Abstract
Soluble nutrient flux is increasingly implicated in the degradation of receiving water quality. With high-frequency sensors, river discharge along with nitrate and orthophosphate concentrations were collected over 2 years. We examined how storms (16 events) affected the dissolved nutrient flux in two watersheds with contrasting landcover—urban and agricultural. The adjacent watersheds, both < 7 km2, had very similar soil, slope, relief, and physiography. Wastewater is conveyed outside of the watersheds minimizing this nutrient source. Cumulative nitrate and orthophosphate fluxes in the agricultural watershed were substantially higher than the urban watershed. In both watersheds, a disproportionate amount of discharge, higher orthophosphate concentrations and flux occurred during the highest flow events—approximately 50–70% of flux occurring in the highest 5% of daily discharge. The nitrate flux was dampened compared to discharge during storm events. Baseflow accounted for 66% of the nitrate flux and had higher or comparable concentrations than storm events. The pattern of flux and concentration within storm events also differed for the two solutes. Nitrate exhibited positive hysteresis (higher concentrations on the rising limb of the hydrograph) and magnification of flux during the first flush of storm runoff. In contrast, orthophosphate concentrations were lower on the rising limb and flux during the first flush of storm runoff was dampened. In addition to targeting source reductions, orthophosphate flux may require runoff reducing strategies (i.e., enhanced infiltration) from large runoff events. First flush stormwater management practices combined with enhancement/protection of groundwater nitrate sinks (e.g., riparian wetlands) may help reduce nitrate fluxes.
Similar content being viewed by others
Abbreviations
- FI :
-
Flushing index
- Fq x :
-
% of total flux that occurs during the highest x% of daily discharge values
- HI :
-
Hysteresis index
- M x :
-
% of total flux that occurs during the highest x% of daily flux values
- MFF x :
-
Mass first flush ratio, the ratio of the proportion of total flux to the proportion of total discharge (x)
- Q :
-
Discharge
- Q x :
-
Daily discharge that is exceeded x% of the yearly daily discharge values
- W x :
-
% of total discharge that occurs during the highest x% of daily discharge values
References
Addy K, Gold AJ, Christianson LE, David MB, Schipper LA, Ratigan NA (2016) Denitrifying bioreactors for nitrate removal: a meta-analysis. J Environ Qual 45:873–881
Arnold JG, Allen PM (1999) Automated methods for estimating baseflow and ground water recharge from streamflow records. J Am Water Resour Assoc 5:411–424
Baker DB, Richards RP, Timothy T, Loftus TT, Kramer JW (2004) A new flashiness index: characteristics and applications to midwestern rivers and streams. J Am Water Resour Assoc 40:503–522
Barco J, Papiri S, Stenstrom MK (2008) First flush in a combined sewer system. Chemosphere 71:827–833
Boyer EW, Goodale CL, Jaworski NA, Howarth RW (2002) Anthropogenic nitrogen sources and relationships to riverine nitrogen export in the northeastern USA. In: Boyer EW, Howarth RW (eds) The Nitrogen Cycle at Regional to Global Scales. Springer, Dordrecht
Brauer VS, Stomp M, Huisman J (2012) The nutrient-load hypothesis: patterns of resource limitation and community structure driving by competition for nutrients and light. Am Nat 179:721–740
Brett MT, Benjamin MM (2008) A review and reassessment of lake phosphorus retention and the nutrient loading concept. Freshw Biol 53:194–211
