Assessment of risks to listed species from the use of atrazine in the USA: a perspective.

Atrazine is a triazine herbicide used predominantly on corn, sorghum, and sugarcane in the US. Its use potentially overlaps with the ranges of listed (threatened and endangered) species. In response to registration review in the context of the Endangered Species Act, we evaluated potential direct and indirect impacts of atrazine on listed species and designated critical habitats. Atrazine has been widely studied, extensive environmental monitoring and toxicity data sets are available, and the spatial and temporal uses on major crops are well characterized. Ranges of listed species are less well-defined, resulting in overly conservative designations of "May Effect". Preferences for habitat and food sources serve to limit exposure among many listed animal species and animals are relatively insensitive. Atrazine does not bioaccumulate, further diminishing exposures among consumers and predators. Because of incomplete exposure pathways, many species can be eliminated from consideration for direct effects. It is toxic to plants, but even sensitive plants tolerate episodic exposures, such as those occurring in flowing waters. Empirical data from long-term monitoring programs and realistic field data on off-target deposition of drift indicate that many other listed species can be removed from consideration because exposures are below conservative toxicity thresholds for direct and indirect effects. Combined with recent mitigation actions by the registrant, this review serves to refine and focus forthcoming listed species assessment efforts for atrazine.Abbreviations: a.i. = Active ingredient (of a pesticide product). AEMP = Atrazine Ecological Monitoring Program. AIMS = Avian Incident Monitoring SystemArach. = Arachnid (spiders and mites). AUC = Area Under the Curve. BE = Biological Evaluation (of potential effects on listed species). BO = Biological Opinion (conclusion of the consultation between USEPA and the Services with respect to potential effects in listed species). CASM = Comprehensive Aquatic System Model. CDL = Crop Data LayerCN = field Curve Number. CRP = Conservation Reserve Program (lands). CTA = Conditioned Taste Avoidance. DAC = Diaminochlorotriazine (a metabolite of atrazine, also known by the acronym DACT). DER = Data Evaluation Record. EC25 = Concentration causing a specified effect in 25% of the tested organisms. EC50 = Concentration causing a specified effect in 50% of the tested organisms. EC50RGR = Concentration causing a 50% reduction in relative growth rate. ECOS = Environmental Conservation Online System. EDD = Estimated Daily Dose. EEC = Expected Environmental Concentration. EFED = Environmental Fate and Effects Division (of the USEPA). EFSA = European Food Safety Agency. EIIS = Ecological Incident Information System. ERA = Environmental Risk Assessment. ESA = Endangered Species Act. ESU = Evolutionarily Significant UnitsFAR = Field Application RateFIFRA = Federal Insecticide, Fungicide, and Rodenticide Act. FOIA = Freedom of Information Act (request). GSD = Genus Sensitivity Distribution. HC5 = Hazardous Concentration for ≤ 5% of species. HUC = Hydrologic Unit Code. IBM = Individual-Based Model. IDS = Incident Data System. KOC = Partition coefficient between water and organic matter in soil or sediment. KOW = Octanol-Water partition coefficient. LC50 = Concentration lethal to 50% of the tested organisms. LC-MS-MS = Liquid Chromatograph with Tandem Mass Spectrometry. LD50 = Dose lethal to 50% of the tested organisms. LAA = Likely to Adversely Affect. LOAEC = Lowest-Observed-Adverse-Effect Concentration. LOC = Level of Concern. MA = May Affect. MATC = Maximum Acceptable Toxicant Concentration. NAS = National Academy of Sciences. NCWQR = National Center of Water Quality Research. NE = No Effect. NLAA = Not Likely to Adversely Affect. NMFS = National Marine Fisheries Service. NOAA = National Oceanic and Atmospheric Administration. NOAEC = No-Observed-Adverse-Effect Concentration. NOAEL = No-Observed-Adverse-Effect Dose-Level. OECD = Organization of Economic Cooperation and Development. PNSP = Pesticide National Synthesis Project. PQ = Plastoquinone. PRZM = Pesticide Root Zone Model. PWC = Pesticide in Water Calculator. QWoE = Quantitative Weight of Evidence. RGR = Relative growth rate (of plants). RQ = Risk Quotient. RUD = Residue Unit Doses. SAP = Science Advisory Panel (of the USEPA). SGR = Specific Growth Rate. SI = Supplemental Information. SSD = Species Sensitivity Distribution. SURLAG = Surface Runoff Lag Coefficient. SWAT = Soil & Water Assessment Tool. SWCC = Surface Water Concentration Calculator. UDL = Use Data Layer (for pesticides). USDA = United States Department of Agriculture. USEPA = United States Environmental Protection Agency. USFWS = United States Fish and Wildlife Service. USGS = United States Geological Survey. WARP = Watershed Regressions for Pesticides.

