Deciphering natural and anthropogenic nitrate and recharge sources in arid region groundwater.

Recently, the subsoils of ephemeral stream (arroyos) floodplains in the northern Chihuahuan Desert were discovered to contain large naturally occurring NO reservoirs (floodplain: ~38,000 kg NO-N/ha; background: ~60 kg NO-N/ha). These reservoirs may be mobilized through land use change or natural stream channel migration which makes differentiating between anthropogenic and natural groundwater NO sources challenging. In this study, the fate and sources of NO were investigated in an area with multiple NO sources such as accidental sewer line releases and sewage lagoons as well as natural reservoirs of subsoil NO. To differentiate sources, this study used a large suite of geochemical tools including δN[NO], δO[NO], δN[N], δC[DIC], C, tritium (H), dissolved gas concentrations, major ion chemistry, and contaminants of emerging concern (CEC) including artificial sweeteners. NO at sites with the highest concentrations (25 to 229 mg/L NO-N) were determined to be largely sourced from naturally occurring subsoil NO based on δN[NO] (<8 ‰) and mass ratios of Cl/Br (〈100) and NO/Cl (>1.5). Anthropogenic NO was deciphered using mass ratios of Cl/Br (>120) and NO/Cl (<1), δN[NO] (>8 ‰), and CEC detections. Nitrogen isotope analyses indicated that denitrification is fairly limited in the field area. CEC were detected at 67 % of sites including H dead sites (<1 pCi/L) with low percent modern carbon-14 (PMC; <30 %). Local supply wells are H dead with low PMC; as H does not re-equilibrate and C is very slow to re-equilibrate during recirculation through infrastructure, sites with low PMC, H < 1 pCi/L, and CEC detections were interpreted as locations with substantial anthropogenic groundwater recharge. Neotame was used to identify locations of very recent (<15 years before present) or ongoing wastewater influxes to the aquifer. This work shows the important influence of naturally occurring subsoil NO reservoirs on groundwater in arid regions and the major contribution of artificial recharge.