Mercury Isotopic Fractionation during Pedogenesis in a Tropical Forest Soil Catena (French Guiana): Deciphering the Impact of Historical Gold Mining

We used natural mercury (Hg) stable isotopes to investigate the Hg cycle in a rainforest soil catena (French Guiana) partially gold-mined during the early 1950s. Litterfall showed homogeneous Delta Hg-199 values [-0.18 +/- 0.05 parts per thousand, i.e., a modern gaseous elemental Hg (GEM) isotopic signature]. After litter decomposition, Hg bound to organic matter (OM) is mixed with Hg from pristine (-0.55 +/- 0.22 parts per thousand) or gold-mined (-0.09 +/- 0.16 parts per thousand) mineral materials. Negative Delta Hg-199 values in deep pristine mineral horizons (-0.60 +/- 0.16700) suggest the transfer of Hg bound to dissolved OM depleted in odd isotopes due to mass-independent fractionation during Hg abiotic reduction. Perennial palm tree leaves collected above gold-mined and pristine soil recorded contrasting Delta Hg-199 signatures likely resulting from GEM re-emission processes from soils and leaf surfaces. Upslope, soil delta Hg-202 signatures showed a negative shift (epsilon similar to -1 parts per thousand) with depth attributed to mass-dependent fractionation during Hg sorption and complexation onto iron oxides and dissolved OM. Downslope, higher delta Hg-202 values in soils resulted from hydromorphy [lower humification, greater Hg(II) reduction, etc.]. The unique Hg isotopic signatures of Amazonian soils probably result in multistep fractionation processes during pedogenesis (millions of years) and in a potentially different Hg isotopic signature of preanthropogenic background GEM.