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. Highlights ► Geochemical data and Cu and Zn isotopes were investigated in the Loire estuary. ► Cu and Zn isotope compositions of sediments vary in spatial and temporal scales. ► Zinc isotopes suggest a mixing process between terrigenous and urban sources. ► Cu isotopes indicate a natural dominant source represented by weathered material.

International audienceCompetitivemechanisms between rare earth elements (REE) and iron (Fe) for humic acid (HA) bindingwere investigated by coupling laboratory experiments and modeling calculations using PHREEQC/Model VI. This study aims, firstly, at determining the effect of Fe on REE-HA binding, in order to explain the REE pattern variability observed in natural organic-rich waters. Secondly, it has previously been shown that light and heavy REE (Land HREE) speciation with HA molecules differ with pH. Therefore, REE-HA complexation patterns have been used as a probe of Fe-HA binding mechanisms. At pH 3, i.e. pH conditions at which Fe3+ binds to HA, Fe is shown to be a strong competitor for heavy REE (HREE), suggesting that Fe3+ has a marked affinity for the few strong HA multidentate sites. At pH 6, i.e. under pH conditions atwhich hydrolyzed Fe species bind to HA, Fe appears to compete equally for every REE, thereby indicating that Fe has the samerelative affinity for carboxylic and phenolic HA sites as LREE and HREE, respectively. Fractionation of REE in organic-rich natural waters depends mainly on the coupling of two factors: (i) the total dissolved metal concentration (i.e. the HA metal loading) and (ii) the competition between REE and major cations (i.e. Fe and Al). The pH, which regulates the speciation of these competitive metals, is, therefore, indirectly the main controlling factor of REE fractionation in organic-rich waters

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Marine mercury (Hg) concentrations have been monitored in the French coastline for the last half a century using bivalves. The analyses presented in this study concerned 192 samples of bivalves (mussels: Mytilus edulis and Mytilus galloprovincialis and oysters: Crassostrea gigas and Isognomon alatus) from 77 sampling stations along the French coast and in the French Antilles sea. The goals of this study were to assess MeHg levels in various common bivalves from French coastline, and to identify possible geographic, taxonomic or temporal variations of concentrations. We show that the evolution of methylmercury (MeHg) concentrations covary with total mercury (HgT) concentrations. Moreover, in most of the study sites, HgT concentrations have not decreased since 1987, despite regulations to decrease or ban mercury used for anthropic activities.

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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 subsystems of Toulon Bay, the Small and Large bays, showed wellmarked 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 δ65CuNIST 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 δ66ZnJMC 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. Highlights ► Cu isotope systematic show a mixing process of natural and anthropogenic sources. ► Low Cu contaminated sediments display δ 65 CuNIST values ranging from 0.0 to +0.2‰. ► Contaminated sediments by diffuse sources tend to negative δ 65 CuNIST values. ► Pb isotopes reveal mixing process involving industrial and natural sources. ► Zn isotope system does not allow identifying mixing source processes. Please note that this is an author-produced PDF of an article accepted for publication following peer review. The definitive publisher-authenticated version is available on the publisher Web site.