Buchanan BP, Archibald JA, Easton ZM, Shaw SB, Schneider RL, Walter MT (2013) A phosphorus index that combines critical source areas and transport pathways using a travel time approach. J Hydrol 486:123–135
Burkholder JM, Dickey DA, Kinder CA, Reed RE, Mallin MA, McIver MR et al (2006) Comprehensive trend analysis of nutrients and related variables in a large eutrophic estuary: a decadal study of anthropogenic and climatic influences. Limnol Oceanogr 51:463–487
Butturini A, Alvarez M, Bernal S, Vazquez E, Sabater F (2008) Diversity and temporal sequences of forms of DOC and NO3-discharge responses in an intermittent stream: predictable or random succession? J Geophys Res. https://doi.org/10.1029/2008JG000721
Cameron KC, Di HJ, Moir JL (2013) Nitrogen losses from the soil/plant system: a review. Ann Appl Biol 162:145–173
Carpenter SR, Caraco NF, Correll DL, Howarth RW, Sharpley AN, Smith VH (1998) Nonpoint pollution of surface waters with phosphorus and nitrogen. Ecol Appl 8:559–568
Collins KA, Lawrence TJ, Stander EK, Jonto RJ, Kaushal SS, Newcomer TA et al (2010) Opportunities and challenges for managing nitrogen in urban stormwater: a review and synthesis. Ecol Eng 36:1507–1519
Conley DJ, Paerl HW, Howarth RW, Boesch DF, Seitzinger SP, Havens KE, Lancelot C, Likens GE (2009) Controlling eutrophication: nitrogen and phosphorus. Science 323:1014–1015
Correll DL, Jordan TE, Weller DE (1999) Transport of nitrogen and phosphorus from Rhode River watersheds during storm events. Water Resour Res 35:2513–2521
Coulter CB, Kolka RK, Thompson JA (2004) Water quality in agricultural, urban and mixed land use watersheds. J Am Water Resour Assoc 40:1593–1601
Dhillon GS, Inamdar S (2013) Extreme storms and changes in particulate and dissolved organic carbon in runoff: entering uncharted waters? Geophys Res Lett 40:1322–1327
Di HJ, Cameron KC (2002) Nitrate leaching in temperate agroecosystems: sources, factors and mitigating strategies. Nutr Cycl Agroecosyst 46:237–256
Dingman SL (2015) Physical hydrology. Waveland press. Longview, p 633
Downing JA, Watson SB, McCauley E (2001) Predicting cyanobacteria dominance in lakes. Can J Fish Aquat Sci 58:1905–1908
Eaton AD, Clesceri LS, Greenberg AE, Franson MH (1998) Standard methods for the examination of water and wastewater. APHA, AWWA, and WEF, Washington, DC
Elrashidi MA, Mays MD, Harder J, Schroeder D, Brakhage P (2005) Loss of phosphorus by runoff for agricultural watersheds. Soil Sci 170:543–558
ESRI (2011) ArcGIS desktop: release 10. Environmental Systems Research Institute, Redlands
Etheridge JR, Birgand F, Osborne JA, Osburn CL, Burchell MR, Irving J (2014) Using in situ ultraviolet-visual spectroscopy to measure nitrogen, carbon, phosphorus, and suspended solids concentrations at a high frequency in a brackish tidal marsh. Limnol Oceanogr 12:10–22
Foley JA, Defries R, Asner GP, Barford C, Bonan G, Carpenter SR, Chapin FS, Coe MT, Daily GC, Gibbs HK, Helkowski JH, Holloway T, Howard EA, Kucharik J, Monfreda C, Patz JA, Prentice IC, Ramankutty N, Snyder PK (2005) Global consequences of land use. Science 309:570–574
Gburek WJ, Sharpley AN (1998) Hydrologic controls on phosphorus loss from upland agricultural watersheds. J Environ Qual 27:267–277
Gold AJ, Loudon TL, Nurnberger FV (1986) Runoff and erosive storm occurrence probabilities. Trans ASAE 29:119–123
Gold AJ, DeRagon WR, Sullivan WM, Lemunyon JL (1990) Nitrate-nitrogen losses to groundwater from rural and suburban land uses. J Soil Water Conserv 45:305–310