Trophic Transfer and Accumulation of Multiwalled Carbon Nanotubes in the Presence of Copper Ions in Daphnia magna and Fathead Minnow (Pimephales promelas).

The increase in use of nanomaterials such as multiwalled carbon nanotubes (MWCNTs) presents a need to study their interactions with the environment. Trophic transfer was measured between Daphnia magna and Pimephales promelas (fathead minnow, FHM) exposed to MWCNTs with different outer diameter (OD) sizes (MWCNT1 = 8-15 nm OD and MWCNT2 = 20-30 nm OD) in the presence and absence of copper. Pristine FHM were fed D. magna, previously exposed for 3 d to MWCNT1 or MWCNT2 (0.1 mg/L) and copper (0.01 mg/L), for 7 d. D. magna bioaccumulated less MWCNT1 (0.02 µg/g) than MWCNT2 (0.06 µg/g), whereas FHM accumulated more MWCNT1 (0.81 µg/g) than MWCNT2 (0.04 µg/g). In the presence of copper, MWCNT bioaccumulation showed an opposite trend. Mostly MWCNT1 (0.03 µg/g) bioaccumulated in D. magna, however less MWCNT1 (0.21 µg/g) than MWCNT2 (0.32 µg/g) bioaccumulated in FHM. Bioaccumulation factors were higher for MWCNT1s than MWCNT2. However, an opposite trend was observed when copper was added. Plasma metallothionein-2 was measured among treatments; however concentrations were not statistically different from the control. This study demonstrates that trophic transfer of MWCNTs is possible in the aquatic environment and further exploration with mixtures can strengthen the understanding of MWCNT environmental behavior.

Advancing ecotoxicological studies: Utilizing new approach methodologies to enable cross-species extrapolation and reduce avian testing.

Ecological risk assessments of agrochemicals have traditionally depended on in vivo guideline tests using northern bobwhite and mallard to provide relevant endpoints for avian species. However, these studies have limitations, including animal welfare concerns, the time and cost involved, limited potential for extrapolation to more realistic exposure conditions, and the lack of mechanistic understanding. The proof-of-concept work presented a case study for thiamethoxam in three avian species, demonstrating the potential of physiologically based kinetic (PBK) modeling to enable dosimetry extrapolations that inform hazard characterization in risk assessment, and reduce the use of avian testing. The model structure for northern bobwhite and mallard contained ten compartments, while an additional ovulation model was included for chicken in the physiological state of egg-laying. The model was first parameterized and evaluated for chicken and northern bobwhite using in vitro kinetic measurements and in vivo toxicokinetic (TK) data. The chicken model was then extrapolated to mallard based on allometric scaling. The models were then used to map the TK profiles across species by simulating internal dose metrics in different avian toxicology studies. These metrics, including peak blood concentrations (Cmax) and area under the curve (AUC) for blood concentration, were determined for acute, subacute, or chronic toxicity endpoints for mallard and northern bobwhite, enabling a quantitative cross-species and cross-route comparison of dosimetry. The results suggested that the chronic toxicological response of birds exposed to thiamethoxam is highly dependent on internal exposure, while mallard appeared to be more dynamically sensitive to thiamethoxam on an acute oral exposure basis. The case study increases the confidence in using new approach methodologies (NAMs) for interpreting avian toxicity studies and facilitating in vitro-in silico-based ecological risk assessments of agrochemicals.

Use of dry bean fields by birds and mammals in Brazil: Insights from a field study and its use in pesticide risk assessment.

