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.

Derivation of combined species sensitivity distributions for acute toxicity of pyrethroids to aquatic animals.

The aquatic toxicity profiles of synthetic pyrethroid insecticides are remarkably similar, and results for a large number of species can be combined across compounds in Species Sensitivity Distributions (SSDs). Normalizing acute toxicity values (median lethal concentrations, LC50s) for each species and each pyrethroid to the LC50 of the same pyrethroid to the freshwater amphipod Hyalella azteca (the most sensitive species to all pyrethroids tested) enabled expression of LC50s as Hyalella equivalents that can be pooled across pyrethroids. The resulting normalized LC50s (geometric means for each species across pyrethroids) were analyzed using SSDs. Based on tests with measured exposure concentrations, the fifth percentiles (Hazard Concentrations, HC5s) of the SSDs were 4.8 Hyalella equivalents for arthropods (36 species) and 256 Hyalella equivalents for fish (24 species). HC5 values are useful as effects metrics for screening-level risk assessments, and the full SSDs can be integrated with estimated exposure distributions for higher-level risk characterization. The combined pyrethroid SSDs provide a more taxonomically representative and statistically robust basis for risk characterization than data for the most sensitive single species or SSDs based on data for a single pyrethroid alone, and are especially useful for pyrethroids that have been tested with smaller numbers of species.

Data quality scoring system for microcosm and mesocosm studies used to derive a level of concern for atrazine.

The US Environmental Protection Agency (USEPA) has historically used different methods to derive an aquatic level of concern (LoC) for atrazine, though all have generally relied on an expanding set of mesocosm and microcosm ("cosm") studies for calibration. The database of results from ecological effects studies with atrazine in cosms now includes 108 data points from 39 studies and forms the basis for assessing atrazine's potential to impact aquatic plant communities. Inclusion of the appropriate cosm studies and accurate interpretation of each data point-delineated as binary scores of "effect" (effect score 1) or "no effect" (effect score 0) of a specific atrazine exposure profile on plant communities in a single study-is critical to USEPA's approach to determining the LoC. We reviewed the atrazine cosm studies in detail and carefully interpreted their results in terms of the binary effect scores. The cosm database includes a wide range of experimental systems and study designs, some of which are more relevant to natural plant communities than others. Moreover, the studies vary in the clarity and consistency of their results. We therefore evaluated each study against objective criteria for relevance and reliability to produce a weighting score that can be applied to the effect scores when calculating the LoC. This approach is useful because studies that are more relevant and reliable have greater influence on the LoC than studies with lower weighting scores. When the current iteration of USEPA's LoC approach, referred to as the plant assemblage toxicity index (PATI), was calibrated with the weighted cosm data set, the result was a 60-day LoC of 21.2 µg/L. Integr Environ Assess Manag 2018;14:489-497. © 2018 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Properties and uses of chlorpyrifos in the United States.

Physical properties and use data provide the basis for estimating environmental exposures to chlorpyrifos (CPY) and for assessing its risks. The vapor pressure ofCPY is low, solubility in water is <1 mg L-1, and its log Kow is 5. Chlorpyrifos has short to moderate persistence in the environment as a result of several dissipation pathways that may proceed concurrently. Primary mechanisms of dissipation include volatilization, photolysis, abiotic hydrolysis, and microbial degradation.Volatilization dominates dissipation from foliage in the initial 12 h after application,but decreases as CPY adsorbs to foliage or soil. In the days after application, CPY adsorbs more strongly to soil, and penetrates more deeply into the soil matrix,becoming less available for volatilization. After the first 12 h, other processes of degradation, such as chemical hydrolysis and catabolism by microbiota become important. The half-life of CPY in soils tested in the laboratory ranged from 2 toI ,575 d (N = 126) and is dependent on properties of the soil and rate of application.At application rates used historically for control of termites, the degradation rate is much slower than for agricultural uses. In agricultural soils under field conditions,half-lives are shorter (2 to 120 d, N=58). The mean water-soil adsorption coefficient(Koc) of CPY is 8,216 mL g-1; negligible amounts enter plants via the roots,and it is not translocated in plants. Half-lives for hydrolysis in water are inversely dependent on pH, and range from 16 to 73 d. CPY is an inhibitor of acetylcholinesterase and is potentially toxic to most animals. Differences in susceptibility result from differences in rates of adsorption,distribution, metabolism, and excretion among species. CPY is an important tool in management of a large number of pests (mainly insects and mites) and is used on a wide range of crops in the U.S. Estimates of annual use in the U.S. from 2008 to 2012 range from 3.2 to 4.1 M kg y-1, which is about 50% less than the amount used prior to 2000. Applications to corn and soybeans accounts for 46-50%of CYP's annual use in the U.S.

