Eight pyrethroids and fipronil and its three major degradates were analyzed in urban estuarine sediments that exhibited a range of toxic effects to an amphipod test species. Sediments from Ballona Creek, an urban estuary in Southern California (USA), collected during three dry season events were analyzed by gas chromatography with electron capture and negative chemical ionization mass spectrometric detection (GC-ECD and GC-NCI-MS). The two detection methods were in agreement for intermediate levels of pyrethroid contamination (10-50 ng/g dry wt) but deviated for both low and high concentrations (< 5 and > 50 ng/g). Sediments contained total pyrethroids as high as 473 ng/g with permethrin, bifenthrin, and cypermethrin as the most abundant compounds. In contrast, fipronil and its desulfinyl, sulfide, and sulfone degradates were detected at much lower levels (

Solid-phase microextraction (SPME) has been used as an in situ sampling technique for a wide range of volatile organic chemicals, but SPME field sampling of nonvolatile organic pollutants has not been reported. This paper describes the development of an SPME-based sampling method employing a poly(dimethylsiloxane) (PDMS)-coated (100-microm thickness) fiber as the sorbent phase. The laboratory-calibrated PDMS-coated fibers were used to construct SPME samplers, and field tests were conducted at three coastal locations off southern California to determine the equilibrium sampling time and compare the efficacy of the SPME samplers with that of an Infiltrex 100 water pumping system (Axys Environmental Systems Ltd., Sidney, British Columbia, Canada). p,p'-DDE and o,p'-DDE were the components consistently detected in the SPME samples among 42 polychlorinated biphenyl congeners and 17 chlorinated pesticidestargeted. SPME samplers deployed attwo locations with moderate and high levels of contamination for 18 and 30 d, respectively, attained statistically identical concentrations of p,p'-DDE and o,p'-DDE. In addition, SPME samplers deployed for 23 and 43 d, respectively, at a location of low contamination also contained statistically identical concentrations of p,p'-DDE. These results indicate that equilibrium could be reached within 18 to 23 d. The concentrations of p,p'-DDE, o,p'-DDE, or p,p'-DDD obtained with the SPME samplers and the Infiltrex 100 system were virtually identical. In particular, two water column concentration profiles of p,p'-DDE and o,p'-DDE acquired by the SPME samplers at a highly contaminated site on the Palos Verdes Shelf overlapped with the profiles obtained by the Infiltrex 100 system in 1997. The field tests not only reveal the advantages of the SPME samplers compared to the Infiltrex 100 system and other integrative passive devices but also indicate the need to improve the sensitivity of the SPME-based sampling technique.

Sediment-quality assessment often is hindered by the lack of agreement between chemical and biological lines of evidence. One limitation is that the bulk sediment toxicant concentration, the most widely used chemical parameter, does not always represent the bioavailable concentration, particularly for hydrophobic organic compounds (HOCs) in highly contaminated sediments. In the present study, we developed and tested a pore-water sampler that uses solid-phase microextraction (SPME) to measure freely dissolved (bioavailable) HOC concentrations. A single polydimethylsiloxane (PDMS)-coated SPME fiber is secured in a compact, protective housing that allows aqueous exchange with whole sediment while eliminating direct contact with sediment particles. Fibers with three PDMS coating thicknesses were first calibrated for 12 model HOCs of current regulatory concern. Precalibrated samplers were exposed to spiked estuarine sediment in laboratory microcosms to determine the time to equilibrium and the equilibrium concentrations across a range of sediment contamination. Time to equilibrium ranged from 14 to 110 d, with 30 d being sufficient for more than half the target HOCs. Equilibrium SPME measurements, ranging from 0.009 to 2,400 ng/L, were highly correlated with but, in general, lower than HOC pore-water concentrations determined independently by liquid-liquid extraction. This concept shows promise for directly measuring the freely dissolved concentration of HOCs in sediment pore water, a previously difficult-to-measure parameter that will improve our ability to assess the impacts of contaminated sediments.