Biogeochemistry

, Volume 108, Issue 1–3, pp 183–198

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

  • Brian A. Pellerin
  • John Franco Saraceno
  • James B. Shanley
  • Stephen D. Sebestyen
  • George R. Aiken
  • Wilfred M. Wollheim
  • Brian A. Bergamaschi
Article

Abstract

Highly resolved time series data are useful to accurately identify the timing, rate, and magnitude of solute transport in streams during hydrologically dynamic periods such as snowmelt. We used in situ optical sensors for nitrate (NO3) and chromophoric dissolved organic matter fluorescence (FDOM) to measure surface water concentrations at 30 min intervals over the snowmelt period (March 21–May 13, 2009) at a 40.5 hectare forested watershed at Sleepers River, Vermont. We also collected discrete samples for laboratory absorbance and fluorescence as well as δ18O–NO3 isotopes to help interpret the drivers of variable NO3 and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO3 and FDOM concentrations. An observed decrease in NO3 concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO3 (mainly from nitrification) from source areas in surficial soils. Stream FDOM concentrations were coupled with flow throughout the study period, suggesting a strong hydrologic control on DOM concentrations in the stream. However, higher FDOM concentrations per unit streamflow after snowmelt likely reflected a greater hydraulic connectivity of the stream to leachable DOM sources in upland soils. We also observed diurnal NO3 variability of 1–2 μmol l−1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO3 and dissolved organic carbon yields (DOC, measured by FDOM proxy) calculated from weekly discrete samples and in situ data sub-sampled daily resulted in small to moderate differences over the entire study period (−4 to 1% for NO3 and −3 to −14% for DOC), but resulted in much larger differences for daily yields (−66 to +27% for NO3 and −88 to +47% for DOC, respectively). Despite challenges inherent in in situ sensor deployments in harsh seasonal conditions, these data provide important insights into processes controlling NO3 and FDOM in streams, and will be critical for evaluating the effects of climate change on snowmelt delivery to downstream ecosystems.

Keywords

Nitrate FDOM Snowmelt Forested Diurnal 

Supplementary material

10533_2011_9589_MOESM1_ESM.pdf (147 kb)
Supplementary material 1 (PDF 147 kb)

