A linear solvation energy relationship model of organic chemical partitioning to particulate organic carbon in soils and sediments

Predicting the association of contaminants with particulate organic matter in the environment is critical in determining the fate and bioavailability of chemicals. A ubiquitous measure of contaminant association with soil and sediment particulate organic matter is the organic carbon partition coefficient K(OC) . Chemical class-specific models relating the K(OC) to the octanol-water partition coefficient K(OW) have been used to predict the partitioning to organic carbon in the water column and sediment for nonpolar hydrophobic pollutants and some polar pollutants. A single linear solvation energy relationship (LSER) is proposed as a simpler and chemically based alternative for predicting K(OC) for a more diverse set of compounds. A chemically diverse set of K(OC) data is used to obtain a more robust and more universally representative model of organic carbon partitioning than previously available LSER models. The resulting model has a root mean square error (RMSE) of prediction for log K(OC) of RMSE?= 0.48 for the fitted data set and RMSE?= 0.55 for an independent data set. An analysis of LSER coefficients highlights the relative importance of hydrogen bonding interactions.     

Bioconcentration of persistent organic pollutants in four species of marine phytoplankton

The uptake of polychlorinated biphenyls (PCBs) was studied in four species of marine algae. A novel experimental system to establish and maintain constant dissolved concentrations of PCBs was employed. Headspace sampling was used to verify that the freely dissolved concentrations remained constant with time. The headspace analysis also allowed sorption to dissolved organic carbon (DOC) to be quantified for all but the most lipophilic PCB congeners. Equilibration with the dissolved phase was rapid for three of the four algae species (<1 d for the majority of congeners). Organic carbon-normalized algae/water partition coefficients (KAlgW) were similar for three of the four species, but were lower by a factor of 10 to 20 for Phaeodactylum tricornutum. The KAlgW values of the first three species were similar to the octanol/water partition coefficient (Kow) for those PCB congeners for which DOC sorption could be quantified. These KAlgW values also agreed well with organic carbon-normalized bioconcentration factors for PCBs in suspended particulate matter (BCF(SPM)) sampled in Baltic Sea surface water during the summer.     

Partitioning and matrix-specific toxicity of bifenthrin among sediments and leaf-sourced organic matter

Synthetic pyrethroids readily partition from the aqueous to the solid phase in aquatic systems. Previous work has focused on pyrethroid partitioning to sediment matrices. Within many aquatic systems, however, other carbon-containing materials are present and can be critically important to certain invertebrate species and ecosystem functioning. For example, some invertebrates readily process leaf material, and these processes may represent an additional route of contaminant exposure. To our knowledge, estimates for partitioning of pyrethroids to these nondissolved organic matter matrices and associated toxicity have not been examined. The objectives of the present study were to examine variation in organic carbon (OC)-based partition coefficient (K(OC)) among three size fractions of particulate organic matter from sugar maple (Acer saccharum) leaf litter and sediments for the pyrethroid insecticide bifenthrin and to examine variation in toxicity to Hyalella azteca among bifenthrin-bound organic matter matrices and sediment. Log K(OC) of [(14)C]bifenthrin was greatest within sediment (6.63+/-0.23; mean +/- standard deviation throughout) and lowest in coarse particulate leaf material (4.86+/-0.03). The H. azteca median lethal concentration was 0.07, 0.11, and 0.15 microg/g OC for leaf material, sediment, and a 50% mix of leaf and sediment, respectively. Nonoverlapping 95% confidence intervals occurred between the leaf treatment and the leaf-sediment treatment. This pattern was supported in an additional experiment, and at 0.22 microg/g OC, H. azteca survival was greater in the leaf-sediment mixture than in sediment or in leaf material alone (F=29.5, p<0.0001). In systems that contain sediment and leaf material, both greater partitioning of bifenthrin to the sediment fraction and preferential use of leaf substrates may drive H. azteca survival.     

Validation of a modified flory-huggins concept for description of hydrophobic organic compound sorption on dissolved humic substances

Sorption coefficients (K(DOC)) on dissolved organic matter (DOM) have been determined by means of solid-phase microextraction (SPME) for hydrophobic organic compounds (HOCs) of various classes, for example, polycyclic aromatic hydrocarbons (PAHs), noncondensed arenes, and alkanes. Relating the K(DOC) values obtained to the octanol-water partition coefficients of the solutes results in class-specific correlations. Obviously, PAHs have a higher affinity to DOM than other HOCs with equal K(OW) values. The different K(DOC) to K(OW) correlations can be combined into one general formula based on a modified Flory-Huggins concept. It permits the calculation of sorption coefficients from the solubility parameters (delta) and K(OW) values of the solutes and the solubility parameter of the sorbent. The latter value, which is specific to the DOM under consideration, can be determined from a single measured sorption coefficient. By applying the proposed Flory-Huggins concept, which is based on the presumption of nonspecific interactions between HOCs and DOM, the different affinities of PAHs, noncondensed arenes, and alkanes to DOM can be accurately predicted.     

