Bioavailability Of Hydrophobic Organic Contaminants Research Articles

Coupling polydimethylsiloxane vials with a physiologically based extraction test to predict bioavailability of hydrophobic organic contaminants in soils

As alternatives to in vivo assays, physiologically based in vitro methods have been developed to measure bioaccessibility of hydrophobic organic contaminants (HOCs) in soils. However, bioaccessibility can usually be underestimated since in vitro tests fail to provide sufficient affinity for HOCs. Sorption sink was therefore included to simulate intestinal cell absorption and to promote the mobilization of HOCs from soils. In this study, polydimethylsiloxane (PDMS) vials, widely used as passive dosing, were introduced as a sorption sink to improve the performance of physiologically based extraction test (PBET). The bioaccessibility of PCBs (representatives of HOCs) in 13 lab-spiked soils measured by PBET coupled with PDMS vials ranged from 56.5 ± 2.7% to 109.3 ± 1.5%. Correlation was conducted between the bioaccessibility and relative bioavailability (RBA) of PCBs assessed using an in vivo mouse model. A significant correlation (p < 0.001, R2 = 0.72, slope = 0.85 ± 0.16) was observed between in vitro and in vivo data, indicating that the proposed method here can be a robust in vitro method to predict PCB RBA in soils. The accuracy of this novel method was further shown by extracting one field contaminated soil with environmental relevant levels of PCBs. The relative standard deviation of bioaccessibility measured by PBET with PDMS vials was 1.2–9.8%, and much lower than those by PBET alone with values of 17.1–63.6%. In addition, the PDMS vials can be reusable as sorption sink, and no significant variation (p = 0.44) in PCB bioaccessibility was observed among 5 cycles of extracting soils with PBET coupled with PDMS vials. Due to the high sorption capacity of PDMS and flexibility of PDMS mass used for vials, the novel method here is expected to be applicable in soils with a wide range of contamination levels.

Bioavailability quantification and uptake mechanisms of pyrene associated with different-sized microplastics to Daphnia magna

Microplastics (MPs) are the significant environmental factor for bioavailability of hydrophobic organic contaminants (HOCs) in aquatic environments. Nevertheless, the bioavailability of microplastic-associated HOCs remains unclear. In this research, the freely dissolved pyrene concentrations were kept stable with passive dosing devices, and the pyrene content in D. magna tissues as well as D. magna immobilization were analyzed to quantify bioavailability of pyrene (a representative HOC) associated with naturally-aged polystyrene (PS) MPs. Furthermore, the uptake mechanisms of pyrene associated with MPs of different sizes were explored by investigating the distribution of MPs in D. magna tissues with scanning electron microscopy. Especially, a new schematic model of bioavailability process was established. The results demonstrated that a part of pyrene associated with 0–1.5 μm MPs could directly cross cell membrane through endocytosis from intestine and exposure solutions to D. magna tissues except the 10–60 and 60–230 μm MPs. The bioavailability of microplastic-associated pyrene was ordered as 0–1.5 μm (20.0–21.6%) > 10–60 μm (10.7–13.8%) > 60–230 μm MPs (6.0–9.8%), which were essentially resulted from the difference in uptake mechanisms of pyrene associated with MPs of different sizes. This work suggests that the bioavailability of microplastic-associated HOCs should be considered when assessing water quality and environmental risk of HOCs in natural waters.

The biological pump effects of phytoplankton on the occurrence and benthic bioaccumulation of hydrophobic organic contaminants (HOCs) in a hypereutrophic lake

The distribution of hydrophobic organic contaminants (HOCs) in eutrophic ecosystems has been widely studied, but how phytoplankton blooms affect their occurrence and benthic bioaccumulation is poorly understood. To fill this knowledge gap, the biological pump effects of phytoplankton on the fate of organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in sediments and benthos (Corbicula fluminea) from Lake Taihu, a hypereutrophic lake in China, were identified. The spatial-temporal distribution of HOCs suggests that higher phytoplankton biomass, coupled with sediment organic matter (SOM) content, greatly increased the concentration of HOCs in sediments in both winter and summer seasons. This could be attributed to the biological pump effects sequestering more HOCs from water to sediments with settling phytoplankton, especially during the summer. The biological pump effects further promoted the uptake of sediment-bound HOCs by benthos. The significant positive relationships between concentrations of HOCs in sediments and benthos were observed during the winter dormancy phase of benthos. Furthermore, the benthic bioaccumulation of HOCs could be strengthened by phytoplankton, due to their contribution to SOM and the following increased bioavailability of HOCs in sediments. Further research is needed to elucidate the phytoplankton biological pump effects on the fate of HOCs in benthic food chain, especially for hypereutrophic waters.

