In contrast to the general research attitude in the basic sciences, environmental sciences are often goal-driven and should provide the scientific basis for risk assessment procedures, cleanup, and precautionary measures and finally provide a decision support for policy and management. Hence, the prominent role of mechanistic studies in ecotoxicology is not only to understand the impact of pollutants on living organisms but also to deduce general principles for the categorization and assessment of effects. The goal of this review is, therefore, not to provide an exhaustive coverage of modes of toxic action and their underlying biochemical mechanisms but rather to discuss critically the application of this knowledge in ecotoxicological risk assessment. Knowing the mechanism or, at least the mode of toxic action is indispensable for developing descriptive and predictive models in ecotoxicology. This review seeks to show the crucial role of target sites, interactions with the target site(s), and mechanisms for an adequate and efficient ecotoxicological risk assessment. Emphasis in the discussion is on target effect concentrations (or target occupancy), species selectivity and species sensitivity, time perspective of effect studies, Quantitative Structure-Activity Relationships (QSAR), and mixture toxicity. A particular focus of this review is on multiple mechanisms. Although the illustrative examples were mainly taken from studies in aquatic ecotoxicology, the proposed conceptual approach is also in principle applicable and even particularly useful for soil and sediment systems. Recommendations for further research and developments include the use of internal effect concentrations and target site concentrations in site-specific risk assessment and as a mixture toxicity parameter as well as general considerations for the derivation of mechanistically meaningful QSAR and other predictive models.

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.

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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.