Solid-Phase Microextraction Measurement of Parent and Alkyl Polycyclic Aromatic Hydrocarbons in Milliliter Sediment Pore Water Samples and Determination of KDOC Values

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Abstract
The U.S. Environmental Protection Agency (EPA) narcosis model for benthic organisms in polycyclic aromatic hydrocarbon (PAH) contaminated sediments requires the measurement of 18 parent PAHs and 16 groups of alkyl PAHs (“34” PAHs) in pore water with desired detection limits as low as nanograms per liter. Solid-phase microextraction (SPME) with gas chromatographic/mass spectrometric (GC/MS) analysis can achieve such detection limits in small water samples, which greatly reduces the quantity of sediment pore water that has to be collected, shipped, stored, and prepared for analysis. Four sediments that ranged from urban background levels (50 mg/kg total “34” PAHs) to highly contaminated (10 000 mg/kg total PAHs) were used to develop SPME methodology for the “34” PAH determinations with only 1.5 mL of pore water per analysis. Pore water was obtained by centrifuging the wet sediment, and alum flocculation was used to remove colloids. Quantitative calibration was simplified by adding 15 two- to six-ring perdeuterated PAHs as internal standards to the water calibration standards and the pore water samples. Response factors for SPME followed by GC/MS were measured for 22 alkyl PAHs compared to their parent PAHs and used to calibrate for the 18 groups of alkyl PAHs. Dissolved organic carbon (DOC) ranging from 4 to 27 mg/L had no measurable effect on the freely dissolved concentrations of two- and three-ring PAHs. In contrast, 5−80% of the total dissolved four- to six-ring PAHs were associated with the DOC rather than being freely dissolved, corresponding to DOC/water partitioning coefficients (KDOC) with log KDOC values ranging from 4.1 (for fluoranthene) to 5.6 (for benzo[ghi]perylene). However, DOC-associated versus freely dissolved PAHs had no significant effect on the total “34” PAH concentrations or the sum of the “toxic units” (calculated by the EPA protocol), since virtually all (86−99%) of the dissolved PAH concentrations and toxic units were contributed by two- and three-ring PAHs.