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Title: 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 » 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.« less

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5];  [1]
  1. Stanford Univ., CA (United States). Department of Geological Sciences
  2. Desert Research Inst. (DRI), Reno, NV (United States). Division of Hydrologic Sciences
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Rocky Mountain Biological Laboratory, Crested Butte, CO (United States)
  4. Colorado School of Mines, Golden, CO (United States). Hydrologic Science and Engineering Program
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (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. https://doi.org/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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