Exposures of aquatic organisms to the organophosphorus insecticide, chlorpyrifos resulting from use in the United States.

Concentrations of CPY in surface waters are an integral determinant of risk to aquatic organisms. CPY has been measured in surface waters of the U.S. in several environmental monitoring programs and these data were evaluated to characterize concentrations, in relation to major areas of use and changes to the label since 2001, particularly the removal of domestic uses. Frequencies of detection and 95th centile concentrations of CPY decreased more than fivefold between 1992 and 2010. Detections in 1992-2001 ranged from 10.2 to 53%, while 2002-2010 detections ranged from 7 to 11%. The 95th centile concentrations ranged from 0.007 to 0.056 j.lg L -I in 1992-2001 and 0.006-0.008 j.lg L -I in 2002-2010.The greatest frequency of detections occurred in samples from undeveloped and agricultural land-use classes. Samples from urban and mixed land-use classes had the smallest frequency of detections and 95th centile concentrations, consistent with the cessation of most homeowner uses in 2001. The active metabolite of CPY, CPYO, was not detected frequently or in large concentrations. In 10,375 analyses from several sampling programs conducted between 1999 and 2012, only 25 detections (0.24% of samples) of CPYO were reported and estimated concentrations were less than the LOQ.Although the monitoring data on CPY provide relevant insight in quantifying the range of concentrations in surface waters, few monitoring programs have sampled at a frequency sufficient to quantify the time-series pattern of exposure. Therefore,numerical simulations were used to characterize concentrations of CPY in water and sediment for three representative high exposure environments in the U.S. Thefate of CPY in the environment is dependent on a number of dissipation and degradation processes. In terms of surface waters, fate in soils is a major driver of the potential for runoff into surface waters and results from a number of dissipation studies in the laboratory were characterized. Aerobic degradation of CPY exhibits hi-phasic behavior in some soils; initial rates of degradation are greater than overal rates by factors of up to threefold. Along with fate in water, these data were considered in selecting parameters for the modeling concentrations in surface waters. An assessment of vulnerability to runoff was conducted to characterize the potential for CPY to be transported beyond a treated field in runoff water and eroded sediment across the conterminous U.S. A sensitivity analysis was performed on use practices of CPY to determine conditions that resulted in the highest potential runoff of CPY to aquatic systems to narrow the application practices and geographical areas of the country for selecting watersheds for detailed modeling. The selected focus-watersheds were Dry Creek in Georgia (production of pecans), Cedar Creekin Michigan (cherries), and Orestimba Creek in California (intensive agricultural uses). These watersheds provided realistic but reasonable worst-case predictions of concentrations of CPY in water and sediment.Estimated concentrations of CPY in water for the three watersheds were in general agreement with ambient monitoring data from 2002 to 20 I 0 in the datasets from US Geological Survey (USGS), California Department of Pesticide Regulation(CDPR), and Washington State Department of Ecology (WDOE). Maximum daily concentrations predicted for the watershed in California, Georgia, and Michigan were 3.2, 0.04 I, and 0.073 Jlg L -I, respectively, with the 28-d aerobic soil metabolism half-life and 4.5, 0.042, and 0. I 22 Jlg L - 1, respectively, with the 96-d soil halflife.These estimated values compared favorably with maximum concentrations measured in surface water, which ranged from 0.33 to 3.96 Jlg L -1• For sediments,the maximum daily concentrations predicted for the watersheds in California,Georgia, and Michigan were I 1.2, 0.077, and 0.058 Jlg kg-1, respectively, with the 28-d half-life and 22.8, 0.080, and 0.087 Jlg kg-1, respectively, with the 96-d soil half-life. CYP was detected in 12 samples (I 0%) out of 123 sample analyses that existed in the USGS, CDPR, and WDOE databases. The concentrations reported in these detections were from <2.0, up to 19 Jlg kg- 1, with the exception of one value reported at 58.6 Jlg kg- 1• Again, the modeled values compared favorably with these measured values. Duration and recovery intervals between toxicity threshold concentrations of 0.1 and 1.0 Jlg L - 1 were also computed. Based on modeling with the half-life of 28 d, no exceedance events were identified in the focus watersheds in Georgia or Michigan. Using the half-life of 96 d, only three events of 1-d duration only were identified in the Michigan focus-watershed. Frequency of exceedancc was greater in the California focus watershed, though the median duration was only I -d.

