The debate on whether highly hydrophobic organic chemicals (with log Kow > 5-6) bioconcentrate less than may be expected from their hydrophobicity is still not settled. The often-observed hydrophobicity "cutoff" might either be explained by artifacts occurring during bioconcentration factor (BCF) measurements or by a true mechanism, i.e., reduced uptake of larger molecules due to decreased membrane permeation. In this paper, we advocate there is no hydrophobicity cutoff, at least not for compounds with log Kow of up to 7.5. Data are presented on the uptake of polycyclic aromatic hydrocarbons (PAHs) in the aquatic worm Lumbriculus variegatus. For this combination of chemicals/organism, BCFs were measured using several approaches, including traditional batch uptake kinetics measurements and alternative ones, involving solid-phase microextraction (SPME), polyoxymethylene solid-phase extraction (POM-SPE), field exposures, and the substitution of living worms by dead worm material or liposomes. A hydrophobicity cutoff was observed at two levels during the traditional approach only, whereas for the other approaches it was absent. The data were used to demonstrate the presence and impact of artifacts due to so-called "third phase effects" and nonequilibrium conditions that can obscure "true uptake". The experiments suggest that previously observed cutoff effects can be ascribed to artifacts, and that current risk assessment (often incorporating a BCF cutoff) as well as BCF measurement techniques of very hydrophobic chemicals should be revised.

Soils from former manufactured gas plant (MGP) sites are often heavily contaminated with polycyclic aromatic hydrocarbons (PAHs). Current risk assessment methods that rely on total PAH concentrations likely overstate adverse effects of such soils since bioavailability is ignored. In this study, solid-phase microextraction (SPME) was applied to estimate bioavailable PAH concentrations and toxicity in earthworms exposed to 15 MGP soils. In addition, PAH sorption to all soils (K0o values) was determined. The results showed a several orders of magnitude variation in Koc values, demonstrating that generic organic carbon-normalized sorption coefficients will typically be overconservative at MGP sites. SPME-predicted bioaccumulation generally was within a factor of 10 of measured bioaccumulation (in earthworm bioassays), in contrast to current risk assessment model estimates that overpredicted bioaccumulation 10-10 000 times. Furthermore, on the basis of estimated total body residues of narcotic PAHs, SPME correctly predicted worm mortality observed during bioassays in the majority of cases. For MGP sites where current risk assessment procedures indicate concerns, SPME thus provides a useful tool for performing a refined, site-specific assessment.

Passive sampling with nondepletive sorbents is receiving increasing interest because of its potential to measure freely dissolved concentrations of hydrophobic organic compounds (HOCs) at very low concentrations, as well as its potential for both laboratory use and field deployment. However, consistent approaches have yet to be developed for the majority of HOCs of environmental and regulatory interest. In the present study, a passive sampling method was developed which allows the freely dissolved concentrations of 18 parent and 16 groups of alkyl polycyclic aromatic hydrocarbons (PAHs) on the U.S. Environmental Protection Agency (USEPA)'s "PAH-34" target compound list to be measured. Commercially available 76-μm-thick polyoxymethylene (POM) was placed in sediment/water slurries and exposed for up to 126 days, with 28 days found to be sufficient to obtain equilibrium among the sediment, water, and POM phases for the target 2- to 6-ring PAHs. The POM/water partition coefficients (K(POM)) necessary to calculate freely dissolved concentrations for parent PAHs were determined in two separate laboratories (one using pure standards, and the other using coal tar/petroleum-contaminated sediments) and agreed very well. Since the so-called "16" alkyl PAHs on the PAH-34 list actually include several hundreds of isomers for which no standards exist, sediments impacted by coal tar, or spiked with a coal tar/petroleum nonaqueous phase liquid (NAPL) were also used to measure K(POM) values for each alkyl PAH cluster. The log K(POM) values ranged from ca. 3.0 to 6.2 for 2- to 6-ring parent PAHs, and correlated well with SPARC octanol/water coefficients (K(OW)) (correlation coefficient of r(2) = 0.986). However, log K(POM) values for alkyl PAHs deviated increasingly from SPARC log K(OW) values with increasing degree of alkylation. A simple empirical model that incorporates the number of carbon atoms in a PAH gave a better fit to the experimental log K(POM) values, and was used to estimate log K(POM) for alkyl PAHs that could not be directly measured. Detection limits (as freely dissolved concentrations) ranged from ca. 1 part per trillion (ng/L) for the 2-ring PAH naphthalene, down to <1 pg/L (part per quadrillion) for the 5- and 6-ring PAHs. Sorption isotherms were linear (r(2) > 0.99) over at least 4 orders of magnitude.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (