The effect of sediment redox chemistry on solubility/chemically active forms of selected metals in bottom sediment receiving produced water discharge

Abstract

The effect of sediment redox conditions on the solubility behavior of Fe, Pb, Ni, Ba, and Cu in bottom sediment collected from a produce water discharge site was investigated using kinetics and chemical fractionation procedures. Sediment collected was composited and subsamples incubated in laboratory microcosms under controlled Eh-pH conditions. Sediment was sequentially extracted for determining metals in five fractions (exchangeable, carbonate, bound to iron and manganese oxide, bound to organic matter and sulfide, mineral matrix or residue). Metal distribution in the fractions indicates that under oxidizing sediment conditions, the behavior of Fe, Pb and Ni were governed by Fe(III) and Mn(IV) oxides; Ba by insoluble complexation with humic compounds; and Cu by carbonates and humic complexation. Under reducing sediment condition, the behaviors of Fe and Cu were controlled by the formation of insoluble sulfides and humic complexes; the behaviors of Ni and Ba by carbonate and Pb behavior by sulfides, carbonates and humic complexes. With increases in sediment redox potential, the affinity between Fe(III), Mn(IV) oxides and Fe, Pb, Ni, Cu increased, the affinity between insoluble large molecular humic and Ba increased, and the affinity between carbonates and Cu increased. With decreasing sediment redox potential, the affinity between carbonates and Fe, Ni, Ba increased; the affinity between sulfides, humic substances and Fe, Pb, Ni, Cu also increased. Upon Fe(III) oxide reduction, it is estimated that 20% of total reducible Fe(III) oxides was reduced by direct bacterial reduction ( K = −42.6 ppm/day), 80% of total reducible Fe(III) oxides was associated with chemical fractions attributed to sulfide oxidation ( K = −171.5 ppm/day). The rate constants (ppm/day) for dissolved Ni (Eh <0 mV), Pb (Eh < −80 mV) and Cu (−80 mV < Eh <0 mV) are −1.6, −0.047 and −0.16, respectively. In our incubation period, the rate constants (ppm/day) for Ni bound to Fe(III) and Mn(IV) oxides, Ba bound to carbonates and Cu bound to insoluble large molecular humic are −3.2, 0.91 and 4.3, respectively.