Insecticides are commonly used around homes for controlling insects such as ants, termites, and spiders. Such uses have been linked to pesticide contamination and toxicity in urban aquatic ecosystems. Fipronil is a relatively new and popular urban-use insecticide that has acute toxicity to arthropods at low-ppb levels. In this study, we collected runoff water from 6 large communities, each consisting of 152 to 460 single-family homes, in Sacramento County and Orange County, California, and evaluated the occurrence of fipronil and its biologically active derivatives over 26 months under dry weather conditions. Statistical modeling showed that the levels of fipronil and derivatives in the runoff water were both spatially and temporally correlated. More than 10-fold differences were observed between the Sacramento and Orange County sites, with the much higher levels for Orange County (southern California) coinciding with heavier use. The median concentrations of combined fipronil and derivatives for the Orange County sites were 204-440 ng L(-1), with the 90th percentile levels ranging from 340 to 1170 ng L(-1). These levels frequently exceeded the LC50 values for arthropods such as mysid shrimp and grass shrimp. The highest levels occurred from April to October, while decreases were seen from October to December and from January to March, likely reflecting seasonal use patterns and the effect of rain-induced washoff. Fipronil and fipronil sulfone (oxidation derivative) each accounted for about 35% of the total concentrations, with desulfinyl fipronil (a photolytic product) contributing about 25%. Results of this study clearly established residential drainage as a direct source for pesticide contamination in urban waterways, and for the first time, identified fipronil as a new and widespread contaminant with potential ecotoxicological significance.

Pyrethroids are commonly used insecticides in both agricultural and urban environments. Recent studies showed that surface runoff facilitated transport of pyrethroids to surface streams, probably by sediment movement. Sediment contamination by pyrethroids is of concern due to their wide-spectrum aquatic toxicity. In this study, we characterized the spatial distribution and persistence of bifenthrin [BF; (2-methyl(1,1'-biphenyl)-3-yl)methyl 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate] and permethrin [PM; 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl)methyl ester] in the sediment along a 260-m runoff path. Residues of BF and PM were significantly enriched in the eroded sediment, and the magnitude of enrichment was proportional to the downstream distance. At 145 m from the sedimentation pond, BF was enriched by >25 times, while PM isomers were enriched by >3.5 times. Pesticide enrichment along the runoff path coincided with enrichment of organic carbon and clay fractions in the sediment, as well as increases in adsorption coefficient K(d), suggesting that the runoff flow caused selective transport of organic matter and chemical-rich fine particles. Long persistence was observed for BF under both aerobic and anaerobic conditions, and the half-life ranged from 8 to 17 mo at 20 degrees C. The long persistence was probably caused by the strong pesticide adsorption to the solid phase. The significant enrichment, along with the prolonged persistence, suggests that movement of pyrethroids to the surface water may be caused predominantly by the chemically rich fine particles. It is therefore important to understand the fate of sediment-borne pyrethroids and devise mitigation strategies to reduce offsite movement of fine sediment.

The shift in land use patterns within many urban areas has the potential to influence the magnitude and nature of nonpoint-source pollution. The presence of pyrethroid insecticides in urban surface streams is of particular concern due to the broad spectrum toxicity of pyrethroids to aquatic organisms and the widespread use of pyrethroid products for agricultural and urban pest control. Sediment samples were collected throughout a mixed land use watershed in southern California during two sampling periods and analyzed for a suite of pyrethroids. Bifenthrin and fenpropathrin were found most frequently in the sediment samples, with the highest concentrations associated with sites adjacent to large commercial nurseries. Sediments from residential areas or residential-commercial mixed areas had fewer detections and significantly lower concentrations than the nursery runoff sediments. No apparent difference was found between wet and dry season concentrations, which may be attributed to the fact that the lack of flow under dry weather conditions rendered pyrethroid residues immobile. Organic carbon-normalized sediment concentrations were poorly correlated with the freely dissolved pore water concentrations measured by solid phase microextraction (SPME), suggesting factors other than sediment organic carbon content should be considered when relating concentrations to potential toxicities.

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Organophosphate and carbamate compounds are among the most widely used pesticides. Contamination of surface water by these compounds is of concern because of potential toxicity to aquatic organisms, especially those at lower trophic levels. In this study we evaluated the persistence of diazinon, chlorpyrifos, malathion, and carbaryl in waters from various sites in the Newport Bay-San Diego Creek watershed in southern California (USA). The persistence of diazinon and chlorpyrifos was much longer than that of malathion or carbaryl and was further prolonged in seawater. Microbial degradation contributed significantly to the dissipation of diazinon and chlorpyrifos in freshwater, but was inhibited in seawater, leading to increased persistence. In contrast, degradation of malathion and carbaryl was rapid and primarily abiotic. A greater temperature dependence was observed for carbaryl degradation in all waters and for diazinon degradation in freshwater. The interactions of pesticide persistence with water location, temperature, and type of pesticides suggest that site- and compound-specific information is needed when evaluating the overall ecotoxicological risks of pesticide pollution in a watershed. Because the persistence of diazinon and chlorpyrifos may increase significantly in seawater, mitigation should occur before the pesticides reach seawater. The relatively short persistence of these compounds in freshwater suggests that practices aimed at extending residence time (e.g., diversion to wetlands) may effectively reduce pesticide output to downstream water bodies.

