Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado

Winnick, Matthew J.; Carroll, Rosemary W.  H.; Williams, Kenneth H.; Maxwell, Reed M.; Dong, Wenming; Maher, Kate

doi:10.1002/2016WR019724

Title: Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado

Journal Article · 02 March 2017 · Water Resources Research

DOI: https://doi.org/10.1002/2016WR019724 · OSTI ID:1476464

Winnick, Matthew J. ^[1]; Carroll, Rosemary W. H. ^[2]; Williams, Kenneth H. ^[3]; Maxwell, Reed M. ^[4];

^[5]; Maher, Kate ^[1]

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)

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. In this study, 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); USDOE

Contributing Organization:: Desert Research Institute; Colorado School of Mines; Rocky Mountain Biological Laboratory

Grant/Contract Number:: AC02-05CH11231; SC0014556; EAR-1254156; AC02- 05CH11231

OSTI ID:: 1476464

Alternate ID(s):: OSTI ID: 1348990; OSTI ID: 1402333

Journal Information:: Water Resources Research, Vol. 53, Issue 3; Related Information: © 2017. American Geophysical Union. All Rights Reserved.; ISSN 0043-1397

Publisher:: American Geophysical Union (AGU)Copyright Statement

Country of Publication:: United States

Language:: English

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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

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