Effects of temperature and salinity on bioconcentration and toxicokinetics of permethrin in pyrethroid-resistant Hyalella azteca.

Recent studies demonstrated pyrethroid resistance associated with voltage-gated sodium channel mutations in populations of the epibenthic amphipod, Hyalella azteca. Resistant populations were able to tolerate and bioconcentrate pyrethroids at concentrations significantly higher than toxic levels for non-resistant populations. In conjunction with elevated bioconcentration potential, environmental alteration particularly as a result of global climate change is anticipated to significantly alter abiotic parameters including temperature and salinity. These changes are expected to influence uptake and biotransformation of contaminants. Thus, the aims of the current study were a) to examine the bioconcentration potential of permethrin in two pyrethroid-resistant clades of H. azteca and b) assess the influence of temperature and salinity changes on toxicokinetic parameters. Two pyrethroid-resistant clades of H. azteca were exposed to 14C-permethrin at three salinities (0.2, 1.0 and 6.0 practical salinity units (PSU)) and temperatures (18, 23 and 28 °C). Tests were conducted for up to 36 h and uptake, elimination and biotransformation rates were calculated. Both populations demonstrated bioconcentration factors (BCFs) between five and seven times greater than published data for non-resistant H. azteca, with significant differences between clades. Calculated BCF values were comparable to field populations of resistant H. azteca, emphasizing the potential for elevated pyrethroid bioconcentration in the natural environment and increased exposure for predators consuming pyrethroid-resistant aquatic invertebrates. Alterations to temperature and salinity had no statistically significant effect on uptake or parent compound half-life in either population, though biotransformation was elevated at higher temperatures in both populations. Salinity had a variable effect between the two populations, with lower BCF values at 1.0 PSU in clade D H. azteca and greater BCFs at 6.0 PSU in clade C H. azteca. This is the first study to demonstrate the potential for future climate scenarios to influence toxicokinetics in pyrethroid-resistant aquatic organisms.

Effects of type and quantity of organic carbon on the bioaccessibility of polychlorinated biphenyls in contaminated sediments.

Organic carbon principally controls sorption and desorption of hydrophobic organic compounds in sediments. We investigated the effects of organic carbon type and quantity on compound bioaccessibility. The desorption of 21 polychlorinated biphenyl (PCB) congeners was determined in spiked sediments amended with black carbon, humic acid, and sawdust at either 3 or 6% organic carbon. Desorption parameters were determined using Tenax sequential extractions and then modeled as operationally defined rapid, slow, and very slow fractions and rate constants. The effects of the amendments on PCB bioaccumulation were also evaluated using Lumbriculus variegatus. The lowest and highest PCB bioaccessibilities were observed in the black carbon and sawdust amendments, respectively. The total amount of PCBs desorbed ranged from 3 to 27% for the black carbon amendments, 12 to 55% for humic acid amendments, 16 to 80% for sawdust amendments, and 35 to 89% for controls. The results also showed that desorption of PCBs was slower in 6% amendments than 3% amendments, and this finding was most evident in humic acid and black carbon amendments. Overall, the trend in PCB bioaccumulation was similar to what was found for compound desorption in that the highest PCB bioaccumulation was observed in controls and sawdust amendments, whereas humic acid and black carbon amendments showed lower bioaccumulation. Finally, the 24-h single-point Tenax and bioaccumulation data were fit to a Tenax regression model. The PCB bioaccumulation was effectively predicted by the model, with 80% of the data falling within the 95% confidence intervals. Environ Toxicol Chem 2018;37:1280-1290. © 2018 SETAC.

Methodological and Environmental Impacts on Bioaccessibility Estimates Provided by Single-Point Tenax Extractions.

