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Kelly L. Smalling

Publications and source records attributed to Kelly L. Smalling.

At least 109 records · Page 6Linked to original sources

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 from two land cover types: 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 >10% of the samples included the insecticides thiamethoxam (46%), bifenthrin (28%), clothianidin (24%), chlorpyrifos (17%), and imidacloprid (13%), the fungicides azoxystrobin (17%), and pyraclostrobin (11%), and the herbicide atrazine (19%). Concentrations ranged from 1.1 to 312 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 buffer 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 both grasslands and wheat fields 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.

Colorado↗

Potential interactions among disease, pesticides, water quality and adjacent land cover in amphibian habitats in the United States

To investigate interactions among disease, pesticides, water quality, and adjacent land cover, we collected samples of water, sediment, and frog tissue from 21 sites in 7 States in the United States (US) representing a variety of amphibian habitats. All samples were analyzed for > 90 pesticides and pesticide degradates, and water and frogs were screened for the amphibian chytrid fungus Batrachochytrium dendrobatidis (Bd) using molecular methods. Pesticides and pesticide degradates were detected frequently in frog breeding habitats (water and sediment) as well as in frog tissue. Fungicides occurred more frequently in water, sediment, and tissue than was expected based upon their limited use relative to herbicides or insecticides. Pesticide occurrence in water or sediment was not a strong predictor of occurrence in tissue, but pesticide concentrations in tissue were correlated positively to agricultural and urban land, and negatively to forested land in 2-km buffers around the sites. Bd was detected in water at 45% of sites, and on 34% of swabbed frogs. Bd detections in water were not associated with differences in land use around sites, but sites with detections had colder water. Frogs that tested positive for Bd were associated with sites that had higher total fungicide concentrations in water and sediment, but lower insecticide concentrations in sediments relative to frogs that were Bd negative. Bd concentrations on frog swabs were positively correlated to dissolved organic carbon, and total nitrogen and phosphorus, and negatively correlated to pH and water temperature. Data were collected from a range of locations and amphibian habitats and represent some of the first field-collected information aimed at understanding the interactions between pesticides, land use, and amphibian disease. These interactions are of particular interest to conservation efforts as many amphibians live in altered habitats and may depend on wetlands embedded in these landscapes to survive.

California, Colorado, Georgia, Idaho, Louisiana, M↗

Restored agricultural wetlands in Central Iowa: habitat quality and amphibian response

Amphibians are declining throughout the United States and worldwide due, partly, to habitat loss. Conservation practices on the landscape restore wetlands to denitrify tile drainage effluent and restore ecosystem services. Understanding how water quality, hydroperiod, predation, and disease affect amphibians in restored wetlands is central to maintaining healthy amphibian populations in the region. We examined the quality of amphibian habitat in restored wetlands relative to reference wetlands by comparing species richness, developmental stress, and adult leopard frog (Lithobates pipiens) survival probabilities to a suite of environmental metrics. Although measured habitat variables differed between restored and reference wetlands, differences appeared to have sub-lethal rather than lethal effects on resident amphibian populations. There were few differences in amphibian species richness and no difference in estimated survival probabilities between wetland types. Restored wetlands had more nitrate and alkaline pH, longer hydroperiods, and were deeper, whereas reference wetlands had more amphibian chytrid fungus zoospores in water samples and resident amphibians exhibited increased developmental stress. Restored and reference wetlands are both important components of the landscape in central Iowa and maintaining a complex of fish-free wetlands with a variety of hydroperiods will likely contribute to the persistence of amphibians in this landscape.

