Regulatory Modeling of Pesticide Aquatic Exposures in California's Agricultural Receiving Waters.

For the aquatic exposure assessment of pesticides, the USEPA uses the Variable Volume Water Model (VVWM) to predict the estimated environmental concentrations (EECs) of a pesticide in a water body that receives runoff inputs from the Pesticide Root Zone Model (PRZM). The standard farm pond and additional generalized static and flowing water bodies used in endangered species assessment (aquatic bins) are used by USEPA to model the worst-case aquatic exposure for the nationwide exposure assessment. However, whether or not model results are relevant to state-specific conditions has not been validated. In this study, the USEPA water body scenarios are examined for their capability of providing a conservatively realistic estimate of pesticide aquatic exposures in California's agricultural settings. The sensitivity of modeled EECs to key water body parameters (dimensions, flow, and mass transfer) was explored with a one-at-a-time approach by using the standard farm pond as a baseline. The EECs generated from different USEPA water bodies for the worst-case loading were compared with the monitoring data observed in California's agriculturally influencing water bodies. Results showed that the farm pond EECs well captured the worst-case monitoring data, whereas the aquatic bins EECs, especially the flowing bins, tended to overestimate data. The conceptual model of the standard farm pond was also found to be relevant to the highly vulnerable water bodies in California's agricultural areas. The study confirms that VVWM with the standard farm pond scenario is appropriate for the screening-level regulatory exposure assessment in California's agricultural settings.

Modeling spray drift and runoff-related inputs of pesticides to receiving water.

Pesticides move to surface water via various pathways including surface runoff, spray drift and subsurface flow. Little is known about the relative contributions of surface runoff and spray drift in agricultural watersheds. This study develops a modeling framework to address the contribution of spray drift to the total loadings of pesticides in receiving water bodies. The modeling framework consists of a GIS module for identifying drift potential, the AgDRIFT model for simulating spray drift, and the Soil and Water Assessment Tool (SWAT) for simulating various hydrological and landscape processes including surface runoff and transport of pesticides. The modeling framework was applied on the Orestimba Creek Watershed, California. Monitoring data collected from daily samples were used for model evaluation. Pesticide mass deposition on the Orestimba Creek ranged from 0.08 to 6.09% of applied mass. Monitoring data suggests that surface runoff was the major pathway for pesticide entering water bodies, accounting for 76% of the annual loading; the rest 24% from spray drift. The results from the modeling framework showed 81 and 19%, respectively, for runoff and spray drift. Spray drift contributed over half of the mass loading during summer months. The slightly lower spray drift contribution as predicted by the modeling framework was mainly due to SWAT's under-prediction of pesticide mass loading during summer and over-prediction of the loading during winter. Although model simulations were associated with various sources of uncertainties, the overall performance of the modeling framework was satisfactory as evaluated by multiple statistics: for simulation of daily flow, the Nash-Sutcliffe Efficiency Coefficient (NSE) ranged from 0.61 to 0.74 and the percent bias (PBIAS) < 28%; for daily pesticide loading, NSE = 0.18 and PBIAS = -1.6%. This modeling framework will be useful for assessing the relative exposure from pesticides related to spray drift and runoff in receiving waters and the design of management practices for mitigating pesticide exposure within a watershed.

A review of diazinon use, contamination in surface waters, and regulatory actions in California across water years 1992-2014.

Diazinon is an organophosphorus insecticide that has been widely used in the USA and in California resulting in contamination of surface waters. Several federal and state regulations have been implemented with the aim of reducing its impact to human health and the environment, e.g., the cancellation of residential use products by the USEPA and dormant spray regulations by the California Department of Pesticide Regulation. This study reviewed the change in diazinon use and surface water contamination in accordance with the regulatory actions implemented in California over water years 1992-2014. We observed that use amounts began declining when agencies announced the intention to regulate certain use patterns and continued to decline after the implementation of those programs and regulations. The reduction in use amounts led to a downward trend in concentration data and exceedance frequencies in surface waters. Moreover, we concluded that diazinon concentrations in California's surface waters in recent years (i.e., water years 2012-2014) posed a de minimis risk to aquatic organisms.

Continuous low-level aquatic monitoring (CLAM) samplers for pesticide contaminant screening in urban runoff: Analytical approach and a field test case.

