexes exist in the center of the structural tunnels of todorokite, yielding a theoretical Zn isotopic fractionation (Δ66Znadsorbed-aqueous) of −0.2‰ to −0.3‰, whereas the tetrahedral inner-sphere surface complex results in a large Δ66Znadsorbed-aqueous of +0.5‰ to +0.8‰. Combined laboratory experiments and theoretical calculations demonstrate that different magnitudes of Zn isotopic fractionation are controlled by structural changes (e.g., coordination and bond distance) in the Zn surface complexes formed on todorokite relative to its aqueous form (i.e., aqua Zn(H2O)62+). These results provide important new constraints for understanding Zn isotope signatures in natural Mn-rich sediments and lead to a more complete understanding of Zn isotopes in the ocean.

A nationwide survey of trace metals and Zn isotopic signatures in mussels (Mytilus edulis) and oysters (Crassostrea gigas) from the coast of South Korea

Thirteen trace metals and Zn isotopic signatures were investigated in mussels and oysters collected from the coast of South Korea to evaluate their bioavailability in bivalve mollusks. The average Cu, Zn, and Cd concentrations were 2.6–17.7 times higher in oysters than mussels, and high biota sediment accumulation factors (>30) were observed for these metals in oysters. Except for Pb in mussels, most metals had no correlation with total sediment concentrations. In oysters, Fe, V, Cu, Zn, Sn, and Pb concentrations were significantly correlated with sediments. The average values of δ66ZnIRMM3702 in mussels, oyster, and sediments were +0.09‰, +0.12‰, and −0.06‰, respectively. Soft tissues of mussels and oysters with high Zn concentrations tended to contain lighter Zn isotopes. The results indicate that oysters are a better biomonitoring organism for metal contamination than mussels and can be used in the monitoring and management of coastal environments and ecosystems.

Characteristics of potentially toxic elements and multi-isotope signatures (Cu, Zn, Pb) in non-exhaust traffic emission sources

Non-exhaust emissions (e.g., particles from brake pads, asphalt, curb, road paint, tire) are important sources of potentially toxic elements (PTEs) pollution in urban environments and are potential causes of PTEs pollution in road dust. We present the PTEs concentrations (Cr, Ni, Cu, Zn, As, Cd, Sn, Sb, Pb) of non-exhaust emission sources and pollution degree of PTEs. Isotopic signatures of Cu, Zn, and Pb were also analyzed to distinguish these sources. Among PTEs, the Cu concentration in all brake pads was significantly high and brake pads from Korea showed remarkably high Sb concentrations. Asphalt had a higher Pb concentration than other non-exhaust emission sources. Mean of δ65CuAE647, δ66ZnIRMM3702, and 206Pb/207Pb values of non-exhaust emission sources in this study ranged from −0.49‰ to +0.19‰, −0.24‰ to +0.16‰, and 1.1535 to 1.4471, respectively. Non-exhaust emission sources could be discriminated by plotting the concentration and isotopic composition of Cu. Cu isotopic compositions (δ65CuAE647) were clearly distinguished between brake pads including domestic and imported products and tires. Zn isotope values (δ66ZnIRMM3702) of brake pads, tires, and asphalt overlapped, but discriminated from road paint and curb. Our results indicate that the combination of Cu and Zn isotopic signatures can distinguish various non-exhaust traffic emissions, especially brake pads and tires.

The isotopic composition of sedimentary organic zinc and implications for the global Zn isotope mass balance

