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<ul><li><p>U.S. Department of the InteriorU.S. Geological Survey</p><p>Data Series 667</p><p>Dissolved Pesticides, Dissolved Organic Carbon, and Water-Quality Characteristics in Selected Idaho Streams, AprilDecember 2010</p></li><li><p>Dissolved Pesticides, Dissolved Organic Carbon, and Water-Quality Characteristics in Selected Idaho Streams, AprilDecember 2010</p><p>By Timothy J. Reilly, Kelly L. Smalling, Emma R. Wilson, and William A. Battaglin</p><p>Data Series 667</p><p>U.S. Department of the InteriorU.S. Geological Survey</p></li><li><p>U.S. Department of the InteriorKEN SALAZAR, Secretary</p><p>U.S. Geological SurveyMarcia K. McNutt, Director</p><p>U.S. Geological Survey, Reston, Virginia: 2012</p><p>For more information on the USGSthe Federal source for science about the Earth, its natural and living resources, natural hazards, and the environment, visit http://www.usgs.gov or call 1888ASKUSGS.</p><p>For an overview of USGS information products, including maps, imagery, and publications, visit http://www.usgs.gov/pubprod</p><p>To order this and other USGS information products, visit http://store.usgs.gov</p><p>Any use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by the U.S. Government.</p><p>Although this report is in the public domain, permission must be secured from the individual copyright owners to reproduce any copyrighted materials contained within this report.</p><p>Suggested citation:Reilly, T.J., Smalling, K.L., Wilson, E.R., and Battaglin, W.A., 2012, Dissolved pesticides, dissolved organic carbon, and water-quality characteristics in selected Idaho streams, AprilDecember 2010: U.S. Geological Survey Data Series 667, 17 p.</p></li><li><p>iii</p><p>AcknowledgmentsThe authors thank Alexandra Etheridge, Kristi Jones, Megan McWayne Holmes, James </p><p>Orlando, Corey Sanders, and Ryan Todd of the U.S. Geological Survey (USGS) for their many hours of field, laboratory, and database work. The authors would also like to thank Lance Steele, Prasanna Kandel, Alison Chamberlin, and Korrine Wade from the Boise State Univer-sity, Department of Biological Sciences, for their assistance collecting water samples. This project was funded by the USGS Toxic Substances Hydrology Program and a grant from the National Science Foundation (award number DEB-0918182) to Dr. Merlin White at Boise State University, Department of Biological Sciences, Boise, Idaho.</p><p>Contents</p><p>Abstract ...........................................................................................................................................................1Introduction.....................................................................................................................................................1</p><p>Purpose and Scope ..............................................................................................................................2Description of Sampling Sites and Watershed Characteristics ...................................................2</p><p>Methods of Study ...........................................................................................................................................4Watershed Delineation and Land-Use Characterization ..............................................................4Sampling Methods ................................................................................................................................4Analysis of Dissolved Pesticides .......................................................................................................4</p><p>Instrument Calibration ................................................................................................................7Quality Assurance/Quality Control ............................................................................................7Method Detection Limits ............................................................................................................7</p><p>Analysis of Dissolved Organic Carbon ..............................................................................................7Dissolved Pesticides in Streams .................................................................................................................7Dissolved Organic Carbon and Water-Quality Characteristics in Streams .......................................13Summary........................................................................................................................................................16References Cited..........................................................................................................................................16</p></li><li><p>iv</p><p>Figures 1. Map showing location of four surface-water sampling sites and associated </p><p>watersheds in Idaho .....................................................................................................................3 