Lionel Dutruch

Evidencing the Impact of Coastal Contaminated Sediments on Mussels Through Pb Stable Isotopes Composition

Heavily contaminated sediments are a serious concern for ecosystem quality, especially in coastal areas, where vulnerability is high due to intense anthropogenic pressure. Surface sediments (54 stations), 50 cm interface cores (five specific stations), river particles, coal and bulk Pb plate from past French Navy activities, seawater and mussels were collected in Toulon Bay (NW Mediterranean Sea). Lead content and Pb stable isotope composition have evidenced the direct impact of sediment pollution stock on both the water column quality and the living organisms, through the specific Pb isotopic signature in these considered compartments. The history of pollution events including past and present contaminant dispersion in Toulon Bay were also demonstrated by historical records of Pb content and Pb isotope ratios in sediment profiles. The sediment resuspension events, as simulated by batch experiments, could be a major factor contributing to the high Pb mobility in the considered ecosystem. A survey of Pb concentrations in surface seawater at 40 stations has revealed poor seawater quality, affecting both the dissolved fraction and suspended particles and points to marina/harbors as additional diffuse sources of dissolved Pb.

Comparison of LA-ICP-MS and LA-ICP-OES for the analysis of some elements in fly ashes

In this work quantitative analysis of minor and trace elements in fly ash by nanosecond laser ablation (LA)-ICP-MS and LA-ICP-OES was investigated in terms of detection limits and accuracy. Different binders and modifiers (silver or chromophores) were added to the fly ash powder to prepare mechanically stable pellets and improve sensitivity (signal to concentration ratio). Maleic acid was found to provide a higher degree of homogeneity between sensitivities across the different fly ashes tested. Ashes were from different origins: domestic waste incinerator or ashes from various coal-fired power plants. A calibration procedure using reference materials as standards was employed, the LA-ICP-MS analysis gave an acceptable accuracy (estimated from NIST 1633), better results were obtained using fused bead preparation. The use of the LA-ICP-OES system gave, when possible (higher concentrations), good results in terms of detection limits (1 to 11 µg g−1) and accuracy.

Gas chromatographic-mass spectrometry and gas chromatographic-Fourier transform infrared spectroscopy assay for the simultaneous identification of fentanyl metabolites.

Fentanyl, a synthetic opioid, undergoes important biotransformation to several metabolites. A gas chromatographic-mass spectrometric assay was applied for the simultaneous analysis of fentanyl and its major metabolites in biological samples. The identification of different metabolites was performed by gas chromatography-mass spectrometry (electronic impact and chemical ionisation modes) and gas chromatography-Fourier transform infrared spectroscopy. In the present study, rat and human microsomes incubation mixtures and human urines were analysed. In vitro formation of already known fentanyl metabolites was confirmed. The presence of metabolites not previously detected in human urine is described.

Tracing platinum accumulation kinetics in oyster Crassostrea gigas, a sentinel species in coastal marine environments

Platinum Group Elements (PGEs) are extremely scarce in the Earths Crust and of strong interest for high-end technologies due to their specific properties. They belong to the Technology Critical Elements (TCEs) for which use is forecast to increase, implying growing emissions into the environment in the following years. In particular, with the intensive use of platinum (Pt) in car catalytic converters, the anthropogenic geochemical cycle of this element has surpassed the natural cycle. Yet, environmental Pt levels are still in the sub picomolar range, making its analytical detection a challenge. Few studies cover the behavior of Pt in marine waters in terms of speciation, reactivity and possible transfer to the biota. In this study, oysters (Crassostrea gigas) from an unpolluted estuary were exposed to the stable isotope 194Pt in seawater at a range of concentrations during 35days. Seawater was renewed daily and spiked to three nominal Pt concentrations (50, 100, and 10,000ng·L-1) for two replicate series. In addition, control conditions were monitored. Five oysters from each tank were dissected after 3, 7, 14, 21, 28, 35days of Pt exposure, and analyzed by ICP-MS. Accuracy of this analytical method applied to biological matrix was checked by an inter-method comparison with a voltammetrical technique. A concentration-dependent accumulation of Pt in oysters increasing with exposure time occurred. After 28days, oyster Pt accumulation from low and intermediate exposure conditions reached a plateau. This was not the case of the highest exposure condition for which oyster tissues showed increasing concentrations until the last day of the experiment. A linear correlation exists between seawater concentrations and Pt content in oysters for low and intermediate exposure concentrations i.e. closer to environmental concentrations. By showing high Pt accumulation potential, oysters may serve as sentinels, ensuring biomonitoring of Pt concentrations in marine coastal waters.