A rapid experimental protocol to determine the desorption resistant fraction of sediment-sorbed hydrophobic organic contaminants.

Desorption of hydrophobic organic contaminants (HOCs) from sedimentary materials plays a vital role in dictating the fate and transport of HOCs in the environment. Desorption irreversibility is a commonly observed phenomenon in laboratory sorption/desorption studies of HOCs. A desorption-resistant fraction (DRF) typically exists during the desorption process. To correctly evaluate the DRF of HOCs can considerably contribute to the understanding of availability and bioavailability of HOCs. This can substantially benefit contaminant remediation and cleanup operations. Conventional batch method to measure the DRF replies on repetitive washing of the sediments, which is time-consuming and can be impractical. This study presents an experimental protocol to quantify the DRF of the sediment-sorbed organic contaminants in a rapid manner. This protocol utilizes cosolvent to expedite desorption kinetics and adopts an ultrafiltration/centrifugation combined method to achieve a complete separation of sediment and solution phases. This proposed experimental protocol can facilitate the quantification of the DRF of sorbed contaminants to understand and minimize the uncertainties associated with risk-based pollution remediation approach. This protocol has the potential to be widely used in environmental studies to characterize sorption and desorption properties of HOCs with soil and sedimentary materials.

Application and validation of isotope dilution method (IDM) for predicting bioavailability of hydrophobic organic contaminants in soil.

Risk assessment of hydrophobic organic contaminants (HOCs) using the total chemical concentration following exhaustive extraction may overestimate the actual availability of HOCs to non-target organisms. Existing methods for estimating HOC bioavailability in soil have various operational limitations. In this study, we explored the application of isotope dilution method (IDM) to quantify the accessible fraction (E) of DDTs and PCBs in both historically-contaminated and freshly-spiked soils. After addition of 13C or deuterated analogues to a soil sample, the phase distribution of isotope-labeled and native chemicals reached an apparent equilibrium within 48 h of mixing. The derived E values in the three soils ranged from 0.19 to 0.82, depending on the soil properties and also the contact time of HOCs (i.e., aging). The isotope dilution method consistently predicted greater accumulation into earthworm (Eisenia fetida) than that by polyethylene (PE) or solid phase microextraction (SPME) sampler, likely because desorption in the gut enhanced bioavailability of soil-borne HOCs. A highly significant linear regression (R2 = 0.91) was found between IDM and 24-h Tenax desorption, with a slope statistically identical to 1. The IDM-derived accessible concentration (Ce) was further shown to accurately predict tissue residues in earthworm exposed in the same soils. Given the relatively short duration and simple steps, IDM has the potential to be readily adopted for measuring HOC bioaccessibility in soil and for improving risk assessment and evaluation of remediation efficiency.

Role of biochar in biodegradation of nonylphenol in sediment: Increasing microbial activity versus decreasing bioavailability

The observed strong sorption of hydrophobic organic contaminants (HOCs) to biochar presents potential implications for HOCs bioavailability and bioaccessibility in sediments, while biochar could impact sediment microbial ecology. However, the comprehensive study on the effects of biochar on HOC biodegradation coupled with bioavailability and microbial ecology are rarely documented. In this paper, the effects of biochar on the biodegradation of nonylphenol (NP) were investigated using 3 different NP concentrations (20, 50 and 500 mg/Kg) in sediments amended with different percentage of rice straw biochar (RC). Results showed that the influence of RC on NP biodegradation varied with different NP concentrations. At low NP concentrations, RC suppressed NP biodegradation by reducing NP bioavailability, while at high NP concentrations, moderate RC addition promoted biodegradation by reducing toxicity of NP to microbes. The effects of NP on microbial community structures were significant (P < 0.01), but those of RC were not significant (P > 0.05). The RC affected microorganisms through altering NP toxicity, microbial quantity and activity, but not microbial community structures. This study indicated that there could be an optimal biochar percentage in biochar-sediment systems at different HOC concentrations, which strengthened HOC biodegradation process and accelerated biodegradation rate, forming adsorption-biodegradation coupled bioremediation.

Evaluating the Relationship between Equilibrium Passive Sampler Uptake and Aquatic Organism Bioaccumulation.