Monitoring of surface waters for organic contaminants is costly. Grab water sampling often results in non-detects for organic contaminants due to missing a pulse event or analytical instrumentation limitations with a small sample size. Continuous Low-Level Aquatic Monitoring (CLAM) samplers (C.I.Agent® Solutions) continually extract and concentrate organic contaminants in surface water onto a solid phase extraction disk. Utilizing CLAM samplers, we developed a broad spectrum analytical screen for monitoring organic contaminants in urban runoff. An intermediate polarity solid phase, hydrophobic/lipophilic balance (HLB), was chosen as the sorbent for the CLAM to target a broad range of compounds. Eighteen urban-use pesticides and pesticide degradates were targeted for analysis by LC/MS/MS, with recoveries between 59 and 135% in laboratory studies. In field studies, CLAM samplers were deployed at discrete time points from February 2015 to March 2016. Half of the targeted chemicals were detected with reporting limits up to 90 times lower than routine 1-L grab samples with good precision between field replicates. In a final deployment, CLAM samplers were compared to 1-L water samples. In this side-by-side comparison, imidacloprid, fipronil, and three fipronil degradates were detected by the CLAM sampler but only imidacloprid and fipronil sulfone were detected in the water samples. However, concentrations of fipronil sulfone and imidacloprid were significantly lower with the CLAM and a transient spike of diuron was not detected. Although the CLAM sampler has limitations, it can be a powerful tool for development of more focused and informed monitoring efforts based on pre-identified targets in the field.

A statistical assessment of pesticide pollution in surface waters using environmental monitoring data: Chlorpyrifos in Central Valley, California.

Pesticides are routinely monitored in surface waters and resultant data are analyzed to assess whether their uses will damage aquatic eco-systems. However, the utility of the monitoring data is limited because of the insufficiency in the temporal and spatial sampling coverage and the inability to detect and quantify trace concentrations. This study developed a novel assessment procedure that addresses those limitations by combining 1) statistical methods capable of extracting information from concentrations below changing detection limits, 2) statistical resampling techniques that account for uncertainties rooted in the non-detects and insufficient/irregular sampling coverage, and 3) multiple lines of evidence that improve confidence in the final conclusion. This procedure was demonstrated by an assessment on chlorpyrifos monitoring data in surface waters of California's Central Valley (2005-2013). We detected a significant downward trend in the concentrations, which cannot be observed by commonly-used statistical approaches. We assessed that the aquatic risk was low using a probabilistic method that works with non-detects and has the ability to differentiate indicator groups with varying sensitivity. In addition, we showed that the frequency of exceedance over ambient aquatic life water quality criteria was affected by pesticide use, precipitation and irrigation demand in certain periods anteceding the water sampling events.

Evaluation of Three Models for Simulating Pesticide Runoff from Irrigated Agricultural Fields.

Three models were evaluated for their accuracy in simulating pesticide runoff at the edge of agricultural fields: Pesticide Root Zone Model (PRZM), Root Zone Water Quality Model (RZWQM), and OpusCZ. Modeling results on runoff volume, sediment erosion, and pesticide loss were compared with measurements taken from field studies. Models were also compared on their theoretical foundations and ease of use. For runoff events generated by sprinkler irrigation and rainfall, all models performed equally well with small errors in simulating water, sediment, and pesticide runoff. The mean absolute percentage errors (MAPEs) were between 3 and 161%. For flood irrigation, OpusCZ simulated runoff and pesticide mass with the highest accuracy, followed by RZWQM and PRZM, likely owning to its unique hydrological algorithm for runoff simulations during flood irrigation. Simulation results from cold model runs by OpusCZ and RZWQM using measured values for model inputs matched closely to the observed values. The MAPE ranged from 28 to 384 and 42 to 168% for OpusCZ and RZWQM, respectively. These satisfactory model outputs showed the models' abilities in mimicking reality. Theoretical evaluations indicated that OpusCZ and RZWQM use mechanistic approaches for hydrology simulation, output data on a subdaily time-step, and were able to simulate management practices and subsurface flow via tile drainage. In contrast, PRZM operates at daily time-step and simulates surface runoff using the USDA Soil Conservation Service's curve number method. Among the three models, OpusCZ and RZWQM were suitable for simulating pesticide runoff in semiarid areas where agriculture is heavily dependent on irrigation.

