We deployed semipermeable membrane devices (SPMDs) and transplanted blue mussels (Mytilus edulis) side-by-side at five sites in New Bedford Harbor, MA. A good correlation was obtained between accumulation in the SPMDs and the caged mussels, with r 2 values ranging from 0.57 to 0.85 for individual pesticides (n = 16) and from 0.81 to 0.96 for individual PCB congeners (n = 20). An excellent correlation also was found between the log K ow and the log BAF (bioaccumulation factor in mussels) and between the log K ow and log AF (accumulation factor in SPMDs). Accumulation in the mussels was approximately 2-fold higher than in the SPMDs when concentrations were expressed on a lipid basis. These correlations are significantly better than any reported previously and probably result from modifications that we made to the original design of the SPMD. A close examination of accumulation into SPMDs demonstrates that the uptake rate and equilibrium status of an SPMD can be easily manipulated by modifying membrane thickness, surface area, and lipid substrate volume. Knowledge of these parameters and their effect on SPMD uptake rates is critical to the interpretation of SPMD data and can be used to optimize the design of SPMDs for specific applications.
The use of semipermeable membrane devices (SPMDs) has become common in environmental sampling of nonpolar organic contaminants, yet few data exist for the uptake or sampling rates of polycyclic aromatic hydrocarbons (PAH). Two separate laboratory calibration experiments were conducted to determine the sampling rates of 28 individual PAH and 19 homologues. PAH with a log Kow > 4.5 remained in the linear uptake phase for 30 days, but PAH with a log Kow < 4.5 began to approach steady state within 15 days. Sampling rates, corrected for dissolved organic carbon, ranged from 2.11 to 6.06 L d(-1). Shear flow across the membrane had no statistically significant effect on rates over the range of 0.01-0.50 cm s(-1). Field verification of these sampling rates yielded agreement within about a factor of 2 for most PAH and a factor of 4 for all PAH. The worst agreement was for the most hydrophobic PAH, where partitioning into dissolved and particulate organic carbon pools are more important and less certain. These SPMD sampling rate data will allow quantitative estimations of freely dissolved concentrations of 47 compounds that are commonly used for PAH and petroleum product source identification and allocation.
The bioavailability of 38 individual polycyclic aromatic hydrocarbon (PAH) compounds was determined through calculation of biota-sediment-accumulation factors (BSAF). BSAF values were calculated from individual PAH concentrations in freshwater mussel, marine clam, and sediment obtained from field and laboratory bioaccumulation studies. Sediment that was amended with different types of soot carbon (SC) was used in some of the bioaccumulation experiments. BSAF values for petrogenic PAH were greater than those for pyrogenic PAH (e.g., 1.57 +/- 0.53 vs 0.25 +/- 0.23, respectively), indicating that petrogenic PAH are more bioavailable than pyrogenic PAH (p < 0.05). This trend was consistent among marine and freshwater sites. Increased SC content of sediment resulted in a linear decrease in the bioavailability of pyrogenic PAHs (r2 = 0.85). The effect of increasing SC content on petrogenic PAH was negligible. SC was considered as an additional sorptive phase when calculating BSAF values, and using PAH-SC partition coefficients from the literature, we obtained unreasonably large BSAF values for all petrogenic PAH and some pyrogenic PAH. This led us to conclude that a quantitative model to assess bioavailability through a combination of organic carbon and soot carbon sorption is not applicable among field sites with a wide range of soot carbon fractions and PAH sources, at least given our current knowledge of PAH-SC partitioning. Our data offer evidence that many factors including analysis of a full suite of PAH analytes, PAH hydrophobicity, sediment organic carbon content, sediment soot carbon content, and PAH source are importantto adequately assess PAH bioavailability in the environment.
The present study measured the occurrence, distribution, and bioaccumulation of fluoxetine in samples of water, polar organic chemical integrative sampler (POCIS), sediment, and caged freshwater mussels at stream sites near a municipal wastewater treatment facility effluent discharge. We assessed the relation of the environmental concentrations to reproductive endpoints in mussels in acute laboratory tests. Concentrations of fluoxetine in water and POCIS samples were similar (<20% difference) within each site and were greatest in the effluent channel (104-119 ng/L), and decreased at 50 m and 100 m downstream. Likewise, concentrations of fluoxetine in sediment and mussel (Elliptio complanata) tissue were greatest in the effluent channel (17.4 ng/g wet wt for sediment and 79.1 ng/g wet wt for mussels). In 96-h lab tests, fluoxetine significantly induced parturition of nonviable larvae from female E. complanata exposed to 300 microg/L (p = 0.0118) and 3,000 microg/L (p < 0.0001) compared to controls. Fluoxetine exposure at 300 microg/L (p = 0.0075) and 3,000 microg/L (p = 0.0001) also resulted in stimulation of lure display behavior in female Lampsilis fasciola and Lampsilis cardium, respectively. In male E. complanata, 3,000 microg fluoxetine/L significantly induced release of spermatozeugmata during a 48-h exposure. These results suggest that fluoxetine accumulates in mussel tissue and has the potential to disrupt several aspects of reproduction in freshwater mussels, a faunal group recognized as one of the most imperiled in the world. Despite the disparity between measured environmental concentrations of fluoxetine and effects concentrations in our short-term tests with these long-lived animals, additional tests are warranted to evaluate the effects of long-term exposure to environmentally relevant concentrations and critical lifestages (e.g., juveniles).
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