Combined Use of Groundwater Dating, Chemical, and Isotopic Analyses to Resolve the History and Fate of Nitrate Contamination in Two Agricultural Watersheds, Atlantic Coastal Plain, Maryland

The history and fate of groundwater nitrate (NO 3 − ) contamination were compared in 2 small adjacent agricultural watersheds in the Atlantic coastal plain by combined use of chronologic (CCl 2 F 2 , 3 H), chemical (dissolved solids, gases), and isotopic (δ 15 N,δ 13 C, δ 34 S) analyses of recharging groundwaters, discharging groundwaters, and surface waters. The results demonstrate the interactive effects of changing agricultural practices, groundwater residence times, and local geologic features on the transfer of NO 3 − through local flow systems. Recharge dates of groundwaters taken in 1990–1992 from the surficial aquifer in the Chesterville Branch and Morgan Creek watersheds near Locust Grove, Maryland, ranged from pre‐1940 to the late 1980’s. When corrected for localized denitrification by use of dissolved gas concentrations, the dated waters provide a 40‐year record of the recharge rate of NO 3 − , which increased in both watersheds by a factor of 3–6, most rapidly in the 1970's. The increase in groundwater NO 3 − over time was approximately proportional to the documented increase in regional N fertilizer use, and could be accounted for by oxidation and leaching of about 20–35% of the fertilizer N. Groundwaters discharging upward beneath streams in both watersheds had measured recharge dates from pre‐1940 to 1975, while chemical data for second‐order reaches of the streams indicated average groundwater residence times in the order of 20+ years. At the time of the study, NO 3 − discharge rates were less than NO 3 − recharge rates for at least two reasons: (1) discharge of relatively old waters with low initial NO 3 − concentrations, and (2) local denitrification. In the Chesterville Branch watershed, groundwaters remained oxic throughout much of the surficial aquifer and discharged relatively unaltered to the stream, which had a relatively high NO 3 − concentration (9–10 mg/L as N). In the Morgan Creek watershed, groundwaters were largely reduced and denitrified before discharging to the stream, which had a relatively low NO 3 − concentration (2–3 mg/L as N). Chemical and isotopic data indicate that quantitative denitrification occurred within buried calcareous glauconitic marine sediments that are present at relatively shallow depths beneath the Morgan Creek watershed. NO 3 − removal by forests, wetlands, and shallow organic‐rich soils in near‐stream environments was largely avoided by groundwaters that followed relatively deep flow paths before converging and discharging rapidly upward to the streams.