This Critcal Review evaluates passive sampler uptake of hydrophobic organic contaminants (HOCs) in water column and interstitial water exposures as a surrogate for organism bioaccumulation. Fifty-seven studies were found where both passive sampler uptake and organism bioaccumulation were measured and 19 of these investigations provided direct comparisons relating passive sampler uptake and organism bioaccumulation. Polymers compared included low-density polyethylene (LDPE), polyoxymethylene (POM), and polydimethylsiloxane (PDMS), and organisms ranged from polychaetes and oligochaetes to bivalves, aquatic insects, and gastropods. Regression equations correlating bioaccumulation (CL) and passive sampler uptake (CPS) were used to assess the strength of observed relationships. Passive sampling based concentrations resulted in log-log predictive relationships, most of which were within one to 2 orders of magnitude of measured bioaccumulation. Mean coefficients of determination (r2) for LDPE, PDMS, and POM were 0.68, 0.76, and 0.58, respectively. For the available raw, untransformed data, the mean ratio of CL and CPS was 10.8 ± 18.4 (n = 609). Using passive sampling as a surrogate for organism bioaccumulation is viable when biomonitoring organisms are not available. Passive sampling based estimates of bioaccumulation provide useful information for making informed decisions about the bioavailability of HOCs.

The effect of natural organic matter on bioaccumulation and toxicity of chlorobenzenes to green algae

The effect of natural organic matter (NOM) on toxicity and bioavailability of hydrophobic organic contaminants (HOCs) to aquatic organisms has been investigated with conflicting results and undefined mechanisms, and few studies have been conducted on volatile HOCs. In this study, six volatile chlorobenzenes (CBs) with 1–6 chlorine substitutions were investigated for their bioaccumulation in an acute toxicity to a green alga (Chlorella pyrenoidosa) in the presence/absence of Suwannee River NOM (SRNOM). The fluorescence quenching efficiency of SRNOM increased as the number of chlorine substitutions of CBs increased. SRNOM increased the cell-surface hydrophobicity of algae and decreased the release rates of algae-accumulated CBs, thus increasing the concentration factor (CF) and accumulation of the CBs in the algae. SRNOM increased the toxicity of monochlorobenzene and 1,2-dichlorobenzene, decreased the toxicity of pentachlorobenzene and hexachlorobenzene, and had no significant effect on the toxicity of 1,2,3-trichlorobenzene and 1,2,3,4-tetrachlorobenzene. Relationships between the 96h CF/IC50 (i.e., the CB concentration leading to a 50% algal growth reduction compared with the control) and physicochemical properties of CBs with/without SRNOM were established, providing reasonable explanations for the experimental results. These findings will help with the accurate assessment of ecological risks of organic pollutants in the presence of NOM.

Tenax extraction of sediments to estimate desorption and bioavailability of hydrophobic contaminants: a literature review.

Characterizing sediment-associated hydrophobic contaminants is problematic, because assessing the total amount of a compound available for chemical exchange with an organism is difficult. To address this, contaminant concentrations have been normalized for specific sediment characteristics (including organic C content) or the chemical activity has been estimated using passive samplers. Another approach to assess compound availability is to determine the extent of readily desorbed compound using resin extractions of sediment slurries. The present paper reviews the literature that uses Tenax® TA, a 2,6-diphenylene-oxide polymer as an extraction tool to measure bioavailability of hydrophobic organic contaminants in sediment. Some work has assessed the extent of desorption with sequential extractions to characterize the maximum rate and pool sizes for different desorbing fractions of bound contaminant. As such, the rapidly desorbing fraction has been well correlated with the extent of degradation, bioaccumulation, and toxicity of hydrophobic contaminants. A shortcut to measuring the full desorption curve to determine the rapidly desorbing compound is to use a single-point extraction, with 6 h or 24 h extractions being the most common. The Tenax extraction has been shown to be effective with laboratory-spiked sediments, field-collected sediments, laboratory-exposed organisms, field-collected organisms, and studies among laboratories. Furthermore, a literature-based model has described the bioaccumulation of polychlorinated biphenyls from independently measured field-collected sediments. Despite the success of this approach, applying the Tenax method to manage contaminated sediments is limited by the absence of a standard set of conditions to perform the extractions, as well as standard methods for using field sediments.

Using in situ solid phase microextraction (SPME) for depth profiling in sediments treated with activated carbon

Purpose Sediment contamination in US waterways is an expensive and complicated issue, and as acceptance of nontraditional sediment remediation strategies broadens, novel and efficient methods to assess and monitor the bioavailability of hydrophobic organic contaminants (HOCs) in contaminated sediments will play an important role.