Monitoring Fipronil and Degradates in California Surface Waters, 2008-2013.

The phenylpyrazole insecticide fipronil has become a popular replacement pest management tool as organophosphorus insecticides have been phased out for residential use and pyrethroids have come under scrutiny as a surface water contaminant. There has been an increasing concern of offsite transport of fipronil to surrounding surface waters and a corresponding increase in potential toxicity to aquatic organisms. The California Department of Pesticide Regulation Environmental Monitoring Program has collected over 500 urban surface water samples throughout California since 2008 to determine the presence and concentrations of fipronil and five degradate products. Statewide, fipronil was detected at high frequency (49%), as were the sulfone (43%) and desulfinyl (33%) degradates. Data collected at long-term monitoring stations indicate higher concentrations in southern California, corresponding to a higher use pattern in the region. There is a clear pattern of increased transport of fipronil with higher flow associated with rain events. However, the lack of seasonality effects on degradates' concentrations suggest a constant source of fipronil with a corresponding lag time of transport to surface waters during the dry season. Receiving waters had a diluting effect on concentrations; however, a significant proportion (46%) of receiving water samples had associated fipronil concentrations above USEPA aquatic life chronic benchmark values. Total mass loading estimates from a long-term monitoring site suggest that the annual fipronil loading is greater in the dry season than during storm events. This could have implications for future mitigation efforts because most runoff during this period was generated from irrigation and outdoor residential use.

Insecticide washoff from concrete surfaces: characterization and prediction.

Pesticide runoff from impervious surfaces is a significant cause of aquatic contamination and ecologic toxicity in urban waterways. Effective mitigation requires better understanding and prediction of off-site transport processes. Presented here is a comprehensive study on pesticide washoff from concrete surfaces, including washoff tests, experimental data analysis, model development, and application. Controlled rainfall experiments were conducted to characterize washoff loads of commercially formulated insecticides with eight different active ingredients. On the basis of the analysis of experimental results, a semimechanistic model was developed to predict pesticide buildup and washoff processes on concrete surfaces. Three pesticide product specific parameters and their time dependences were introduced with empirical functions to simulate the persistence, transferability, and exponential characteristics of the pesticide washoff mechanism. The parameters were incorporated using first-order kinetics and Fick's second law to describe pesticide buildup and washoff processes, respectively. The model was applied to data from 21 data sets collected during 38 rainfall events, with parameters calibrated to pesticide products and environmental conditions. The model satisfactorily captured pesticide mass loads and their temporal variations for pesticides with a wide range of chemical properties (log KOW = 0.6-6.9) under both single and repeated (1-7 times) rainfall events after varying set times (1.5 h∼238 days after application). Results of this study suggested that, in addition to commonly reported physicochemical properties for the active ingredient of a pesticide product, additional parameters determined from washoff experiments are required for risk assessments of pesticide applications on urban impervious surfaces.

Chlorpyrifos-treated crops in the vicinity of surface water contamination in the San Joaquin Valley, California, USA.

Due to frequent contamination of streams in the San Joaquin Valley, California, USA, with the insecticide chlorpyrifos, researchers are working to identify crop-specific management practices that will reduce the offsite movement of this compound into surface waters. To guide this effort, crops treated with chlorpyrifos in the vicinity of contaminated streams were identified; walnut, alfalfa, and almond were the primary crops identified. Use was higher on walnut and almond, but due to irrigation practices offsite movement in surface runoff may be more likely from alfalfa. Based on these findings, development of management practices to reduce off-site movement of chlorpyrifos in irrigation runoff from treated alfalfa fields is recommended.

Pesticide washoff from concrete surfaces: literature review and a new modeling approach.

Use of pesticides over impervious surfaces like concrete and subsequent washoff and offsite transport significantly contribute to pesticide detection and aquatic toxicity in urban watersheds. This paper presents a comprehensive study on pesticide washoff from concrete surfaces, including reviews of reported experiments and existing models, development of a new model, and its application to controlled experimental conditions. The existing modeling approaches, mainly the exponential function and power-law function, have limitations in explaining pesticide washoff processes characterized from experimental data. Here we develop a mathematical and conceptual framework for pesticide washoff from concrete surfaces. The new modeling approach was designed to characterize pesticide buildup and washoff processes on concrete surfaces, including the time-dependence of the washoff potential after application and the dynamics in pesticide washoff during a runoff event. One benefit is the ability to integrate and quantify multiple processes that influence pesticide washoff over concrete surfaces, including product formulation, aging effects, multiple applications, and rainfall duration and intensity. The model was applied to experimental configurations in two independent studies, and satisfactorily simulated the measured temporal variations of pesticide washoff loads from concrete surfaces for the five selected pyrethroids in 15 runoff events. Results suggested that, with appropriate parameterization and modeling scenarios, the model can be used to predict washoff potentials of pesticide products from concrete surfaces, and support pesticide risk assessments in urban environmental settings.

