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

Abstract

Concentrations of inorganic tin (Sninorg), 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 210Pb-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 SninorgBT 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 BDImod. 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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Acknowledgments

The authors thank the French Navy for logistical support (access to restricted areas, vessel, scuba divers) and D. François, G. Tua, G. Durrieu and B. Oursel for their participation in sampling campaigns and sample preparation. This collaborative work within the CARTOCHIM project has been performed by a multi-agency consortium (IFREMER, IRSN, University laboratories PROTEE and UMR EPOC), financially supported by the “Region PACA”, “Toulon-Provence-Méditerranée” and the “Agence de l’Eau Rhône-Méditerranée et Corse” and is a contribution to MerMex-WP3-C3A and the international IMBER projects.

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Correspondence to Jörg Schäfer.

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Responsible editor: Céline Guéguen

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Fig. SI1

Vertical distribution of Al-normalized Sn and butyl-Sn concentrations in the cores C-12 and C-15. (DOCX 25 kb)

Fig. SI2

Spatial distribution of Sntot Enrichment Factors (EF) in Toulon Bay surface sediment. (DOCX 147 kb)

Fig. SI3

Vertical distribution of (A) BDI and (B) BDImod in the cores C-12 and C-15. (DOCX 47 kb)

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Pougnet, F., Schäfer, J., Dutruch, L. et al. Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay, France). Environ Sci Pollut Res 21, 6640–6651 (2014). https://doi.org/10.1007/s11356-014-2576-6

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Keywords

  • Tin
  • TBT
  • Butyl-Sn
  • Isotope dilution
  • Sediment core
  • Contamination
  • Toulon Bay