Chemistry of metal sulfides in anoxic sediments

Abstract

Using sequential extraction of solid sulfides, the determination of acid volatile sulfides (AVS) and chromium reducible sulfurs (CRS) in anoxic sediments from the Authie Bay (in northern France) has been undertaken because of the importance of the sediments as sinks for iron, sulfur and trace metals and as possible sources of pollution when reduced sediments are mixed with oxic waters (as a result of a sediment remobilization induced by physical disturbances such as tidal currents and dredgings), and subsequently oxidized. Chemical analysis of solutions recovered after sequential leaching of sediments with 1 M HCl, 1 M HF and concentrated HNO₃ has enabled us to obtain profiles, s. sediment depth, of trace metals associated with pyrite. Porewater concentration profiles s. depth have been determined for several cations (Ca²⁺, Cd²⁺, Cu²⁺, Fe²⁺, Mg²⁺, Mn²⁺, Na⁺, Pb²⁺, Sr²⁺ and Zn²⁺) and anions (CO₃²⁻, PO₄³⁻, SO₄²⁻ and S²⁻). Using the chemical equilibrium modeling program MINEQL⁺ with these analytical data, thermodynamic calculations have given information about the possibility of precipitation of discrete metal sulfide phases (FeS as greigite and amorphous FeS; ZnS, PbS, CuS and CdS), and coprecipitation with adsorption on solid FeS to produce solid solutions with iron sulfides. The degree of trace metal pyritization, DTMP, has been determined for these metals and compared to the degree of pyritization, DOP. The findings suggest that in Authie-bay sediments Mn is well pyritized; whereas Zn, Cu, Ni and above all Cd are weakly pyritized (MnZn≃Cu>NiCd). These observations seem to be intimately related to the existence of the discrete/separate solid phases CuS, CdS and ZnS, as predicted by thermodynamic calculations. Finally, analysis of crude sediments, heavy minerals and pyrite extracted by a heavy liquid density separation method, has been performed with a Raman microprobe to gain information about the geochemical and mineralogical characteristics of these sediments. The efficiency of sequential leachings of sediments (which were used for sedimentary pyrite recovery/attack and analysis of pyritic Fe and trace metal) has also been evaluated by these techniques.