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WITHDRAWN AD -sT~i~Bñ~c i~tZ4-2-ABSTRACT Polychlorinated biphenyls (PCBs) were used as model hydrophobic organic compounds (HOC) to study physical-chemical processes which affect the speciation and fate of HOC in coastal environments. The focus of this study is on the sorption of PCBs with colloidal organic matter in seawater, and the influence of this process on the distribution of PCBs in coastal sediments. Laboratory and field experiments were used to make quantitative estimates of PCB-organic matter sorption, and to test predictions of three-phase equilibrium models.A static headspace partitioning method was developed to measure the sorption of several individual chlorobiphenyls with colloidal organic matter enriched from coastal seawater by hollow fiber ultrafiltration. This technique directly measured the dissolved phase fugacity of PCBs in experimental bottles, and avoided uncertain separation techniques often used in isolating various chemical phases. Colloidal organic carbon normalized partition coefficients (Koc) were determined from linear sorption isotherms, and increased from 1.9 x 10' (L/Kg) for 2,4'-dichlorobiphenyl to 3.5 x 10 s for 2,2',3,4,5'-pentachlorobiphenyl. Sorption tended to increase with increasing octanol-water partition coefficients (Kow) of the sorbate, and values of Koc were within a range of those reported in other experimental sorption studies with sediments and dissolved humic substances. Experimental partitioning results support the hypothesis that HOC-organic colloid sorption is similar to HOC sorption by sediment organic matter.PCBs were measured in the interstitial waters and sediments of three box cores obtained from New Bedford Harbor and Buzzards Bay, Massachusetts. The three sites studied had a wide range of sediment PCB concentrations, and reducing conditions provided environments containing high concentrations of colloidal organic matter. Dissolved organic carbon (DOC) and total sediment organic carbon (TOC) were measured in two cores to test the role of organic matter on the observed partitioning of PCBs. PCB concentrations, particularly those of less soluble chlorobiphenyls, were highly elevated in interstitial waters compared to water column concentrations at all three sites. The measured apparent distribution coefficients (K'd) of individual chlorobiphenyls did not increase with hydrophobicity (Kow) and indicate that a large fraction of PCBs in interstitial waters must be sorbed to organic colloids. A three-phase equilibrium sorption model, in which dissolved PCBs are in a dynamic equilibrium with colloidal and sediment organic matter, accounts for many aspects of the field data. There is good agreement of observed partitioning at New Bedford Station 67 and Buzzards Bay Station M with model calculations based on predictions derived from laboratory experiments of HOC sorption with sediments and organic colloids, but model calculations underpredict K'd at Station 84 in New Bedford Harbor.-3-The sediment-interstitial water results were contrasted with a study of PCB pa...
WITHDRAWN AD -sT~i~Bñ~c i~tZ4-2-ABSTRACT Polychlorinated biphenyls (PCBs) were used as model hydrophobic organic compounds (HOC) to study physical-chemical processes which affect the speciation and fate of HOC in coastal environments. The focus of this study is on the sorption of PCBs with colloidal organic matter in seawater, and the influence of this process on the distribution of PCBs in coastal sediments. Laboratory and field experiments were used to make quantitative estimates of PCB-organic matter sorption, and to test predictions of three-phase equilibrium models.A static headspace partitioning method was developed to measure the sorption of several individual chlorobiphenyls with colloidal organic matter enriched from coastal seawater by hollow fiber ultrafiltration. This technique directly measured the dissolved phase fugacity of PCBs in experimental bottles, and avoided uncertain separation techniques often used in isolating various chemical phases. Colloidal organic carbon normalized partition coefficients (Koc) were determined from linear sorption isotherms, and increased from 1.9 x 10' (L/Kg) for 2,4'-dichlorobiphenyl to 3.5 x 10 s for 2,2',3,4,5'-pentachlorobiphenyl. Sorption tended to increase with increasing octanol-water partition coefficients (Kow) of the sorbate, and values of Koc were within a range of those reported in other experimental sorption studies with sediments and dissolved humic substances. Experimental partitioning results support the hypothesis that HOC-organic colloid sorption is similar to HOC sorption by sediment organic