Bioavailability of PCBs from field-collected sediments: application of Tenax extraction and matrix-SPME techniques

Two chemical approaches, Tenax extraction and matrix solid phase microextraction (matrix-SPME), were evaluated for their potential to improve the prediction of bioavailability by equilibrium partitioning theory (EPT) across sediments with various characteristics. Biota-sediment accumulation factors (BSAFs) and body residues were quantified by exposing Lumbriculus variegatus to three PCB-contaminated field sediments. The concentration of PCBs in biota was positively correlated to the total PCB sediment concentration, the PCB concentration in the rapidly desorbing fraction estimated using Tenax extraction, and the PCB concentration on the SPME fibers. Results showed EPT was acceptable for estimating bioavailability from the tested sediments with sum PCB BSAFs of 1.18-2.47; however, it overestimated PCB bioavailability from sandy sediment. Both Tenax extraction and matrix-SPME, which take sequestration into account, reduced variability in prediction of PCB bioavailability across sediments, including the sandy sediment, and could be used as cost- and time-efficient alternatives for bioassay. Matrix-SPME was considered the better technique due to its ability to directly predict PCB body residues in the exposed biota and its potential use with in situ applications in the field.     

Desorption of sediment-associated polychlorinated dibenzo-p-dioxins, dibenzofurans, diphenyl ethers and hydroxydiphenyl ethers from contaminated sediment

The transport and bioavailability of sediment-associated contaminants are often controlled by the contaminants' desorbing behaviour. This study examines the desorption kinetics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), diphenyl ethers (PCDEs) and hydroxydiphenyl ethers (HO-PCDEs) from the highly contaminated River Kymijoki sediment in Finland. The desorption kinetics data were generated using Tenax((R)) extraction, and a first-order three-compartment kinetic model was fitted to the data. The desorption data was compared to the previously published accumulation data from this same location to investigate the relationship between the rapidly desorbing fraction (F(r)) and biota-sediment accumulation factors (BSAFs) as well as semipermeable membrane device sediment accumulation factors (SSAFs). The PCDDs, PCDFs, PCDEs and HO-PCDEs were tightly attached to sediment particles and formed a large very slowly desorbing fraction (F(vs)). Rapidly desorbing fractions (F(r)) varied between 0.8% and 8% of total amount in sediment. The size of the desorbing fraction was congener-specific and F(r) decreased with the increasing lipophilicity of congeners. The size of the F(r) was unable to explain the small variation in the BSAFs of Lumbriculus variegatus but may help to explain the observed variation in the SSAFs. To our best knowledge, this study is the first effort to investigate the desorption of PCDDs, PCDFs, PCDEs and HO-PCDEs in field-contaminated sediments. The major finding that the very slow desorption of these chemicals will continue years, provides essential information for the modern risk assessment process.     

Selective supercritical fluid extraction to identify aged sediment-bound PCBs available for uptake by eel

A naturally contaminated sediment was partially extracted with selective supercritical fluid extraction (SFE) to remove a fraction of supposedly bioavailable PCBs from the matrix. Eels (Anguilla anguilla) were cultured in systems with untreated and pre-extracted sediment, respectively, and it was shown that the SFE treatment selectively removed bioavailable PCBs from the sediment, since relative biota-to-sediment accumulation factors (BSAFs) for the eight studied PCB congeners were much lower in the pre-extracted than in the untreated system at the end of the study. Relative BSAF values decreased with about the same relative amount for all eight congeners, independent of the degree of chlorination and the initial concentration in the sediment. The results demonstrate the ability of SFE to selectively remove sediment-bound PCBs that are available for uptake by the eels, thus demonstrating the feasibility of using selective SFE to estimate bioavailability of PCBs in sediments.     

Biota–sediment accumulation factor (BSAF), bioaccumulation factor (BAF), and contaminant levels in prey fish to indicate the extent of PAHs and OCPs contamination in eggs of waterbirds

Samples of pond sediment, fish, and shrimp were collected from the Ramsar site at Mai Po marshes, Hong Kong (south China), and samples of pond sediment, fish, and shrimp, as well as eggs of water birds (Chinese Pond Herons (Ardeola bacchus) and Little Egrets (Egretta garzetta)), were collected from two smaller wetland sites at Jiangsu Province (mid-China), between 2004 and 2007. Accumulation levels of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in the biota were used to calculate biota–sediment accumulation factor (BSAF) and bioaccumulation factor (BAF). For fish and shrimp, BSAFs of OCPs (3.8–56) were greater than those of PAHs (0.12–6.3). BSAFs and BAFs of 11–79 and 4–34, respectively, were registered for OCPs in eggs of the birds and were greater than those for PAHs (0.11–1.5 and 0.02–1.3, respectively). Assuming that fish were the main prey of the birds, greater bioaccumulation of OCPs was detected for both bird species (BAFs?=?4.5–34), while accumulation of PAHs was only detected in Little Egret (BAF?=?1.3). A significant linear relationship (p?<?0.01) was observed between concentrations of OCPs in bird eggs and in the prey fish. The present study provides a new possibility of using OCP levels detected in prey fish to predict the extent of OCPs contamination in eggs of waterbirds including the endangered species, as a noninvasive method.     

