Zinc and copper isotope fractionation in metal leaching from hydrothermal ore deposits: Environmental implications for deep-sea mining.

Deep-sea mining can remobilize large amounts of inert metals from hydrothermal seafloor massive sulfides (SMSs) into bioavailable toxic forms that are dissolved in the water column, potentially impacting marine ecosystems. It is thus critical to assess the impacts of deep-sea mining on the reactivities and behaviors of crucial elements (e.g., Zn and Cu) and their isotopes during mineral leaching processes. To this end, we conducted leaching experiments using different SMS mineral types (CuFe rich, Fe rich, and ZnFe rich) to assess metal releases and the isotope fractionations of Zn and Cu. Significant correlations were observed between Ni, Cu, Zn, Cd, and Pb concentrations in leachates and the SMSs, suggesting that metal leaching into seawater depended on individual SMS metal content. The Zn and Cu concentrations in leachates varied greatly by both SMS type and the leaching time. Zn concentrations from ZnFe rich SMSs exceeded the recommended effluent limits set by the IFC World Bank and the USEPA. SMS ore leachates exhibited Cu and Zn isotope ratios distinct from those of Indian Ocean deep seawater. The isotope fractionation magnitude (Δore-seawater) of Cu was more pronounced than that of Zn, likely due to the redox process involved in the leaching processes. In contrast, the Zn isotope signatures in leachates conserve those of minerals, although slight isotope fractionations occurred in solution following the adsorption and precipitation processes of Fe-oxyhydroxides. Our findings confirm that leveraging the chemical and isotope signatures of toxic metals offers a valuable approach for assessing the extent of metal contamination of leachates and mine tailings stemming from deep-sea mining operations, concerning their influence on the surrounding water columns.

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.

Seasonal and multi-decadal zinc isotope variations in blue mussels from two sites with contrasting zinc contamination levels.

Zinc (Zn) isotope compositions in soft mussel tissues help identify internal biological processes and track coastal Zn sources in coastal environments, thus aiding in managing marine metal pollution. This study investigated the seasonal and multi-decadal Zn isotope compositions of blue mussels (genus Mytilus) from two French coastal sites with contrasting Zn environmental contamination. Concurrently, we characterized the isotope ratios of sediments and plankton samples at each site to understand the associations between organisms and abiotic compartments. Our primary objective was to determine whether these isotope compositions trace long-term anthropogenic emission patterns or if they reflect short-term biological processes. The multi-decadal isotope profiles of mussels in the Loire Estuary and Toulon Bay showed no isotope variations, implying the enduring stability of the relative contributions of natural and anthropogenic Zn sources over time. At seasonal scales, Zn isotope ratios were also constant; hence, isotope effects related to spawning and body growth were not discernible. The multi-compartmental analysis between the sites revealed that Toulon Bay exhibits a remarkably lower Zn isotope ratio across all studied matrices, suggesting the upward transfer of anthropogenic Zn in the food web. In contrast, the Zn isotope variability observed for sediments and organisms from the Loire Estuary fell within the natural baseline of this element. In both sites, adsorptive geogenic material carrying significant amounts of Zn masks the biological isotope signature of plankton, making it difficult to determine whether the Zn isotope ratio in mussels solely reflects the planktonic diet or if it is further modified by biological homeostasis. In summary, Zn isotope ratios in mussels offer promising avenues for delineating source-specific isotope signatures, contingent upon a comprehensive understanding of the isotope fractionation processes associated with the trophic transfer of this element through the plankton.

Copper and zinc isotope systematics in different bivalve mollusk species from the French coastline: Implications for biomonitoring.

Zinc (Zn) and copper (Cu) stable isotopic compositions have been analyzed in various species of bivalve mollusks worldwide, but no comprehensive systematic interspecies comparison exists. Thus, we assessed isotope differences between species harvested in emblematic French coastal ecosystems to unveil biologically driven Cu and Zn isotope fractionation patterns. Inter-species isotopic variability of Cu is larger than Zn, with organisms that regulate internal concentrations displaying preferential bioaccumulation of heavy isotopes. The degree of internal isotope fractionation decreases from mussels > clams > oysters, affecting Cu more than Zn. The less pronounced Zn inter-specie variability helps preserve source information more reliably. Spatial analysis of a single oyster species denotes thus an important isotope variability of environmental Zn sources, including natural, anthropogenic and dietary components. Overall, results highlight the importance of considering systematic offset in Cu and Zn isotope values when comparing data from different bivalve species.

