Abstract
Agrochemicals can be transported from agricultural fields into streams where they might have adverse effects on water quality and ecosystems. Three enrichment experiments were conducted in a central Indiana stream to quantify pesticide and nitrogen transport dynamics. In an enrichment experiment, a compound solution is added at a constant rate into a stream to increase compound background concentration. A conservative tracer (e.g., bromide) is added to determine discharge. Water and sediment samples are taken at several locations downstream to measure uptake metrics. We assessed transport of nitrate, atrazine, metolachlor, and carbaryl through direct measurement of uptake length (S w ), uptake velocity (V f ), and areal uptake (U). S w measures the distance traveled by a nutrient along the stream reach. V f measures the velocity a nutrient moves from the water column to immobilization sites. U represents the amount of nutrient immobilized in an area of streambed per unit of time. S w varied less than one order of magnitude across pesticides. The highest S w for atrazine suggests greater transport to downstream ecosystems. Across compounds, pesticide S w was longest in August relative to October and July. V f varied less than one order of magnitude across pesticides with the highest V f for metolachlor. U varied three orders of magnitude across pesticides with the highest U associate with sediment-bound carbaryl. Increasing nitrate S w suggests a lower nitrate demand of biota in this stream. Overall, pesticide transport was best predicted by compound solubility which can complement and improve models of pesticide abundance used by water quality programs and risk assessments.
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References
American Public Health Association. (1995). Standard methods for the examination of water and wastewater. Washington, D.C.: American Public Health Association.
Aminot, A., Kirkwood, D. S., & Kerouel, R. (1997). Determination of ammonia in seawater by the indophenol-blue method: evaluation of the ICES NUTS I/C 5 questionnaire. Marine Chemistry, 56, 59–75.
Bacci, E., Renzoni, A., Gaggi, C., Calamari, D., Franchi, A., Vighi, M., & Severi, A. (1989). Models, field studies, laboratory experiments: an integrated approach to evaluate the environmental fate of atrazine (s-triazine herbicide). Agriculture, Ecosystems and Environment, 27(1), 513–522.
Balci, B., Oturan, N., Cherrier, R., & Oturan, M. A. (2009). Degradation of atrazine in aqueous medium by electrocatalytically generated hydroxyl radicals. A kinetic and mechanistic study. Water Research, 43(7), 1924–1934.
Battaglin, W. A. (2002) Using ratios of atrazine transformation products to atrazine to determine its source in midwestern streams
Bernot, M. J., & Dodds, W. K. (2005). Nitrogen retention, removal, and saturation in lotic ecosystems. Ecosystems, 8(4), 442–453.
Bernot, M. J., Tank, J. L., Royer, T. V., & David, M. B. (2006). Nutrient uptake in streams draining agricultural catchments of the Midwestern United States. Freshwater Biology, 51(3), 499–509.
Bobbink, R., Hicks, K., Galloway, J., Spranger, T., Alkemade, R., Ashmore, M., & De Vries, W. (2010). Global assessment of nitrogen deposition effects on terrestrial plant diversity: a synthesis. Ecological Applications, 20(1), 30–59.
Community Collaborative Rain, Hail and Snow Network (2017) Daily Precipitation Reports. Available at http://www.cocorahs.org/ViewData/ListDailyPrecipReports.aspx (Accessed 8 Feb 2017)
Conley, D. J., Paerl, H. W., Howarth, R. W., Boesch, D. F., Seitzinger, S. P., Havens, K. E., & Likens, G. E. (2009). Controlling eutrophication: nitrogen and phosphorus. Science, 323(5917), 1014–1015.
Cope, O. B. (1966) Contamination of the freshwater ecosystem by pesticides. J. Appl. Ecology. 33–44
Croghan, C., & Egeghy, P. P. (2003). Methods of dealing with values below the limit of detection using SAS (pp. 22–24). St. Petersburg: Southeastern SAS User Group.
Daniels, W. M., House, W. A., Rae, J. E., & Parker, A. (2000). The distribution of micro-organic contaminants in river bed-sediment cores. The Science of the Total Environment, 253(1), 81–92.