Application of surrogate methods for assessing the bioavailability of PAHs in sediments to a sediment ingesting bivalve

The usefulness of two surrogate methods for rapidly determining the bioavailability of PAHs in hydrocarbon-contaminated marine sediments was assessed. Comparisons are made between the PAHs accumulated by the benthic bivalve, Tellina deltoidalis, and the extractable-PAHs determined using a 6-h XAD-2 resin desorption method and a 4-h gut fluid mimic (GFM) extraction method. There were significant positive relationships between PAH bioaccumulation by the bivalves and sediment PAH concentrations. These relationships were not improved by normalising the sediment PAH concentrations to the organic carbon concentration. The average percentage lipid content of the bivalves was 1.47 ± 0.22% and BSAFs for total-PAHs ranged from 0.06 to 0.80 (kg OC/kg lipid). The XAD-2 and GFM methods both extracted varying amounts of PAHs from the sediments. Low concentrations of PAHs were extracted by the GFM method (0.2–3.6% of total-PAHs in sediments) and the GFM results were inadequate for generalising about the bioavailability of the PAHs in the sediments. The XAD-2 method extracted greater amounts of PAHs (3–34% of total-PAHs in sediments), however, the total-PAH concentrations in the sediments provided a better, or equally good, prediction of PAH bioaccumulation by T. deltoidalis. The results indicated that these methods required further development before they can be applied routinely as surrogate methods for assessing the bioavailability of PAHs in sediments. Future research should be directed towards lowering detection limits and obtaining comparative data for a greater range of sediment types, contaminant classes and concentrations, and organisms of different feeding guilds and with different gut chemistry.     

Selective supercritical fluid extraction as a tool for determining the PCB fraction accessible for uptake by chironomid larve in a limnic sediment

Selective supercritical fluid extraction (SFE) at 40 degrees C, 400 bar and 60 min was used to selectively remove bioavailable PCBs from a naturally contaminated limnic sediment. The extraction decreased the sediment concentrations of the nine studied PCBs by 54% (on average). Chironomid larvae were thereafter cultured in pre-extracted sediment as well as in untreated sediment to study the differences in uptake of PCBs in the two cultures. While the prevailing equilibrium partitioning (EqP) theory predicts a 54% decrease in PCB uptake by the chironomids in the pre-extracted sediment, with a maintained biota-to-sediment accumulation factor (BSAF), a decrease in PCB uptake by 91% was observed. For all investigated PCBs the BSAFs were on average 81% lower in the cultures with pre-extracted sediment than in the untreated systems. The data allowed for a calculation of the bioavailable fraction, which was estimated to 60%. This is very close to the 54% removed by selective SFE, demonstrating the possibility of using SFE as a tool to determine the bioavailable PCB fraction in a polluted sediment.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.     

Contribution ratio of freely to total dissolved concentrations of polycyclic aromatic hydrocarbons in natural river waters

The bioavailability and ecological risk of hydrophobic organic compounds (HOCs) in aquatic environments largely depends on their freely dissolved concentrations. In this work, the freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) including phenanthrene, pyrene, and chrysene were determined for the Yellow River, Haihe River and Yongding River of China using polyethylene devices (PEDs). The results indicated that the order of ratios of freely to total dissolved concentrations of the three PAHs was phenanthrene (66.8 ± 20.1%) > pyrene (48.8 ± 26.4%) > chrysene (5.5 ± 3.3%) for the three rivers. The ratios were significantly negatively correlated with the log K_ow values of the PAHs. In addition, the ratios were negatively correlated with the suspended sediment (SPS) and dissolved organic carbon (DOC) concentrations in the river water, and the characteristics of the SPS and DOC were also important factors. Simulation experiments showed that the ratio of freely to total dissolved concentrations of pyrene in the aqueous phase decreased with increasing SPS concentration; when the sediment concentration increased from 2 g L^?1 to 10 g L^?1, the ratio decreased from 67.6% to 38.4% for Yellow River sediment and decreased from 50.4% to 33.6% for Haihe River sediment. This was because with increasing SPS concentration, more and more DOC, small particles and colloids (<0.45 μm) would enter the aqueous phase. Because high SPS and DOC concentrations exist in many rivers, their effect on the freely dissolved concentrations of HOCs should be considered when conducting an ecological risk assessment.     