Concentrations and partitioning of polychlorinated biphenyls in the surface waters of the southern Baltic Sea-seasonal effects

In the marine environment, the partitioning of hydrophobic organic contaminants, such as polychlorinated biphenyls (PCBs), between the dissolved and suspended matter phases in the water column plays a fundamental role in determining contaminant fate (e.g., air-water exchange or food-chain uptake). Despite the pronounced seasonality in physical, chemical, and biological conditions in temperate marine ecosystems, little is known about the seasonality in organic contaminant partitioning behavior. Surface water from the western Baltic Sea was sampled regularly during an 18-month period between February 2003 and July 2004. The concentrations of seven PCB congeners were determined in the dissolved and particulate organic carbon (POC) phases. An inverse relationship was found between K(POC) (i.e., the ratio between the POC-normalized PCB concentration [pg/kg POC] and the dissolved concentration [pg/L]) and temperature. The decrease in the water temperature of 20 degrees C between summer and winter resulted in an increase in K(POC) by a factor of approximately five. The POC-normalized PCB concentrations were higher in winter than in summer by a factor of 9 to 20. This reflected the higher K(POC) and somewhat greater PCB concentrations in the dissolved phase, and it could have consequences for bioaccumulation of these chemicals in aquatic food webs. The results demonstrate a clear seasonality in contaminant partitioning in the temperate marine environment that should be accounted for when interpreting field data or modeling contaminant fate.     

A potential link between the turnover of soil organic matter and the release of aged organic contaminants

Soil column experiments were conducted to investigate the release of aged organic contaminants (adsorbable organohalogens, [AOX]) and the potential effects of microbial turnover of soil organic matter onto the contaminant release from two different soils of former wastewater infiltration sites. Under reference conditions, the total carbon flux ranged from 6 to 9 mg/kg/d from the two soils. More than 92% of it was due to mineralization (CO2) and below 8% to the dissolved organic carbon (DOC) in the column effluent. Despite very different organohalogen levels in the two soils, the fluxes of AOX were similar (1 microg/kg/d). Microbial activity was altered by changing temperature and the solution pH and by drying. In all experiments where increased microbial respiration (CO2 production) was observed, the release of organic contaminants in the column effluent also increased. Fluxes of nickel, zinc, and phosphate showed a completely different pattern, suggesting that their retention in soil is determined by chemical parameters. A linear correlation analysis provided clear evidence that AOX and DOC fluxes are closely linked to each other. However, the superimposition of abiotic and biotic processes in the soils did not allow a causal relation to be established between the mineralization of soil organic matter and the release of organic contaminants sequestered in the soil. Our findings suggest that microbial activity may have a significant impact on the extent to which contaminated soils may act as a source of persistent organic pollutants.     

Copper toxicity in relation to surface water-dissolved organic matter: biological effects to Daphnia magna

Water quality standards for copper are usually stated in total element concentrations. It is known, however, that a major part of the copper can be bound in complexes that are biologically not available. Natural organic matter, such as humic and fulvic acids, are strong complexing agents that may affect the bioavailable copper (Cu2+) concentration. The aim of this study was to quantify the relation between the concentration of dissolved natural organic matter and free Cu2+ in surface waters, and the biological effect, as measured in a standardized ecotoxicological test (48 h-median effective concentration [EC50] Daphnia magna, mobility). Six typical Dutch surface waters and an artificial water, ranging from 0.1 to 22 mg/L dissolved organic carbon (DOC), were collected and analyzed quarterly. Chemical speciation modeling was used as supporting evidence to assess bioavailability. The results show clear evidence of a linear relation between the concentration of dissolved organic carbon (in milligrams DOC/L) and the ecotoxicological effect (as effect concentration, EC50, expressed as micrograms Cu/L): 48-h EC50 (Daphnia, mobility) = 17.2 x DOC + 30.2 (r2 = 0.80, n = 22). Except for a brook with atypical water quality characteristics, no differences were observed among water type or season. When ultraviolet (UV)-absorption (380 nm) was used to characterize the dissolved organic carbon, a linear correlation was found as well. The importance of the free copper concentration was demonstrated by speciation calculations: In humic-rich waters the free Cu2+ concentration was estimated at approximately 10(-11) M, whereas in medium to low dissolved organic carbon waters the [Cu2+] was approximately 10(-10) M. Speciation calculations performed for copper concentrations at the effective concentration level (where the biological effect is considered the same) resulted in very similar free copper concentrations (approximately 10(-8) M Cu) in these surface waters with different characteristics. These observations consistently show that the presence of organic matter decreases the bioavailability, uptake, and ecotoxicity of copper in the aquatic environment. It demonstrates that the DOC content must be included in site-specific environmental risk assessment for trace metals (at least for copper). It is the quantification of the effects described that allows policy makers to review the criteria for copper in surface waters.     