The French Mussel Watch Program reveals the attenuation of coastal lead contamination over four decades.

The mid-20th century industrial peak caused severe global lead (Pb) marine contamination. Although Europe initiated Pb emission reduction regulations in the 1980s, the short- and long-term impacts remain unclear. This study investigates the evolution of Pb contamination on the French coast through elemental and isotope analysis in oysters and mussels from the French "Mussel Watch" Program. Observations at 114 monitoring stations over four decades have shown decreasing Pb levels in these bivalve mollusks. In 1988, 95 % exceeded the background reference values; this level had dropped to 39 % by 2021. The Pb isotope ratios in bivalves from eight target sites revealed a reduction in bioaccumulated anthropogenic Pb, albeit without complete elimination. The long residence time of legacy Pb combined with inputs from diffuse urban sources likely explains the persistent presence of anthropogenic Pb on the French coast. This study endorses the importance of continuous biomonitoring to evaluate environmental regulations and policies.

Contrasting copper concentrations and isotopic compositions in two Great Lakes watersheds.

Copper (Cu) stable isotopes can elucidate the biogeochemical controls and sources governing Cu dynamics in aquatic environments, but their application in larger rivers and catchments remains comparatively scarce. Here, we use major and trace element hydrogeochemical data, Cu isotope analyses, and mixing modeling, to assess Cu loads and sources in two major river systems in Ontario, Canada. In both the Spanish River and Trent River catchments, aqueous hydrochemical compositions appeared reasonably consistent, but Cu concentrations were more variable spatially. In the Spanish River, waters near (historic) industrial mining activities displayed positive Cu isotope compositions (δ65CuSRM-976 between +0.75 ‰ and +1.01 ‰), but these signatures were gradually attenuated downstream by mixing with natural background waters (δ65Cu -0.65 ‰ to -0.16 ‰). In contrast, Trent River waters exhibited more irregular in-stream Cu isotope patterns (δ65Cu from -0.75 ‰ to +0.21 ‰), beyond the variability in Cu isotope signatures observed for adjacent agricultural soils (δ65Cu between -0.26 ‰ and +0.30 ‰) and lacking spatial correlation, reflective of the more diffuse sourcing and entwined endmember contributions to Cu loads in this catchment. This work shows that metal stable isotopes may improve our understanding of the sources and baseline dynamics of metals, even in large river systems.

Copper and lead isotope records from an electroplating activity in sediments and biota from Sepetiba Bay (southeastern Brazil).

An old electroplating plant in Sepetiba Bay discharged metal-enriched wastes into the surrounding mangroves for 30 years (from the 1960s to 1990s), resulting in a hotspot zone of legacy sediments highly concentrated in toxic trace metals. This study applies Cu and Pb isotope systems to investigate the contributions of past punctual sources relative to emerging modern diffuse sources. The electroplating activity imprinted particular isotopic signatures (average δ65CuSRM-976: 0.4 ‰ and 206Pb/207Pb: 1.14) distinct from the natural baseline and urban fluvial sediments. The isotopic compositions of tidal flat sediments show intermediate isotope compositions reflecting the mixing of Cu and Pb from the hotspot zone and terrigenous materials carried by rivers. Oyster isotope fingerprints match legacy sediments, attesting that anthropogenic Cu and Pb are bioavailable to the biota. These findings confirm the interest in combining two or more metal isotope systems to discriminate between modern and past metal source emissions in coastal environments.

Isotopic (Cu, Zn, and Pb) and elemental fingerprints of antifouling paints and their potential use for environmental forensic investigations.

