Skip to main content
SpringerLink
Log in

Tracing Sources of Streamwater Sulfate During Snowmelt Using S and O Isotope Ratios of Sulfate and 35S Activity

  • Published:
Biogeochemistry Aims and scope Submit manuscript

Abstract

The biogeochemical cycling of sulfur (S) was studied during the 2000 snowmelt at Sleepers River Research Watershed in northeastern Vermont, USA using a hydrochemical and multi-isotope approach. The snowpack and 10 streams of varying size and land use were sampled for analysis of anions, dissolved organic carbon (DOC), 35S activity, and δ34S and δ18O values of sulfate. At one of the streams, δ18O values of water also were measured. Apportionment of sulfur derived from atmospheric and mineral sources based on their distinct δ34S values was possible for 7 of the 10 streams. Although mineral S generally dominated, atmospheric-derived S contributions exceeded 50% in several of the streams at peak snowmelt and averaged 41% overall. However, most of this atmospheric sulfur was not from the melting snowpack; the direct contribution of atmospheric sulfate to streamwater sulfate was constrained by 35S mass balance to a maximum of 7%. Rather, the main source of atmospheric sulfur in streamwater was atmospheric sulfate deposited months to years earlier that had microbially cycled through the soil organic sulfur pool. This atmospheric/pedospheric sulfate (pedogenic sulfate formed from atmospheric sulfate) source is revealed by δ18O values of streamwater sulfate that remained constant and significantly lower than those of atmospheric sulfate throughout the melt period, as well as streamwater 35S ages of hundreds of days. Our results indicate that the response of streamwater sulfate to changes in atmospheric deposition will be mediated by sulfate retention in the soil.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • C. Alewell M.J. Mitchell G.E. Likens H.R. Krouse (1999) ArticleTitleSources of stream sulfate at the Hubbard Brook Experimental Forest: Long-term analyses using stable isotopes Biogeochemistry 44 281–299

    Google Scholar 

  • C. Alewell M.J. Mitchell G.E. Likens H.R. Krouse (2000) ArticleTitleAssessing the origin of sulfate deposition at the Hubbard Brook Experimental Forest J. Environ. Qual. 29 759–767

    Google Scholar 

  • C. Alewell (2001) ArticleTitlePredicting reversibility of acidification: the European sulfur story Water Air Soil Pollut. 130 1271–1276 Occurrence Handle10.1023/A:1013989419580

    Article  Google Scholar 

  • C. Alewell M. Novak (2001) ArticleTitleSpotting zones of dissimilatory sulfate reduction in a forested catchment: the 34S–35S approach Environ. Pollut. 112 369–377 Occurrence Handle10.1016/S0269-7491(00)00137-8 Occurrence Handle11291443

    Article  PubMed  Google Scholar 

  • Bailey S.W., Mayer B. and Mitchell M.J. 2004. The influence of mineral weathering on drainage water sulfate in Vermont and New Hampshire. Hydrol. Proc. DOI: 10.1002/hyp.1410.

  • H. Bao G.M. Michalski M.H. Thiemans (2001) ArticleTitleSulfate oxygen-17 anomalies in desert varnishes Geochim. Cosmochim. Acta 65 2029–2036 Occurrence Handle10.1016/S0016-7037(00)00490-7

    Article  Google Scholar 

  • Burns D.A. and Kendall C. 2002. Analysis of S15N and S18O to differentiate NO −3 sources in runoff at two watersheds in the Catskill Mountains of New York. Water Resourc. Res. 38: 1051, doi: 10.1029/2001 WR000292.

  • D.H. Campbell J.S. Baron K.A. Tonnessen P.D. Brooks P.F. Schuster (2000) ArticleTitleControls on nitrogen flux in alpine/subalpine watersheds of Colorado Water Resourc. Res. 36 37–47 Occurrence Handle10.1029/1999WR900283

    Article  Google Scholar 

  • D.W. Clow M.A. Mast (1999) ArticleTitleLong-term trends in stream water and precipitation chemistry at five headwater basins in the northeastern United States Water Resourc. Res. 35 541–554 Occurrence Handle10.1029/1998WR900050

