Tenax extraction and matrix solid-phase microextraction (matrix-SPME) were used to study desorption of hydrophobic contaminants (HOC) from sediments. 14C-labeled hexachlorobiphenyl, DDE, permethrin, chlorpyrifos, and phenanthrene were individually spiked into sediments differing in physical characteristics. Sequestration of the HOCs into sediment was observed for all compounds, and desorption was described by rapid, slow, and very slow rates. The freely dissolved HOC concentration in the sediment porewater was estimated by matrix-SPME, and serial sampling was used to ensure equilibrium was achieved among sediment, porewater and matrix-SPME fiber. Differences in partitioning of the HOCs between sediment and porewater for the different sediments were reduced by replacing the HOC concentration in sediment with the rapidly desorbing fraction. The significantly lower porewater concentration determined from matrix-SPME, than predicted from equilibrium partitioning theory (EPT), showed that only a small fraction of sediment HOCs were available for equilibrium and the predictability of EPT can be improved with the consideration of sequestration in sediment. A good correlation was noted between sediment concentration in the rapidly desorbing fraction measured by Tenax extraction, and SPME fiber concentration as determined by matrix-SPME. Thus, the two methods both tracked the readily desorbed contaminant equally well though Tenax extraction measures the accessible pool, and matrix-SPME measures the chemical activity of the HOCs.

Tenax extraction is a simple, inexpensive approach to estimate the bioavailability of hydrophobic organic contaminants from sediment. In the present study, a single-point Tenax extraction was evaluated regarding its correlation with the acute toxicity to Hyalella azteca using field-collected sediments in California, USA. Pyrethroids were believed to be the primary contributor to the observed toxicity, and a significant correlation existed between the expected toxicity (given pyrethroid concentrations) and the mortality at most sampling sites. A small subset of sites, however, showed unexpectedly low toxicity to H. azteca despite high concentrations of pyrethroids. These samples were evaluated by Tenax extraction with the expectation that this procedure, which qualifies bioavailable instead of total pyrethroid concentration in sediment, would better explain the anomalously low toxicity. The term bioavailable toxic unit was proposed to link sediment toxicity with chemical availability, and the toxicity in the 17 selected sediments was better explained using Tenax extraction. The r2 value of the regression between sediment toxicity and toxic unit for the 17 sediments increased from 0.24 to 0.60 when the Tenax-extractable concentration was used in place of the total concentration. Results also showed that adsorption to sand particles might play a controlling role in pyrethroid bioavailability and, in turn, sediment toxicity to benthic invertebrates.

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