Volatile losses were measured from polydimethylsiloxane (PDMS) passive samplers during determination of contaminant porewater concentrations in sediments. Volatile losses could occur between the time of retrieval and processing of the passive sampler or in intertidal environments where the passive sampler could potentially be exposed above the water surface at low tide. A model was developed to predict losses of absorbed compounds as a function of sorbent geometry and the Henry’s Law Coefficient and PDMS-water partition coefficient of the compound of interest. The model suggests that thin layers of PDMS typically used to minimize equilibration times in passive sampling (≤30 µm) may not provide quantitative measurement of naphthalenes or other lighter volatile compounds without special efforts to reduce losses. The results suggest that the samplers should be processed rapidly onsite or kept at low temperatures after retrieval to maximize retention of more volatile compounds or designed with thick PDMS layers. The results also suggest that less volatile compounds, including phenanthrene, and higher molecular weight polynuclear aromatic hydrocarbons (PAHs) exhibit minimal evaporative losses with typical sample processing times.
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