Zinc (Zn) is a bioessential element whose cycling in the marine environment is closely linked to the biological pump. As a vital micronutrient, Zn is depleted in marine surface waters and enriched in deep waters. This has given rise to the longstanding hope that Zn could serve as a robust paleoproductivity proxy. There has been a recent focus on how Zn isotope signatures can be used to track the evolution of the biological pump. However, the factors controlling variations in the sedimentary Zn isotope composition of core-top sediments are debated and these values are influenced by changes in the relative contributions of biological uptake and scavenging processes and by mineral fractionations. In order to provide a new perspective on the Zn isotopic signature of marine core-top sediments and their potential for tracing ocean biogeochemical processes, we developed a sample preparation procedure to extract organically bound Zn (excluding inorganic Zn) without a significant isotope fractionation. We tested five potential organic solvents and found that the isopropanol extraction procedure provided a reproducible and robust result that yielded the highest recovery rate of organically bound Zn without a significant associated isotopic fractionation and appeared to exclude common mineral bound forms of Zn. This extraction procedure was used to analyze the Zn concentrations and isotopic compositions (δ66Zn) of core-top sediment samples from Long Island Sound and the Peruvian continental margin. Our results suggest that the δ66Zn value of organic Zn increases with water depth, thus providing additional support for the finding that burial of isotopically light Zn occurs predominantly in shallow high-productivity sediments. However, we also found that the δ66Zn values of the estimated authigenic Zn component are consistently lighter than those of the organic Zn fraction, consistent with diagenetic (sediment pile) scavenging of organic derived Zn in sulfides imparting an isotope fractionation.

Fingerprinting the Cretaceous-Paleogene boundary impact with Zn isotopes

Numerous geochemical anomalies exist at the K-Pg boundary that indicate the addition of extraterrestrial materials; however, none fingerprint volatilization, a key process that occurs during large bolide impacts. Stable Zn isotopes are an exceptional indicator of volatility-related processes, where partial vaporization of Zn leaves the residuum enriched in its heavy isotopes. Here, we present Zn isotope data for sedimentary rock layers of the K-Pg boundary, which display heavier Zn isotope compositions and lower Zn concentrations relative to surrounding sedimentary rocks, the carbonate platform at the impact site, and most carbonaceous chondrites. Neither volcanic events nor secondary alteration during weathering and diagenesis can explain the Zn concentration and isotope signatures present. The systematically higher Zn isotope values within the boundary layer sediments provide an isotopic fingerprint of partially evaporated material within the K-Pg boundary layer, thus earmarking Zn volatilization during impact and subsequent ejecta transport associated with an impact at the K-Pg.

Zinc isotopic fractionation between aqueous fluids and silicate magmas: An experimental study

Fluids in magmas play a key role in magma differentiation and transportation of economic metals for ore deposits. As a chalcophile and incompatible element, zinc and its isotopes have been increasingly applied to study the magmatic-hydrothermal processes. However, zinc isotopic fractionation between aqueous fluids and magmas has not been well constrained. Here we experimentally determined equilibrium fractionation factors of Zn isotopes between aqueous fluids and silicate magmas (Δ66Znfluid-magma = δ66Znfluid – δ66Znmagma). The results reveal that aqueous fluids are isotopically heavier than the coexisting silicate magmas. No correlation between Δ66Znfluid-magma and temperature or chlorine contents in fluids is observed under our experimental conditions. Instead, Δ66Znfluid-magma is negatively corresponded with NBO/T of the melt (the ratio of non-bridge oxygen and tetrahedron ions), and positively correlated with the molar ratio of Al/(0.5 K + Ca + Fe) in the bulk magmas, suggesting the controlling of silicate composition on Zn isotope fractionation. Our data therefore indicate that the isotopically heavier Zn in the fluids exsolved from magmas may account for the higher δ66Zn of pegmatites and high-silica granitic rocks. Moreover, involvement of magmatic fluids can explain the highly variable and remarkably heavier Zn isotopic signatures of fumaroles, thermal spring waters, and seafloor hydrothermal fluids compared to the igneous rocks. This study provides information that can be used to guide research using Zn isotopes to trace fluid activity and magmatism.

