Silver behaviour along the salinity gradient of the Gironde Estuary

Dissolved and particulate Ag concentrations (Ag_D and Ag_P, respectively) were measured in surface water and suspended particulate matter (SPM) along the salinity gradient of the Gironde Estuary, South West France, during three cruises (2008–2009) covering contrasting hydrological conditions, i.e. two cruises during intermediate and one during high freshwater discharge (~740 and ~2,300 m³/s). Silver distribution reflected non-conservative behaviour with 60–70 % of Ag_P in freshwater particles being desorbed by chlorocomplexation. The amount of Ag_P desorbed was similar to the so-called reactive, potentially bioavailable Ag_P fraction (60?±?4 %) extracted from river SPM by 1 M HCl. Both Ag_P (0.22?±?0.05 mg/kg) and Ag_P/Th_P (0.025–0.028) in the residual fraction of fluvial and estuarine SPM were similar to those in SPM from the estuary mouth and in coastal sediments from the shelf off the Gironde Estuary, indicating that chlorocomplexation desorbs the reactive Ag_P. The data show that desorption of reactive Ag_P mainly occurs inside the estuary during low and intermediate discharge, whereas expulsion of partially Ag_P-depleted SPM (Ag_P/Th_P ~0.040) during the flood implies ongoing desorption in the coastal ocean, e.g. in the nearby oyster production areas (Marennes-Oléron Bay). The highest Ag_D levels (6–8 ng/L) occurred in the mid-salinity range (15–20) of the Gironde Estuary and were decoupled from freshwater discharge. In the maximum turbidity zone, Ag_D were at minimum, showing that high SPM concentrations (a) induce Ag_D adsorption in estuarine freshwater and (b) counterbalance Ag_P desorption in the low salinity range (1–3). Accordingly, Ag behaviour in turbid estuaries appears to be controlled by the balance between salinity and SPM levels. The first estimates of daily Ag_D net fluxes for the Gironde Estuary (Boyle’s method) showed relatively stable theoretical Ag_D at zero salinity (Ag _D ⁰ = 25–30 ng/L) for the contrasting hydrological situations. Accordingly, Ag_D net fluxes were very similar for the situations with intermediate discharge (1.7 and 1.6 g/day) and clearly higher during the flood (5.0 g/day) despite incomplete desorption. Applying Ag _D ⁰ to the annual freshwater inputs provided an annual net Ag_D flux (0.64–0.89 t/year in 2008 and 0.56–0.77 t/year in 2009) that was 12–50 times greater than the Ag_D gross flux. This estimate was consistent with net Ag_D flux estimates obtained from gross Ag_P flux considering 60 % desorption in the estuarine salinity gradient.     

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.     

Development of an analytical strategy based on liquid chromatography-high resolution mass spectrometry for measuring perfluorinated compounds in human breast milk: application to the generation of preliminary data regarding perinatal exposure in France

Perfluorinated compounds (PFCs) are man-made chemicals for which endocrine disrupting properties and related possible side effects on human health have been reported, particularly in the case of an exposure during the early stages of development, (notably the perinatal period). Existing analytical methods dedicated to PFCs monitoring in food and/or human fluids are currently based on liquid chromatography coupled to tandem mass spectrometry, and were recently demonstrated to present some limitations in terms of sensitivity and/or specificity. An alternative strategy dedicated to the analysis of fourteen PFCs in human breast milk was proposed, based on an effective sample preparation followed by a liquid chromatography coupled to high resolution mass spectrometry measurement (LC-HRMS). This methodology confirmed the high interest for HRMS after negative ionization for such halogenated substances, and finally permitted to reach detection limits around the pg mL(-1) range with an outstanding signal specificity compared to LC-MS/MS. The proposed method was applied to a first set of 30 breast milk samples from French women. The main PFCs detected in all these samples were PFOS and PFOA with respective median values of 74 (range from 24 to 171) and 57 (range from 18 to 102) pg mL(-1), respectively. These exposure data appeared in the same range as other reported values for European countries.     

