Measuring Low Picogram Per Liter Concentrations of Freely Dissolved Polychlorinated Biphenyls in Sediment Pore Water Using Passive Sampling with Polyoxymethylene

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 mu m 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.