Bioavailability Of Polycyclic Aromatic Hydrocarbons Research Articles

Influence of soot carbon on the bioaccumulation of sediment‐bound polycyclic aromatic hydrocarbons by marine benthic invertebrates: An interspecies comparison

The sorption of polycyclic aromatic hydrocarbons (PAHs) to soot carbon in marine sediments has been hypothesized to reduce PAH bioavailability. This hypothesis was tested for eight species of marine benthic invertebrates (four polychaete worms, Clymenella torquata, Nereis virens, Cirriformia grandis, and Pectinaria gouldii, and four bivalve mollusks, Macoma balthica, Mulinia lateralis, Yoldia limatula, and Mya arenaria) that span a wide range of feeding behavior, ability to metabolize PAHs, and gut chemistry. Organisms were exposed for 20 d to two PAH-spiked sediments, one with soot and one without soot. The soot treatment generally resulted in lower bioaccumulation than the no soot treatment, though the differences between treatments were not significant for all species. All but one species accumulated significant PAH concentrations in their tissues from the soot treatment, indicating that soot-bound PAH cannot be dismissed as unavailable to infaunal benthic biota. Bioaccumulation factors were correlated negatively to both the organisms' ability to metabolize PAHs and the gut fluid contact angle, supporting the hypotheses that high PAH metabolism results in lower bioaccumulation factors and bioavailability of PAHs may be limited partially by PAH solubilization in the gut lumen. The variability in bioaccumulation due to the soot treatment was much less than the variability between species and between PAH analytes. Comparatively low bioaccumulation was observed in Nereis virens, a species commonly used in bioaccumulation tests. These results suggest that more effort is needed in understanding the salient characteristics of species present in a threatened environment, rather than focusing solely on the sediment geochemistry (e.g., soot and organic carbon content) and contaminant characteristics when predicting ecological risk of PAH-contaminated sediments.

Evaluation of the role of black carbon in attenuating bioaccumulation of polycyclic aromatic hydrocarbons from field‐contaminated sediments

The significance of black carbon (BC) for the bioavailability of polycyclic aromatic hydrocarbons (PAHs) was examined by using historically contaminated intact sediment cores in laboratory exposure experiments with the deposit-feeding amphipod Monoporeia affinis. Log values of amphipod biota-sediment accumulation factors (BSAFs) were significantly related to log BC, whereas log BSAFs were related to log octanol-water partition coefficients only in background sediments containing less BC. In the background sediments, the BSAF for polycyclic aromatic hydrocarbons (PAHs) was 1 to 2 for phenanthrene, with lower values for more hydrophobic PAHs, indicating an increase in nonequilibrium conditions with increasing PAH molecular size. For the near-equilibrated phenanthrene and fluoranthene, higher BSAFs were measured during exposure to background sediments, with BSAF decreasing to <0.1 in contaminated sediments in the Stockholm waterways. In situ caged mussels (Dreissena polymorpha) exhibited field BSAF values (relative to sediment-trap-collected suspended matter) for polychlorinated biphenyls (PCBs) of 0.1 to 0.4, but for PAHs of similar hydrophobicity and molecular size, the field BSAFs were much lower and in the range 0.002 to 0.05. This PAH-PCB dichotomy is consistent with recently reported much stronger binding to diesel soot (a form of BC) for PAHs than for PCBs of equal hydrophobicities. Lower BSAFs for the near-equilibrated PAHs (phenanthrene and fluoranthene) in the urban sediments relative to the background sediments were consistent with the larger presence of BC in the urban sediments. This study provides the first linked BSAF-BC field data that supports a causal relationship between strong soot sorption and reduced bioavailability for PAHs.