2. Maps showing crop and land-cover types for (A) Sand Run Gulch at Highway 95 </p><p>crossing near Parma (USGS station number 13210360) and (B) Ditch near Wanstad Road near Parma (USGS station number 13213008) in Idaho ..............................5</p><p> 3. Maps showing crop and land-cover types for sampling sites (A) Cottonwood Creek near Boise (USGS station number 433711116110700) and (B) Dry Creek near Bogus Basin Road near Boise (USGS station number 434006116112100) in Idaho ...........6</p><p>Tables 1. Description of four surface-water sampling sites and associated watershed </p><p>characteristics in Idaho ...............................................................................................................2 2. Dissolved pesticides with types, method detection limits, and instrumental </p><p>limits of detection .........................................................................................................................8 3. Dissolved pesticide concentrations measured in surface-water samples collected </p><p>from sampling sites on four streams in Idaho, AprilDecember 2010 ...............................10 4. Dissolved pesticides with type; detection frequency; and median, minimum, and </p><p>maximum concentrations measured in surface-water samples collected from Sand Run Gulch at Highway 95 crossing near Parma, Idaho (USGS station number 13210360) and Ditch near Wanstad Road near Parma, Idaho (USGS station number 13213008), in Idaho, AprilDecember, 2010. ...........................................................................13</p><p> 5. Dissolved organic carbon concentrations and water-quality characteristics measured in surface-water samples collected from four streams in Idaho, AprilDecember 2010 .................................................................................................................14</p></li><li><p>v</p><p>Conversion Factors</p><p>SI to Inch/Pound</p><p>Multiply By To obtain</p><p>Length</p><p>centimeter (cm) 0.3937 inch (in.)millimeter (mm) 0.03937 inch (in.)meter (m) 3.281 foot (ft) kilometer (km) 0.6214 mile (mi)</p><p>Area</p><p>square kilometer (km2) 0.3861 square mile (mi2)</p><p>Volume</p><p>liter (L) 1.057 quart (qt)liter (L) 0.2642 gallon (gal)</p><p>Mass</p><p>gram (g) 0.03527 ounce, avoirdupois (oz)kilogram (kg) 2.205 pound, avoirdupois (lb)microgram (g) 3.527 x 10-8 ounce, avoirdupois (oz)nanogram (ng) 3.527 x 10-11 ounce, avoirdupois (oz)</p><p>Temperature in degrees Celsius (C) may be converted to degrees Fahrenheit (F) as follows:</p><p>F=(1.8C)+32</p><p>Vertical coordinate information is referenced to the North American Vertical Datum of 1988 (NAVD 88). </p><p>Horizontal coordinate information is referenced to the North American Datum of 1983 (NAD 83).</p><p>Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (S/cm at 25C).</p><p>Concentrations of chemical constituents in water are given in milligrams per liter (mg/L), micrograms per liter (g/L), or nanograms per liter (ng/L).</p></li><li><p>vi</p><p>Unit Abbreviations C Degrees Celsius</p><p> C/min Degrees Celsius per minute</p><p> cm3 cubic centimeters</p><p> dd decimal degrees</p><p> g gram</p><p> L liter</p><p> m meter</p><p> mg milligrams</p><p> mg/L milligrams per liter</p><p> min minute</p><p> mL milliliter</p><p> mm millimeter</p><p> ng/L nanograms per liter</p><p> ng/L nanograms per microliter</p><p> NTU Nephelometric turbidity unit</p><p> g/kg micrograms per kilogram</p><p> L microliter</p><p> m micrometer</p><p> S/cm microsiemens per centimeter at 25 degrees Celsius</p><p>Acronyms DCM dichloromethane</p><p> DOC dissolved organic carbon</p><p> GC-EIMS gas chromatograph/election ionization mass spectrometer</p><p> GC-ITMS gas chromatograph/ion trap mass spectrometer</p><p> GF/F glass fiber filter</p><p> H2SO4 sulfuric acid</p><p> i.d. inner diameter</p><p> KHP potassium hydrogen phthalate</p><p> LOD limit of detection</p><p> MDL method detection limit</p><p> N2 nitrogen gas</p><p> Na2SO4 sodium sulfate</p></li><li><p>vii</p><p> ND not detected</p><p> NWIS National Water-Quality Information System</p><p> QA/QC quality assurance/quality control</p><p> SPE solid-phase extraction</p><p> SD standard deviation</p><p> SIM selective ion monitoring</p><p> SIS selective ion storage</p><p> USDA U.S. Department of Agriculture </p><p> USEPA U.S. Environmental Protection Agency</p><p> USGS U.S. Geological Survey</p></li><li><p>AbstractWater-quality samples were collected from April </p><p>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 pes-ticides, 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 agricul-tural 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 (0.51.0 nanograms per liter) to 771 nanograms per liter (hexazinone). The total num-ber 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.