Competition for adsorption between added phenanthrene and in situ PAHs in two sediments

A study was performed on the influence of the addition of a relatively large amount of phenanthrene to two in situ contaminated sediments on the fractions of native PAHs in both the slowly desorbing domain and the very slowly desorbing domain in comparison to the undisturbed situation. Added phenanthrene was found to be present in both the slowly desorbing domain and the very slowly desorbing domain. The extent of removal of native PAHs from the very slowly desorbing domain induced by the presence of a large excess of phenanthrene was in line with expectations based on the incubation time and the rate constants for desorption of native PAHs from the very slowly desorbing domain. In contrast, the addition of phenanthrene did not result in a removal of native PAHs from the slowly desorbing domain. This was tentatively explained by assuming that native PAHs in the slowly desorbing domain are at adsorption sites with dimensions specific to each PAH and which are, therefore, less suited to other PAHs.     

Assessing PAH and PCB emissions from the relocation of harbour sediments using equilibrium passive samplers

Large-scale dredging of contaminated sediments is taking place in the harbor of Oslo, Norway. The dredged sediment masses are transferred into a confined aquatic disposal facility (CAD) in a natural 70-m deep basin within the Oslofjord. Currently there is no established method to determine how much dissolved contaminants are released during relocation and deposition of these sediments. For this reason we tested the use of equilibrium passive samplers consisting of 55 microm thin polyoxymethylene (POM-55) for studying the release of freely dissolved and thus bioavailable PAHs and PCBs at the disposal site, and found this to be a suitable method. In order to use POM-55 for monitoring PCBs, it was necessary to measure their POM-55/water partition coefficients, which was also presented as part of this study. Elevated turbidity (average 4.1 mg l(-1)) was observed at one side of the basin where no natural sill exists. Analysis of POM-55 at this location before and after deposition revealed that there was an increase in freely dissolved concentrations (C(W,free)) during deposition by a factor 37.5 for PAHs and a factor of 2.9 for PCBs. In addition, during deposition phenanthrene-to-anthracene aqueous concentration ratios at this location (values of 3-4) were more similar to those of the deposited sediments (approximately 2) than to those of the CAD water prior to deposition (approximately 14). This was not observed for the other locations where a natural sill exists at approximately 30 m water depth. The POM-55 equilibrium passive samplers are here shown to be useful tools for measuring and understanding the dynamics involved in the release of dissolved contaminants during sediment relocation.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Bioaccumulation Factors (BAFs) and Biota to Sediment Accumulation Factors (BSAFs) for PCBs in pike and eels

“Freely-dissolved” aqueous concentrations of 9 trichlorothrough heptachlorobiphenyls are reported, alongside those in sediments and fish from the R. Severn. For most congeners, BSAFs and lipid-normalised BAFs for pike exceed those for eels. Whilst R. Severn BSAFs are comparable with those for L. Ontario trout and New Bedford Harbour flounder, R. Severn BAFs are 1–2 orders of magnitude lower. This discrepancy may be due to inter-species variability, as well as inter-laboratory differences between operational definitions of “freely-dissolved” aqueous PCB, underlining that the same operational definition must be employed if R. Severn BAFs are extrapolated elsewhere. For eels, correlation of Log K^ow with Log BAF is better (R² = 0.66) than with BSAF (R² = 0.13), whilst similar correlation coefficients (R² = 0.81 and 0.82) were observed for pike. When Log K^ow is plotted against BSAF and Log BAF for both species combined, better correlation is observed for Log BAF (R² = 0.65), than BSAF (R² = 0.36). For both species combined, the observed relationship between Log BAF and Log K^ow for trichloro-through heptachlorobiphenyls is: Log BAF = 0.96 * Log K^ow −0.24.     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.     

Exposure of the marine deposit feeder Hydrobia ulvae to sediment associated LAS

Linear Alkylbenzene Sulfonates (LAS) effects (mortality, egestion rate, behaviour) on the marine deposit feeder Hydrobia ulvae were assessed in whole-sediment and water-only systems. The results were combined with a bioenergetic-based kinetic model of exposure pathways to account for the observed toxicity. The 10-d LC50 value based on the freely dissolved fraction was 9.3 times lower in spiked sediment (0.152 ± 0.001 (95% CI) mg/L) than in water-only (1.390 ± 0.020 (95% CI) mg/L). Consequently, the actual 10-d LC50 value (208 mg/kg) was overestimated by the Equilibrium Partitioning calculation (1629 mg/kg). This suggests that the sediment associated LAS fraction was bioavailable to the snails. It could also be due to modifications in physiological parameters in absence of sediment, the organism natural substrate.     