References

  1. Ågren A, Buffam I, Berggren M, Bishop K, Jansson M, Laudon H (2008) Dissolved organic carbon characteristics in boreal streams in a forest-wetland gradient during the transition between winter and summer. J Geophys Res 113:G03031. doi:10.1029/2007JG000674 CrossRefGoogle Scholar
  2. Aiken GR (1992) Chloride interference in the analysis of dissolved organic carbon by the wet oxidation method. Environ Sci Technol 26:2435–2439CrossRefGoogle Scholar
  3. Blough NV, Del Vecchio R (2002) Chromophoric DOM in the coastal environment. In: Hansell D, Carlson C (eds) Biogeochemistry of marine dissolved organic matter. Academic, San Diego, CA, pp 509–546CrossRefGoogle Scholar
  4. Boss E, Zaneveld JRV (2003) The effect of bottom substrate on inherent optical properties: evidence of biogeochemical processes. Limnol Oceanogr 48:346–354CrossRefGoogle Scholar
  5. Boyer EW, Hornberger GM, Bencala KE, McKnight DM (1997) Response characteristics of DOC flushing in an alpine catchment. Hydrol Process 11:1635–1647CrossRefGoogle Scholar
  6. Boyer EW, Hornberger GM, Bencala KE, McKnight DM (2000) Effects of asynchronous snowmelt on flushing of dissolved organic carbon: a mixing model approach. Hydrol Process 14:3291–3308CrossRefGoogle Scholar
  7. 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 113:G03016. doi:1029/2008JG000721 CrossRefGoogle Scholar
  8. Campbell JL, Hornbeck JW, Mitchell MJ, Adams MB, Castro MS, Driscoll CT, Kahl JS, Kochenderfer JN, Likens GE, Lynch JA, Murdoch PS, Nelson SJ, Shanley JB (2004) Input–output budgets of inorganic nitrogen for 24 forest watersheds in the northeastern United States: a review. Water Air Soil Pollut 151:373–396CrossRefGoogle Scholar
  9. Campbell JL, Mitchell MJ, Mayer B, Groffman PM, Christenson LM (2007) Mobility of nitrogen-15-labeled nitrate and sulfur-34-labeled sulfate during snowmelt. Soil Sci Soc Am J 71:1934–1944CrossRefGoogle Scholar
  10. Campbell JL, Rustad LE, Boyer EW, Christopher SF, Driscoll CT, Fernandez IJ, Groffman PM, Houle D, Kiekbusch J, Magill AH, Mitchell MJ, Ollinger SV (2009) Consequences of climate change for biogeochemical cycling in forests of northeastern North America. Can J For Res 39:264–284CrossRefGoogle Scholar
  11. Casciotti KL, Sigman DM, Galanter Hastings M, Böhlke JK, Hilkert A (2002) Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method. Anal Chem 74:4905–4912CrossRefGoogle Scholar
  12. Coble PG (1996) Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy. Mar Chem 51:325–346CrossRefGoogle Scholar
  13. Cory RM, McKnight DM (2005) Fluorescence spectroscopy reveals ubiquitous presence of reduced and oxidized quinone moiety in dissolved organic matter. Environ Sci Technol 39:8142–8149CrossRefGoogle Scholar
  14. Doctor DH, Kendall C, Sebestyen SD, Shanley JB, Ohte N, Boyer EW (2008) Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream. Hydrol Process 22:2410–2423CrossRefGoogle Scholar
  15. Downing BD, Boss E, Bergamaschi BA, Fleck JA, Lionberger MA, Ganju NK, Schoellhamer DH, Fujii R (2009) Quantifying fluxes and characterizing compositional changes of dissolved organic matter in aquatic systems in situ using combined acoustic and optical measurements. Limnol Oceanogr:Methods 7:119–131CrossRefGoogle Scholar
  16. Eckhardt BW, Moore TR (1990) Controls on dissolved organic carbon concentrations in Streams, Southern Québec. Can J Fish Aquat Sci 47:1537–1544CrossRefGoogle Scholar
  17. Ensign SH, Doyle MW (2006) Nutrient spiraling in streams and river networks. J Geophys Res 111:G04009. doi:10.1029/2005JG000114 CrossRefGoogle Scholar
  18. Fisher SG, Grimm NB, Martí E, Holmes RM, Jones JB (1998) Material spiraling in stream corridors: a telescoping ecosystem model. Ecosystems 1:19–34CrossRefGoogle Scholar
  19. Genereux D (1998) Quantifying uncertainty in tracer-based hydrograph separations. Water Resour Res 34:915–919CrossRefGoogle Scholar
