%0 Journal Article %T Effective kinetics driven by dynamic concentration gradients under coupled transport and reaction %+ Géosciences Rennes (GR) %+ Stanford University %A Traon, Charlotte Le %A Aquino, Tomás %A Bouchez, Camille %A Maher, Kate %A Borgne, Tanguy Le %Z EU Framework Programme for Research and Innovation Marie Sklodowska-Curie Actions %Z European Research Council %Z Région Bretagne %< avec comité de lecture %@ 0016-7037 %J Geochimica et Cosmochimica Acta %I Elsevier %V 306 %P 189-209 %8 2021-08 %D 2021 %R 10.1016/j.gca.2021.04.033 %Z Sciences of the Universe [physics]/Earth Sciences/Hydrology %Z Sciences of the Universe [physics]/Earth Sciences/GeochemistryJournal articles %X Biogeochemical reaction kinetics are generally established from batch reactors where concentrations are uniform. In natural systems, many biogeochemical processes are characterized by spatially and temporally variable concentration gradients that often occur at scales which are not resolved by field measurements or biogeochemical and reactive transport models. Yet, it is not clear how these sub-scale chemical gradients affect reaction kinetics compared to batch kinetics. Here we investigate this question by studying the paradigmatic case of localized pulses of solute reacting with a solid or a dissolved species in excess. We consider non-linear biogeochemical reactions, representative of mineral dissolution, adsorption and redox reactions, which we quantify using simplified power-law kinetics. The combined effect of diffusion and reaction leads to effective kinetics that differ quantitatively and qualitatively from the batch kinetics. Depending on the nonlinearity (reaction order) of the local kinetics, these effects lead to either enhancement or decrease of the overall reaction rate, and result in a rich variety of reaction dynamics. We derive analytical results for the effective kinetics, which are validated by comparison to direct numerical simulations for a broad range of Damköhler numbers and reaction order. Our findings provide new insights into the interpretation of imperfectly mixed lab experiments, the effective kinetics of field systems characterized by intermittent reactant release and the integration of sub-scale concentration gradients in reactive transport models. %G English %2 https://insu.hal.science/insu-03225145/document %2 https://insu.hal.science/insu-03225145/file/LeTraon-2021.pdf %L insu-03225145 %U https://insu.hal.science/insu-03225145 %~ INSU %~ UNIV-RENNES1 %~ UR2-HB %~ CNRS %~ GR %~ OSUR %~ OPENAIRE %~ GIP-BE %~ UR1-HAL %~ UR1-SDLM %~ GR-DIMENV %~ UNIV-RENNES2 %~ OSUR-OSU %~ TEST-UR-CSS %~ UNIV-RENNES %~ INRAE %~ UR1-ENV %~ GR-TERA %~ TEST3-HALCNRS %~ TEST4-HALCNRS %~ RESEAU-EAU %~ TEST5-HALCNRS