Davis, A., & Galloway, J. N. (1993). Distribution of Pb between sediments and pore water in Woods Lake, Adirondack State Park, New York. USA. Appl. Geochemistry, 8(1), 51–65.
Dinnes, D. L., Karlen, D. L., Jaynes, D. B., Kaspar, T. C., Hatfield, J. L., Colvin, T. S., & Cambardella, C. A. (2002). Nitrogen management strategies to reduce nitrate leaching in tile-drained Midwestern soils. Agronomy Journal, 94(1), 153–171.
Dodds, W. K., Lopez, A. J., Bowden, W. B., Gregory, S., Grimm, N. B., Hamilton, S. K., Hershey, A. E., Marti, E., et al. (2002). N uptake as a function of concentration in streams. Journal of the North American Benthological Society, 21(2), 206–220.
Dubrovsky, N. M., Burow, K. R., Clark, G. M., Gronberg, J. M., Hamilton, P. A., & Hitt, K. J., et al. (2010) The quality of our nation’s waters—nutrients in the nation’s streams and groundwater, 1992–2004 (No. 1350). U.S. Geological Survey
Duff, J. H., Carpenter, K. D., Snyder, D. T., Lee, K. K., Avanzino, R. J., & Triska, F. J. (2009). Phosphorus and nitrogen legacy in a restoration wetland, Upper Klamath Lake, Oregon. Wetlands, 29(2), 735–746.
Elias, D., & Bernot, M. J. (2014). Effects of atrazine, metolachlor, carbaryl and chlorothalonil on benthic microbes and their nutrient dynamics. PloS One, 9(10), e109190.
Enserink, M., Hines, P. J., Vignieri, S. N., Wigginton, N. S., & Yeston, J. S. (2013). Smarter pest control. The pesticide paradox. Introduction. Science, 341, 728–729.
Fenn, M. E., & Poth, M. A. (1999). Temporal and spatial trends in streamwater nitrate concentrations in the San Bernardino Mountains, southern California. Journal of Environmental Quality, 28(3), 822–836.
Fenner, K., Canonica, S., Wackett, L. P., & Elsner, M. (2013). Evaluating pesticide degradation in the environment: blind spots and emerging opportunities. Science, 341(6147), 752–758.
Fewtrell, L. (2004). Drinking-water nitrate, methemoglobinemia, and global burden of disease: a discussion. Environ. Health Perspect 1371–1374.
Finizio, A., Mackay, D., Bidleman, T., & Harner, T. (1997). Octanol-air partition coefficient as a predictor of partitioning of semi-volatile organic chemicals to aerosols. Atmospheric Environment, 31(15), 2289–2296.
Gamble, D. S. (2009). Herbicide sorption by immersed soils: stoichiometry and the law of mass action in support of predictive kinetics. Environmental Science & Technology, 43(6), 1930–1934.
Gavrilescu, M. (2005). Fate of pesticides in the environment and its bioremediation. Engineering in Life Sciences, 5(6), 497–526.
Gerland, P., Raftery, A. E., Ševčíková, H., Li, H. N., Gu, D., Spoorenberg, T., & Wilmoth, J. (2014). World population stabilization unlikely this century. Science, 346(6206), 234–237.
Gilliom, R. J. (2007). Pesticides in US streams and groundwater. Environmental Science & Technology, 41(10), 3408–3414.
Graves, R. L. (1989) Method 531.1 Measurement of n-methylcarbamoyloximes and n-methylcarbamates in water by direct aqueous injection HPLC with post column derivatization. U.S. Environmental Protection Agency. Available at http://water.epa.gov/scitech/methods/cwa/bioindicators/upload/2007_11_06_methods_method_531_1.pdf Accessed 19 Aug 2015
Gregory, S. V. (1980) Effects of light, nutrients, and grazing on periphyton communities in streams
Grimm, N. B. (1987). Nitrogen dynamics during succession in a desert stream. Ecology, 68, 1157–1170.
Grube, A., Donaldson, D., Kiely, T., & Wu, L. (2011) Pesticides industry sales and usage. U.S. Environmental Protection Agency
Gunasekara, A. S., Rubin, A. L., Goh, K. S., Spurlock, F. C., & Tjeerdema, R. S. (2008). Environmental fate and toxicology of carbaryl. Environ. Contam. Toxicol, 196, 95–121.