Single-point Tenax extractions (SPTEs) of hydrophobic organic contaminants provide estimates of bioaccessibility through consistent measures of the chemical concentration initially in the rapidly desorbing fraction in sediment (C rapT0), such that a constant ratio is expected between SPTE and C rapT0 (C T /C rapT0, where T is the duration of the SPTE). As environmental factors (i.e., aging time and organic carbon content) and contaminant hydrophobicity can affect the C rapT0, the utility of the SPTEs as exposure estimates hinges on the consistency of the C T /C rapT0 ratio. Individually these factors have little impact on the ability of SPTEs to represent bioaccumulation, but the effect of these factors in combination, as well as SPTE methodological variation on the C T /C rapT0 ratio is poorly understood. The current study evaluated how environmental and methodological variation-expressed as varying Tenax to organic carbon mass (Tenax:OC) ratios-impacts the C 24h/C rapT0 ratio of pyrethroids in laboratory-spiked sediments. A multiple regression analysis was used to examine the impact of organic carbon, pyrethroid hydrophobicity, Tenax mass, and aging time on the C 24h/C rapT0 ratio. Only aging time of the pyrethroids in sediment significantly affected the C 24h/C rapT0 ratio with a slight decline of -0.0027/d in the C 24h/C rapT0 ratio, and this decline was considered negligible as a consistent C 24h/C rapT0 ratio of 1.46 ± 0.03 was observed across all experimental treatments. This result further demonstrates the consistency of SPTEs to estimate bioaccessibility of hydrophobic contaminants in sediment and subsequent exposure.

The robustness of single-point Tenax extractions of pyrethroids: Effects of the Tenax to organic carbon mass ratio on exposure estimates.

Use of Tenax extractable concentrations to estimate biological exposure to hydrophobic organic contaminants is well documented, yet method variation exists between studies, specifically in the ratio of Tenax mass to organic carbon mass in the sediment (Tenax:OC ratio) being extracted. The effects of this variation on exposure estimates are not well understood. As Tenax is theoretically in direct competition with organic carbon for freely dissolved chemical in sediment interstitial water, varying the Tenax:OC ratio could impact single-point Tenax extraction (SPTE) exposure estimates. Therefore, the effects of varying Tenax:OC ratios on SPTE pyrethroid concentrations from field-contaminated and laboratory-spiked sediments were compared to bioaccumulation by Lumbriculus variegatus. The Tenax:OC ratio had minimal effect on SPTE pyrethroid concentrations. The SPTE pyrethroid concentrations obtained using the highest and lowest Tenax:OC ratios ranged from 0.85- to 3.91-fold different, which is unlikely to contribute substantial error to bioaccessibility estimates. Comparisons to Tenax exposure endpoints from previous research reveal the variation in these endpoints is likely due to toxicokinetic and toxicodynamic differences; processes common to exposure estimates provided by any chemical extraction technique. As the pyrethroid concentrations in the experimental sediments caused toxicity to L. variegatus, thus affecting bioaccumulation, the SPTE concentrations overestimated bioaccumulation. However, SPTE concentrations strongly correlated with growth inhibition regardless of the Tenax:OC ratio, providing accurate estimates of the correct exposure endpoint. Tenax masses of 0.500-0.800 g should provide sufficient Tenax to achieve Tenax:OC ratios of at least 5:1, which will provide accurate exposure estimates while retaining the ease of conducting SPTEs.

Tenax extraction as a simple approach to improve environmental risk assessments.

It is well documented that using exhaustive chemical extractions is not an effective means of assessing exposure of hydrophobic organic compounds in sediments and that bioavailability-based techniques are an improvement over traditional methods. One technique that has shown special promise as a method for assessing the bioavailability of hydrophobic organic compounds in sediment is the use of Tenax-extractable concentrations. A 6-h or 24-h single-point Tenax-extractable concentration correlates to both bioaccumulation and toxicity. This method has demonstrated effectiveness for several hydrophobic organic compounds in various organisms under both field and laboratory conditions. In addition, a Tenax bioaccumulation model was developed for multiple compounds relating 24-h Tenax-extractable concentrations to oligochaete tissue concentrations exposed in both the laboratory and field. This model has demonstrated predictive capacity for additional compounds and species. Use of Tenax-extractable concentrations to estimate exposure is rapid, simple, straightforward, and relatively inexpensive, as well as accurate. Therefore, this method would be an invaluable tool if implemented in risk assessments.

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.

Application of a Tenax model to assess bioavailability of polychlorinated biphenyls in field sediments.

Recent literature has shown that bioavailability-based techniques, such as Tenax extraction, can estimate sediment exposure to benthos. In a previous study by the authors, Tenax extraction was used to create and validate a literature-based Tenax model to predict oligochaete bioaccumulation of polychlorinated biphenyls (PCBs) from sediment; however, its ability to assess sediment remediation was unknown. The present study further tested the Tenax model by examining the impacts of remediation on surface sediment concentrations, Tenax extractable concentrations, and tissue concentrations of laboratory-exposed Lumbriculus variegatus. Tenax extractable concentration was an effective exposure metric to evaluate changes in Lumbriculus exposure preremediation and postremediation, with 75% of the postremediation data corresponding to the Tenax model. At nondredged sites, bioaccumulation was better predicted by the Tenax model, with 86% of the data falling within the 95% confidence intervals, than at dredged sites, for which only 64% of the data fit the Tenax model. In both pre- and postdredge conditions, when the model failed, it was conservative, predicting higher PCB concentrations than observed in the oligochaetes, particularly for the postdredge data. The present study advances understanding of the applicability of the Tenax model for use when examining systems that may have undergone significant disturbances. The Tenax model provides a unique tool for quickly quantifying potential exposure to benthic organisms.

