Concentrations and leachability of chemical elements in estuarine sulfur-rich sediments, W. Finland

Concentrations, distributions and mobility of chemical elements were investigated in reduced sulfur-rich estuarine sediments located in western Finland. The main objective was to determine the possible extent of metal leaching when dredged masses of these sulfur-rich sediments are dumped on the land and thus exposed to air. When dredged, the reduced sulfur in the sediments oxidises resulting in a lowering of pH, which in turn is expected to leach metals. The study area is an artificial lake claimed from the Botnian sea in 1962. In this lake, several mass-kills of fish have occurred, believed partly to be due to dredging. Two sediment samples (0-50 and 50-100 cm) were taken from 39 sampling points in the lake. These samples were leached in aqua regia (2:2:2 HNO3/HCl/H2O1) and analysed for Fe, Al, Mg, Ca, K, P, Na, Mn, Zn, Ba, V, Sr, Cr, Ni, Cu, Co, As, Pb, B, Mo and Cd with ICP-AES. Sulfur and organic carbon were analysed with Leco. In a controlled laboratory experiment, the sediments were allowed to oxidise for 1 year while moisturised with deionised water every month. The pH and conductivity were determined in the beginning of the experiment (reduced state) and in the end (oxidised state). In the supernatants in the oxidised states the amount of leached metals (Na, Al, Mn, Zn, Sr, Co, Ni, Cu, Cd, Cr, Pb, U, Li, Rb and As) were determined with ICP-MS. The sediments were found to contain low levels of toxic metals but, as expected, high concentrations of sulfur. In the experiment, pH was lowered (down to 3.0) and the conductivity increased in all samples due to oxidation and release of metal ions. The extent of leaching varied between 0.03% for As and 12.3% for Na. Critical pH values, at which high amounts of metals begin to leach, were obtained graphically. These values varied between 4.8 (Ni) and 3.3 (Cr). Not all elements were controlled by pH, e.g. Mn correlated well with its aqua regia leachable concentration. In a planned dredging operation in the area some 23,300 t (10,500 m3) (dry wt.) of sediments will be dredged. The amounts of metals likely to be leached, according to the results from this study, are as follows (kg): Al (1710), Mn (1230), Zn (59), Sr (39), Co (13), Ni (12), Cu (2) and less than 1 kg of Cd-Cr-As-Pb.