Biomimetic Extraction Research Articles

Comprehensive characterization of organics in oil sands process water in constructed mesocosms utilizing multiple analytical methods

This study aims to provide a thorough characterization of dissolved organics in oil sands process water (OSPW) in field-based aquatic mesocosms at both molecular and bulk measurement levels using multiple analytical methods. In a 3-year outdoor mesocosm experiment, the analysis of naphthenic acid (NA) species was conducted using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). The results revealed the removal of both total NAs (38% and 35%) and classical NAs (O2–NAs, 58% and 49%) in undiluted and half-diluted OSPW, respectively. The increased ratios of oxidized NAs (O3–O6 NAs) to classical NAs suggested a transformation trend. The results also indicated that O2–NAs with higher carbon number and lower double bond equivalent (DBE) were more easily degraded in the mesocosm systems. Biomimetic extraction using solid-phase microextraction (BE-SPME) measurement displayed 26% (undiluted OSPW) and 30% (half-diluted OSPW) decrease in total bioavailable organics over 3 years. Naphthenic acids fraction compounds (NAFCs) obtained by liquid-liquid extraction (LLE) were also determined using Fourier transform infrared spectroscopy (FTIR). Reduction in acute toxicity for undiluted (43%) and half-diluted (26%) OSPW was observed over 3 years, which are well correlated with the decreases of NAs and BE-SPME concentrations. Moreover, BE-SPME values were found to be linearly correlated with total NAs concentrations (r = 0.96) and NAFCs (r = 0.96). Additionally, the linear relationships of individual O2–O6 NA species and BE-SPME concentrations unveiled the changes in the relative abundances of O2–O6 NA species in total bioavailable organics over time in the mesocosms. The present study has provided comprehensive insights by integrating various analytical methods, contributing valuable information for assessing the effectiveness of aquatic mesocosm systems in studying the temporal changes of organics in OSPW.

Bioavailability and health risk assessment of Zn and Cd in edible tissues of two typical shellfish species using in vitro gastrointestinal digestion

Dynamic extraction of edible tissues of Jinjiang oyster (Crassostrea rivularis) and Flower clam (Paphia undulata) was conducted using a fully biomimetic digestion (in vitro) method. The impact of different cooking methods on the bioavailability of Zn and Cd in the edible shellfish tissues was analyzed, and the human health risk of Zn and Cd was evaluated. The results show that the gastric biomimetic extractions of Zn and Cd in unheated samples of C. rivularis and P. undulata were higher than those in the intestinal biomimetic extraction. The extraction patterns of cooked samples were consistent with those of raw samples. The bioavailability of Zn and Cd in cooked samples of C. rivularis was 94.9% and 82.5%, respectively, indicating increased Zn bioavailability but decreased Cd bioavailability compared to the raw samples. The bioavailability of Zn and Cd in cooked samples of P. undulata was 85.1% and 83.0%, respectively, both of which decreased compared to the raw samples. Consumption of C. rivularis can provide 21.0% to 34.2% of the daily required Zn intake, while consumption of P. undulata can provide 3.8% to 6.4%. The intake of Cd from both shellfish species is below the monthly tolerable intake recommended by FAO/WHO. Consuming cooked C. rivularis can increase the intake of Zn and decrease the intake of Cd.

Biomimetic Dispersive Solid-Phase Microextraction: A Novel Concept for High-Throughput Estimation of Human Oral Absorption of Organic Compounds.

There is a quest for a novel in vitro analytical methodology that is properly validated for the prediction of human oral absorption and bioaccumulation of organic compounds with no need of animal models. The traditional log P parameter might not serve to predict bioparameters accurately inasmuch as it merely accounts for the hydrophobicity of the compound, but the actual interaction with the components of eukaryotic cells is neglected. This contribution proposes for the first time a novel biomimetic microextraction approach capitalized on immobilized phosphatidylcholine as a plasma membrane surrogate onto organic polymeric sorptive phases for the estimation of human intestinal effective permeability of a number of pharmaceuticals that are also deemed contaminants of emerging concern in environmental settings. A comprehensive exploration of the conformation of the lipid structure onto the surfaces is undertaken so as to discriminate the generation of either lipid monolayers or bilayers or the attachment of lipid nanovesicles. The experimentally obtained biomimetic extraction data is proven to be a superb parameter against other molecular descriptors for the development of reliable prediction models of human jejunum permeability with R2 = 0.76, but the incorporation of log D and the number of aromatic rings in multiple linear regression equations enabled improved correlations up to R2 = 0.88. This work is expected to open new avenues for expeditious in vitro screening methods for oral absorption of organic contaminants of emerging concern in human exposomics.