    Article  Google Scholar 

  • B.R. Dhamala M.J. Mitchell (1995) ArticleTitleSulfur speciation, vertical distribution, and seasonal variation in a northern hardwood forest soil, USA Can. J. For. Res. 25 234–243

    Google Scholar 

  • C.T. Driscoll G.E. Likens M.R. Church (1998) ArticleTitleRecovery of soil and surface waters in the northeastern U.S. from decreases in atmospheric deposition of sulfur, Water Air Soil Pollut 105 319–329 Occurrence Handle10.1023/A:1005008315977

    Article  Google Scholar 

  • C.T. Driscoll G.B. Lawrence A.J. Bulger T.J. Butler C.S. Cronan C. Eagar K.F. Lambert G.E. Likens J.L. Stoddard K.C. Weathers (2001) ArticleTitleAcidic deposition in the northeastern U.S.: sources and inputs, ecosystems effects, and management strategies BioScience 51 180–198

    Google Scholar 

  • T. Dunne R.D. Black (1970a) ArticleTitleAn experimental investigation of runoff production in permeable soils Water Resourc. Res. 6 478–490

    Google Scholar 

  • T. Dunne R.D. Black (1970b) ArticleTitlePartial area contributions to storm runoff in a small New England watershed Water Resourc. Res. 6 1296–1311

    Google Scholar 

  • T. Dunne R.D. Black (1971) ArticleTitleRunoff processes during snowmelt Water Resourc. Res. 7 1160–1172

    Google Scholar 

  • C. Eimers P.J. Dillon S.L. Schiff (2004) ArticleTitleA S-isotope approach to determine the relative contribution of redox processes to net SO4 export from uplandand wetland- dominated catchments Geochim. Cosmochim. Acta 68 3665–3674 Occurrence Handle10.1016/j.gca.2004.03.010

    Article  Google Scholar 

  • S.S. Gbondo-Tugbawa C.T. Driscoll M.J. Mitchell J.D. Aber G.E. Likens (2002) ArticleTitleA model to simulate the response of a Northern Hardwood Forest to changes in S deposition Ecol. Appl. 12 8–23

    Google Scholar 

  • D. Genereux (1998) ArticleTitleQuantifying uncertainty in tracer-based hydrograph separations Water Resourc. Res. 34 915–919 Occurrence Handle10.1029/98WR00010

    Article  Google Scholar 

  • C.A. Johnson M.A. Mast C.L. Kester (2001) ArticleTitleUse of 17O/16O to trace atmospherically-deposited sulfate in surface waters: a case study in alpine watersheds in the Rocky Mountains Geophys. Res. Lett. 28 4483–4486 Occurrence Handle10.1029/2001GL012966

    Article  Google Scholar 

  • L.M. Hall (1959) The geology of the St. Johnsbury QuadrangleVermont and New HampshireBulletin No. 13 Vermont Development Commission Montpelier 105

    Google Scholar 

  • J.W. Hornbeck S.W. Bailey D.C. Buso J.B. Shanley (1997) ArticleTitleStreamwater chemistry and nutrient budgets for forested watersheds in New England: variability and management implications Forest Ecol. Mgmt. 93 73–89 Occurrence Handle10.1016/S0378-1127(96)03937-0

    Article  Google Scholar 

  • Kendall C., Silva S.R., Chang C.C., Campbell D.H., Burns D.A. and Shanley J.B. 1995. Use of oxygen and nitrogen isotopes to trace sources of nitrate during snowmelt in forested catchments.In: Tonnessen K.A., Williams M.W. and Tranter M. (eds), Biogeochemistry of Seasonally Snow-Covered Catchments. (Proceedings of a Boulder Symposium, July 1995), IAHS Publ. no. 228, pp. 339–347.

