Michelle L. Hladik

Occurrence and Potential Sources of Pyrethroid Insecticides in Stream Sediments from Seven U.S. Metropolitan Areas

A nationally consistent approach was used to assess the occurrence and potential sources of pyrethroid insecticides in stream bed sediments from seven metropolitan areas across the United States. One or more pyrethroids were detected in almost half of the samples, with bifenthrin detected the most frequently (41%) and in each metropolitan area. Cyhalothrin, cypermethrin, permethrin, and resmethrin were detected much less frequently. Pyrethroid concentrations and Hyalella azteca mortality in 28-d tests were lower than in most urban stream studies. Log-transformed total pyrethroid toxic units (TUs) were significantly correlated with survival and bifenthrin was likely responsible for the majority of the observed toxicity. Sampling sites spanned a wide range of urbanization and log-transformed total pyrethroid concentrations were significantly correlated with urban land use. Dallas/Fort Worth had the highest pyrethroid detection frequency (89%), the greatest number of pyrethroids (4), and some of the highest concentrations. Salt Lake City had a similar percentage of detections but only bifenthrin was detected and at lower concentrations. The variation in pyrethroid concentrations among metropolitan areas suggests regional differences in pyrethroid use and transport processes. This study shows that pyrethroids commonly occur in urban stream sediments and may be contributing to sediment toxicity across the country.

Discharges of produced waters from oil and gas extraction via wastewater treatment plants are sources of disinfection by-products to receiving streams

Fluids co-produced with oil and gas production (produced waters) are often brines that contain elevated concentrations of bromide. Bromide is an important precursor of several toxic disinfection by-products (DBPs) and the treatment of produced water may lead to more brominated DBPs. To determine if wastewater treatment plants that accept produced waters discharge greater amounts of brominated DBPs, water samples were collected in Pennsylvania from four sites along a large river including an upstream site, a site below a publicly owned wastewater treatment plant (POTW) outfall (does not accept produced water), a site below an oil and gas commercial wastewater treatment plant (CWT) outfall, and downstream of the POTW and CWT. Of 29 DBPs analyzed, the site at the POTW outfall had the highest number detected (six) ranging in concentration from 0.01 to 0.09 μg L(-1) with a similar mixture of DBPs that have been detected at POTW outfalls elsewhere in the United States. The DBP profile at the CWT outfall was much different, although only two DBPs, dibromochloronitromethane (DBCNM) and chloroform, were detected, DBCNM was found at relatively high concentrations (up to 8.5 μg L(-1)). The water at the CWT outfall also had a mixture of inorganic and organic precursors including elevated concentrations of bromide (75 mg L(-1)) and other organic DBP precursors (phenol at 15 μg L(-1)). To corroborate these DBP results, samples were collected in Pennsylvania from additional POTW and CWT outfalls that accept produced waters. The additional CWT also had high concentrations of DBCNM (3.1 μg L(-1)) while the POTWs that accept produced waters had elevated numbers (up to 15) and concentrations of DBPs, especially brominated and iodinated THMs (up to 12 μg L(-1) total THM concentration). Therefore, produced water brines that have been disinfected are potential sources of DBPs along with DBP precursors to streams wherever these wastewaters are discharged.

Pesticide concentrations in frog tissue and wetland habitats in a landscape dominated by agriculture

Habitat loss and exposure to pesticides are likely primary factors contributing to amphibian decline in agricultural landscapes. Conservation efforts have attempted to restore wetlands lost through landscape modifications to reduce contaminant loads in surface waters and providing quality habitat to wildlife. The benefits of this increased wetland area, perhaps especially for amphibians, may be negated if habitat quality is insufficient to support persistent populations. We examined the presence of pesticides and nutrients in water and sediment as indicators of habitat quality and assessed the bioaccumulation of pesticides in the tissue of two native amphibian species Pseudacris maculata (chorus frogs) and Lithobates pipiens (leopard frogs) at six wetlands (3 restored and 3 reference) in Iowa, USA. Restored wetlands are positioned on the landscape to receive subsurface tile drainage water while reference wetlands receive water from overland run-off and shallow groundwater sources. Concentrations of the pesticides frequently detected in water and sediment samples were not different between wetland types. The median concentration of atrazine in surface water was 0.2 μg/L. Reproductive abnormalities in leopard frogs have been observed in other studies at these concentrations. Nutrient concentrations were higher in the restored wetlands but lower than concentrations thought lethal to frogs. Complex mixtures of pesticides including up to 8 fungicides, some previously unreported in tissue, were detected with concentrations ranging from 0.08 to 1,500 μg/kg wet weight. No significant differences in pesticide concentrations were observed between species, although concentrations tended to be higher in leopard frogs compared to chorus frogs, possibly because of differences in life histories. Our results provide information on habitat quality in restored wetlands that will assist state and federal agencies, landowners, and resource managers in identifying and implementing conservation and management actions for these and similar wetlands in agriculturally dominated landscapes.