Partitioning of tetra- and pentabromo diphenyl ether and benzo[a]pyrene among water and dissolved and particulate organic carbon along a salinity gradient in coastal waters

This study assessed the partitioning of 2,2',4,4'-tetrabromo diphenyl ether (BDE-47), 2,2',4,4',5-pentabromo diphenyl ether (BDE-99) and benzo[a]pyrene (BaP) among water, dissolved organic carbon (DOC: 4.93-8.72?mg/L), and particulate organic carbon (POC: 191-462 μg/L) along the salinity gradient (0-5.5‰) of the Baltic Sea off the coast of Finland. Equilibrium dialysis and two solid-phase extraction techniques using polyoxymethylene polymer (POM) were used to determine partitioning coefficients. Experiments using artificial coastal water (ACW) with Nordic fulvic (FAs) and humic acids (HAs) were used to assess the effect of salinity (0 and 5.5‰) on the DOC-water partitioning of the model compounds. All three compounds bound more (2.2-3.8-fold) to the HAs than to the FAs. Increasing salinity from 0 to 5.5‰ decreased sorption to dissolved humic substances in the ACW and Baltic Sea water samples. Along the salinity gradient, the sorption of compounds to organic material decreased when the salinity increased. Particulate organic matter sorbed model compounds per unit of carbon more than dissolved organic matter. Along the studied salinity gradient, the freely dissolved portion increased from 10 to 29% to 52 to 80% in the coastal water samples, mainly because of the increasing salinity and changes in DOC and quality of POC.     

Influence of dissolved organic matter source on silver toxicity to Pimephales promelas

In the environment, the formation of organic and inorganic silver complexes can decrease Ag bioavailability (toxicity) to aquatic organisms. However, current water quality regulations do not consider the protective effects of water quality parameters such as dissolved organic carbon (DOC) concentration. To determine the effect of DOC concentration and source on silver toxicity, nine different natural organic matter isolates were used in 96-h static-renewal toxicity tests with fathead minnow (Pimephales promelas). The 96-h dissolved silver median lethal concentrations (LC50) among different sources of dissolved organic matter varied by up to fivefold (4.5-23.3 microg/L). Further, toxicity tests with organic matter from the site with the lowest 96-h LC50 value suggested only limited additional attenuation of silver toxicity when DOC concentration was increased from 5.1 to 14.0 mg/L. With this site excluded, we found little more than a twofold difference among 96-h dissolved Ag LC50s for the remaining sources (10.1-23.3 microg/L). However, significant toxicological differences among sites remained. It was apparent that organic matter from different sources varied both chemically and toxicologically, but no conclusions could be drawn that related compositional variation to observed Ag toxicity for these isolates.     

Influence of soil pH on the sorption of ionizable chemicals: modeling advances

The soil-water distribution coefficient of ionizable chemicals (K(d)) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K(d) values normalized to organic carbon (K(OC)) from the literature, a method was developed to estimate the K(OC) of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P(n)). Probably because of the lower pH near the organic colloid-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals.     