The relationship between agriculture and wildlife can be both synergetic and challenging, as the increased surface of agricultural land makes it increasingly important for agriculture and wildlife to coexist. This study aims to describe the use of freshly drilled dry bean fields by birds and mammals in Brazilian Cerrado and Atlantic Forest sites and their diversity and abundance within in-crop and off-crop areas (with native permanent vegetation and other surrounding crop fields) at four different farms. A comprehensive survey was conducted, using various sampling methods, including point counts, foraging counts, trail cameras, and occasional encounters. In all, contacts for 12 518 birds across 306 species and 313 mammals across 34 species were registered. The off-crop areas exhibited greater species richness, abundance, and diversity than the in-crop areas on all farms. For birds, 47 species were recorded in-crop, of which 15 were classified as insectivores, 15 as granivores, seven as omnivores, seven as carnivores, and three as frugivores. The number of in-crop observations per species was small. The abundance off-crop was greater for 31 species observed in-crop, indicating that dry bean fields are probably not a preferred habitat for those species. Species classified as granivorous are most likely to feed on dry bean seeds. However, almost all granivorous species observed in-crop areas are too small to be able to feed on dry bean seeds. For mammals, nine species were recorded in-crop, of which four were classified as carnivores, three as omnivores, one as insectivore, and one as granivore. Additionally, despite the considerable effort in this study, no evidence was found that birds and mammals feed on dry bean seeds. The results highlight the importance of off-crop areas in dry bean fields, characterized by a more diverse and abundant bird community than in-crop. Integr Environ Assess Manag 2024;20:864-874. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Development of a mechanistic model for analyzing avian reproduction data for pesticide risk assessment.

Mechanistic effect models are increasingly recommended as tools for refining evaluations of risk from exposure to pesticides. In the context of bird and mammal risk assessments, DEB-TKTD models have been recommended for characterizing sublethal effects at lower tiers. However, there are currently no such models. Currently, chronic, multi-generational studies are performed to characterize potential effects of pesticides on avian reproduction, but it is has not been established to what extent results from these studies can inform effect models. Here, a standard Dynamic Energy Budget (DEB) model was extended to account for the avian toxicity endpoints observed in regulatory studies. We linked this new implementation to a toxicological module to capture observed pesticide effects on reproduction via a decreased efficiency of egg production. We analysed ten reproduction studies with five different pesticides conducted with the mallard (Anas platyrhynchos) and the northern bobwhite (Colinus virginianus). The new model implementation accurately distinguished between effects on egg production from direct mechanism of toxicity and from food avoidance. Due to the specific nature of regulatory studies, model applicability for risk refinement is currently limited. We provide suggestions for next steps in model development.

Natural and anthropogenic factors and their interactions drive stream community integrity in a North American river basin at a large spatial scale.

Urbanization, agriculture, and other human activities can exert considerable influence on the health and integrity of stream ecosystems. These influences vary greatly over space, time, and scale. We investigated trends in stream biotic integrity over 19 years (1997-2016) in relation to natural and anthropogenic factors in their spatial context using data from a stream biomonitoring program in a region dominated by agricultural land use. Macroinvertebrate and fish diversity and abundance data were used to calculate four multimetric indices (MMIs) that described biotic integrity of streams from 1997 to 2016. Boosted regression trees (BRT), a machine learning technique, were used to model how stream integrity responded to catchment-level natural and anthropogenic drivers including land use, human population density, road density, runoff potential, and natural factors such as latitude and elevation. Neither natural nor anthropogenic factors were consistently more influential on the MMIs. Macroinvertebrate indices were most responsive to time, latitude, elevation, and road density. Fish indices were driven mostly by latitude and longitude, with agricultural land cover among the most influential anthropogenic factors. We concluded that 1) stream biotic integrity was mostly stable in the study region from 1997 to 2016, although macroinvertebrate MMIs had decreased approximately 10% since 2010; 2) stream biotic integrity was driven by a mix of factors including geography, human activity, and variability over yearly time intervals; 3) MMI responses to environmental drivers were nonlinear and often nonmonotonic; 4) MMI composition could influence causal inferences; and 5) although our findings were mostly consistent with the literature on drivers of stream integrity, some commonly seen patterns were not evident. Our findings highlight the utility of large-scale, publicly available spatial data for understanding drivers of stream biodiversity and illustrate some potential pitfalls of large scale, integrative analyses.

