Larry J. Puckett

Nitrogen contamination of surficial aquifers - A growing legacy

The virtual ubiquity of fertilizer-fed agriculture, increasing over several decades, has become necessary to support the global human population. Ironically, widespread use of nitrogen (N) has contaminated another vital resource: surficial fresh groundwater. Further, as nitrous oxide (N2O) is a potent greenhouse gas, anthropogenic manipulation of N budgets has ramifications that can extend far beyond national borders. To get a handle on the size of the problem, Puckett et al. present an approach to track historical contamination and thus analyze trends now and in the past with implications for the future.

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.

Transport and fate of nitrate at the ground-water/surface-water interface

Although numerous studies of hyporheic exchange and denitrification have been conducted in pristine, high-gradient streams, few studies of this type have been conducted in nutrient-rich, low-gradient streams. This is a particularly important subject given the interest in nitrogen (N) inputs to the Gulf of Mexico and other eutrophic aquatic systems. A combination of hydrologic, mineralogical, chemical, dissolved gas, and isotopic data were used to determine the processes controlling transport and fate of NO(3)(-) in streambeds at five sites across the USA. Water samples were collected from streambeds at depths ranging from 0.3 to 3 m at three to five points across the stream and in two to five separate transects. Residence times of water ranging from 0.28 to 34.7 d m(-1) in the streambeds of N-rich watersheds played an important role in allowing denitrification to decrease NO(3)(-) concentrations. Where potential electron donors were limited and residence times were short, denitrification was limited. Consequently, in spite of reducing conditions at some sites, NO(3)(-) was transported into the stream. At two of the five study sites, NO(3)(-) in surface water infiltrated the streambeds and concentrations decreased, supporting current models that NO(3)(-) would be retained in N-rich streams. At the other three study sites, hydrogeologic controls limited or prevented infiltration of surface water into the streambed, and ground-water discharge contributed to NO(3)(-) loads. Our results also show that in these low hydrologic-gradient systems, storm and other high-flow events can be important factors for increasing surface-water movement into streambeds.

estimates of ion sources in deciduous and coniferous throughfall

Abstract Estimates of external and internal sources of ions in net througfall deposition were derived for a deciduous and coniferous canopy by use of multiple regression. The external source component appears to be dominated by dry deposition of Ca 2+ , SO 2 and NO 3 − during dormant and growing seasons for the two canopy types. Increases in the leaching rates of K + and Mg 2+ during the growing season reflect the presence of leaves in the deciduous canopy and increased physiological activity in both canopies. Internal leaching rates for SO 4 2− doubled during the growing season presumably caused by increased physiological activity and uptake of SO 2 through stomates. Net deposition of SO 4 2− in throughfall during the growing season appears highly dependent on stomatal uptake of SO 2 . Estimates of SO 2 deposition velocities were 0.06 cm s −1 and 0.13 cm s −1 for the deciduous and coniferous canopies, respectively, during the dormant seasons, and 0.30 cm s −1 and 0.43 cm s −1 for the deciduous and coniferous canopies, respectively, during the growing season. For the ions of major interest with respect to ecosystem effects, namely H + , NO 3 − and SO 4 2− , precipitation inputs generally outweighed estimates of dry deposition input. However, net throughfall deposition of NO 3 − and SO 4 2− accounted for 20–47 and 34–50 per cent, respectively, of total deposition of those ions. Error estimates of ion sources were at least 50–100 per cent and the method is subject to several assumptions and limitations.

Predicting Unsaturated Zone Nitrogen Mass Balances in Agricultural Settings of the United States

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond [Prunus dulcis (Mill.) D.A. Webb] orchard and cornfield (Zea mays L.) in the lower Merced River study basin, California; and corn-soybean [Glycine max (L.) Merr.] rotations in study basins at Maple Creek, Nebraska, and at Morgan Creek, Maryland. We used inverse modeling with a new version of the Root Zone Water Quality Model (RZWQM2) to estimate soil hydraulic and nitrogen transformation parameters throughout the unsaturated zone; previous versions were limited to 3-m depth and relied on manual calibration. The overall goal of the modeling was to derive unsaturated zone N mass balances for the four sites. RZWQM2 showed promise for deeper simulation profiles. Relative root mean square error (RRMSE) values for predicted and observed nitrate concentrations in lysimeters were 0.40 and 0.52 for California (6.5 m depth) and Nebraska (10 m), respectively, and index of agreement (d) values were 0.60 and 0.71 (d varies between 0 and 1, with higher values indicating better agreement). For the shallow simulation profile (1 m) in Maryland, RRMSE and d for nitrate were 0.22 and 0.86, respectively. Except for Nebraska, predictions of average nitrate concentration at the bottom of the simulation profile agreed reasonably well with measured concentrations in monitoring wells. The largest additions of N were predicted to come from inorganic fertilizer (153-195 kg N ha(-1) yr(-1) in California) and N fixation (99 and 131 kg N ha(-1) yr(-1) in Maryland and Nebraska, respectively). Predicted N losses occurred primarily through plant uptake (144-237 kg N ha(-1) yr(-1)) and deep seepage out of the profile (56-102 kg N ha(-1) yr(-1)). Large reservoirs of organic N (up to 17,500 kg N ha(-1) m(-1) at Nebraska) were predicted to reside in the unsaturated zone, which has implications for potential future transfer of nitrate to groundwater.

Sinks for trace metals, nutrients, and sediments in wetlands of the Chickahominy River near Richmond, Virginia

The Chickahominy River drains 790 km2 in southeastern Virginia, including approximately 155 km2 of dense commercial, industrial, and urban development in the upper basin near Richmond, Virginia. Previous studies have shown that total stream concentrations of trace metals and nutrients increased during storms, suggesting resuspension of contaminated sediments and (or) stormwater influxes of pollutants. The possible role of wetlands in maintaining water quality is of concern because the river furnishes about 46 percent of the water supply for the City of Newport News. Particle sizes of sediments and their corresponding total concentrations of carbon, nitrogen, copper, nickel, lead, and zinc were determined to assess their distribution within wetlands adjacent to the river. Except for Zn, concentrations of all measured constituents in the <63-μm-particle fraction were lower downstream of Richmond, suggesting that most contaminants are retained in the upper basin. Zinc concentrations increased along downstream reaches, peaking at 510 mg kg−1 approximately 8 km below the confluence of Upham Brook with the Chickahominy River. Lead concentrations up to 192 mg kg−1 were measured in sediments along Upham Brook near Richmond. Concentrations of Zn and Cu were highest in streambed sediments and lowest in elevated forested wetlands. The results suggest that the developing regions of the basin have a significant effect on sediment chemistry within the basin and that wetlands play a role in retaining these sediment-borne contaminants in upper reaches of the basin. Studies are underway to asses the stablity, of these sediments and the capacity of these contaminated wetlands to continue to assimilate them.