R. Scott Teed

Estimating the Toxicity of Pesticide Mixtures to Aquatic Organisms: A Review

ABSTRACT A major difficulty in addressing chemical mixtures through legislation or regulations revolves around our limited understanding of their potential impacts. This review provides an overview of recent research on pesticide mixture toxicity to aquatic biota and the methods employed to predict toxic effects. The most common approaches are to assume concentration-addition or independent action of chemicals in a mixture. There are a number of cases in the literature of interactions between pesticides. However, models accounting for possible interactions between mixture components are used infrequently. Although results are limited, studies investigating the effects of pesticide mixtures have not demonstrated significant synergism at environmentally relevant concentrations. Based on the results of our review, we conclude that the concentration-addition model is a generally conservative and practical first-tier model for the ecological assessment of pesticide mixtures in aquatic systems.

Refined Avian Risk Assessment for Chlorpyrifos in the United States

Refined risk assessments for birds exposed to flowable and granular formulations ofCPY were conducted for a range of current use patterns in the United States. Overall,the collective evidence from the modeling and field study lines of evidence indicate that flowable and granular CPY do not pose significant risks to the bird communities foraging in agro-ecosystems in the United States. The available information indicates that avian incidents resulting from the legal, registered uses of CPY have been very infrequent since 2002 (see SI Appendix 3). The small number of recent incidents suggests that the current labels for CPY are generally protective of birds.However, incident data are uncertain because of the difficulties associated with finding dead birds in the field and linking any mortality observed to CPY.Plowable CPY is registered for a variety of crops in the United States including alfalfa, brassica vegetables, citrus, corn, cotton, grape, mint, onion, peanut, pome and stone fruits, soybean, sugar beet, sunflower, sweet potato, tree nuts, and wheat under the trade name Lorsban Advanced. The major routes of exposure for birds to flowable CPY were consumption of treated dietary items and drinking water. The Liquid Pesticide Avian Risk Assessment Model (Liquid PARAM) was used to simulate avian ingestion of CPY by these routes of exposure. For acute exposure,Liquid PARAM estimated the maximum retained dose in each of 20 birds on each of1,000 fields that were treated with CPY over the 60-d period following initial application.The model used a 1-h time step. For species lacking acceptable acute oral toxicity data (all focal species except northern bobwhite (C. virginianus) and redwinged blackbird (A. phoeniceus)), a species sensitivity distribution (SSD) approach was used to generate hypothetical dose-response curves assuming high, median and low sensitivity to CPY. For acute risk, risk curves were generated for each use pattern and exposure scenario. The risk curves show the relationship between exceedence probability and percent mortality. The results of the Liquid PARAM modeling exercise indicate that flow able CPY poses an acute risk to some bird species, particularly those species that are highly sensitive and that forage extensively in crops with high maximum application rates (e.g., grapefruit, orange). Overall, most bird species would not experience significant mortality as a result of exposure to flowable CPY.The results of a number of field studies conducted at application rates comparable to those on the Lorsban Advanced label indicate that flowable CPY rarely causes avian mortality. The results of the field studies suggest that Liquid PARAM is likely over-estimating acute risk to birds for flowable CPY.For chronic exposure, Liquid PARAM estimated the maximum total daily intake (TDI) over a user-specified exposure duration (28-d in the case of CPY).The maximum average TDI was compared to the chronic NOEL and LOEL from the most sensitive species tested for CPY, the mallard. This comparison was done for each of the 20 birds in each of the 1000 fields simulated in Liquid PARAM.The outpu· ~ are estimates of the probabilities of exceeding the NOEL and LOEL.Liquid PAkAM did not predict significant adverse effects resulting from chronic exposure to flowable CPY. The small number of incidents (2) involving CPY reported since 2002 suggests that the current labels for CPY are generally protective of birds.Granular CPY is registered for a wide variety of crops including brassica vegetables, corn, onion, peanut, sugar beet, sunflower, and tobacco under the trade name Lorsban 15G. Consumption of grit is required by many birds to aid in digestion of hard dietary items such as seeds and insects. Because CPY granules are in the same size range as natural grit particles consumed by birds, there is a potential for birds to mistakenly ingest granular CPY instead of natural grit. We developed the Granular Pesticide Avian Risk Model (GranPARAM) to simulate grit ingestion behavior by birds. The model accounts for proportion of time that birds forage for grit in treated fields, relative proportions of natural grit versus pesticide granules onthe surface of treated fields, rates of ingestion of grit, attractiveness of pesticide granules relative to natural grit and so on. For CPY, each model simulation included20 birds on each of 1,000 fields to capture variability in rates of ingestion of grit and for aging behavior between birds within a focal species, and variability in soil composition between fields for the selected use pattern. The estimated dose for each birdwas compared with randomly chosen doses from relevant dose-response curves forCPY. Our analysis for a wide variety of use patterns on the Lorsban 15G label found that granular CPY poses little risk of causing mortality to bird species that frequent treated fields immediately after application. The predictions of the model have been confirmed in several avian field studies conducted with Lorsban 15G at application rates similar to or exceeding maximum application rates on the Lorsban 15G label.

