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Balancing watershed nitrogen budgets: accounting for biogenic gases in streams

Abstract

Denitrification is critical for removal of reactive nitrogen (Nr) from ecosystems. However, measuring realistic, scalable rates and understanding the role of denitrification and other dissimilatory processes in watershed nitrogen (N) budgets remains a significant challenge in biogeochemistry. In this study, we focused on the stream reach and network scale in three Mid-Atlantic coastal plain watersheds. We applied open channel methods to measure biogenic N2 and N2O gas fluxes derived from both in-stream and terrestrial nitrogen processing. A large portion of biogenic N2 flux through streams (33–100 %, mean = 74 %) was a result of groundwater delivery of biogenic N2 with the remaining portion due to in-stream N2 production. In contrast, N2O was largely produced in-stream, with groundwater delivery contributing on average 12 % of the total biogenic N2O flux. We scaled these measurements across one stream network and compared them to hydrologic Nr export and net anthropogenic N inputs (NANI) to a 4.8 km2 watershed. The N budget revealed that, during the study period, the biogenic N2 flux through streams was comparable to the difference between NANI and hydrologic Nr export (i.e. the “missing” N). This study provides a methodological and conceptual framework for incorporating terrestrial and in-stream derived biogenic N gas fluxes into watershed N budgets and supports the hypothesis that denitrification is the primary fate of NANI that is not exported in streamflow.

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References

  1. Baulch HM, Schiff SL, Maranger R, Dillon PJ (2011) Nitrogen enrichment and the emission of nitrous oxide from streams. Glob Biogeochem Cycles 25(4): GB4013

  2. Baulch H, Venkiteswaran J, Dillon P, Maranger R (2010) Revisiting the application of open-channel estimates of denitrification. Limnol Oceanogr: Methods 8(5):202–215

  3. Beaulieu JJ, Arango CP, Hamilton SK, Tank JL (2007) The production and emission of nitrous oxide from headwater streams in the Midwestern United States. Glob Change Biol 14(4):878–894

  4. Beaulieu JJ, Tank JL, Hamilton SK, Wollheim WM, Hall RO, Mulholland PJ, Peterson BJ, Ashkenas LR, Cooper LW, Dahm CN (2011) Nitrous oxide emission from denitrification in stream and river networks. Proc Natl Acad Sci 108(1):214–219

  5. Böhlke J, Denver J (1995) Combined use of groundwater dating, chemical, and isotopic analyses to resolve the history and fate of nitrate contamination in two agricultural watersheds, Atlantic coastal plain, Maryland. Water Resour Res 31(9):2319–2339

  6. Burgin AJ, Hamilton SK (2007) Have we overemphasized the role of denitrification in aquatic ecosystems? A review of nitrate removal pathways. Front Ecol Environ 5(2):89–96

  7. Cey BD, Hudson GB, Moran JE, Scanlon BR (2009) Evaluation of noble gas recharge temperatures in a shallow unconfined aquifer. Groundwater 47(5):646–659

  8. Chapra SC, Di Toro DM (1991) Delta method for estimating primary production, respiration, and reaeration in streams. J Environ Eng-Asce 117(5):640–655

  9. Colt J (1984) Computation of dissolved gas concentrations in water as functions of temperature, salinity, and pressure. In: American Fisheries Society special publication (USA)

  10. Darling JM (1962) Maryland streamflow characteristics. Bull. 25. State of Maryland Board of Natural Resources, Department of Geology, Mines, and Water Resources

  11. Diaz RJ (2001) Overview of hypoxia around the world. J Environ Qual 30(2):275–281

  12. Diaz RJ, Rosenberg R (2008) Spreading dead zones and consequences for marine ecosystems. Science 321(5891):926–929

  13. Duff JH, Triska FJ (1990) Denitrifications in sediments from the hyporheic zone adjacent to a small forested stream. Can J Fish Aquat Sci 47(6):1140–1147

  14. Duncan JM, Groffman PM, Band LE (2013) Towards closing the watershed nitrogen budget: spatial and temporal scaling of denitrification. J Geophys Res 118(3):1105–1119

  15. Dunkle S, Plummer L, Busenberg E, Phillips P, Denver J, Hamilton P, Michel R, Coplen T (1993) Chlorofluorocarbons (CCl3F and CCl2F2) as dating tools and hydrologic tracers in shallow groundwater of the Delmarva Peninsula, Atlantic Coastal Plain, United States. Water Resour Res 29(12):3837–3860

