Bioaccumulation factors (BAFs) play a key role in risk assessment of chemicals in sediments and soils. For hydrophobic organic chemicals (HOCs), BAFs are, however, difficult to determine and values are mostly obtained by modeling. Apart from a lack of reliable data, the applicability of lab-derived values in the field situation is unknown, as exposure conditions (e.g., temperature, pH, salinity, test species, number of chemicals) are standardized in the lab, whereas they may vary in the field. In this study, the effect of temperature on the bioaccumulation of a series of moderate to very hydrophobic PAHs in aquatic worms was studied by using polydimethylsiloxane (PDMS)-coated solid phase microextraction (SPME) fibers. The results indicated that bioaccumulation of nonmetabolizable HOCs is an exothermic, enthalpy-driven process, thus decreasing with increasing temperature. As such, biotic concentrations may be several times higher in winter than in summertime, which could have ecotoxicological consequences. A two-parameter linear free energy relationship was derived with which PAH bioaccumulation can be predicted from temperature and the chemicals' hydrophobicities. Comparing the determined (thermodynamics of) PAH partitioning into organisms and PDMS indicated that the latter phase cannot be used as a surrogate phase for animal lipids. Still, SPME provides an appropriate analytical tool for the measurement of aqueous concentrations, from which bioaccumulation can subsequently be estimated by using BAFs.

Abstract-The accumulation of four polycyclic aromatic hydrocarbons ([PAHs]; phenanthrene, pyrene, fluoranthene, and benzo[a]pyrene) was tested in the earthworm Eisenia andrei in a spiked artificial soil medium. A typical peak in the body residues was observed for all PAHs around day 7, which could not be explained from changes in the total soil concentration. It is argued that the most likely cause of this peak is a decrease in the concentration in pore water, the main bioavailable phase for earthworms. This decrease is caused by biodegradation while the low rate of mass transfer from the solid state precludes replenishment. To describe the data, bioavailability was assumed to decline exponentially in time, but the shape of the accumulation curves suggests a more abrupt change. Estimates of the uptake rate (k 1 ) are similar for all PAHs when expressed on soil solution basis (approximately 2,000 L/kg/d); the elimination rate (k 2 ) shows a decrease with K ow as expected, but the values tend to be slightly lower than literature data. The dynamic bioconcentration factors (k 1 /k 2 ) agree well with an equilibrium partitioning between soil water and the phases inside the organism.

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Petroleum hydrocarbons (oils) are ubiquitous in the aquatic environment, and adequate risk assessment is thus essential. Bioaccumulation plays a key role in risk assessment, but the current knowledge on bioaccumulation of oils is limited. Therefore, this process was studied in detail, using the aquatic worm, Lumbriculus variegatus, and 14 field-contaminated sediments. The main focus during the present study was on uptake kinetics, the relationship between oil boiling point fraction and uptake, and effects of sediment characteristics. Uptake kinetics became slower with increasing boiling point fraction, but 70 to 90% of the equilibrium situation was reached within the standard exposure duration of 28 d. Worms accumulated sedimentary petroleum hydrocarbons in the range of C(10) to C(34), a range much wider than expected. Biota-to-sediment accumulation factors (BSAFs) for separate boiling point fractions were constant and around the proposed value of 1 to 2 up to C(22), but gradually decreased beyond this point. The decrease was probably caused by a combination of nonequilibrium conditions and enhanced sorption of higher boiling point fractions to sediments; the latter possibly due to the presence of strongly sorbing separate oil phases or black carbon. A negative relationship was observed between BSAF and oil concentration in sediment, which was explained by the presence of separate oil phases at high oil concentrations. These strongly sorbing phases may limit their own availability, particularly when being highly weathered; worms may also avoid them. The observed phenomena have obvious implications for bioaccumulation assessment of oils and suggest that the current risk assessment procedure for oils in sediments may lead to erroneous results.

Several experimental methods have been developed to assess the bioavailability of individual organic compounds. So far none of them has however been applied to complex mixtures, such as oil (petroleum hydrocarbons), which is an ubiquitous pollutant. In the present study, we tested the potential of five of these experimental methods and that of a model approach to predict bioaccumulation of oil in the aquatic worm Lumbriculus variegatus exposed to 14 field-contaminated sediments. Actual and predicted bioaccumulation were compared in terms of both total bioaccumulative petroleum hydrocarbon concentrations and the relative distribution pattern of separate boiling point fractions (hydrocarbon blocks). None of the experimental methods was able to directly assess bioaccumulation in L. variegatus and correction factors were needed to match predicted and actual concentrations. These factors appeared concentration-dependent for solid phase micro extraction (SPME) and extractions with Tenax and cyclodextrin, most probably due to artifacts. Moreover, the hydrocarbon block pattern produced by these methods considerably differed from the pattern observed for worms; an additional reason for disqualification also applying to headspace-SPME. In contrast, the pattern produced by polyoxymethylene solid phase extraction (POM-SPE) closely mimicked the worm pattern and a sediment, hydrocarbon block, and concentration-independent correction factor (17) could be derived, based on which actual bioaccumulation could be predicted within a factor of 3. Finally, the model predicted bioaccumulation directly within a factor of 2. The accompanying hydrocarbon block pattern however deviated significantly more from the worm pattern than the POM-SPE pattern did. We therefore conclude that POM-SPE may be the overall best approach for predicting bioaccumulation of complex hydrocarbon mixtures in aquatic worms, all the more since an experimental approach will implicitly capture all factors determining bioavailability, which may prove difficult through a modeling approach.