Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado
Abstract
Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyrite oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changesmore »
- Authors:
-
[5];
- Stanford Univ., CA (United States). Department of Geological Sciences
- Desert Research Inst. (DRI), Reno, NV (United States). Division of Hydrologic Sciences
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Rocky Mountain Biological Laboratory, Crested Butte, CO (United States)
- Colorado School of Mines, Golden, CO (United States). Hydrologic Science and Engineering Program
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)
- Contributing Org.:
- Desert Research Institute; Colorado School of Mines; Rocky Mountain Biological Laboratory
- OSTI Identifier:
- 1476464
- Alternate Identifier(s):
- OSTI ID: 1348990; OSTI ID: 1402333
- Grant/Contract Number:
- AC02-05CH11231; SC0014556; EAR-1254156; AC02- 05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Water Resources Research
- Additional Journal Information:
- Journal Volume: 53; Journal Issue: 3; Related Information: © 2017. American Geophysical Union. All Rights Reserved.; Journal ID: ISSN 0043-1397
- Publisher:
- American Geophysical Union (AGU)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; 58 GEOSCIENCES; water quality; watersheds; catchments; carbon cycle; concentration-discharge; critical zone; pyrite oxidation
Citation Formats
Winnick, Matthew J., Carroll, Rosemary W. H., Williams, Kenneth H., Maxwell, Reed M., Dong, Wenming, and Maher, Kate. Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado. United States: N. p., 2017.
Web. doi:10.1002/2016WR019724.
Winnick, Matthew J., Carroll, Rosemary W. H., Williams, Kenneth H., Maxwell, Reed M., Dong, Wenming, & Maher, Kate. Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado. United States. https://doi.org/10.1002/2016WR019724
Winnick, Matthew J., Carroll, Rosemary W. H., Williams, Kenneth H., Maxwell, Reed M., Dong, Wenming, and Maher, Kate. Thu .
"Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado". United States. https://doi.org/10.1002/2016WR019724. https://www.osti.gov/servlets/purl/1476464.
@article{osti_1476464,
title = {Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado},
author = {Winnick, Matthew J. and Carroll, Rosemary W. H. and Williams, Kenneth H. and Maxwell, Reed M. and Dong, Wenming and Maher, Kate},
abstractNote = {Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyrite oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.},
doi = {10.1002/2016WR019724},
journal = {Water Resources Research},
number = 3,
volume = 53,
place = {United States},
year = {2017},
month = {3}
}
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Works referenced in this record:
Response characteristics of DOC flushing in an alpine catchment
journal, October 1997
- Boyer, Elizabeth W.; Hornberger, George M.; Bencala, Kenneth E.
- Hydrological Processes, Vol. 11, Issue 12
Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer
journal, February 2015
- Long, Philip E.; Williams, Kenneth H.; Davis, James A.
- Geochimica et Cosmochimica Acta, Vol. 150
Temperature and soil organic matter decomposition rates - synthesis of current knowledge and a way forward
journal, August 2011
- Conant, Richard T.; Ryan, Michael G.; Ågren, Göran I.
- Global Change Biology, Vol. 17, Issue 11
Role of discrete landscape units in controlling catchment dissolved organic carbon dynamics: CATCHMENT DOC EXPORT
journal, April 2003
- McGlynn, Brian L.; McDonnell, Jeffrey J.
- Water Resources Research, Vol. 39, Issue 4
Consistency of patterns in concentration-discharge plots: PATTERNS IN CONCENTRATION-DISCHARGE PLOTS
journal, August 2002
- Chanat, Jeffrey G.; Rice, Karen C.; Hornberger, George M.
- Water Resources Research, Vol. 38, Issue 8
Naturally Occurring Contamination in the Mancos Shale
journal, January 2012
- Morrison, Stan J.; Goodknight, Craig S.; Tigar, Aaron D.
- Environmental Science & Technology, Vol. 46, Issue 3
The delivery of dissolved organic carbon from a forested hillslope to a headwater stream in southeastern Pennsylvania, USA
journal, July 2014
- Mei, Yi; Hornberger, George M.; Kaplan, Louis A.
- Water Resources Research, Vol. 50, Issue 7
The dependence of chemical weathering rates on fluid residence time
journal, May 2010
- Maher, K.
- Earth and Planetary Science Letters, Vol. 294, Issue 1-2
Probing deep weathering in the Shale Hills Critical Zone Observatory, Pennsylvania (USA): the hypothesis of nested chemical reaction fronts in the subsurface: NESTED REACTION FRONTS
journal, April 2013
- Brantley, Susan L.; Holleran, Molly E.; Jin, Lixin
- Earth Surface Processes and Landforms, Vol. 38, Issue 11
Quantifying changes in age distributions and the hydrologic balance of a high-mountain watershed from climate induced variations in recharge
journal, March 2015
- Engdahl, Nicholas B.; Maxwell, Reed M.