Exposure of native bees foraging in an agricultural landscape to current-use pesticides

The awareness of insects as pollinators and indicators of environmental quality has grown in recent years, partially in response to declines in honey bee (Apis mellifera) populations. While most pesticide research has focused on honey bees, there has been less work on native bee populations. To determine the exposure of native bees to pesticides, bees were collected from an existing research area in northeastern Colorado in both grasslands (2013-2014) and wheat fields (2014). Traps were deployed bi-monthly during the summer at each land cover type and all bees, regardless of species, were composited as whole samples and analyzed for 136 current-use pesticides and degradates. This reconnaissance approach provides a sampling of all species and represents overall pesticide exposure (internal and external). Nineteen pesticides and degradates were detected in 54 composite samples collected. Compounds detected in >2% of the samples included: insecticides thiamethoxam (46%), bifenthrin (28%), clothianidin (24%), chlorpyrifos (17%), imidacloprid (13%), fipronil desulfinyl (7%; degradate); fungicides azoxystrobin (17%), pyraclostrobin (11%), fluxapyroxad (9%), and propiconazole (9%); herbicides atrazine (19%) and metolachlor (9%). Concentrations ranged from 1 to 310 ng/g for individual pesticides. Pesticides were detected in samples collected from both grasslands and wheat fields; the location of the sample and the surrounding land cover at the 1000 m radius influenced the pesticides detected but because of a small number of temporally comparable samples, correlations between pesticide concentration and land cover were not significant. The results show native bees collected in an agricultural landscape are exposed to multiple pesticides, these results can direct future research on routes/timing of pesticide exposure and the design of future conservation efforts for pollinators.

Assessing the occurrence and distribution of pyrethroids in water and suspended sediments.

The distribution of pyrethroid insecticides in the environment was assessed by separately measuring concentrations in the dissolved and suspended sediment phases of surface water samples. Filtered water was extracted by HLB solid-phase extraction cartridges, while the sediment on the filter was sonicated and cleaned up using carbon and aluminum cartridges. Detection limits for the 13 pyrethroids analyzed by gas chromatography-tandem mass spectrometry were 0.5 to 1 ng L(-1) for water and 2 to 6 ng g(-1) for the suspended sediments. Seven pyrethroids were detected in six water samples collected from either urban or agricultural creeks, with bifenthrin detected the most frequently and at the highest concentrations. In spiked water samples and field samples, the majority of the pyrethroids were associated with the suspended sediments.

First national-scale reconnaissance of neonicotinoid insecticides in streams across the USA

Environmental context Neonicotinoids are under increased scrutiny because they have been implicated in pollinator declines and, more recently, as potential aquatic toxicants. Nevertheless, there is currently little information on concentrations of multiple neonicotinoids in surface water. This paper presents a summary of concentrations of six neonicotinoids in streams from across the United States in both urban and agricultural areas. These environmental data are important in determining the potential risk of neonicotinoids to non-target aquatic and terrestrial organisms. Abstract To better understand the fate and transport of neonicotinoid insecticides, water samples were collected from streams across the United States. In a nationwide study, at least one neonicotinoid was detected in 53% of the samples collected, with imidacloprid detected most frequently (37%), followed by clothianidin (24%), thiamethoxam (21%), dinotefuran (13%), acetamiprid (3%) and thiacloprid (0%). Clothianidin and thiamethoxam concentrations were positively related to the percentage of the land use in cultivated crop production and imidacloprid concentrations were positively related to the percentage of urban area within the basin. Additional sampling was also conducted in targeted research areas to complement these national-scale results, including determining: (1) neonicotinoid concentrations during elevated flow conditions in an intensely agricultural region; (2) temporal patterns of neonicotinoids in heavily urbanised basins; (3) neonicotinoid concentrations in agricultural basins in a nationally important ecosystem; and (4) in-stream transport of neonicotinoids near a wastewater treatment plant. Across all study areas, at least one neonicotinoid was detected in 63% of the 48 streams sampled.