</p><p>IntroductionFungicides are used to prevent the outbreak of persistent, </p><p>historically significant plant diseases like late blight (caused by Phytophthora infestans and responsible for the Irish Potato Famine of 1846) and newer plant diseases, such as Asian Soy Rust. Both late blight and Asian Soy Rust are potentially devastating if not controlled (Leadbeater and Gisi, 2009). Of the more than 67,000 pesticide products currently regis-tered for use in the United States, more than 3,600 are used to combat fungal diseases (U.S. Environmental Protection </p><p>1U.S. Geological Survey2Boise State University</p><p>Agency, 2011). Even with the use of chemical-based crop-protection measures, fungal pathogens were responsible for 7 to 24 percent of losses in yields to commodity crops, such as potatoes, worldwide during 200103 (Oercke, 2006). Pesticide manufacturers are continually developing new fungicides to find more effective treatments and to outpace the rate at which pathogens acquire resistance to these chemicals. For example, Phytophthora infestans rapidly developed strains resistant to widely used phenylamide fungicides, leading to its classifica-tion as a high-risk pathogen and necessitating co-application of other fungicides to provide the necessary crop protection (Brent and Hollomon, 2007). Depending on the pathogen genome and the mode of fungicidal action (single versus multiple pathways), pathogens can develop resistance to newly introduced fungicides within a few years of exposure. For example, field and laboratory studies identified Alternaria alernata strains (responsible for Alternaria late blight of pista-chio crops) resistant to boscalid within 2 years of registration and to azoxystrobin within 3 to 4 years of continuous applica-tion (Ma and Others, 2003; Avenot and Michailides, 2007).</p><p>Relatively little is known about the fate and effects of fungicides at environmentally relevant concentrations in the aquatic environment. Recent studies have documented the presence of some fungicides in runoff from greenhouse production and commercial foliage plant nurseries (Roseth and Haarstad, 2010; Wilson and Riiska, 2010), soil and water associated with banana production (Geissen and others, 2010), streams and bed sediment (Battaglin and others, 2010; Small-ing and Orlando, 2011), and the atmosphere (Schummer and others, 2010). Even less is known about the presence in the environment of recently registered fungicides. For example, the presence of boscalid (first registered for use in the United States in 2003) has been documented in only four studies; it has been found in streams and groundwater (Smalling and Orlando, 2011; Reilly and others, in press) using field experi-ments to determine soil dissipation and residuals (Chen and Zhang, 2010), and in the atmosphere (Schummer and others, 2010). </p><p>The potential for chronic exposure of nontarget fungi to fungicides at environmentally relevant concentrations exists but has not been extensively evaluated. Unlike most other pesticides, multiple fungicides typically are applied as </p><p>Dissolved Pesticides, Dissolved Organic Carbon, and Water-Quality Characteristics in Selected Idaho Streams, AprilDecember 2010</p><p>By Timothy J. Reilly1, Kelly L. Smalling1, Emma R. Wilson2, and William A. Battaglin1 </p></li><li><p>2 Pesticides, Dissolved Organic Carbon, and Water-Quality Characteristics in Selected Idaho Streams, AprilDecember 2010</p><p>a prophylactic crop protectant more than 10 times per season (depending on conditions and crop type) but at lower applica-tion rates than herbicides or insecticides. This difference in usage increases the likelihood of chronic exposure of aquatic ecosystems to low concentrations of fungicides. The effects of fungicides at environmentally relevant concentrations on aquatic organisms and communities are poorly understood. However, recent studies have documented the potential effects of fungicides on amphibians and macroinvertebrate communi-ties (Schfer and others, 2011; Belden and others, 2010). The genotoxic, teratogenic, and endocrine-disrupting properties of several fungicides have been established by field, mesocosm, in vivo (zebrafish and human lymphocytes), and in vitro stud-ies (Bony and others, 2008; iman and Trkez, 2010; Orton and others, 2011; Taxvig and others, 2008).</p><p>Aside from studies conducted by manufacturers during the registration process, data on the effects of fungicides on aquatic organisms and nontarget fungi are limited. Environ-mental concentrations of fungicides are typically less than 100 nanograms per liter (ng/L) (Battaglin and others, 2010; Small-ing and Orlando, 2011). On the basis of current literature, the effect on aquatic communities of fungicides at these concen-tration levels is likely to be sublethal or an indirect disruption of community structure by altering fungal, phytoplankton, and zooplankton popula...</p></li></ul>

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