Darren Haver

Persistence of selected organophosphate and carbamate insecticides in waters from a coastal watershed.

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.

Occurrence of fipronil and its biologically active derivatives in urban residential runoff.

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.

Transformation and sorption of fipronil in urban stream sediments.

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.

Wash‐off potential of urban use insecticides on concrete surfaces

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.

Sorption and Desorption of Pyrethroid Insecticide Permethrin on Concrete

Use of pesticides around residential homes is linked to contamination of urban waterways, where impervious surfaces like concrete are considered as sources or facilitators of the contamination. However, the fate of pesticides on urban hard surfaces is poorly understood. We characterized sorption and desorption of permethrin, the most used pyrethroid insecticide, on concrete surfaces, to understand its availability for contaminating runoff water. Sorption of (14)C-permethrin to concrete was rapid, and the sorption isotherm was linear, with surface area-normalized K(d) of 1.91 ± 0.1 mL/cm(2). When small permethrin-treated concrete cubes (14 × 14 × 8 mm) were subjected to 300 h sequential desorption, both the parent compound and total (14)C showed an initial rapid desorption, followed by prolonged slow desorption. Meanwhile, permethrin became more resistant to desorption as the pesticide contact time on the concrete increased. When desorption was performed 1 and 7 d after the treatment, the desorbed permethrin after 300 h was 34.1 ± 3.2% and 23.7 ± 1.1% of the spiked amount, respectively, as compared to 56.2 ± 6.1% for the freshly spiked samples. The decreased desorption was partially attributed to permethrin decomposition on the alkaline concrete. However, even after 300 h, over 20% of the applied (14)C still remained in the concrete. Therefore, when pesticide-treated concrete surfaces come in contact with runoff water, elevated concentrations may be expected initially, while the extended desorption implies a potential for sustained contamination.

Persistence and sorption of fipronil degradates in urban stream sediments.

Fipronil, an increasingly popular insecticide used for urban pest control, is known to readily transform into several degradates that generally have similar or greater toxicity to aquatic organisms than the parent compound. However, knowledge on the fate of these degradates in the environment is obscure. In the present study, degradation kinetics and sorption of desthiofipronil, fipronil sulfide, and fipronil sulfone were investigated in urban stream sediments. All degradates showed enhanced persistence in sediments compared to fipronil under facultative or anaerobic conditions. Under facultative conditions, the estimated half-lives of desthiofipronil, fipronil sulfide, and fipronil sulfone were 217 to 497, 195 to 352, and 502 to 589 d, respectively. Under anaerobic conditions, the corresponding half-lives were over one year in one sediment, while no detectable degradation occurred in the other two sediments after 280 d. Sorption isotherms of fipronil and its degradates in the sediments were linear, with mean K(OC) values of 802, 1,296, 3,684, and 3,543 L/kg for fipronil, desthiofipronil, fipronil sulfide, and fipronil sulfone, respectively, suggesting that the degradates generally have a higher sorption capacity than fipronil. Sorption coefficient K(d) increased up to fourfold over 280 d, suggesting an aging effect on sorption. The inherent toxicity, long persistence, and strong sorption potential highlight the importance for a better understanding of the sediment toxicity of fipronil degradates in surface water bodies.

Impact of ant control technologies on insecticide runoff and efficacy

BACKGROUND Insecticides are commonly used for ant control around residential homes, but post-treatment runoff may contribute to contamination of surface water in urban watersheds. This study represents the first instance where runoff of insecticides was directly measured after applications around single family residences. During 2007, houses were treated with bifenthrin or fipronil sprays following standard practices. During 2008, pin stream applicators, spray-free zones and restricting sprays to the house foundation were considered as management options. RESULTS During 2007, the resulting runoff from the bifenthrin spray in the irrigation water had a mean concentration of 14.9 microg L(-1) at 1 week post-treatment and 2.5 microg L(-1) at 8 weeks, both high enough to be toxic to sensitive aquatic organisms. In comparison, treatments with bifenthrin granules resulted in no detectable concentrations in the runoff water after 8 weeks. The mean concentration for fipronil used as a perimeter spray was 4.2 microg L(-1) at 1 week post-treatment and 0.01 microg L(-1) at 8 weeks, with the first value also suggesting a potential for causing acute aquatic toxicity to sensitive organisms. During 2008, insecticide runoff was reduced by using spray-free zones and pin stream perimeter applications. CONCLUSIONS It is shown that insecticide runoff from individual home treatments for ants can be measured and used to improve techniques that minimize runoff. The pin stream application and applications limited to the house foundation should be further evaluated for their potential to reduce pesticide runoff from residential homes.

Exposure of Petunia seedlings to ethylene decreased apical dominance by reducing the ratio of auxin to cytokinin

Seedlings of Petunia x hybrida ‘Orchid’ treated with the ethylene-releasing compound ethephon at 0.9, 1.7, and 3.5 mM evolved ethylene at a higher rate as the concentration of ethephon increased. Regardless of the concentration of ethephon applied, ethylene evolution peaked 6 to 8 h following application. Evidence that ethephon application decreased apical dominance included an increase in the number of new nodes on the main stem and a sustained increase in the length of new and existing lateral shoots compared to the control (no ethephon). Plants treated with 3.5 mM ethephon developed mild chlorosis, whereas a concentration of 1.7 mM ethephon decreased apical dominance without phytotoxic effects. The auxin/cytokinin ratio decreased in the apical shoot section as early as 1 h after ethephon treatment. In contrast, a decrease in the ratio in the subapical shoot section was not detected until 24 h after ethephon application. Reduction in auxin/cytokinin ratio was a result of a decrease in indole-3-acetic acid (IAA) and an increase of zeatin riboside (ZR), but not isopentenyladenosine (iPA). These results suggest that exposing ‘Orchid’ petunia seedlings to ethylene via ethephon lowers the auxin/cytokinin ratio, thereby promoting the outgrowth of lateral shoots.

Role of Sediments in Insecticide Runoff from Urban Surfaces: Analysis and Modeling

Insecticides, such as pyrethroids, have frequently been detected in runoff from urban areas, and their offsite transport can cause aquatic toxicity in urban streams and estuaries. To better understand the wash-off process of pesticide residues in urban runoff, the association of pyrethroids with sediment in runoff from residential surfaces was investigated in two watersheds located in Northern California (Sacramento County). Rainfall, flow rate, and event mean concentrations/loads of sediments and pyrethroids, collected during seasonal monitoring campaigns from 2007 to 2014, were analyzed to identify relationships among stormwater quality and rainfall characteristics, primarily using Principal Component Analysis (PCA). Pyrethroid wash-off was strongly related to sediment wash-off whenever sediment loads exceeded 10 mg; this value was conveniently selected as a threshold between dissolved and particle-bound control of off-site pyrethroid transport. A new mechanistic model for predicting pyrethroid wash-off profiles from residential surfaces at basin-scale was implemented in the Storm Water Management Model (SWMM). The accuracy of the model predictions was estimated by evaluating the root mean square error (RMSE), Nash–Sutcliff efficiency (NSE), and Kling–Gupta efficiency (KGE) for each pyrethroid detected (RMSEtot = 0.13; NSEtot = 0.28; KGEtot = 0.56). The importance of particle-bound transport revealed in this work confirms previous field investigations at a smaller scale, and it should be a key consideration when developing policies to mitigate pesticide runoff from urban areas.

Managing urban runoff in residential neighborhoods: Nitrogen and phosphorus in lawn irrigation driven runoff

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.