Novel insights into the predominant factors affecting the bioavailability of polycyclic aromatic hydrocarbons in industrial contaminated areas using PLS-developed model

Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl-β-cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH.

Temporal chemical composition changes in water below a crude oil slick irradiated with natural sunlight

Photooxidation can alter the environmental fate and effects of spilled oil. To better understand this process, oil slicks were generated on seawater mesocosms and exposed to sunlight for 8 days. The molecular composition of seawater under irradiated and non-irradiated oil slicks was characterized using ion mobility spectrometry-mass spectrometry and polyaromatic hydrocarbons analyses. Biomimetic extraction was performed to quantify neutral and ionized constituents. Results show that seawater underneath irradiated oil showed significantly higher amounts of hydrocarbons with oxygen- and sulfur-containing by-products peaking by day 4–6; however, concentrations of dissolved organic carbon were similar. Biomimetic extraction indicated toxic units in irradiated mesocosms increased, mainly due to ionized components, but remained <1, suggesting limited potential for ecotoxicity. Because the experimental design mimicked important aspects of natural conditions (freshly collected seawater, natural sunlight, and relevant oil thickness and concentrations), this study improves our understanding of the effects of photooxidation during a marine oil spill.

Interlaboratory Comparison of a Biomimetic Extraction Method Applied to Oil Sands Process-Affected Waters.

Biomimetic extraction using solid‐phase microextraction is a passive sampling analytical method that can predict the aquatic toxicity of complex petroleum substances. The method provides a nonanimal alternative to traditional bioassays with the potential to reduce both vertebrate and invertebrate aquatic toxicity testing. The technique uses commercially available polydimethylsiloxane‐coated fibers that, following nondepletive extraction of water samples, are injected into a gas chromatograph with flame ionization detection. As the predictive nature of the method is operationally defined, it is critical that its application be harmonized with regard to extraction, analysis, and standardization parameters. Results are presented from a round robin program comparing the results from 10 laboratories analyzing four different sample sets of dissolved organics in water. Samples included two incurred oil sands process–affected waters and a cracked gas oil water accommodated fraction. A fourth sample of cracked gas oil blended in an oil sands process–affected water was analyzed to demonstrate the method's ability to differentiate between neutral and ionizable dissolved hydrocarbons. Six of the 10 laboratories applied an automated version of the method using a robotic autosampler where the critical extraction steps are precisely controlled and which permits batch screening of water samples for aquatic toxicity potential. The remaining four laboratories performed the solid‐phase microextraction manually. The automated method demonstrated good reproducibility with between‐laboratory variability across the six laboratories and four samples yielding a mean relative standard deviation of 14%. The corresponding between‐laboratory variability across the four laboratories applying the manual extraction was 53%, demonstrating the importance of precisely controlling the extraction procedure. Environ Toxicol Chem 2022;41:1613–1622. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Treatment of naphthenic acids in oil sands process-affected waters with a surface flow treatment wetland: mass removal, half-life, and toxicity-reduction

This study is the first to investigate the removal of naphthenic acids in a full-scale constructed wetland within the Alberta Oil Sands region. The average mass-removal efficiency for all O2-naphthenic acids measured in three separate deployments in the wetland ranged from 7.5% to 68.9% and appeared sensitive to physicochemical properties of the naphthenic acids, environmental conditions, and water quality. Treatment efficiency of individual naphthenic acids was found to increase with increasing carbon number and decreasing number of double bond equivalents in the molecule. Treatment efficiency was also found to increase with both higher initial turbidity in OSPW entering the wetland, and warmer average OSPW temperatures during wetland operation. Half-life times of naphthenic acids in the treatment wetland ranged between 8.9 and 39 days and were substantially lower than those in tailings ponds (i.e., 12.9–13.6 years) and laboratory studies focussed on bench-scale aerobic microbial biodegradation (i.e., 44–315 days). Using published dose-response data, biomimetic extraction measurements using solid phase microextraction fibers indicate that 14 days of wetland treatment resulted in a reduction in (4 d) deformity of Danio rerio from 50 to 16%, while exhibiting less than 1% toxic response for less sensitive toxic endpoints. The study concludes that wetland treatment is a feasible and productive treatment method for naphthenic acids in oil sands process-affected water due to a combination of sorption and biodegradation.