Gustafson, D. I. (1989). Groundwater ubiquity score: a simple method for assessing pesticide leachability. Environmental Toxicology and Chemistry, 8(4), 339–357.
Hall Jr., R., & Tank, J. L. (2003). Ecosystem metabolism controls nitrogen uptake in streams in Grand Teton National Park. Wyoming. Limnol. Oceanogr, 48(3), 1120–1128.
Hayes, T. B. (2001) Atrazine contamination in water and the impact on amphibian populations: a bioassay that measures water quality. In AGU Fall Meeting Abstracts (Vol. 1, p. 0363)
Helsel, D. R. (2005). Nondetects and data analysis. New York: John Wiley and Sons.
Johnson, L. T., Tank, J. L., & Arango, C. P. (2009). The effect of land use on dissolved organic carbon and nitrogen uptake in streams. Freshwater Biology, 54(11), 2335–2350.
Johnson, Z. C., Warwick, J. J., & Schumer, R. (2015). Nitrogen retention in the main channel and two transient storage zones during nutrient addition experiments. Limnology and Oceanography, 60(1), 57–77.
Jordan, M. J., Nadelhoffer, K. J., & Fry, B. (1997). Nitrogen cycling in forest and grass ecosystems irrigated with 15N-enriched wastewater. Ecological Applications, 7(3), 864–881.
Katagi, T. (2006) Behavior of pesticides in water-sediment systems. In Reviews of Environ. Contam. Toxicol. 133–251
Kawamoto, K., & Urano, K. (1989). Parameters for predicting fate of organochlorine pesticides in the environment (I) octanol-water and air-water partition coefficients. Chemosphere, 18(9), 1987–1996.
Knobeloch, L., Salna, B., Hogan, A., Postle, J., & Anderson, H. (2000). Blue babies and nitrate-contaminated well water. Environmental Health Perspectives, 108(7), 675.
Kolpin, D. W., Barbash, J. E., & Gilliom, R. J. (1998). Occurrence of pesticides in shallow groundwater of the United States: Initial results from the National Water-Quality Assessment Program. Environ. Science Technol, 32(5), 558–566.
Kruger, E. L., Coats, J. R., & Zhu, B. E. (1996). Relative mobilities of atrazine, five atrazine degradates, metolachlor, and simazine in soils of Iowa. Environmental Toxicology and Chemistry, 15(5), 691–695.
Kuivila, K. M., & Foe, C. G. (1995). Concentrations, transport and biological effects of dormant spray pesticides in the San-Francisco estuary, California. Environmental Toxicology and Chemistry, 14(7), 1141–1150.
Kuzyakov, Y., & Xu, X. (2013). Competition between roots and microorganisms for nitrogen: mechanisms and ecological relevance. The New Phytologist, 198(3), 656–669.
Kwon, J. W., & Armbrust, K. L. (2006). Degradation of chlorothalonil in irradiated water/sediment systems. Journal of Agricultural and Food Chemistry, 54, 3651–3657.
Larson, S. J., Gilliom, R. J. & Capel, P. D. (1999) Pesticides in streams of the United States—initial results from the national Water-Quality Assessment Program: U.S. Department of the Interior, U.S. Geological Survey
Leavesley, G. H., Lichty, R. W., Thoutman, B. M., & Saindon, L. G. (1983). Precipitation-runoff modeling system: User's manual (p. 207). Washington: USGS.
Li, C. C., Huo, S. L., Xi, B. D., Yu, Z. Q., Zeng, X. Y., Zhang, J. T., & Liu, H. L. (2015). Historical deposition behaviors of organochlorine pesticides (OCPs) in the sediments of a shallow eutrophic lake in eastern China: roles of the sources and sedimentological conditions. Ecological Indicators, 53, 1–10.