Role of source matrix in the bioavailability of polycyclic aromatic hydrocarbons to deposit‐feeding benthic invertebrates

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) to benthic organisms is complicated by the variety of ways that they are introduced to coastal waters (dissolved, as nonaqueous phase liquids, and tightly bound to soot, coal, tire rubber, and eroded shale). In order to better understand the controlling variables that affect chemical and biological availability of PAHs, a study was conducted in which three deposit-feeding infaunal benthic invertebrate species (Cirriformia grandis, Clymenella torquata, and Macoma balthica) were exposed to sediments amended with PAH-rich materials (coal dust, tire rubber, diesel soot, creosote, crude oil, and fuel oil). Lipid and organic carbon normalized bioaccumulation factors (BAF(1oc)s) were calculated after 20 d of exposure and PAH bioavailability from the different treatments was assessed. Bioaccumulation of coal-derived PAHs usually was too low to be measured, though PAHs associated with soot and tire rubber showed significant accumulation in organism tissues. Polycyclic aromatic hydrocarbons from the fuel oil, creosote, and crude oil treatments were more bioavailable than PAHs bound in solid carbonaceous matrices (soot, coal, and tire rubber). Desorption of PAHs from the amended sediments into seawater also was measured using XAD resin. As was observed with bioaccumulation, PAHs in coal were desorbed the least; tire rubber and diesel soot were intermediate; and creosote, fuel oil, and crude oil desorbed to the greatest extent. In only one out of the three species evaluated was PAH bioaccumulation related to extent of desorption after 20 d. Decoupling between biological and chemical availability may be due to species-specific factors such as surfactant-mediated solubilization in the guts of some deposit-feeding organisms. A significant finding of this work was the demonstration that PAHs associated with soot and tire rubber in their native state (rather than experimentally added) are available to some benthic biota.

Digestive bioavailability to a deposit feeder (Arenicola marina) of polycyclic aromatic hydrocarbons associated with anthropogenic particles

Marine sediments around urban areas serve as catch basins for anthropogenic particles containing polycyclic aromatic hydrocarbons (PAHs). Using incubations with gut fluids extracted from a deposit-feeding polychaete (Arenicola marina), we determined the digestive bioavailability of PAHs from fly ashes, coal dusts, diesel soots, tire tread materials, and urban particulates. We found that gut fluids solubilize significant concentrations of PAHs from two tire treads, two diesel soots, and the urban particulates. However, PAHs in fly ashes and coal dusts were not available to the digestive agents in gut fluid. Potential digestive exposure to PAHs is much greater than that predicted to be available from these materials using equilibrium partitioning theory (EqP). Amending an already-contaminated sediment with fly ash decreased phenanthrene solubilization by gut fluid. In contrast, addition of tire tread to the sediment resulted in increased solubilization of four PAHs by gut fluid. Therefore, addition of certain types of anthropogenic particles to sediments may result in an increase in bioavailable PAHs rather than a net decrease, as predicted by EqP. Difficulty in predicting the amount of change due to amendment may be due to interactions occurring among the mixture of compounds solubilized by gut fluid.

Importance of black carbon in distribution and bioaccumulation models of polycyclic aromatic hydrocarbons in contaminated marine sediments

The roles and relative importance of nonpyrogenic organic carbon (NPOC) and black carbon (BC) as binding phases of polycyclic aromatic hydrocarbons (PAHs) were assessed by their ability to estimate pore water concentrations and biological uptake in various marine sediments. Sediment bioaccumulation tests were performed with the marine polychaete Nereis virens, using a polyethylene device to estimate pore water concentrations of PAHs. Using existing partitioning data for pyrene and phenanthrene, it was found that the traditional Equilibrium Partitioning model, which assumes all organic carbon is NPOC (EqP(OC)), overestimated the measured pore water concentrations in the test sediments by one to three orders of magnitude. Instead, the measured pore water concentrations were better predicted from a distribution scenario that uses both BC and NPOC (EqP(NPOc,BC)) When comparing actual worm body burdens of pyrene and phenanthrene with the two model estimates of worm tissue concentrations, the EqP(OC) model tended to overestimate actual body burdens by three orders of magnitude, while the EqP(NPOC,BC) model came much closer to the true body burden values. The observed distribution of PAHs in the test sediments was used to calculate BC partition coefficients for five PAHs, which were one to two orders of magnitude higher than their corresponding organic carbon-normalized distribution coefficients, or K(OC)s. Together, these results suggest that, in certain situations, adding black carbon to distribution models may be necessary to predict accurately the bioavailability of PAHs.

