Humic Acid Toxicity in Biologically Treated Soil Contaminated with Polycyclic Aromatic Hydrocarbons and Pentachlorophenol

Contaminated soil from a land treatment unit at the Libby Groundwater Superfund Site in Libby, MT, was amended with ¹⁴C pyrene and incubated for 396 days to promote biodegradation and the formation of soil-associated bound residues. Humic and fulvic acids were extracted from the treated soil microcosms and analyzed for the presence of pyrene residues. Biologic activity promoted ¹⁴C association with the fulvic acid fraction, but humic acid–associated ¹⁴C did not increase with biologic activity. The Aboatox flash toxicity assay was used to assess the toxicity of humic and fulvic acid fractions. The fulvic acid gave no toxic response, but the humic acid showed significant toxicity. The observed toxicity was likely associated with pentachlorophenol, a known contaminant of the soil that was removed by solvent extraction of the humic acid and that correlated well with toxicity reduction.     

Influences of aging on the bioavailability of sediment-bound Cd and Zn to deposit-feeding sipunculans and soldier crabs

The radiotracer technique was used to assess the influences of sediment-metal contact time or aging (up to two years) on the bioavailability and geochemical speciation of Cd and Zn in sediments. Bioavailability was quantified by measuring the assimilation efficiency of metals in two deposit-feeding invertebrates (sipunculans and soldier crabs) and the extraction by the sipunculans' gut juices. Sediment aging generally did not significantly affect the Cd speciation in the sediments, Cd assimilation, and Cd extraction. In contrast, sediment aging significantly affected the Zn distribution in different geochemical phases and the Zn bioavailability. With increasing aging, the Zn distributed in the carbonate phase decreased, whereas that in the reducible phase increased. Accordingly, the Zn gut-juice extraction decreased significantly. Two years of aging were not sufficient for Zn to be associated with the organic and residual phases. A significant positive correlation was found between Cd gut-juice extraction and assimilation efficiency. Gut-juice extraction of Cd and Zn generally increased with metal distribution in the exchangeable and carbonate phases but decreased with that in the reducible phase. Our results suggest that different metals are influenced by sediment aging differently and that geochemical speciation analysis is useful in studying the bioavailability of sediment-bound metals. This study may have implications for designing sediment toxicity tests using spiking techniques and for understanding the fates of anthropogenically derived metals in sediments.     

Quantitative and mid-infrared changes of humic substances from burned soils

The humic substances are an abundant and important part of soil organic matter which plays many roles in ecosystems. On the other hand, forest fires are known to have a potential impact on the soil organic matter. Consequently, we chose to study the impact of forest fires on humic substances and the three relevant fractions, e.g. humic acids (HA), fulvic acids (FA) and non-humified fraction (NHF), NHF being the fulvic acids not adsorbed on XAD-8 resins. The studied site is a Mediterranean forest called “Maures Mountains”, in France, where 30 sites were sampled in two layers: 0–5 and −5 to 15 cm. In order to validate the method, the 2 horizons from 5 sites randomly chosen were analyzed in triplicates. The extraction and fractionation procedures were achieved using alkali- and acid-solutions. The measurement of total organic carbon (TOC) using the TOC-meter and the use of Fourier transform infra-red (FTIR) spectroscopy gave us quantitative and qualitative results to evaluate the impact of forest fires and the role of their repetition. The results show that the fires led to significant decreases (Student test, P=0.05) of humic substances (HS), HA and of the fulvic fractions (FF=FA+NHF) in surface layers, corresponding to 40%, 34% and 35%, respectively. Moreover, the significant HA/FF ratio increases (Student test, P=0.05), as a result of the fire, indicate that NHF was probably transformed in FA-like compounds. About the qualitative impact, the results showed a significant decrease of alkyl and hydroxyl groups (OH), carboxylic acids and carbohydrates in HA after a wildfire, whereas the decrease was significant only for alkyl groups and carboxylic acids in FA. Lastly, the design of this work (control and burned sites, number of samples, time elapsed after fires, etc.) enables one to show the recovery of the Mediterranean forest ecosystem. FA quality and OH groups in HA are recovered between 3 and 16 years after the fire whereas alkyl groups, carboxylic acids and carbohydrates in HA as well as HS contents are not returned to the control state 16 years after the last fire.     