Passive sampling methods for contaminated sediments: state of the science for organic contaminants.

This manuscript surveys the literature on passive sampler methods (PSMs) used in contaminated sediments to assess the chemical activity of organic contaminants. The chemical activity in turn dictates the reactivity and bioavailability of contaminants in sediment. Approaches to measure specific binding of compounds to sediment components, for example, amorphous carbon or specific types of reduced carbon, and the associated partition coefficients are difficult to determine, particularly for native sediment. Thus, the development of PSMs that represent the chemical activity of complex compound-sediment interactions, expressed as the freely dissolved contaminant concentration in porewater (Cfree ), offer a better proxy for endpoints of concern, such as reactivity, bioaccumulation, and toxicity. Passive sampling methods have estimated Cfree using both kinetic and equilibrium operating modes and used various polymers as the sorbing phase, for example, polydimethylsiloxane, polyethylene, and polyoxymethylene in various configurations, such as sheets, coated fibers, or vials containing thin films. These PSMs have been applied in laboratory exposures and field deployments covering a variety of spatial and temporal scales. A wide range of calibration conditions exist in the literature to estimate Cfree , but consensus values have not been established. The most critical criteria are the partition coefficient between water and the polymer phase and the equilibrium status of the sampler. In addition, the PSM must not appreciably deplete Cfree in the porewater. Some of the future challenges include establishing a standard approach for PSM measurements, correcting for nonequilibrium conditions, establishing guidance for selection and implementation of PSMs, and translating and applying data collected by PSMs.

The importance of both potency and mechanism in dose-response analysis: an example from exposure of Pacific herring (Clupea pallasi) embryos to low concentrations of weathered crude oil.

This paper reanalyzes data from an earlier study that used effluents from oiled-gravel columns to assess the toxicity of aqueous fractions of weathered crude oil to Pacific herring embryos and larvae. This reanalysis has implications for future similar investigations, including the observance of two distinct dose-response curves for lethal and sublethal endpoints for different exposures in the same experiment, and the need to consider both potency and slope of dose-response curves for components of a toxicant mixture that shows potentially different toxicity mechanisms/causation. Contrary to conclusions of the original study, the aqueous concentration data cannot support the hypothesis that polycyclic aromatic hydrocarbons (PAHs) were the sole cause of toxicity and that oil toxicity increased with weathering. Confounding issues associated with the oiled gravel columns include changes in the concentration and composition of chemicals in exposure water, which interfere with the production of reliable and reproducible results relevant to the field.

Dietary exposure of Antarctic krill to p,p'-DDE: uptake kinetics and toxicological sensitivity in a key polar species.

This study evaluated the dietary uptake kinetics and sublethal toxicity of p,p'-dichlorodiphenyl dichloroethylene (p,p'-DDE) in Antarctic krill. The uptake rate constant (characterised by the seawater volume stripped of contaminant sorbed to algae) of 200 ± 0.32 mL g(-1) wet weight h(-1), average absorption efficiency of 86 ± 13% and very low elimination rate constant of 5 × 10(-6) ± 0.0031 h(-1) demonstrate the importance of feeding for p,p'-DDE bioaccumulation in Antarctic krill. Faecal egestion of unabsorbed p,p'-DDE of 8.1 ± 2.7% indicates that this pathway contributes considerably to p,p'-DDE sinking fluxes. A median internal effective concentration (IEC50) of 15 mmol/kg lipid weight for complete immobility indicates baseline toxicity and that Antarctic krill exhibit comparable toxicological sensitivity as temperate species under similar 10 d exposure conditions. These findings support the critical body residue approach and provide insight to the role of Antarctic krill in the biogeochemical cycling of p,p'-DDE in the Southern Ocean.

Bioavailability-based toxicity endpoints of bifenthrin for Hyalella azteca and Chironomus dilutus.