Effects of humic substances and soya lecithin on the aerobic bioremediation of a soil historically contaminated by polycyclic aromatic hydrocarbons (PAHs).

The high hydrophobicity of polycyclic aromatic hydrocarbons (PAHs) strongly reduces their bioavailability in aged contaminated soils, thus limiting their bioremediation. The biodegradation of PAHs in soils can be enhanced by employing surface-active agents. However, chemical surfactants are often recalcitrant and exert toxic effects in the amended soils. The effects of two biogenic materials as pollutant-mobilizing agents on the aerobic bioremediation of an aged-contaminated soil were investigated here. A soil historically contaminated by about 13 g kg(-1) of a large variety of PAHs, was amended with soya lecithin (SL) or humic substances (HS) at 1.5% w/w and incubated in aerobic solid-phase and slurry-phase reactors for 150 days. A slow and only partial biodegradation of low-molecular weight PAHs, along with a moderate depletion of the initial soil ecotoxicity, was observed in the control reactors. The overall removal of PAHs in the presence of SL or HS was faster and more extensive and accompanied by a larger soil detoxification, especially under slurry-phase conditions. The SL and HS could be metabolized by soil aerobic microorganisms and enhanced the occurrence of both soil PAHs and indigenous aerobic PAH-degrading bacteria in the reactor water phase. These results indicate that SL and HS are biodegradable and efficiently enhance PAH bioavailability in soil. These natural surfactants significantly intensified the aerobic bioremediation of a historically PAH-contaminated soil under treatment conditions similar to those commonly employed in large-scale soil bioremediation.

Addition of Carbon Sorbents to Reduce PCB and PAH Bioavailability in Marine Sediments: Physicochemical Tests

The addition of activated carbon as particulate sorbent to the biologically active layer of contaminated sediment is proposed as an in-situ treatment method to reduce the chemical and biological availability of hydrophobic organic contaminants (HOCs) such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We report results from physicochemical experiments that assess this concept. PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay, CA, was contacted with coke and activated carbon for periods of 1 and 6 months. Sediment treated with 3.4 wt % activated carbon showed 92% and 84% reductions in aqueous equilibrium PCB and PAH concentrations, 77% and 83% reductions in PCB and PAH uptake by semipermeable membrane devices (SPMD), respectively, and reductions in PCB flux to overlying water in quiescent systems up to 89%. Adding coke to contaminated sediment did not significantly decrease aqueous equilibrium PCB concentrations nor PCB or PAH availability in SPMD measurements. Coke decreased PAH aqueous equilibrium concentrations by 38-64% depending on coke dose and particle size. The greater effectiveness of activated carbon as compared to coke is attributed to its much greater specific surface area and a pore structure favorable for binding contaminants. The results from the physicochemical tests suggest that adding activated carbon to contaminated field sediment reduces HOC availability to the aqueous phase. The benefit is manifested relatively quickly under optimum contact conditions and improves in effectiveness with contact time from 1 to 6 months. Activated carbon application is a potentially attractive method for in-situ, nonremoval treatment of marine sediment contaminated with HOCs.

Bioavailability and Risk Assessment of Orally Ingested Polycyclic Aromatic Hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are a family of toxicants that are ubiquitous in the environment. These contaminants generate considerable interest, because some of them are highly carcinogenic in laboratory animals and have been implicated in breast, lung, and colon cancers in humans. These chemicals commonly enter the human body through inhalation of cigarette smoke or consumption of contaminated food. Of these two pathways, dietary intake of PAHs constitutes a major source of exposure in humans. Although many reviews and books on PAHs have been published, factors affecting the accumulation of PAHs in the diet, their absorption following ingestion, and strategies to assess risk from exposure to these hydrocarbons following ingestion have received much less attention. This review, therefore, focuses on concentrations of PAHs in widely consumed dietary ingredients along with gastrointestinal absorption rates in humans. Metabolism and bioavailability of PAHs in animal models and the processes, which influence the disposition of these chemicals, are discussed. The utilitarian value of structure and metabolism in predicting PAH toxicity and carcinogenesis is also emphasized. Finally, based on intake, disposition, and tumorigenesis data, the exposure risk to PAHs from diet, and contaminated soil is presented. This information is expected to provide a framework for refinements in risk assessment of PAHs from a multimedia exposure perspective.

