Persisting impact of historical mining activity to metal (Pb, Zn, Cd, Tl, Hg) and metalloid (As, Sb) enrichment in sediments of the Gardon River, Southern France

In this study, we assessed past and present influence of ancient mining activity on metal(loid) enrichment in sediments of a former mining watershed (Gardon River, SE France), that is now industrialized and urbanized. A sedimentary archive and current sediments were characterized combining geochemical analyses, zinc isotopic analyses and sequential extractions. The archive was used to establish local geochemical background and recorded (i) increasing enrichment factors (EFs) for Pb, Zn, Cd, Tl, Hg, As and Sb throughout the industrial era, (ii) a contamination peak in 1976 attributed to a tailings dam failure, and (iii) current levels in 2002 and 2011 similar to those of 1969, except for Sb and Hg, reflecting a persisting contamination pattern. Inter-element relationships and spatial distribution of EF values of current sediments throughout the watershed suggested that both ancient and current contamination had a common origin for Pb, Zn, Cd, Tl and As related to the exploitation of Pb/Zn mineralization while old Sb mines and coal extraction area were the main sources for Sb and Hg respectively. This prevailing mining origin was reflected for Zn by a relatively uniform isotopic composition at δ66Zn=0.23±0.03‰, although slight decrease from 0.23‰ to 0.18‰ was recorded from upstream to downstream sites along the river course in relation with the contribution of the lighter δ66Zn signature (~0.08‰) of acid mine drainage impacted tributaries. Results from sequential extractions revealed that the potential mobility of the studied metal(loid)s varied in the order Sb<Tl≈As<Zn<Pb<Cd, with an increase of the mobile pool for Cd, Pb, Zn and to a lesser extent for As and Tl associated to increased enrichment. Altogether, these results tend to demonstrate that ancient mining activity still contributes to metal enrichment in the sediments of the Gardon River and that some of these metals may be mobilized toward the water compartment.