Pesticide occurrence and aquatic benchmark exceedances in urban surface waters and sediments in three urban areas of California, USA, 2008-2011.

Urban pesticide use has a direct impact on surface water quality. To determine the extent of pesticide contamination, the California Department of Pesticide Regulation initiated a multi-area urban monitoring program in 2008. Water and sediment samples were collected at sites unaffected by agricultural inputs in three areas: Sacramento (SAC), San Francisco Bay (SFB), and Orange County (OC). Samples were analyzed for up to 64 pesticides or degradates. Multiple detections were common; 50 % of the water samples contained five or more pesticides. Statewide, the most frequently detected insecticides in water were bifenthrin, imidacloprid, fipronil, fipronil sulfone, fipronil desulfinyl, carbaryl, and malathion. Bifenthrin was the most common contaminant in sediment samples. Key differences by area: OC had more pesticides detected than SAC or SFB with higher concentrations of fipronil, whereas SAC had higher concentrations of bifenthrin. The most frequently detected herbicides were 2,4-D, triclopyr, dicamba, diuron, and pendimethalin. Key differences by area: OC and SFB had higher concentrations of triclopyr, whereas SAC had higher concentrations of 2,4-D and dicamba. Detection frequency, number of pesticides per sample, and pesticide concentration increased during rainstorm events. In water samples, all of the bifenthrin, malathion, fipronil, permethrin, and λ-cyhalothrin detections, and most of the fipronil sulfone and cyfluthrin detections were above their lowest US EPA aquatic benchmark. Diuron was the only herbicide that was detected above its lowest benchmark. Based on the number of pesticides and exceedances of aquatic benchmarks or the high number of sediment toxicity units, pesticides are abundant in California surface waters.

Diazinon-chemistry and environmental fate: a California perspective.

Diazinon, first introduced in USA in 1956, is a broad-spectrum contact organophosphate pesticide that has been used as an insecticide, and nematicide. It has been ond of the most widely used insecticides in the USA for household and agricultural pest control. In 2004, residential use of diazinon was discontinued; as a result, the total amount applied has drastically decreased. [corrected]. Consequently, the amounts of diazinon applied have been drastically decreased. For example, in California, the amount of diazinon applied decreased from 501,784 kg in 2000 to 64,122 kg in 2010. Diazinon has a K(oc) value of 40-432 and is considered to be moderately mobile in soils. Diazinon residues have been detected in groundwater, drinking water wells, monitoring wells, and agricultural well. The highest detection frequencies and highest percentages of exceedance of the water quality criterion value of 0.1 µg/L have been reported from the top five agricultural counties n California that had the highest diazinon use. Diazinon is transported in air via atmospheric processes such as direct air movement and wet deposition in snow and rain, although concentrations decrease with distance and evaluation from the source. In the environment, diazinon undergoes degradation by several processes, the most important of which is microbial degradation in soils. The rate of diazinon degradation is affected by pH, soil type, organic amendments, soil moisture, and the concentration of diazinon in the soil, with soil pH being a major influencing factor in diazinon degradation rate. Studies indicate tha soil organic matter is the most important factor that influences diazinon sorption by soils, although clay content and soil ph also play an important role in diazinon sorption. Diazinon is very highly to moderately toxic aquatic arganisms, Diazinon inhibits the enzyme acetylcholinesterase, which hydrolyzes the neurotransmitter acetylcholine and leads to a suite of intermediate syndromes including anorexia, diarrhea, generalized weakness, muscle tremors, abnormal posturing and behavior, depression, and health. Differences in metabolism among species and exposure concentrations play a vital role in diazinon's bioaccumulation among different aquatic organisms in a wide range of accumulating rates and efficiencies.

Modeling complexity in simulating pesticide fate in a rice paddy.