  16. Ellins KK, Romanmas A, Lee R (1990) Using Rn-222 to examine groundwater surface discharge interaction in the Rio-Grande-De-Manati,Puerto-Rico. J Hydrol 115(1–4):319–341

  17. Fisher TR, Benitez JA, Lee KY, Sutton AJ (2006) History of land cover change and biogeochemical impacts in the Choptank River basin in the mid-Atlantic region of the US. Int J Remote Sens 27(17):3683–3703

  18. Fisher TR, Gustafson AB, Koskelo AI, Fox RJ, Kana TM, Beckert KA, Stone JP, Jordan TE, Staver KW, Sutton AJ, McCarty GW, Lang MW (2010) The Choptank basin in transition: Intensifying agricutlure, slow urbanization, and estuarine eutrophication. In: Kennish ML, Paerl HW (eds) Coastal Lagoons: critical habitats of environmental change. CRC Press, Boca Raton

  19. Fortuin NP, Willemsen A (2005) Exsolution of nitrogen and argon by methanogenesis in Dutch ground water. J Hydrol 301(1):1–13

  20. Foster P, Ramaswamy P, Artaxo P, Berntsen T, Betts R, Fahey DW, Haywood J, Lean J, Lowe DC, Myhre G, Nganga J, Prinn R, Raga G, Schultz M, Van Dorland R (2007) Changes in the atmospheric constituents and in radiative forcing. In: Climate Change 2007: the physical science bases. Contribution of working group I to the 4th assessment report of the IPCC. Cambridge University Press, Cambridge

  21. Fox RJ, Fisher TR, Gustafson AB, Jordan TE, Kana TM, Lang MW (2014) Searching for the missing nitrogen: biogenic nitrogen gases in groundwater and streams. J Agric Sci 152:96–106

  22. Garcia HE, Gordon LI (1992) Oxygen solubility in seawater: better fitting equations. Limnol Oceanogr 37(6):1307–1312

  23. Garcia-Ruiz R, Pattinson S, Whitton B (1998) Denitrification and nitrous oxide production in sediments of the Wiske, a lowland eutrophic river. Sci Total Environ 210–211:307–320

  24. Gardner J (2014) Denitrification, N2O emissions, and nutrient export in Maryland coastal plain streams (MS Thesis). University of Maryland

  25. Genereux DP, Hemond HF, Mulholland PJ (1993) Use of radon-222 and calcium as tracers in a three-end-member mixing model for streamflow generation on the West Fork of Walker Branch Watershed. J Hydrol 142(1):167–211

  26. Golterman HL (2004) The chemistry of phosphate and nitrogen compounds in sediments. Springer Science & Business Media, Dordrecht

  27. Groffman PM, Altabet MA, Böhlke J, Butterbach-Bahl K, David MB, Firestone MK, Giblin AE, Kana TM, Nielsen LP, Voytek MA (2006) Methods for measuring denitrification: diverse approaches to a difficult problem. Ecol Appl 16(6):2091–2122

  28. Gu C, Hornberger GM, Herman JS, Mills AL (2008) Influence of stream-groundwater interactions in the streambed sediments on NO3 flux to a low-relief coastal stream. Water Resources Research 44(11)

  29. Gu C, Anderson W, Maggi F (2012) Riparian biogeochemical hot moments induced by stream fluctuations. Water Resour Res 48(11):W09546

  30. Hamilton PA, Denver JM, Phillips PJ, Shedlock RJ (1993) Water quality assessment of the Delmarva Peninsula, Delaware, Maryland, and Virginia: Effects of agricultural activities on, and distribution of, nitrate and other inorganics constituents in the surficial aquifer, vol 93-40. USGS

  31. Hamme RC, Emerson SR (2004) The solubility of neon, nitrogen and argon in distilled water and seawater. Deep Sea Res Part I 51(11):1517–1528

  32. Harrison JA, Matson PA, Fendorf SE (2005) Effects of a diel oxygen cycle on nitrogen transformations and greenhouse gas emissions in a eutrophied subtropical stream. Aquat Sci 67(3):308–315

  33. Hasegawa K, Hanaki K, Matsuo T, Hidaka S (2000) Nitrous oxide from the agricultural water system contaminated with high nitrogen. Chemosphere-Glob Change Sci 2(3):335–345

  34. Hemond HF, Duran AP (1989) Fluxes of N2O at the sediment-water and water-atmosphere boundaries of a nitrogen-rich river. Water Resour Res 25(5):839–846

