Long-term, landscape-level assessment of aquatic pesticide exposure to identify amphibian ontological traits affecting vulnerability.

Amphibians worldwide are threatened by habitat loss, some of which is driven by a changing climate, as well as exposure to pesticides, among other causes. The timing and duration of the larval development phase vary between species, thereby influencing the relative impacts of stochastic hydroregime conditions as well as potential aquatic pesticide exposure. We describe the stages of breeding through metamorphosis for eight amphibian species, based on optimal hydroregime conditions, and use a model of pesticide fate and exposure representative of central Florida citrus groves to simulate hydrodynamics based on observed weather data over a 54-year period. Using the Pesticide in Water Calculator and Plant Assessment Tool, we estimated daily wetland depth and pyraclostrobin exposure, with label-recommended application quantities. Species' timing and duration of larval development determined the number of years of suitable hydroregime for breeding and the likelihood of exposure to peak aquatic concentrations of pyraclostrobin. Although the timing of pesticide application determined the number of surviving larvae, density-dependent constraints of wetland hydroregime also affected larval survival across species and seasons. Further defining categorical amphibian life history types and habitat requirements supports the development of screening-level assessments by incorporating environmental stochasticity at the appropriate temporal resolution. Subsequent refinement of these screening-level risk assessment strategies to include spatially explicit landscape data along with terrestrial exposure estimates would offer additional insights into species vulnerability to pesticide exposure throughout the life cycle. Computational simulation of ecologically relevant exposure scenarios, such as these, offers a more realistic interpretation of differential agrichemical risk among species based on their phenology and habits and provides a more situation-specific risk assessment perspective for threatened species. Integr Environ Assess Manag 2024;00:1-10. Published 2024. This article is a U.S. Government work and is in the public domain in the USA.

Per- and polyfluoroalkyl substances in the environment.

Over the past several years, the term PFAS (per- and polyfluoroalkyl substances) has grown to be emblematic of environmental contamination, garnering public, scientific, and regulatory concern. PFAS are synthesized by two processes, direct fluorination (e.g., electrochemical fluorination) and oligomerization (e.g., fluorotelomerization). More than a megatonne of PFAS is produced yearly, and thousands of PFAS wind up in end-use products. Atmospheric and aqueous fugitive releases during manufacturing, use, and disposal have resulted in the global distribution of these compounds. Volatile PFAS facilitate long-range transport, commonly followed by complex transformation schemes to recalcitrant terminal PFAS, which do not degrade under environmental conditions and thus migrate through the environment and accumulate in biota through multiple pathways. Efforts to remediate PFAS-contaminated matrices still are in their infancy, with much current research targeting drinking water.

Using metabolomic profiling to inform use of surrogate species in ecological risk assessment practices.

The U.S. EPA frequently uses avian or fish toxicity data to set protective standards for amphibians in ecological risk assessments. However, this approach does not always adequately represent aquatic-dwelling and terrestrial-phase amphibian exposure data. For instance, it is accepted that early life stage tests for fish are typically sensitive enough to protect larval amphibians, however, metamorphosis from tadpole to a terrestrial-phase adult relies on endocrine cues that are less prevalent in fish but essential for amphibian life stage transitions. These differences suggest that more robust approaches are needed to adequately elucidate the impacts of pesticide exposure in amphibians across critical life stages. Therefore, in the current study, methodology is presented that can be applied to link the perturbations in the metabolomic response of larval zebrafish (Danio rerio), a surrogate species frequently used in ecotoxicological studies, to those of African clawed frog (Xenopus laevis) tadpoles following exposure to three high-use pesticides, bifenthrin, chlorothalonil, or trifluralin. Generally, D. rerio exhibited greater metabolic perturbations in both number and magnitude across the pesticide exposures as opposed to X. laevis. This suggests that screening ecological risk assessment surrogate toxicity data would sufficiently protect amphibians at the single life stage studied but care needs to be taken to understand the suite of metabolic requirements of each developing species. Ultimately, methodology presented, and data gathered herein will help inform the applicability of metabolomic profiling in establishing the risk pesticide exposure poses to amphibians and potentially other non-target species.

Per- and polyfluoroalkyl substances (PFAS) in sediments collected from the Pensacola Bay System watershed.

