Stratification of reactivity determines nitrate removal in groundwater

Biogeochemical reactions occur unevenly in space and time, but this heterogeneity is often simplified as a linear average due to sparse data, especially in subsurface environments where access is limited. For example, little is known about the spatial variability of groundwater denitrification, an important process in removing nitrate originating from agriculture and land use conversion. Information about the rate, arrangement, and extent of denitrificationis needed to determine sustainable limits of human activity and to predict recovery time frames. Here, we developed and validated a method for inferring the spatial organizationof sequential biogeochemical reactions in an aquiferin France. We applied it to five other aquifersin different geological settings located in the United States and compared results among 44 locations across the six aquifersto assess the generality of reactivity trends. Of the sampling locations, 79% showed pronounced increases of reactivity with depth. This suggests that previous estimates of denitrificationhave underestimated the capacity of deep aquifersto remove nitrate, while overestimating nitrate removal in shallow flow paths. Oxygen and nitrate reduction likely increases with depth because there is relatively little organic carbon in agricultural soils and because excess nitrate input has depleted solid phase electron donors near the surface. Our findings explain the long-standing conundrum of why apparent reaction rates of oxygen in aquifersare typically smaller than those of nitrate, which is energetically less favorable. This stratified reactivity framework is promising for mapping vertical reactivity trends in aquifers, generating new understanding of subsurface ecosystems and their capacity to remove contaminants.