Evaluation of Biochars and Activated Carbons for In Situ Remediation Of Sediments Impacted With Organics, Mercury, And Methylmercury

In situ amendment of activated carbon (AC) to sediments can effectively reduce the bioavailability of hydrophobic organic contaminants. While biochars have been suggested as low-cost and sustainable alternatives to ACs, there are few comparative sorption data especially for mercury (Hg) and methylmercury (MeHg) at the low porewater concentrations in sediments. Here we compare the ability of a wide range of commercially available and laboratory synthesized ACs and biochars to sorb PAHs, PCBs, DDTs, inorganic Hg, and MeHg at environmentally relevant concentrations. Compared to natural organic matter, sorption capacity for most organic compounds was at least 1-2 orders of magnitude higher for unactivated biochars and 3-4 orders of magnitude higher for ACs which translated to sediment porewater PCB concentration reductions of 18-80% for unactivated biochars, and >99% for ACs with 5% by weight amendment to sediment. Steam activated carbons were more effective than biochars in Hg sorption and translated to modeled porewater Hg reduction in the range of 94-98% for sediments with low native Kd and 31-73% for sediments with high native Kd values for Hg. Unactivated biochars were as effective as the steam activated carbons for MeHg sorption. Predicted reductions of porewater MeHg were 73-92% for sediments with low native Kd and 57-86% for sediment with high native K(d). ACs with high surface areas therefore are likely to be effective in reducing porewater concentrations of organics, Hg, and MeHg in impacted sediments. Unactivated biochars had limited effectiveness for organics and Hg but can be considered when MeHg exposure is the primary concern.

Solid-phase Microextraction (SPME) with Stable Isotope Calibration for Measuring Bioavailability of Hydrophobic Organic Contaminants

Solid-phase microextraction (SPME) is a biomimetic tool ideally suited for measuring bioavailability of hydrophobic organic compounds (HOCs) in sediment and soil matrices. However, conventional SPME sampling requires the attainment of equilibrium between the fiber and sample matrix, which may take weeks or months, greatly limiting its applicability. In this study, we explored the preloading of polydimethylsiloxane fiber with stable isotope labeled analogs (SI-SPME) to circumvent the need for long sampling time, and evaluated the performance of SI-SPME against the conventional equilibrium SPME (Eq-SPME) using a range of sediments and conditions. Desorption of stable isotope-labeled analogs and absorption of PCB-52, PCB-153, bifenthrin and cis-permethrin were isotropic, validating the assumption for SI-SPME. Highly reproducible preloading was achieved using acetone-water (1:4, v/v) as the carrier. Compared to Eq-SPME that required weeks or even months, the fiber concentrations (Cf) under equilibrium could be reliably estimated by SI-SPME in 1 day under agitated conditions or 20 days under static conditions in spiked sediments. The Cf values predicted by SI-SPME were statistically identical to those determined by Eq-SPME. The SI-SPME method was further applied successfully to field sediments contaminated with PCB 52, PCB 153, and bifenthrin. The increasing availability of stable isotope labeled standards and mass spectrometry nowadays makes SI-SPME highly feasible, allowing the use of SPME under nonequilibrium conditions with much shorter or flexible sampling time.

Observations of limited secondary effects to benthic invertebrates and macrophytes with activated carbon amendment in river sediments

Amendment of activated carbon to sediments has been shown to effectively reduce the bioavailability of hydrophobic organic contaminants, but concerns have been raised about the potential toxicological impacts of administering a strong sorbent into sediments. The present study provides a summary of several investigations carried out as part of a pilot-scale study in a river to understand the secondary effects of activated carbon added to reduce the bioavailability of sediment-associated polychlorinated biphenyls. While some previous laboratory amendment studies have found reduced lipid content in freshwater worms exposed to activated carbon-treated sediments, the authors did not observe an impact with fine-granular activated carbon-amended sediments aged in the field. Benthic community studies did not find differences between control and activated carbon-treated field sites over 3 yr of postapplication monitoring. Laboratory studies with submerged aquatic plants indicated reduced growth in sediments amended with ≥5% activated carbon, which was attributed to volume dilution of nutritional sediment or bulk density changes and was also observed when the sediment was amended with biochar and inert perlite. Since in situ sorbent amendment is likely to be implemented in depositional sediment environments, potential negative impacts will likely be short-term if the treated site is slowly covered with new sediment over time. Overall suitability of activated carbon amendment for a site will depend on balancing ecosystem and human health benefits from contaminant bioavailability reduction with any potential negative impacts expected under field conditions.