Antifouling paints (APs) are one of the important sources of Cu and Zn contamination in coastal environments. This study applied for the first-time a multi-isotope (Cu, Zn, and Pb) and multi-elemental characterization of different AP brands to improve their tracking in marine environments. The Cu and Zn contents of APs were shown to be remarkably high ∼35% and ∼8%, respectively. The δ65CuAE647, δ66ZnIRMM3702, and 206Pb/207Pb of the APs differed depending on the manufacturers and color (-0.16 to +0.36‰, -0.34 to +0.03‰, and 1.1158 to 1.2140, respectively). A PCA analysis indicates that APs, tires, and brake pads have also distinct elemental fingerprints. Combining isotopic and elemental ratios (e.g., Zn/Cu) allows to distinguish the environmental samples. Nevertheless, a first attempt to apply this approach in highly urbanized harbor areas demonstrates difficulties in source apportionments, because the sediment was chemically and isotopically homogeneous. The similarity of isotope ranges between the harbor and non-exhaust traffic emission sources suggests that most metals are highly affected by urban runoff, and that APs are not the main contributors of these metals. It is suspected that AP-borne contamination should be punctual rather than dispersed, because of APs low solubility properties. Nevertheless, this study shows that the common coastal anthropogenic sources display different elemental and isotopic fingerprints, hence the potential for isotope source tracking applications in marine environments. Further study cases, combined with laboratory experiments to investigate isotope fractionation during releasing the metal sources are necessary to improve non-traditional isotope applications in environmental forensics.

Isotopic compositions of copper and zinc in plankton from the Mediterranean Sea (MERITE-HIPPOCAMPE campaign): Tracing trophic transfer and geogenic inputs.

This study uses Cu and Zn isotopic compositions as proxies of sources and metal transfers in the planktonic food webs from the Mediterranean Sea. Plankton was collected in spring 2019 in the deep chlorophyll maximum (DCM) along a North-South transect including coastal and offshore zones (MERITE-HIPPOCAMPE campaign). δ65Cu and δ66Zn were determined on four planktonic size fractions from 60 to 2000 µm. Combined δ65Cu and δ66Zn with geochemical tracers (Ti, particulate organic phosphorus) showed that geogenic particles were ubiquitous with plankton assemblages. The δ15N ecological tracer showed that planktonic food web was enriched in heavy isotopes of Cu and Zn in the higher trophic levels. δ65Cu were correlated with picoplankton in the offshore zone, and with zooplankton in the southern coastal zone. Firmicutes bacteria were found correlated with δ66Zn in northern and southern coastal zones suggesting decomposition of particulate matter at the DCM. These findings suggest that biogeochemical process may impact Cu and Zn isotopy in the planktonic community.

Cu isotope records of Cu-based antifouling paints in sediment core profiles from the largest European Marina, The Port Camargue.

The intensive use of copper (Cu) compounds as an alternative biocide in antifouling paints (APs) has resulted in wide Cu contamination into the marine environment, especially near marina harbor activities. In this work, the applicability of Cu isotopes to discriminate Cu origins related to the use of Cu-based APs in marine environments was tested. To this, Cu isotopes in APs, shipyard sludges, and sediment cores sampled in the Cu-contaminated Mediterranean marina of Port Camargue were determined. APs represent an important dominant anthropogenic source for metals in this site, making it ideal to test Cu isotopes as tracers. The overall isotope composition of four sediment cores and a surface sample varied between -0.13 and 0.44 ‰ (δ65Cu relative to NIST-976). Selected APs brands show a similar Cu concentration ~0.15 % and δ65Cu average of 0.54 ± 0.05 ‰. The plot of δ65Cu vs concentration for all datasets allowed dissociating natural and APs end-members. However, sample isotope systematics were not consistent with a conservative mixing binary source process. Heavily Cu-contaminated sediments show isotope signatures lighter than APs brands. However, the most Cu-contaminated sample, located directly above the careening area, shows a δ65Cu slightly lighter than APs (0.44 ‰ vs 0.54 ‰, respectively). Results suggest the preferential releasing of a heavy isotope pool by APs when these compounds are solubilized in seawater. The isotope fractionation was attributed to potential chemical Cu coordination changes during its elemental partition between paint and marina seawater and the fractionation induced by the organic ligands in the water column, before deposition. Further laboratory experiments are recommended to model the isotope fractionation mechanisms related to Cu release by APs. Because the APs' isotope signature is modified in marine environments, the use of Cu isotopes as tracers of AP in marine environments is challenging and needs more investigation.