Mechanisms regulating bioavailability of phenanthrene sorbed on a peat soil-origin humic substance

The organic matter-mineral complex plays an important role in regulating the fate of hydrophobic organic compounds (HOCs) in the environment. In the present study, the authors investigated the microbial bioavailability of phenanthrene (PHE) sorbed on the original and demineralized humic acids (HAs) and humin (HM) that were sequentially extracted from a peat soil. Demineralization treatment dramatically decreased the 720-h mineralized percentage of HM-sorbed PHE from 42.5 ± 2.6% to 3.4 ± 1.3%, whereas the influence of this treatment on the biodegradability of HA-associated PHE was much lower. Degradation kinetics of HA- and HM-sorbed PHE showed that its initial degradation rate was negatively correlated with the aromatic carbon content of humic substances (p<0.05). This was attributed to the strong interactions between PHE and the aromatic components of humic substances, which hampered its release and subsequent biodegradation. The 720-h mineralized percentage of PHE was inversely correlated with the estimated thickness of the organic matter layer at the surfaces of HAs and HMs. Therefore, in a relatively long term, diffusion of PHE within the organic matter layer could be an important factor that may limit the bioavailability of PHE to bacteria. Results of the present study highlight the molecular-scaled mechanisms governing bioavailability of PHE sorbed on humic substances.     

Identification of mobile aliphatic sorptive domains in soil humin by solid-state 13C nuclear magnetic resonance

Many sorption studies aim to elucidate organic matter structure and contaminant sorption relationships. Through this pursuit, a great deal of insight has been gained about contaminant interactions with humic fractions, namely the fulvic and humic acid isolates. Comparatively, less is known about the structure and environmental reactivity of the humin fraction; however, researchers have reported that the humin fraction consistently produces higher sorption coefficients than the corresponding source material and other humic fractions. In this paper, we report on a study that uses solid-state 13C nuclear magnetic resonance (NMR) to characterize six humin samples extracted from soil. In addition, 1-naphthol sorption was measured for each whole-soil and humin sample. With the exception of the peat sample, the humin samples yielded significantly higher organic carbon-normalized sorption coefficients (K(oc)) compared with the whole-soil samples. The solid-state 13C NMR analysis reveals the presence of amorphous, polymethylene-rich domains in all of the humin samples. Other researchers have indicated that these domains exhibit a high affinity for hydrophobic organic contaminants. Consequently, we hypothesize that the concentration of amorphous, polymethylene-rich domains in soil humin is responsible for the high sorption coefficients reported here and by other researchers.     

Investigating Arsenic Bioavailability and Bioaccumulation by the Freshwater Oligochaete <Emphasis Type="Italic">Lumbriculus variegatus</Emphasis>

The complex and variable composition of natural sediments makes it difficult to predict the bioavailability and bioaccumulation of sediment-bound contaminants. Several approaches, including an experimental model using artificial particles as analogues for natural sediments, have been proposed to overcome this problem. For this work, we applied this experimental device to investigate the uptake and bioaccumulation of As^III by the freshwater oligochaete Lumbriculus variegatus. Five different particle systems were selected, and particle–water partition coefficients for As^III were calculated. The influence of different concentrations of commercial humic acids was also investigated, but this material had no effect on bioaccumulation. In the presence of particulate matter, the bioaccumulation of As^III by the oligochaetes did not depend solely on the levels of chemical dissolved but also on the amount sorbed onto the particles and the strength of that binding. This study confirms that the use of artificial particles may be a suitable experimental model for understanding the possible interactions that may occur between contaminants and particulate matter. In addition, it was found that the most hydrophobic resin induced an increase in arsenic bioavailability, leading to the highest bioaccumulation to L. variegatus compared with animals that were exposed to water only.     

