Anthropogenic accumulation of metals and metalloids in carbonate-rich sediments: Insights from the ancient harbor setting of Tyre (Lebanon)

The Antique and Byzantine sediments of the northern harbor of Tyre (Lebanon) store high amounts of metals and metalloids as the result of a millennial anthropogenic contamination as well as of efficient trapping and immobilization processes. Geochemical and mineralogical analyses reveal the contrasted patterns for the accumulation of trace metal(loid)s in the sedimentary sequence recovered by coring the inner part, now emerged, of the ancient harbor. Lead, Sn, Cu and Ag concentrations can be as high as 3000, 150, 1000, and 1.2μg/g, respectively. Enrichment factors were calculated with respect to (1) Th and (2) the chemistry of the substratum and appear to be driven by anthropogenic inputs. Indeed, a drastic change in both excess concentrations and concentration ratios is observed through Roman and Byzantine times, pointing to major intensification of the trade and use of metals in Tyre, coherent with historical data. Good preservation of the archeological signal, despite (1) sediment disturbances that have caused age depth inversions, and (2) the large time lapse since the time of deposition of anthropogenic trace metal(loid)s is probably due to the reducing character of the sediments. Tyre's sedimentary sequence provides an interesting analog for modern carbonate-rich harbor environments, in which a millenary accumulation of trace metal(loid)s has been overall well preserved and suggests a restricted mobility of anthropogenic contamination for a period of time in excess of 1500. years.