Distinct Source Water Chemistry Shapes Contrasting Concentration-Discharge Patterns

Zhi, Wei; Li, Li; Dong, Wenming; Brown, Wendy; Kaye, Jason; Steefel, Carl; Williams, Kenneth H.

doi:10.1029/2018wr024257

Distinct Source Water Chemistry Shapes Contrasting Concentration-Discharge Patterns

Journal Article · Mon Apr 15 00:00:00 EDT 2019 · Water Resources Research

DOI:https://doi.org/10.1029/2018wr024257· OSTI ID:1572814

Zhi, Wei ^[1]; ^[2]; ^[3]; ^[4]; Kaye, Jason ^[5]; ^[3]; ^[6]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Energy and Mineral Engineering
Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil and Environmental Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth and Environmental Sciences Area
The Rocky Mountain Biological Lab., Crested Butte, CO (United States)
Pennsylvania State Univ., University Park, PA (United States). Dept. of Ecosystem Science and Management
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth and Environmental Sciences Area; The Rocky Mountain Biological Lab., Crested Butte, CO (United States)

Understanding concentration-discharge (C–Q) relationships are essential for predicting chemical weathering and biogeochemical cycling under changing climate and anthropogenic conditions. Contrasting C–Q relationships have been observed widely, yet a mechanistic framework that can interpret diverse patterns remains elusive. This work hypothesizes that seemingly disparate C–Q patterns are driven by switching dominance of end-member source waters and their chemical contrasts arising from subsurface biogeochemical heterogeneity. We use data from Coal Creek, a high-elevation mountainous catchment in Colorado, and a recently developed watershed reactive transport model (BioRT-Flux-PIHM). Sensitivity analysis and Monte-Carlo simulations (500 cases) show that reaction kinetics and thermodynamics and distribution of source materials across depths govern the chemistry gradients of shallow soil water and deeper groundwater entering the stream. The alternating dominance of organic-poor yet geo-solute-rich groundwater under dry conditions and organic-rich yet geo-solute-poor soil water during spring melt leads to the flushing pattern of dissolved organic carbon and the dilution pattern of geogenic solutes (e.g., Na, Ca, and Mg). In addition, the extent of concentration contrasts regulates the power law slopes (b) of C–Q patterns via a general equation $$b = \frac{δ_b C_{ratio}}{C_{ratio,1/2} + C_{ratio}} +b_{min} $$ (Formula presented.). At low ratios of soil water versus groundwater concentrations ($$C_{ratio} = C_{sw}/C_{gw}$$ < 0.6), dilution occurs; at high ratios ($$C_{ratio}$$ > 1.8), flushing arises; chemostasis occurs in between. This equation quantitatively interprets b values of 11 solutes (dissolved organic carbon, dissolved P, NO₃^-, K, Si, Ca, Mg, Na, Al, Mn, and Fe) from three catchments (Coal Creek, Shale Hills, and Plynlimon) of differing climate, geologic, and land cover conditions. Finally, this indicates potentially broad regulation of subsurface biogeochemical heterogeneity in determining C–Q patterns and wide applications of this equation in quantifying b values, which can have broad implications for predicting chemical weathering and biogeochemical transformation at the watershed scale.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pennsylvania State Univ., University Park, PA (United States); Pennsylvania State University, University Park, PA (United States)

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

Grant/Contract Number:: AC02-05CH11231; SC0016221; SC0020146

OSTI ID:: 1572814

Alternate ID(s):: OSTI ID: 2318732
OSTI ID: 1515610
OSTI ID: 1582560

Journal Information:: Water Resources Research, Journal Name: Water Resources Research Journal Issue: 5 Vol. 55; ISSN 0043-1397

Publisher:: American Geophysical Union (AGU)Copyright Statement

Country of Publication:: United States

Language:: English

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