Bioavailability of permethrin and cyfluthrin in surface waters with low levels of dissolved organic matter

Pyrethroids are widely used insecticides in both agricultural and urban environments, and their potential movement to surface streams and toxicity to susceptible aquatic species is an emerging concern. Natural surface waters usually contain low levels of dissolved organic matter (DOM). Limited data have shown that DOM preparations can significantly alter the bioavailability and toxicity effects of pyrethroids. However, the importance of these effects in natural waters has not been investigated. In this study we measured uptake and acute toxicity of permethrin and cyfluthrin by Daphnia species in 15 surface water samples. Low levels of DOM (3-20 mg L(-1)) inhibited cyfluthrin uptake by Daphnia magna and acute toxicity to Ceriodaphnia dubia in most samples. For permethrin, the effects of DOM on bioavailability and toxicity were generally not significant. The effects of DOM on bioavailability of cyfluthrin could not be explained from the DOC concentration alone, suggesting that properties of DOM were also important in regulating bioavailability. Regression of K DOC with selected DOM properties revealed significant dependence of K DOC on the carboxylic acid content of DOM. Moreover, concentrations sensed by solid-phase microextraction (SPME) fibers were well correlated with the observed changes in bioaccumulation by D. magna and acute toxicity to C. dubia. Therefore, selective sampling methods such as SPME may be used for measuring the bioavailable concentrations of pyrethroids in waters with naturally occurring DOM levels and predicting the actual toxicity effects.     

Summary of well water sampling in California to detect pesticide residues resulting from nonpoint-source applications

This report summarizes well sampling protocols, data collection procedures, and analytical results for the presence of pesticides in ground water developed by the California Department of Pesticide Regulation (DPR). Specific well sampling protocols were developed to meet regulatory mandates of the Pesticide Contamination Prevention Act (PCPA) of 1986 and to provide further understanding of the agronomic, chemical, and geographic factors that contribute to movement of residues to ground water. The well sampling data have formed the basis for the DPR's regulatory decisions. For example, a sampling protocol, the Four-Section Survey, was developed to determine if reported detections were caused by nonpoint-source agricultural applications, a determination that can initiate formal review and subsequent regulation of a pesticide. Selection of sampling sites, which are primarily rural domestic wells, was initially based on pesticide use and cropping patterns. Recently, soil and depth-to-ground water data have been added to identify areas where a higher frequency of detection is expected. In accordance with the PCPA, the DPR maintains a database for all pesticide well sampling in California with submission required by all state agencies and with invitations for submission extended to all local and federal agencies or other entities. To date, residues for 16 active ingredients and breakdown products have been detected in California ground water as a result of legal agricultural use. Regulations have been adopted for all detected parent active ingredients, and they have been developed regardless of the level of detection.     

Vegetated ditches as a management practice in irrigated alfalfa

The organophosphate (OP) insecticides diazinon and chlorpyrifos have been frequently detected in the San Joaquin River, California, USA. Irrigation tail waters are a significant source of OP pesticides in the watershed. This study tested several management practices for reducing offsite movement of chlorpyrifos to surface water from flood irrigated alfalfa. Management practices evaluated include (1) a constructed, vegetated irrigation tailwater return ditch and (2) increased lag time between chlorpyrifos application and start of flood irrigation. Chlorpyrifos concentrations in whole-water samples of irrigation runoff were variable and ranged from 0.22 mug/l to a maximum of 1.67 mug/l. The median concentration reduction at the end of a 200 m vegetated ditch was 38% compared to 1% in an adjacent conventional tail water ditch. Runoff data collected represented first flush runoff from sets that were irrigated between 48 and 144 h after chlorpyrifos application. There was no consistent effect of irrigation lag time on chlorpyrifos concentration in tailwater for lag times of up to 144 h. Consequently these data indicate that delayed irrigation is not an effective management practice for reducing chlorpyrifos off-site movement to surface water in California flood irrigated alfalfa.     

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007�C2008

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 ??g 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 ??g L^???1. These concentrations were well below reported C. dubia LC₅₀s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and ??-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 ??-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 ??-cyhalothrin likely contributed to the toxicity.     

A Probabilistic Screening Model for Evaluating Pyrethroid Surface Water Monitoring Data

Synthetic pyrethroids have been detected in recent California surface water monitoring. Filtration is avoided during sample workup because pyrethroids are extremely hydrophobic, tending to sorb to most surfaces. The resultant analytical pyrethroid concentrations reflect both dissolved pyrethroid and pyrethroid associated with suspended sediment in the water column. Such “whole-water” analytical data are not directly comparable to aquatic acute toxicity effect concentrations measured in laboratory sediment-free water. Consequently, any potential aquatic toxicity risk is indeterminate. In this study a simple probabilistic model was developed to allow a screening-level assessment of pyrethroid whole-water monitoring data. The results suggest that water column toxicity of pyrethroids is possible in California's agriculturally-dominated tributaries, and indicate that additional monitoring to better characterize pyrethroid water-column concentrations are warranted. Model refinement will depend on future work that more firmly establishes the relationship between pyrethroid partitioning and bioavailability, and that addresses the potential influence of dissolved organic carbon on pyrethroid sorption and bioavailability.