TY - JOUR
T1 - Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado
AU - Winnick, Matthew J.
AU - Carroll, Rosemary W.H.
AU - Williams, Kenneth H.
AU - Maxwell, Reed M.
AU - Dong, Wenming
AU - Maher, Kate
N1 - Publisher Copyright:
© 2017. American Geophysical Union. All Rights Reserved.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - 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 flow paths 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 base flow 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 flow paths. 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. 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.
AB - 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 flow paths 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 base flow 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 flow paths. 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. 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.
KW - concentration-discharge
KW - critical zone
KW - pyrite oxidation
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U2 - 10.1002/2016WR019724
DO - 10.1002/2016WR019724
M3 - Article
AN - SCOPUS:85016977258
SN - 0043-1397
VL - 53
SP - 2507
EP - 2523
JO - Water Resources Research
JF - Water Resources Research
IS - 3
ER -