In situ high-resolution two-dimensional profiles of redox sensitive metal mobility in sediment-water interface and porewater from estuarine sediments

Metals in contaminated sediments may present high environmental risks and ecological threats to benthic organisms. Redox sensitive elements with different oxidation states show variations in solubility as a function of redox status of the sediment water environment. The novel high-resolution ZrO-Chelex-AgI diffusive gradients in thin film (HR-ZCA DGT) technique provided sensitive in situ mapping of metals in the estuarine sediments. The present study investigated the sub-millimeter two-dimensional distributions of DGT-labile S(-II), P(V), and six redox sensitive metals (Fe, Mn, V, Cu, Ni, and Zn) across sediment-water interface (SWI) severely influenced by anthropogenic activity. We for the first time used the V-turning value (the V/Fe ratios at ~0.03) to accurately identify the actual SWI. The diffusion boundary layer (DBL) thickness of Ni, Cu and Zn was consistent with those identified by the dissolved oxygen microelectrode method, and was 3-6 mm above the SWI. No significant release of dissolved Fe and P from sediments into the overlying water was found by diffusion process. The estimated fluxes (Fdif) of Ni, Cu, and Zn at DBL were 4.0-176, -1.1-235, and 5.0-108 μg m-2 d-1, respectively, and were significantly higher in sediments near the industrial effluent dumping sites than those in sediments impacted by domestic wastewater releases. Metal diffusion flux was mainly controlled by the particulate matter on the surface sediment and organic degradation. Traditional diffusion flux may have underestimated the flux of metals from the surface sediments. The discharge of hypoxic tributary was an important source of metal pollution in the contaminated estuarine sediments.