Iowa↗

Chemical and ancillary data associated with bed sediment, young of year Bluefish ( Pomatomus saltatrix ) tissue, and mussel ( Mytilus edulis and Geukensia demissa ) tissue collected after Hurricane Sandy in bays and estuaries of New Jersey and New York, 2013–14

This report describes the methods and data associated with a reconnaissance study of young of year bluefish and mussel tissue samples as well as bed sediment collected as bluefish habitat indicators during August 2013–April 2014 in New Jersey and New York following Hurricane Sandy in October 2012. This study was funded by the Disaster Relief Appropriations Act of 2013 (PL 113-2) and was conducted by the U.S. Geological Survey (USGS) in cooperation with the National Oceanic and Atmospheric Administration (NOAA). Young of year Pomatomus saltatrix (bluefish) were collected from nine sites in New Jersey (N.J.) and New York (N.Y.) including Barnegat Bay, N.J., Sandy Hook Bay, N.J., Jamaica Bay, N.Y., and Great South Bay, N.Y., and analyzed for indicators of health and chemical contamination. At each bluefish sampling location, bed sediment was also collected and analyzed for a suite of contaminants. Resident mussels, Mytilus edulis (blue mussels) and (or) Geukensia demissa (ribbed mussels), were collected from 11 historic NOAA Mussel Watch Program sites along the N.J. and N.Y. coastlines in the winter/spring of 2014 and analyzed for contaminants. Individual age of a subset of the mussels sampled was also determined at each site. Bed sediment samples were analyzed for a suite of organic contaminants including 34 polychlorinated biphenyl (PCB) congeners, 28 polybrominated diphenyl ether (PBDE) congeners, 24 organochlorine pesticides (OCPs), 53 polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs, 33 aliphatic hydrocarbons (AHs), and 10 petroleum biomarkers (steranes and hopanes). Bed sediment collected from the Navesink River (Sandy Hook, N.J.), Metedeconk River (Barnegat Bay, N.J.), and Toms River (Barnegat Bay, N.J.) had the highest concentrations of contaminants compared to the other sites. Bluefish and mussel tissue collected throughout the study area was analyzed for 34 PCB congeners, 28 PBDE congeners, and 24 OCPs. Thirty-three PCB congeners, 22 PBDE congeners, and 24 OCPs were detected in the bluefish analyzed. The highest median concentrations of total PCBs were present in tissue from Jamaica Bay, N.Y., whereas the highest median concentrations of total PBDEs and total OCPs were present in tissue from Sandy Hook Bay. Of the OCPs detected, p,p’ -DDE was found in 99 percent (%) of the tissue samples and at the highest median concentrations compared to the other OCPs. Fish health assessments were conducted on 20 fish from the 4 bays. Results indicate that the sex ratio and the mean total length varied by site. Physical fish damage, such as lesions and parasites, was observed in fish from all four bays. The most common parasite observed visually was the presence of Livoneca redmanii , an ectoparasitic gill isopod, which can cause localized gill erosion. The prevalence of the gill isopod infestation ranged from 20% at Great South Bay, N.Y., to 35% at Jamaica Bay, N.Y. Twenty three PCB congeners, 9 PBDE congeners, and 20 OCPs were detected in composite mussel samples collected throughout the study area. The co-eluting PCB congeners 153 and 132, PBDE 47, 99, and 100, and p,p’ -DDE were detected in samples from each site. The highest median concentrations of PCBs and PBDEs were present in mussels from Raritan Bay, N.Y., whereas the highest median concentrations of OCPs were present in mussels from Fire Island Inlet, N.Y., and Shark River, N.J. Mytilus edulis (blue mussels) and Geukensia demissa (ribbed mussels) were thin-sectioned and aged. The blue mussels collected ranged in age from 4 to 13 years, and the ribbed mussels ranged in age from 3 to 12 years.

New Jersey, New York↗

Pesticide concentrations in frog tissue and wetland habitats in alandscape 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 1500 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.