  • C. Kendall (1998) Tracing nitrogen sources and cycling in catchments C. Kendall J.J. McDonnell (Eds) Isotope Tracers in Catchment Hydrology Elsevier Amsterdam 519–576

    Google Scholar 

  • K.A. Kendall J.B. Shanley J.J. McDonnell (1999) ArticleTitleA hydrometric and geochemical approach to testing the transmissivity feedback hypothesis during snowmelt J. Hydrol. 219 188–205 Occurrence Handle10.1016/S0022-1694(99)00059-1

    Article  Google Scholar 

  • C.L. Kester J.S. Baron J.T. Turk (2003) ArticleTitleIsotopic study of sulfate sources and residence times in a subalpine watershed Environ. Geol. 43 606–613

    Google Scholar 

  • P. Kroopnick H. Craig (1972) ArticleTitleAtmospheric oxygen: isotopic composiiton and solubility fractionation Science 175 54–55

    Google Scholar 

  • H.R. Krouse V.A. Grinenko (1991) Stable Isotopes: Natural and Anthropogenic Sulfur in the Environment SCOPE 43 John Wiley and Sons Chichester 440

    Google Scholar 

  • Krouse H.R. and Mayer B. 2000. Sulphur and oxygen isotopes in sulphate. In: Cook P. and Herczeg A.L. (eds), Environmental Tracers in Subsurface Hydrology. Kluwer Academic Publishers, pp.195–231.

  • C.C.-W. Lee J. Savarino M.H. Thiemens (2001) ArticleTitleMass independent oxygen isotopic composition of atmospheric sulfate: origin and implications for the present and past atmosphere of Earth and Mars Geophys. Res. Lett. 28 1783–1786 Occurrence Handle10.1029/2000GL011826

    Article  Google Scholar 

  • G.E. Likens F.H. Bormann (1995) Biogeochemistry of a Forested Ecosystem Springer-Verlag New York 159

    Google Scholar 

  • G.E. Likens C.T. Driscoll D.C. Buso M.J. Mitchell G.M. Lovett S.W. Bailey T.G. Siccama W.A. Reiners C. Alewell (2002) ArticleTitleThe biogeochemistry of sulfur at Hubbard Brook Biogeochemistry 60 235–316 Occurrence Handle10.1023/A:1020972100496

    Article  Google Scholar 

  • M.A. Mast J.T. Turk G.P. Ingersoll D.W. Clow C.L. Kester (2001) ArticleTitleUse of stable sulfur isotopes to identify sources of sulfate in Rocky Mountain snowpacks Atmos. Env. 35 3303–3313 Occurrence Handle10.1016/S1352-2310(00)00507-0

    Article  Google Scholar 

  • B. Mayer K.H. Feger A. Giesemann H.-J. Jäger (1995a) ArticleTitleInterpretation of sulfur cycling in two catchments in the Black Forest (Germany) using stable sulfur and oxygen isotope data Biogeochem. 30 51–58 Occurrence Handle10.1007/BF02181039

    Article  Google Scholar 

  • B. Mayer P. Fritz J. Prietzel H.R. Krouse (1995b) ArticleTitleThe use of stable sulfur and oxygen isotope ratios for interpreting the mobility of sulfate in aerobic forest soils Appl. Geochem. 10 161–173 Occurrence Handle10.1016/0883-2927(94)00054-A

    Article  Google Scholar 

  • B. Mayer S.M. Bollwerk T. Mansfeldt B. Hütter J. Veiver (2001a) ArticleTitleThe oxygen isotope composition of nitrate generated by nitrification in acid forest soils Geochim. Cosmochim. Acta 65 2743–2756 Occurrence Handle10.1016/S0016-7037(01)00612-3

    Article  Google Scholar 

  • B. Mayer J. Prietzel H.R. Krouse (2001b) ArticleTitleThe influence of sulfur deposition rates on sulfate retention patterns and mechanisms in aerated forest soils Appl. Geochem. 16 1003–1019 Occurrence Handle10.1016/S0883-2927(01)00010-5

    Article  Google Scholar 

  • Michel R.L. and Naftz D.L. 1995. Use of sulphur-35 and tritium to study runoff from an alpine glacier, Wind River Range, Wyoming. In: Tonnessen K.A., Williams M.W. and Tranter M. (eds), Biogeochemistry of Seasonally Snow-Covered Catchments. (Proceedings of a Boulder Symposium, July 1995), IAHS Publ. no. 228, pp. 441–445.