Risks of carbamate and organophosphate pesticide mixtures to salmon in the Pacific Northwest.

Salmon populations in the Pacific Northwest are being affected by a variety of environmental stressors including intense fishing pressure, parasites and disease, climatic variability and change, land development, hatchery production, hydropower operations, stormwater runoff, and exposure to toxic contaminants. In recent years, there has been much concern that mixtures of pesticides are causing toxic effects to Pacific salmon. In this study, we compared measured stream water concentrations from 2 monitoring studies conducted in the Pacific Northwest with concentration-response curves derived for inhibition of brain acetylcholinesterase activity in juvenile coho salmon (Oncorhynchus kisutch) for mixtures of organophosphate (OPs) and carbamate (CBs) pesticides. In the first monitoring study, samples were collected from 2003 to 2007 in salmonid-bearing waters of 5 urban or agricultural watersheds in Washington State. This study was targeted to areas of high pesticide use and generally involved weekly sampling during the pesticide use season. The second monitoring study was the United States Geological Survey National Water Quality Assessment that included samples taken from 2003 to 2010 in California, Idaho, Oregon, and Washington. OPs and CBs were frequently detected in both studies. The available monitoring data collected since 2003, however, demonstrates that mixtures of OPs and CBs in surface waters rarely occur at levels capable of producing significant physiological and behavioral effects in Pacific salmon. The observed mixtures never reached concentrations capable of causing mortality. We conclude that mixtures of organophosphates and carbamates do not pose a significant direct risk to Pacific salmon.

An Ecological Risk Assessment of Phenol in the Aquatic Environment

A probabilistic ecological risk assessment of phenol was undertaken to determine the risks posed to biota as a result of phenol release to the Canadian environment. A three-tiered approach was used to estimate risks, with progressively more realistic assumptions being applied at each tier. In Canada, the major sources of phenol are municipal wastewater treatment plants, pulp, paper and wood products mills, steel and metal products facilities and refineries. Thus, the highest exposures will occur in receiving waters near these point sources, primarily due to the short half-life of phenol in the aquatic environment. Sensitive aquatic organisms include salmonids (e.g., rainbow trout Oncorhynchus mykiss) and amphibians (e.g., leopard frog Rana pipiens). The results of the risk assessment indicate that species are exposed to elevated levels of phenol near point sources, but these levels represent only a minor risk to aquatic biota.

Derivation of an ambient water quality criterion for mercury: taking account of site-specific conditions.