Atrazine and estradiol effects on development of Acris blanchardi (Blanchard's cricket frog) exposed in outdoor enclosures.

BACKGROUND: The herbicide atrazine has been proposed as a potential endocrine disrupting compound (EDC) for amphibians. Using atrazine concentrations below or at those typically found in surface waters (0.5, 5.0, 50 µg/L), we exposed Acris blanchardi (Blanchard's cricket frog) larvae throughout development until metamorphosis (i.e. Gosner stages 26-45). An additional 50 µg/L treatment (50s µg/L) was utilized where supplemented algae was added to control for indirect atrazine effects from reduced food sources. In addition to atrazine, experimental groups also included a negative control and two positive controls, 17ß-estradiol (E2) at 2.3 and 25 µg/L. At 60 days post-metamorphosis, A. blanchardi metamorphs were euthanized for analysis of gross and histopathological development. RESULTS: Atrazine did not significantly influence mortality (mean recovery of 54% across treatments), sex ratio, body mass (BM), snout-vent length (SVL), gonad size, nor gonad development of A. blanchardi. Females exposed to 50s µg/L atrazine had 29% less mass, were 10% shorter, and had a 29% lower mean ovary area (mm2 ) as compared to negative controls, suggesting algae enrichment had a significant negative effect. Males exposed to estradiol (25 µg/L) showed an increased level of oviduct development. Ovary area was also significantly influenced by estradiol treatment at 2.3 and 25 µg/L. CONCLUSION: Overall, estradiol had much less effect than predicted based on other model species (e.g. Xenopus laevis). Development of A. blanchardi, overall, was not affected by long-term exposure to environmentally relevant concentrations of atrazine. However, this species also was largely insensitive to exogenous estradiol in this test system. © 2022 Society of Chemical Industry.

Effects of chronic 2,4,6,-trinitrotoluene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene exposure on developing bullfrog (Rana catesbeiana) tadpoles.

Chronic aqueous exposures were conducted using bullfrog (Rana catesbeiana) tadpoles (8 d old) exposed to TNT (0-4 mg/L), 2,4-DNT (0-4 mg/L), and 2,6-DNT (0-8 mg/L) for 90 d. Survival of tadpoles examined using Cox proportional hazard models was reduced at all concentrations tested. Percent of abnormal swimming and other morphological abnormalities after sublethal exposure to TNT, 2,4-DNT, and 2,6-DNT at 2 mg/L were also evaluated. The effects of TNT, 2,4-DNT, and 2,6-DNT on wet body mass, snout vent length (SVL), and developmental stage of surviving tadpoles were examined. Only 2,4-DNT did not have a significant effect on body mass or SVL, but all three compounds tested had significant effects on survival. Long-term continuous exposure to these compounds at concentrations of 0.25 mg/L could lead to significant changes in growth and survival of larval amphibians.

Uptake of 17α-ethynylestradiol and triclosan in pinto bean, Phaseolus vulgaris.

Pharmaceuticals and personal care products (PPCPs) have emerged as a group of potential environmental contaminants of concern. PPCPs in soil may enter terrestrial food webs via plant uptake. We evaluated uptake of 17α-ethynylestradiol (EE2) and triclosan in bean plants (Phaseolus vulgaris) grown in sand and soil. The extent of uptake and accumulation of EE2 and triclosan in plants grown in sand was higher than in plants grown in soil. In sand (conditions of maximum contaminant bioavailability), bioconcentration factors (BCFs) of EE2 and triclosan in roots (based on dry weights) were 1424 and 16,364, respectively, whereas BCFs in leaves were 55 for EE2 and 85 for triclosan. In soil, the BCF of EE2 decreased from 154 in the first week to 32 in the fourth week while it fluctuated in leaves from 18 to 20. The BCF for triclosan in plants grown in soil increased over time to 12 in roots and 8 in leaves. These results indicate that the potential for uptake and accumulation of PPCPs in plants exists. This trophic transfer pathway should be considered when assessing exposure to certain PPCPs, particularly with the use of recycled wastewater for irrigation.