PYRETHROID INSECTICIDE CONCENTRATIONS AND TOXICITY IN STREAMBED SEDIMENTS AND LOADS IN SURFACE WATERS OF THE SAN JOAQUIN VALLEY, CALIFORNIA, USA

Pyrethroid insecticide use in California, USA, is growing, and there is a need to understand the fate of these compounds in the environment. Concentrations and toxicity were assessed in streambed sediment of the San Joaquin Valley of California, one of the most productive agricultural regions of the United States. Concentrations were also measured in the suspended sediment associated with irrigation or storm-water runoff, and mass loads during storms were calculated. Western valley streambed sediments were frequently toxic to the amphipod, Hyalella azteca, with most of the toxicity attributable to bifenthrin and cyhalothrin. Up to 100% mortality was observed in some locations with concentrations of some pyrethroids up to 20 ng/g. The western San Joaquin Valley streams are mostly small watersheds with clay soils, and sediment-laden irrigation runoff transports pyrethroid insecticides throughout the growing season. In contrast, eastern tributaries and the San Joaquin River had low bed sediment concentrations (<1 ng/g) and little or no toxicity because of the preponderance of sandy soils and sediments. Bifenthrin, cyhalothrin, and permethrin were the most frequently detected pyrethroids in irrigation and storm water runoff. Esfenvalerate, fenpropathrin, and resmethrin were also detected. All sampled streams contributed to the insecticide load of the San Joaquin River during storms, but some compounds detected in the smaller creeks were not detected in the San Joaquin River. The two smallest streams, Ingram and Hospital Creeks, which had high sediment toxicity during the irrigation season, accounted for less than 5% of the total discharge of the San Joaquin River during storm conditions, and as a result their contribution to the pyrethroid mass load of the larger river was minimal.

Neutral degradates of chloroacetamide herbicides: Occurrence in drinking water and removal during conventional water treatment

Treated drinking water samples from 12 water utilities in the Midwestern United States were collected during Fall 2003 and Spring 2004 and were analyzed for selected neutral degradates of chloroacetamide herbicides, along with related compounds. Target analytes included 20 neutral chloroacetamide degradates, six ionic chloroacetamide degradates, four parent chloroacetamide herbicides, three triazine herbicides, and two neutral triazine degradates. In the fall samples, 17 of 20 neutral chloroacetamide degradates were detected in the finished drinking water, while 19 of 20 neutral chloroacetamide degradates were detected in the spring. Median concentrations for the neutral chloroacetamide degradates were approximately 2-60ng/L during both sampling periods. Concentrations measured in the fall samples of treated water were nearly the same as those measured in source waters, despite the variety of treatment trains employed. Significant removals (average of 40% for all compounds) were only found in the spring samples at those utilities that employed activated carbon.

Expanded Target-Chemical Analysis Reveals Extensive Mixed-Organic-Contaminant Exposure in U.S. Streams

Surface water from 38 streams nationwide was assessed using 14 target-organic methods (719 compounds). Designed-bioactive anthropogenic contaminants (biocides, pharmaceuticals) comprised 57% of 406 organics detected at least once. The 10 most-frequently detected anthropogenic-organics included eight pesticides (desulfinylfipronil, AMPA, chlorpyrifos, dieldrin, metolachlor, atrazine, CIAT, glyphosate) and two pharmaceuticals (caffeine, metformin) with detection frequencies ranging 66-84% of all sites. Detected contaminant concentrations varied from less than 1 ng L-1 to greater than 10 μg L-1, with 77 and 278 having median detected concentrations greater than 100 ng L-1 and 10 ng L-1, respectively. Cumulative detections and concentrations ranged 4-161 compounds (median 70) and 8.5-102 847 ng L-1, respectively, and correlated significantly with wastewater discharge, watershed development, and toxic release inventory metrics. Log10 concentrations of widely monitored HHCB, triclosan, and carbamazepine explained 71-82% of the variability in the total number of compounds detected (linear regression; p-values: < 0.001-0.012), providing a statistical inference tool for unmonitored contaminants. Due to multiple modes of action, high bioactivity, biorecalcitrance, and direct environment application (pesticides), designed-bioactive organics (median 41 per site at μg L-1 cumulative concentrations) in developed watersheds present aquatic health concerns, given their acknowledged potential for sublethal effects to sensitive species and lifecycle stages at low ng L-1.

Concentrations and loads of suspended sediment-associated pesticides in the San Joaquin River, California and tributaries during storm events.

Current-use pesticides associated with suspended sediments were measured in the San Joaquin River, California and its tributaries during two storm events in 2008. Nineteen pesticides were detected: eight herbicides, nine insecticides, one fungicide and one insecticide synergist. Concentrations for the herbicides (0.1 to 3,000 ng/g; median of 6.1 ng/g) were generally greater than those for the insecticides (0.2 to 51 ng/g; median of 1.5 ng/g). Concentrations in the tributaries were usually greater than in the mainstem San Joaquin River and the west side tributaries were higher than the east side tributaries. Estimated instantaneous loads ranged from 1.3 to 320 g/day for herbicides and 0.03 to 53 g/day for insecticides. The greatest instantaneous loads came from the Merced River on the east side. Instantaneous loads were greater for the first storm of 2008 than the second storm in the tributaries while the instantaneous loads within the San Joaquin River were greater during the second storm. Pesticide detections generally reflected pesticide application, but other factors such as physical-chemical properties and timing of application were also important to pesticide loads.