The total concentration of contaminants in an environmental matrix is not predictive of the potential for adverse ecological or public health effects. Contaminants introduced in the environment undergo a variety of reactions that reduce their activity and thus their bioavailability to target organisms. These reactions include sorption onto or into particles, complexation with detrital organic matter, or precipitation as insoluble complexes. What is needed from a decision making standpoint is an ability to determine the fraction of contaminants in a sample available for partitioning into target receptors. This is obviously necessary to truly estimate the effects contaminants will have a given ecosystem. Current techniques to examine bioavailability involve rigorous analytical separations in a laboratory setting. These methods can be time consuming, and potentially suffer from artifacts introduced through alteration of sample conditions during sampling and analysis. The goal of this proposal is to develop and field test sampling devices that determine the free activity (as opposed to the total concentration) of metal and organic contaminants in the aquatic sediments. The basis premise of the samplers is to introduce a solid or liquid substrate with a known thermodynamic affinity for a contaminant of interest. The extent of contaminant partitioning to the substrate can be used to determine the contaminant's activity in the original sample. These samplers can be used to further examine specific environmental factors that control the activity and original sample. These samplers an be used to further examine specific environmental factors that control the activity and bioavailability of contaminants in the environment. Semipermeable membrane devices (SPMDs) will be used to examine the bioavailability of sedimentary PAHs under both laboratory and field conditions. The primary hypothesis to be tested is that the presence of soot phase carbon (in addition to total organic carbon) from hydrocarbon combustion will alter the partitioning of PAHs such that a pyrogenic mixture of PAH's from combustion sources will be less bioavailable than a similar concentration of a petrogenic mixture of PAH's arising from oil spills. For metal contaminants, a silica plate with immobilized 8-Hydroxyquinoline that samples free metal ions will be constructed to test the hypothesis that the free ion concentration of metal concentrations from the sulfide and total organic carbon concentrations.
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