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 (

Passive sampling was used to deduce water concentrations of persistent organic pollutants (POPs) in the vicinity of a marine Superfund site on the Palos Verdes Shelf, California, USA. Precalibrated solid phase microextraction (SPME) fibers and polyethylene (PE) strips that were preloaded with performance reference compounds (PRCs) were codeployed for 32 d along an 11-station gradient at bottom, surface, and midwater depths. Retrieved samplers were analyzed for DDT congeners and their breakdown products (DDE, DDD, DDMU, and DDNU) and 43 PCB congeners using GC-EI- and NCI-MS. PRCs were used to calculate compound-specific fractional equilibration achieved in situ for the PE samplers, using both an exponential approach to equilibrium (EAE) and numerical integration of Fickian diffusion (NI) models. The highest observed concentrations were for p,p'-DDE, with 2200 and 990 pg/L deduced from PE and SPME, respectively. The difference in these estimates could be largely attributed to uncertainty in equilibrium partition coefficients, unaccounted for disequilibrium between samplers and water, or different time scales over which the samplers average. The concordance between PE and SPME estimated concentrations for DDE was high (R(2) = 0.95). PCBs were only detected in PE samplers, due to their much larger size. Near-bottom waters adjacent to and down current from sediments with the highest bulk concentrations exhibited aqueous concentrations of DDTs and PCBs that exceeded Ambient Water Quality Criteria (AWQC) for human and aquatic health, indicating the need for future monitoring to determine the effectiveness of remedial activities taken to reduce adverse effects of contaminated surface sediments.

Passive samplers were deployed to the seafloor at a marine Superfund site on the Palos Verdes Shelf, California, USA, and used to determine water concentrations of persistent organic pollutants (POPs) in the surface sediments and near-bottom water. A model of Fickian diffusion across a thin water boundary layer at the sediment-water interface was used to calculate flux of contaminants due to molecular diffusion. Concentrations at four stations were used to calculate the flux of DDE, DDD, DDMU, and selected PCB congeners from sediments to the water column. Three passive sampling materials were compared: PE strips, POM strips, and SPME fibers. Performance reference compounds (PRCs) were used with PE and POM to correct for incomplete equilibration, and the resulting POP concentrations, determined by each material, agreed within 1 order of magnitude. SPME fibers, without PRC corrections, produced values that were generally much lower (1 to 2 orders of magnitude) than those measured using PE and POM, indicating that SPME may not have been fully equilibrated with waters being sampled. In addition, diffusive fluxes measured using PE strips at stations outside of a pilot remedial sand cap area were similar to those measured at a station inside the capped area: 240 to 260 ng cm(-2) y(-1) for p,p'-DDE. The largest diffusive fluxes of POPs were calculated at station 8C, the site where the highest sediment concentrations have been measured in the past, 1100 ng cm(-2) y(-1) for p,p'-DDE.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

No abstract

In the present work, a novel method for the determination of trihalomethanes (THMs) such as chloroform, dichlorobromomethane, chlorodibromomethane and bromoform in drinking water has been described. It is based on coupling headspace liquid-phase microextraction (HS-LPME) with gas chromatography-electron capture detector (GC-ECD). A microdrop of organic solvent at the tip of a commercial microsyringe was used to extract analytes from aqueous samples. Three organic solvents-xylene, ethylene glycol and 1-octanol-were compared and 1-octanol was the most sensitive solvent for the analytes. Extraction conditions such as headspace volume, extraction time, stirring rate, content of NaCl and extraction temperature were found to have significant influence on extraction efficiency. The optimized conditions were 15 ml headspace volume in a 40 ml vial, 10 min extraction time and 800 rpm stirring rate at 20 • C with 0.3 g ml −1 NaCl. The linear range was 1-100 g l −1 for THMs. The limits of detection (LODs) ranged from 0.15 g l −1 (for dichlorobromomethane and chlorodibromomethane) to 0.4 g l −1 (for chloroform); and relative standard deviations (RSD) for most of THMs at the 10 g l −1 level were below 10%. Real samples collected from tap water and well water were successfully analyzed using the proposed method. The recovery of spiked water samples was from 101 to 112%.

No abstract

No abstract