Iowa↗

Estuarine bed-sediment-quality data collected in New Jersey and New York after Hurricane Sandy, 2013

This report describes a reconnaissance study of estuarine bed-sediment quality conducted June–October 2013 in New Jersey and New York after Hurricane Sandy in October 2012 to assess the extent of contamination and the potential long-term human and ecological impacts of the storm. The study, funded through the Disaster Relief Appropriations Act of 2013 (PL 113-2), was conducted by the U.S. Geological Survey in cooperation with the U.S. Environmental Protection Agency and the National Oceanographic and Atmospheric Administration. In addition to presenting the bed-sediment-quality data, the report describes the study design, documents the methods of sample collection and analysis, and discusses the steps taken to assure the quality of the data. Bed-sediment samples were collected from June to October 2013 from 167 estuarine sites extending from Cape May, New Jersey, to the New York Harbor and the eastern end of Long Island. Each sampling location and study region was characterized by using geographic information to identify potential contaminant sources. Characterizations included land cover, locations and types of businesses (industrial, financial, and others), spills (sewage, chemical, and others), bulk storage facilities, effluent discharges within 2 kilometers of the sampling point, and discharges within inundated and non-inundated regions near the sampling location. Samples were analyzed for particle size, total organic carbon, metals and trace elements, semivolatile organic compounds, wastewater compounds, hormones, and sediment toxicity. Samples were also screened using x-ray fluorescence, Fourier transform infrared spectroscopy, and x-ray diffraction. In addition, bioassays for endocrine disruptors and protein phosphatase 2A inhibition were conducted. The study was designed to provide the data needed to understand the extent and sources of contamination resulting from Hurricane Sandy, to compare the chemistry and toxicity of estuarine bed sediments before and after the storm, and to evaluate the usefulness of rapid screening and bioassay approaches in disaster settings.

New Jersey, New York↗

Occurrence of contaminants of emerging concern along the California coast (2009-10) using passive sampling devices

Three passive sampling devices (PSDs), polar organic chemical integrative samplers (POCIS), polyethylene devices (PEDs), and solid-phase microextraction (SPME) samplers were used to sample a diverse set of chemicals in the coastal waters of San Francisco Bay and the Southern California Bight. Seventy one chemicals (including fragrances, phosphate flame retardants, pharmaceuticals, PAHs, PCBs, PBDEs, and pesticides) were measured in at least 50% of the sites. The chemical profile from the San Francisco Bay sites was distinct from profiles from the sites in the Southern California Bight. This distinction was not due to a single compound or class, but by the relative abundances/concentrations of the chemicals. Comparing the PSDs to mussel ( Mytilus spp.) tissues, a positive correlation exists for the 25 and 26 chemicals in common for the PEDs and SPME, respectively. Diphenhydramine was the only common chemical out of 40 analyzed in both POCIS and tissues detected at a common site.

California↗

Assessing the potential effects of fungicides on nontarget gut fungi (trichomycetes) and their associated larval black fly hosts

Fungicides are moderately hydrophobic and have been detected in water and sediment, particularly in agricultural watersheds, but typically are not included in routine water quality monitoring efforts. This is despite their widespread use and frequent application to combat fungal pathogens. Although the efficacy of these compounds on fungal pathogens is well documented, little is known about their effects on nontarget fungi. This pilot study, a field survey in southwestern Idaho from April to December 2010 on four streams with varying pesticide inputs (two agricultural and two reference sites), was conducted to assess nontarget impact of fungicides on gut fungi, or trichomycetes. Tissues of larval black flies (Diptera: Simuliidae), hosts of gut fungi, were analyzed for pesticide accumulation. Fungicides were detected in hosts from streams within agricultural watersheds but were not detected in hosts from reference streams. Gut fungi from agricultural sites exhibited decreased percent infestation, density and sporulation within the gut, and black fly tissues had elevated pesticide concentrations. Differences observed between the sites demonstrate a potential effect on this symbiotic system. Future research is needed to parse out the details of the complex biotic and abiotic relationships; however, these preliminary results indicate that impacts to nontarget organisms could have far-reaching consequences within aquatic ecosystems.

