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.

Synthetic pyrethroids (SPs) are a group of hydrophobic compounds with significant aquatic toxicity. Their strong affinity to suspended solids and humic materials suggests that SPs in natural surface water are distributed in solid-adsorbed, dissolved organic matter (DOM)-adsorbed, and freely dissolved phases. The freely dissolved phase is of particular importance because of its mobility and bioavailability. In the present study, we used solid-phase microextraction to detect the freely dissolved phase, and we evaluated the phase distribution of bifenthrin and permethrin in stream and runoff waters. In stream water, most SPs were associated with the suspended solids and, to a lesser extent, with DOM. The freely dissolved phase contributed only 0.4% to 1.0%. In runoff effluents, the freely dissolved concentration was 10% to 27% of the overall concentration. The predominant partitioning into the adsorbed phases implies that the toxicity of SPs in surface water is reduced because of decreased bioavailability. This also suggests that monitoring protocols that do not selectively define the freely dissolved phase can lead to significant overestimation of toxicity or water-quality impacts by SPs.

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Recent studies showed that synthetic pyrethroids (SPs) can move via surface runoff into aquatic systems. Fifty-six of SP-degrading bacteria strains were isolated from contaminated sediments, of which six were evaluated for their ability to transform bifenthrin and permethrin in the aqueous phase and bifenthrin in the sediment phase. In the aqueous phase, bifenthrin was rapidly degraded by strains of Stenotrophomonas acidaminiphila, and the half-life (t1/2) was reduced from >700 h to 30 to 131 h. Permethrin isomers were degraded by Aeromonas sobria, Erwinia carotovora, and Yersinia frederiksenii. Similar to bifenthrin, the t1/2 of cis- and trans-permethrin was reduced by approximately 10-fold after bacteria inoculation. However, bifenthrin degradation by S. acidaminiphila was significantly inhibited in the presence of sediment, and the effect was likely caused by strong adsorption to the solid phase. Bifenthrin t1/2 was 343 to 466 h for a field sediment, and increased to 980 to 1200 h for a creek sediment. Bifenthrin degradation in the inoculated slurry treatments was not greatly enhanced when compared with the noninoculated system. Therefore, although SP-degrading bacteria may be widespread in aquatic systems, adsorption to sediment could render SPs unavailable to the degraders, thus prolonging their persistence.

Monitoring for synthetic pyrethroids in surface water at the sub-parts per billion level requires reproducible sampling and analytical methods. We studied the recovery of bifenthrin, permethrin, and deltamethrin in water during storage in glass containers and extraction using solid-phase membranes. In solid-free water, the concentration of all compounds quickly decreased and then remained constant at 58-72% of the initial concentration, likely due to adsorption to the glass surface. The recovery was enhanced in runoff samples that contained suspended solids, which was attributed to the association of pesticides to the suspended solids. However, the greatest loss occurred when runoff samples were not agitated before extraction, and the loss was largely caused by the exclusion of the suspended solids from the aqueous phase. Nearly 100% extraction recoveries were obtained when C(8) or C(18) membranes were used for extracting runoff samples. Adsorption to glass surfaces and suspended solids can result in substantial underestimation of pyrethroid concentrations or biological activity and therefore should be considered when designing monitoring protocols.

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.

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.

The brown widow spider, Latrodectus geometricus C. L. Koch, has become newly established in southern California during the first decade of the 21st century. Brown widows and egg sacs were collected within the urban Los Angeles Basin using timed searches. We also collected and compared the abundance and distribution of the native western black widow spider, Latrodectus hesperus Chamberlin & Ivie, to brown widows. Brown widows were very common around urban structures especially outside homes, in parks, under playground equipment, in plant nurseries and landscaping areas, greatly outnumbering native western black widows, and were very rare or nonexistent in garages, agricultural crops, and natural areas. Western black widows predominated in xeric habitats and were less prevalent around homes. Neither species was found in the living space of homes. In southern California, envenomation risk exists because brown widows are now common in urban areas and the spiders hide where people place their fingers and exert pressure to move objects (e.g., under the curled lip of potted plants, in the recessed handle of plastic trash bins). Nonetheless, brown widow spider bites are less toxic than those of native western black widow spiders and, hence, if they are displacing black widows, overall widow envenomation risk may actually be lower than before brown widow establishment.