Changes in Chemical Composition and Copepod Toxicity during Petroleum Photo-oxidation.

Photoproducts can be formed rapidly in the initial phase of a marine oil spill. However, their toxicity is not well understood. In this study, oil was irradiated, chemically characterized, and tested for toxicity in three copepod species (Acartia tonsa, Temora longicornis, and Calanus finmarchicus). Irradiation led to a depletion of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in oil residues, along with an enrichment in aromatic and aliphatic oil photoproducts. Target lipid model-based calculations of PAH toxicity units predicted that PAH toxicities were lower in water-accommodated fractions (WAFs) of irradiated oil residues ("irradiated WAFs") than in WAFs of dark-control samples ("dark WAFs"). In contrast, biomimetic extraction (BE) measurements showed increased bioaccumulation potential of dissolved constituents of irradiated WAFs compared to dark WAFs, mainly driven by photoproducts present in irradiated oil. In line with the BE results, copepod mortality increased in irradiated WAFs compared to dark WAFs. However, low copepod toxicities were observed for WAFs produced with photo-oxidized oil slicks collected during the Deepwater Horizon oil spill. The results of this study suggest that while oil photoproducts have the potential to be a significant source of copepod toxicity, dilution and dispersion of these higher solubility products appear to help mitigate their toxicity at sea.

The sensitivity of the deepsea species northern shrimp (Pandalus borealis) and the cold-water coral (Lophelia pertusa) to oil-associated aromatic compounds, dispersant, and Alaskan North Slope crude oil

This study investigated the sensitivity of two deepsea species using mortality of northern shrimp (Pandalus borealis) and polyp activity of stony coral (Lophelia pertusa) to dispersant, Corexit 9500 and aromatic hydrocarbons (toluene, 2-methylnaphthalene, phenanthrene) in 96-h tests. Resulting hydrocarbon toxicity data were fit to the Target Lipid Model to generate predictive models and determine species sensitivity. Toxicity of chemically enhanced water accommodated fractions of Alaskan North Slope crude oil (ANS-oil) was also investigated with shrimp using nominal loading, total petroleum hydrocarbons and biomimetic extraction (BE) as oil exposure metrics. Coral were more sensitive to dispersant than shrimp while similar sensitivity was observed for hydrocarbons. Study and literature findings indicate deepsea species exhibit acute sensitivities to dispersant, hydrocarbons and oil that are comparable to pelagic species. Results support use of passive sampling methods to quantify dissolved oil for interpreting oil toxicity tests and suggest models for predicting time-dependence of toxicity warrant re-evaluation.

Analysis of Sublethal Toxicity in Developing Zebrafish Embryos Exposed to a Range of Petroleum Substances.

The Organisation for Economic Co‐operation and Development (OECD) test guideline 236 (fish embryo acute toxicity test; 2013) relies on 4 endpoints to describe exposure‐related effects (coagulation, lack of somite formation, tail‐bud detachment from the yolk sac, and the presence of a heartbeat). Danio rerio (zebrafish) embryos were used to investigate these endpoints along with a number of additional sublethal effects (cardiac dysfunction, pericardial edema, yolk sac edema, tail curvature, hatch success, pericardial edema area, craniofacial malformation, swim bladder development, fin development, and heart rate) following 5‐d exposures to 7 petroleum substances. The substances investigated included 2 crude oils, 3 gas oils, a diluted bitumen, and a petrochemical containing a mixture of branched alcohols. Biomimetic extraction–solid‐phase microextraction (BE–SPME) was used to quantify freely dissolved concentrations of test substances as the exposure metric. The results indicated that the most prevalent effects observed were pericardial and yolk sac edema, tail curvature, and lack of embryo viability. A BE–SPME threshold was determined to characterize sublethal morphological alterations that preceded embryo mortality. Our results aid in the understanding of aquatic hazards of petroleum substances to developing zebrafish beyond traditional OECD test guideline 236 endpoints and show the applicability of BE–SPME as a simple analytical tool that can be used to predict sublethal embryo toxicity. Environ Toxicol Chem 2019;38:1302–1312. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Investigating predictive tools for refinery effluent hazard assessment using stream mesocosms.