Sediment samples from 25 locations in the Pensacola Bay System (PBS) watershed were analyzed for the presence of 51 per- and polyfluoroalkyl substances (PFAS) using ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) and selected reaction monitoring. Results revealed quantifiable concentrations of PFAS in all sampling locations. More specifically, perfluorobutanoic acid (PFBA) was present in every sediment sample with a minimum and maximum concentration of 0.04 to 0.48 ng g-1 dry weight, respectively, across the 25 sites with an average of 0.1 ± 0.09 ng g-1. While PFOS, with an average of 0.11 ± 0.14 ng g-1 (range:

Cross-Taxa Distinctions in Mechanisms of Developmental Effects for Aquatic Species Exposed to Trifluralin.

Standard ecological risk assessment practices often rely on larval and juvenile fish toxicity data as representative of the amphibian aquatic phase. Empirical evidence suggests that endpoints measured in fish early life stage tests are often sufficient to protect larval amphibians. However, the process of amphibian metamorphosis relies on endocrine cues that affect development and morphological restructuring and are not represented by these test endpoints. The present study compares developmental endpoints for zebrafish (Danio rerio) and the African clawed frog (Xenopus laevis), 2 standard test species, exposed to the herbicide trifluralin throughout the larval period. Danio rerio were more sensitive and demonstrated a reduction in growth measurements with increasing trifluralin exposure. Size of X. laevis at metamorphosis was not correlated with exposure concentration; however, time to metamorphosis was delayed relative to trifluralin concentration. Gene expression patterns indicate discrepancies in response by D. rerio and X. laevis, and dose-dependent metabolic activity suggests that trifluralin exposure perturbed biological pathways differently within the 2 species. Although many metabolites were correlated with exposure concentration in D. rerio, nontargeted hepatic metabolomics identified a subset of metabolites that exhibited a nonmonotonic response to trifluralin exposure in X. laevis. Linking taxonomic distinctions in cellular-level response with ecologically relevant endpoints will refine assumptions used in interspecies extrapolation of standard test effects and improve assessment of sublethal impacts on amphibian populations. Environ Toxicol Chem 2020;39:1797-1812. Published 2020. This article is a US government work and is in the public domain in the USA.

Simulated developmental and reproductive impacts on amphibian populations and implications for assessing long-term effects.

Fish endpoints measured in early life stage toxicity tests are often used as representative of larval amphibian sensitivity in Ecological Risk Assessment (ERA). This application potentially overlooks the impact of developmental delays on amphibian metamorphosis, and thereby reduced survival, in amphibian populations constrained by habitat availability. Likewise, the effects of reduced productivity or altered sexual development as a result of chemical exposure are not presented in terms of lower population fecundity in these surrogate tests. Translating endpoints measured in toxicity tests to those that are more representative of amphibian ecology and population dynamics provides a means of identifying how developmental effects result in long-term impacts. Here we compare effects of developmental delay on metamorphosis success in six anuran species and simulate population-level impacts of subsequent reductions in larval survival as well as potential reductions in fecundity as a result of developmental impacts. We use deterministic matrix models to compare realistic combinations of amphibian demographic rates and relative impacts of reduced growth on larval survival and subsequently on population growth. Developmental delays are less detrimental in species with longer and less synchronous larval periods. All six species were most sensitive to changes in first-year survival, and damping ratios were generally a good indicator of resilience to perturbations in both larval survival and fecundity. Further identification of species and population-level vulnerabilities can improve the evaluation of sublethal effects in relevant context for ERA.

Spatially explicit assessment of estuarine fish after Deepwater Horizon oil spill: trade-off in complexity and parsimony.

