Kathryn M. Kuivila

Widespread occurrence of neonicotinoid insecticides in streams in a high corn and soybean producing region, USA.

Neonicotinoid insecticides are of environmental concern, but little is known about their occurrence in surface water. An area of intense corn and soybean production in the Midwestern United States was chosen to study this issue because of the high agricultural use of neonicotinoids via both seed treatments and other forms of application. Water samples were collected from nine stream sites during the 2013 growing season. The results for the 79 water samples documented similar patterns among sites for both frequency of detection and concentration (maximum:median) with clothianidin (75%, 257xa0ng/L:8.2xa0ng/L)xa0> thiamethoxam (47%, 185xa0ng/L:<2xa0ng/L)xa0>xa0imidacloprid (23%, 42.7xa0ng/L: <2xa0ng/L). Neonicotinoids werexa0detected at all nine sites sampled even though the basin areas spanned four orders of magnitude. Temporal patterns in concentrations reveal pulses of neonicotinoids associated with rainfall events during crop planting, suggesting seed treatments as their likely source.

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.

Genetic variation among interconnected populations of Catostomus occidentalis: implications for distinguishing impacts of contaminants from biogeographical structuring

Exposure to contaminants can affect survivorship, recruitment, reproductive success, mutation rates and migration, and may play a significant role in the partitioning of genetic variation among exposed and nonexposed populations. However, the application of molecular population genetic data to evaluate such influences has been uncommon and often flawed. We tested whether patterns of genetic variation among native fish populations (Sacramento sucker, Catostomus occidentalis) in the Central Valley of California were consistent with long‐term pesticide exposure history, or primarily with expectations based on biogeography. Field sampling was designed to rigorously test for both geographical and contamination influences. Fine‐scale structure of these interconnected populations was detected with both amplified fragment length polymorphisms (AFLP) and microsatellite markers, and patterns of variation elucidated by the two marker systems were highly concordant. Analyses indicated that biogeographical hypotheses described the data set better than hypotheses relating to common historical pesticide exposure. Downstream populations had higher genetic diversity than upstream populations, regardless of exposure history, and genetic distances showed that populations from the same river system tended to cluster together. Relatedness among populations reflected primarily directions of gene flow, rather than convergence among contaminant‐exposed populations. Watershed geography accounted for significant partitioning of genetic variation among populations, whereas contaminant exposure history did not. Genetic patterns indicating contaminant‐induced selection, increased mutation rates or recent bottlenecks were weak or absent. We stress the importance of testing contaminant‐induced genetic change hypotheses within a biogeographical context. Strategic application of molecular markers for analysis of fine‐scale structure, and for evaluating contaminant impacts on gene pools, is discussed.

Occurrence of boscalid and other selected fungicides in surface water and groundwater in three targeted use areas in the United States.

To provide an assessment of the occurrence of fungicides in water resources, the US Geological Survey used a newly developed analytical method to measure 33 fungicides and an additional 57 current-use pesticides in water samples from streams, ponds, and shallow groundwater in areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within farms using prophylactic fungicides at rates and types typical of their geographic location. At least one fungicide was detected in 75% of the surface waters and 58% of the groundwater wells sampled. Twelve fungicides were detected including boscalid (72%), azoxystrobin (51%), pyraclostrobin (40%), chlorothalonil (38%) and pyrimethanil (28%). Boscalid, a carboxamide fungicide registered for use in the US in 2003, was detected more frequently than atrazine and metolachlor, two herbicides that are typically the most frequently occurring pesticides in many large-scale water quality studies. Fungicide concentrations ranged from less than the method detection limit to approximately 2000 ngL(-1). Currently, limited toxicological data for non-target species exists and the environmental impacts are largely unknown. The results of this study indicate the importance of including fungicides in pesticide monitoring programs, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.

Multi-residue method for the analysis of 85 current-use and legacy pesticides in bed and suspended sediments

A multi-residue method was developed for the simultaneous determination of 85 current-use and legacy organochlorine pesticides in a single sediment sample. After microwave-assisted extraction, clean-up of samples was optimized using gel permeation chromatography and either stacked carbon and alumina solid-phase extraction cartridges or a deactivated Florisil column. Analytes were determined by gas chromatography with ion-trap mass spectrometry and electron capture detection. Method detection limits ranged from 0.6 to 8.9 microg/kg dry weight. Bed and suspended sediments from a variety of locations were analyzed to validate the method and 29 pesticides, including at least 1 from every class, were detected.

A multi-residue method for the analysis of pesticides and pesticide degradates in water using HLB solid-phase extraction and gas chromatography-ion trap mass spectrometry.