  20. Glynn PD, Larsen MC, Greene EA, Buss HL, Clow DW, Hunt RJ, Mast MA, Murphy SF, Peters NE, Sebestyen SD, Shanley JB, Walker JF (2009) Selected achievements, science directions, and new opportunities for the WEBB small watershed research program. In: Webb RMT, Semmens DJ (eds) Proceedings of the third interagency conference on Research in the watersheds: planning for an uncertain future: monitoring, integration, and adaptation. Scientific Investigations Report 2009-5049. US Geological Survey, Washington, DCGoogle Scholar
  21. 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 67:308–315Google Scholar
  22. Hayhoe K, Wake CP, Huntington TG, Luo L, Schwartz MD, Sheffield J, Wood E, Anderson B, Bradbury J, DeGaetano A, Troy TJ, Wolfe D (2007) Past and future changes in climate and hydrological indicators in the US Northeast. Clim Dyn 28:381–407CrossRefGoogle Scholar
  23. Heffernan JB, Cohen MJ (2010) Direct and indirect coupling of primary production and diel nitrate dynamics in a subtropical spring-fed river. Limnol Oceanogr 55(2):677–688CrossRefGoogle Scholar
  24. Hodgkins GA, Dudley RW (2006a) Changes in late-winter snowpack depth, water equivalent, and density in Maine, 1926–2004. Hydrol Process 20:741–751CrossRefGoogle Scholar
  25. Hodgkins GA, Dudley RW (2006b) Changes in the timing of winter–spring streamflows in eastern North America, 1913–2002. Geophys Res Lett 33:L06402. doi:10.1029/2005GL025593 CrossRefGoogle Scholar
  26. Hornberger GM, Bencala KE, McKnight DM (1994) Hydrological controls on dissolved organic carbon during snowmelt in the Snake River near Montezuma, Colorado. Biogeochemistry 25:147–165CrossRefGoogle Scholar
  27. Houlton BZ, Driscoll CT, Fahey TJ, Likens GE, Groffman PM, Bernhardt ES, Buso DC (2003) Nitrogen dynamics in ice-storm damaged forest ecosystems: implications for nitrogen limitation theory. Ecosystems 6:431–443CrossRefGoogle Scholar
  28. Huntington TG, Hodgkins GA, Keim BD, Dudley RW (2004) Changes in the proportion of precipitation occurring as snow in Northeast (1949 to 2000). J Clim 17:2626–2636CrossRefGoogle Scholar
  29. Huntington TG, Richardson AD, McGuire KJ, Hayhoe K (2009) Climate and hydrological changes in the northeastern United States: recent trends and implications for forested and aquatic ecosystems. Can J For Res 39:199–212CrossRefGoogle Scholar
  30. 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 20:3423–3439CrossRefGoogle Scholar
  31. Johnson KS, Colletti LJ (2002) In situ ultraviolet spectrophotometry for high resolution and long-term monitoring of nitrate, bromide and bisulfide in the ocean. Deep Sea Res I 49:1291–1305CrossRefGoogle Scholar
  32. Judd KE, Likens GE, Groffman PM (2007) High nitrate retention during winter in soils of the Hubbard Brook Experimental Forest. Ecosystems 10:217–225CrossRefGoogle Scholar
  33. Kendall KA, Shanley JB, McDonnell JJ (1999) A hydrometric and geochemical approach to test the transmissivity feedback hypothesis during snowmelt. J Hydrol 219:188–205CrossRefGoogle Scholar
  34. Kirchner JW, Feng X, Neal C, Robson AJ (2004) The fine structure of water-quality dynamics: the (high-frequency) wave of the future. Hydrol Process 18:1353–1359CrossRefGoogle Scholar
  35. Lewis GP, Likens GE (2007) Changes in stream chemistry associated with insect defoliation in a Pennsylvania hemlock-hardwoods forest. For Ecol Manag 238:199–211CrossRefGoogle Scholar
  36. McGlynn BL, McDonnell JJ (2003) Role of discrete landscape units in controlling dissolved organic carbon dynamics. Water Resour Res 39. doi:10.1029/2002WR001525
  37. McGlynn BL, McDonnell JJ, Shanley JB, Kendall C (1999) Riparian zone flow path dynamics during snowmelt in a small headwater catchment. J Hydrol 222:75–92. doi:10.1016/S0022-1694(99)00102-X CrossRefGoogle Scholar