Effects of ZnO nanomaterials on Xenopus laevis growth and development.

The objectives of this study were to quantify uptake and developmental effects of zinc oxide nanomaterials (nano-ZnO) on Xenopus laevis throughout the metomormosis process. To accomplish this, X. laevis were exposed to aqueous suspensions of 40-100 nm nano-ZnO beginning in-ovo and proceeding through metamorphosis. Nanomaterials were dispersed via sonication methods into reconstituted moderately hard water test solutions. A flow-through system was utilized to decrease the likelihood of depletion in ZnO concentration. Exposure to 2 mg/L nano-ZnO significantly increased mortality incidence to 40% and negatively affected metamorphosis of X. laevis. Tadpoles exposed to 2 mg/L nano-ZnO developed slower as indicated by tadpoles with an average stage of 56 at the conclusion of the study which was significantly lower than the control tadpole stages. No tadpoles exposed to 2 mg/L of nano-ZnO completed metamorphosis by the conclusion of the study. Tadpoles exposed to 0.125 mg/L nano-ZnO experienced faster development along with larger body measurements indicating that low dose exposure to nano-ZnO can stimulate growth and metamorphosis of X. laevis.

Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO2) to earthworms (Eisenia fetida).

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.

Evaluating a developmental endocrine toxicity assay for Blanchard's cricket frog (Acris blanchardi) in outdoor enclosures.

A developmental toxicity testing design was evaluated for larval and post-metamorphic Blanchard's cricket frogs (Acris blanchardi) raised in outdoor enclosures. Larvae were chronically exposed to 17ß-estradiol (0.0-2.3 µg/L E2) from free swimming (Gosner stage 26) until metamorphosis. Juvenile frogs were allowed to mature within the enclosures for 60 days to assess effects of larval exposure on development, including body mass, snout-vent length (SVL), sex ratio, gonad size, and gonadal histopathology. Forty-eight percent of the initial 600 animals were recovered at the end of the study. Recovery was not influenced by E2 exposure, but larval losses were negatively impacted by unusually high spring rain events that flooded some larval tanks, and heat-related mortality of late stage larvae during summer. All surviving larvae completed metamorphosis within an average of 47 days. Overall, E2 exposure did not influence sex ratio, or the body mass, SVL, or gonad size of either males or females. Development of testes was not influenced by E2 exposure, but oviduct development in males was 4.5-fold greater in the highest treatment. Oviduct and ovary development in females exposed to the two highest E2 treatments were half that of control females. Although not treatment related and despite ad-lib feeding, variation in terminal body mass and SVL within enclosures was pronounced, with minimum - maximum differences ranging from 207 to 1442 mg for body mass and 1 mm to 15 mm for SVL. This design allowed us to assess the effects of larval exposure to a contaminant on post-metamorphic development of a native amphibian in a semirealistic field environment. With modifications to decrease flooding or overheating, this enclosure design and species is a good test system for assessing contaminant effects on development of an amphibian from early larval stages through reproductive maturity.

Identifying the causes of sediment-associated contamination in the Illinois River (USA) using a whole-sediment toxicity identification evaluation.

Whole-sediment toxicity identification evaluation (TIE) techniques were employed on the Illinois River Complex (IRC), USA to identify the sources of sediment toxicity that may have contributed to the decline in benthic invertebrate populations. The TIE focused on three classes of contaminants: ammonia, metals, and organics. Sediment toxicity was assessed using the amphipod Hyalella azteca, and the focus of the TIE was on assessing spatial and temporal patterns of contamination. Past studies suggested that ammonia was the major source of contamination in IRC sediments. However, the present study suggested that polycyclic aromatic hydrocarbons (PAHs) were the primary contributor to sediment toxicity. Phase I testing showed 46% of the site trials (12 of 26) exhibited increased H. azteca survival (p < 0.05) with the addition of powdered coconut charcoal (organic amendment), whereas zeolite (ammonia amendment) and Resin Tech SIR 300 (cationic metals amendment) did not increase H. azteca survival. Phase II testing revealed PAH concentrations were high enough to cause the observed toxicity, confirming phase I results. Spatially, sediment toxicity as well as pore-water ammonia concentrations declined with distance downstream from suspected contaminant sources, indicating a potential dilution or remedial effect. Temporally, pore-water ammonia, metals, and PAH concentrations varied among sampling periods over an annual cycle for some sites near urbanized areas, while remaining temporally consistent at others. The results of the present study provide new information on the sources of toxicity within the IRC, and demonstrate the importance of evaluating spatial and temporal aspects in sediment TIEs. This is particularly important for evaluations in riverine systems in which hydrologic processes can result in large variation in sediment toxicity on temporal and spatial scales.

