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The boron isotope composition (δ11B) of marine biogenic carbonates has been predominantly studied as a proxy for monitoring past changes in seawater pH and carbonate chemistry. However, a number of assumptions regarding chemical kinetics and thermodynamic isotope exchange reactions are required to derive seawater pH from δ11B biogenic carbonates. It is also probable that δ11B of biogenic carbonate reflects seawater pH at the organism's site of calcification, which may or may not reflect seawater pH. Here, we report the development of methodology for measuring the δ11B of biogenic carbonate samples at the multi-collector inductively coupled mass spectrometry facility at Ifremer (Plouzané, France) and the evaluation of δ11BCaCO3 in a diverse range of marine calcifying organisms reared for 60 days in isothermal seawater (25 °C) equilibrated with an atmospheric pCO2 of ca. 409 µatm. Average δ11BCaCO3 composition for all species evaluated in this study range from 16.27 to 35.09 ‰, including, in decreasing order, coralline red alga Neogoniolithion sp. (35.89 ± 3.71 ‰), temperate coral Oculina arbuscula (24.12 ± 0.19 ‰), serpulid worm Hydroides crucigera (19.26 ± 0.16 ‰), tropical urchin Eucidaris tribuloides (18.71 ± 0.26 ‰), temperate urchin Arbacia punctulata (16.28 ± 0.86 ‰), and temperate oyster Crassostrea virginica (16.03 ‰). These results are discussed in the context of each species' proposed mechanism of biocalcification and other factors that could influence skeletal and shell δ11B, including calcifying site pH, the proposed direct incorporation of isotopically enriched boric acid (instead of borate) into biogenic calcium carbonate, and differences in shell/skeleton polymorph mineralogy. We conclude that the large inter-species variability in δ11BCaCO3 (ca. 20 ‰) and significant discrepancies between measured δ11BCaCO3 and δ11BCaCO3 expected from established relationships between abiogenic δ11BCaCO3 and seawater pH arise primarily from fundamental differences in calcifying site pH amongst the different species. These results highlight the potential utility of δ11B as a proxy of calcifying site pH for a wide range of calcifying taxa and underscore the importance of using species-specific seawater-pH–δ11BCaCO3 calibrations when reconstructing seawater pH from δ11B of biogenic carbonates.

This study characterises for the first time isotope ratio measurements by multi-collector ICPMS when performed at liquid flow rates as low as 10–15 µL min−1. An evolution of the torch integrated sample introduction system (TISIS) was employed, which combined an OpalMist nebulizer and a heated single pass spray chamber, allowing the transport of almost 100% of the solvent. The different factors potentially influencing the isotope ratio measured values and the associated sources of uncertainty (sensitivity and interferences, mass discrimination effects, repeatability of isotope ratio measurement, and rinsing time and memory effects) were investigated systematically under varying experimental conditions. Results showed that the liquid flow rate has a large impact on mass discrimination effects, making the control of this variable critical. From 5 to 30 µL min−1, when using the exponential model, the mass discrimination per mass unit changed from −1.6 to −2.1 and from −1.1 to −1.9, for 88Sr+/86Sr+and 208Pb+/206Pb+ratios respectively. Moreover, extrapolations from these results lead to the conclusion that a syringe pump may be required instead of a free aspiration regime to control the liquid flow rate and eliminate the possibility of undesired variations of isotope ratio results (typically, 0.05‰ error for 1–2% fluctuations at 10 µL min−1). The validity of the exponential model also depends on the experimental conditions selected. When working at 15 µL min−1and heating the chamber walls at 60–80 °C, the performance was as good as it could be with a MicroMist/water cooled cinnabar combination operated at 200 µL min−1(thus, the efficiency was 12 times better for the TISIS). Both systems were compared for the measurement of the Sr isotopic signature in honey samples. Since the TISIS allowed for a preconcentration of samples by a factor 5, the combined uncertainty on results could be improved by 1.6 to 4.4. The main drawback was, however, the longer rinsing time required to reach a stable background signal (10–12 minutes rather than 4). [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., 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.)

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., Competing Interests: Declaration of competing interest All authors have approved the submission of this manuscript, and we collectively affirm that the content of the manuscript is original and has not been published or is currently under consideration elsewhere., (Copyright © 2024. Published by Elsevier Ltd.)

The behavior, and history of lead (Pb) contamination in the ecosystem of the Loire estuary was examined using elemental concentrations and Pb isotope data in water, sediment, bivalves, shrimps, and fish. In the estuary and in the surrounding coastal area, Pb concentrations in water and sediment decreased compared to concentrations determined in the 1980s, with concentrations ranging from 15.8 to 65.7 mg kg -1 in the surface sediment, 0.04-0.26 nM in the water column, and 48.0-77.9 mg kg -1 in suspended particles. Pb biomonitoring using blue mussels collected by the French Mussel Watch Program over the last 40 years showed a concentration decrease from 3.8 to 0.8 mg kg -1 . A similar trend is observed in an estuarine sediment core. Changes in accompanying Pb isotope compositions strongly suggest a binary mixing process between Pb derived from terrigenous material and anthropogenic sources. Thus, environmental regulations restricting the release of lead into the environment contribute to a decrease in estuarine levels of this pollutant, which occurs on a decadal time scale., 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.)

