Interlaboratory study of polyethylene and polydimethylsiloxane polymeric samplers for ex situ measurement of freely dissolved hydrophobic organic compounds in sediment porewater

Abstract

We evaluated the precision and accuracy of multilaboratory measurements for determining freely dissolved concentrations (Cfree) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediment porewater using polydimethylsiloxane and low-density polyethylene polymeric samplers. Four laboratories exposed performance reference compound (PRC) preloaded polymers to actively mixed and static ex situ sediment for approximately one month or more. For Cfree results, intralaboratory precision was high for single compounds; most PAHs and PCBs variability was low. Variability was higher for most hydrophobic PAHs, PCBs, and naphthalene, which were present at low concentrations and required larger PRC-based corrections. Intra- and interlaboratory variability between methods was low. Cfree polymer equilibrium was achieved in approximately one month during active exposures, suggesting using PRCs may be avoided for ex situ analysis using comparable active exposure; however, such testing may not reflect field conditions. Polymer-derived Cfree concentrations for most PCBs and PAHs averaged within a factor of 2 compared with concentrations in isolated porewater; difference factors of up to 6 were observed for naphthalene and the most hydrophobic PAHs and PCBs. Cfree results were similar for academic and private sector laboratories. The accuracy and precision demonstrated for determinating Cfree using polymer sampling are anticipated to increase regulatory acceptance and confidence.