- Journal of Hydrology, Vol. 522
Hydrological controls on dissolved organic carbon during snowmelt in the Snake River near Montezuma, Colorado
journal, January 1994
- Hornberger, G. M.; Bencala, K. E.; McKnight, D. M.
- Biogeochemistry, Vol. 25, Issue 3
Sulfuric acid as an agent of carbonate weathering constrained by δ13CDIC: Examples from Southwest China
journal, June 2008
- Li, Si-Liang; Calmels, Damien; Han, Guilin
- Earth and Planetary Science Letters, Vol. 270, Issue 3-4
The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California
journal, May 2009
- Maher, Kate; Steefel, Carl I.; White, Art F.
- Geochimica et Cosmochimica Acta, Vol. 73, Issue 10
Climate-Change-Driven Deterioration of Water Quality in a Mineralized Watershed
journal, August 2012
- Todd, Andrew S.; Manning, Andrew H.; Verplanck, Philip L.
- Environmental Science & Technology, Vol. 46, Issue 17
High sensitivity of the continental-weathering carbon dioxide sink to future climate change
journal, February 2012
- Beaulieu, E.; Goddéris, Y.; Donnadieu, Y.
- Nature Climate Change, Vol. 2, Issue 5
Chromium fluxes and speciation in ultramafic catchments and global rivers
journal, May 2016
- McClain, C. N.; Maher, K.
- Chemical Geology, Vol. 426
The Geochemical Behavior of Aluminum in Acidified Surface Waters
journal, April 1986
- Nordstrom, Darrell Kirk; Ball, James W.
- Science, Vol. 232, Issue 4746
Weathering processes in the Ganges–Brahmaputra basin and the riverine alkalinity budget
journal, July 1999
- Galy, Albert; France-Lanord, Christian
- Chemical Geology, Vol. 159, Issue 1-4
Hydrologic Regulation of Chemical Weathering and the Geologic Carbon Cycle
journal, March 2014
- Maher, K.; Chamberlain, C. P.
- Science, Vol. 343, Issue 6178
Stream water carbon controls in seasonally snow-covered mountain catchments: impact of inter-annual variability of water fluxes, catchment aspect and seasonal processes
journal, November 2013
- Perdrial, Julia N.; McIntosh, Jennifer; Harpold, Adrian
- Biogeochemistry, Vol. 118, Issue 1-3
Response of lake chemistry to changes in atmospheric deposition and climate in three high-elevation wilderness areas of Colorado
journal, April 2010
- Mast, M. Alisa; Turk, John T.; Clow, David W.
- Biogeochemistry, Vol. 103, Issue 1-3
Cascading impacts of bark beetle‐caused tree mortality on coupled biogeophysical and biogeochemical processes
journal, September 2012
- Edburg, Steven L.; Hicke, Jeffrey A.; Brooks, Paul D.
- Frontiers in Ecology and the Environment, Vol. 10, Issue 8
Time-variable transit time distributions and transport: Theory and application to storage-dependent transport of chloride in a watershed
journal, January 2015
- Harman, Ciaran J.
- Water Resources Research, Vol. 51, Issue 1
Impact of atmospheric CO 2 levels on continental silicate weathering : IMPACT OF ATMOSPHERIC CO
journal, July 2010
- Beaulieu, E.; Goddéris, Y.; Labat, D.
- Geochemistry, Geophysics, Geosystems, Vol. 11, Issue 7
Concentration-discharge relationships reflect chemostatic characteristics of US catchments
journal, June 2009
- Godsey, Sarah E.; Kirchner, James W.; Clow, David W.
- Hydrological Processes, Vol. 23, Issue 13
A model of dissolved organic carbon concentrations in soil and stream waters
journal, July 1991
- Grieve, Ian. C.
- Hydrological Processes, Vol. 5, Issue 3
Sustained sulfide oxidation by physical erosion processes in the Mackenzie River basin: Climatic perspectives
journal, January 2007
- Calmels, Damien; Gaillardet, Jérôme; Brenot, Agnès
- Geology, Vol. 35, Issue 11
Modeling the influence of organic acids on soil weathering
journal, August 2014
- Lawrence, Corey; Harden, Jennifer; Maher, Kate
- Geochimica et Cosmochimica Acta, Vol. 139
Overview of a simple model describing variation of dissolved organic carbon in an upland catchment
journal, May 1996
- Boyer, Elizabeth W.; Hornberger, George M.; Bencala, Kenneth E.