"Non-traditional" stable isotopes applied to the study of trace metal contaminants in anthropized marine environments.

The advent of Multicollector ICP-MS inaugurated the analysis of new metal isotope systems, the so-called "non-traditional" isotopes. They are now available tools to study geochemical and ecotoxicological aspects of marine metal contamination and hence, to push the frontiers of our knowledge. However, such applications are still in their infancy, and an accessible state-of-the-art describing main applications, obstacles, gaps, and directions for further development was missing from the literature. This paper fills this gap and aims to encourage the marine scientific community to explore the contributions of this newly available information for the fields of chemical risk assessment, biomonitoring, and trophic transfer of metal contaminants. In the current "Anthropocene" epoch, metal contamination will continue to threaten marine aquatic ecosystems, and "non-traditional" isotopes can be a valuable tool to detect human-induced changes across time-space involving metal contaminants, and their interaction with marine biota.

Metal stable isotopes in transplanted oysters as a new tool for monitoring anthropogenic metal bioaccumulation in marine environments: The case for copper.

Metal release into the environment from anthropogenic activities may endanger ecosystems and human health. However, identifying and quantifying anthropogenic metal bioaccumulation in organisms remain a challenging task. In this work, we assess Cu isotopes in Pacific oysters (C. gigas) as a new tool for monitoring anthropogenic Cu bioaccumulation into marine environments. Arcachon Bay was taken as a natural laboratory due to its increasing contamination by Cu, and its relevance as a prominent shellfish production area. Here, we transplanted 18-month old oysters reared in an oceanic neighbor area into two Arcachon Bay mariculture sites under different exposure levels to continental Cu inputs. At the end of their 12-month long transplantation period, the oysters' Cu body burdens had increased, and was shifted toward more positive δ65Cu values. The gradient of Cu isotope compositions observed for oysters sampling stations was consistent with relative geographic distance and exposure intensities to unknown continental Cu sources. A binary isotope mixing model based on experimental data allowed to estimate the Cu continental fraction bioaccumulated in the transplanted oysters. The positive δ65Cu values and high bioaccumulated levels of Cu in transplanted oysters support that continental emissions are dominantly anthropogenic. However, identifying specific pollutant coastal source remained unelucidated mostly due to their broader and overlapping isotope signatures and potential post-depositional Cu isotope fractionation processes. Further investigations on isotope fractionation of Cu-based compounds in an aqueous medium may improve Cu source discrimination. Thus, using Cu as an example, this work combines for the first time a well-known caged bivalve approach with metal stable isotope techniques for monitoring and quantifying the bioaccumulation of anthropogenic metal into marine environments. Also, it states the main challenges to pinpoint specific coastal anthropogenic sources utilizing this approach and provides the perspectives for further studies to overcome them.

Rare Earth Element in Bivalves' Soft Tissues of French Metropolitan Coasts: Spatial and Temporal Distribution.

Rare earth elements (REE) are becoming an environmental pollutant of emerging concern, linked to their use in various anthropic processes. Because REE bioconcentrate in marine organisms throughout their food webs, a better understanding of biogeochemical processes leading to REE concentrations found in coastal species is necessary. This study was designed to assess REEs concentrations in various common bivalves from the French coastline to identify possible geographic, taxonomic, or temporal variations of concentrations. Based on the French Mussel Watch program, three species of bivalves (oyster Crassostrea gigas and mussels Mytilus edulis and Mytilus galloprovincialis) were collected all along the French metropolitan coast and soft tissues were analyzed for REE concentrations. Results have shown higher REE concentrations in bivalve soft tissues near estuaries without taxonomic nor national geographic differences. The highest levels have been observed in the Gironde estuary with total REE concentrations (∑REE) in oysters up to 10.94 µg g-1 d.w. The REE distribution pattern in both mussel species described a particle-like (inverse V-shape) pattern, whereas C. gigas REE distribution pattern changes from a particle-like to a dissolved-like pattern with a heavy REE (HREE) enrichment. However, no environmental parameter could be linked to these pattern changes. Finally, neither Gd anomalies nor an evolution of REE concentrations over a 30-year period have been detected in bivalves' soft tissues.