Effects of XAD-8 fractions of dissolved organic carbon on the sorption and bioavailability of organic micropollutants

The dissolved organic carbon (DOC) from a stream water near a peat deposit was fractionated into hydrophobic-acid (HbA), hydrophobic-neutral (HbN), and hydrophilic (Hl) subcomponents by XAD-8 chromatography. The capacity of these fractions and the total (unfractionated) water to bind hydrophobic organic contaminants was measured by equilibrium dialysis, and the effect of binding on contaminant bioavailability was measured inDaphnia magna. Model contaminants were the poly cyclic aromatic hydrocarbons, naphthalene (NPH) and benzo(a)pyrene (BaP), and the polychlorinated biphenyl, 2,2,5,5-tetrachlorobiphenyl (TCB).Both BaP and TCB exhibited high partition coefficients (Kp's) for binding to both the total DOC and the hydrophobic components of the DOC. BaP had a higher affinity for binding to the HbA fraction, while TCB (and 3 other PCB's had a higher affinity for the HbN fraction. The K_p's for binding to the Hl fraction were twofold to tenfold lower than for binding to the hydrophobic fractions. The less hydrophobic compound, NPH, had a much lower K_p, and little difference was seen between the fractions. The total water and the different DOC fractions reduced the uptake and accumulation of BaP and TCB byD. magna in proportion to the capacity of the DOC for binding the contaminants. Data were consistent with the hypothesis that a contaminant bound to DOC (total water or any of the fractions) is unavailable for uptake by biota. Uptake of NPH was not substantially affected by the DOC, consistent with its lower K_p.     

Measuring the bioavailability of two hydrophobic organic compounds in the presence of dissolved organic matter

Bioavailability of benzo[a]pyrene (BaP) and 3,3',4,4'-tetrachlorobiphenyl (TCB) was studied in natural lake water containing dissolved organic matter (DOM). Lake water was diluted to give a dissolved organic carbon (DOC) range of 1 to 20 mg/L. Partition coefficients for the model compounds were assessed at different DOM concentrations and over time with three different methods, namely equilibrium dialysis and reverse-phase and liquid-liquid extraction. In addition, biological partition coefficients were estimated from the difference in the bioconcentration of the model compounds in Daphnia magna in the presence and absence of DOM. Results showed that bioavailability of the model compounds was reduced by the presence of DOM. The equilibrium dialysis method gave the best estimates for bioavailability of the model compounds when compared with biologically determined values. Both the reverse-phase and the liquid-liquid extraction overestimated the bioavailable fraction. The more pronounced overestimation of bioavailable fraction of TCB suggested that the sorption of TCB was not only lower but the interaction was also weaker than that of BaP. Increasing DOM concentration produced lower partition coefficients and the effect seemed to be more pronounced when measured by the reverse-phase and the extraction methods.     

Effects of dissolved organic carbon concentration and source, pH, and water hardness on chronic toxicity of copper to Daphnia magna

The effects of pH (5.3-8.7), water hardness (CaCO3 at 25-500 mg/L), dissolved organic carbon (DOC) concentration (1.6-18.4 mg/L), and DOC source on the chronic toxicity of copper to Daphnia magna were investigated by using a multifactorial, central composite test design. Natural dissolved organic matter (DOM) was collected at three sites in Belgium and The Netherlands by using reverse osmosis. For a total number of 35 toxicity tests performed, 21-d no-observed-effect concentrations (NOECs) of copper based on reproduction ranged from 29.4 to 228 microg/L and 21-d concentrations of copper causing 50% reduction of reproduction (EC50s) ranged from 41.5 to 316 microg/L. Statistical analysis revealed that DOC concentration and pH had a significant effect on copper toxicity but hardness (at the levels tested) did not. In general, an increase in pH or DOC resulted in a linear increase of 21-d NOEC and EC50 values. All DOMs (originating from three different sources) reduced copper toxicity to the same extent. Multiple linear regression analysis on the results of all 35 toxicity tests revealed that DOC concentration is the most important factor for chronic toxicity of copper to D. magna, explaining about 60% of the observed variability, whereas pH only explained about 15% of the observed variability. Regression models were developed (with DOC and pH as parameters) that were capable of predicting NOECs and EC50s within a factor of 1.9 from observed NOEC and EC50 values obtained with eight natural surface waters spiked with copper. Until future research further elucidates the mechanisms underpinning the observed bioavailability relations, these empirical regression models can become a first simple tool for regulatory applications.     

Occurrence and Partitioning of Phenolic Endocrine-Disrupting Chemicals (EDCs) Between Surface Water and Suspended Particulate Matter in the North Tai Lake Basin, Eastern China

Concentrations and distribution of octylphenol (OP), nonylphenol (NP), and bisphenol A (BPA) in surface water and suspended particulate matter (SPM) from the north Tai Lake basin, China were studied. Aqueous and particulate (dry weight) concentrations for OP, NP, and BPA varied from 10.5–1,175 ng/L to <1.52–5,365 ng/g, respectively. The spatial distribution of endocrine-disrupting chemicals (EDCs) in dissolved and particulate phases showed that the amount of EDCs in water that were adsorbed to SPM gradually increased from upstream to downstream. There were good correlations between particulate EDCs and particulate organic carbon, with correlation coefficients of 0.46–0.57. Regression analysis of in situ SPM–water partition coefficients (log K’ _oc) and log K _ow for EDCs indicated that the hydrophobicity of chemicals greatly contributed to their SPM–water partitioning. Strong positive correlations (r = 0.68–0.82) among in situ log K’ _oc of OP, NP, and BPA and flow velocity of water were observed, indicating the critical importance of riverine hydrodynamics on the sorption of these compounds.     