Bioaccumulation of PAHs from creosote-contaminated sediment in a laboratory-exposed freshwater oligochaete, Lumbriculus variegatus

The oligochaete, Lumbriculus variegatus, was used for a bioaccumulation assay in the creosote-contaminated sediment of Lake J?ms?nvesi in a 28-day experiment. The PAH concentrations of the whole body tissue of worms, sediments and water samples were determinated by GC-MS. Chemical analyses showed that benzo(k)fluoranthene, anthracene and fluorene were the main PAH compounds present in the tissue of oligochaetes, just as in the sediment. The biota-sediment accumulation factors (BSAFs) of the individual PAHs varied from 1.2 to 5.7. It is concluded that oligochaetes have a marked ability to accumulate and retain PAHs from creosote-contaminated sediment.     

Bioavailability assessment and environmental fate of polycyclic aromatic hydrocarbons in biostimulated creosote-contaminated soil

When hydrocarbon-contaminated soil is subjected to bioremediation technology, hydrocarbon depletion is typically marked by an initially rapid reduction rate. This rate decreases over time and frequently a residual concentration remains in the soil. This kinetic has been attributed primarily to the enrichment of more recalcitrant fractions, as well as to the lack of resting hydrocarbon bioavailability. Thus, at the end of the bioremediation process, a part of the residual hydrocarbon soil concentration represents the non-bioavailable fraction, which is difficult to degrade by microbial populations and which poses a minor hazard. Therefore, determination of the bioavailable fraction in a bioremediation project represents both an estimation of the maximum level of achievable biodegradation, as well as an additional indication of the environmental health hazard. In the present study, aged creosote-contaminated soil was subjected to biostimulation processes, and the bioavailable fraction for several target polycyclic aromatic hydrocarbons (PAHs) was calculated using a mild extraction with cyclodextrines. The amount of PAH extracted corresponded to the desorbing fraction and can be regarded as the bioavailable fraction. The non-desorbing fraction data obtained from this procedure were compared to the remaining PAH concentrations following bioremediation treatment of soil microcosms. These results permitted the establishment of a theoretical biodegradation limit based on the desorbing fraction. In addition, neither accumulation of intermediate metabolites, nor the formation of bound-residues or reduced acute toxicity was observed.     

The estimation of PAH bioavailability in contaminated sediments using hydroxypropyl-beta-cyclodextrin and Triton X-100 extraction techniques

A study was conducted to investigate whether cyclodextrins and surfactants can be used to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in contaminated sediments. Two sediment samples were extracted with aqueous solutions of hydroxypropyl-beta-cyclodextrin (HPCD) and Triton X-100. PAH removal during extraction was compared with PAH removal during biodegradation and solid-phase extraction. The latter two methods were used as reference methods to establish which part of the PAHs could be biodegraded and to what extent biodegradation was governed by bioavailability limitations. It was demonstrated that HPCD extraction followed solid-phase extraction and removed primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly bioavailable PAHs. Moreover, HPCD did not affect the degradation of PAHs in biodegradation experiments, while Triton X-100 enhanced the degradation of low molecular weight PAHs. It was concluded that HPCD extraction may provide a good method for the prediction of PAH bioavailability. Triton X-100 extraction is unfit for the prediction of PAH bioavailability.     

Effects of aging and sediment composition on hexachlorobenzene desorption resistance compared to oral bioavailability in rats

Studies were conducted to assess the effects of black carbon, clay type and aging (1-1.5yr) on desorption and bioavailability of hexachlorobenzene (HCB) in spiked artificial sediments. Tenax (a super sorbent)-mediated desorption was used to examine the effects of these parameters on the physicochemical availability of HCB. The Tenax-mediated desorption of HCB from the four aged artificial sediments exhibited biphasic kinetics. The fast desorbing fractions ranged from 64.8% to 22.3%, showing reductions of 4.0-18.9% compared with freshly-spiked sediments. Statistical analysis on the fast desorbing fractions showed that all three treatment effects (i.e., montmorillonite clay, black carbon content, and aging) were significant. Two sediments with higher black carbon content exhibited much greater aging effects (i.e., greater reduction in fast desorbing fraction) than the other two sediments without the addition of black carbon. For both freshly-spiked and aged sediments, the desorption resistant sediment-bound HCB (i.e., slow desorbing fraction) correlated reasonably well to previously reported rat fecal elimination of HCB, which is a measure of the non-bioavailable fraction of sediment-bound HCB. A similar correlation was also observed between fast desorbing fraction and previously reported accumulation of HCB in the rat body (carcass+skin). These observations suggest that physicochemical availability, as defined by the desorption of HCB from sediments, provides a reasonable prediction of the oral bioavailability of sediment-bound HCB to rats. These results showed that montmorillonite clay, black carbon and aging reduced physicochemical availability and ultimately bioavailability of sediment-bound HCB.