  • R.L. Michel D.H. Campbell D.W. Clow J.T. Turk (2000) ArticleTitleTimescales for migration of atmospherically derived sulfate through an alpine/subalpine watershedLoch ValeColorado Water Resourc. Res. 36 27–36 Occurrence Handle10.1029/1999WR900276

    Article  Google Scholar 

  • M.J. Mitchell H.R. Krouse B. Mayer A.C. Stam Y. Zhang (1998) Use of stable isotopes in evaluating sulfur biogeochemistry of forest ecosystems C. Kendall J.J. McDonnell (Eds) Catchment Hydrology Elsevier Amsterdam 489–518

    Google Scholar 

  • M.J. Mitchell B. Mayer S.W. Bailey J.W. Hornbeck C. Alewell C.T. Driscoll G.E. Likens (2001a) ArticleTitleUse of stable isotope ratios for evaluating sulfur sources and losses at the Hubbard Brook Experimental Forest WaterAir and Soil Pollut. 130 75–86 Occurrence Handle10.1023/A:1012295301541

    Article  Google Scholar 

  • M.J. Mitchell P.J. McHale S. Inamdar D.R. Raynal (2001b) ArticleTitleRole of within lake processes and hydrobiogeochemical changes over 16 years in a watershed in the Adirondack Mountains of New York State, USA Hydrol. Proc. 15 1951–1965 Occurrence Handle10.1002/hyp.249

    Article  Google Scholar 

  • L. Newman H.R. Krouse V.A. Grinenko (1991) Sulfur isotope variations in the atmosphere H.R. Krouse V.A. Grinenko (Eds) Stable Isotopes: Natural and Anthropogenic Sulfur in the Environment SCOPE 43 John Wiley and Sons Chichester 133–176

    Google Scholar 

  • H. Nielsen J. Pilot L.N. Grinenko V.A. Grinenko A.Y. Lein J.W. Smith R.G. Pankina (1991) Lithospheric sources of sulfur H.R. Krouse V.A. Grinenko (Eds) Stable Isotopes: Natural and Anthropogenic Sulfur in the Environment SCOPE 43 John Wiley and Sons Chichester 65–132

    Google Scholar 

  • M. Novak S.H. Bottrell E. Prechova (2001) ArticleTitleSulfur isotope inventories of atmospheric deposition, spruce forest floor and living Sphagnum along a NW-SE transect across Europe Biogeochem. 53 23–50 Occurrence Handle10.1023/A:1010792205756

    Article  Google Scholar 

  • M. Novak R.L. Michel E. Prechova M. Stepanova (2004) ArticleTitleThe missing flux in a 35S budget for the soils of a small polluted catchment Water Air and Soil Pollut. Focus 4 517–529 Occurrence Handle10.1023/B:WAFO.0000028375.96356.eb

    Article  Google Scholar 

  • J. Park M.J. Mitchell P.J. McHale S.F. Christopher T.P. Myers (2003) ArticleTitleInteractive effects of changing climate and atmospheric deposition on N and S biogeochemistry in a forested watershed of the Adirondack Mountains, New York State Glob. Change Biol. 9 1602–1619 Occurrence Handle10.1046/j.1365-2486.2003.00686.x

    Article  Google Scholar 

  • J.O. Reuss D.W. Johnson (1986) Acid Deposition and the Acidification of Soils and Waters, Ecol. Studies 59 Springer New York

    Google Scholar 

  • B.P. Rochelle M.R. Church M.B. David (1987) ArticleTitleSulfur retention at intensively studies sites in the U.S. and Canada Water Air Soil Pollut. 33 73–83 Occurrence Handle10.1007/BF00191379

    Article  Google Scholar 

  • S.C. Schindler M.J. Mitchell T.J. Scott R.D. Fuller C.T. Driscoll (1986) ArticleTitleIncorporation of 35S-sulfate into inorganic and organic constituents of two forest soils Soil Sci. Soc. Am. J. 50 457–463

    Google Scholar 

  • J.B. Shanley C. Kendall T.E. Smith D.M. Wolock J.J. McDonnell (2002a) ArticleTitleControls on old and new water contributions to streamflow in some nested catchments in Vermont USA Hydrol. Proc. 16 589–609 Occurrence Handle10.1002/hyp.312

    Article  Google Scholar 

  • J.B. Shanley P.F. Schuster M.M. Reddy D.A. Roth H.E. Taylor G.R. Aiken (2002b) ArticleTitleMercury on the move during snowmelt in VermontEOS Trans. Am. Geophys. Union 83 45–48

