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The goal of this research is to develop models for predicting the toxicity and mobilization of individual metals
and metal mixtures in sediments. These predictions are critical in evaluating the risk associated with
contaminated sediments at Superfund sites. In past Superfund basic research projects, we have developed
methods of assessing the toxicity of individual metals - Cd, Cu, Ni, Pb and Zn - for sediments with excess
acid volatile sulfides (AVS). We propose to develop a model that predicts the toxicity of metals in sediments
with little or no AVS. This requires a prediction of the partitioning of sediment metals to the other important
sediment phases - sediment organic carbon if it is in sufficient supply, and then the other phases (e.g. iron
oxyhydroxides) that are important in the aerobic layer of sediments. We also propose to develop the next
generation of models for the prediction of mobilization of metals from sediments that explicitly include the
mechanisms of mobilization. We intend to model the mechanisms of metal sulfide oxidation directly and to
relate them to the cycles of manganese and iron in sediments. We have included such a mechanism
nvolving the Fe(ll)-facilitated oxidation of arsenic in our present project. We propose to extend this work to
the oxidation of metal sulfides.
Our specific aims are:
1. For cationic metals, to extend the sediment Biotic Ligand Model (BLM) so that it can predict the toxicity of
metals and metal mixtures by considering competitive interactions of metals and major ions to the organic
carbon, (hydrous) oxide surfaces, clays and to uptake sites on benthic organisms.
2. For metals that form insoluble metal sulfides in sediments (Cd, Cu, Ni, Pb, Zn), to determine the rates of
metal sulfide oxidation and their dependence on solution parameters for inclusion in metal mobilization
models.
3. For arsenic, to investigate the effects of inorganic and organic ligands present in sediments that affect
the rate of Fe(ll)-catalyzed oxidation of arsenite and ultimately the rates of arsenic mobilization from
sediments.
4. For chromium, to investigate the effect of natural organic matter on the rates of chromium(lll) oxidation
by manganese oxide in sediments, and the subsequent release of chromium(VI) to the pore water and the
overlying water.
5. For the metals discussed above, to construct an integrated model that combines the metal mobilization
and toxicity mechanisms, together with a model of the seasonal cycling of redox-sensitive species including
oxygen, organic matter, iron, manganese and sulfur in sediments.