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 (K(DOC)) with log K(DOC) 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 bythe EPA protocol), since virtually all (86-99%) of the dissolved PAH concentrations and toxic units were contributed by two- and three-ring PAHs.
Soil and sediment samples from oil gas (OG) and coal gas (CG) manufactured gas plant (MGP) sites were selected to represent a range of PAH concentrations (150-40,000 mg/kg) and sample matrix compositions. Samples varied from vegetated soils to lampblack soot and had carbon contents from 3 to 87 wt %. SFE desorption (120 min) and water/XAD2 desorption (120 days) curves were determined and fit with a simple two-site model to determine the rapid-released fraction (F) for PAHs ranging from naphthalene to benzo[ghi]perylene. F values varied greatly among the samples, from ca. 10% to >90% for the two- and three-ring PAHs and from <1% to ca. 50% for the five- and six-ring PAHs. Release rates did not correlate with sample matrix characteristics including PAH concentrations, elemental composition (C, H, N, S), or "hard" and "softs" organic carbon, indicating that PAH release cannot easily be estimated on the basis of sample matrix composition. Fvalues for CG site samples obtained with SFE and water desorption agreed well (linear correlation coefficient, r2 = 0.87, slope = 0.93), but SFE yielded higher F values for the OG samples. These behaviors were attributed to the stronger ability of carbon dioxide than water to desorb PAHs from the highly aromatic (hard) carbon of the OG matrixes, while carbon dioxide and water showed similar abilities to desorb PAHs from the more polar (soft) carbon of the CG samples. The combined SFE and water desorption approaches should improve the understanding of PAH sequestration and release from contaminated soils and sediments and provide the basis for subsequent studies using the same samples to compare PAH release with PAH availability to earthworms.
Studies into bioaccumulation of polychlorinated biphenyls (PCBs) have increasingly focused on congeners that are freely dissolved in sediment interstitial pore water. Because of their low water solubilities and their tendency to persist and concentrate as they progress in the food chain, interest has grown in methods capable of measuring individual PCB congeners at low part-per-quadrillion (picogram per liter) concentrations. Obtaining large volumes of pore water is difficult (or impossible), which makes conventional analytical approaches incapable of attaining suitable detection limits. In the present study, nondepletive sampling is used to achieve very low detection limits of freely dissolved PCBs, while requiring no separation of the sediment and water slurry. Commercially available 76 microm thick polyoxymethylene (POM) coupons were placed directly into wet sediments and left to reach equilibrium with the pore water and sediment PCBs for up to 84 days, with 28 days found to be sufficient. Freely dissolved concentrations were then calculated by dividing the PCB concentration found in the POM by its POM/water partitioning coefficient (K(POM)). The K(POM) values required for determining water concentrations were measured using two spiked sediments and two historically contaminated sediments for all 62 PCB congeners that are present at greater than trace concentrations in commercial Aroclors. Log K(POM) values ranged from ca. 4.6 for dichloro-congeners to ca. 7.0 for octachloro-congeners and correlate well with octanol/water coefficients (K(OW)) (r(2) = 0.947) so that a simple linear equation can be used to calculate dissolved concentrations within a factor of 2 or better for congeners having no measured K(POM) value. Detection limits for freely dissolved PCBs ranged from ca. 20 pg/L (part-per-quadrillion) for dichloro-congeners down to ca. 0.2 pg/L for higher-molecular-weight congeners. Sorption isotherms were found to be linear (r(2) > 0.995) over at least 3 orders of magnitude for all congeners, demonstrating good quantitative linearity of the method for determining freely dissolved PCB concentrations at environmentally relevant levels.
Polycyclic aromatic hydrocarbon (PAH) partitioning coefficients between sediment organic carbon and water (K(OC)) values were determined using 114 historically contaminated and background sediments collected from eight different rural and urban waterways in the northeastern United States. More than 2100 individual K(OC) values were measured in quadruplicate for PAHs ranging from two to six rings, along with the first reported K(OC) values for alkyl PAHs included in the U.S. Environmental Protection Agency's (U.S. EPA) sediment narcosis model for the prediction of PAH toxicity to benthic organisms. Sediment PAH concentrations ranged from 0.2 to 8600 microg/g (U.S. EPA 16 parent PAHs), but no observable trends in K(OC) values with concentration were observed for any of the individual PAHs. Literature K(OC) values that are commonly used for environmental modeling are similar to the lowest measured values for a particular PAH, with actual measured values typically ranging up to two orders of magnitude higher for both background and contaminated sediments. For example, the median log K(OC) values we determined for naphthalene, pyrene, and benzo[a]pyrene were 4.3, 5.8, and 6.7, respectively, compared to typical literature K(OC) values for the same PAHs of 2.9, 4.8, and 5.8, respectively. Our results clearly demonstrate that the common practice of using PAH K(OC) values derived from spiked sediments and modeled values based on n-octanol-water coefficients can greatly overestimate the actual partitioning of PAHs into water from field sediments.
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