  35. Higgins TM, McCutchan JH, Lewis WM (2008) Nitrogen ebullition in a Colorado plains river. Biogeochemistry 89(3):367–377

  36. Hiscock K, Bateman A, Mühlherr I, Fukada T, Dennis P (2003) Indirect emissions of nitrous oxide from regional aquifers in the United Kingdom. Environ Sci Technol 37(16):3507–3512

  37. Holtgrieve GW, Schindler DE, Branch TA, A’mar ZT (2010) Simultaneous quantification of aquatic ecosystem metabolism and reaeration using a Bayesian statistical model of oxygen dynamics. Limnol Oceanogr 55(3):1047–1063

  38. Hotchkiss E, Hall R Jr, Sponseller R, Butman D, Klaminder J, Laudon H, Rosvall M, Karlsson J (2015) Sources of and processes controlling CO2 emissions change with the size of streams and rivers. Nat Geosci 8(9):696–699

  39. Howarth RW, Billen G, Swaney D, Townsend A, Jaworski N, Lajtha K, Downing J, Elmgren R, Caraco N, Jordan T (1996) Regional nitrogen budgets and riverine N & P fluxes for the drainages to the North Atlantic Ocean: Natural and human influences. In Nitrogen cycling in the North Atlantic Ocean and its watersheds. Biogeochemistry 35:75–139

  40. Howarth R, Swaney D, Billen G, Garnier J, Hong B, Humborg C, Johnes P, Mörth C-M, Marino R (2012) Nitrogen fluxes from the landscape are controlled by net anthropogenic nitrogen inputs and by climate. Front Ecol Environ 10(1):37–43

  41. IPCC (2006) 2006 IPCC Guidelines for National Greenhouse Gas Inventories, Prepared by the National. In Eggleston HS, Buendia L, Miwa K, Ngara T and Tanabe K (eds) Greenhouse Gas Inventories Programme, IGES, Japan

  42. Jähne B, Heinz G, Dietrich W (1987) Measurement of the diffusion coefficients of sparingly soluble gases in water. J Geophys Res 92(C10):10767

  43. Jordan TE, Weller DE (1996) Human contributions to terrestrial nitrogen flux. BioScience 46:655–664

  44. Jordan TE, Correll DL, Weller DE (1997) Effects of agriculture on discharges of nutrients from coastal plain watersheds of Chesapeake Bay. J Environ Qual 26(3):836–848

  45. Kana TM, Darkangelo C, Hunt MD, Oldham JB, Bennett GE, Cornwell JC (1994) Membrane inlet mass spectrometer for rapid high-precision determination of N2, O2, and Ar in environmental water samples. Anal Chem 66(23):4166–4170

  46. Kemp W, Boynton W, Adolf J, Boesch D, Boicourt W, Brush G, Cornwell J, Fisher T, Glibert P, Hagy J (2005) Eutrophication of Chesapeake Bay: historical trends and ecological interactions. Mar Ecol Prog Ser 303(21):1–29

  47. Knowles R (1982) Denitrification. Microbiol Rev 46(1):43

  48. Kulkarni MV, Groffman PM, Yavitt JB (2008) Solving the global nitrogen problem: it’s a gas! Front Ecol Environ 6(4):199–206

  49. Laursen AE, Seitzinger SP (2002) Measurement of denitrification in rivers: an integrated, whole reach approach. Hydrobiologia 485(1–3):67–81

  50. Laursen AE, Seitzinger SP (2004) Diurnal patterns of denitrification, oxygen consumption and nitrous oxide production in rivers measured at the whole-reach scale. Freshw Biol 49(11):1448–1458

  51. Laursen A, Seitzinger S (2005) Limitations to measuring riverine denitrification at the whole reach scale: effects of channel geometry, wind velocity, sampling interval, and temperature inputs of N2-enriched groundwater. Hydrobiologia 545(1):225–236

  52. Leopold LB, Maddock T (1953) the hydraulic geometry of stream channels and some phyriographic implications: quantitative measurement of some of the hydraulic factors that help to determine the shape of natural stream channels: depth, width, velocity, and suspended load, and how they vary with discharge as simple power functions; Teir Interrelations are Described by the Term “hydraulic Geometry”. U.S. Government Printing Office

  53. Marzolf ER, Mulholland PJ, Steinman AD (1994) Improvements to the diurnal upstream-downstream dissolved oxygen change technique for determining whole-stream metabolism in small streams. Can J Fish Aquat Sci 51(7):1591–1599