ChemInform Abstract: Chemical Techniques for Assessing Bioavailability of Sediment‐Associated Contaminants — SPME Versus Tenax Extraction

AbstractReview: 66 refs.

Influences of multiwalled carbon nanotubes and plant residue chars on bioaccumulation of polycyclic aromatic hydrocarbons by Chironomus plumosus larvae in sediment

Carbonaceous materials (CMs), including carbon nanotubes (CNTs), and black carbon have been suggested as potential remediation materials for hydrophobic organic contaminants (HOCs) in sediments or soils. However, the concentration-dependent and potential effects of CMs on the decrease in HOC bioavailability are not well understood. In this research, the effects of two types of multiwalled CNTs (MWNT-1 and MWNT-2) and chars (char-stalk produced from stalk and char-wood from wood) on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), including phenanthrene, pyrene, and chrysene, in the benthic organism Chironomus plumosus larvae were studied. When CM content was 1.5% or less in sediments, biota-sediment accumulation factor (BSAF) values for PAHs decreased sharply as CM increased. However, when char and MWNT-1 content was greater than 1.5% in sediments, reduction rates of BSAF were slight. Furthermore, when MWNT-2 content was greater than 1.5%, BSAF values were elevated. This indicated that the MWNT-associated PAHs may have been absorbed by larvae through particle ingestion, and suggested that some CNTs may not be suitable for the remediation of HOC-contaminated sediments because they probably could increase the exposure risk of PAHs to benthic organisms, possibly because of their unique structure.

Influence of single-walled carbon nanotubes on microbial availability of phenanthrene in sediment

Increasing production and use of single-walled carbon nanotubes (SWCNT) will inevitably lead to release of these nanoparticles to aquatic ecosystems. Similar to black carbon (BC) particles, SWCNT have a high affinity for hydrophobic organic contaminants (HOCs) and therefore the presence of SWCNT in sediment may lead to altered bioavailability of HOCs. We compared SWCNT with biochar and charcoal on their effect on the microbial degradability of 0.05 mg kg(-1) (14)C-phenanthrene (PHE) by Mycobacterium vanbaalenii PYR-1 in two sediments with different organic carbon (OC) contents. When the amendment rate of SWCNT or BC was 1 mg g(-1), PHE mineralization was inhibited much more significantly by SWCNT than by either biochar or charcoal. After 360 h of incubation, the mineralized fraction of PHE in the presence of SWCNT was 59.5% of the non-amended control in the sediment with low OC content, and only 42.4% in the other sediment with a higher OC content. Analysis of the freely dissolved concentration (C (free)) using disposable polydimethylsiloxane (PDMS) fibers showed that SWCNT decreased C (free) by 85-95%, apparently due to preferential sorption of PHE to SWCNT particles that had a much larger specific surface area and pore volume than biochar or charcoal. However, pre-interaction of SWCNT with dissolved organic matter (peptone, tannic acid, and humic acid) led to attachment of polar functional groups and reduced surface area on SWCNT, resulting in decreased PHE sorption and an alleviated effect on PHE biodegradation in the order of peptone > tannic acid > humic acid.

Chemical techniques for assessing bioavailability of sediment-associated contaminants: SPME versus Tenax extraction

The traditional approach for predicting the risk of hydrophobic organic contaminants (HOCs) in sediment is to relate organic carbon normalized sediment concentrations to body residues or toxic effects to organisms. However, due to the multiple variables controlling bioavailability, this method has limitations. A matrix independent method of predicting bioavailability needs to be used in order to be universally applicable. Both chemical activity (freely dissolved chemical concentrations) measured by solid-phase microextraction (SPME) and bioaccessibility (rapidly desorbing fraction) estimated by Tenax extraction have been developed to predict bioavailability of sediment-associated HOCs. The objectives of this review are to summarize a number of studies using matrix-SPME or Tenax extraction to estimate bioavailability and/or toxicity of different classes of HOCs and evaluate the strengths and weakness of these two techniques. Although the two chemical techniques assess different components of the matrix, estimates obtained from both techniques have been correlated to organism body residues. The advantages of SPME fibers are their applicability for use in situ and their potential usage for a wide array of contaminants by selection of appropriate coatings. Single time-point Tenax extraction, however, is more time- and labor-effective. Tenax extraction also has lower detection limits, making it more applicable for highly toxic contaminants. This review also calls for additional research to evaluate the role of sequestrated contaminants and ingestion of sediment particles by organisms on HOC bioavailability. The use of performance reference compounds to reduce SPME sampling time and linking chemical based bioavailability estimates to toxicological endpoints are essential to expand the applications of these methods.

