The objective of this study was to evaluate an organic carbon partitioning model for predicting bioavailability of the organophosphate chlorpyrifos in sediments, in support of the development of a sediment-quality criterion for the pesticide. Initial 10-d water-only toxicity tests were conducted with the midge Chironomus tentans to define the sensitivity of this species to chlorpyrifos. Two uncontaminated sediments with differing organic carbon contents (approximately 3 and 8.5%) were spiked with varying amounts of chlorpyrifos designed to result in equilibrium interstitial (pore) water concentrations that would bracket the effects concentrations observed in the water-only exposures. Ten-day toxicity tests with Chironomus tentans were conducted with the spiked sediments under conditions similar to those in the water-only exposure. Based on predicted pore-water concentrations of chlorpyrifos, results of the water-only and sediment tests were in close agreement. The water-only LC50 of chlorpyrifos to Chironomus tentans was 70 ng/L, whereas LC50 values based on predicted pore-water concentrations in the two test sediments were 40 and 70 ng/L. Total concentrations of chlorpyrifos measured in pore water from the test sediments were always at least an order of magnitude greater than predicted pore-water concentrations of the pesticide. However, upon correction for that fraction of the measured chlorpyrifos potentially bound to DOC in the pore water, measured and predicted chlorpyrifos concentrations were in much closer agreement, with the former typically about threefold greater than the latter. Overall, these results suggest that within the range of organic carbon tested in the present study, an equilibrium partitioning model based on organic carbon is appropriate for predicting the bioavailability of sediment-associated chlorpyrifos to benthic invertebrates.