Journal of the American Water Resources Associatio↗

Occurrence of pesticides in groundwater and sediments and mineralogy of sediments and grain coatings underlying the Rutgers Agricultural Research and Extension Center, Upper Deerfield, New Jersey, 2007

Water and sediment samples were collected from June through October 2007 from seven plots at the Rutgers Agricultural Research and Extension Center in Upper Deerfield, New Jersey, and analyzed for a suite of pesticides (including fungicides) and other physical and chemical parameters (including sediment mineralogy) by the U.S. Geological Survey. Plots were selected for inclusion in this study on the basis of the crops grown and the pesticides used. Forty-one pesticides were detected in 14 water samples; these include 5 fungicides, 13 herbicides, 1 insecticide, and 22 pesticide degradates. The following pesticides and pesticide degradates were detected in 50 percent or more of the groundwater samples: 1-amide-4-hydroxy-chorothalonil, alachlor sulfonic acid, metolachlor oxanilic acid, metolachlor sulfonic acid, metalaxyl, and simazine. Dissolved-pesticide concentrations ranged from below their instrumental limit of detection to 36 micrograms per liter (for metolachlor sulfonic acid, a degradate of the herbicide metolachlor). The total number of pesticides found in groundwater samples ranged from 0 to 29. Fourteen pesticides were detected in sediment samples from continuous cores collected within each of the seven sampled plots; these include 4 fungicides, 2 herbicides, and 7 pesticide degradates. Pesticide concentrations in sediment samples ranged from below their instrumental limit of detection to 34.2 nanograms per gram (for azoxystrobin). The total number of pesticides found in sediment samples ranged from 0 to 8. Quantitative whole-rock and grain-coating mineralogy of sediment samples were determined by x-ray diffraction. Whole-rock analysis indicated that sediments were predominantly composed of quartz. The materials coating the quartz grains were removed to allow quantification of the trace mineral phases present.

New Jersey↗

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 California's 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 13 µg/kg to 235 µg/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.

California↗

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.

California↗

Occurrence and persistence of fungicides in bed sediments and suspended solids from three targeted use areas in the United States

To document the environmental occurrence and persistence of fungicides, a robust and sensitive analytical method was used to measure 34 fungicides and an additional 57 current-use pesticides in bed sediments and suspended solids collected from areas of intense fungicide use within three geographic areas across the United States. Sampling sites were selected near or within agricultural research farms using prophylactic fungicides at rates and types typical of their geographic location. At least two fungicides were detected in 55% of the bed and 83% of the suspended solid samples and were detected in conjunction with herbicides and insecticides. Six fungicides were detected in all samples including pyraclostrobin (75%), boscalid (53%), chlorothalonil (41%) and zoxamide (22%). Pyraclostrobin, a strobilurin fungicide, used frequently in the United States on a variety of crops, was detected more frequently than p,p′ -DDE, the primary degradate of p,p′ -DDT, which is typically one of the most frequently occurring pesticides in sediments collected within highly agricultural areas. Maximum fungicide concentrations in bed sediments and suspended solids were 198 and 56.7 μg/kg dry weight, respectively. There is limited information on the occurrence, fate, and persistence of many fungicides in sediment and the environmental impacts are largely unknown. The results of this study indicate the importance of documenting the persistence of fungicides in the environment and the need for a better understanding of off-site transport mechanisms, particularly in areas where crops are grown that require frequent treatments to prevent fungal diseases.

Science of the Total Environment↗

Occurrence of fungicides and other pesticides in surface water, groundwater, and sediment from three targeted-use areas in the United States, 2009