Speciation of aqueous methylmercury influences uptake by a freshwater alga (Selenastrum capricornutum)

Uptake of methylmercury (MeHg) by the alga Selenastrum capricornutum was measured in freshwater batch culture bioassays. The concentration of MeHg in the alga increased rapidly (within 15 min), reached a maximum by 6 h, and then declined because of growth dilution. The alga's rapid growth rate (doubling time, approximately 10 h) contributed to the importance of growth dilution. Conditional first-order rate constants were calculated for uptake (k1 = 6.95 x 10(-9) L/cell/h) and growth (kG = 0.07/h). A competitive synthetic ligand, disodium ethylenediaminetetra-acetate, formed strong complexes with MeHg and reduced MeHg uptake, consistent with the biotic ligand model. A conditional equilibrium formation constant (K) for the MeHg-algae complex was estimated to be approximately 10(16) and was used to model the influence of natural ligands on MeHg bioavailability. Model results suggested MeHg would be most bioavailable at concentrations of dissolved organic matter (DOM) less than 10 mg/L and increasingly unavailable at higher DOM concentrations for the specific humic acid modeled. Similarly, at molar concentrations of sulfide (and, possibly, metal-sulfide clusters) equal to approximately half the MeHg concentration, MeHg was predicted to be unavailable to algae because of the formation of strong 2:1 MeHg-sulfide complexes.     

Distribution of atrazine into three chemical fractions: impact of sediment depth and organic carbon content

The fate and transport of organic contaminants in aquatic sediments are impacted largely by microbial degradation and sorption to organic matter. Atrazine, a pre-emergent herbicide, has the potential to contaminate groundwater because of its slight water solubility, long half-life, and sorption to organic matter. Mineralization and distribution of 14C-atrazine into three chemical fractions were monitored over time in surface and subsurface coastal aquatic sediments of different land use. Sediments were extracted with an organic solvent followed by an alkali hydrolysis, and 14C activity was measured in the aqueous, solvent, and basic fractions (representing nonsorbed compounds, loosely sorbed compounds, and humic or fulvic acid bound compounds, respectively). Limited mineralization of atrazine occurred (< 4%). The 14C activity in the aqueous and basic fractions increased over time, was greater in surface versus subsurface sediments, and was positively correlated with sediment organic carbon (SOC) content, indicating greater biological and chemical activity. Total 14C recovered ranged from 50 to 90%, was less in surface versus subsurface sediments, and was not correlated with SOC after 80 d. These results suggest that in native aquatic surface sediments, atrazine sorption plays a major role, whereas in subsurface sediments atrazine may be available for degradation and transport to shallow groundwater.     

Effect of pH,Sulphate Concentration and Total Organic Carbon on Mercury Accumulation in Sediments in the Volta Lake at Yeji,Ghana

In this study, pH, total organic carbon, sulphate concentration and mercury concentrations of sediment samples from the Volta Lake at Yeji in the northern part of Ghana were determined. The results indicate that pH ranged from 6.32 to 8.21, total organic carbon ranged from 0.17 to 3.02 g/kg and sulphate concentration from 10.00 to 57.51 mg/kg. Total mercury concentrations ranged from 32.61 to 700 ng/g which is below the International Atomic Energy Agency recommended value of 810 ng/g. Humic substance-bound mercury ranged from 81.15 to 481.31 mg/kg in sediments and its two fractions existed as humic acid-bound mercury > fulvic acid-bound mercury with the ratio of humic substance-bound mercury to fulvic acid-bound mercury as 1.62 on the average. Humic substance-bound mercury and the two fractions fulvic acid-bound mercury and humic substance-bound mercury in sediments were favorably determined and found to correlate significantly positive with total organic carbon (r = 0.538) and total mercury (r = 0.574). However, there were poor correlations between SO₄ ²⁻ concentrations and humic substance-bound mercury (r = −0.391) as well as the two fractions; fulvic acid (r = −0.406) and humic acid (r = −0.381). By assuming that methyl mercury is mostly formed in sediments, these significant relations suggest that the efficiency of mercury being methylated from a given inorganic form depends on the amount, and most likely biochemical composition of total organic carbon in the lake sediment but not the SO₄ ²⁻ concentration.     

