Sources, chronology of deposition, and mobility of mercury and methylmercury in the sediments of a contaminated Mediterranean bay.

Coastal sediments constitute a major reservoir for natural and anthropogenic mercury (Hg) and can be used as geochronological records of past Hg deposition. They may also act as secondary Hg sources for pelagic ecosystems via the efflux of toxic methylmercury (MeHg) diffusing from sediment porewaters and/or mobilized by sediment resuspension. In Toulon Bay sediments, which are known as one of the Hg hot spots of the northwestern Mediterranean Sea, we explored Hg species accumulation and mobility. The total Hg concentrations averaged 0.014 µg g-1 ca. 2000 years ago, then exhibited three major peaks during the Medieval Period, the Early Modern Period of Europe, and the Industrial Era, reaching 0.06, 0.07, and 13 µg g-1, respectively. The Medieval peak is attributed to the massive development of metallurgy in Europe accompanied by the burning of soil and vegetation, the second peak to the optimum of Hg extraction in Europe (Almadén mine), and the resumption of deforestation after the great plague. The third most recent Hg enrichment is associated with Hg-fulminate production, the scuttling of the French navy fleet during World War II, and ship salvaging and removal in the post-war years. Sampling of the dissolved phase at high vertical resolution above and below the sediment-water interface (SWI) enables us to conclude that MeHg was produced in situ by microbiological pathways and its diffusion across the SWI was negligible. On the other hand, ex-situ resuspension experiments showed that sorption and/or photodemethylation restrict MeHg from the dissolved phase.

Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay, France).

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.

Study of the spatial and historical distribution of sediment inorganic contamination in the Toulon bay (France).

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.