Fipronil is an urban-use insecticide, and the increased use has led to its frequent detections in urban streams. Most studies on the environmental fate of fipronil so far have focused on soils, and little is known about its behavior in sediment-water systems. In this study, we investigated the transformation and sorption of fipronil in urban stream sediments from California, incubated under facultative and anaerobic conditions. Degradation of fipronil in sediments generally followed exponential decay kinetics, and the first-order half-lives of fipronil were only 4.6-18.5 days in anaerobic sediments. The persistence of fipronil under facultative conditions was considerably longer, with half-lives from 25 to 91 days. Sterilization generally decreased the dissipation of fipronil, indicating that microbial activity was an important factor in fipronil transformations in sediments. Under facultative conditions, fipronil sulfide and sulfone were observed, while only fipronil sulfide was detected in anaerobic samples. The sorption coefficient K d consistently increased with organic carbon contents of sediments. In the same sediment, K d usually also increased with contact time, suggesting decreased availability for aged residues. Results from this study showed that the stability of fipronil in sediments depends closely on the oxygen status and that due to the readily conversion of fipronil to the sulfone and sulfide metabolites, the overall risk assessment of fipronil in surface aquatic systems should take into consideration fipronil as well as its metabolites.

Contamination of surface aquatic systems by insecticides is an emerging concern in urban watersheds, but sources of contamination are poorly understood, hindering development of regulatory or mitigation strategies. Hardscapes such as concrete surfaces are considered an important facilitator for pesticide runoff following applications around homes. However, pesticide behavior on concrete has seldom been studied, and standardized evaluation methods are nonexistent. In the present study, a simple batch method for measuring pesticide wash-off potential from concrete surfaces was developed, and the dependence of washable pesticide residues was evaluated on pesticide types, formulations, time exposed to outdoor conditions, and number of washing cycles. After application to concrete, the washable fraction of four pyrethroids (bifenthrin, permethrin, cyfluthrin, and cyhalothrin) and fipronil rapidly decreased, with half-lives < or =3 d, likely due to irreversible retention in micropores below the concrete surface. The initial fast decrease was followed by a much slower declining phase with half-lives ranging from one week to two months, and detectable residues were still found in the wash-off solution for most treatments after 112 d. The slow decrease may be attributed to a fraction of pesticides being isolated from degradation or volatilization after retention below the concrete surface. Wash-off potential was consistently higher for solid formulations than for liquid formulations, implying an increased runoff contamination risk for granular and powder formulations. Trace levels of pyrethroids were detected in the wash-off solution even after 14 washing-drying cycles over 42 d under outdoor conditions. Results from the present study suggest that pesticide residues remain on concrete and are available for contaminating runoff for a prolonged time. Mechanisms for the long persistence were not clearly known from the present study and merit further investigation.

Sources and mechanisms of nutrient transport in lawn irrigation driven surface runoff are largely unknown. We investigated the transport of nitrogen (N) and phosphorus (P) in lawn irrigation driven surface runoff from a residential neighborhood (28 ha) of 56% impervious and 44% pervious areas. Pervious areas encompassing turfgrass (lawns) in the neighborhood were irrigated with the reclaimed water in common areas during the evening to late night and with the municipal water in homeowner’s lawns during the morning. The stormwater outlet pipe draining the residential neighborhood was instrumented with a flow meter and Hach autosampler. Water samples were collected every 1-h and triple composite samples were obtained at 3-h intervals during an intensive sampling period of 1-week. Mean concentrations, over 56 sampling events, of total N (TN) and total P (TP) in surface runoff at the outlet pipe were 10.9±6.34 and 1.3±1.03 mg L–1, respectively. Of TN, the proportion of nitrate–N was 58% and other–N was 42%, whereas of TP, orthophosphate–P was 75% and other–P was 25%. Flow and nutrient (N and P) concentrations were lowest from 6:00 a.m. to noon, which corresponded with the use of municipal water and highest from 6:00 p.m. to midnight, which corresponded with the use of reclaimed water. This data suggests that N and P originating in lawn irrigation driven surface runoff from residential catchments is an important contributor of nutrients in surface waters.