Bioavailability of Hydrophobic Organic Contaminants in Sediment with Different Particle-Size Distributions

Few studies have been conducted examining the distribution of different-sized particles in sediment and its potential impact on bioavailability of sediment-associated contaminants. In the current study, three sediments composed of different particle sizes, i.e., fine (0-180 μm), combined (0-500 μm), and coarse (180-500 μm), were used to evaluate the bioaccumulation potential and toxicokinetic rates of four hydrophobic organic contaminants (HOCs) including two polychlorinated biphenyls (PCB-101 and PCB-118), a metabolite of an organochlorine insecticide (p,p'-DDE), and a polybrominated diphenyl ether (BDE-47) to the benthic oligochaete Lumbriculus variegatus. Two chemical approaches, Tenax extraction and matrix-solid phase microextraction (SPME), were also used to measure bioavailability of the sediment-associated HOCs. The uptake and elimination rates of HOCs by L. variegatus from coarse sediment were greater than those from fine sediment, although the biota-sediment accumulation factors (BSAFs) were not significantly different among sediments with different particle sizes. The freely dissolved HOC concentrations measured by matrix-SPME were greater in coarse sediment, however, no difference was found in uptake and desorption rates for the matrix-SPME and Tenax extraction measurements. Although BSAFs in L. variegatus were the same among sediments, kinetic rates of HOCs for organisms and freely dissolved HOC concentrations were lower in fine sediment, suggesting that sediment ingestion may also play a role in organism uptake, especially for HOCs in fine sediment.

Comparison of Earthworm Bioaccumulation between Readily Desorbable and Desorption-Resistant Naphthalene: Implications for Biouptake Routes

The bioaccumulation of readily desorbable naphthalene and that of desorption-resistant naphthalene in earthworms were compared to examine the effect of desorption resistance on bioavailability of hydrophobic organic contaminants in soil. A series of naphthalene-contaminated soil samples representing different degrees of desorption resistance were prepared using a batch sorption-repetitive desorption approach, and bioaccumulation of these samples was evaluated using earthworms (Eisenia fetida). Soil samples representing high-degree of desorption resistance exhibited considerably lower bioavailability, as indicated by the lower body burden (naphthalene concentration in worm tissue) at a given sorbed-phase naphthalene concentration. Moreover, the body burden of the highly desorption-resistant samples exhibited a significantly different pore-water dependency than that of the readily desorbable samples, indicating that different biouptake mechanisms are likely controlling readily desorbable contaminants and desorption-resistant contaminants. We propose that for readily desorbable contaminants, the primary biouptake route is the pore-water uptake, but for desorption-resistant contaminants enhanced uptake from ingested soil particles can also be important. The surfactant-like substances in worm gut fluids and physical stress such as abrasion are the likely causes for the enhanced release of desorption-resistant contaminants in worm guts. The difference in bioavailability between readily desorbable and desorption-resistant contaminants needs to be taken into account in risk assessment practices.

Chemical availability and sediment toxicity of pyrethroid insecticides to Hyalella azteca: Application to field sediment with unexpectedly low toxicity

Tenax extraction is a simple, inexpensive approach to estimate the bioavailability of hydrophobic organic contaminants from sediment. In the present study, a single-point Tenax extraction was evaluated regarding its correlation with the acute toxicity to Hyalella azteca using field-collected sediments in California, USA. Pyrethroids were believed to be the primary contributor to the observed toxicity, and a significant correlation existed between the expected toxicity (given pyrethroid concentrations) and the mortality at most sampling sites. A small subset of sites, however, showed unexpectedly low toxicity to H. azteca despite high concentrations of pyrethroids. These samples were evaluated by Tenax extraction with the expectation that this procedure, which qualifies bioavailable instead of total pyrethroid concentration in sediment, would better explain the anomalously low toxicity. The term bioavailable toxic unit was proposed to link sediment toxicity with chemical availability, and the toxicity in the 17 selected sediments was better explained using Tenax extraction. The r2 value of the regression between sediment toxicity and toxic unit for the 17 sediments increased from 0.24 to 0.60 when the Tenax-extractable concentration was used in place of the total concentration. Results also showed that adsorption to sand particles might play a controlling role in pyrethroid bioavailability and, in turn, sediment toxicity to benthic invertebrates.