  38. Mitchell MJ, Driscoll CT, Kahl JS, Likens GE, Murdoch PS, Pardo LH (1996) Climatic control of nitrate loss from forested watershed in the Northeastern United States. Environ Sci Technol 30:2609–2612CrossRefGoogle Scholar
  39. Mulholland PJ (2004) The importance of in-stream uptake for regulating stream concentrations and outputs of N and P from a forested watershed: evidence from long-term chemistry records for Walker Branch Watershed. Biogeochemistry 70:403–426. doi:10.1007/s10533-004-0364-y CrossRefGoogle Scholar
  40. Mulholland PJ, Kuenzler EJ (1979) Organic carbon export from upland and forested wetland watersheds. Limnol Oceanogr 24:960–966CrossRefGoogle Scholar
  41. Mulholland PJ, Thomas SA, Valett HM, Webster JR, Beaulieu J (2006) Effects of light on NO3 uptake in small forested streams: diurnal and day-to-day variations. J N Am Benthol Soc 25:583–595CrossRefGoogle Scholar
  42. Mulholland PJ, Roberts BJ, Hill WR, Smith JG (2009) Stream ecosystem responses to the 2007 spring freeze in the southeastern United States: unexpected effects of climate change. Glob Change Biol 15:1767–1776CrossRefGoogle Scholar
  43. Murdoch PS, Stoddard JL (1992) The role of nitrate in the acidification of streams in the Catskill Mountains of New York. Water Resour Res 28:2707–2720CrossRefGoogle Scholar
  44. Oczkowski AJ, Pellerin BA, Hunt CW, Wollheim WM, Vörösmarty CJ, Loder TC III (2006) The role of snowmelt and spring rainfall in inorganic nutrient fluxes from a large temperate watershed, the Androscoggin River basin (Maine and New Hampshire). Biogeochemistry 80:191–203CrossRefGoogle Scholar
  45. Ohno T (2002) Fluorescence inner-filtering correction for determining the humification index of dissolved organic matter. Environ Sci Technol 36:742–746CrossRefGoogle Scholar
  46. Ohte N, Sebestyen SD, Shanley JB, Doctor DH, Kendall C, Wankel SD, Boyer EW (2004) Tracing sources of nitrate in snowmelt runoff using a high-resolution isotopic technique. Geophys Res Lett 31:L21506. doi:10.1029/2004GL020908 CrossRefGoogle Scholar
  47. Pacific VJ, Jencso KG, McGlynn BL (2010) Variable flushing mechanisms and landscape structure control stream DOC export during snowmelt in a set of nested catchments. Biogeochemistry 99:193–211CrossRefGoogle Scholar
  48. Pellerin BA, Downing BD, Kendall C, Dahlgren RA, Kraus TEC, Spencer RG, Bergamaschi BA (2009) Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an in situ optical nitrate sensor and dual nitrate isotopes. Freshw Biol 54:376–387CrossRefGoogle Scholar
  49. Raymond PA, Hopkinson CS (2003) Ecosystem modulation of dissolved carbon age in a temperate marsh-dominated estuary. Ecosystems 6:694–705CrossRefGoogle Scholar
  50. Raymond PA, Saiers JA (2010) Event controlled DOC export from forested watersheds. Biogeochemistry. doi:10.1007/s10533-010-9416-7
  51. Riscassi AL, Scanlon TM (2009) Nitrate variability in hydrological flow paths for three mid-Appalachian forested watersheds following a large-scale defoliation. J Geophys Res 114:G02009. doi:10.1029/2008JG000860 CrossRefGoogle Scholar
  52. Roberts BJ, Mulholland PJ (2007) In-stream biotic control on nutrient biogeochemistry in a forested stream, West Fork of Walker Branch. J Geophys Res Biogeosci 112:G04002. doi:10.1029/2007JG000422 CrossRefGoogle Scholar
  53. Rusjan S, Mikoš M (2010) Seasonal variability of diurnal in-stream nitrate concentration oscillations under hydrologically stable conditions. Biogeochemistry 97:123–140CrossRefGoogle Scholar
  54. Sakamoto CM, Johnson KS, Coletti LJ (2009) Improved algorithm for the computation of nitrate concentrations in seawater using an in situ ultraviolet spectrophotometer. Limnol Oceanogr 7:132–143CrossRefGoogle Scholar
  55. Saraceno J, Pellerin BA, Downing BD, Boss E, Bachand PAM, Bergamaschi BA (2009) High frequency in situ optical measurements during a storm event: assessing relationships between dissolved organic matter, sediment concentrations and hydrologic processes. J Geophys Res Biogeosci 114:G00F09. doi:10.1029/2009JG000989 CrossRefGoogle Scholar
