Contributions of theory to method development in solid-phase extraction.

The kinetic and retention properties of solid-phase extraction devices are reviewed from the perspective of method development strategies. Models based on frontal analysis are used to correct retention properties of solid-phase extraction devices to account for the fact that too few theoretical plates are provided for retention to be independent of kinetic factors. The available pressure drop for the sampling device largely dictates the choice of useful particle sizes and maximum bed length. The use of octanol--water partition coefficients and extrapolated values of the retention factor obtained by liquid chromatography are poor empirical models for the estimation of breakthrough volumes with water as the sample solvent. The solvation parameter model provides an adequate description of sorbent retention for the estimation of breakthrough volumes, rinse solvent volume and composition, and elution solvent volume and composition. Combining the frontal analysis and solvation parameter models offers a comprehensive approach to computer-aided method development in solid-phase extraction. This is the first step in the development of a structure-driven approach to method development in solid-phase extraction that should be more reliable and less tedious than traditional trial and error approaches.

Models for estimating the non-specific toxicity of organic compounds in short-term bioassays.

The solvation parameter model is used to construct equations for the estimation of the non-specific toxicity of neutral organic compounds to five organisms used for short-term toxicity testing. For the bacteria Vibrio fischeri (Microtox test) and Pseudomonas putida, the protozoan Tetrahymena pyriformis (Tetratox test), the green alga Scendesmus quadricauda and the brine shrimp Artemia salina, the main factors resulting in increased non-specific toxicity are size (dominantly) and lone-pair electron interactions, with hydrogen-bond basicity the most important solute property reducing toxicity. Species differences in relative non-specific toxicity are largely related to differences in cohesion and hydrogen-bond acidity of the biomembranes. The models for non-specific toxicity are proposed as an alternative to the octanol-water distribution constant for the determination of baseline toxicity. Failure of the octanol-water distribution constant to model non-specific toxicity is quantitatively explained by its inability to adequately characterize the sorption properties of the biomembranes for compounds with varied properties.