Mercury is considered to be a serious risk to wildlife. As a result, the Great Lakes Water Quality Initiative and others have developed ambient water quality criteria (AWQC) for the protection of wildlife. These AWQC have been controversial, however, because the AWQC were single values that did not account for site-specific conditions, derivation of the AWQC relied on a single no-observed-adverse-effect level, and the AWQC had an unknown level of conservatism because of reliance on both average and conservative assumptions and uncertainty factors. Rather than develop a single-value AWQC for total mercury, we derived an AWQC model that explicitly incorporates factors controlling bioavailability, methylation rates, and bioaccumulation in the aquatic environment (e.g., pH, dissolved organic carbon). To derive our AWQC model, field data were collected from 31 lakes in Ontario and an additional 10 lakes in Nova Scotia (North America). In the field study, levels of total and methylmercury in water and fish as well as levels of key water quality variables were determined. We conducted multiple-regression analysis to derive a model that estimates mercury levels in prey of mink. Mink are very sensitive to mercury exposure. An independent dataset consisting of 51 water bodies in the United States was then used to confirm the validity and robustness of the AWQC model. Next, we combined the results of chronic-feeding studies with similar protocols and endpoints in a meta-analysis to derive a dose-response curve for mink exposed to mercury in the diet. In the final step, we used a probabilistic risk model to estimate the concentrations of methylmercury in water that would lead to levels in fish sufficient for a 10% probability of exceeding the lethal dose affecting 5% of the mink population. The result is an AWQC equation for mercury for the protection of wildlife that can be used with a variety of site-specific conditions.

An Ecological Risk Assessment of Inorganic Chloramines in Surface Water

Inorganic chloramines are formed when chlorine and ammonia are combined in water. These substances are frequently used as a secondary disinfectant for drinking water and are by-products of processes involving the disinfection of wastewaters and the control of biological fouling in cooling water systems. For chloraminate drinking water, the total residual chlorine (TRC) concentration may be almost completely due to monochloramine. Based on 1995 and 1996 survey data, the most significant and prevalent TRC loading to the Canadian environment is from municipal wastewater releases. Drinking water releases are the next most important source of chloramine entry into the Canadian environment, while TRC releases from other sources, such as cooling water, zebra mussel control practices and industrial wastewater, are much less important. A probabilistic water quality model was used to model two wastewater discharges and a cooling water discharge to different freshwater systems. The resulting exposure distributions were then compared with three incipient lethality endpoints, i.e., 50% mortality to the invertebrate Ceriodaphnia dubia and 50% and 20% mortality to juvenile chinook salmon (Oncorhynchus tshawytscha). For each discharge scenario studied, there were moderate to high probabilities of significant adverse effects on aquatic life up to 1.9 km from the effluent sources.

Ecological risk assessment for Pacific salmon exposed to dimethoate in California

A probabilistic risk assessment of the potential direct and indirect effects of acute dimethoate exposure to salmon populations of concern was conducted for 3 evolutionarily significant units (ESUs) of Pacific salmon in California. These ESUs were the Sacramento River winter-run chinook, the California Central Valley spring-run chinook, and the California Central Valley steelhead. Refined acute exposures were estimated using the Soil and Water Assessment Tool, a river basin-scale model developed to quantify the impact of land-management practices in large, complex watersheds. Both direct effects (i.e., inhibition of brain acetylcholinesterase activity) and indirect effects (i.e., altered availability of aquatic invertebrate prey) were assessed. Risk to salmon and their aquatic invertebrate prey items was determined to be de minimis. Therefore, dimethoate is not expected to have direct or indirect adverse effects on Pacific salmon in these 3 ESUs. Environ Toxicol Chem 2017;36:532-543.