Linde, C. D. (1994) Physicochemical properties and environmental fate of pesticides. Environmental hazards assessment program. U.S. Environmental Protection Agency:53
Mulholland, P.J., Tank, J.L., Sanzone, D.M., Webster, J.R., Wollheim, W., Peterson, B.J. and Meyer, J.L. (1998) Ammonium and nitrate uptake lengths in a small forested stream determined by 15N tracer and short-term nutrient enrichment experiments (No. ORNL/CP--99394; CONF-980848--). Oak Ridge National Lab., TN (United States)
Mulholland, P. J., Tank, J. L., Webster, J. R., Bowden, W. B., Dodds, W. K., Gregory, S. V., et al. (2002). Can uptake length in streams be determined by nutrient addition experiments? Results from an interbiome comparison study. Journal of the North American Benthological Society, 21(4), 544–560.
Mulholland, P. J., et al. (2008). Stream denitrification across biomes and its response to anthropogenic nitrate loading. Nature, 452(7184), 202–205.
Munch, J. W. (1995). Method 525.2 Determination of organic compounds in drinking water by liquid-solid extraction and capillary column gas chromatography/mass spectrometry. U.S. Environmental Protection Agency. Available at http://water.epa.gov/scitech/methods/cwa/upload/525_2-SOCs.pdf (Accessed 19 Aug 2015
National Oceanic Atmospheric Administration. (2017). Quality Controlled Local Climatological Data. Available at https://www.ncdc.noaa.gov/qclcd/QCLCD (Accessed February 8th, 2017).
National Research Council U.S. (2014). A framework to guide selection of chemical alternatives. Washington, D.C.: The National Academies Press. Available at http://search.ebscohost.com/login.aspx?direct=true&scope=site&db=nlebk&db=nlabk&AN=907909 (Accessed October 30, 2015).
Neumann, M., Schulz, R., Schäfer, K., Müller, W., Mannheller, W., & Liess, M. (2002). The significance of entry routes as point and non-point sources of pesticides in small streams. Water Research, 36(4), 835–842.
Newbold, J. D., O'neill, R. V., Elwood, J. W., & Van Winkle, W. (1982). Nutrient spiraling in streams: implications for nutrient limitation and invertebrate activity. Amer. Nat, 628-652.
Nowell, L. H., Capel, P. D. & Dileanis, P. D. (2010). Pesticides in stream sediment and aquatic biota: distribution, trends, and governing factors. Boca Raton, FL: Lewis Publishers.
O'Brien, J. M., & Dodds, W. K. (2010). Saturation of NO3− uptake in prairie streams as a function of acute and chronic N exposure. Journal of the North American Benthological Society, 29(2), 627–635.
Peterson, B. J., Wollheim, W. M., Mulholland, P. J., Webster, J. R., Meyer, J. L., Tank, J. L., & Morrall, D. D. (2001). Control of nitrogen export from watersheds by headwater streams. Science, 29,2(5514), 86–90.
Roley, S. S., Tank, J. L., Stephen, M. L., Johnson, L. T., Beaulieu, J. J., & Witter, J. D. (2012). Floodplain restoration enhances denitrification and reach-scale nitrogen removal in an agricultural stream. Ecological Applications, 2012 22(1), 281–297.
Sabljic, A. (2001). QSAR models for estimating properties of persistent organic pollutants required in evaluation of their environmental fate and risk. Chemosphere, 43(3), 363–375.
Schade, J. D., Seybold, E. C., Drake, T., Spawn, S., Sobczak, W. V., Frey, K. E., ... & Zimov, N. (2016). Variation in summer nitrogen and phosphorus uptake among Siberian headwater streams. Polar Res 35.
Schulz, R. (2004). Field studies on exposure, effects, and risk mitigation of aquatic nonpoint-source insecticide pollution. Journal of Environmental Quality, 33(2), 419–448.
Sharratt, B., Sander, K., & Tierney, D. (2003). Fate of autumn applied metolachlor in a clay loam in the northern U.S. Corn Belt. Journal of Environmental Science and Health, Part B: Pesticides, Food Contaminants, and Agricultural Wastes, 38, 37–48.
Smiley Jr., P. C., King, K. W., & Fausey, N. R. (2014). Annual and seasonal differences in pesticide mixtures within channelized agricultural headwater streams in central Ohio. Agriculture, Ecosystems and Environment, 193, 83–95.