Improving Source Apportionment of Urban Aerosol Using Multi-Isotopic Fingerprints (MIF) and Positive Matrix Factorization (PMF): Cross-Validation and New Insights

Urban air pollution is a matter of concern due to its health hazards and the continuous population growth exposed to it at different urban areas worldwide. Nowadays, more than 55% of the world population live in urban areas. One of the main challenges to guide pollution control policies is related to pollutant source assessment. In this line, U.S. Environmental Protection Agency's Positive Matrix Factorization (EPA-PMF) has been extensively employed worldwide as a reference model for quantification of source contributions. However, EPA-PMF presents issues associated to source identification and discrimination due to the collinearities among the source tracers. Multi-Isotopic Fingerprints (MIF) have demonstrated good resolution for source discrimination, since urban sources are characterized by specific isotopic signatures. Source quantification based on total aerosol mass is the main limitation of MIF. This study reports strategies for PMF and MIF combination to improve source identification/discrimination and its quantification in urban areas. We have three main findings: (1) cross-validation of PMF source identification based on Pb and Zn isotopic fingerprints, (2) source apportionment in the MIF model for total PM mass, and (3) new insights into potential Zn isotopic signatures of biomass burning and secondary aerosol. We support future studies on the improvement of isotopic fingerprints database of sources based on diverse elements or compounds to boost advances of MIF model applications in atmospheric sciences.

Determining sedimentary material sources in a Brazilian urban lake using Zn stable isotope compositions of bottom sediments: a preliminary study

Zinc isotopes ratios provide qualitative and quantitative information about contributions from different Zn sources in the environment. Here we present the results of a preliminary study to identify the main sources controlling Zn isotope signatures of sediments from Lake Paranoá (Brazil), an urban water reservoir. The Zn isotope ratios were measured by MC-ICP-MS and expressed as δ66/64Zn notation relative to the JMC 3-0749-L solution. The studied sediments showed a narrow isotopic range (+0.00 to +0.13 ‰; n = 10) similar to that reported for intensely weathered soils worldwide (from -0.4 to +0.2‰). The geoaccumulation index (Igeo) also suggests low or negligible influence of Zn anthropogenic source. This research provides a baseline assessment of the Zn isotopes signatures in lake sedimentary environments under the influence of these weathered soils.

Tracking anthropogenic sources in a small catchment using Zn-isotope signatures

Tracking metal pollution in surface water is a major environmental, public-health and economic issue. Knowledge of the behaviour of metals such as zinc (Zn), in stream sediments and water, is a key factor to improving river water quality. Because the isotopic compositions of Zn can be used as an environmental tracer for tracking the sources of man-made materials and its transport into water and soil, we have used Zn isotopes for studying the anthropogenic impact on a watershed. As a case study, we chose a small watershed in the Loire River basin, near Orléans (France). The Egoutier spring issues in a pristine area, but its water is affected a few kilometres downstream by liquid effluents from a wastewater treatment plant (WWTP) and farther down still by diffuse pollution from road traffic. We sampled the liquid effluents as well as water and sediments along an upstream to downstream transect. For liquid samples, we took “grab” samples and integrated samples using passive DGT (Diffusive Gradients in Thin films) samplers. The advantages of DGT are (1) to pre-concentrate in-situ the Zn dissolved in water—avoiding a time-consuming chemical preparation—and (2) to integrate the potential variations of Zn isotopic signature over time. The mobile fraction of sediments—that released by the leaching in 0.2N HCl—was also investigated. The δ66/64Zn values in water and sediments along the upstream/downstream profile clearly showed the anthropogenic input of WWTP effluents in the river, which was still visible several kilometres downstream in water. This dissolved anthropogenic contribution is easily transported along the transect and only slightly fixed by adsorption on sediments, probably due to their low clay-mineral content. For the farthest downstream sample, affected by road traffic, the pollution source is difficult to discern due to the similar δ66/64Zn values in WWTP effluents and in road-traffic particles. Here, the use of DGT has proved to be a major asset: during a rainfall event, road traffic particles were leached by rainwater, forming runoff with a relatively high Zn content that flowed into the river, and DGT monitoring showed it to be an adequate method for discerning discontinuous anthropogenic input into the river water.

