Abstract

The hyporheic corridor (HC) encompasses the river–groundwater continuum, where the mixing of groundwater (GW) with river water (RW) in the HC can stimulate biogeochemical activity. Here we propose a novel thermodynamic mechanism underlying this phenomenon and reveal broader impacts on dissolved organic carbon (DOC) and microbial ecology. We show that thermodynamically favorable DOC accumulates in GW despite lower DOC concentration, and that RW contains thermodynamically less-favorable DOC, but at higher concentrations. This indicates that GW DOC is protected from microbial oxidation by low total energy within the DOC pool, whereas RW DOC is protected by lower thermodynamic favorability of carbon species. We propose that GW–RW mixing overcomes these protections and stimulates respiration. Mixing models coupled with geophysical and molecular analyses further reveal tipping points in spatiotemporal dynamics of DOC and indicate important hydrology–biochemistry–microbial feedbacks. Previously unrecognized thermodynamic mechanisms regulated by GW–RW mixing may therefore strongly influence biogeochemical and microbial dynamics in riverine ecosystems.

Highlights

  • River water the hyporheic corridor (HC) by coupling end-member mixing models with time-lapse electrical resistivity tomography (ERT)

  • Integrating results across our analyses suggests a conceptual model that connects river water (RW) discharge dynamics, biogeochemistry, and microbiomes across the HC as follows: RW contains CHO lignin-like organic compounds—potentially indicating significant terrestrial carbon inputs to the RW—which are thermodynamically unfavorable for microbial oxidation, and these compounds enter the hyporheic zone following a rise in river stage

  • Once in the hyporheic zone, the CHO lignin-like compounds mix with more thermodynamically favorable GW dissolved organic carbon (DOC) that, in turn, primes microorganisms to mineralize the riverderived DOC. This results in an increase in microbial activity, depletion of CHO lignin-like compounds and an increase in amino-acid-associated biochemical transformations in the hyporheic zone. These shifts in DOC composition are associated with a clear shift in deterministic ecological selection pressures that differentiate RW and hyporheic zone microbiomes, potentially due to selection for proteolytic activity in the hyporheic zone associated with N or S limitation

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Summary

Introduction

River water the HC by coupling end-member mixing models with time-lapse electrical resistivity tomography (ERT). Concentrations in the river (Fig. 3a) are associated with less thermodynamically favorable DOC.

Results
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