Bioavailability of PAHs: effects of soot carbon and PAH source.

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.

Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils

The fate of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils may be affected by several environmental factors including the presence of co-contaminants. This study was conducted in order to assess the effect of metals on (i) the adsorption of 14C-phenanthrene in soils and (ii) its extractability and ability to form non-extractable residues. The first objective was accomplished using batch adsorption experiments with an uncontaminated agricultural soil spiked with the metals Cd, Cu, Pb, and Zn. Adsorption of phenanthrene was significantly higher after the addition of the metals ( K f=21.48 vs. 8.55) and the desorption less readily reversible when compared to the unspiked soil. The extractability of phenanthrene was assessed with incubation (4 months, laboratory conditions) and microlysimeter experiments (6 months, natural climatic conditions) on three soils spiked with metals. All the soils were labelled with 14C-phenanthrene. The amount of extractable phenanthrene residues was significantly higher when the metals had been added to the soils. Nevertheless, the quantity of non-extractable residues was non-significantly different between the spiked and unspiked soils. The mechanism leading to increased adsorption and extractability of phenanthrene in the presence of metals is still unknown. In perspective, it would be interesting to assess the bioavailability of PAHs in the presence of metals in further experiments.

Assessing the bioavailability of PAHs in field-contaminated sediment using XAD-2 assisted desorption.

An XAD-2 assisted desorption assay was evaluated to assess its functionality in determining the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in an aged field-contaminated sediment. In the study, various dosages of XAD-2 resin were added to abiotic sediment-water slurry systems to adsorb the PAHs from the aqueous phase thus accelerating the desorbability of these contaminants from the sediment. A parallel experiment on the biodegradation of these PAHs by microorganisms indigenous to the sediment was also conducted. Both the desorbability of the PAHs in the XAD-2 assisted desorption assay and their biodegradability decreased with time and eventually approached constant values. The two procedures showed very similar residual concentrations of PAHs for compounds with less than five benzene rings. This suggests that the XAD-2 assisted desorption assay shows promise in measuring the bioavailability of PAHs in field-contaminated sediments and could be used for predicting the end point of PAH bioremediation.

Use of passive samplers to mimic uptake of polycyclic aromatic hydrocarbons by benthic polychaetes.

Experiments were conducted to test whether passive samplers made of low-density polyethylene (polyethylene devices, or PEDs) can estimate the extent of uptake of polycyclic aromatic hydrocarbons (PAHs) by benthic polychaetes (Nereis virens) in contaminated marine sediments. For a variety of PAHs, PEDs reached 90% equilibrium with sediment PAHs in 60 days or less. Using 60-day sediment bioaccumulation tests, we have demonstrated a significant relationship between PAH concentrations in the polychaetes and the PEDs (R2 = 0.67, p = 0.002), with the PEDs taking up less PAHs than the polychaetes. Because of this relationship, PEDs can potentially be used in a regulatory context to simulate uptake of bioavailable PAHs in contaminated marine sediments. The PED PAH concentrations were also used to calculate porewater PAH concentrations that allowed for the estimation of a linear free-energy relationship between the lipid-water distribution coefficient (Klip) and the octanol-water distribution coefficient (KOW) for PAH uptake in marine polychaetes (R2 = 0.94, p < 0.0001).

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp ( Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients ( K ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw fish) and SPMD data (Cw spmd) were more in line for compounds with lower K ow than for compounds with higher K ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw sed) were comparable with the Cw spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.