    Google Scholar 

  • Shanley J.B., Clark S.F.Jr. and Denner J.C. 2002c. Patterns and trends in snowpack water equivalent at a northern Vermont site1960–2002, (Abstract). Proc. 59th Eastern Snow ConferenceJune 5–7, 2002, StoweVermontpp. 325

  • J.B. Shanley P. Krám J. Hruska T.D. Bullen (2004) ArticleTitleA biogeochemical comparison of two well-buffered catchments with contrasting histories of acid deposition WaterAir Soil Pollut.: Focus 4 325–342 Occurrence Handle10.1023/B:WAFO.0000028363.48348.a4

    Article  Google Scholar 

  • A. Stam M.J. Mitchell H.R. Krouse J.S. Kahl (1992) ArticleTitleStable sulfur isotopes of sulfate in precipitation and stream solutions in a northern hardwood watershed Water Resourc. Res. 28 231–236 Occurrence Handle10.1029/91WR02481

    Article  Google Scholar 

  • J.L. Stoddard D.S. Jeffries A. Lükewille T.A. Clair P.J. Dillon C.T. Driscoll M. Forsius M. Johannessen J.S. Kahl J.H. Kellogg A. Kemp J. Mannio D.T. Monteith P.S. Murdoch S. Patrick A. Rebsdorf B.L. Skjelkvåle M.P. Stainton T. Traaen H. Dam ParticleVan K.E. Webster J. Wietung A. Wilander (1999) ArticleTitleRegional trends in aquatic recovery from acidification in North America and Europe Nature 401 575–578 Occurrence Handle10.1038/44114

    Article  Google Scholar 

  • J.K. Sueker J.T. Turk R.L. Michel (1999) ArticleTitleUse of cosmogenic 35S for comparing ages of water from three alpine-subalpine basins in the Colorado Front Range Geomorphology 27 61–74 Occurrence Handle10.1016/S0169-555X(98)00090-7

    Article  Google Scholar 

  • A.C. Titus J.J. McDonnell J.B. Shanley C. Kendall (1995) ArticleTitleSnowmelt runoff production in a small forested catchment: a combined hydrometric and isotopic tracing approach (abs), EOS Trans Am. Geophys. Union 76 F216

    Google Scholar 

  • J.T. Turk D.H. Campbell N.E. Spahr (1993) ArticleTitleUse of chemistry and stable sulfur isotopes to determine sources and trends in sulfate in Colorado lakes Water Air Soil Pollut. 79 279–298

    Google Scholar 

  • Y. Zhang M.J. Mitchell M. Christ G.E. Likens H.R. Krouse (1998) ArticleTitleStable sulfur isotopic biogeochemistry of the Hubbard Brook Experimental Forest New Hampshire Biogeochem. 41 259–275 Occurrence Handle10.1023/A:1005992430776

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. U.S. Geological Survey, P.O. Box 628, 05602, Montpelier, VT, USA

    James B. Shanley

  2. Department of Geology and Geophysics, University of Calgary, 2500 University Drive NW, T2N 1N4, Calgary, Alberta, Canada

    Bernhard Mayer

  3. College of Environmental Science and Forestry, State University of New York, 1 Forestry Drive, 13210, Syracuse, NY, USA

    Myron J. Mitchell

  4. U.S. Geological Survey, 345 Middlefield Road, MS 434, 94025, Menlo Park, CA, USA

    Robert L. Michel & Carol Kendall

  5. Northeastern Research Station, Hubbard Brook Experimental Forest, USDA Forest Service, 234 Mirror Lake Road, 03223, Campton, NH, USA

    Scott W. Bailey

Authors
  1. James B. Shanley
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bernhard Mayer
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Myron J. Mitchell
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Robert L. Michel
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Scott W. Bailey
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Carol Kendall
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to James B. Shanley.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shanley, J.B., Mayer, B., Mitchell, M.J. et al. Tracing Sources of Streamwater Sulfate During Snowmelt Using S and O Isotope Ratios of Sulfate and 35S Activity. Biogeochemistry 76, 161–185 (2005). https://doi.org/10.1007/s10533-005-2856-9

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10533-005-2856-9

Keywords

Search

Navigation