matter.PCBs were measured in the interstitial waters and sediments of three box cores obtained from New Bedford Harbor and Buzzards Bay, Massachusetts. The three sites studied had a wide range of sediment PCB concentrations, and reducing conditions provided environments containing high concentrations of colloidal organic matter. Dissolved organic carbon (DOC) and total sediment organic carbon (TOC) were measured in two cores to test the role of organic matter on the observed partitioning of PCBs. PCB concentrations, particularly those of less soluble chlorobiphenyls, were highly elevated in interstitial waters compared to water column concentrations at all three sites. The measured apparent distribution coefficients (K'd) of individual chlorobiphenyls did not increase with hydrophobicity (Kow) and indicate that a large fraction of PCBs in interstitial waters must be sorbed to organic colloids. A three-phase equilibrium sorption model, in which dissolved PCBs are in a dynamic equilibrium with colloidal and sediment organic matter, accounts for many aspects of the field data. There is good agreement of observed partitioning at New Bedford Station 67 and Buzzards Bay Station M with model calculations based on predictions derived from laboratory experiments of HOC sorption with sediments and organic colloids, but model calculations underpredict K'd at Station 84 in New Bedford Harbor.-3-The sediment-interstitial water results were contrasted with a study of PCB pa...
Bioconcentration of triphenyltin (TPT) and tributyltin (TBT) was studied in the freshwater organisms Daphnia magna (zooplankton), Chironomus riparius (sediment organism) and Thymallus thymallus (fish yolk‐sac larvae). TPT bioconcentration factors (BCFs) at pH 8 were highest for Thymallus (2200), followed by Chironomus (680) and Daphnia (190). The differences could not be fully explained by different total lipid contents. Metabolism and lower bioconcentration were observed for TBT in Chironomus. The BCFs of both TBT and TPT were higher at pH 8 than at pH 5, but the difference was much less pronounced than predicted by the octanol–water partition model. This suggests that, besides the hydroxide species (TBTOH and TPTOH), the cations (TBT+ and TPT+) are also taken up by the organisms to some extent and that the octanol–water partition model underestimates the uptake of the charged species. Low concentrations of humic substances (HS) led to small reduction in the bioconcentration of TPT in Daphnia and Thymallus, and a significant reduction occurred at relatively high concentrations of HS (>10 mg C l−1). The results of this study provide an important basis for future investigations aiming at a better understanding of the bioavailability and fate of TBT and TPT in freshwater ecosystems. © 1998 John Wiley & Sons, Ltd.
In freshwater ecosystems, dissolved humic substances (HS) can sorb hydrophobic organic chemicals and thereby reduce their bioconcentration and toxicity. The extent of the sorption depends both on the concentration and on the origin of HS. This paper summarizes work that characterized HS from different origins by various spectroscopic and chemical properties, and related these properties to (1) the sorption of polycyclic aromatic hydrocarbons (PAHs) by HS (measured by a fluorescence quenching method), (2) effects of HS on the bioconcentration of PAHs and (3) effects of HS on the toxicity of PAHs. The most powerful predictor of the association between 26 different HS and the PAHs pyrene, fluoranthene, and anthracene was the content of aromatic carbons of the HS. The influence of HS on the bioconcentration of PAHs was investigated by measuring the effect of seven different humic and fulvic acids on the uptake of pyrene and benzo[a]pyrene into the nematode Caenorhabditis elegans. Again, parameters describing aromatic properties of the HS, such as the content of aromatic carbons, or the specific absorptivity at 254 nm gave the best prediction of HS effects on bioconcentration. Studies on the effect of HS on the toxicity of PAHs (impact on grazing activity of Daphnia magna) gave similar results: The detoxifying ability (= reduction of toxicity) of HS could be correlated to the quotient between aromatic carbons and aliphatic carbons in the HS. Taking these results together, we can describe the relationship between structure and effects of HS on bioavailability and toxicity of PAHs as follows: HS associate with PAHs, making the PAHs unavailable for uptake into organisms, and consequently reducing toxic effects of the PAHs. Aromatic properties of the HS can be used to predict the effect of HS in each of these steps.
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