Nickel speciation in the presence of different sources and fractions of dissolved organic matter

This study evaluated nickel (Ni) speciation in the presence of different fractions (humic acid (HA), fulvic acid (FA)) and sources (natural sediment, Suwannee River, peat moss) of dissolved organic matter (DOM) at Ni concentrations toxicologically relevant to the freshwater amphipod, Hyalella azteca. The free Ni ion, Ni(2+), was measured in reconstituted water (with or without DOM) using a miniaturized ion-exchange technique (IET). Ni speciation from these experiments was compared to calculated results obtained from equilibrium modelling (WHAM, Model VI). While it is known that Ni will complex with DOM, it was found that under acutely toxic Ni exposure concentrations ([Ni(Total)]=5mg/L, or 85.1 microM) representative surface-water DOC concentrations ( approximately 10mg/L) played little or no role in Ni speciation. Conversely, at sublethal Ni exposure concentrations ([Ni(Total)]=0.2 and 0.5 microg/L, or 3.4 and 8.51 microM, respectively) DOM significantly affected Ni speciation with [Ni(2+)] decreasing with increasing concentration of DOM. It was found that for similar concentrations of DOC (same fraction, different sources), the measured Ni(2+) concentrations were reduced (relative to the control), but similar to one another. Conversely, at similar DOC concentrations, the HA fraction reduced Ni(2+) levels to a greater extent than the associated FA fraction. Overall, this study provides proof of principle that Suwannee River and peat humic substances are suitable analogues for natural sediment pore-water DOM when evaluating Ni bioavailability in freshwater.     

Influence of humic acid on the uptake of aqueous metals by the killifish Fundulus heteroclitus

The role of humic acids, over a concentration range of 0 to 20?mg?L(-1) , was investigated in the uptake of three metals (Cd, Cr, and Hg-as both inorganic Hg [Hg(II)] and methylmercury [MeHg]) and a metalloid (As) from the aqueous phase by the killifish (Fundulus heteroclitus). Cadmium uptake showed no relationship with humic acid concentration, whereas Cr, Hg(II), and MeHg uptake showed an inverse relationship, and As uptake increased with increasing humic acid concentration. Concentration factors were >1 for Cd, Hg(II), and MeHg at all humic acid concentrations, indicating killifish were more enriched in the metal than the experimental media, whereas As and Cr generally had concentration factors <1 at the end of a 72-h exposure. The uptake of As and Cr reached steady state within the 72-h exposure, whereas uptake of Cd, Hg(II), and MeHg did not. Uptake rate constants (k(u) s;?ml?g(-1) d(-1) ) were highest for MeHg (91-3,936), followed by Hg(II), Cd, and Cr, and lowest for As (0.17-0.29). Dissection data revealed that the gills generally had the highest concentration of all metals under all humic acid treatments. The present study concludes that changes in humic acid concentration can influence the accumulation of aqueous metals in killifish and should be considered when modeling metal bioaccumulation. Environ. Toxicol. Chem. 2012; 31: 2225-2232. ? 2012 SETAC.     

Extraction of spiked metals from contaminated coastal sediments: a comparison of different methods

Various extraction methods have been developed to assess metal bioavailability from sediments. In this study, we compared the extraction of Cd, Cr, and Zn from contaminated sediments using different extractants (normal seawater, acidic seawater of pH = 5. seawater with 1% sodium dodecyl sulfate [SDS], and gut digestive fluids collected in vitro from deposit-feeding peanut worm Sipunculus nudus) coupled with concurrent metal speciation measurements. The influences of sediment aging on metal extraction were also examined using radiotracer-spiked techniques. Sediments aging up to 100 d did not significantly affect the partitioning of spiked Cd and Cr in different geochemical phases, but the spiked Zn was partitioned more into the reducible fraction and less into the carbonate phase with increasing sediment aging. There was a major difference in the partitioning into different geochemical phases between the spiked metals and the native metals within the 100-d sediment aging. The difference between the spiked and native Cd and Zn extraction using gut juices was somewhat smaller than the strong geochemical contrast. Metals bound with the anoxic sediments were hardly extracted by different extractants. There was a significant relationship between the extraction of spiked Cd and its distribution in the exchangeable phase (positive correlation) or in the reducible phase (negative correlation). For Cr and Zn, extraction was not correlated with their partitioning in any of the geochemical phases. Further, extraction of all three metals by digestive gut fluids was not correlated with the concentrations of simultaneously extractable metals (SEM), nor with the difference between SEM and acid volatile sulfide (AVS). Our study suggests that there were large differences in extraction among metals using different extractants and only Cd extraction was significantly related to its geochemical speciation in sediments.     