Gold AJ, Groffman PM, Addy K, Kellogg DQ, Stolt MS, Rosenblatt AE (2001) Landscape attributes as controls on ground water nitrate removal capacity of riparian zones. J Am Water Resour Assoc 37:1457–1464
Grimm NB, Faeth SH, Golubiewski NE, Redman CL, Wu J, Bai X, Briggs JM (2008) Global change and the ecology of cities. Science 319:756–760
Groffman PM, Law NL, Belt KT, Band LE, Fisher GT (2004) Nitrogen fluxes and retention in urban watershed ecosystems. Ecosystems 7:393–403
Groffman PM, Williams CO, Pouyat RV, Band LE, Yesilonis ID (2009) Nitrate leaching and nitrous oxide flux in urban forests and grasslands. J Environ Qual 38:1848–1860
Gross CM, Angle JS, Welterlen MS (1990) Nutrient and sediment losses from turfgrass. J Environ Qual 19:663–668
Guilford SJ, Hecky RE (2000) Total nitrogen, total phosphorus, and nutrient limitation in lakes and oceans: is there a common relationship? Limnol Oceanogr 45:1213–1223
Gurwick NP, Groffman PM, Yavitt JB, Gold AJ, Blazejewski G, Stolt M (2008) Microbially available carbon in buried riparian soils in a glaciated landscape. Soil Biol Biochem 40:85–96
Han Y, Lau SL, Kayhanian M, Stenstrom MK (2006) Characteristics of highway stormwater runoff. Water Environ Res 78:2377–2388
Hathaway JM, Tucker RS, Spooner JM, Hunt WF (2012) A traditional analysis of the first flush effect for nutrients in stormwater runoff from two small urban catchments. Water Air Soil Pollut 223:5903–5915
Henjum MB, Hozalski RM, Wennen CR, Arnold WA, Novak PJ (2010) Correlations between in situ sensor measurements and trace organic pollutants in urban streams. J Environ Monit 12:225–233
Hobbie SE, Finlay JC, Janke BD, Nidzgorski DA, Millet DB, Baker LA (2017) Contrasting nitrogen and phosphorus budgets in urban watersheds and implications for managing urban water pollution. Proc Natl Acad Sci 114:4177–4182
Homer CG, Dewitz JA, Yang L, Jin S, Danielson P, Xian G, Coulston J, Herold ND, Wickham JD, Megown K (2015) Completion of the 2011 National Land Cover Database for the conterminous United States—representing a decade of land cover change information. Photogramm Eng Remote Sens 81:345–354
Inamdar SP, O'Leary N, Mitchell MJ, Riley JT (2006) The impact of storm events on solute exports from a glaciated forested watershed in western New York, USA. Hydrol Process 20:3423–3439
Isles PDF, Xu Y, Stockwell JD, Schroth AW (2017) Climate-driven changes in energy and mass inputs systematically alter nutrient concentration and stoichiometry in deep and shallow regions of Lake Champlain. Biogeochemistry 133:201–217
Jarvie HP, Withers PJA, Bowes MJ, Palmer-Felgate EJ, Harper DM, Wasiak K, Neal M (2010) Streamwater phosphorus and nitrogen across a gradient in rural–agricultural land use intensity. Agric Ecosyst Environ 135:238–252
Johnson ER, Inamdar S, Kan J, Vargas R (2018) Particulate organic matter composition in stream runoff following large storms: role of POM sources, particle size, and event characteristics. J Geophys Res 123:660–675
Kaushal SS, Groffman PM, Band LE, Shields CA, Morgan RP, Palmer MA et al (2008) Interaction between urbanization and climate variability amplifies watershed nitrate export in Maryland. Environ Sci Technol 42:5872–5878
Kaushal SS, Mayer PM, Vidon PG, Smith RM, Pennino MJ, Newcomer TA et al (2014) Land use and climate variability amplify carbon, nutrient, and contaminant pulses: a review with management implications. J Am Water Resour Assoc 50:585–614
Kaushal SS, Gold AJ, Bernal S, Newcomer Johnson TA, Addy K, Burgin A, Burns DA et al (2018) Watershed ‘chemical cocktails’: forming novel elemental combinations in Anthropocene fresh waters. Biogeochemistry 141:281–305
