Permeability/performance reference compounds (PRCs) are analytically noninterfering organic compounds with moderate to high fugacity from semipermeable membrane devices (SPMDs) that are added to the lipid prior to membrane enclosure. Assuming that isotropic exchange kinetics (IEK) apply and that SPMD-water partition coefficients are known, measurement of PRC dissipation rate constants during SPMD field exposures and laboratory calibration studies permits the calculation of an exposure adjustment factor (EAF). In theory, PRC-derived EAF ratios reflect changes in SPMD sampling rates (relative to laboratory data) due to differences in exposure temperature, membrane biofouling, and flow velocity-turbulence at the membrane surface. Thus, the PRC approach should allow for more accurate estimates of target solute/vapor concentrations in an exposure medium. Undersome exposure conditions, the impact of environmental variables on SPMD sampling rates may approach an order of magnitude. The results of this study suggest that most of the effects of temperature, facial velocity-turbulence, and biofouling on the uptake rates of analytes with a wide range of hydrophobicities can be deduced from PRCs with a much narrower range of hydrophobicities. Finally, our findings indicate that the use of PRCs permits prediction of in situ SPMD sampling rates within 2-fold of directly measured values.

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The seasonal occurrence of organic contaminants, many of which are potential endocrine disruptors, entering the Potomac River, USA, watershed was investigated using a two-pronged approach during the fall of 2005 and spring of 2006. Passive samplers (semipermeable membrane device and polar organic chemical integrative sampler [POCIS]) were deployed in tandem at sites above and below wastewater treatment plant discharges within the watershed. Analysis of the samplers resulted in detection of 84 of 138 targeted chemicals. The agricultural pesticides atrazine and metolachlor had the greatest seasonal changes in water concentrations, with a 3.1- to 91-fold increase in the spring compared with the level in the previous fall. Coinciding with the elevated concentrations of atrazine in the spring were increasing concentrations of the atrazine degradation products desethylatrazine and desisopropylatrazine in the fall following spring and summer application of the parent compound. Other targeted chemicals (organochlorine pesticides, polycyclic aromatic hydrocarbons, and organic wastewater chemicals) did not indicate seasonal changes in occurrence or concentration; however, the overall concentrations and number of chemicals present were greater at the sites downstream of wastewater treatment plant discharges. Several fragrances and flame retardants were identified in these downstream sites, which are characteristic of wastewater effluent and human activities. The bioluminescent yeast estrogen screen in vitro assay of the POCIS extracts indicated the presence of chemicals that were capable of producing an estrogenic response at all sampling sites.

Passive sampling methodologies were used to conduct a chemical and toxicologic assessment of organic contaminants in the surface waters of three geographically distinct agricultural watersheds. A selection of current-use agrochemicals and persistent organic pollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides, were targeted using the polar organic chemical integrative sampler (POCIS) and the semipermeable membrane device passive samplers. In addition to the chemical analysis, the Microtox assay for acute toxicity and the yeast estrogen screen (YES) were conducted as potential assessment tools in combination with the passive samplers. During the spring of 2004, the passive samplers were deployed for 29 to 65 d at Leary Weber Ditch, IN; Morgan Creek, MD; and DR2 Drain, WA. Chemical analysis of the sampler extracts identified the agrochemicals predominantly used in those areas, including atrazine, simazine, acetochlor, and metolachlor. Other chemicals identified included deethylatrazine and deisopropylatrazine, trifluralin, fluoranthene, pyrene, cis- and trans-nonachlor, and pentachloroanisole. Screening using Microtox resulted in no acutely toxic samples. POCIS samples screened by the YES assay failed to elicit a positive estrogenic response.

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