- Ecological Modelling, Vol. 86, Issue 2-3
The potential for snow to supply human water demand in the present and future
journal, November 2015
- Mankin, Justin S.; Viviroli, Daniel; Singh, Deepti
- Environmental Research Letters, Vol. 10, Issue 11
Acetate Availability and its Influence on Sustainable Bioremediation of Uranium-Contaminated Groundwater
journal, June 2011
- Williams, Kenneth H.; Long, Philip E.; Davis, James A.
- Geomicrobiology Journal, Vol. 28, Issue 5-6
The kinetics and electrochemical rate-determining step of aqueous pyrite oxidation
journal, December 1994
- Williamson, Mark A.; Rimstidt, J. Donald
- Geochimica et Cosmochimica Acta, Vol. 58, Issue 24
Global silicate weathering and CO2 consumption rates deduced from the chemistry of large rivers
journal, July 1999
- Gaillardet, J.; Dupré, B.; Louvat, P.
- Chemical Geology, Vol. 159, Issue 1-4
Changes in the Timing of Snowmelt and Streamflow in Colorado: A Response to Recent Warming
journal, May 2010
- Clow, David W.
- Journal of Climate, Vol. 23, Issue 9
Geomorphic regime modulates hydrologic control of chemical weathering in the Andes–Amazon
journal, October 2015
- Torres, Mark A.; West, A. Joshua; Clark, Kathryn E.
- Geochimica et Cosmochimica Acta, Vol. 166
Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales
journal, March 2014
- Torres, Mark A.; West, A. Joshua; Li, Gaojun
- Nature, Vol. 507, Issue 7492
Formation of soil organic matter via biochemical and physical pathways of litter mass loss
journal, September 2015
- Cotrufo, M. Francesca; Soong, Jennifer L.; Horton, Andrew J.
- Nature Geoscience, Vol. 8, Issue 10
The master transit time distribution of variable flow systems: MASTER TRANSIT TIME DISTRIBUTION
journal, June 2012
- Heidbüchel, Ingo; Troch, Peter A.; Lyon, Steve W.
- Water Resources Research, Vol. 48, Issue 6
Causes of concentration/discharge hysteresis and its potential as a tool for analysis of episode hydrochemistry
journal, January 1998
- Evans, Christopher; Davies, Trevor D.
- Water Resources Research, Vol. 34, Issue 1
Process dominance shift in solute chemistry as revealed by long-term high-frequency water chemistry observations of groundwater flowing through weathered argillite underlying a steep forested hillslope
journal, September 2014
- Kim, Hyojin; Bishop, James K. B.; Dietrich, William E.
- Geochimica et Cosmochimica Acta, Vol. 140
Disproportionately high rates of sulfide oxidation from mountainous river basins of Taiwan orogeny: Sulfur isotope evidence: SULFIDE OXIDATION FROM MOUNTAINOUS BASIN
journal, June 2012
- Das, Anirban; Chung, Chuan-Hsiung; You, Chen-Feng
- Geophysical Research Letters, Vol. 39, Issue 12
SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000°C
journal, August 1992
- Johnson, James W.; Oelkers, Eric H.; Helgeson, Harold C.
- Computers & Geosciences, Vol. 18, Issue 7
The role of fluid residence time and topographic scales in determining chemical fluxes from landscapes
journal, December 2011
- Maher, K.
- Earth and Planetary Science Letters, Vol. 312, Issue 1-2
Global chemical erosion over the last 250 my; variations due to changes in paleogeography, paleoclimate, and paleogeology
journal, November 1999
- Gibbs, M. T.
- American Journal of Science, Vol. 299, Issue 7-9
Cenozoic carbon cycle imbalances and a variable weathering feedback
journal, September 2016
- Caves, Jeremy K.; Jost, Adam B.; Lau, Kimberly V.
- Earth and Planetary Science Letters, Vol. 450
Differential weathering of basaltic and granitic catchments from concentration–discharge relationships
journal, October 2016
- Ibarra, Daniel E.; Caves, Jeremy K.; Moon, Seulgi
- Geochimica et Cosmochimica Acta, Vol. 190
Anthropogenically enhanced fluxes of water and carbon from the Mississippi River
journal, January 2008
- Raymond, Peter A.; Oh, Neung-Hwan; Turner, R. Eugene
- Nature, Vol. 451, Issue 7177
Thickness of the chemical weathering zone and implications for erosional and climatic drivers of weathering and for carbon-cycle feedbacks
journal, September 2012
- West, A. Joshua
- Geology, Vol. 40, Issue 9
Modelling transport of dissolved silica in a forested headwater catchment: the effect of hydrological and chemical time scales on hysteresis in the concentration-discharge relationship
journal, January 2001
- Hornberger, George M.; Scanlon, Todd M.; Raffensperger, Jeff P.
