More Like this

1. Nitrous oxide processing in carbonate karst aquifers

   https://doi.org/https://doi.org/10.1016/j.jhydrol.2020.125936  

   Flint, Madison K; Martin, Jonathan B.; Summerall, Tatiana I.; Barry-Sosa, Adrian; Christner, Brent C. (March 2021, Journal of hydrology)

   null (Ed.)

   The increased environmental abundance of anthropogenic reactive nitrogen species (Nr = ammonium [NH4+], nitrite [NO2−] and nitrate [NO3−]) may increase atmospheric nitrous oxide (N2O) concentrations, and thus global warming and stratospheric ozone depletion. Nitrogen cycling and N2O production, reduction, and emissions could be amplified in carbonate karst aquifers because of their extensive global range, susceptibility to nitrogen contamination, and groundwater-surface water mixing that varies redox conditions of the aquifer. The magnitude of N2O cycling in karst aquifers is poorly known, however, and thus we sampled thirteen springs discharging from the karstic Upper Floridan Aquifer (UFA) to evaluate N2O cycling. The springs can be separated into three groups based on variations in subsurface residence times, differences in surface–groundwater interactions, and variable dissolved organic carbon (DOC) and dissolved oxygen (DO) concentrations. These springs are oxic to sub-oxic and have NO3− concentrations that range from < 0.1 to 4.2 mg N-NO3−/L and DOC concentrations that range from < 0.1 to 50 mg C/L. Maximum spring water N2O concentrations are 3.85 μg N-N2O/L or ~ 12 times greater than water equilibrated with atmospheric N2O. The highest N2O concentrations correspond with the lowest NO3− concentrations. Where recharge water has residence times of a few days, partial denitrification to N2O occurs, while complete denitrification to N2 is more prominent in springs with longer subsurface residence times. Springs with short residence times have groundwater emission factors greater than the global average of 0.0060, reflecting N2O production, whereas springs with residence times of months to years have groundwater emission factors less than the global average. These findings imply that N2O cycling in karst aquifers depends on DOC and DO concentrations in recharged surface water and subsequent time available for N processing in the subsurface. 

   more » « less
2. Groundwater‐surface water interaction, dissolved organic carbon oxidation and dissolution in carbonate aquifers

   https://doi.org/10.1002/esp.5830  

   Oberhelman, Andrew; Martin, Jonathan_B; Flint, Madison_K (April 2024, Earth Surface Processes and Landforms)

   Abstract The high primary porosity and permeability of eogenetic karst aquifers permit water recharged through secondary dissolution features to be temporarily stored in aquifer matrix porosity. The recharged water contains elevated dissolved organic carbon (DOC) concentrations that, when oxidized, enhance limestone dissolution and impact carbon cycling. We evaluate the relationship between DOC oxidation and limestone dissolution using observations at a stream sink‐rise system and reversing spring in the Floridan aquifer, north‐central Florida, USA, where subsurface residence times of recharged water are days and months, respectively. We estimate water chemical compositions during surface water‐groundwater interactions at these two systems with mixing models of surface water and groundwater compositions and compare them with measured DOC, dissolved inorganic carbon (DIC), Ca²⁺and dissolved organic nitrogen (DON) concentrations. Differences between measured and modelled concentrations represent net changes that can be attributed to calcite dissolution and redox reactions, including DOC oxidation. DOC losses and Ca²⁺gains exhibit significant (p < 0.01) inverse linear correlations at both the reversing spring (slope = −0.9, r² = 0.99) and the sink‐rise system (slope = −0.4, r² = 0.72). DOC oxidation in both systems was associated with decreases in the molar C:N ratio (DOC:DON). Significant (p < 0.01) positive linear correlations between increases in Ca²⁺and DIC concentrations after correcting for DIC derived from calcite dissolution occurred at both the reversing spring (slope = 1.3, r² = 0.99) and the sink‐rise system (slope = 1.61, r² = 0.75). Greater deviations from the expected slope of −1 or +1 at the sink‐rise system than at the reversing spring indicate DOC oxidation contributes less dissolution at the sink‐rise system than at the reversing spring, likely from shorter storage in the subsurface. A portion of the deviation from expected slope values can be explained by the dissolution of Mg‐rich carbonate or dolomite rather than pure calcite dissolution. Despite this, slope values reflect kinetic effects controlling incomplete consumption of carbonic acid during dissolution reactions. 

   more » « less
3. Hydrotectonics of Grand Canyon Groundwater

   https://doi.org/10.1146/annurev-earth-080723-083513  

   Crossey, LJ; Karlstrom, KE; Curry, B; McGibbon, C; Reed, C; Wilgus, J; Whyte, CJ; Darrah, T (May 2024, Annual Review of Earth and Planetary Sciences)