Effects of Benzo(a)pyrene and Size of Organic Matter Particles on Bioaccumulation and Growth of Asellus aquaticus

The effects of sediment-bound toxicants to aquatic invertebrates may vary due to differences in bioavailability, food quality, or food structure. The equilibrium partitioning theory (EPT) assumes that organic matter content of sediments and not structure of organic matter is relevant for biological effects of polycyclic aromatic hydrocarbons. To test this hypothesis effects of benzo(a)pyrene (B(a)P) and size of sediment organic matter particles on the bioaccumulation and growth of the waterlouse Asellus aquaticus were studied in laboratory microcosms. Sediments and A. aquaticus were both sampled in an unpolluted, spring-fed pond. The sampled sediment was divided into two portions. From one portion the size of the organic matter particles was mechanically reduced. One set of each sediment fraction (fine and coarse) was spiked with B(a)P and incubated for 3 weeks resulting in a concentration of 70 mg B(a)P per kg sediment. Bioassays of 32 days were performed in a 2 × 2 factorial design with four replicas of each treatment. The results showed that the growth of A. aquaticus was mainly influenced by the size of organic matter particles. Growth was significantly less (27%) on finer sediments than on coarser sediments. The increase in length was 9–14% lower in the spiked sediments, but this difference was not significant. The reduced growth of A. aquaticus on finer sediments may be due to a change in the availability and/or quality of food together with a change in feeding behavior. The coarse and fine spiked sediment types did not differ significantly with respect to the sediment water partition coefficient, the organic carbon water partition coefficient, and the bioconcentration factor. In contrast, the biota to sediment accumulation factors were significantly 15% higher in the cosms with coarse sediments than in cosms with fine sediments. However, this difference is too small to conflict with EPT. Received: 9 November 1999/Accepted: 3 May 2000     

Mercury Speciation and Total Organic Carbon in Marine Sediments Along the Mediterranean Coast of Israel

Along the Israeli Mediterranean Coast, three areas are considered “hot spots” of mercury (Hg) pollution: (1) Northern Haifa Bay (NHB), (2) the lower Qishon River at the southern part of Haifa Bay, and (3) a marine outfall of activated sewage sludge at the southern coast off Palmachim (sewage-sludge disposal site [SDS]). Even though the total Hg (HgT) concentrations in the sediments at the three areas are of the same order of magnitude (250–500?μg?kg^?1), Hg was shown to bioaccumulate in fish and benthic fauna from Haifa Bay but not in benthic fauna or in commercial fish caught along the southern Mediterranean Coast of Israel near the SDS outfall. The primary goal of this study was to measure the concentrations of Hg species (HgT, methyl-Hg [MeHg], and Hg in different biogeochemical fractions)—in conjunction with organic carbon—in sediments of NHB and the lower Qishon River to assess its impact on Hg transitions among the species as characterized by different bioavailability and bioaccessibility. HgT concentrations in NHB and the Qishon River ranged from 249 to 347 and 165 to 667?μg?kg^?1, respectively. MeHg was significantly higher in the Qishon River (6.3–34.0?μg?kg^?1) than in NHB (0.22–0.70?μg?kg^?1) as were total organic carbon (TOC) concentrations (average 2.5 vs. 0.13?%). The relative Hg distribution in the biogeochemical fractions in NHB was 2.3?% in the most bioaccessible fractions (F1?+?F2), 55?% in the organo-chelated species fraction (F3), 42?% in the strong-complexed species fraction (F4), and 0.7?% in the mercuric-sulfide fraction (F5). In the Qishon River, the bioavailable F1?+?F2 and F3 fractions were lower than in NHB (<0.01 and 23?%, respectively) and the more refractory F4 and F5 fractions higher (73 and 3.3?%, respectively). The fractionation of Hg in Qishon River sediments was similar to the distribution found in polluted stations at the SDS. TOC and MeHg were positively and negatively correlated, respectively, in Qishon River and NHB sediments. Methylation depended on TOC availability when its concentration was in the range of 2–4 wt%. It is possible that TOC in the sediment controlled Hg speciation: Hg in F3 decreased and in F4 increased with increasing TOC concentrations. In contrast, MeHg/HgT was significantly positively correlated with TOC and Hg in the stable F4 fraction and negatively correlated with Hg in the F3 fraction. It was therefore assumed that higher TOC concentrations enhanced microbial activity and decomposition of organic matter. Hg was released from the F3 fraction and was either transferred to the F4 fraction or made available for methylation processes.     