Surface-water, groundwater, and suspended- and bedsediment samples were collected in three targeted-use areas in the United States where potatoes were grown during 2009 and analyzed for an extensive suite of fungicides and other pesticides by gas chromatograph/mass spectrometry and liquid chromatography with tandem mass spectrometry. Fungicides were detected in all environmental matrices sampled during the study. The most frequently detected fungicides were azoxystrobin, boscalid, chlorothalonil, and pyraclostrobin. Other pesticides that were detected frequently included amino phosphonic acid (AMPA), atrazine, metolaclor, and the organochlorine insecticide p,p’-DDT and its degradates p,p’-DDD and p,p’-DDE. A greater number of pesticides were detected in surface water relative to the other environmental matrices sampled, and at least one pesticide was detected in 62 of the 63 surfacewater samples. The greatest numbers of pesticides and the maximum observed concentrations for most pesticides were measured in surface-water samples from Idaho. In eight surface- water samples (six from Idaho and two from Wisconsin), concentrations of bifenthrin, metolachlor, or malathion exceeded U.S. Environmental Protection Agency freshwater aquatic-life benchmarks for chronic toxicity to invertebrates. Thirteen pesticides, including seven fungicides, were detected in groundwater samples. Shallow groundwater samples collected beneath recently harvested potato fields contained more pesticides and had higher concentrations of pesticides than samples collected from other groundwater sources sampled during the study. Generally, pesticide concentrations were lower in groundwater samples than in surfacewater or sediment samples, with the exception of the fungicide boscalid, which was found to have its highest concentration in a shallow groundwater sample collected in Wisconsin. Thirteen pesticides, including four fungicides, were detected in suspended-sediment samples. The most frequently detected compounds were the fungicides boscalid, pyraclostrobin, and zoxamide, and the degradates p,p’-DDD and p,p’-DDE. Twenty pesticides, including six fungicides, were detected in bed-sediment samples. The most frequently detected compounds were pyraclostrobin, p,p’-DDT, p,p’-DDD, and p,p’-DDE.

Idaho, Maine, Wisconsin↗

Dissolved pesticides, dissolved organic carbon, and water-quality characteristics in selected Idaho streams, April--December 2010

Water-quality samples were collected from April through December 2010 from four streams in Idaho and analyzed for a suite of pesticides, including fungicides, by the U.S. Geological Survey. Water samples were collected from two agricultural and two nonagricultural (control) streams approximately biweekly from the beginning of the growing season (April) through the end of the calendar year (December). Samples were analyzed for 90 pesticides using gas chromatography/mass spectrometry. Twenty-three pesticides, including 8 fungicides, 10 herbicides, 3 insecticides, and 2 pesticide degradates, were detected in 45 water samples. The most frequently detected compounds in the two agricultural streams and their detection frequencies were metolachlor, 96 percent; azoxystrobin, 79 percent; boscalid, 79 percent; atrazine, 46 percent; pendimethalin, 33 percent; and trifluralin, 33 percent. Dissolved-pesticide concentrations ranged from below instrumental limits of detection (0.5-1.0 nanograms per liter) to 771 nanograms per liter (hexazinone). The total number of pesticides detected in any given water sample ranged from 0 to 11. Only three pesticides (atrazine, fipronil, and simazine) were detected in samples from the control streams during the sampling period.

Idaho↗

Occurrence of pesticides in water and sediment collected from amphibian habitats located throughout the United States, 2009-10