Kellogg DQ, Gold AJ, Cox S, Addy K, August PV (2010) A geospatial approach for assessing denitrification sinks within lower-order catchments. Ecol Eng 36:1596–1606
Le Moal M, Gascuel-Odoux C, Ménesguen A, Souchon Y, Étrillard C, Levain A et al (2019) Eutrophication: a new wine in an old bottle? Sci Total Environ 651:1–11
Mallakpour I, Villarini G (2015) The changing nature of flooding across the central United States. Nat Clim Change 5:250–254
McClain ME, Boyer EW, Dent CL, Gergel SE, Grimm NB, Groffman PM et al (2003) Biogeochemical hot spots and hot moments at the interface of terrestrial and aquatic ecosystems. Ecosystems 6:301–312
McMahon G, Harned DA (1998) Effect of environmental setting on sediment, nitrogen, and phosphorus concentrations in Albemarle-Palmico drainage basin, North Carolina and Virginia, USA. Environ Manag 22:887–903
Melillo JM, Richmond TTC, Yohe GW (eds) (2014) Climate change impacts in the United States: the third national climate assessment. US Global Change Research Program, p 841. https://doi.org/10.7930/J0Z31WJ2
Mevik B, Wehrens R, Liland KH (2016) pls: Partial least squares and principal component regression, R package version 2.6-0. http://CRAN.R-project.org/package=pls
Meybeck M, Moatar F (2012) Daily variability of river concentrations and fluxes: indicators based on the segmentation of the rating curve. Hydrol Process 26:1188–1207
Milly PCD, Betancourt J, Falkenmark M, Hirsch RM, Kundzewicz ZB, Lettenmaier DP, Stouffer RJ (2008) Stationarity is dead: whither water management. Science 319:573–574
Moatar F, Meybeck M, Raymon S, Birgand F, Curie F (2013) River flux uncertainties predicted by hydrological variability and riverine material behaviour. Hydrol Process 27:3535–3546
Moatar F, Abbott BW, Minaudo C, Curie F, Pinay G (2017) Elemental properties, hydrology, and biology interact to shape concentration-discharge curves for carbon, nutrients, sediment, and major ions. Water Resour Res 53:1270–1287
Nixon SW (1995) Coastal marine eutrophication: a definition, social causes, and future concerns. Ophelia 41:199–219
Novotny V (1995) Nonpoint pollution and urban stormwater management. Technomic Publishing Co., Inc., Lancaster, p 434
Paerl HW (1997) Coastal eutrophication and harmful algal blooms: importance of atmospheric deposition and groundwater as “new” nitrogen and other nutrient sources. Limnol Oceanogr 42:1154–1165
Pellerin BA, Saraceno JF, Shanley JB, Sebestyen SD, Aiken GR, Wollheim WM, Bergamaschi BA (2011) Taking the pulse of snowmelt: in situ sensors reveal seasonal, event and diurnal patterns of nitrate and dissolved organic matter variability in an upland forest stream. Biogeochemistry 108:183–198
Pellerin BA, Bergamaschi BA, Gilliom RJ, Crawford CG, Saraceno J, Frederick CP, Downing BD, Murphy JC (2014) Mississippi River nitrate loads from high frequency sensor measurements and regression-based load estimation. Environ Sci Technol 48:12612–12619
Poor CJ, McDonnell JJ (2007) The effects of land use on stream nitrate dynamics. J Hydrol 332:54–68
Potter SR, Andrews S, Atwood JD, Kellogg RL, Lemunyon J, Norfleet L, Oman D (2006) Model simulation of soil loss, nutrient loss, and change in soil organic carbon associated with crop production. USDA, Natural Resources Conservation Service, Washington DC. https://www.nrcs.usda.gov/Internet/FSE_DOCUMENTS/nrcs143_013138.pdf
Puckett LJ (1995) Identifying the major sources of nutrient water pollution. Environ Sci Technol 29:408–414