Hazard assessment of refinery effluents is challenging because of their compositional complexity. Therefore, a weight-of-evidence approach using a combination of tools is often required. Previous research has focused on several predictive tools for sophisticated chemical analyses: biomimetic extraction to quantify the potentially bioaccumulative substances, 2-dimensional gas chromatography, modeling approaches to link oil composition to toxicity (PETROTOX), and whole-effluent toxicity assessments using bioassays. The present study investigated the value of these tools by comparing predicted effects to actual effects observed in stream mesocosm toxicity studies with refinery effluents. Three different effluent samples, with and without fortification by neat petroleum substances, were tested in experimental freshwater streams. The results indicate that the biological community shifted at higher exposure levels, consistent with chronic toxicity effects predicted by both modeled toxic units and potentially bioaccumulative substance measurements. The present study has demonstrated the potential of the predictive tools and the robustness of the stream mesocosm design to improve our understanding of the environmental hazards posed by refinery effluents. Environ Toxicol Chem 2019;38:650-659. © 2018 SETAC.

Comparative evaluation of influence of aging, soil properties and structural characteristics on bioaccessibility of polychlorinated biphenyls in soil

Though bioaccessibility commonly recognized as a guideline for risk assessment is closely related with pollution occurrence and chemical species of compounds, the mechanistic links are barely evaluated particularly for widespread polychlorinated biphenyls (PCBs) in soil. With the biomimetic extraction of hydroxypropyl-β-cyclodextrin (β-HPCD), the temporal and spatial influences of soil properties, aging and structural characteristics, e.g. polarity of PCB congeners on bioaccessibility were investigated for PCBs. Sensitive variation of bioaccessibility with aging, soil organic matter (SOM), particle size and soil moisture were clearly evidenced for different PCB congeners. Due to aging, the bioaccessibility decreased in the long term after stabilization for 36 h. In concert with the first-order kinetics, the decay rates of bioaccessibility were shown with congener-specificity and were well correlated with dipoles of PCBs. The increment of SOM diminished the bioaccessibility for the strengthened adsorption while the increased particle size and soil moisture elevated it possibly due to the less adsorption on soil particles and more accommodation of PCBs in soil pore water. Except the positive correlations with particle size, soil moisture and dipole moment, the greater dependency on aging and SOM was highlighted for bioaccessibility by partial least squares (PLS) analysis. The mutual relationship with influential factors was quantitatively formulated for accelerative prediction of bioaccessibility, and the comparative evaluation and detailed insights into the mechanistic links would thus help enhance the precise determination of bioaccessibility and risk assessment of PCBs in soil.

Application of the Target Lipid Model and Passive Samplers to Characterize the Toxicity of Bioavailable Organics in Oil Sands Process-Affected Water.

Oil sand operations in Alberta, Canada will eventually include returning treated process-affected waters to the environment. Organic constituents in oil sand process-affected water (OSPW) represent complex mixtures of nonionic and ionic (e.g., naphthenic acids) compounds, and compositions can vary spatially and temporally, which has impeded development of water quality benchmarks. To address this challenge, it was hypothesized that solid phase microextraction fibers coated with polydimethylsiloxane (PDMS) could be used as a biomimetic extraction (BE) to measure bioavailable organics in OSPW. Organic constituents of OSPW were assumed to contribute additively to toxicity, and partitioning to PDMS was assumed to be predictive of accumulation in target lipids, which were the presumed site of action. This method was tested using toxicity data for individual model compounds, defined mixtures, and organic mixtures extracted from OSPW. Toxicity was correlated with BE data, which supports the use of this method in hazard assessments of acute lethality to aquatic organisms. A species sensitivity distribution (SSD), based on target lipid model and BE values, was similar to SSDs based on residues in tissues for both nonionic and ionic organics. BE was shown to be an analytical tool that accounts for bioaccumulation of organic compound mixtures from which toxicity can be predicted, with the potential to aid in the development of water quality guidelines.