Behavior of metallurgical zinc contamination in coastal environments: A survey of Zn from electroplating wastes and partitioning in sediments

The contamination of coastal environments by metallurgical wastes involves multiple biogeochemical processes; accordingly, understanding metal behavior and risk evaluation of contaminated areas, such as Sepetiba Bay (Rio de Janeiro, Brazil), remains challenging. This study coupled Zn isotopic analyses with sequential extractions (BCR) to investigate the mechanisms of Zn transfer between legacy electroplating waste and the main environments in Sepetiba Bay. This metallurgical waste showed a light bulk isotopic signature (δ66/64ZnbulkJMC = +0.30 ± 0.01‰, 2 s, n = 3) that was not distinct from the lithogenic geochemical baseline, but was different from signature of mangrove sediment considered as anthropogenic end member (δ66/64ZnJMC = +0.86 ± 0.15‰) in a previous isotopic study in this area. Zn isotopic compositions of sediment samples (ranging from +0.20 to +0.98‰) throughout the bay fit a mixing model involving multiple sources, consistent with previous studies. In the metallurgic zone, the exchangeable/carbonate fraction (ZnF1) exhibited high Zn concentrations (ZnF1 = 9840 μg g−1) and a heavy isotopic composition (δ66/64ZnF1JMC = +1.10 ± 0.01‰). This finding showed that, in some cases, the bulk isotopic signature of waste is not the most relevant criterion for evaluating trace metal dispersion in the environment. Indeed, based on the BCR, it was observed that part of the anthropogenic metallurgical Zn was redistributed from the exchangeable/carbonate fraction in the waste to the surrounding mangrove sediment. Then, this contaminated sediment with heavy δ66/64Zn values was exported to other coastal environments. In Sepetiba Bay, contaminated sediments revealed a large concentration of ZnF1 fraction (up to 400 μg g−1) with a heavy Zn isotopic signature. This signature also matched the Zn isotopic signature of oysters in Sepetiba Bay reported by other studies; hence, measurement of the isotopic exchangeable/carbonate fraction has important implications for tracing the transfer of anthropogenic Zn to biota.

Using Zn Isotopic Signatures for Source Identification in a Contaminated Estuary of Southern China.

Zinc isotope ratios in water and suspended particles (SP) were measured in the Pearl River Estuary (PRE), China. Site-to-site δ66Zn values in water varied by approximately 1.3‰ (i.e., -0.66‰ to 0.65‰ relative to IRMM-3702 in August 2017). There were larger variations in δ66Zn values in water collected from the east shore (i.e., -0.66‰ to 0.37‰) of the PRE close to industrialized areas, in comparison to those from the western shore (i.e., -0.23‰ to 0.13‰), indicating that the PRE was influenced by different Zn sources. The variations in δ66Zn values in water from estuarine locations were much larger than those collected from river mouths. Similarly, larger variations in δ66Zn values were observed in suspended particles (i.e., -1.45‰ to 0.63‰) relative to the water. Zinc isotopic differences (i.e., Δ66Zn‰) between particles and water were significantly (p < 0.05) and linearly correlated with Zn concentrations in particles between 0.8 and 10 μm in size at most of the estuary stations, suggesting that Zn partitioning between dissolved and particulate phases influences the observed differences in Zn isotope ratios. A significant (p < 0.0001) linear correlation between the predicted δ66Zn values (using variations in water salinities) vs observed δ66Zn values indicates that Zn isotope ratios in water in the PRE can be useful for predicting the mixing processes in the water.

Isotope geochemistry of Zn, Pb and S in the Ediacaran strata hosted Zn-Pb deposits in Southwest China