  54. McClain ME, Boyer EW, Dent CL, Gergel SE, Grimm NB, Groffman PM, Hart SC, Harvey JW, Johnston CA, Mayorga E, McDowell WH, Pinay G (2003) Biogeochemical hot spots and hot moments at the interface of terrestrial and aquatic ecosystems. Ecosystems 6(4):301–312

  55. McCutchan J, Lewis W (2008) Spatial and temporal patterns of denitrification in an effluent-dominated plains river. Internationale Vereinigung fur Theoretische und Angewandte Limnologie Verhandlungen 30(2):323

  56. McCutchan JH, Saunders JF, Pribyl AL, Lewis WM (2003) Open-channel estimation of denitrification. Limnol Oceanogr Methods 1:74–81

  57. McIsaac G, Hu X (2004) Net N input and riverine N export from Illinois agricultural watersheds with and without extensive tile drainage. Biogeochemistry 70(2):253–273

  58. Mosier A, Kroeze C, Nevison C, Oenema O, Seitzinger S, Van Cleemput O (1998) Closing the global N2O budget: nitrous oxide emissions through the agricultural nitrogen cycle. Nutr Cycl Agroecosyst 52(2–3):225–248

  59. Nixon SW (1995) Coastal marine eutrophication: a definition, social causes, and future concerns. Ophelia 41(1):199–219

  60. Norton M, Fisher T (2000) The effects of forest on stream water quality in two coastal plain watersheds of the Chesapeake Bay. Ecol Eng 14(4):337–362

  61. Nowicki BL (1994) The effect of temperature, oxygen, salinity, and nutrient enrichment on estuarine denitrification rates measured with a modified nitrogen gas flux technique. Estuar Coast Shelf Sci 38(2):137–156

  62. Ocampo CJ, Oldham CE, Sivapalan M (2006) Nitrate attenuation in agricultural catchments: shifting balances between transport and reaction. Water Resour Res 42(1):W01408

  63. Peng TH, Broecker WS, Mathieu GG, Li YH, Bainbridge AE (1979) Radon evasion rates in the Atlantic and Pacific oceans as determined during the Geosecs Program. J Geophys Res 84(C5):2471

  64. Pfenning K, McMahon P (1997) Effect of nitrate, organic carbon, and temperature on potential denitrification rates in nitrate-rich riverbed sediments. J Hydrol 187(3):283–295

  65. Piña-Ochoa E, Álvarez-Cobelas M (2006) Denitrification in aquatic environments: a cross-system analysis. Biogeochemistry 81(1):111–130

  66. Pribyl AL, Mccutchan JH, Lewis WM, Saunders Iii JF (2005) Whole-system estimation of denitrification in a plains river: a comparison of two methods. Biogeochemistry 73(3):439–455

  67. Ravishankara AR, Daniel JS, Portmann RW (2009) Nitrous oxide (N2O): the dominant ozone-depleting substance emitted in the 21st century. Science 326(5949):123–125

  68. Raymond PA, Zappa CJ, Butman D, Bott TL, Potter J, Mulholland P, Laursen AE, McDowell WH, Newbold D (2012) Scaling the gas transfer velocity and hydraulic geometry in streams and small rivers. Limnol Oceanogr 2:41–53

  69. Roley SS, Tank JL, Williams MA (2012) Hydrologic connectivity increases denitrification in the hyporheic zone and restored floodplains of an agricultural stream. J Geophys Res 117(G3):G00N04

  70. Seitzinger SP (1988) Denitrification in freshwater and coastal marine ecosystems: ecological and geochemical significance. Limnol Oceanogr 33(4):702–724

  71. Seitzinger SP, Kroeze C (1998) Global distribution of nitrous oxide production and N inputs in freshwater and coastal marine ecosystems. Global Biogeochem Cycles 12(1):93–113

  72. Seitzinger S, Harrison JA, Böhlke J, Bouwman A, Lowrance R, Peterson B, Tobias C, Drecht GV (2006) Denitrification across landscapes and waterscapes: a synthesis. Ecol Appl 16(6):2064–2090

  73. Shine KP, Fuglestvedt JS, Hailemariam K, Stuber N (2005) Alternatives to the global warming potential for comparing climate impacts of emissions of greenhouse gases. Clim Change 68(3):281–302