Technical basis for using passive sampling as a biomimetic extraction procedure to assess bioavailability and predict toxicity of petroleum substances

Solid-phase microextraction fibers coated with polydimethylsiloxane (PDMS) provide a convenient passive sampling format to characterize bioavailability of petroleum substances. Hydrocarbons absorb onto PDMS in proportion to both freely dissolved concentrations and partitioning properties of the individual constituents, which parallels the mechanistic basis used to predict aquatic toxicity in the PETROTOX model. When deployed in a non-depletive manner, combining SPME with thermal desorption and quantification using gas chromatography-flame ionization creates a biomimetic extraction (BE) procedure that has the potential to simplify aquatic hazard assessments of petroleum substances since the total moles of all hydrocarbons sorbed to the fiber can be related to toxic thresholds in target lipid of aquatic organisms. The objective of this work is to describe the technical basis for applying BE measurements to predict toxicity of petroleum substances. Critical BE-based PDMS concentrations corresponding to adverse effects were empirically derived from toxicity tests on different petroleum substances with multiple test species. The resulting species sensitivity distribution (SSD) of PDMS effect concentrations was then compared and found consistent with the previously reported target lipid-based SSD. Further, BE data collected on samples of aqueous media dosed with a wide range of petroleum substances were highly correlated to predicted toxic units derived using the PETROTOX model. These findings provide justification for applying BE in environmental hazard and risk evaluations of petroleum substances and related mixtures.

Aquatic hazard assessment of a commercial sample of naphthenic acids

This paper presents chemical composition and aquatic toxicity characteristics of a commercial sample of naphthenic acids (NAs). Naphthenic acids are derived from the refining of petroleum middle distillates and can contribute to refinery effluent toxicity. NAs are also present in oil sands process-affected water (OSPW), but differences in the NAs compositions from these sources precludes using a common aquatic toxicity dataset to represent the aquatic hazards of NAs from both origins. Our chemical characterization of a commercial sample of NAs showed it to contain in order of abundance, 1-ring>2-ring>acyclic>3-ring acids (∼84%). Also present were monoaromatic acids (7%) and non-acids (9%, polyaromatic hydrocarbons and sulfur heterocyclic compounds). While the acyclic acids were only the third most abundant group, the five most abundant individual compounds were identified as C10–14n-acids (n-decanoic acid to n-tetradecanoic acid). Aquatic toxicity testing of fish (Pimephales promelas), invertebrate (Daphnia magna), algae (Pseudokirchneriella subcapitata), and bacteria (Vibrio fischeri) showed P. promelas to be the most sensitive species with 96-h LL50=9.0mgL−1 (LC50=5.6mgL−1). Acute EL50 values for the other species ranged 24–46mgL−1 (EC50 values ranged 20–30mgL−1). Biomimetic extraction via solid-phase-microextraction (BE–SPME) suggested a nonpolar narcosis mode of toxic action for D. magna, P. subcapitata, and V. fischeri. The BE analysis under-predicted fish toxicity, which indicates that a specific mode of action, besides narcosis, may be a factor for fishes.

Evaluating toxicity of heavy fuel oil fractions using complementary modeling and biomimetic extraction methods.

The toxicity of chemically dispersed heavy fuel oil (HFO) and 3 distillate fractions to rainbow trout (Oncorhynchus mykiss) embryos was evaluated using the PETROTOX model and a biomimetic extraction technique that involved passive sampling of oil-contaminated test media with solid-phase microextraction (SPME) fibers. Test solutions for toxicity testing were generated using a combination of dispersant and high-energy mixing. The resulting water accommodated fractions (WAF) provided complex exposure regimens that included both dissolved hydrocarbons and oil droplets. The toxicity of the various fractions differed by approximately 3 orders of magnitude when expressed on the basis of WAF dilution. Using detailed compositional data, the PETROTOX model predicted the speciation of hydrocarbons between dissolved and oil droplet phases and explained observed toxicity based on computed dissolved phase toxic units (TUs). A key finding from model calculations was that dissolved hydrocarbon exposures and associated TUs were a nonlinear function of WAF dilution, because dissolved hydrocarbons were largely controlled by the dissolution of oil droplets that were transferred in WAF dilutions. Hence, oil droplets served to "buffer" dissolved concentrations in WAF dilutions at loadings greater than 1 mg/L, resulting in higher dissolved concentrations and TUs than expected based on dilution. The TUs computed at each WAF dilution explained the observed toxicity among the HFO and fractions to within a factor of 3. Dissolved material measured by SPME showed a consistent relationship with model-predicted TUs, confirming the utility of this approach for providing an integrated measure of exposure to bioavailable hydrocarbons. These 2 approaches provide complementary tools for better defining bioavailability of complex petroleum substance.