Binding interactions of 1-naphthol with dissolved organic matter of Lake Biwa and treated sewage wastewater: The role of microbial fulvic acid

The binding interactions of 1-naphthol with effluent and whole natural dissolved organic matter (DOM) samples were analyzed by using a fluorescence quenching technique. Nonfractionated DOM samples from Lake Biwa (Japan), creek water, treated sewage effluents, and an extracted Lake Biwa fulvic acid (LBFA) standard were used as quenchers and compared at the same 1-naphthol with DOM organic carbon ratios found for low natural dissolved organic carbon (DOC) levels (～4.5?mg/L). Natural and effluent DOM (eDOM) samples were characterized by the DOC level, relative hydrophobicity (RH%), ultraviolet (UV)-visible absorbance and fluorescence excitation emission spectroscopy. These parameters were compared with those of the reference LBFA standard. Concave-up Stern-Volmer plots accounted for both the partitioning and the adsorptive binding in the eDOM-polycyclic aromatic hydrocarbons (PAH) system as compared with the nonspecific partitioning in the natural DOM-PAH system. Strong linear regressions (r(2) >?0.80) between the log K(DOC) values, the RH%, the UV absorbances, and the Fl(340-435) -UV(340) indices for the structural composition and molecular weights of the DOM samples were obtained. These results suggest that low molecular weight microbial fulvic acid (<800 Da) is dominant in the eDOM-PAH binding interactions, as well as in the distinct molecular structure of the eDOM samples, which resulted in fivefold to sixfold higher binding magnitude for 1-naphthol than for the other samples. Environ. Toxicol. Chem. 2012; 31: 2201-2209. ? 2012 SETAC.     

Effect of dissolved organic matter of various origins and biodegradabilities on the bioaccumulation of polycyclic aromatic hydrocarbons in Daphnia magna

As a preliminary study of the influence of urban organic matter on the bioavailability of polycyclic aromatic hydrocarbons (PAHs), the effect of different types of dissolved organic matter (DOM) on the bioaccumulation of fluoranthene, pyrene, or benzo[a]pyrene in Daphnia magna was studied. Commercial humic substances, DOM from the aeration basin of a wastewater treatment plant, and highly biodegradable DOM (algae or animal extracts) were tested. The bioaccumulation of benzo[a]pyrene was reduced by each DOM (up to 80% reduction with humic substances). Pyrene bioaccumulation was also decreased by each DOM to a lesser extent. Fluoranthene bioaccumulation was affected by the presence of humic acids only. In each experiment, the solution containing humic DOM led to the lowest bioaccumulation. Supposing that only dissolved PAHs were bioavailable, the reduction of bioaccumulation allowed a biological estimate of the partition coefficients of DOM and PAH, K(DOC). The estimated coefficients were positively related to the aromaticity of DOM and negatively related to its biodegradability.     

Persistent organic pollutants (POPs) in the conventional activated sludge treatment process: fate and mass balance

The fate and the mass balance of persistent organic pollutants (POPs) during the conventional activated sludge treatment process were investigated in the wastewater treatment plant of the city of Thessaloniki, northern Greece. The POPs of interest were 7 polychlorinated biphenyls and 19 organochlorine pesticides. Target compounds were determined at six different points across the treatment system: the influent, the effluent of the primary sedimentation tank, the effluent of the secondary sedimentation tank, the primary sludge, the activated sludge from the recirculation stream, and the digested/dewatered sludge. The distribution of POPs between the dissolved and the adsorbed phases of wastewater and sludge was investigated. A good linear relationship between the distribution coefficients, Kd, and the octanol-water partition coefficients, Kow, of the solutes was observed only in raw wastewater, suggesting that other factors affect the phase distribution of organic compounds in treated wastewater. For all POPs, a significant increase in partitioning with a decreasing solids concentration was observed, revealing an effect from non-settling microparticles remaining in the "dissolved" phase during the separation procedure. A good linear relationship was also revealed between logKd and the dissolved organic carbon (DOC) content of wastewater, suggesting that DOC favors the advective transport of POPs in the dissolved phase. Almost all POPs showed good mass balance agreements at both the primary and the secondary treatment. The losses observed for some species could be attributed to biodegradation/biotransformation rather than volatilization. The relative distribution between the treated effluent and the waste sludge streams varied largely among different compounds, with p-p'-DDE being highly accumulated in the waste sludge (98%) but almost 60% of alpha-HCH remaining in the treated effluent.     