Risks to aquatic organisms from use of chlorpyrifos in the United States.

The risk of chlorpyrifos (CPY) to aquatic organisms in surface water of North America was assessed using measured concentrations in surface waters and modeling of exposures to provide daily concentrations that better characterize peak exposures.Ecological effects were compared with results of standard laboratory toxicity tests with single species as well as microcosm and mesocosm studies comprised of complex aquatic communities. The upper 90th centile 96-h concentrations(annual maxima) of chlorpyrifos in small streams in agricultural watersheds in Michigan and Georgia were estimated to be :-:;0.02 llg L-1; in a reasonable worstcase California watershed, the 90th centile 96-h annual maximum concentrations ranged from 1.32 to 1.54 llg L - 1• Measured concentrations of chlorpyrifos are less than estimates from simulation models. The 95th centile for more than I 0,000 records compiled by the US Geological Survey was 0.008 llg L -1• Acute toxicity endpoints for 23 species of crustaceans ranged from 0.035 to 457 llg L -I; for 18 species of aquatic insects, from 0.05 to 27 llg L -I; and for 25 species of fish, from 0.53to >806 llg L -I. The No Observed Adverse Effect Concentration (NOAECeco) in more than a dozen microcosm and mesocosm studies conducted in a variety of climatic zones, was consistently 0.1 llg L -1• These results indicated that concentrations of CPY in surface waters are rarely great enough to cause acute toxicity to even the most sensitive aquatic species. This conclusion is consistent with the lack of fish kills reported for CPY's normal use in agriculture in the U.S.Analysis of measured exposures showed that concentrations in surface waters declined after labeled use-patterns changed in 2001, and resulted in decreased risks for crustaceans, aquatic stages of insects, and fish. Probabilistic analysis of 96-h time-weighted mean concentrations, predicted by use of model simulation for three focus-scenarios selected for regions of more intense use of CPY and vulnerability to runoff, showed that risks from individual and repeated exposures to CPY in the Georgia and Michigan watersheds were de minimis. Risks from individual exposures in the intense-use scenario from California were de minimis for fish and insects and low for crustaceans. Risks from repeated exposures in the Californiain tense-use scenario were judged not to be ecologically relevant for insects and fish,but there were some risks to crustaceans. Limited data show that chlorpyrifos oxon(CPYO), the active metabolite of CPY is of similar toxicity to the parent compound.Concentrations of CPYO in surface waters are smaller than those of CPY and less frequently detected. Risks for CPYO in aquatic organisms were judged to be deminimis.Several uncertainties common to all AChE inhibitors were identified. Insufficient data were available to allow interpretation of the relevance of effects of CPY (and other pesticides that also target AChE) on behavior to assessment endpoints such as survival, growth, development, and reproduction. Data on the recovery of AChE from inhibition by CPY in fish are limited. Such data are relevant to the characterization of risks from repeated exposures, and represent an uncertainty in the assessment of risks for CPY and other pesticides that share the same target and toxico dynamics. More intensive monitoring of areas of greater use and more comprehensive models of cumulative effects that include rates of accumulation, metabolism and recovery of AChE in the more sensitive species would be useful in reducing this uncertainty.