Water and bed-sediment samples were collected by the U.S. Geological Survey (USGS) in 2009 and 2010 from 11 sites within California and 18 sites total in Colorado, Georgia, Idaho, Louisiana, Maine, and Oregon, and were analyzed for a suite of pesticides by the USGS. Water samples and bed-sediment samples were collected from perennial or seasonal ponds located in amphibian habitats in conjunction with research conducted by the USGS Amphibian Research and Monitoring Initiative and the USGS Toxic Substances Hydrology Program. Sites selected for this study in three of the states (California, Colorado, and Orgeon) have no direct pesticide application and are considered undeveloped and remote. Sites selected in Georgia, Idaho, Louisiana, and Maine were in close proximity to either agricultural or suburban areas. Water and sediment samples were collected once in 2009 during amphibian breeding seasons. In 2010, water samples were collected twice. The first sampling event coincided with the beginning of the frog breeding season for the species of interest, and the second event occurred 10-12 weeks later when pesticides were being applied to the surrounding areas. Additionally, water was collected during each sampling event to measure dissolved organic carbon, nutrients, and the fungus, Batrachochytrium dendrobatidis , which has been linked to amphibian declines worldwide. Bed-sediment samples were collected once during the beginning of the frog breeding season, when the amphibians are thought to be most at risk to pesticides. Results of this study are reported for the following two geographic scales: (1) for a national scale, by using data from the 29 sites that were sampled from seven states, and (2) for California, by using data from the 11 sampled sites in that state. Water samples were analyzed for 96 pesticides by using gas chromatography/mass spectrometry. A total of 24 pesticides were detected in one or more of the 54 water samples, including 7 fungicides, 10 herbicides, 4 insecticides, 1 synergist, and 2 pesticide degradates. On a national scale, aminomethylphosphonic acid (AMPA), the primary degradate of the herbicide glyphosate, which is the active ingredient in Roundup®, was the most frequently detected pesticide in water (16 of 54 samples) followed by glyphosate (8 of 54 samples). The maximum number of pesticides observed at a single site was nine compounds in a water sample from a site in Louisiana. The maximum concentration of a pesticide or degradate observed in water was 2,880 nanograms per liter of clomazone (a herbicide) at a site in Louisiana. In California, a total of eight pesticides were detected among all of the low and high elevation sites; AMPA was the most frequently detected pesticide, but glyphosate was detected at the highest concentrations (1.1 micrograms per liter). Bed-sediment samples were analyzed for 94 pesticides by using accelerated solvent extraction, gel permeation chromatography for sulfur removal, and carbon/alumina stacked solid-phase extraction cartridges to remove interfering sediment matrices. In bed sediment, 22 pesticides were detected in one or more of the samples, including 9 fungicides, 3 pyrethroid insecticides, p,p' -dichlorodiphenyltrichloroethane ( p,p' -DDT) and its major degradates, as well as several herbicides. Pyraclostrobin, a strobilurin fungicide, and bifenthrin, a pyrethroid insecticide, were detected most frequently. Maximum pesticide concentrations ranged from less than their respective method detection limits to 1,380 micrograms per kilogram (tebuconazole in California). The number of pesticides detected in samples from each site ranged from zero to six compounds. The sites with the greatest number of pesticides were in Maine and Oregon with six pesticides detected in one sample from each state, followed by Georgia with four pesticides in one sample. For California, a total of 10 pesticides were detected among all sites, and 4 pesticides were detected at both low and high elevation sites; tebuconazole and pyraclostrobin were the two most frequently detected pesticides in California. For the other six selected states, the most frequently detected pesticides in bed sediment were pyraclostrobin (detected in 17 of 42 samples), bifenthrin (detected in 14 of 42 samples), and tebuconazole (detected in 10 of 42 samples). The fungus, Batrachochytrium dendrobatidis (Bd), was detected in water samples in sites from four of the seven states during 2009 and 2010, and the number of zoospore equivalents per liter of water in samples where Bd was detected ranged from 1.6 to 343. Bd was not detected in water samples from sites in Georgia, Louisiana, and Oregon.

Data Series↗

Occurrence of pesticides in surface water and sediments from three central California coastal watersheds, 2008-2009

Water and sediment (bed and suspended) were collected from January 2008 through October 2009 from 12 sites in 3 of the largest watersheds along California's Central Coast (Pajaro, Salinas, and Santa Maria Rivers) and analyzed for a suite of pesticides by the U.S. Geological Survey. Water samples were collected in each watershed from the estuaries and major tributaries during 4 storm events and 11 dry season sampling events in 2008 and 2009. Bed sediments were collected from depositional zones at the tributary sampling sites three times over the course of the study. Suspended sediment samples were collected from the major tributaries during the four storm events and in the tributaries and estuaries during three dry season sampling events in 2009. Water samples were analyzed for 68 pesticides using gas chromatography/mass spectrometry. A total of 38 pesticides were detected in 144 water samples, and 13 pesticides were detected in more than half the samples collected over the course of the study. Dissolved pesticide concentrations ranged from below their method detection limits to 36,000 nanograms per liter (boscalid). The most frequently detected pesticides in water from all the watersheds were azoxystrobin, boscalid, chlorpyrifos, DCPA, diazinon, oxyfluorfen, prometryn, and propyzamide, which were found in more than 80 percent of the samples. On average, detection frequencies and concentrations were higher in samples collected during winter storm events compared to the summer dry season. With the exception of the fungicide, myclobutanil, the Santa Maria estuary watershed exhibited higher pesticide detection frequencies than the Pajaro and Salinas watersheds. Bed and suspended sediment samples were analyzed for 55 pesticides using accelerated solvent extraction, gel permeation chromatography for sulfur removal, and carbon/alumina stacked solid-phase extraction cartridges to remove interfering sediment matrices. In bed sediment samples, 17 pesticides were detected including pyrethroid and organophosphate (OP) insecticides, p,p'-DDT and its degradates, as well as several herbicides. The only pesticides detected more than half the time were p,p'-DDD, p,p'-DDE, and p,p'-DDT. Maximum pesticide concentrations ranged from less than their respective method detection limits to 234 micrograms per kilogram (p,p'-DDE). Four pyrethroids (bifenthrin, &# 955;-cyhalothrin, permethrin, and &# 964;-fluvalinate) were detected in bed sediment samples, though concentrations were relatively low (less than 10 microgram per kilogram). The greatest number of pesticides were detected in samples collected from Lower Orcutt Creek, the major tributary to the Santa Maria estuary. In suspended sediment samples, 19 pesticides were detected, and maximum concentrations ranged from less than the method detection limits to 549 micrograms per kilogram (chlorpyrifos). The most frequently detected pesticides were p,p'-DDE (49 percent), p,p'-DDT (38 percent), and chlorpyrifos (32 percent). During storm events, 19 pesticides were detected in suspended sediment samples compared to 10 detected during the dry season. Pesticide concentrations commonly were higher in suspended sediments during storm events than during the dry season, as well.