Monitoring cyanobacterial toxins in a large reservoir: relationships with water quality parameters.

Cyanobacteria are widely distributed in fresh, brackish, and ocean water environments, as well as in soil and on moist surfaces. Changes in the population of cyanobacteria can be an important indicator of alterations in water quality. Metabolites produced by blooms of cyanobacteria can be harmful, so cell counts are frequently monitored to assess the potential risk from cyanobacterial toxins. A frequent uncertainty in these types of assessments is the lack of strong relationships between cell count numbers and algal toxin concentrations. In an effort to use ion concentrations and other water quality parameters to determine the existence of any relationships with cyanobacterial toxin concentrations, we monitored four cyanobacterial toxins and inorganic ions in monthly water samples from a large reservoir over a 2-year period. Toxin concentrations during the study period never exceeded safety limits. In addition, toxin concentrations at levels above the limit of quantitation were infrequent during the 2-year sampling period; non-detects were common. Microcystin-LA was the least frequently detected analyte (86 of 89 samples were ND), followed by the other microcystins (microcystin-RR, microcystin-LR). Cylindrospermopsin and saxitoxin were the most frequently detected analytes. Microcystin and anatoxin concentrations were inversely correlated with Cl-, SO 4 - 2 , Na+, and NH 4 + , and directly correlated with turbidity and total P. Cylindrospermopsin and saxitoxin concentrations in water samples were inversely correlated with Mg+2 and directly correlated with water temperature. Results of our study are expected to increase the understanding of potential relationships between human activities and water quality.

Partitioning and matrix-specific toxicity of bifenthrin among sediments and leaf-sourced organic matter.

Synthetic pyrethroids readily partition from the aqueous to the solid phase in aquatic systems. Previous work has focused on pyrethroid partitioning to sediment matrices. Within many aquatic systems, however, other carbon-containing materials are present and can be critically important to certain invertebrate species and ecosystem functioning. For example, some invertebrates readily process leaf material, and these processes may represent an additional route of contaminant exposure. To our knowledge, estimates for partitioning of pyrethroids to these nondissolved organic matter matrices and associated toxicity have not been examined. The objectives of the present study were to examine variation in organic carbon (OC)-based partition coefficient (K(OC)) among three size fractions of particulate organic matter from sugar maple (Acer saccharum) leaf litter and sediments for the pyrethroid insecticide bifenthrin and to examine variation in toxicity to Hyalella azteca among bifenthrin-bound organic matter matrices and sediment. Log K(OC) of [(14)C]bifenthrin was greatest within sediment (6.63+/-0.23; mean +/- standard deviation throughout) and lowest in coarse particulate leaf material (4.86+/-0.03). The H. azteca median lethal concentration was 0.07, 0.11, and 0.15 microg/g OC for leaf material, sediment, and a 50% mix of leaf and sediment, respectively. Nonoverlapping 95% confidence intervals occurred between the leaf treatment and the leaf-sediment treatment. This pattern was supported in an additional experiment, and at 0.22 microg/g OC, H. azteca survival was greater in the leaf-sediment mixture than in sediment or in leaf material alone (F=29.5, p<0.0001). In systems that contain sediment and leaf material, both greater partitioning of bifenthrin to the sediment fraction and preferential use of leaf substrates may drive H. azteca survival.

Effect of sediment-associated pyrethroids, fipronil, and metabolites on Chironomus tentans growth rate, body mass, condition index, immobilization, and survival.