R Core Team (2015) R: A Language and Environment for Statistical Computing. R Found for Stat Comput, Vienna, Austria. http://www.R-project.org
R Core Team (2019) R: A Language and Environment for Statistical Computing. R Found for Stat Comput, Vienna, Austria. http://www.R-project.org
Renard KG, Freimund JR (1994) Using monthly precipitation data to estimate the R-factor in the revised USLE. J Hydrol 157:287–306
Renard KG, Foster GR, Weesies GA, Porter JP (1991) RUSLE: revised universal soil loss equation. J Soil Water Conserv 46:30–33
RIGIS (1998) Hydrolines of Rhode Island. Rhode Island Geographical Information System, Kingston. http://www.rigis.org/datasets/hydrolines. Accessed 11 Nov 2017
RIGIS (2013) Impervious Surfaces 2011; impervious11. Rhode Island Geographic Information System (RIGIS) Data Distribution System, Environmental Data Center, University of Rhode Island, Kingston, Rhode Island. URL: http://www.rigis.org. Accessed 11 Nov 2017
RIGIS (2016) Soils 2016. Rhode Island Geographical Information System, Kingston, RI. http://www.rigis.org/datasets/soils. Accessed 11 Nov 2017
Rissman AR, Carpenter SR (2015) Progress on nonpoint pollution: barriers & opportunities. Dædalus J Am Acad Arts Sci 144:35–47
Rosenberg BD, Schroth AW (2017) Coupling the reactive riverine phosphorus and iron species during hot transport moments: impacts of land cover and seasonality. Biogeochemistry 132:103–122
Royer TV, David MB, Gentry LE (2006) Timing of riverine export of nitrate and phosphorus from agricultural watersheds in Illinois: implications for reducing nutrient loading to the Mississippi River. Environ Sci Technol 40:4126–4131
Schipper LA, Gold AJ, Davidson EA (2010) Managing denitrification in human dominated landscape. Ecol Eng 36:1503–1606
Sharpley AN, Chapra SC, Wedepohl R, Sims JT, Daniel TC, Reddy KR (1994) Managing agricultural phosphorus for protection of surface waters: issues and options. J Environ Qual 23:437–451
Sharpley AN, Kleinman PJA, Heathwaite AL, Gburek WJ, Folmar GJ, Schmidt JP (2007) Phosphorus loss from an agricultural watershed as a function of storm size. J Environ Qual 37:362–368
Shields CA, Band LE, Law N, Groffman PM, Kaushal SS, Savvas K, Fisher GT, Belt KT (2008) Streamflow distribution of non-point source nitrogen export from urban-rural catchments in the Chesapeake Bay watershed. Water Resour Res 44:W09416. https://doi.org/10.1029/2007WR006360
Smith VH (2006) Responses of estuarine and coastal marine phytoplankton to nitrogen and phosphorus enrichment. Limnol Oceanogr 51:377–384
Smith VH, Tilman GD, Nekola JC (1999) Eutrophication: impacts of excess nutrients on freshwater, marine, and terrestrial ecosystems. Environ Poll 100:179–196
Soldat DJ, Petrovic AM (2008) The fate and transport of phosphorus in turfgrass ecosystems. Crop Sci 48:2051–2065
Stumpf RP, Johnson LT, Wynne TT, Baker DB (2016) Forecasting annual cyanobacterial bloom biomass to inform management decisions in Lake Erie. J Great Lakes Res 42:1174–1183
Tilman D, Balzer C, Hill J, Befort BL (2011) Global food demand and the sustainable intensification of agriculture. Proc Natl Acad Sci 108:20260–20264
Texas A&M University (2012) ArcSWAT Software; ArcSWAT 2012.10.19; Texas A&M University: College Station, TX, USA. http://swat.tamu.edu/. Accessed 3 Sept 2017
Underwood KL, Rizzo DM, Schroth AW, Dewoolkar M (2017) Evaluating spatial variability in sediment and phosphorus concentration-discharge relationships using Bayesian inference and self-organizing maps. Water Resour Res 53:10293–10316