Data Series↗

Analysis of current-use pesticides in aquatic and terrestrial organisms collected throughout California, USA

A wide variety of pesticides are applied concurrently in agricultural and urban areas and transported off site dissolved in water and bound to sediments. But the exposure of aquatic and terrestrial organisms to current-use pesticides and the resulting effects are not well understood. One approach is to directly analyze tissue concentrations of contaminants. The overall objective of this study was to develop a sensitive method to analyze current-use pesticides with a wide range of Kow's in tissue to better understand the accumulation of these contaminants in different aquatic and terrestrial organisms. This method was then used to analyze current-use pesticides in tissues from a variety of organisms from sites with different land-use practices.

California↗

Methods of analysis: Determination of pyrethroid insecticides in water and sediment using gas chromatography/mass spectrometry

A method for the determination of 14 pyrethroid insecticides in environmental water and sediment samples is described. The method was developed by the U.S. Geological Survey in response to increasing concern over the effects of pyrethroids on aquatic organisms. The pyrethroids included in this method are ones that are applied to many agricultural and urban areas. Filtered water samples are extracted for pyrethroids using solid-phase extraction (SPE) with no additional cleanup steps. Sediment and soil samples are extracted using a microwave-assisted extraction system, and the pyrethroids of interest are separated from co-extracted matrix interferences by passing the extracts through stacked graphitized carbon and alumina SPE cartridges, along with the use of high-performance liquid chromatography and gel-permeation chromatography (HPLC/GPC). Quantification of the pyrethroids from the extracted water and sediment samples is done using gas chromatography with mass spectrometry (GC/MS) or gas chromatography with tandem mass spectrometry (GC/MS/MS). Recoveries in test water samples fortified at 10 ng/L ranged from 83 to 107 percent, and recoveries in test sediment samples fortified at 10 ug/kg ranged from 82 to 101 percent; relative standard deviations ranged from 5 to 9 percent in the water samples and 3 to 9 percent in the sediment samples. Method detection limits (MDLs), calculated using U.S. Environmental Protection Agency procedures (40 CFR 136, Appendix B), in water ranged from 2.0 to 6.0 ng/L using GC/MS and 0.5 to 1.0 ng/L using GC/MS/MS. For sediment, the MDLs ranged from 1.0 to 2.6 ug/kg dry weight using GC/MS and 0.2 to 0.5 ug/kg dry weight using GC/MS/MS. The matrix-spike recoveries for each compound, when averaged for 12 environmental water samples, ranged from 84 to 96 percent, and when averaged for 27 environmental sediment samples, ranged from 88 to 100 percent.

Techniques and Methods↗