Recent studies show sulfur redox processes in terrestrial settings are more important than previously considered, but much remains uncertain about how these processes respond to dynamic hydrologic conditions in natural field settings. We used field observations from a sulfate-impacted wetland and stream in the mining region of Minnesota (USA) to calibrate a reactive transport model and evaluate sulfur and coupled geochemical processes under contrasting hydrogeochemical scenarios. Simulations of different hydrological conditions showed that flux and chemistry differences between surface water and deeper groundwater strongly control hyporheic zone geochemical profiles. However, model results for the stream channel versus wetlands indicate sediment organic carbon content to be the more important driver of sulfate reduction rates. A complex nonlinear relationship between sulfate reduction rates and geochemical conditions is apparent from the model's higher sensitivity to sulfate concentrations in settings with higher organic content. Across all scenarios, simulated e− balance results unexpectedly showed that sulfate reduction dominates iron reduction, which is contrary to the traditional thermodynamic ladder but corroborates recent experimental findings by Hansel et al. (2015) that “cryptic” sulfur cycling could drive sulfate reduction in preference over iron reduction. Following the thermodynamic ladder, our models shows that high surface water sulfate slows methanogenesis in shallow sediments, but field observations suggest that sulfate reduction may not entirely suppress methane. Overall, our results show that sulfate reduction may serve as a major component making up and influencing terrestrial redox processes, with dynamic hyporheic fluxes controlling sulfate concentrations and reaction rates, especially in high organic content settings.
Bibliographical noteFunding Information:
This work was supported by a University of Minnesota-Water Resources Center grant from the U.S. Geological Survey awarded to Ng and Myrbo. Groundwater monitoring wells were installed with help from Andrew Streitz (Minnesota Pollution Control Agency) with funds from Minnesota’s Clean Water, Land & Legacy Amendment. Professor William Seyfried (University of Minnesota) assisted with methane analyses. Edward Swain (Minnesota Pollution Control Agency) contributed key insights throughout the project. Scott Alexander (University of Minnesota) supplied invaluable field and lab assistance. Isabelle Cozzarelli (USGS) provided guidance on the CH4 sample collection. Field equipment was partially supported by LacCore from a grant from the National Science Foundation (NSF-0949962 to Myrbo and others). The authors thank two reviewers who provided helpful comments on the manuscripts. Additional field measurements and model simulation results may be found in our supporting information. Model files are available on GitHub (https://github.com/UMN-Hydro/ SecondCreek2015). The corresponding author may be contacted for further details regarding the field data and model.
- hyporheic zone
- iron reduction
- reactive transport modeling
- sulfate reduction
- surface water-groundwater exchange