A method was developed for the analysis of over 60 pesticides and degradates in water by HLB solid-phase extraction and gas-chromatography/mass spectrometry. Method recoveries and detection limits were determined using two surface waters with different dissolved organic carbon (DOC) concentrations. In the lower DOC water, recoveries and detection limits were 80%–108% and 1–12xa0ng/L, respectively. In the higher DOC water, the detection limits were slightly higher (1–15xa0ng/L). Additionally, surface water samples from four sites were analyzed and 14 pesticides were detected with concentrations ranging from 4 to 1,200xa0ng/L.

Pesticides Associated with Suspended Sediments Entering San Francisco Bay Following the First Major Storm of Water Year 1996

Estuaries receive large quantities of suspended sediments following the first major storm of the water year. The first-flush events transport the majority of suspended sediments in any given year, and because of their relative freshness in the hydrologic system, these sediments may carry a significant amount of the sediment-associated pesticide load transported into estuaries. To characterize sediment-associated pesticides during a first-flush event, water and suspended sediment samples were collected at the head of the San Francisco Bay during the peak in suspended sediment concentration that followed the first major storm of the 1996 hydrologic year. Samples were analyzed for a variety of parameters as well as 19 pesticides and degradation products that span a wide range of hydrophobicity. Tidal mixing at the head of the estuary mixed relatively fresh suspended sediment transported down the rivers with suspended sediments in estuary waters. Segregation of the samples into groups with similar degrees of mixing between river and estuary water revealed that transport of suspended sediments from the Sacramento-San Joaquin drainage basin strongly influenced the concentration and distribution of sediment-associated pesticides entering the San Francisco Bay. The less-mixed suspended sediment contained a different distribution of pesticides than the sediments exposed to greater mixing. Temporal trends were evident in pesticide content after samples were segregated according to mixing history. These results indicate sampling strategies that collect at a low frequency or do not compare samples with similar mixing histories will not elucidate basin processes. Despite the considerable influence of mixing, a large number of pesticides were found associated with the suspended sediments. Few pesticides were found in the concurrent water samples and in concentrations much lower than predicted from equilibrium partitioning between the aqueous and sedimentary phases. The observed sediment-associated pesticide concentrations may reflect disequilibria between sedimentary and aqueous phases resulting from long equilibration times at locations where pesticides were applied, and relatively short transit times over which re-equilibration may occur.

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.

Environmental fate of fungicides and other current-use pesticides in a central California estuary

The current study documents the fate of current-use pesticides in an agriculturally-dominated central California coastal estuary by focusing on the occurrence in water, sediment and tissue of resident aquatic organisms. Three fungicides (azoxystrobin, boscalid, and pyraclostrobin), one herbicide (propyzamide) and two organophosphate insecticides (chlorpyrifos and diazinon) were detected frequently. Dissolved pesticide concentrations in the estuary corresponded to the timing of application while bed sediment pesticide concentrations correlated with the distance from potential sources. Fungicides and insecticides were detected frequently in fish and invertebrates collected near the mouth of the estuary and the contaminant profiles differed from the sediment and water collected. This is the first study to document the occurrence of many current-use pesticides, including fungicides, in tissue. Limited information is available on the uptake, accumulation and effects of current-use pesticides on non-target organisms. Additional data are needed to understand the impacts of pesticides, especially in small agriculturally-dominated estuaries.

Accumulation of pesticides in Pacific chorus frogs (Pseudacris regilla) from California's Sierra Nevada Mountains, USA.

Pesticides are receiving increasing attention as potential causes of amphibian declines, acting singly or in combination with other stressors, but limited information is available on the accumulation of current-use pesticides in tissue. The authors examined potential exposure and accumulation of currently used pesticides in pond-breeding frogs (Pseudacris regilla) collected from 7 high elevations sites in northern California. All sites sampled are located downwind of Californias highly agricultural Central Valley and receive inputs of pesticides through precipitation and/or dry deposition. Whole frog tissue, water, and sediment were analyzed for more than 90 current-use pesticides and pesticide degradates using gas chromatography-mass spectrometry. Two fungicides, pyraclostrobin and tebuconazole, and one herbicide, simazine, were the most frequently detected pesticides in tissue samples. Median pesticide concentration ranged from 13u2009µg/kg to 235u2009µg/kg wet weight. Tebuconazole and pyraclostrobin were the only 2 compounds observed frequently in frog tissue and sediment. Significant spatial differences in tissue concentration were observed, which corresponded to pesticide use in the upwind counties. Data generated indicated that amphibians residing in remote locations are exposed to and capable of accumulating current-use pesticides. A comparison of P. regilla tissue concentrations with water and sediment data indicated that the frogs are accumulating pesticides and are potentially a more reliable indicator of exposure to this group of pesticides than either water or sediment.