The relative sensitivity of macrophyte and algal species to herbicides and fungicides: an analysis using species sensitivity distributions.

Lemna spp. are the standard test species representing aquatic macrophytes in the current risk assessment schemes for herbicides and plant growth regulators in the European Union and North America. At a Society of Environmental Toxicology and Chemistry (SETAC) 2008 workshop on Aquatic Macrophyte Risk Assessment for Pesticides (AMRAP), a Species Sensitivity Distribution (SSD) working group was formed to address uncertainties about the sensitivity of Lemna spp. relative to other aquatic macrophyte species. For 11 herbicides and 3 fungicides for which relevant and reliable data were found for at least 6 macrophyte species, SSDs were fitted using lognormal regression. The positions of L. gibba (the most commonly tested Lemna species) and Myriophyllum spicatum (for which standardized test methods are under development) in each SSD were determined where data were available. The sensitivity of standard algal test species required for pesticide registration in the United States under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) relative to the macrophytes in each SSD was also examined (algae were not included in the SSD). L. gibba was among the most sensitive macrophyte species for approximately 50% of the chemicals examined. M. spicatum was among the most sensitive macrophytes for approximately 25% of the chemicals. In most cases, the lowest FIFRA algal species endpoint was lower than the most sensitive macrophyte endpoint. Although no single species consistently represented the most sensitive aquatic plant species, for 12 of 14 chemicals L. gibba and the FIFRA algae included an endpoint near or below the 5th percentile of the macrophyte SSD. For the other compounds, M. spicatum was the most sensitive species of all aquatic plants considered.

Comparative aquatic toxicity of the pyrethroid insecticide lambda-cyhalothrin and its resolved isomer gamma-cyhalothrin.

In this review we compare the sensitivity of a range of aquatic invertebrate and fish species to gamma-cyhalothrin (GCH), the insecticidally active enantiomer of the synthetic pyrethroid lambda-cyhalothrin (LCH), in single-species laboratory tests and outdoor multi-species ecosystem tests. Species sensitivity distribution curves for GCH gave median HC(5) values of 0.47 ng/L for invertebrates, and 23.7 ng/L for fish, while curves for LCH gave median HC(5) values of 1.05 ng/L and 40.9 ng/L for invertebrates and fish, respectively. A model ecosystem test with GCH gave a community-level no observed effect concentration (NOEC(community)) of 5 ng/L, while model ecosystem tests with LCH gave a NOEC(community) of 10 ng/L. These comparisons between GCH and LCH indicate that the single active enantiomer causes effects at approximately one-half the concentration at which the racemate causes similar effects.

Effects analysis of time-varying or repeated exposures in aquatic ecological risk assessment of agrochemicals.

Exposure to agrochemicals in the aquatic environment often occurs as time-varying or repeated pulses. Time-varying exposures may occur due to runoff events and spray drift associated with precipitation and application events. Hydrologic dilution, dispersion, and degradation also produce pulsed exposures. Standard laboratory toxicity tests using constant exposure concentrations typically do not investigate the toxicity of time-varying or repeated exposures. Detoxification, elimination, and recovery may occur within organisms or populations during the periods between exposures. The difficulty of estimating effects of realistic time-varying exposures from measurements made under constant exposure conditions is often an important source of uncertainty in ecological risk assessment of pesticides. This article discusses the criteria and tools for deciding whether time-varying exposures are relevant in a particular risk assessment, approaches for laboratory toxicity testing with time-varying exposure, modeling approaches for addressing effects oftime-varying exposure, deterministic and probabilistic ecological risk characterization of time-varyingexposures and toxicity, and uncertainty analysis.