  56. Scholefield D, Goff TL, Braven J, Ebdon L, Long T, Bulter M (2005) Concerted diurnal patterns in riverine nutrient concentrations and physical conditions. Sci Total Environ 344:201–210CrossRefGoogle Scholar
  57. Schuster PF, Shanley JB, Marvin-Dipasquale M, Reddy MM, Aiken GR, Roth DA, Taylor HE, Krabbenhoft DP, DeWild JF (2008) Mercury and organic carbon dynamics during runoff episodes from a Northeastern USA watershed. Water Air Soil Pollut 187:89–108CrossRefGoogle Scholar
  58. Sebestyen SD (2008) Coupled hydrological and biogeochemical processes that control stream nitrogen and dissolved organic carbon at the Sleepers River Research Watershed. PhD dissertation, State University of New York College of Environmental Science and Forestry, Syracuse, NYGoogle Scholar
  59. Sebestyen SD, Boyer EW, Shanley JB, Kendall C, Doctor DH, Aiken GR, Ohte N (2008) Sources, transformations, and hydrological processes that control stream nitrate and dissolved organic matter concentrations during snowmelt in an upland forest. Water Resour Res 44:W12410. doi:10.1029/2008WR006983 CrossRefGoogle Scholar
  60. Sebestyen SD, Boyer EW, Shanley JB (2009) Responses of stream nitrate and DOC loadings to hydrologic forcing and climate change in an upland forest of the northeastern United States. J Geophys Res 114:G02002. doi:10.1029/2008JG000778 CrossRefGoogle Scholar
  61. Shanley JB, Chalmers A (1999) The effect of frozen soil on snowmelt runoff at Sleepers River, Vermont. Hydrol Process 13:1843–1857. doi:10.1002/(SICI)1099-1085 CrossRefGoogle Scholar
  62. Shanley JB, Kendall C, Smith TE, Wolock DM, McDonnell JJ (2002) Controls on old and new water contributions to stream flow at some nested catchments in Vermont, USA. Hydrol Process 16:589–609. doi:10.1002/hyp.312 CrossRefGoogle Scholar
  63. Shanley JB, Hjerdt KN, McDonnell JJ, Kendall C (2003) Shallow water table fluctuations in relation to soil penetration resistance. Ground Water 41:964–972CrossRefGoogle Scholar
  64. Spencer RGM, Pellerin BA, Bergamaschi BA, Downing BD, Kraus TEK, Smart DE, Dahlgren RD, Hernes PJ (2007a) Diurnal variability in riverine dissolved organic matter composition determined by in situ optical measurement in the San Joaquin River (California, USA). Hydrol Process 21:3181–3189CrossRefGoogle Scholar
  65. Spencer RGM, Baker A, Ahad JME, Cowie GL, Ganeshram R, Upstill-Goddard RC, Uher G (2007b) Discriminatory classification of natural and anthropogenic waters in two U.K. estuaries. Sci Total Environ 373:305–323CrossRefGoogle Scholar
  66. Stream Solute Workshop (1990) Concepts and methods for assessing solute dynamics in stream ecosystems. J N Am Benthol Soc 9:95–119CrossRefGoogle Scholar
  67. van Verseveld WJ, McDonnell JJ, Lajtha K (2008) A mechanistic assessment of nutrient flushing at the catchment scale. J Hydrol 358:268–287CrossRefGoogle Scholar
  68. Weishaar JL, Aiken GR, Bergamaschi BA, Fram MS, Fujii R (2003) Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environ Sci Technol 37:4702–4708CrossRefGoogle Scholar
  69. Wollheim WM, Vorosmarty CJ, Peterson BJ, Seitzinger SP, Hopkinson CS (2006) Relationship between river size and nutrient removal. Geophys Res Lett 33:L06410. doi:10.1029/2006GL025845 CrossRefGoogle Scholar

Copyright information

© US Government 2011

Authors and Affiliations

  • Brian A. Pellerin
    • 1
  • John Franco Saraceno
    • 1
  • James B. Shanley
    • 2
  • Stephen D. Sebestyen
    • 3
  • George R. Aiken
    • 4
  • Wilfred M. Wollheim
    • 5
  • Brian A. Bergamaschi
    • 1
  1. 1.U.S. Geological SurveySacramentoUSA
  2. 2.U.S. Geological SurveyMontpelierUSA
  3. 3.USDA Forest Service, Northern Research StationGrand RapidsUSA
  4. 4.U.S. Geological SurveyBoulderUSA
  5. 5.Water Systems Analysis GroupUniversity of New HampshireDurhamUSA

Personalised recommendations