Modeling approaches for pesticide regulation are required to provide generic and conservative evaluations on pesticide fate and exposure based on limited data. This study investigates the modeling approach for pesticide simulation in a rice paddy, by developing a component-based modeling system and characterizing the dependence of pesticide concentrations on individual fate processes. The developed system covers the modeling complexity from a "base model" which considers only the essential processes of water management, water-sediment exchange, and aquatic dissipation, to a "full model" for all commonly simulated processes. Model capability and performance were demonstrated by case studies with 5 pesticides in 13 rice fields of the California's Sacramento Valley. With registrant-submitted dissipation half-lives, the base model conservatively estimated dissolved pesticide concentrations within one order of magnitude of measured data. The full model simulations were calibrated to characterize the key model parameters and processes varying with chemical properties and field conditions. Metabolism in water was identified as an important process in predicting pesticide fate in all tested rice fields. Relative contributions of metabolism, hydrolysis, direct aquatic photolysis, and volatilization to the overall pesticide dissipation were significantly correlated to the model sensitivities to the corresponding physicochemical properties and half-lives. While modeling results were sensitive to metabolism half-lives in water for all fields, significances of metabolism in sediment and water-sediment exchange were only observed for pesticides with pre-flooding applications or with rapid dissipation in sediment. Results suggest that, in addition to the development of regional modeling scenarios for rice production, the registrant-submitted maximum values for the aquatic dissipation half-lives could be used for evaluating pesticide for regulatory purposes.

Detections of the neonicotinoid insecticide imidacloprid in surface waters of three agricultural regions of California, USA, 2010-2011.

Seventy-five surface water samples were collected from three agricultural regions of California and analyzed for the neonicotinoid insecticide imidacloprid. Samples were collected during California's relatively dry-weather irrigation seasons in 2010 and 2011. Imidacloprid was detected in 67 samples (89%); concentrations exceeded the United States Environmental Protection Agency's chronic invertebrate Aquatic Life Benchmark of 1.05 µg/L in 14 samples (19%). Concentrations were also frequently greater than similar toxicity guidelines developed for use in Europe and Canada. The results indicate that imidacloprid commonly moves offsite and contaminates surface waters at concentrations that could harm aquatic organisms following use under irrigated agriculture conditions in California.

Analysis of diazinon agricultural use in regions of frequent surface water detections in California, USA.

For five agricultural regions in California, USA, detection frequency of diazinon in surface water and several aspects of its use were determined from recent data (2005-2010): application method, product formulation and primary crops. Diazinon detection frequencies ranged from 10% to 91%. Application method and product formulations used were similar in all regions. The primary crops treated varied from lettuce (77%) in the regions with highest detections frequencies to tree crops (53%) in those with the lowest. The results suggest that the variation in diazinon detection frequencies likely was not due to the application method or formulation type.

Detections of eleven organophosphorus insecticides and one herbicide threatening Pacific salmonids, Oncorhynchus spp., in California, 1991-2010.

California's surface water monitoring results from 1991 through 2010 were analyzed to determine whether 12 organophosphorus insecticides and herbicides (i.e., azinphos methyl, bensulide, dimethoate, disulfoton, ethoprop, fenamiphos, methamidophos, methidathion, methyl parathion, naled, phorate, and phosmet) and their degradates have been detected above maximum concentration limits (MCLs) in Pacific salmonid habitats. Methidathion, methyl parathion, phorate, phosmet, and the oxygen analogue of naled (DDVP) detections exceeded MCLs. Methyl parathion detections may be accounted for by monthly use trends, while methidathion detections may be explained by yearly use trends. There were inadequate phorate, phosmet, or DDVP data to evaluate for correlations with use.

Removal mechanisms and fate of insecticides in constructed wetlands.

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time. In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 µm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K(d) values for the suspended solids were in the order of 10(4)-10(5), substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 µm). Retention of suspended particles, especially the very large particles (>250 µm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT(50) values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007-2008.