Stackelberg, P. E., Furlong, E. T., Meyer, M. T., Zaugg, S. D., Henderson, A. K., & Reissman, D. B. (2004). Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water-treatment plant. The Science of the Total Environment, 329(1), 99–113.
Stone, W. W., Crawford, C. G., & Gilliom, R. J. (2013). Watershed regressions for pesticides WARP models for predicting stream concentrations of multiple pesticides. Journal of Environmental Quality, 42, 1838–1851.
Sullivan, D. J., Vecchia, A. V., Lorenz, D. L., Gilliom, R. J., & Martin, J. D. (2009). Trends in pesticide concentrations in corn-belt streams, 1996–2006. U.S. Geological Survey.
Tank, J. L., Bernot, M. J., & Rosi-Marshall, E. J. (2006). Nitrogen limitation and uptake. Methods in stream ecology (pp. 213–238). San Diego: Academic Press.
Toccalino, P. L., Gilliom, R. J., Lindsey, B. D. & Rupert, M. G. (2014). Pesticides in groundwater of the United States: Decadal-scale changes (1993 - 2011). Ground water 52 Suppl, 1(S1), 112–125.
U.S. Census Bureau. (2015). 2014 National Population Projections. Available at: https://www.census.gov/population/projections/data/national/2014.html (Accessed 12 June 2015).
U.S. Environmental Protection Agency. (2007). Method 3550C Ultrasonic extraction. Available at: http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3550c.pdf (Accessed August 19, 2015).
Wauchope, R. D., & Leonard, R. A. (1978). Maximum pesticide concentrations in agricultural runoff: a semiempirical prediction formula. Journal of Environmental Quality, 9(4), 665–672.
Wauchope, R. D., Buttler, T., Hornsby, A., Augustijn-Beckers, P., & Burt, J. A. (1992). The SCS/ARS/CES pesticide properties database for environmental decision-making. Reviews of Environ. Contam. Toxicol, 1–155.
Wauchope, R. D., Yeh, S., Linders, J. B., Kloskowski, R., Tanaka, K., Rubin, B., Katayama, A., Kordel, W., Gerstl, Z., & Lane, M. (2002). Pesticide soil sorption parameters: theory, measurement, uses, limitations and reliability. Pest Management Science, 58(5), 419–445.
Webster, J. R., Mulholland, P. J., Tank, J. L., Valett, H. M., Dodds, W. K., Peterson, B. J., et al. (2003). Factors affecting ammonium uptake in streams—an inter-biome perspective. Freshwater Biology, 48(8), 1329–1352.
White River Watershed Project. (2010). Background information. Available at http://whiteriverwatershedproject.org/ (Accessed August 21, 2014).
Wijekoon, K. C., Hai, F. I., Kang, J., Price, W. E., Guo, W., Ngo, H. H., & Nghiem, L. D. (2013). The fate of pharmaceuticals, steroid hormones, phytoestrogens, UV-filters and pesticides during MBR treatment. Bioresource Technology, 144, 247–254.
Wilson, C., Albano, J., Mozdzen, M., & Riiska, C. (2010). Irrigation water and nitrate-nitrogen loss characterization in Southern Florida nurseries: cumulative volumes, runoff rates, nitrate-nitrogen concentrations and loadings, and implications for management. HortTechnology, 20(2), 325–330.
Workshop, S. S. (1990). Concepts and methods for assessing solute dynamics in stream ecosystems. Journal of the North American Benthological Society, 9(2), 95–119.
Yang, Y. Y., Toor, G. S., & Williams, C. F. (2015). Pharmaceuticals and organochlorine pesticides in sediments of an urban river in Florida, U.S. J. Soils Sediments, 15(4), 993–1004.
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We thank the Indiana Water Resources Research Consortium and Ball State Aspire Grant for funding and Patrick Ferguson, Ben England, Ann Raffel, Rob Osborne, James Justice, and Lindy Caffo for field assistance.
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Elias, D., Bernot, M.J. Pesticide and nitrate transport in an agriculturally influenced stream in Indiana. Environ Monit Assess 189, 162 (2017). https://doi.org/10.1007/s10661-017-5870-1
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DOI: https://doi.org/10.1007/s10661-017-5870-1