Ecological risk assessment for mink and short-tailed shrew exposed to PCBs, dioxins, and furans in the Housatonic River area

A probabilistic risk assessment was conducted to characterize risks to a representative piscivorous mammal (mink, Mustela vison) and a representative carnivorous mammal (short-tailed shrew, Blarina brevicauda) exposed to PCBs, dioxins, and furans in the Housatonic River area downstream of the General Electric (GE) facility in Pittsfield, Massachusetts. Contaminant exposure was estimated using a probabilistic total daily intake model and parameterized using life history information of each species and concentrations of PCBs, dioxins, and furans in prey collected in the Housatonic River study area. The effects assessment preferentially relied on dose-response curves but defaulted to benchmarks or other estimates of effect when there were insufficient toxicity data. The risk characterization used a weight of evidence approach. Up to 3 lines of evidence were used to estimate risks to the selected mammal species: 1) probabilistic exposure and effects modeling, 2) field surveys, and 3) species-specific feeding or field studies. The weight of evidence assessment indicated a high risk for mink and an intermediate risk for short-tailed shrew.

A PROBABILISTIC RISK ASSESSMENT FOR THE KIRTLAND'S WARBLER POTENTIALLY EXPOSED TO CHLORPYRIFOS AND MALATHION DURING THE BREEDING SEASON AND MIGRATION

Two organophosphate pesticides, chlorpyrifos and malathion, are currently undergoing reregistration in the United States and were recently used by the US Environmental Protection Agency (USEPA) as case studies to develop a national procedure for evaluating risks to endangered species. One of the endangered bird species considered by the USEPA was the Kirtlands warbler (Setophaga kirtlandii). The Kirtlands warbler is an endangered migratory species that nests exclusively in young jack pine stands in Michigan and Wisconsin, and winters in the Bahamas. We developed probabilistic models to assess the risks of chlorpyrifos and malathion to Kirtlands warblers during the breeding season and the spring and fall migrations. The breeding area model simulates acute and chronic exposure and risk to each of 10 000 birds over a 60-d period following initial pesticide application. The model is highly species specific with regard to the foraging behavior of Kirtlands warblers during the breeding season. We simulated the maximum application rate and number of applications allowed on the labels for representative use patterns that could be found within 3 km of the breeding areas of Kirtlands warbler. The migration model simulates 10 000 birds during the course of their 12- to 23-d migration between their breeding area and the Bahamas. The model takes advantage of more than a century of observations of when, where, and for how long Kirtlands warblers forage in different habitats during the course of their migration. The data indicate that warblers only infrequently stop over in habitats that could be treated with chlorpyrifos and malathion. The breeding area and migration models resulted in predictions of very low acute and chronic risk for both pesticides to Kirtlands warblers. These results were expected, given that field observations indicate that the Kirtlands warbler has dramatically increased in abundance in recent decades. Integr Environ Assess Manag 2018;14:252-269.

Deriving a water quality guideline for protection of aquatic communities exposed to triclosan in the Canadian environment

Triclosan is an antibacterial and antifungal chemical used in a variety of consumer products, including soaps, detergents, moisturizers, and cosmetics. Aquatic ecosystems may be exposed to triclosan following the release of remaining residues in wastewater effluents and biosolids. In December 2017, Environment and Climate Change Canada (ECCC) released a federal environmental quality guideline (FEQG) report that contained a federal water quality guideline (FWQG) for triclosan. This guideline will be used as an adjunct to the risk assessment and risk management of priority chemicals identified under the Government of Canadas Chemicals Management Plan (CMP). The FWQG value for triclosan (0.47 μg/L) was derived by ECCC using a hazardous concentration for 5% of species (HC5) from a species sensitivity distribution (SSD). We recalculated the FWQG after performing an independent analysis and evaluation of the available aquatic toxicity data for triclosan and compared our results with the ECCC FWQG value. Our independent analysis of the available aquatic toxicity data entailed conducting a literature search of all available and relevant studies, evaluating the quality and reliability of all studies considered using thorough and consistent study evaluation criteria, and thereby generating a data set of high-quality toxicity values. The selected data set includes 22 species spanning 5 taxonomic groups. An SSD was developed using this data set following the ECCC approaches. The HC5 from the SSD derived based on our validated data set is 0.76 μg/L. This HC5 value is slightly greater (i.e., less sensitive) than the value presented in ECCCs final FWQG. Integr Environ Assess Manag 2018;14:437-441.