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 δ 65 Cu SRM-976 : 0.4 ‰ and 206 Pb/ 207 Pb: 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., 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.)

In order to move forward in the acceptance of a novel contaminant monitoring technique (Diffusive Gradients in Thin-films: DGT) for assessment of marine water bodies, sensu the WFD, an Inter-Laboratories Comparison (ILC) exercise (nine Europeans laboratories) was organized in the framework of the Interreg Atlantic Area MONITOOL project, which focused on the use of the DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb). Reproducible results were obtained for each metal by several laboratories, supporting the assertion that DGT analysis can be performed satisfactorily by laboratories experienced in measuring metals at trace levels in marine environments, even if they have limited practice in DGT analysis. According to the Z-score analysis, among the 9 participating laboratories, 3 had 100 % of satisfactory results for Cd, Ni, and Pb, 3 had >80 % satisfactory results and 2 had about 60 % satisfactory results. This work highlights the need to clearly describe the DGT method in order to control sources of contamination during analytical steps, in particular the resin gel retrieval and the elution steps. Such international intercomparison exercise is an important step to develop the laboratory network involved in DGT analysis and contributes to the improvement of data quality., 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. Published by Elsevier B.V.)

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., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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 δ 65 Cu 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 δ 65 Cu 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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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 δ 65 Cu 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.

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.)

Continental ice sheets are a key component of the Earth's climate system, but their internal dynamics need to be further studied. Since the last deglaciation, the northern Eurasian Fennoscandian Ice Sheet (FIS) has been connected to the Black Sea (BS) watershed, making this basin a suitable location to investigate former ice-sheet dynamics. Here, from a core retrieved in the BS, we combine the use of neodymium isotopes, high-resolution elemental analysis, and biomarkers to trace changes in sediment provenance and river runoff. We reveal cyclic releases of meltwater originating from Lake Disna, a proglacial lake linked to the FIS during Heinrich Stadial 1. Regional interactions within the climate-lake-FIS system, linked to changes in the availability of subglacial water, led to abrupt drainage cycles of the FIS into the BS watershed. This phenomenon raised the BS water level by ∼100 m until the sill of the Bosphorus Strait was reached, flooding the vast northwestern BS shelf and deeply affecting the hydrology and circulation of the BS and, probably, of the Marmara and Aegean Seas.

About 3000 years ago, a major vegetation change occurred in Central Africa, when rainforest trees were abruptly replaced by savannas. Up to this point, the consensus of the scientific community has been that the forest disturbance was caused by climate change. We show here that chemical weathering in Central Africa, reconstructed from geochemical analyses of a marine sediment core, intensified abruptly at the same period, departing substantially from the long-term weathering fluctuations related to the Late Quaternary climate. Evidence that this weathering event was also contemporaneous with the migration of Bantu-speaking farmers across Central Africa suggests that human land-use intensification at that time had already made a major impact on the rainforest.

A long known way of anchoring isotope ratio values to the SI system is by means of gravimetrically prepared isotopic mixtures. Thermal ionization mass spectrometry (TIMS) is the traditionally associated measurement technique, but multi-collector double focusing inductively coupled plasma (MC-ICP)-MS now appears to be an attractive alternative. This absolute calibration strategy necessitates that mass discrimination effects remain invariant in time and across the range of isotope ratios measured. It is not the case with MC-ICPMS and the present work illustrates, in the case of Zn isotopic measurements carried out using locally produced synthetic Zn isotope mixtures (IRMM-007 series), how this calibration strategy must be adjusted. First, variation in mass discrimination effects across the measurement sequence is propagated as an uncertainty component. Second, linear proportionality during each individual measurement between normalized mass discrimination and the average mass of the isotope ratios is used to evaluate mass discrimination for the ratios involving low abundance isotopes. Third, linear proportionality between mass discrimination and the logarithm of the isotope ratio values for n(67Zn)/n(64Zn) and n(68Zn)/n(64Zn) in the mixtures is used iteratively to evaluate mass discrimination for the same ratios in the isotopically enriched materials. Fourth, ratios in natural-like materials (including IRMM-3702 and IRMM-651) are calibrated by external bracketing using the isotopic mixtures. The relative expanded uncertainty (k = 2) estimated for n(68Zn)/n(64Zn) and n(67Zn)/n(64Zn) ratio values in the synthetic isotopic mixtures and the natural-like zinc samples was in the range of 0.034 to 0.048%. The uncertainty on the weighing (0.01%, k = 1) was the largest contributor to these budgets. The agreement between these results and those obtained with a single detector TIMS and with another MC-ICPMS further validated this work. The absolute isotope ratio values found for IRMM-3702-material also proposed as "delta 0" for delta-scale isotopic measurements-are n(66Zn)/n(64Zn) = 0.56397 (30), n(67Zn)/n(64Zn) = 0.082166 (35), n(68Zn)/n(64Zn) = 0.37519 (16), and n(70Zn)/n(64Zn) = 0.012418 (23). The derived Zn atomic weight value Ar(Zn) = 65.37777 (22) differs significantly from the current IUPAC value by Chang et al. [1]. Remeasurement, with isotopic mixtures from the IRMM-007 series, of the Zn isotope ratios in the same Chang et al. [1] material have revealed large systematic differences (1.35 (27)% per atomic mass unit) that suggest unrecognized measurement biases in their results.