Preliminary Assessment of Legacy and Current-Use Pesticides in Franciscana Dolphins from Argentina

Mercury contamination is a growing concern for freshwater food webs in ecosystems without point sources of mercury. Methylmercury (MeHg) is of particular concern, as this is the form of mercury that crosses the blood–brain barrier and is neurotoxic to organisms. Wetlands and benthic sediments have high organic content and low oxygen availability. Anaerobic bacteria drive the metabolic function in these ecosystems and subsequently can methylate mercury. The bioavailability of MeHg is controlled by physicochemical characteristics such as pH, binding affinities, and dissolved organic matter (DOM). Similarly, photodemethylation is influenced by similar characteristics and thereby the two processes should be studied in tandem. The degradation of MeHg through photochemistry is an effective destruction mechanism in freshwater lakes. This review will highlight the uncertainties and known effects of DOM on subsequent photoreactions that lead to the occurrence of mercury photodemethylation and reduction in mercury bioavailability in freshwater ecosystems.     

Stage change in binding of pyrene to selected humic substances under different ionic strengths

Influence of ionic strength (I) on the pyrene binding constant (Koc) in six different humic substance (HS) solutions, three soil humic acids, one freshwater humic acid, one freshwater fulvic acid, and one freshwater natural organic matter was investigated by fluorescence quenching technique. Specific two-stage changes of Koc with increasing ionic strength were only observed in three soil humic acid solutions with varying to different extents. Two primary governing factors for the differences of these HS systems are binding potential and the abundance of acidic functional groups (carboxyl and phenolic) of HS. Experimental results demonstrated that within the ionic strength range studied in the present research, ionic strength had a major effect on molecular size of HS and brought about change of Koc. The salting-out effect did not. The change in molecular size was caused by the associations between cations and acidic groups of HS. Using pyrene as a probe, we also investigated the interaction of cation and dissolved HS and found relatively slow kinetics (at least 5 d), leading us to believe that the special cation-HS kinetics may influence the results of geochemical studies involving the measurement of ionic strength effect.     

Implication of Organic Matter on Arsenic and Antimony Sequestration in Sediment: Evidence from Sundarban Mangrove Forest, India

This study reports the measurement of stability constants for the interaction of As (V and III) and Sb (V and III) with humic substances extracted from aquatic sediments of the Sundarban mangrove forest ecosystem. It was observed that As and Sb formed a slightly more stable association with fulvic acid (FA) than with its humic acid (HA) counterpart. Quenching of fluorescence at increasing As (III and V) or Sb (III and V): FA or HA ratios was obtained that ideally correspond to a 1:1 complexation model. Quite strong complexation of As and Sb by FA and HA occurs at neutral pH, indicating that HA and FA probably markedly affect the mobility of As and Sb in the mangrove environment.     

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.     

A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon

Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43.     

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.