631 National assessment of long-term use of paraquat for its food and environmental-safety in Korea

Polycyclic aromatic hydrocarbons (PAHs) have been recognised as priority pollutants due to their carcinogenic, mutagenic and teratogenic properties. Bioremediation of PAHs is limited by low bioavailability of soil-bound PAHs due to their low aqueous solubility, high hydrophobicity and strong sorption to soil. The purpose of this study was to investigate the biodegradation enhancement potential of a heavy molecular mass lipopeptidal biosurfactant produced by Bacillus cereus SPL-4 on an aged wood treatment plant soil heavily contaminated with PAHs. In the laboratory scale batch treatments conducted (concentration of 6745.5 mg kg−1, sum of 13 PAHs) the high molecular weight PAHs removal rate was significantly enhanced in the biosurfactant supplemented microcosms than in the surfactant free controls. In the microcosms supplemented with 0.2 and 0.6% (w/w) lipopeptide, 51.2% of 4-ring and 55% of 5- and 6-ring PAHs; 64.1% of 4-ring and 79% of 5- and 6-ring PAHs were removed respectively, compared to 29% of 4-ring and 25.5% of 5- and 6-ring PAHs removal in the surfactant free control after 64 days of incubation. However, there was no statistically significant change in the degradation rates of low molecular weight PAHs in surfactant amended and surfactant free controls. Fitting the experimental data to two compartment model showed that the biosurfactant addition at 0.2 and 0.6% (w/w) increased the fast degradation fraction to 34.2 and 63% respectively, compared to 6% at the surfactant free controls. The degradation of 5 and 6 ring PAHs was significantly enhanced (p < 0.05) in the higher surfactant dosage compared to the lower dosage. The results suggest that biosurfactant assisted degradation by microbial consortium may be a promising practical bioremediation strategy for aged PAH-contaminated soils.

Influence of the growth substrate on ester-linked phospho- and glycolipid fatty acids of PAH-degrading Mycobacterium sp. LB501T.

The influences of poorly water-soluble anthracene on ester-linked phospholipid fatty acid (PLFA) and glycolipid fatty acid (GLFA) profiles of Mycobacterium sp. LB501T were studied. Bacteria were cultivated on either anthracene or glucose (one culture with successively amended small doses of this substrate and one with excess concentrations) to distinguish between influences of the chemical structure and the bioavailability of the growth substrate. Results revealed that GLFA and PLFA profiles of M. sp. LB501T depended on the availability and the structure of the carbon source. Fatty acid profiles obtained with anthracene differed from those obtained with excess glucose. They were interpreted as a specific adaptation to this poorly bioavailable polycyclic aromatic hydrocarbon (PAH). In contrast, profiles obtained with low glucose concentrations showed clear signs of starvation stress. Stable carbon isotopic ratios (delta13C) of GLFA and PLFA of M. sp. LB501T were analysed to characterize the 13C-fractionation during the biosynthesis of individual fatty acids and to evaluate their value as markers for substrate usage. Although the delta13C values of PLFA and GLFA showed differential isotope fractionation during anthracene- and glucose-degradation, they were sufficiently distinct to be used as signatures of bacterial substrate usage.

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.

The Chemical Baseline as a Key to Defining Continuing Injury and Recovery of Prince William Sound

ABSTRACT Studies of records and data pertaining to anthropogenic and natural sources of petroleum, and specifically of the polycyclic aromatic hydrocarbons (PAH), have indicated a generally constant background, with episodic input spikes of bioavailable PAH to the marine environment of Prince William Sound (PWS), Alaska. The Exxon Valdez oil spill (EVOS) was one such PAH spike. However, hundreds of smaller spills, occurring prior to and since the EVOS, contribute a background of bioavailable petrogenic PAH to PWS. The widespread historical and contemporary uses of PWS by man have left chronic, sizeable, and widespread petrogenic and pyrogenic PAH fingerprints and bioavailable PAH at many locations in PWS. Evidence from mussel samples, taken both prior to and since EVOS, and from subtidal sediments, indicates that bioavailable PAH are a constant feature of the PWS system. While EVOS may continue to add some bioavailable PAH to highly localized areas, most PAH inputs to the PWS marine environment are unrelated to EVOS. Such findings indicate that biological, sublethal effects studies, which rely on tissue body burdens and biomarkers as leading indicators of continuing effects from EVOS (e.g. CYP1A-P450, etc.) may have been misinterpreted, as they are confounded by this easily detectable, significant, and continuing background of bioavailable PAH. Therefore measurements of exposure to PAH as indicating lingering effects from EVOS, 13 years after the spill, are speculative and ignore the baseline PAH from non-EVOS inputs.