Evaluating long-term contaminant effects on wildlife populations depends on spatial information about habitat quality, heterogeneity in contaminant exposure, and sensitivities and distributions of species integrated into a systems modeling approach. Rarely is this information readily available, making it difficult to determine the applicability of realistic models to quantify population-level risks. To evaluate the trade-offs between data demands and increased specificity of spatially explicit models for population-level risk assessments, we developed a model for a standard toxicity test species, the sheepshead minnow (Cyprinodon variegatus), exposed to oil contamination following the Deepwater Horizon oil spill and compared the output with various levels of model complexity to a standard risk quotient approach. The model uses habitat and fish occupancy data collected over five sampling periods throughout 2008-2010 in Pensacola and Choctawhatchee Bays, Florida, USA, to predict species distribution, field-collected and publically available data on oil distribution and concentration, and chronic toxicity data from laboratory assays applied to a matrix population model. The habitat suitability model established distribution of fish within Barataria Bay, Louisiana, USA, and the population model projected the dynamics of the species in the study area over a 5-yr period (October 2009-September 2014). Vital rates were modified according to estimated contaminant concentrations to simulate oil exposure effects. To evaluate the differences in levels of model complexity, simulations varied from temporally and spatially explicit, including seasonal variation and location-specific oiling, to simple interpretations of a risk quotient derived for the study area. The results of this study indicate that species distribution, as well as spatially and temporally variable contaminant concentrations, can provide a more ecologically relevant evaluation of species recovery from catastrophic environmental impacts but might not be cost-effective or efficient for rapid assessment needs.

Effects of Louisiana crude oil on the sheepshead minnow (Cyprinodon variegatus) during a life-cycle exposure to laboratory oiled sediment.

Determining the long-term effects of crude oil exposure is critical for ascertaining population-level ecological risks of spill events. A 19-week complete life-cycle experiment was conducted with the estuarine sheepshead minnow (Cyprinodon variegatus) exposed to reference (uncontaminated) sediment spiked with laboratory weathered South Louisiana crude (SLC) oil at five concentrations as well as one unspiked sediment control and one seawater (no sediment) control. Newly hatched larvae were exposed to the oiled sediments at measured concentrations of < 1 (sediment control), 50, 103, 193, 347, and 711 mg total polyaromatic hydrocarbons (tPAH)/kg dry sediment. Juveniles were exposed through the reproductively active adult phase at measured concentrations of <1 (sediment control), 52, 109, 199, 358, and 751 mg tPAH/kg sediment. Throughout the exposure, fish were assessed for growth, survival, and reproduction. Resulting F1 embryos were then collected, incubated, and hatched in clean water to determine if parental full life-cycle exposure to oiled sediment produced trans-generational effects. Larvae experienced significantly reduced standard length (5-13% reduction) and wet weight (13-35% reduction) at concentrations at and above 50 and 103 mg tPAH/kg sediment, respectively. At 92 and 132 days post hatch (dph), standard length was reduced (7-13% reduction) at 199 and 109 mg tPAH/kg dry sediment, respectively, and wet weight for both time periods was reduced at concentrations at and above 109 mg tPAH/kg dry sediment (21-38% reduction). A significant reduction (51-65%) in F0 fecundity occurred at the two highest test concentrations, but no difference was observed in F1 embryo survival. This study is the first to report the effects of chronic laboratory exposure to oiled sediment, and will assist the development of population models for evaluating risk to benthic spawning fish species exposed to oiled sediments. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 1627-1639, 2016.

Developmental toxicity of Louisiana crude oil-spiked sediment to zebrafish.

Embryonic exposures to the components of petroleum, including polycyclic aromatic hydrocarbons (PAHs), cause a characteristic suite of developmental defects and cardiotoxicity in a variety of fish species. We exposed zebrafish embryos to reference sediment mixed with laboratory weathered South Louisiana crude oil and to sediment collected from an oiled site in Barataria Bay, Louisiana in December 2010. Laboratory oiled sediment exposures caused a reproducible set of developmental malformations in zebrafish embryos including yolk sac and pericardial edema, craniofacial and spinal defects, and tissue degeneration. Dose-response studies with spiked sediment showed that total polycyclic aromatic hydrocarbons (tPAH) concentrations of 27mg tPAH/kg (dry weight normalized to 1 percent organic carbon [1 percent OC]) caused a significant increase in defects, and concentrations above 78mg tPAH/kg 1 percent OC caused nearly complete embryo mortality. No toxicity was observed in Barataria sediment with 2mg tPAH/kg 1 percent OC. Laboratory aging of spiked sediment at 4°C resulted in a nearly 10-fold decrease in sensitivity over a 40-day period. This study demonstrates oiled sediment as an exposure pathway to fish with dose-dependent effects on embryogenesis that are consistent with PAH mechanisms of developmental toxicity. The results have implications for effects on estuarine fish from oiled coastal areas during the Deepwater Horizon spill.