Recent studies have determined that techniques, such as solid phase microextraction (SPME) fibers and Tenax beads, can predict bioaccumulation and potentially could predict toxicity for several compounds and species. Toxicity of bifenthrin was determined using two standard sediment toxicity tests with the benthic species Hyalella azteca and Chironomus dilutus in three reference sediments with different characteristics. The objectives of the current study were to establish bioavailability-based median lethal concentrations (LC50) and median effect concentrations (EC50) of the pyrethroid insecticide bifenthrin, compare their ability to assess toxicity to the use of whole sediment concentrations, as well as to make comparisons of the concentrations derived using each method in order to make assessments of accuracy and extrapolation potential. Four metrics were compared including SPME fiber concentration, pore water concentration derived using SPMEs, 6 h Tenax extractable concentration, and 24 h Tenax extractable concentration. The variation among the LC50s and EC50s in each sediment derived using bioavailability-based methods was comparable to variation among organic carbon normalized sediment concentrations, but improved over whole sediment concentrations. There was a significant linear relationship between SPME or Tenax and organic carbon normalized sediment concentrations. Additionally, there was a significant relationship between the SPME and Tenax concentrations across sediments. The significant linear relationship between SPME and Tenax concentrations further demonstrates that these bioavailability-based endpoints are interrelated. This study derived bioavailability-based benchmarks that may prove to be more accurate than sediment-based ones in predicting toxicity across sediment types.

Assessing bioavailability and toxicity of permethrin and DDT in sediment using matrix solid phase microextraction.

Matrix solid phase microextraction (matrix-SPME) was evaluated as a surrogate for the absorbed dose in organisms to estimate bioavailability and toxicity of permethrin and dichlorodiphenyltrichloroethane (DDT) in laboratory-spiked sediment. Sediments were incubated for 7, 28, and 90 days at room temperature to characterize the effect of aging on bioavailability and toxicity. Sediment toxicity was assessed using two freshwater invertebrates, the midge Chironomus dilutus and amphipod Hyalella azteca. Disposable polydimethylsiloxane fibers were used to estimate the absorbed dose in organisms and to examine bioavailability and toxicity. The equilibrium fiber concentrations substantially decreased with an increase in sediment aging time, indicating a reduction in bioavailability. Based on median lethal fiber concentrations (fiber LC50), toxicity of permethrin was not significantly different among the different aging times. Due to the substantial degradation of DDT to dichlorodiphenyldichloroethane (DDD) in sediment, sediment toxicity to C. dilutus increased, while it decreased for H. azteca with extended aging times. A toxic unit-based fiber LC50 value represented the DDT mixture (DDT and DDD) toxicity for both species. Significant linear relationships were found between organism body residues and the equilibrium fiber concentrations for each compound, across aging times. The study suggested that the matrix-SPME fibers mimicked bioaccumulation in the organisms, and enabled estimation of body residues, and could potentially be used in environmental risk assessment across matrices (e.g. sediment and water) to measure bioavailability and toxicity of hydrophobic pesticides.

Influence of exposure and toxicokinetics on measures of aquatic toxicity for organic contaminants: a case study review.

This theoretical and case study review of dynamic exposures of aquatic organisms to organic contaminants examines variables important for interpreting exposure and therefore toxicity. The timing and magnitude of the absorbed dose change when the dynamics of exposure change. Thus, the dose metric for interpreting toxic responses observed during such exposure conditions is generally limited to the specific experiment and cannot be extrapolated to either other experiments with different exposure dynamics or to field exposures where exposure dynamics usually are different. This is particularly true for mixture exposures, for which the concentration and composition and, therefore, the timing and magnitude of exposure to individual components of different potency and potentially different mechanisms of action can vary. Aquatic toxicology needs studies that develop temporal thresholds for absorbed toxicant doses to allow for better extrapolation between conditions of dynamic exposure. Improved experimental designs are required that include high-quality temporal measures of both the exposure and the absorbed dose to allow better interpretation of data. For the short term, initial water concentration can be considered a conservative measure of exposure, although the extent to which this is true cannot be estimated specifically unless the dynamics of exposure as well as the toxicokinetics of the chemicals in the exposure scenario for the organism of interest are known. A better, but still limited, metric for interpreting the exposure and, therefore, toxicity is the peak absorbed dose, although this neglects toxicodynamics, requires appropriate temporal measures of accumulated dose to determine the peak concentration, and requires temporal thresholds for critical body residue for each component of the mixture.

Using SPME fibers and Tenax to predict the bioavailability of pyrethroids and chlorpyrifos in field sediments.