Role of participate organic matter in decreasing accumulation of polynuclear aromatic hydrocarbons byDaphnia magna

Accumulation of benzo[a]pyrene (BaP) and anthracene (A) byDaphnia magna in the presence of suspended yeast cells was analyzed using multicompartment models. The rate coefficient for uptake of polynuclear aromatic hydrocarbon (PAH) due to ingestion of yeast cells laden with sorbed chemical was only 3 to 15% of the rate coefficient for uptake of dissolved PAH. Uptake and accumulation of BaP was reduced 97% due to sorption of PAH to naturally occurring organic matter (humic acids). Accumulation of hydrophobic chemicals in aqueous systems appears to depend on the amount of chemical in solution and on the amount of chemical sorbed to particles entering the food chain. Chemicals sorbed to suspended organic matter, including dissolved or colloidal organic matter, have greatly reduced availability.Research sponsored by the Office of Health and Environmental Research, U.S. Department of Energy, under contract W-7405eng-26 with Union Carbide Corp. Publication No. 2127, Environmental Sciences Division, ORNLBy acceptance of this article, the publisher or recipient acknowledges the U.S. Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering the article     

The ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability increases with DOM biodegradation

The biodegradation of two substrates and the ability of dissolved organic matter (DOM) to influence benzo[a]pyrene bioavailability as DOM biodegradation progressed were monitored in reactors. Substrates were composed of algae extracts and an artificial substrate that mimics raw wastewater, which were considered to be autochthonous and anthropogenic allochthonous models for DOM, respectively. The soluble microbial products formed during biomass activity were also studied. The aromaticity of DOM was investigated with specific ultraviolet absorbance. Partitioning coefficients between DOM and benzo[a]pyrene, K(DOC)(biol), were biologically determined by means of 4-h bioaccumulation experiments on Daphnia magna. Parent and degraded substrates always significantly reduced the bioaccumulation of benzo[a]pyrene at environmental DOM concentrations. Soluble microbial products also significantly affected the benzo[a]pyrene bioaccumulation. K(DOC)(biol) ranged between 2 x 10(4) and 4 x 10(5) L/kg. As the artificial wastewater biodegraded, DOM aromaticity increased, as did K(DOC)(biol). During the biodegradation of algae extract DOM, K(DOC)(biol) increased, whereas their aromaticity slightly decreased.     

Resuspension of polychlorinated biphenyl-contaminated field sediment: release to the water column and determination of site-specific K DOC

Sediments from the New Bedford Harbor (NBH) U.S. Environmental Protection Agency (U.S. EPA) Superfund site (Massachusetts, USA), contaminated with polychlorinated biphenyls (PCBs), were resuspended under different water column redox conditions: untreated, oxidative, and reductive. The partitioning of PCBs to the overlying water column was measured with polyethylene samplers and compared to partitioning without resuspension. Greater concentrations of total aqueous (freely dissolved + dissolved organic carbon (DOC)-associated) PCBs were found in all resuspended treatments for PCBs with mid-range K(OW)s, but no difference was observed in total aqueous concentrations among different redox conditions. The magnitude of increased concentrations depended on resuspension time and congener K(OW), but ranged from approximately one to eight times those found without resuspension. In a parallel study, DOC was flocculated and removed from smaller-scale NBH sediment resuspensions. In situ K(DOC)s were determined and used to calculate freely dissolved and DOC-associated fractions of the increase in total aqueous PCB concentrations due to resuspension. The importance of DOC-associated PCBs increased with increasing K(OW). In situ K(DOC)s were approximately one to two orders of magnitude greater than those calculated with a commonly used linear free energy relationship (LFER). The present study demonstrates that resuspension of contaminated sediments releases PCBs to the water column, of which a significant fraction are DOC-associated (e.g., 28, 65, and 90% for PCBs 28, 66, and 110, respectively). Results also imply that site-specific PCB K(DOC)s are superior to those calculated with generic LFERs.