Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

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

doi:10.1002/2016WR019724

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

Journal Article · Wed Mar 01 00:00:00 EST 2017 · Water Resources Research

DOI:https://doi.org/10.1002/2016WR019724· OSTI ID:1348990

Winnick, Matthew J. ^[1]; Carroll, Rosemary W. H. ^[2]; Williams, Kenneth H. ^[3]; Maxwell, Reed M. ^[4]; ^[5]; Maher, Kate ^[6]

Department of Geological Sciences, Stanford University, Stanford California USA; Stanford University
Division of Hydrologic Sciences, Desert Research Institute, Reno Nevada USA
Lawrence Berkeley National Laboratory, Berkeley California USA; Rocky Mountain Biological Laboratory, Crested Butte Colorado USA
Hydrologic Science and Engineering Program, Colorado School of Mines, Golden Colorado USA
Lawrence Berkeley National Laboratory, Berkeley California USA
Department of Geological Sciences, Stanford University, Stanford California USA

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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: US National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

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

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

OSTI ID:: 1348990

Alternate ID(s):: OSTI ID: 1402333
OSTI ID: 1476464

Journal Information:: Water Resources Research, Journal Name: Water Resources Research Journal Issue: 3 Vol. 53; ISSN 0043-1397

Publisher:: American Geophysical Union (AGU)Copyright Statement

Country of Publication:: United States

Language:: English

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Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

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