Assessing oral bioaccessibility of trace elements in soils under worst-case scenarios by automated in-line dynamic extraction as a front end to inductively coupled plasma atomic emission spectrometry

A novel biomimetic extraction procedure that allows for the in-line handing of ≥400mg solid substrates is herein proposed for automatic ascertainment of trace element (TE) bioaccessibility in soils under worst-case conditions as per recommendations of ISO norms. A unified bioaccessibility/BARGE method (UBM)-like physiological-based extraction test is evaluated for the first time in a dynamic format for accurate assessment of in-vitro bioaccessibility of Cr, Cu, Ni, Pb and Zn in forest and residential-garden soils by on-line coupling of a hybrid flow set-up to inductively coupled plasma atomic emission spectrometry. Three biologically relevant operational extraction modes mimicking: (i) gastric juice extraction alone; (ii) saliva and gastric juice composite in unidirectional flow extraction format and (iii) saliva and gastric juice composite in a recirculation mode were thoroughly investigated. The extraction profiles of the three configurations using digestive fluids were proven to fit a first order reaction kinetic model for estimating the maximum TE bioaccessibility, that is, the actual worst-case scenario in human risk assessment protocols. A full factorial design, in which the sample amount (400–800mg), the extractant flow rate (0.5–1.5mLmin−1) and the extraction temperature (27–37°C) were selected as variables for the multivariate optimization studies in order to obtain the maximum TE extractability. Two soils of varied physicochemical properties were analysed and no significant differences were found at the 0.05 significance level between the summation of leached concentrations of TE in gastric juice plus the residual fraction and the total concentration of the overall assayed metals determined by microwave digestion. These results showed the reliability and lack of bias (trueness) of the automatic biomimetic extraction approach using digestive juices.

Advances in using passive sampling techniques to measure bioavailability and toxicity of organic contaminants in sediment

Passive sampling techniques have been used as biomimetic extraction methods to measure the bioavailability and toxicity of organic contaminants in sediment. The advantages and disadvantages of the commonly used passive samplers including semi-permeable membrane device, polyethylene device, polyoxymethylene and solid-phase microextraction are reported. The challenges of using passive samplers in sediment risk assessment are discussed, and the possible solutions and future studies are also proposed.

Comparison of different exhaustive and biomimetic extraction techniques for chemical and biological analysis of polycyclic aromatic compounds in river sediments

Purpose The importance of the bioaccessible fractions of particle-bound contaminants is a key feature for the assessment of their likely risks to the aquatic environment. The present study investigated the extractability and potential toxicity of polycyclic aromatic hydrocarbons (PAHs) in river sediments. This study combined chemical with bioanalytical tools to establish a more in-depth insight into the relationship between the extractability of sediment contaminants, the chemodynamic properties of each extraction approach, and resulting toxicity.

Application of a Tenax model to assess bioavailability of PCBs in field sediments

Bioavailability has been estimated in the past using equilibrium partitioning-based biota-sediment accumulation factors. These values are not always reliable using field-collected sediments, however, likely due to varying amounts of different organic carbons, particularly black carbon, in sediments. Therefore, improving approaches to better evaluate contaminant bioavailability in sediment are needed. In the present study, a literature-based model was constructed that relied on both laboratory-exposed and field-collected oligochaete bioaccumulation data. The model system used 24-h Tenax extraction data paired with bioaccumulation tests using oligochaetes to establish the ability and utility of the biomimetic extraction. The model was then tested to confirm its utility and reliability to estimate bioavailability of oligochaetes exposed to polychlorinated biphenyl (PCB) contaminated sediments from the Ottawa River in Ohio, USA. The model correctly identified the bioaccumulation of PCBs for 94.9% of the data and 97% of the dioxin-like congeners. The mono- and di-substituted chlorinated biphenyls were the least well described, but the estimates were conservative, for example, the model overpredicted bioaccumulation. Thus, the Tenax model was robust and reliable across a wide range of sediment characteristics for estimating PCB bioaccumulation in oligochaetes.