The Sichuan–Yunnan–Guizhou (SYG) area is a world-class Zn-Pb metallogenic zone and contains over four hundred of carbonate-hosted hydrothermal Zn-Pb deposits, six of which are super large-scale deposits with significant sources of Cd, Ge, and Ag, including the Huize, Wusihe, Xiaoshifang, Maozu, Tianbaoshan and Daliangzi deposits. Although previous studies focused fully on these deposits, the ore genesis of which are still in controversial. Interestedly, four of those super large scale deposits are hosted in the Ediacaran Dengying Formation, including the Maozu, Wusihe, Tianbaoshan and Daliangzi deposits. Based upon previous studies, we investigate the extent, causes and consequences of Zn and Pb isotope signatures at hand specimen scale and ore genesis of the Daliangzi and Tianbaoshan deposits, associated with published data for the Wusihe deposit. Lead isotope ratios, coupled with published data, demonstrate that Pb in the studied deposits was predominantly derived from two components: basements and sedimentary rocks. Meanwhile, a strong positive linear correlation between δ66Zn and δ34SCDT values was observed in hand specimen D-2084, suggesting the variations may be resulted by fluid mixing. Furthuremore, the Zn isotope and Cd/Zn dataset from the Tianbaoshan, Daliangzi and Wusihe deposits defines a logarithmic curve (R2 = 0.82), which, to our knowledege, is firstly reported and lies between two indentified components: a low Cd/Zn end-member with high δ66Zn values and a high Cd/Zn end-member with low δ66Zn values. Based upon previous studies, we suggest that Zn and Pb in the Wusihe and Tianbaoshan deposits were predominantly derived from basements and Ediacaran sediments; in contrast, Zn and Pb in the Daliangzi deposit were predominantly derived from Ediacaran sediments and upper sedimentary rocks, but we cannot rule out metal contributions of the basements. Furthermore, we suggest that fluid mixing is more propreate to better explain Zn isotope signatures in the studied deposits.In summary, Zn and Pb isotope ratios reflect similar ore genesis and metal sources of the Daliangzi, Tianbaoshan and Wusihe Zn-Pb deposits in the SYG area. The application to the studied deposits with the discovery of Zn, S and Pb isotope compositions for sulfides indicates the potential of Zn isotope, combined with Cd/Zn raito, as new geochemical tracers, which may be useful for distinguishing the metal sources in large hydrothermal systems as suggested previously.

Extreme Mg and Zn isotope fractionation recorded in the Himalayan leucogranites

High-silica granites (typically > 70 wt.% SiO2) represent the products of extreme crustal differentiation, but whether their distinctive chemical compositions reflect source lithology or are produced via magmatic differentiation is commonly difficult to discriminate. To provide new insights into this issue, here we present high-precision Mg and Zn isotope data for high-silica, peraluminous leucogranites from the Himalayan orogen. The samples are subdivided into two-mica leucogranite, tourmaline leucogranite and garnet-bearing leucogranite based on their mineral assemblages. The two-mica leucogranites, representing the least evolved Himalayan leucogranites, have similar δ66ZnJMC 3-0749L (mean = 0.31 ± 0.06‰) but heavier δ26MgDSM-3 values (mean = −0.01 ± 0.12‰) relative to more mafic igneous rocks. This indicates that they were formed by anatexis of weathered silicates, consistent with the well-acknowledged metasedimentary source of the Himalayan leucogranites. In contrast, the more evolved tourmaline leucogranites and garnet-bearing leucogranites have lower δ26Mg and higher δ66Zn values compared with the two-mica leucogranites. The extremely low δ26Mg (−1.32‰ to −0.54‰) and high δ66Zn values (0.35–0.69‰) of garnet-bearing leucogranites vary systematically with indices of granitic differentiation (e.g., Zr/Hf, K/Rb, Eu/Eu*, 1/TiO2). Although exsolution of chlorine-rich fluid may result in elevated δ66Zn values, it is unlikely to explain the low δ26Mg signatures of the same samples. Analysis of major Mg-bearing minerals suggests that substantial segregation of tourmaline and/or Fe-Ti oxide could have driven the differentiated leucogranites towards very low δ26Mg values. In this regard, the slightly lower δ26Mg values (mean = −0.17 ± 0.06‰) of tourmaline leucogranites relative to the two-mica leucogranites may also reflect that the former were more differentiated than the latter. Thus, although source heterogeneity may be responsible for the Mg isotopic variations observed in some high-silica granites, our study implies that high-silica granites could be remarkably heterogeneous in terms of Mg isotopes primarily as a result of prolonged fractional crystallization at the late stage of melt evolution. The anomalously light Mg and heavy Zn isotopic signatures of garnet-bearing leucogranites highlight that Mg and Zn isotopes may be treated as important makers of highly fractionated granites in future studies.