The California's San Joaquin River and its tributaries including Orestimba (ORC) and Del Puerto (DPC) Creeks are listed on the 2006 US EPA Clean Water Act §303(d) list for pesticide impairment. From December 2007 through June 2008, water and sediment samples were collected from both creeks in Stanislaus County to determine concentrations of organophosphorus (OP) and pyrethroid insecticides and to identify toxicity to Ceriodaphnia dubia and Hyalella azteca. OPs were detected in almost half (10 of 21) of the water samples, at concentrations from 0.005 to 0.912 µg L(-1). Diazinon was the most frequently detected OP, followed by chlorpyrifos and dimethoate. Two water samples were toxic to C. dubia; based on median lethal concentrations (LC50), chlorpyrifos was likely the cause of this toxicity. Pyrethroids were detected more frequently in sediment samples (18 detections) than in water samples (three detections). Pyrethroid concentrations in water samples ranged from 0.005 to 0.021 µg L(-1). These concentrations were well below reported C. dubia LC50s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and λ-cyhalothrin were detected in sediment samples at concentrations ranging from 1.0 to 74.4 ng g(-1), dry weight. At DPC, all but one sediment sample caused 100% toxicity to H. azteca. Based on estimated toxicity units (TUs), bifenthrin was likely responsible for this toxicity and λ-cyhalothrin also contributed. At ORC, survival of H. azteca was significantly reduced in four of the 11 sediment samples. However, pyrethroids were detected in only two of these samples. Based on TUs, bifenthrin and λ-cyhalothrin likely contributed to the toxicity.

Efficacy of constructed wetlands in pesticide removal from tailwaters in the Central Valley, California.

Pollutants in agricultural irrigation return flow (tailwater) constitute a significant nonpoint source of pollution in intensive agricultural regions such as the Central Valley of California. Constructed wetlands (CWs) represent a feasible mitigation option to remove pollutants including pesticides in the tailwater. In this study, we evaluated two CWs in the Central Valley for their performance in removing pyrethroid and organophosphate insecticides under field-scale production conditions. Both CWs were found to be highly effective in reducing pyrethroid concentrations in the tailwater, with season-average concentration reductions ranging from 52 to 94%. The wetlands also reduced the flow volume by 68-87%, through percolation and evapotranspiration. When both concentration and volume reductions were considered, the season-average removal of pyrethroids ranged from 95 to 100%. The primary mechanism for pyrethroid removal was through sedimentation of pesticide-laden particles, which was influenced by hydraulic residence time and vegetation density. Temporal analysis indicates a potential efficiency threshold during high flow periods. The season-average removal of chlorpyrifos ranged 52-61%. The wetlands, however, were less effective at removing diazinon, likely due to its limited sorption to sediment particles. Analysis of pesticide partitioning showed that pyrethroids were enriched on suspended particles in the tailwater. Monitoring of pesticide association with suspended solids and bed sediments suggested an increased affinity of pyrethroids for lighter particles with the potential to move further downstream before subject to sedimentation. Results from this study show that flow-through CWs, when properly designed, are an effective practice for mitigating hydrophobic pesticides in the irrigation tailwater.

Environmental fate and toxicology of carbaryl.

Carbaryl is an agricultural and garden insecticide that controls a broad spectrum of insects. Although moderately water soluble, it neither vaporizes nor volatilizes readily. However, upon spray application the insecticide is susceptible to drift. It is unstable under alkaline conditions, thus easily hydrolyzed. Carbaryl has been detected in water at ppb concentrations but degradation is relatively rapid, with 1-naphthol identified as the major degradation product. Indirect and direct photolysis of carbaryl produces different naphthoquinones as well as some hydroxyl substituted naphthoquinones. Sorption of the insecticide to soil is kinetically rapid. However, although both the mineral and organic fractions contribute, because of its moderate water solubility it is only minimally sorbed. Also, sorption to soil minerals strongly depends on the presence of specific exchangeable cations and increases with organic matter aromaticity and age. Soil microbes (bacteria and fungi) are capable of degrading carbaryl; the process is more rapid in anoxic than aerobic systems and with increased temperature and moisture. Carbaryl presents a significant problem to pregnant dogs and their offspring, but some have questioned the applicability of these data to humans. In addition, for toxicokinetic and/or physiological reasons, it has been argued that dogs are more sensitive than humans to carbaryl-induced reproductive or developmental toxicity. However, these arguments are based on either older pharmacokinetic studies or on speculation about possible reproductive differences between dogs on the one hand and rats and humans on the other. In view of the wider evidence from both human epidemiological and laboratory animal studies, the question of the possible developmental and reproductive toxicity of carbaryl should be considered open and requiring further study.