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This study investigates the applicability of elemental and Cu isotope compositions in sediments and bivalves from the Korean coast to monitor anthropogenic Cu contamination. Sediments with high Cu (>64.4 mg/kg) and/or moderate enrichment levels (EF Cu ) exhibit homogenous δ 65 Cu AE647 values (-0.12 to +0.16 ‰), suggesting similar anthropogenic Cu fingerprints along the Korean coast. Sediments with Cu concentrations near natural background levels (< 20.6 mg/kg) display large isotopic variability (Δ 65 Cu max-mim : ~0.8 ‰), encompassing those from sediments under anthropic influences. We hypothesize that Cu isotopic compositions of Korean geology are heterogeneous, therefore, natural end-members of source mixing models should be established locally at small scales. Cu concentrations in Oysters correlate with sediments, and their isotopic compositions are more suitable for monitoring Cu contamination, while mussel's regulatory mechanisms seem to affect source records. The current Cu isotope data will help to detect shifts attributable to anthropic contamination in future biomonitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Marinas are central hubs of global maritime leisure and transport, yet their operations can deteriorate the environmental quality of sediments. In response, this study investigated the metal contamination history associated with antifouling paint uses in a sediment core collected from Bracuhy marina (Southeast Brazil). Analysis target major and trace elements (Cu, Zn, Pb, Cd and Sn), rare earth elements (REEs), and Pb isotopes. The modification in Pb isotopic ratios and REEs pattern unequivocally revealed sediment provenance disruption following the marina construction. Metal distribution in the sediment core demonstrates that concentrations of Cu and Zn increased by up to 15 and 5 times, respectively, compared to the local background. This severe Cu and Zn contamination coincides with the onset of marina operations and can be attributed to the use of antifouling paints., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

This study investigates the chronology of copper (Cu) contamination and its stable isotopes within an emblematic Brazilian mangrove impacted by multiple urban and industrial Cu sources, deforestation, and eutrophication. In particular, it tests Cu isotopes as tracers of anthropogenic inputs into an anthropized watershed impacted by multiple sources. To do so, we used multi-isotopic approaches (δ 65 Cu, δ 13 C, and δ 15 N), elemental analyses (Al, Ca, Fe, P, Cu, C, and N), and selective and sequential extractions in a 210 Pb-dated sediment core. This geochemical "toolbox" allowed identifying two main stages of Cu evolution in the sediment core. In the first stage, before 1965, Cu isotope fingerprints responded to landscape changes, indicating a shift from marine to geogenic dominance due to the remobilization and erosion of terrestrial materials. In the second stage, after 1965, the sediment geochemical profile showed increased Cu total concentrations with a higher bioavailability (as reflected by sequential extraction data) accompanying changes in Cu isotope signatures towards anthropogenic values. The findings evidence that local industrial sources, possibly combined with diffuse urban sources, export Cu into downstream mangroves with a distinguishable isotope signature compared to natural values. This study demonstrates the applicability of Cu isotopes as new environmental forensic tools to trace anthropogenic sources in mangrove sediments. Incorporated into a robust geochemical toolbox that combines inorganic and organic proxies for sedimentary materials, this new tool provides a comprehensive understanding of Cu dynamics in mangrove ecosystems, shedding light on the historical and current sources of Cu., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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). δ 65 Cu and δ 66 Zn were determined on four planktonic size fractions from 60 to 2000 μm. Combined δ 65 Cu and δ 66 Zn with geochemical tracers (Ti, particulate organic phosphorus) showed that geogenic particles were ubiquitous with plankton assemblages. The δ 15 N ecological tracer showed that planktonic food web was enriched in heavy isotopes of Cu and Zn in the higher trophic levels. δ 65 Cu were correlated with picoplankton in the offshore zone, and with zooplankton in the southern coastal zone. Firmicutes bacteria were found correlated with δ 66 Zn 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2019. Published by Elsevier Ltd.)

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. • Large spatial variability in Cu, Zn, and Pb concentrations in Lakes Huron and Erie. • Temporally similar Cu, Zn, Pb isotopes imply consistent export to sediment record. • Zn and Pb isotopes are suggestive of predominantly geogenic supply to the lakes. • Minor Cu isotope variability appears linked to hydrochemistry and redoxsensitivity [ABSTRACT FROM AUTHOR]

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. [Display omitted] • Cu and Zn isotope differences between bivalve mollusks species were studied. • Inter-species isotopic variability of Cu is larger than Zn. • The degree of internal isotope fractionation decreases from mussels > clams > oysters. • Low Zn inter-specie variability helps preserve source information more reliably. [ABSTRACT FROM AUTHOR]

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 δ65Cu SRM-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. [Display omitted] • Electroplating wastes imprint particular metal isotope ratios in legacy sediments. • Isotope analysis reveals the anthropogenic Cu and Pb dispersion across the bay. • Tidal flat isotope ratios reflect mixing of legacy and fluvial sediment particles. • Isotope fingerprints of Cu and Pb in oysters match legacy contaminated sediments. [ABSTRACT FROM AUTHOR]

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 δ65Cu AE647 , δ66Zn IRMM3702 , 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. [Display omitted] • First multi-isotopic and elemental fingerprints of antifouling paints (APs). • APs isotopic compositions vary depending on manufacturer and color. • Unique chemical fingerprint of APs differentiates them from other pollutants. • Major contribution of harbor sediments in Korea indicated urban sources than APs. • Metal isotopic signatures may enable source discrimination in forensic studies. [ABSTRACT FROM AUTHOR]

Toulon bay is severely impacted by metal contamination induced by past and recent naval activities. In this work, Cu, Zn and Pb isotope compositions and elemental concentrations of fifty-five surface sediments were determined in order to map the spatial distribution of anthropogenic and natural sources along this land-sea continuum. Two sub-systems of Toulon Bay, the Small and Large bays, showed well-marked patterns on metal contamination levels and isotope signatures for Cu and Pb. The Small bay had the highest metal concentrations, and displayed average Pb and Cu isotope compositions of 1.1664 ± 0.0043 (1s, expressed as 206Pb/207Pb ratios) and −0.17 ± 0.19‰ (1s, expressed as δ65Cu NIST values), respectively. It contrasted with the Large bay, with moderate to pristine metal concentrations and average Pb and Cu isotope compositions of 1.1763 ± 0.0079 (1s) and +0.08 ± 0.23‰ (1s), respectively. Lead isotope systematics indicated a binary source mixing process involving industrial and natural sources, while Cu isotope systematics showed a ternary mixing process involving two distinct anthropogenic signatures, interpreted as associated to new diffuse anthropogenic sources and old warfare material. In contrast, Zn isotope compositions in the Small and Large bays were practically the same: +0.06 ± 0.05‰ and +0.06 ± 0.11‰ (1s, expressed δ66Zn JMC values), respectively, denoting an overlap between isotope signatures of natural and anthropogenic sources. This study presents the first detailed spatial distributions of Cu and Zn isotope compositions for an aquatic system, and demonstrates the feasibility to use Cu isotopes as tracers of anthropogenic sources in coastal environments. • Cu isotope systematic show a mixing process of natural and anthropogenic sources. • Low Cu contaminated sediments display δ65Cu NIST values ranging from 0.0 to +0.2‰. • Contaminated sediments by diffuse sources tend to negative δ65Cu NIST values. • Pb isotopes reveal mixing process involving industrial and natural sources. • Zn isotope system does not allow identifying mixing source processes. [ABSTRACT FROM AUTHOR]