   The Grand Canyon provides a deeply dissected view of the aquifers of the Colorado Plateau and its public and tribal lands. Stacked sandstone and karst aquifers are vertically connected by a network of faults and breccia pipes creating a complex groundwater network. Hydrochemical variations define structurally controlled groundwater sub-basins, each with main discharging springs. North Rim (N-Rim), South Rim (S-Rim), and far-west springs have different stable isotope fingerprints, reflecting different mean recharge elevations. Variation within each region reflects proportions of fast/slow aquifer pathways. Often considered perched, the upper Coconino (C) aquifer has a similar compositional range as the regional Redwall-Muav (R-M) karst aquifer, indicating connectivity. Natural and anthropogenic tracers show that recharge can travel 2 km vertically and tens of kilometers laterally in days to months via fracture conduits to mix with older karst baseflow. Six decades of piping N-Rim water to S-Rim Village and infiltration of effluent along the Bright Angel fault have sustained S-Rim groundwaters and likely induced S-Rim microseismicity. Sustainable groundwater management and uranium mining threats require better monitoring and application of hydrotectonic concepts. ▪ Hydrotectonic concepts include distinct structural sub-basins, fault fast conduits, confined aquifers, karst aquifers, upwelling geothermal fluids, and induced seismicity. ▪ N-Rim, S-Rim, and far-west springs have different stable isotope fingerprints reflecting different mean recharge elevations and residence times. ▪ The upper C and lower R-M aquifers have overlapping stable isotope fingerprints in a given region, indicating vertical connectively between aquifers. ▪ S-Rim springs and groundwater wells are being sustained by ∼60 years of piping of N-Rim water to S-Rim, also inducing seismicity. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 52 is May 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates. 

   more » « less
4. Nitrate Legacy in a Tropical and Complex Fractured Volcanic Aquifer System

   https://doi.org/10.1029/2023JG007554  

   Sánchez‐Gutiérrez, R.; Sánchez‐Murillo, R.; Esquivel‐Hernández, G.; Birkel, C.; Boll, J.; Rojas‐Jiménez, L. D.; Castro‐Chacón, L. (August 2023, Journal of Geophysical Research: Biogeosciences)

   Abstract Nitrate legacy is affecting groundwater sources across the tropics. This study describes isotopic and ionic spatial trends across a tropical, fractured, volcanic multi‐aquifer system in central Costa Rica in relation to land use change over four decades. Springs and wells (from 800 to 2,400 m asl) were sampled for NO₃⁻and Cl⁻concentrations, δ¹⁸O_water, δ¹⁵N_NO3, and δ¹⁸O_NO3. A Bayesian isotope mixing model was used to estimate potential source contributions to the nitrate legacy in groundwater. Land use change was evaluated using satellite imagery from 1979 to 2019. The lower nitrate concentrations (<1 mg/L NO₃⁻N) were reported in headwater springs near protected forested areas, while greater concentrations (up to ∼63 mg/L) were reported in wells (mid‐ and low‐elevation sites in the unconfined unit) and low‐elevation springs. High‐elevation springs were characterized by low Cl⁻and moderate NO₃⁻/Cl⁻ratios, indicating the potential influence of soil nitrogen (SN) inputs. Wells and low‐elevation springs exhibited greater NO₃⁻/Cl⁻ratios and Cl⁻concentrations above 100 μmol/L. Bayesian calculations suggest a mixture of sewage (domestic septic tanks), SN (forested recharge areas), and chemical fertilizers (coffee plantations), as a direct result of abrupt land use change in the last 40 years. Our results confirm the incipient trend in increasing groundwater nitrogen and highlight the urgent need for a multi‐municipal plan to transition from domestic septic tanks to regional sewage treatment and sustainable agricultural practices to prevent future groundwater quality degradation effectively. 

   more » « less
5. Where the past meets the present: connecting nitrogen from watersheds to streams through groundwater flowpaths

   https://doi.org/10.1088/1748-9326/ad0c86  

   Moore, Eric M; Barclay, Janet R; Haynes, Adam B; Jackson, Kevin E; Bisson, Alaina M; Briggs, Martin A; Helton, Ashley M (November 2023, Environmental Research Letters)

   Abstract Groundwater discharge to streams is a nonpoint source of nitrogen (N) that confounds N mitigation efforts and represents a significant portion of the annual N loading to watersheds. However, we lack an understanding of where and how much groundwater N enters streams and watersheds. Nitrogen concentrations at the end of groundwater flowpaths are the culmination of biogeochemical and physical processes from the contributing land area where groundwater recharges, within the aquifer system, and in the near-stream riparian area where groundwater discharges to streams. Our research objectives were to quantify the spatial distribution of N concentrations at groundwater discharges throughout a mixed land-use watershed and to evaluate how relationships among contributing and riparian land cover, modeled aquifer characteristics, and groundwater discharge biogeochemistry explain the spatial variation in groundwater discharge N concentrations. We accomplished this by integrating high-resolution thermal infrared surveys to locate groundwater discharge, biogeochemical sampling of groundwater, and a particle tracking model that links groundwater discharge locations to their contributing area land cover. Groundwater N loading from groundwater discharges within the watershed varied substantially between and within streambank groundwater discharge features. Groundwater nitrate concentrations were spatially heterogeneous ranging from below 0.03–11.45 mg-N/L, varying up to 20-fold within meters. When combined with the particle tracking model results and land cover metrics, we found that groundwater discharge nitrate concentrations were best predicted by a linear mixed-effect model that explained over 60% of the variation in nitrate concentrations, including aquifer chemistry (dissolved oxygen, Cl⁻, SO₄²⁻), riparian area forested land cover, and modeled physical aquifer characteristics (discharge, Euclidean distance). Our work highlights the significant spatial variability in groundwater discharge nitrate concentrations within mixed land-use watersheds and the need to understand groundwater N processing across the many spatiotemporal scales within groundwater cycling. 

   more » « less