Judith M. Denver

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 (NO3−) contamination were compared in 2 small adjacent agricultural watersheds in the Atlantic coastal plain by combined use of chronologic (CCl2F2, 3H), chemical (dissolved solids, gases), and isotopic (δ15N,δ13C, δ34S) 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 NO3− 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 NO3−, which increased in both watersheds by a factor of 3–6, most rapidly in the 1970s. The increase in groundwater NO3− 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, NO3− discharge rates were less than NO3− recharge rates for at least two reasons: (1) discharge of relatively old waters with low initial NO3− 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 NO3− 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 NO3− 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. NO3− 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.

Limited Occurrence of Denitrification in Four Shallow Aquifers in Agricultural Areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N(2) from denitrification increases with age. Stable isotopes and excess N(2) imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 micromol N L(-1)d(-1), comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

EFFECT OF FORESTED WETLANDS ON NITRATE CONCENTRATIONS IN GROUND WATER AND SURFACE WATER ON THE DELMARVA PENINSULA

The Delmarva Peninsula is an extensively farmed region in which nitrate from commercial fertilizers and poultry has entered the ground water and streams. The peninsula contains forested wetlands in a variety of settings, and their size and location are a result of the surrounding hydrologic and soil conditions. Three regions, here referred to as hydrogeomorphic regions, were selected for study. Each region has characteristic geologic and geomorphic features, soils, drainage patterns, and distribution of farmland, forests, and forested wetlands. In all three regions, forested wetlands generally occupy poorly drained areas whereas farmlands generally occupy well-drained areas. The three hydrogeomorphic regions studied are the well-drained uplands, the poorly drained uplands, and the surficial-confined region. The well-drained uplands have the largest amount of farmland and the smallest amount of forested wetlands of the three regions; here the forested wetlands are generally restricted to narrow riparian zones. The poorly drained uplands contain forested wetlands in headwater depressions and riparian zones that are interspersed among well-drained farmlands. The surficial-confined region has the smallest amount of farmland and largest amount of forested wetlands of the three regions studied. Wetlands in this region occupy the same topographic settings as in the poorly drained uplands. Much of the farmland in the surficial-confined region was previously wetland. Nitrate concentrations in ground water and surface water on the peninsula range widely, and their distribution reflects (1) the interspersion of forests among farmland, (2) hydrogeologic conditions, (3) types of soils, and (4) the ground-water hydrology of forested wetlands. The well-drained uplands had higher median nitrate concentrations in ground water than the poorly drained uplands or the surficial-confined region. The highest nitrate concentrations were in oxic parts of the aquifer, which are beneath well-drained soils that are farmed, and the lowest were in anoxic parts of the aquifer, which are beneath poorly drained soils overlain by forested wetlands. The effect of forested wetlands on water quality depends on the hydrogeologic conditions, extent of farming, and type of soils. The three regions contain differing combinations of these factors and thus are useful for isolating the effects of forested wetlands on water quality.

Temporal trends in nitrate and selected pesticides in mid-atlantic ground water

Evaluating long-term temporal trends in regional ground-water quality is complicated by variable hydrogeologic conditions and typically slow flow, and such trends have rarely been directly measured. Ground-water samples were collected over near-decadal and annual intervals from unconfined aquifers in agricultural areas of the Mid-Atlantic region, including fractured carbonate rocks in the Great Valley, Potomac River Basin, and unconsolidated sediments on the Delmarva Peninsula. Concentrations of nitrate and selected pesticides and degradates were compared among sampling events and to apparent recharge dates. Observed temporal trends are related to changes in land use and chemical applications, and to hydrogeology and climate. Insignificant differences in nitrate concentrations in the Great Valley between 1993 and 2002 are consistent with relatively steady fertilizer application during respective recharge periods and are likely related to drought conditions in the later sampling period. Detecting trends in Great Valley ground water is complicated by long open boreholes characteristic of wells sampled in this setting which facilitate significant ground-water mixing. Decreasing atrazine and prometon concentrations, however, reflect reported changes in usage. On the Delmarva Peninsula between 1988 and 2001, median nitrate concentrations increased 2 mg per liter in aerobic ground water, reflecting increasing fertilizer applications. Correlations between selected pesticide compounds and apparent recharge date are similarly related to changing land use and chemical application. Observed trends in the two settings demonstrate the importance of considering hydrogeology and recharge date along with changing land and chemical uses when interpreting trends in regional ground-water quality.

Suburban groundwater quality as influenced by turfgrass and septic sources, delmarva peninsula, USA.

