Research during the last decade has led to several competing concepts of bioavailability and to many more methods to measure bioavailability. One reason for disagreement is the confusion of two fundamentally different parameters, accessible quantity and chemical activity. The accessible quantity describes a mass of contaminants, which can become available to, for example, biodegradation and biouptake. It can be determined with mild extraction schemes or depletive sampling techniques. The chemical activity, on the other hand, quantifies the potential for spontaneous physicochemical processes, such as diffusion, sorption, and partitioning. For instance, the chemical activity of a sediment contaminant determines its equilibrium partitioning concentration in sediment-dwelling organisms, and differences in chemical activity determine the direction and extent of diffusion between environmental compartments. Chemical activity can be measured with equilibrium sampling devices and, theoretically, is closely linked to fugacity and freely dissolved concentration. The distinction between accessibility and chemical activity is outlined, and the benefits and limitation of both endpoints are provided. Finally, examples of how to measure and apply them are presented.

A major thrust of environmental science over the past four decades has been improved and more extensive monitoring of organic and metallic contaminants in environmental media. We now recognize that the release of contaminants inevitably results in finite, and usually detectable, concentrations in air, water, soils, sediments, and animal and plant biota. These concentrations may exert adverse effects on ecosystems and human health through multiple sources and pathways with variable and often poorly understood degradation routes and rates. For example, significant concentrations can be established in unexpected places, such as cold climates.

Polymer coated glass fibers were applied as disposable samplers to measure dissolved concentrations of persistent and bioaccumulative pollutants (PBPs) in sediment porewater. The method is called matrix solid-phase microextraction (matrix-SPME), because it utilizes the entire sediment matrix as a reservoir for an equilibrium extraction:  a glass fiber with a 15 μm coating of poly(dimethylsiloxane) (PDMS) was placed in a sediment sample until the PBPs reached their equilibrium distribution between the PDMS and the sediment matrix (1−30 days). PBP concentrations in the PDMS were determined by gas chromatography, and they were divided by PDMS water partition coefficients to derive at dissolved porewater concentrations. This approach was applied to measure porewater concentrations of spiked as well as field sediment, and several hydrophobic organic substances (log K OW 5.2−7.5) were measured with high precision in the pg to ng/L range. Simple equilibrium partitioning is the basis for the substantial concentration factors that are built into matrix-SPME and for the low demands in materials and operation time. Matrix-SPME was in this study directed at the determination of dissolved porewater concentrations in sediment, and it is further expected to be applicable to other environmental media, to field sampling, and to the sensing of fugacity.

There is an increasing body of evidence that the bioaccumulation of sediment-associated hydrophobic organic compounds (HOCs) is strongly influenced by sequestration. At present, it is not known how equilibrium partitioning theory (EqP), the most commonly employed approach for describing sediment bioaccumulation can be applied to sediments with sequestered contaminants. In this paper, we present freely dissolved pore-water concentrations of HOCs. These data were employed to interpret sediment bioaccumulation and sequestration data in order to arrive at a process based evaluation of EqP. The data analysis suggests that sediment bioaccumulation of compounds up to log K(ow) 7.5 in Tubificidae can be described as bioconcentration from pore-water. In addition, the pore-water concentrations of HOCs (4.5 < log K(ow) < 7.5) are established by equilibrium partitioning between the rapidly desorbing HOCs fraction in the sediment and the pore-water. Taken together, these findings indicate that EqP is a conceptually correct representation of sediment bioaccumulation, provided that sequestration is accounted for. This implies that the risk assessment of sediment-associated HOCs can be significantly simplified: With a method at hand for measuring freely dissolved pore-water concentrations of HOCs, it appears that HOCs' body residues in sediment dwelling organisms can be estimated on the basis of concentrations in pore-water and bioconcentration factors.

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