title: Understanding the sources and fate of nitrate in a highly developed aquifer system.
abstract: Understanding the processes affecting the transport and fate of nitrate in coastal aquifers has become of great interest in recent years due to concerns of nutrient loading to coastal waters. Novel dual isotopic methods have shown promise for identifying sources and fate of nitrate in shallow groundwater. However, in relatively deep dynamic aquifer systems, the isotopic signatures may be overprinted by mixing of different end-member waters and biogeochemical processes. In this study, δ(15)N and δ(18)O of groundwater nitrate are coupled with other forensic geochemistry methods such as Cl/Br, SO4/Cl, and Cl/NO3 mass ratios and land use analysis in order to constrain the isotope correlations and better understand contaminant sources and biogeochemical processes. Most δ(15)NNO3 values were within ranges expected for nitrate formed by ammonia nitrification in soil. Furthermore, the persistent presence of nitrate in concentrations above background levels (median 2.3 mg/L) and the relatively low δ(15)NNO3 and δ(18)ONO3 (median: 4.5±0.2‰ AIR and 5.2±0.5‰ VSMOW, respectively) indicate no direct evidence of denitrification. However, denitrification was inferred for a few samples whereby more enriched δ(15)NNO3 and δ(18)ONO3 values coupled with an increase in SO4/Cl and Cl/NO3 ratios were observed. Finally, mixing trends were identified for a few of the samples as indicated by δ(15)NO3 and δ(18)ONO3 mixing ratios and were consistent with the study area's land-use/land-cover distribution. The combination of methods utilized in this study revealed that in some cases mass ratios were better diagnostics in elucidating the impact of denitrification, mixing processes, and source identification within dynamic aquifer systems than the dual-isotope technique.
authors.affiliation: Department of Physical and Environmental Sciences, Texas A&M University-Corpus Christi, Corpus Christi, TX, United States. Electronic address: dorina.murgulet@tamucc.edu.
authors.forename: Dorina
authors.initials: D
authors.lastname: Murgulet
authors.forename: Geoffrey R
authors.initials: GR
authors.lastname: Tick
mesh_terms: D000407:Alabama; D004784:Environmental Monitoring / Q000379:methods*; D060587:Groundwater / Q000032:analysis*; D009566:Nitrates / Q000032:analysis*; D009587:Nitrogen Isotopes / Q000032:analysis; D010103:Oxygen Isotopes / Q000032:analysis; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D009566:Nitrates; D009587:Nitrogen Isotopes; D010103:Oxygen Isotopes; D014874:Water Pollutants, Chemical
keywords: Denitrification; End-member mixing; Forensic analysis; Groundwater; Isotopes; Nitrate sources