Suburban land use is expanding in many parts of the United States and there is a need to better understand the potential water-quality impacts of this change. This study characterized groundwater quality in a sandy, water-table aquifer influenced by suburban development and compared the results to known patterns in water chemistry associated with natural, background conditions and agricultural effects. Samples for nutrients, major ions, and isotopes of N and O in NO were collected in 2011 beneath turfgrass from 29 shallow wells (median depth 3.7 m) and from 18 deeper wells (median depth 16.9 m) in a long-term suburban development. Nitrate (as N) concentrations in groundwater beneath turfgrass were highly variable (0.02-22.3 mg L) with a median of 2.7 mg L, which is higher than natural water chemistry (>0.4 mg L; Na-Cl-HCO water type), but significantly lower than concentrations beneath a nearby agricultural area (median 16.9 mg L; < .0001). Dissolved Fe concentrations in shallow suburban groundwater, attributed to chelated Fe in turfgrass fertilizers, were significantly higher ( < .005) than concentrations from the agricultural site, although a Ca-Mg-Cl-NO water type was dominant in both areas. A Na-Cl-NO water type indicated a septic-system source for nitrate in deep suburban groundwater (0.06-6.0 mg L; median 1.5 mg L). Isotopic data indicated denitrification; however, geochemical techniques were more helpful in identifying nitrate sources. Results indicate that suburban expansion into agricultural areas may significantly decrease overall nitrate concentrations in groundwater, but excessive turfgrass fertilization could result in localized contamination.

Monitoring the water-quality response of agricultural conservation practices in the Bucks Branch watershed, Sussex County, Delaware, 2014–16

The purpose of this study was to evaluate the effects of irrigation and cover crops as conservation practices on water quality in groundwater and streams. Bucks Branch, a stream in the Nanticoke River watershed in southwestern Delaware, was identified as having one of the highest concentrations of nitrate in all surface-water sites sampled by the Delaware Department of Natural Resources and Environmental Control (DNREC). The study site is on two adjacent fields bordering Bucks Branch, one that has used irrigation since 2000 and one with dryland farming; both under conservation tillage and long-term rotation of corn, soybean, and small grain crops. A streamgage was installed near the study site fields to measure streamflow and water quality. The study area is typical of farming practices and environmental conditions throughout much of the intensively farmed agricultural land of the Coastal Plain of Delaware and surrounding parts of Maryland. Monitoring was conducted from January 2014 through June 2016. Corn was grown on both fields during the two growing seasons of the study period, and cover crops were planted before or shortly after harvest on both fields. During the second year of data collection, the effects of radish and rye grass cover crops on nutrient transport were studied. The combined results from data collected for this study show that water and nitrate moved below the root zone year round when soil moisture was high, especially after significant rainfall and frequently after irrigation. Soil water sampled 2 to 3 weeks after nutrients were applied had nitrate concentrations greater than 50 milligrams per liter as nitrogen (mg/L as N) and may be a significant source of nitrate to groundwater. Whereas recharge containing elevated nitrate concentrations also occurred under the dryland field, it was less frequent and of lower concentration than recharge under the irrigated field. Nitrate was present in all groundwater samples from these sites. Groundwater estimated to have recharged within 10 years or less had higher median concentrations of nitrate than in older water samples. The oldest groundwater encountered was over 30 years old, and had traveled along the longest, deep flowpaths from upland fields to the stream. The median nitrate concentration was 18 mg/L as N in younger water (less than 10 years old) beneath the irrigated field, compared to about 10 mg/L as N in younger water beneath the dryland field. Samples from the shallow upland wells in both study fields showed little, if any, evidence of denitrification. Several samples from deeper wells and from wells near forested riparian zone wetlands that border both fields did show partial denitrification. A mixing model estimated that between 12 and 22 percent of the nitrate discharging to the stream was lost through uptake and denitrification upstream of the streamgage on Bucks Branch. Continuous data collected at this site and evidence of denitrification in the surface-water samples showed a greater potential for loss of nitrate during the warmer months than the colder months. This pattern was similar to that seen below the streamgage at the most downstream site in the watershed. A mixed cover crop of radishes and rye was planted prior to removal (radishes) and just after harvest (rye) of the corn crop on the irrigated field. Rye grass was planted shortly after crop harvest on the dryland field. Cover crop biomass samples collected while radishes were growing and after they were killed by freezing temperatures indicates that the early planted radish crop effectively scavenged available nitrogen from the soil. Whereas radish biomass initially held more nitrogen than rye, at 55 to 8 pounds per acre, respectively, leaching of inorganic nitrate following radish die-off was minimal. Soilwater nitrate concentrations during the cover-crop growing period were lower than during the growing season prior to planting of the cover crop. There also was an increase in soil fertility and dissolved organic nitrate in samples of soil water that was likely related to increased soil microbial metabolism. Results indicate that cover crops stored plant nutrients over the winter and did not increase shallow groundwater concentrations of nitrate. Although conservation practices such as cover crops and nutrient management have been applied to these fields, there was still significant leaching of nitrate to groundwater, especially under the irrigated field. This will likely continue to be a challenge in this area and other parts of the Coastal Plain 2 Monitoring Water Quality in the Bucks Branch Watershed, Sussex County, Delaware where soil moisture capacity is relatively low and managing irrigation around rainfall is difficult. Cover crops, when planted in standing corn, are one practice that can effectively pull nitrate from below the root zone to the top layer of soil, thus limiting the amount of potential nitrate leaching to groundwater. Irrigation management that would lower average soil moisture conditions during the growing season also could potentially limit nitrogen transport.