Combining polar organic chemical integrative samplers (POCIS) with toxicity testing to evaluate pesticide mixture effects on natural phototrophic biofilms

Polar organic chemical integrative samplers (POCIS) are valuable tools in passive sampling methods for monitoring polar organic pesticides in freshwaters. Pesticides extracted from the environment using such methods can be used to toxicity tests. This study evaluated the acute effects of POCIS extracts on natural phototrophic biofilm communities. Our results demonstrate an effect of POCIS pesticide mixtures on chlorophyll a fluorescence, photosynthetic efficiency and community structure. Nevertheless, the range of biofilm responses differs according to origin of the biofilms tested, revealing spatial variations in the sensitivity of natural communities in the studied stream. Combining passive sampler extracts with community-level toxicity tests offers promising perspectives for ecological risk assessment.     

Groundwater quality assessment of one former industrial site in Belgium using a TRIAD-like approach

Contaminated industrial sites are important sources of pollution and may result in ecotoxicological effects on terrestrial, aquatic and groundwater ecosystems. An effect-based approach to evaluate and assess pollution-induced degradation due to contaminated groundwater was carried out in this study. The new concept, referred to as “Groundwater Quality TRIAD-like” (GwQT) approach, is adapted from classical TRIAD approaches. GwQT is based on measurements of chemical concentrations, laboratory toxicity tests and physico-chemical analyses. These components are combined in the GwQT using qualitative and quantitative (using zero to one subindices) integration approaches. The TRIAD approach is applied for the first time on groundwater from one former industrial site located in Belgium. This approach will allow the classification of sites into categories according to the degree of contaminant-induced degradation. This new concept is a starting point for groundwater characterization and is open for improvement and adjustment.     

The anthropogenic atmospheric elements fraction: A new interpretation of elemental deposits on tree barks

The superficial deposit on the bark surface of several trees (mainly Fraxinus excelsior L.) was sampled in the experimental station of the university campus in Grenoble (France). Its composition was studied by scanning electron microscopy–energy dispersive X-ray emission (SEM–EDX) and, after digestion, by inductively coupled plasma-mass spectrometry (ICP-MS). The deposit was composed of 81.3% ± 7.4 organic matter, 9.4% ± 4.9 of geogenic minerals issued from the atmosphere (atmospheric geogenic fraction: AGF) and 9.3% ± 2.7 of a mixture of elements which was called anthropogenic atmospheric elements fraction (AAEF). The SEM–EDX analysis showed the presence of particles of geogenic compounds such as different types of silicates, phosphates, carbonates, sulphates, oxides and also particles of metals such as iron or of alloys of Fe–Zn, Fe–Ni, Ni–Cr and Ca sulphates or phosphates. Typical spheres of “fly ashes” composed of pure iron or Al-silicates were detected. Using the SEM–EDX analysis of the deposit and the average local soil composition, an empiric formula for the AGF (without polluting elements) was chosen, which presented a clear analogy with the global formula of the upper continental crust. In the same way, a formula for the pure organic matter fraction was chosen. Withdrawing the elements corresponding to these two fractions allows a tentative estimation of the content of the AAEF which was supposed to better represent the elemental anthropogenic contamination issued from the atmosphere. In the station, most of Sb, Cd, Sn, Pb, Cu, V and Zn were found in the AAEF. This AAEF composition was compared to that of the deposit in a highway tunnel where Pb and Cu were at a very high level. The meaning and the limits of the AAEF concept were critically discussed.     

Impact of biogas digestates on soil microbiota in agriculture: a review

Environmental Chemistry Letters - The global production of biogas has increased threefold during the last decade to partly replace fossil fuels, yet biogas production by anaerobic digestion...     

Cyclodextrin-based supramolecular low melting mixtures: efficient absorbents for volatile organic compounds abatement

Environmental Science and Pollution Research - Cyclodextrins (CDs) and deep eutectic solvents (DESs) are emerging absorbent materials for the removal of volatile organic compounds (VOCs). In this...