Origin of arsenic pollution in Southwest Tuscany: comparison of fluvial sediments

The Colline Metallifere in SW Tuscany are characterized by strong anomalies in arsenic concentrations and distribution. The area is sparsely populated and largely wild, though it has been subject to human impact due to mining and metal processing since Etruscan and Roman times. In the Middle Ages it was exploited intensively for silver and copper. Until 1995, pyrite (FeS2) was mined and roasted to produce sulphuric acid and iron. Hypotheses based on geological and mineralogical factors formulated in the last 20 years have failed to explain the peculiar distribution of arsenic in the Colline Metallifere. Here we report preliminary results of widespread sampling and analysis of the fluvial sediments of rivers originating in this mining area. The data was analysed in relation to the archaeological features of the area, since the presence of ancient mining and ore processing sites can shed light on the peculiar distribution of arsenic. Comparison of data from two rivers and their respective contaminated and uncontaminated coastal lagoons also clarified the general mechanisms of arsenic mobility, pinpointing the source of arsenic contamination. The study methods also promise to be useful for discovering unknown archaeological sites.