One of the principal questions in hydrology is how and when water leaves the critical zone storage as either stream flow or evapotranspiration. We investigated subsurface water storage and storage selection of the Southern Sierra Critical Zone Observatory (California, USA) within the age-ranked storage selection framework, constrained by a novel combination of cosmogenic radioactive and stable isotopes: tritium, sodium-22, sulfur-35, and oxygen-18. We found a significant positive correlation between tritium and stream flow rate and between sulfur-35 and stream flow rate, indicating that the age distribution of stream flow varies with stream flow rate. Storage selection functions that vary with stream flow rate are better able to reproduce tritium concentrations in stream flow than functions that are constant in time. For the Southern Sierra Critical Zone, there is a strong preference to discharge the oldest water in storage during dry conditions but only a weak preference for younger water during wet conditions. The preference of evapotranspiration for younger water, constrained by oxygen-18 in stream water, is essential to parameterize subsurface storage but needs to be confirmed by isotopic or other investigations of evapotranspiration. This is the first study to illustrate how a combination of cosmogenic radioactive isotopes reveals the hydrochronology and water storage dynamics of catchments, constrains the subsurface architecture of the critical zone, and provides insight into landscape evolution.Plain Language Summary Watersheds store water underground in soils and weathered bedrock.How long it takes for water to flow through the subsurface to feed streams is difficult to measure but important to understand how watersheds function. We used a novel combination of isotopic tracer methods to study the mixture of water ages in Providence Creek, a stream in the southern Sierra Nevada, California (USA). We studied naturally occurring radioactive isotopes of hydrogen (tritium), sodium-22, and sulfur-35. The abundance of these isotopes decreases because of radioactive decay as water spends more time underground. Each of these isotopes has a distinct half-life (12.3 years, 2.6 years, and 87 days, respectively). By using this combination of isotopes we were able to tease out the mixture of water ages in the stream. This level of detail helps us understand how the subsurface "selects" water from storage to generate stream flow. We find that Providence Creek has a strong preference to remove the oldest water in storage during dry conditions but shows only a slight preference to remove younger water during wet conditions. Based on the age mixtures of stream water, we estimate that the Providence Creek watershed stores 3 m of water in the subsurface.

The contamination of water resources with nitrate is a growing and significant problem. Here we report the use of ultramicroporous carbon as a capacitive deionization (CDI) electrode for selectively removing nitrate from an anion mixture. Through moderate activation, we achieve a micropore-size distribution consisting almost exclusively of narrow (<1 nm) pores that are well suited for adsorbing the planar, weakly hydrated nitrate molecule. Cyclic voltammetry measurements reveal an enhanced capacitance for nitrate when compared to chloride as well as significant ion sieving effects when sulfate is the only anion present. We measure high selectivities (S) of both nitrate over sulfate (S NO 3 /SO 4 = 17.8 ± 3.6 at 0.6 V) and nitrate over chloride (S NO 3 /Cl = 6.1 ± 0.4 at 0.6 V) when performing a constant voltage CDI separation on 3.33 mM/3.33 mM/1.67 mM Cl/NO 3 /SO 4 feedwater. These results are particularly encouraging considering that a divalent interferant was present in the feed. Using molecular dynamics simulations, we examine the solvation characteristics of these ions to better understand why nitrate is preferentially electrosorbed over sulfate and chloride.

s u m m a r yNitrate is a major source of contamination of groundwater in the United States and around the world. We tested the applicability of multiple groundwater age tracers ( 3 H, 3 He, 4 He, 14 C, 13 C, and 85 Kr) in projecting future trends of nitrate concentration in 9 long-screened, public drinking water wells in Turlock, California, where nitrate concentrations are increasing toward the regulatory limit. Very low 85 Kr concentrations and apparent 3 H/ 3 He ages point to a relatively old modern fraction (40-50 years), diluted with pre-modern groundwater, corroborated by the onset and slope of increasing nitrate concentrations. An inverse Gaussian-Dirac model was chosen to represent the age distribution of the sampled groundwater at each well. Model parameters were estimated using a Bayesian inference, resulting in the posterior probability distribution -including the associated uncertainty -of the parameters and projected nitrate concentrations. Three scenarios were considered, including combined historic nitrate and age tracer data, the sole use of nitrate and the sole use of age tracer data. Each scenario was evaluated based on the ability of the model to reproduce the data and the level of reliability of the nitrate projections. The tracer-only scenario closely reproduced tracer concentrations, but not observed trends in the nitrate concentration. Both cases that included nitrate data resulted in good agreement with historical nitrate trends. Use of combined tracers and nitrate data resulted in a narrower range of projections of future nitrate levels. However, use of combined tracer and nitrate resulted in a larger discrepancy between modeled and measured tracers for some of the tracers. Despite nitrate trend slopes between 0.56 and 1.73 mg/L/year in 7 of the 9 wells, the probability that concentrations will increase to levels above the MCL by 2040 are over 95% for only two of the wells, and below 15% in the other wells, due to a leveling off of reconstructed historical nitrate loadings to groundwater since about 1990.

Capacitive deionization (CDI) is a promising water desalination technology that is applicable to the treatment of low-salinity brackish waters and the selective removal of ionic contaminants. In this work, we show that by making a small change in the synthetic procedure of hierarchical carbon aerogel monolith (HCAM) electrodes, we can adjust the pore-size distribution and tailor the selectivity, effectively switching between selective adsorption of calcium or sodium ions. Ion selectivity was measured for a mixture of 5 mM NaCl and 2.5 mM CaCl 2 . For the low activated flowthrough CDI (fteCDI) cell, we observed extremely high sodium selectivity over calcium (S Na/Ca ≫ 10, no Ca 2+ adsorbed) at all of the applied potentials, while for the highly activated fteCDI cell, we observed a selectivity value of 6.6 ± 0.8 at 0.6 V for calcium over sodium that decreased to 2.2 ± 0.03 at 1.2 V. Molecular dynamics simulations indicated that the loss in Ca 2+ selectivity over Na + at high applied voltages could be due to a competition between ion-pore electrostatic interactions and volume exclusion ("crowding") effects. Interestingly, we also find with these simulations that the relative sizes of the ions change due to changes in hydration at a higher voltage.