US Census Bureau (2011) 2010 census summary file. US Census Bureau, Rhode Island
Vanni MJ, Renwick WH, Headworth JL, Auch JD, Schaus MH (2001) Dissolved and particulate nutrient flux from three adjacent agricultural watersheds: a five-year study. Biogeochemistry 54:85–114
Vaughan MCH, Bowden WB, Shanley JB, Vermilyea A, Sleeper R, Gold AJ, Pradhanang SM, Inamdar SP, Levia DF, Andres AS, Birgand F, Schroth AW (2017) High-frequency dissolved organic carbon and nitrate measurements reveal differences in storm hysteresis and loading in relation to land cover and seasonality. Water Resour Res. https://doi.org/10.1002/2017WR020491
Vaughan MCH, Bowden WB, Shanley JB, Vermilyea A, Wemple B, Schroth AW (2018) Using in situ UV-Visible spectrophotometer sensors to quantify riverine phosphorus partitioning and concentration at a high frequency. Limnol Oceanogr Meth 16:840–855
Vidon P, Darwan DL, Andres AS, Inamdar S, Kaushal S, Morrison J et al (2018) In the path of the Hurricane: impact of Hurricane Irene and Tropical Storm Lee on watershed hydrology and biogeochemistry from North Caroline to Maine, USA. Biogeochemistry 141:351–364
Wake CP, Burakowski EA, Wilkinson P, Hayhoe K, Stoner A, Keeley C, LaBranche J (2014) Climate change in southern New Hampshire: past, present and future. Sustainability Institute, University of New Hampshire, p 88
Walling D, Webb B (1985) Estimating the discharge of contaminants to coastal waters by rivers: some cautionary comments. Mar Pollut Bull 16:488–492
Walter MT, Walter MF, Brooks ES, Steenhuis TS, Boll J, Weiler KR (2000) Hydrologically sensitive areas: variable source area hydrology implications for water quality risk assessment. J Soil Water Conserv 3:277–284
Yang Z, Zhang M, Shi X, Kong F, Ma R, Yu Y (2016) Nutrient reduction magnifies the impact of extreme weather on cyanobacterial bloom formation in large shallow Lake Taihu (China). Water Res 103:302–310
Zarnetske JP, Bouda M, Abbott BW, Saiers J, Raymond PA (2018) Generality of hydrologic transport limitation of watershed organic carbon flux across ecoregions of the United States. Geophys Res Lett 45:702–711
Zhang JZ, Kelble CR, Fischer CJ, Moore L (2009) Hurricane Katrina induced nutrient runoff from an agricultural area to coastal waters in Biscayne Bay, Florida. Estuar Coast Shelf Sci 84:209–218
Acknowledgements
We thank the undergraduate and graduate students who were instrumental in installing and maintaining the water quality sensors in the field, collecting grab and storm samples, and conducting QA/QC of the data: Joseph Loffredo, Wyndom Chace, Mason Garfield, Nicole Stevens-Murphy, Matthew Wallace, Matt Dunn, Frances Vazques, Jon Aguire, Josh Sargent and Ian Armitstead. We thank Britta Chambers and Valerie Preler for watershed delineation and refinements to land use coverages and Josh Sawyer and David Gold for their assistance with statistical analyses. This work was supported by the National Science Foundation under RI EPSCoR NEWRnet Grant No. IIA-1330406 and by the USDA National Institute of Food and Agriculture, Multistate Hatch S-1063 (Project Accession No. 1005742).
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible Editor: Sujay Kaushal.
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Frazar, S., Gold, A.J., Addy, K. et al. Contrasting behavior of nitrate and phosphate flux from high flow events on small agricultural and urban watersheds. Biogeochemistry 145, 141–160 (2019). https://doi.org/10.1007/s10533-019-00596-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10533-019-00596-z