- Hydrological Processes, Vol. 15, Issue 10
Hydrological effects of forest transpiration loss in bark beetle-impacted watersheds
journal, April 2014
- Bearup, Lindsay A.; Maxwell, Reed M.; Clow, David W.
- Nature Climate Change, Vol. 4, Issue 6
Evaluating Aeration Criteria by Simultaneous Measurement of Oxygen Diffusion rate and Soil-Water Regime
journal, January 2002
- Feng, G.; Wu, L.; Letey, J.
- Soil Science, Vol. 167, Issue 8
A Unified Assessment of Hydrologic and Biogeochemical Responses in Research Watersheds in Eastern Puerto Rico Using Runoff–Concentration Relations
journal, December 2013
- Stallard, Robert F.; Murphy, Sheila F.
- Aquatic Geochemistry, Vol. 20, Issue 2-3
A model for atmospheric CO 2 over Phanerozoic time
journal, April 1991
- Berner, R. A.
- American Journal of Science, Vol. 291, Issue 4
A bottom-up control on fresh-bedrock topography under landscapes
journal, April 2014
- Rempe, D. M.; Dietrich, W. E.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 18
Hydrologic Sensitivities of Colorado River Runoff to Changes in Precipitation and Temperature
journal, June 2012
- Vano, Julie A.; Das, Tapash; Lettenmaier, Dennis P.
- Journal of Hydrometeorology, Vol. 13, Issue 3
Lithologic and climatologic controls of river chemistry
journal, May 1994
- Bluth, Gregg J. S.; Kump, Lee R.
- Geochimica et Cosmochimica Acta, Vol. 58, Issue 10
Efficient organic carbon burial in the Bengal fan sustained by the Himalayan erosional system
journal, November 2007
- Galy, Valier; France-Lanord, Christian; Beyssac, Olivier
- Nature, Vol. 450, Issue 7168
Modeling transport of dissolved silica in a forested headwater catchment: Implications for defining the hydrochemical response of observed flow pathways
journal, April 2001
- Scanlon, Todd M.; Raffensperger, Jeff P.; Hornberger, George M.
- Water Resources Research, Vol. 37, Issue 4
Soil C:N ratio as a predictor of annual riverine DOC flux at local and global scales
journal, March 2000
- Aitkenhead, J. A.; McDowell, W. H.
- Global Biogeochemical Cycles, Vol. 14, Issue 1
Weathering, plants, and the long-term carbon cycle
journal, August 1992
- Berner, Robert A.
- Geochimica et Cosmochimica Acta, Vol. 56, Issue 8
Links between climate change, water-table depth, and water chemistry in a mineralized mountain watershed
journal, October 2013
- Manning, Andrew H.; Verplanck, Philip L.; Caine, Jonathan Saul
- Applied Geochemistry, Vol. 37
The potential for snow to supply human water demand in the present and future
text, January 2015
- Mankin, Justin S.; Viviroli, Daniel; Singh, Deepti
- IOP Publishing
Elevation-dependent warming in mountain regions of the world
text, January 2015
- Williamson, S. N.; Greenwood, Gregory; Schöner, W.
- Nature Publishing Group
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- Olshansky, Yaniv; White, Alissa M.; Moravec, Bryan G.
- Frontiers in Earth Science, Vol. 6
Sensitivity analysis of hydraulic conductivity and Manning's n parameters lead to new method to scale effective hydraulic conductivity across model resolutions
journal, November 2018
- M. Foster, Lauren; M. Maxwell, Reed
- Hydrological Processes, Vol. 33, Issue 3
Neogene cooling driven by land surface reactivity rather than increased weathering fluxes
journal, July 2019
- Caves Rugenstein, Jeremy K.; Ibarra, Daniel E.; von Blanckenburg, Friedhelm
- Nature, Vol. 571, Issue 7763
Factors controlling seasonal groundwater and solute flux from snow-dominated basins
journal, June 2018
- Carroll, Rosemary W. H.; Bearup, Lindsay A.; Brown, Wendy
- Hydrological Processes, Vol. 32, Issue 14
Anthropogenic and catchment characteristic signatures in the water quality of Swiss rivers: a quantitative assessment
journal, January 2019
- Botter, Martina; Burlando, Paolo; Fatichi, Simone
- Hydrology and Earth System Sciences, Vol. 23, Issue 4