This study presents trace elements levels in surface and deep sediments of the Toulon bay (SE France) subjected to anthropogenic inputs (navy base, harbors, etc.). The studied elements (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) are defined as priority contaminants in aquatic systems. Fifty-five points scattered on the entire bay were sampled, allowing the determination of contaminants distribution with a high resolution. Several approaches were used to assess the degree of contamination and the potential toxicity of the Toulon bay sediments: comparison to the French legislation, surface-weighted average metal concentrations, enrichment factors (EF), geoaccumulation indices (Igeo), trace element stock calculation and comparison to sediment quality guidelines. A principal component analysis was performed to reveal common behavior of the studied contaminants. Results demonstrated the very high contamination of the small bay, especially in Hg (EF up to 1500), Cu, Pb and Zn, with export to the large bay further governed by hydrodynamics.
International audienceMethylation of mercury (Hg) is the crucial process that controls Hg biomagnification along the aquatic food chains. Aquatic sediments are of particular interest because they constitute an essential reservoir where inorganic divalent Hg (Hg II) is methylated. Methylmercury (MeHg) concentrations in sediments mainly result from the balance between methylation and demethylation reactions, two opposite natural processes primarily mediated by aquatic microorganisms. Thus, Hg availability and the activity of methylating microbial communities control the MeHg abundance in sediments. Consistently, some studies have reported a significant positive correlation between MeHg and Hg II or total Hg (Hg T), taken as a proxy for Hg II , in aquatic sediments using enzyme-catalyzed methylation/demethylation mechanisms. By compiling 1,442 published and unpublished Hg T –MeHg couples from lacustrine, riverine, estuarine and marine sediments covering various environmental conditions, from deep pristine abyssal to heavily contaminated riverine sediments, we show that a Michaelis–Menten type relationship is an appropriate model to relate the two parameters: MeHg = aHg T /(K m + Hg T), with a = 0.277 ± 0.011 and K m = 188 ± 15 (R 2 = 0.70, p < 0.001). From K m variations, which depend on the various encountered environmental conditions, it appears that MeHg formation and accumulation are favoured in marine sediments compared to freshwater ones, and under oxic/suboxic conditions compared to anoxic ones, with redox potential and organic matter lability being the governing factors
Concentrations of inorganic tin (Sn(inorg)), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3-112 μg g(-1)), TBT (<0.5-2,700 ng g(-1)), DBT (<0.5-1,800 ng g(-1)) and MBT (0.5-1,000 ng g(-1)) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two (210)Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn(inorgBT) is by far the dominant species after 10-12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI(mod). Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species.
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