Pyrethroids and fipronil insecticides partition to sediment and organic matter in aquatic systems and may pose a risk to organisms that use these matrices. It has been suggested that bioavailability of sediment-sorbed pesticides is reduced, but data on toxicity of sediment-associated pesticides for pyrethroids and fipronil are limited. In the current study, 10-d sediment exposures were conducted with larval Chironomus tentans for bifenthrin, lambda-cyhalothrin, permethrin, fipronil, fipronil-sulfide, and fipronil-sulfone, the last two being common fipronil metabolites. Sublethal endpoints included immobilization, instantaneous growth rate (IGR), body condition index, and growth estimated by ash-free dry mass (AFDM). Pyrethroid lethal concentrations to 50% of the population (LC50s) were 6.2, 2.8, and 24.5 microg/g of organic carbon (OC) for bifenthrin, lambda-cyhalothrin, and permethrin, respectively; with the former two lower than previously published estimates. Fipronil, fipronil-sulfide, and fipronil-sulfone LC50 values were 0.13, 0.16, and 0.12 microg/g of OC, respectively. Ratios of LC50s to sublethal endpoints (immobilization, IGR, and AFDM) ranged from 0.90 to 9.03. The effects on growth observed in the present study are important because of the unique dipteran life cycle involving pupation and emergence events. Growth inhibition would likely lead to ecological impacts similar to mortality (no emergence and thus not reproductively viable) but at concentrations up to 4.3 times lower than the LC50 for some compounds. In addition, C. tentans was highly sensitive to fipronil and metabolites, suggesting that dipterans may be important for estimating risk and understanding effects of phenylpyrazole-class insecticides on benthic macroinvertebrate communities.

Derivation of avian dermal LD50 values for dermal exposure models using in vitro percutaneous absorption of [14C]-atrazine through rat, mallard, and northern bobwhite full thickness skin.

Understanding dermal exposure is important for higher-tier avian ecological risk assessments. However, dermal exposure and toxicity are often unknown for avifauna. The US EPA's Terrestrial Investigation Model (TIM) uses a method to estimate avian dermal LD50 values (and ultimately dermal exposure) that frequently results in unusually high dermal exposure and low dermal LD50 estimates. This is primarily a result of using organophosphate and carbamate toxicity data to develop the oral-dermal relationship. An estimated dermal LD50 is necessary to generate a dermal route equivalency factor that normalizes potency relative to oral toxicity within the dermal pathway dose equation. In this study, atrazine dermal absorption experiments were conducted with mallard, northern bobwhite, and rat skin. These data were used to derive an avian-mammal dermal route equivalency factor for atrazine and introduce a new approach for estimating dermal LD50 values and ultimately predicting exposure via the TIM dermal pathway. Compared to the default TIM method, this new approach yielded TIM output with lower mean total dose, lower dermal fraction of total dose, greater oral fraction of total dose, and reduced model predicted mortality for atrazine. In addition, the new approach was compared with other methods for estimating avian dermal LD50 values such as those proposed for use with mammalian data and physico-chemical properties and a triazine-specific oral-dermal equation using mammalian LD50 data. The three alternative approaches resulted in output similar to one another and different from the default TIM methods. These results indicate that a dermal route equivalency factor derived from empirical data provides a higher avian dermal LD50 estimate that is consistent with other methods. In addition, the use of this dermal route equivalency factor results in greatly reduced modeled atrazine risk to birds than previously reported in US EPA risk assessments using TIM.

Relative Abundance Trends of Bird Populations in High Intensity Croplands in the Central United States.

Declining bird populations across the United States have been noted in a number of studies. Although multiple explanations have been proposed as causes of these declines, agricultural intensification has often been suggested as a significant driver of bird population dynamics. Using spatially explicit USDA-NASS Cropland Data Layer, we examined this relationship by comparing bird count data from the Breeding Bird Survey collected between 1995 and 2016 across 13 states in the central United States to corresponding categorical changes in land cover within a 2-km radius of each survey transect. This approach allowed us to compare the slopes of counts for 31 species of birds between grassland- and cropland-dominated landscapes and against increasing levels of cropland (all types combined) and pooled corn and soybean land cover types. Nearly all birds demonstrated significant responses to land cover changes. In all cases, the number of species exhibiting positive or negative responses was comparable, and median differences in percent change per year ranged from -0.5 to 0.7%. Species that responded either positively or negatively did not appear to fall into any particular foraging guild. If changes in agricultural practices are a major cause of declines, we would expect to see it across the spatial scale studied and across the majority of species. While these results do not rule out potential agricultural effects, such as toxicity resulting from pesticide exposure, which may have species-specific or localized effects, a variety of factors related to habitat are likely the most significant contributor overall. Given these results over a large spatial scale basis (multistate) and across numerous bird species, there is not a broad general trend of greater decline in crop-intensive areas. Integr Environ Assess Manag 2018;14:692-702. © 2018 SETAC.