Augmenting aquatic species sensitivity distributions with interspecies toxicity estimation models.

Species sensitivity distributions (SSDs) are cumulative distribution functions of species toxicity values. The SSD approach is being used increasingly in ecological risk assessment but is often limited by available toxicity data needed for diverse species representation. In the present study, the authors evaluate augmenting aquatic species databases limited to standard test species using toxicity values extrapolated from interspecies correlation estimation (ICE) models for SSD development. The authors compared hazard concentrations at the 5th centile (HC5) of SSDs developed using limited measured data augmented with ICE toxicity values (augmented SSDs) with those estimated using larger measured toxicity datasets of diverse species (reference SSDs). When SSDs had similar species composition to the reference SSDs, 0.76 of the HC5 estimates were closer to the reference HC5; however, the proportion of augmented HC5s that were within 5-fold of the reference HC5s was 0.94, compared with 0.96 when predicted SSDs had random species assemblages. The range of toxicity values among represented species in all SSDs also depended on a chemical's mode of action. Predicted HC5 estimations for acetylcholinesterase inhibitors showed the greatest discrepancies from the reference HC5 when SSDs were limited to commonly tested species. The results of the present study indicate that ICE models used to augment datasets for SSDs do not greatly affect HC5 uncertainty. Uncertainty analysis of risk assessments using SSD hazard concentrations should address species composition, especially for chemicals with known taxa-specific differences in toxicological effects. This article is a US Government work and is in the public domain in the USA.

Sensitivity of species to chemicals: dose-response characteristics for various test types (LC(50), LR(50) and LD(50)) and modes of action.

While variable sensitivity of model species to common toxicants has been addressed in previous studies, a systematic analysis of inter-species variability for different test types, modes of action and species is as of yet lacking. Hence, the aim of the present study was to identify similarities and differences in contaminant levels affecting cold-blooded and warm-blooded species administered via different routes. To that end, data on lethal water concentrations LC50, tissue residues LR50 and oral doses LD50 were collected from databases, each representing the largest of its kind. LC50 data were multiplied by a bioconcentration factor (BCF) to convert them to internal concentrations that allow for comparison among species. For each endpoint data set, we calculated the mean and standard deviation of species' lethal level per compound. Next, the means and standard deviations were averaged by mode of action. Both the means and standard deviations calculated depended on the number of species tested, which is at odds with quality standard setting procedures. Means calculated from (BCF) LC50, LR50 and LD50 were largely similar, suggesting that different administration routes roughly yield similar internal levels. Levels for compounds interfering biochemically with elementary life processes were about one order of magnitude below that of narcotics disturbing membranes, and neurotoxic pesticides and dioxins induced death in even lower amounts. Standard deviations for LD50 data were similar across modes of action, while variability of LC50 values was lower for narcotics than for substances with a specific mode of action. The study indicates several directions to go for efficient use of available data in risk assessment and reduction of species testing.

Evaluation of in silico development of aquatic toxicity species sensitivity distributions.

Determining the sensitivity of a diversity of species to environmental contaminants continues to be a significant challenge in ecological risk assessment because toxicity data are generally limited to a few standard test species. This study assessed whether species sensitivity distributions (SSDs) could be generated with reasonable accuracy using only in silico modeling of toxicity to aquatic organisms. Ten chemicals were selected for evaluation that spanned several modes of actions and chemical classes. Median lethal concentrations (LC50s) were estimated using three internet-based quantitative structure activity relationship (QSAR) tools that employ different computational approaches: ECOSAR (Ecological Structure Activity Relationships), ASTER (Assessment Tools for the Evaluation of Risk), and TEST (Toxicity Estimation Software Tool). Each QSAR estimate was then used as input into the SSD module of the internet-based toxicity estimation program Web-ICE to generate an in silico estimated fifth percentile hazard concentration (HC5) for each of the ten chemicals. The accuracy of the estimated HC5s was determined by comparison to measured HC5s developed from an independent dataset of experimental acute toxicity values for a diversity of aquatic species. Estimated HC5s showed generally poor agreement with measured HC5s determined for all available aquatic species, but showed better agreement when species composition of the chemical specific SSDs were identical. These results indicated that LC50 variability and species composition were large sources of error in estimated HC5s. Additional research is needed to reduce uncertainty in HC5s using only in silico approaches and to develop computational approaches for predicting species sensitivity.