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics.

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ66/64ZnJMC ≈ + 0.30‰) and anthropogenic (δ66/64ZnJMC ≈ + 0.15‰) end members. The lighter δ66/64ZnJMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.

Differences in Copper Isotope Fractionation Between Mussels (Regulators) and Oysters (Hyperaccumulators): Insights from a Ten-Year Biomonitoring Study.

Copper (Cu) isotope compositions in bivalve mollusks used in marine-monitoring networks is a promising tool to monitor anthropogenic Cu contamination in coastal and marine ecosystems. To test this new biomonitoring tool, we investigated Cu isotope variations of two bivalves-the oyster Crassostrea gigas and the mussel Mytilus edulis-over 10 years (2009-2018) in a French coastal site contaminated by diffuse Cu anthropogenic sources. Each species displayed temporal concentration profiles consistent with their bioaccumulation mechanisms, that is, the Cu-regulating mussels with almost constant Cu concentrations and the Cu-hyperaccumulating oysters with variable concentrations that track Cu bioavailability trends at the sampling site. The temporal isotope profiles were analogous for both bivalve species, and an overall shift toward positive δ65Cu values with the increase of Cu bioavailabilities was associated with anthropogenic Cu inputs. Interestingly, mussels showed wider amplitudes in the isotope variations than oysters, suggesting that each species incorporates Cu isotopes in their tissues at different rates, depending on their bioaccumulation mechanisms and physiological features. This study is the first to demonstrate the potential of Cu isotopes in bivalves to infer Cu bioavailability changes related to anthropogenic inputs of this metal into the marine environment.

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 ±â€¯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 ±â€¯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 ±â€¯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.

Assessment of the metal contamination evolution in the Loire estuary using Cu and Zn stable isotopes and geochemical data in sediments.

In this work, a multi-elemental approach combining Cu and Zn stable isotopes is used to assess the metal contamination evolution in the Loire estuary bulk sediments. Elemental geochemical data indicate an increase of metal concentrations from the beginning of the industrial period peaking in the 1990s, followed by an attenuation of metal contamination inputs to the estuary. Zinc isotope compositions suggest a binary mixing process between Zn derived from terrigenous material and multi-urban anthropogenic sources. Copper isotope systematics indicate a single natural dominant source represented by weathered silicate particles from soils and rocks. This work demonstrates the applicability of Zn isotopes to identify anthropogenic Zn sources in coastal systems, even under a low to moderate degree of contamination. Further studies are required to constrain Cu sources and to elucidate possible effects of grain-size and mineralogy in the Cu isotope composition of sediment in the Loire estuary.

Co-protoporphyrin IX and Sn-protoporphyrin IX inactivate Zika, Chikungunya and other arboviruses by targeting the viral envelope.

The global situation of diseases transmitted by arthropod-borne viruses such as Dengue (DENV), Yellow Fever (YFV), Chikungunya (CHIKV) and Zika (ZIKV) viruses is alarming and treatment of human infection by these arboviruses faces several challenges. The discovery of broad-spectrum antiviral molecules, able to inactivate different groups of viruses, is an interesting approach. The viral envelope is a common structure among arboviruses, being a potential target for antivirals. Porphyrins are amphipathic molecules able to interact with membranes and absorb light, being widely used in photodynamic therapy. Previously, we showed that heme, Co-protoporphyrin IX (CoPPIX) and Sn-protoporphyrin IX (SnPPIX) directly inactivate DENV and YFV infectious particles. Here we demonstrate that the antiviral activity of these porphyrins can be broadened to CHIKV, ZIKV, Mayaro virus, Sindbis virus and Vesicular Stomatitis virus. Porphyrin treatment causes viral envelope protein loss, affecting viral morphology, adsorption and entry into target cells. Also, light-stimulation enhanced the SnPPIX activity against all tested arboviruses. In summary, CoPPIX and SnPPIX were shown to be efficient broad-spectrum compounds to inactivate medically and veterinary important viruses.