  74. Smethie WM, Takahashi T, Chipman DW, Ledwell JR (1985) Gas exchange and CO2 flux in the tropical Atlantic Ocean determined from 222Rn and pCO2 measurements. J Geophys Res 90(C4):7005

  75. Smith TE, Laursen AE, Deacon JR (2008) Nitrogen attenuation in the Connecticut River, northeastern USA; a comparison of mass balance and N2 production modeling approaches. Biogeochemistry 87(3):311–323

  76. Stanford G, Dzienia S, Vander Pol RA (1975) Effect of temperature on denitrification rate in soils. Soil Sci Soc Am J 39(5):867–870

  77. Stow CA, Walker JT, Cardoch L, Spence P, Geron C (2005) N2O emissions from streams in the Neuse river watershed, North Carolina. Environ Sci Technol 39(18):6999–7004

  78. Ueda S, Ogura N, Yoshinari T (1993) Accumulation of nitrous oxide in aerobic groundwaters. Water Res 27(12):1787–1792

  79. Van Breemen N, Boyer E, Goodale C, Jaworski N, Paustian K, Seitzinger S, Lajtha K, Mayer B, Van Dam D, Howarth R (2002) Where did all the nitrogen go? Fate of nitrogen inputs to large watersheds in the northeastern USA. Biogeochemistry 57(1):267–293

  80. Vilain G, Garnier J, Tallec G, Tournebize J (2011) Indirect N2O emissions from shallow groundwater in an agricultural catchment (Seine Basin, France). Biogeochemistry 111(1–3):253–271

  81. Wanninkhof R (1992) Relationship between wind speed and gas exchange over the ocean. J Geophys Res 97(C5):7373

  82. Wanninkhof R, Mulholland P, Elwood J (1990) Gas exchange rates for a first-order stream determined with deliberate and natural tracers. Water Resour Res 26(7):1621–1630

  83. Weiss R, Price B (1980) Nitrous oxide solubility in water and seawater. Mar Chem 8(4):347–359

  84. Well R, Weymann D, Flessa H (2005) Recent research progress on the significance of aquatic systems for indirect agricultural N2O emissions. Environ Sci 2(2–3):143–151

  85. Werner SF, Browne BA, Driscoll CT (2010) Three-dimensional spatial patterns of trace gas concentrations in baseflow-dominated agricultural streams: implications for surface–ground water interactions and biogeochemistry. Biogeochemistry 107(1–3):319–338

  86. Weymann D, Well R, Flessa H, von der Heide C, Deurer M, Meyer K, Konrad C, Walther W (2008) Groundwater N2O emission factors of nitrate-contaminated aquifers as derived from denitrification progress and N2O accumulation. Biogeosciences 5(5):1215–1226

  87. Weymann D, Well R, Heide C, Böttcher J, Flessa H, Duijnisveld WHM (2009) Recovery of groundwater N2O at the soil surface and its contribution to total N2O emissions. Nutr Cycl Agroecosyst 85(3):299–312

  88. Wilson G, Andrews J, Bath A (1990) Dissolved gas evidence for denitrification in the Lincolnshire Limestone groundwaters, eastern England. J Hydrol 113(1):51–60

  89. Yan W, Laursen AE, Wang F, Sun P, Seitzinger SP (2004) Measurement of denitrification in the Changjiang River. Environ Chem 1(2):95

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Acknowledgments

We thank the members of the Fisher lab group (Anne Gustafson, Rebecca Fox, Dana Bunnell-Young, Keota Silaphone, and Lindsay Tempison) and Todd Kana at the Horn Point Laboratory for their support. The following people from the Jordan lab group at Smithsonian Environmental Research Center provided field and lab assistance: Joe Miklas, Jake Wilhelm, and Carey Pelc. We thank Keith Eshleman for comments that led to the improvement of the manuscript. Funding sources include NSF (DEB# 0919181, DEB#0919141, DEB #1252923), Maryland Water Resources Research Center, Izaak Walton League-Midshore Chapter, and a Horn Point Laboratory Graduate Student Fellowship.

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Correspondence to John R. Gardner.

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Gardner, J.R., Fisher, T.R., Jordan, T.E. et al. Balancing watershed nitrogen budgets: accounting for biogenic gases in streams. Biogeochemistry 127, 231–253 (2016). https://doi.org/10.1007/s10533-015-0177-1

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Keywords

  • Denitrification
  • Greenhouse gases
  • Headwater streams
  • Nitrogen
  • Radon
  • Watershed budget