Assessment of indirect pesticide effects on worm-eating warbler populations in a managed forest ecosystem.

Ecological risk assessments rarely evaluate indirect pesticide effects. Pesticides causing no direct mortality in wildlife can still reduce prey availability, resulting in a lower reproductive rate or poor juvenile condition. Few studies have examined these consequences at the population level. We use a four-year data set from a forest ecosystem in which Bacillus thuringiensis kurstaki (Btk) was applied to control gypsy moths (Lymantria dispar L.). Lower worm-eating warbler (Helmitheros vermivorus) productivity on Btk plots contributed to an intrinsic growth rate <1. Altered provisioning behavior by adults led to lower nestling mass in Btk-treated plots, and simulations of reduced juvenile survival expected as a result further reduced population growth rate. The present study explored different spatial representations of treated areas, using a two-patch matrix model incorporating dispersal. Minimal migration from areas with increasing subpopulations could compensate for detrimental reductions in reproductive success and juvenile survival within treated subpopulations. We also simulated population dynamics with different proportions of treated areas to inform management strategies in similar systems. Nontoxic insecticides are capable of impacting nontarget populations with consistent, long-term use and should be evaluated based on the spatial connectivity representative of habitat availability and the time period appropriate for risk assessment of pesticide effects in wildlife populations.

Estimation of wildlife hazard levels using interspecies correlation models and standard laboratory rodent toxicity data.

Toxicity data from laboratory rodents are widely available and frequently used in human health assessments as animal model data. This study explores the possibility of using single rodent acute toxicity values to predict chemical toxicity to a diversity of wildlife species and estimate hazard levels from modeled species sensitivity distributions (SSD). Interspecies correlation estimation (ICE) models predict toxicity values for untested species using the sensitivity relationship between measured toxicity values of two species. Predicted toxicity values can subsequently populate SSD for application in ecological risk assessments. Laboratory mouse and rat toxicity values were used to estimate toxicity to wildlife and the predicted values then were used to derive SSD hazard dose levels. Toxicity values were predicted within fivefold of measured toxicity values for 78% of ICE models using laboratory rat or mouse toxicity as a surrogate value. Hazard dose levels (HD5) were within fivefold of measured estimates for 72% of SSD developed using laboratory rodent ICE models. Rodents were most often in the least sensitive quartile of species sensitivity distributions, and therefore toxicity values alone may not adequately represent the toxicity to many species of concern without appropriate safety or assessment factors. Laboratory rodent toxicity data offer an additional source of information that can be used to predict hazard levels for wildlife species, and thus offer a starting point for both health and ecological risk assessment.

Development of species sensitivity distributions for wildlife using interspecies toxicity correlation models.

Species sensitivity distributions (SSD) are probability distributions of chemical toxicity of multiple species and have had limited application in wildlife risk assessment because of relatively small data sets of wildlife toxicity values. Interspecies correlation estimation (ICE) models predict the acute toxicity to untested taxa from known toxicity of a single surrogate species. ICE models were used to predict toxicity values to wildlife species and generate SSDs for 23 chemicals using four avian surrogates. The hazard levels associated with the fifth percentile of the distribution (HD5) were compared for ICE SSDs and independent SSDs created with measured data. SSDs were composed of either avian only or avian and mammalian taxa. ICE HD5s were within 5-fold of 90% of measured HD5s and were generally higher than measured HD5s. The first percentile of the distribution (HD1) and the fifth percentile of the lower confidence limit (HDL) of ICE SSDs produced values that were not significantly different from measured HD5s. Using a bird surrogate to predicttoxicity to birds and the Norway rat to predict toxicity to mammals improved some estimates of ICE HD5s compared with those generated using only bird surrogates. These results indicate that ICE models can be used to generate SSDs comparable to those derived from measured wildlife toxicity data and provide robust estimates of the HD5.