Platinum in sediments and mussels from the northwestern Mediterranean coast: Temporal and spatial aspects

Platinum (Pt) is considered a Technology Critical Element (TCE) and an emerging metallic contaminant with increasing release into the environment. Gaps in knowledge and understanding of environmental levels, fate and effects of Pt still exist, especially in the marine environment. This work presents Pt concentrations in the northwestern Mediterranean coast including: (i) temporal variability from sediment cores and farmed mussels in the Toulon Bay (historically affected by intense human activities) and (ii) spatial distribution from recent wild mussels collected along ∼ 700 km coastline with contrasting ecosystems (including natural reserves), quantified using voltammetry and inductively coupled plasma-mass spectrometry. The historical (>100 years) record of Pt in sediments from the Toulon Bay suggests the existence of non-negligible Pt sources older than those related to vehicle emission devices, such as petrol industry and coal-fired activities. A strong Pt increase in more recent sediments (from ∼12 to 16 ng g-1) and mussels (8-fold increase from ∼0.12 to 0.80 ng g-1) covering the past 25 years reflect the overall evolution of Pt demand in Europe (∼20-fold increase for vehicle catalysts in 20 years). Spatial biomonitoring of Pt in mussels along the northwestern Mediterranean coast is assumed to reflect inter-site differences of Pt exposure (0.09-0.66 ng g-1) despite seasonal effect on tissue development. This study highlights the need for thorough and regular monitoring of Pt levels in sediments and biota from urbanized coastal areas in order to better assess the environmental impact of this TCE, including potential risks for marine organisms.

Antimony in the Lot–Garonne river system: a 14-year record of solid–liquid partitioning and fluxes

Environmental context Antimony is a trace element ubiquitously present in the environment, but data are lacking on its spatio-temporal distribution in aquatic environments. Long-term records serve as essential tools to decipher temporal patterns, historical sources and sinks and background concentrations in an area. We characterise the temporal concentrations, transport and behaviour of antimony in the Garonne River watershed, the main tributary to the Gironde Estuary, the largest estuary in south-west Europe. Abstract Knowledge of the environmental chemistry of antimony (Sb) in aquatic systems is limited, and a better understanding of its geochemical behaviour is needed. Based on a fourteen-year survey (2003–2016) with monthly measurements of dissolved and particulate Sb at five sites in the Lot–Garonne river system, combined with daily measurements of water discharge and suspended particulate matter, this work characterises Sb behaviour in the upstream major river watershed of the Gironde Estuary. The survey provides a first regional geochemical Sb background in the Garonne River watershed for dissolved (~0.2 µg L−1) and Th-normalised particulate Sb (Sbp/Thp ~0.25) concentrations. Observed decreasing temporal trends (<1 ng L−1 in dissolved and <0.02 mg kg−1 in particulate concentrations per month) at sites representing natural concentrations probably reflect global atmospheric Sb dynamics at the watershed scale. Regular seasonal cycles of solid/liquid partitioning, with higher solubility in summer (matching high dissolved and low particulate concentrations), reflect water-discharge and suspended particulate matter transport dynamics and possibly seasonal (bio)geochemical processes. Furthermore, this coefficient decreases from the river to the estuarine reaches (from average log10Kd 4.3 to minimum 3.7 L kg−1), suggesting an increased solubility of Sb in estuarine systems. Flux estimates indicate the relevance of the dissolved fraction in Sb transport (with negligible influence of the colloidal fraction) and a total flux (dissolved + particulate) entering the Gironde Estuary of 5.66 ± 2.96 t year−1 (~50 % particulate). These results highlight the importance of timescales and environmental parameters for understanding and prediction of future Sb biogeochemistry.