Influence of black carbon and chemical planarity on bioavailability of sediment-associated contaminants.

Black carbon (BC) and chemical properties may play a significant role in defining the bioavailability of hydrophobic organic compounds (HOCs) in sediment. In the current study, bioavailability of four HOCs with differing planarity was determined in sediments amended with two types of BC (soot and charcoal) at different concentrations by matrix solid-phase microextraction (matrix-SPME) and bioaccumulation testing using the freshwater oligochaete Lumbriculus variegatus. Furthermore, the applicability of the matrix-SPME method to bioavailability estimation in BC-amended sediment was tested. The charcoal treatment significantly reduced the bioaccumulation of the planar compounds (3,3',4,4'-tetrachlorobiphenyl and benzo[a]pyrene) in L. variegatus, and the matrix-SPME method showed a similar trend as contaminant bioaccumulation in L. variegatus. Conversely, manipulation of sediment with soot had no effect or slightly increased bioavailability of the planar compounds in both bioaccumulation and matrix-SPME tests. Little if any affect was noted in bioavailability of the nonplanar compounds (2,2',4,4',5,5'-hexachlorobiphenyl and permethrin) with the soot and charcoal amendments. Results showed that the role of BC in defining bioavailability of HOCs depends not only on the type and concentrations of BC present, but also the planarity of the HOCs.

Chemical availability and sediment toxicity of pyrethroid insecticides to Hyalella azteca: application to field sediment with unexpectedly low toxicity.

Tenax extraction is a simple, inexpensive approach to estimate the bioavailability of hydrophobic organic contaminants from sediment. In the present study, a single-point Tenax extraction was evaluated regarding its correlation with the acute toxicity to Hyalella azteca using field-collected sediments in California, USA. Pyrethroids were believed to be the primary contributor to the observed toxicity, and a significant correlation existed between the expected toxicity (given pyrethroid concentrations) and the mortality at most sampling sites. A small subset of sites, however, showed unexpectedly low toxicity to H. azteca despite high concentrations of pyrethroids. These samples were evaluated by Tenax extraction with the expectation that this procedure, which qualifies bioavailable instead of total pyrethroid concentration in sediment, would better explain the anomalously low toxicity. The term bioavailable toxic unit was proposed to link sediment toxicity with chemical availability, and the toxicity in the 17 selected sediments was better explained using Tenax extraction. The r2 value of the regression between sediment toxicity and toxic unit for the 17 sediments increased from 0.24 to 0.60 when the Tenax-extractable concentration was used in place of the total concentration. Results also showed that adsorption to sand particles might play a controlling role in pyrethroid bioavailability and, in turn, sediment toxicity to benthic invertebrates.

Bioaccumulation and biotransformation of polycyclic aromatic hydrocarbons during sediment tests with oligochaetes (Lumbriculus variegatus).

In some kinetic studies with aquatic invertebrates, the bioaccumulation of polyaromatic hydrocarbons (PAHs) has been observed to peak at the beginning of the test. This has been explained by the depletion of PAHs from pore water due to limited desorption during the bioaccumulation test or, alternatively, by the activation of biotransformation mechanisms in the organisms. In the present study, we exposed the aquatic oligochaetes, Lumbriculus variegatus, to creosote oil-contaminated sediments to examine the bioaccumulation of PAHs and to clarify the importance of contaminant depletion and biotransformation for it. The contaminant depletion was studied by replanting test organisms into fresh, nondepleted test sediments at 3-d intervals over 12 d and by comparing the resulting body burdens to those of the organisms that were not replanted. The biotransformation capability of L. variegatus was assessed by following the concentration of 1-hydroxypyrene (1-HP), a phase I metabolite of pyrene, in oligochaete tissue during a 15-d test. We observed that the bioaccumulation of most PAHs indeed peaked at the beginning of the test. The concentrations in the replanted organisms were only 1.5 to 2 times higher than in nonreplanted organisms during the first 9 d of the test and, by day 12, no differences were detected. 1-Hydroxypyrene was detected in oligochaete tissue throughout the exposures, and concentrations decreased over time. However, the proportion of 1-HP to pyrene increased linearly during the test. These results indicated that the depletion of contaminants has only a minor effect on their bioaccumulation in oligochaetes and that the cause for the observed bioaccumulation curve shape is rapid elimination of the contaminants and, possibly to some degree, their metabolites.

Desorption of hydrophobic compounds from laboratory-spiked sediments measured by Tenax absorbent and matrix solid-phase microextraction.

Tenax extraction and matrix solid-phase microextraction (matrix-SPME) were used to study desorption of hydrophobic contaminants (HOC) from sediments. 14C-labeled hexachlorobiphenyl, DDE, permethrin, chlorpyrifos, and phenanthrene were individually spiked into sediments differing in physical characteristics. Sequestration of the HOCs into sediment was observed for all compounds, and desorption was described by rapid, slow, and very slow rates. The freely dissolved HOC concentration in the sediment porewater was estimated by matrix-SPME, and serial sampling was used to ensure equilibrium was achieved among sediment, porewater and matrix-SPME fiber. Differences in partitioning of the HOCs between sediment and porewater for the different sediments were reduced by replacing the HOC concentration in sediment with the rapidly desorbing fraction. The significantly lower porewater concentration determined from matrix-SPME, than predicted from equilibrium partitioning theory (EPT), showed that only a small fraction of sediment HOCs were available for equilibrium and the predictability of EPT can be improved with the consideration of sequestration in sediment. A good correlation was noted between sediment concentration in the rapidly desorbing fraction measured by Tenax extraction, and SPME fiber concentration as determined by matrix-SPME. Thus, the two methods both tracked the readily desorbed contaminant equally well though Tenax extraction measures the accessible pool, and matrix-SPME measures the chemical activity of the HOCs.

Bioaccumulation of paraquat by Lumbriculus variegatus in the presence of dissolved natural organic matter and impact on energy costs, biotransformation and antioxidative enzymes.

Dissolved organic matter from natural sources (DNOM) is omnipresent in aquatic ecosystems. Besides affecting bioavailability of substances including xenobiotics, it directly influences physico-chemistry of the habitat and there is increasing evidence for it is interaction with organisms. We investigated direct and interacting effects of DNOM from three sources, Lake Valkea-Kotinen, Svartberget Brook, and Lake Fuchskuhle with the herbicide paraquat on the oligochaete worm Lumbriculus variegatus. Bioavailability of paraquat to L. variegates as well as activities of antioxidative enzymes catalase (CAT) and peroxidase (POD) and biotransformation enzyme soluble glutathione S-transferase (sGST) were assessed without and in the presence of DNOM. Furthermore, metabolic heat dissipation due to the exposure was quantified. Uptake of paraquat into the worms was concentration dependently reduced by DNOM, and with differences concerning the DNOM sources. sGST and CAT responded with increased activities to DNOM (5 and 25 mg C l-1) and paraquat (5.0, 50, and 500 microg l-1) separately. Paraquat at 5.0 microg l-1 and DNOM in combination caused increased activities of sGST, especially at 5 mgC l-1, but inhibition of CAT activities. The latter probably occurred due to saturation of the enzyme. Changes in enzyme activities were independent from the source of DNOM. Increasing DNOM concentrations raised metabolic heat dissipation in L. variegatus with maximum at 3h of exposure. In the combined treatments, metabolic heat dissipation changed more due to the source of DNOM than due to the bioavailability of paraquat.