Monitoring Recovery of Prince William Sound, Alaska, Following the Exxon Valdez Oil Spill: Bioavailability of PAH in Offshore Sediments

ABSTRACT We determined the bioavailability to sediment-dwelling marine worms of polycyclic aromatic hydrocarbons (PAHs) associated with offshore sediments from 3 spill path and 3 non-spill path areas of Prince William Sound (PWS), Alaska, 12 years after the Exxon Valdez oil spill. The PAHs in sediments from 4 sites sampled in 2001 were primarily from a regional natural petrogenic background derived from organic-rich shales and natural oil seeps associated with sources southeast of PWS. Pyrogenic (combustion) PAHs, primarily from former human and industrial activities, were more abundant than petrogenic PAHs in nearshore sediments from 2 bays associated with past and current human activities. We performed sediment bioaccumulation tests with the six sediments and polychaete worms according to standard EPA protocols. All the PAHs had a very low bioavailability, as indicated by low values for biota/sediment accumulation factors (BSAFs) in the worms. Mean BSAFs for total PAHs (sum of 41 analyte groups) ranged from 0.002 to 0.009. The worms exposed to spill path and non-spill path sediments bioaccumulated small amounts of 4- and 5-ring PAHs, particularly fluoranthene and pyrene; these higher molecular weight PAHs are responsible for induction of mixed function oxygenase (MFO) activity in marine fish, birds, and mammals. These results may help to explain in part why fish from throughout PWS exhibit induced MFO activity. Elevated levels of MFO activity cannot be used as evidence of recent exposure by marine fish, birds, and mammals in the sound to Exxon Valdez oil.

Availability of polycyclic aromatic hydrocarbons to earthworms (Eisenia andrei, Oligochaeta) in field‐polluted soils and soil‐sediment mixtures

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) for earthworms (Eisenia andrei) was experimentally determined in seven field-polluted soils and 15 soil-sediment mixtures. The pore-water concentration of most PAHs was higher than predicted. However, most of the compound was associated with dissolved organic carbon (DOC) and not directly available for uptake by earthworms. The apparent sorption could be reasonably predicted on the basis of interactions with DOC; however, the biota-soil accumulation factors (BSAFs) for earthworms were up to two orders of magnitude lower than predicted by equilibrium partitioning. The large variability between sites was not fully explained by differences in sorption. Experimental results indicate that the pool of freely dissolved PAHs in the pore water became partially depleted because of uptake by the earthworms and that bioaccumulation is thus also influenced by the kinetics of PAH desorption and mass transport. A pilot study with Lumbricus rubellus showed that steady-state body residues were well correlated to E. andrei. Current results show that depositing dredge spoil on land may lead to increased bioavailability of the lower-molecular-weight PAHs. However, risk assessment can conservatively rely on equilibrium partitioning, but accurate prediction requires quantification of the kinetics of bioavailability.

Effects of carbon substrate enrichment and DOC concentration on biodegradation of PAHs in soil.

Two common reasons to explain slow environmental biodegradation of polycyclic aromatic hydrocarbons (PAHs), namely lack of appropriate carbon sources for microbial growth and limited bioavailability of PAHs, were tested in a laboratory bioassay using a creosote-contaminated soil. The soil, containing a total of 8 mg g-1 of 16 PAHs, was sieved and incubated in bottles for 45 days. The first explanation was tested by enrichment with the analogue anthracene and the non-analogue myristic acid, and both failed to stimulate degradation of all PAHs except anthracene. The second explanation was tested by addition of different concentrations of dissolved organic carbon (DOC), with effects depending on the DOC concentration and the molecular size of the PAH. The degradation was enhanced from 10 to 35% for 12 PAHs when the soil was saturated. The degraded amounts of individual PAHs were proportional to their concentration in the soil. The slow in situ degradation of PAHs was enhanced by more than three times by adding water as a solvent. Addition of DOC facilitated the degradation of four- to six-ring PAHs. Bioremediation of PAH-contaminated sites may be facilitated by creating water-saturated conditions but retarded by addition of other carbon substrates, such as analogue compounds.