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Abstract-For the Chesapeake Bay, sediments in regions such as Baltimore Harbor have total mercury (Hg) concentrations that exceed environmental effects guidelines. However, fish concentrations do not appear elevated. Indeed, the factors controlling the transfer of sedimentary Hg, especially as monomethylmercury (MMHg), the most bioaccumulative form of Hg, to these aquatic organisms are poorly understood. To examine this, we have investigated the distribution and bioavailability of Hg and MMHg to benthic organisms in Baltimore Harbor and the Chesapeake Bay, in Maryland, USA. The results discussed here show that sediment concentration for both total Hg and MMHg covaries with sediment organic content and that this parameter is a better predictor, for surface sediments, of concentration than iron content, acid volatile sulfide (AVS), or other factors. Furthermore, correlations between inorganic Hg and MMHg in benthic biota with sediment levels suggest that variation in the bioaccumulation factor (SBAF) for invertebrates is best explained in terms of sediment organic content. Thus, the results from this study emphasize the importance of organic matter in regions removed from point source input in controlling both the concentration and bioavailability of MMHg to organisms. Because of the exponential nature of the SBAF/organic content relationship, there is a nonlinear organism response to MMHg in sediments that must be considered in any estimation of the toxic effect of sediment MMHg. Also, as a result of the decoupling between total Hg and MMHg concentration and bioavailability in surface sediments, any remediation evaluation of bioavailability and/or toxicity that is based only on total Hg concentration is unlikely to provide a reliable prediction.

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The bioavailability of particle-associated inorganic mercury (HgI) and monomethylmercury (MMHg) was evaluated in vitro using digestive fluid of the deposit feeding lugworm, Arenicola marina. Digestive fluid, removed from the midgut of the polychaete, was incubated with contaminated sediment, and the proportion of HgI or MMHg solubilized by the digestive fluid was determined. Digestive fluid was found to be a more effective solvent than seawater in solubilizing particle-associated HgI and MMHg. A greater percentage of MMHg than HgI was solubilized from most sediments, suggesting that sediment-associated MMHg is generally more readily available from sediment for biological uptake. The proportion of MMHg released from the sediment was inversely correlated with sediment organic matter content, decreasing exponentially with increasing organic matter content of the sediment. The results for HgI were equivocal. MMHg bioaccumulation factors (BAFs) from previous studies showed a similar trend with organic content of sediment, suggesting that solubilization may be the process limiting the bioaccumulation of particle-bound MMHg. It is concluded that in vitro extraction with a deposit feeder's digestive fluid provides a potential tool to study the process of Hg bioaccumulation via ingestion routes, although its application to various sediments and organisms needs further investigation.

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