The presence of pyrethroids in both urban and agricultural sediments at levels lethal to invertebrates has been well documented. However, variations in bioavailability among sediments make accurate predictions of toxicity based on whole sediment concentrations difficult. A proposed solution to this problem is the use of bioavailability-based estimates, such as solid phase microextraction (SPME) fibers and Tenax beads. This study compared three methods to assess the bioavailability and ultimately toxicity of pyrethroid pesticides including field-deployed SPME fibers, laboratory-exposed SPME fibers, and a 24-h Tenax extraction. The objective of the current study was to compare the ability of these methods to quantify the bioavailable fraction of pyrethroids in contaminated field sediments that were toxic to benthic invertebrates. In general, Tenax proved a more sensitive method than SPME fibers and a correlation between Tenax extractable concentrations and mortality was observed.

A Perspective on the Toxicity of Low Concentrations of Petroleum-Derived Polycyclic Aromatic Hydrocarbons to Early Life Stages of Herring and Salmon.

This article presents a critical review of two groups of studies that reported adverse effects to salmon and herring eggs and fry from exposure to 1 µg/L or less of aqueous total polycyclic aromatic hydrocarbons (TPAH), as weathered oil, and a more toxic aqueous extract of "very weathered oil." Exposure media were prepared by continuously flowing water up through vertical columns containing gravel oiled at different concentrations of Prudhoe Bay crude oil. Uncontrolled variables associated with the use of the oiled gravel columns included time- and treatment-dependent variations in the PAH concentration and composition in the exposure water, unexplored toxicity from other oil constituents/degradation products, potential toxicity from bacterial and fungal activity, oil droplets as a potential contaminant source, inherent differences between control and exposed embryo populations, and water flow rate differences. Based on a review of the evidence from published project reports, peer-reviewed publications, chemistry data in a public database, and unpublished reports and laboratory records, the reviewed studies did not establish consistent dose (concentration) response or causality and thus do not demonstrate that dissolved PAH alone from the weathered oil resulted in the claimed effects on fish embryos at low µg/L TPAH concentrations. Accordingly, these studies should not be relied on for management decision-making, when assessing the risk of very low-level PAH exposures to early life stages of fish.

Use of solid phase microextraction to estimate toxicity: relating fiber concentrations to body residues--part II.

In the companion paper, solid phase microextraction (SPME) fiber concentrations were used as a dose metric to evaluate the toxicity of hydrophobic pesticides, and concentration-response relationships were found for the hydrophobic pesticides tested in the two test species. The present study extends the use of fiber concentrations to organism body residues to specifically address biotransformation and provide the link to toxic response. Test compounds included the organochlorines p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE); two pyrethroids, permethrin and bifenthrin; and an organophosphate, chlorpyrifos. Toxicity, body residues, and biotransformation of the target compounds were determined for the midge Chironomus dilutus and the amphipod Hyalella azteca. Significant regression relationships were found without regard to chemical, extent of biotransformation, or whether the chemical reached steady state in the organisms. The equilibrium SPME fiber concentrations correlated with the parent compound concentration in the biota; however, the regressions were duration specific. Furthermore, the SPME fiber-based toxicity values yielded species-specific regressions with the parent compound-based toxicity values linking the use of SPME fiber as a dose metric with tissue residues to estimate toxic response.

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.

Use of solid phase microextraction to estimate toxicity: relating fiber concentrations to toxicity--part I.

Use of solid-phase microextraction (SPME) fibers as a dose metric for toxicity testing was evaluated for hydrophobic pesticides to the midge Chironomus dilutus and the amphipod Hyalella azteca. Test compounds included p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT), p,p'-dichlorodiphenyldichloroethane (p,p'-DDD), p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE), permethrin, bifenthrin, tefluthrin, and chlorpyrifos. Acute water toxicity tests were determined for 4- and 10-d exposures in both species. Median lethal and sublethal concentrations were expressed both on a water concentration (LC50 and EC50) and on an equilibrium SPME fiber concentration (LC50(fiber) and EC50(fiber)) basis. A significant log dose-response relationship was found between log fiber concentration and organism mortality. It has been shown in the literature that equilibrium SPME fiber concentrations reflect the bioavailable concentrations of hydrophobic contaminants, so these fiber concentrations should be a useful metric for assessing toxic effects from the bioavailable contaminant providing a framework to expand the use of SPME fibers beyond estimation of bioaccumulation.