Comprehensive characterization of the acute and chronic toxicity of the neonicotinoid insecticide thiamethoxam to a suite of aquatic primary producers, invertebrates, and fish.

Thiamethoxam is a neonicotinoid insecticide used widely in agriculture to control a broad spectrum of chewing and sucking insect pests. Recent detection of thiamethoxam in surface waters has raised interest in characterizing the potential impacts of this insecticide to aquatic organisms. We report the results of toxicity testing (acute and chronic) conducted under good laboratory practices for more than 30 freshwater species (insects, molluscs, crustaceans, algae, macrophytes, and fish) and 4 marine species (an alga, a mollusc, a crustacean, and a fish). As would be anticipated for a neonicotinoid, aquatic primary producers and fish were the least sensitive organisms tested, with acute median lethal and effect concentrations (LC50/EC50) observed to be ≥80 mg/L in all cases, which far exceeds surface water exposure concentrations. Tested molluscs, worms, and rotifers were similarly insensitive (EC50 ≥ 100 mg/L), except for Lumbriculus sp., with an EC50 of 7.7 mg/L. In general, insects were the most sensitive group in the study, with most acute EC50 values < 1 mg/L. However, the crustaceans Asellus aquaticus and Ostracoda exhibited a sensitivity similar to that of insects (acute EC50 < 1 mg/L), and the midge larvae Chaoborus sp. were relatively insensitive compared with other insects (EC50 > 5.5 mg/L). The most sensitive chronic response was for Chironomus riparius, with a 30-d no-observed-effect concentration (NOEC; emergence) of 0.01 mg/L. Observed toxicity to the tested marine organisms was comparable to that of freshwater species. We used the reported data to construct species sensitivity distributions for thiamethoxam, to calculate 5% hazard concentrations (HC5s) for acute data (freshwater invertebrates), and compared these with measured concentrations from relevant North American surface waters. Overall, based on acute toxicity endpoints, the potential acute risk to freshwater organisms was found to be minimal (likelihood of exceeding HC5s < 1%). Environ Toxicol Chem 2017;36:2838-2848. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Bioaccumulation, stress, and swimming impairment in Daphnia magna exposed to multiwalled carbon nanotubes, graphene, and graphene oxide.

The use of carbon-based nanomaterials (CNMs) such as multiwalled carbon nanotubes (MWCNTs), graphene, and graphene oxide (GO) is increasing across many applications because of their unique and versatile properties. These CNMs may enter the aquatic environment through many pathways, creating the potential for organism exposure. The present study addresses the bioaccumulation and toxicity seen in Daphnia magna exposed to CNMs dispersed in sodium dodecyl benzene sulfonate (SDBS). In study I, D. magna were exposed to varying outer diameters of MWCNTs for 24 h in moderately hard or hard freshwater. Bioaccumulation of MWCNT was found in all treatments, with the highest concentrations (0.53 ± 0.27 µg/g) in D. magna exposed in hard freshwater (p < 0.005). The median lethal concentration (LC50) was determined for D. magna exposed to CNMs in moderately hard and hard freshwater. In study II, D. magna were exposed to CNMs for 72 h in moderately hard freshwater to assess swimming velocity and generation of reactive oxygen species (ROS) detected by dichlorofluorescein fluorescence. An overall decrease was seen in D. magna swimming velocity after exposure to CNMs. The generation of ROS was significantly higher (1.54 ± 0.38 dichlorofluorescein mM/mg dry wt) in D. magna exposed to MWCNTs of smaller outer diameters than in controls after 72 h (p < 0.05). These results suggest that further investigation of CNM toxicity and behavior in the aquatic environment is needed. Environ Toxicol Chem 2017;36:2199-2204. © 2017 SETAC.