Applicability of the dual isotopes δ15N and δ18O to identify nitrate in groundwater beneath irrigated cropland.

Identification of the nitrate sources that adversely impact groundwater quality is a necessary first step in the control of this major worldwide pollutant. The impact of nitrate leachate from urea-ammonium nitrate (UAN) (50% urea-N, 25% ammonium-N, 25% nitrate-N) fertilizer, whose use has increased dramatically in the last three decades largely because it can be applied through sprinkler irrigation systems to corn in all growth stages, is investigated. The dual isotopes δ15NNO3 and δ18ONO3 were measured in groundwater samples from 39 irrigation wells in two intensively sprinkler-irrigated, corn-growing areas of Nebraska with nitrate-contaminated (N > 10 mg/L) groundwater and documented UAN use to ascertain whether nitrified ammonia and nitrate fertilizers can be distinguished in the High Plains aquifer. The areas, which are highly vulnerable to nitrate leaching and differ only in the composition and thickness of their unsaturated zones, are uniquely suited to provide scientific evidence of the feasibility of identifying nitrate fertilizer leachate in groundwater and thereby add significantly to the small body of existing and inconclusive data. The dual isotope method (DIM) results indicate that the nitrate contamination in 38 wells is mostly nitrified ammonium fertilizer. Most importantly, nitrate fertilizer from UAN was not identified isotopically in groundwater beneath almost all fields with documented heavy UAN use. This could be a potentially valuable finding for fertilizer management or it could convey limitations on the appropriateness of the DIM for nitrate fertilizer source identification in groundwater. Slightly enriched δ15NNO3 values in a few wells coincide with the practice of wintering cattle on corn stubble, which reportedly occurred more frequently in one focus area. The absence of natural soil-N leachates and denitrification in groundwater enabled an apparently reliable identification of manure leachates in both areas.

Analysis of oxytetracycline, tetracycline, and chlortetracycline in water using solid-phase extraction and liquid chromatography-tandem mass spectrometry.

A method using liquid chromatography-tandem mass spectrometry has been developed for determination of trace levels of tetracycline antibiotics in ground water and confined animal feeding operation waste water. Oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) were extracted from water samples using both polymeric and C18 extraction cartridges. The addition of a buffer containing potassium phosphate and citric acid improved tetracycline recoveries in lagoon water. Method detection limits determined in reagent water fortified with 1 microg l(-1) OTC, TC, and CTC were 0.21, 0.20, and 0.28 microg l(-1). Method detection limits in lagoon water samples fortified at 20 microg l(-1) for OTC, TC, and CTC were 3.6, 3.1, and 3.8 microg l(-1). Variability in recovery from laboratory fortified blanks ranged from 86 to 110% during routine analysis.

Controlling nitrate leaching in irrigated agriculture.

The impact of improved irrigation and nutrient practices on ground water quality was assessed at the Nebraska Management System Evaluation Area using ground water quality data collected from 16 depths at 31 strategically located multilevel samplers three times annually from 1991 to 1996. The site was sectioned into four 13.4-ha management fields: (i) a conventional furrow-irrigated corn (Zea mays L.) field; (ii) a surge-irrigated corn field, which received 60% less water and 31% less N fertilizer than the conventional field; (iii) a center pivot-irrigated corn field, which received 66% less water and 37% less N fertilizer than the conventional field; and (iv) a center pivot-irrigated alfalfa (Medicago sativa L.) field. Dating (3H/3He) indicated that the uppermost ground water was <1 to 2 yr old and that the aquifer water was stratified with the deepest water approximately 20 yr old. Recharge during the wet growing season in 1993 reduced the average NO3-N concentration in the top 3 m 20 mg L(-1), effectively diluting and replacing the NO3-contaminated water. Nitrate concentrations in the shallow zone of the aquifer increased with depth to water. Beneath the conventional and surge-irrigated fields, shallow ground water concentrations returned to the initial 30 mg NO3-N L(-1) level by fall 1995; however, beneath the center pivot-irrigated corn field, concentrations remained at approximately 13 mg NO3-N L(-1) until fall 1996. A combination of sprinkler irrigation and N fertigation significantly reduced N leaching with only minor reductions (6%) in crop yield.

Trace analysis of ethanol, MTBE, and related oxygenate compounds in water using solid-phase microextraction and gas chromatography/mass spectrometry.

Solid-phase microextraction (SPME) and gas chromatography/mass spectrometry have been combined for trace-level determination of very polar compounds in water, including the widely used gasoline oxygenates ethanol and methyl tert-butyl ether (MTBE). A relatively simple extraction method using a divinylbenzene/Carboxen/poly(dimethylsiloxane) SPME fiber was optimized for the routine analysis of ethanol and MTBE in groundwater and reagent water. A sodium chloride concentration of 25% (w/w) combined with an extraction time of 25 min provided the greatest sensitivity while maintaining analytical efficiency. Replicate analyses in fortified reagent and groundwater spiked with microgram per liter concentrations of ethanol and MTBE indicate quantitative and reproducible recovery of these and related oxygenate compounds. Method detection limits were 15 microg L(-1) for ethanol, 1.8 microg L(-1) for tert-butyl alcohol, 0.038 microg L(-1) for tert-amyl methyl ether, 0.025 microg L(-1) for ethyl-tert-butyl ether, and 0.008 microg L(-1) for MTBE.

Sensitive determination of RDX, nitroso-RDX metabolites, and other munitions in ground water by solid-phase extraction and isotope dilution liquid chromatography-atmospheric pressure electro-spray [correction of chemical] ionization mass spectrometry.

Recent improvements in the LC-MS interface have increased the sensitivity and selectivity of this instrument in the analysis of polar and thermally-labile aqueous constituents. Determination of RDX, nitroso-RDX metabolites, and other munitions was enhanced using LC-MS with solid-phase extraction, 15N3-RDX internal standard, and electrospray ionization (ESI) in negative ion mode. ESI produced a five-fold increase in detector response over atmospheric pressure chemical ionization (APCI) for the nitramine compounds, while the more energetic APCI produced more than twenty times the ESI response for nitroaromatics. Method detection limits in ESI for nitramines varied from 0.03 microgram l-1 for MNX to 0.05 microgram l-1 for RDX.

Pesticides in ground water beneath irrigated farmland in Nebraska, August 1978.

During the 1978 irrigation season, 14 ground water samples were collected in the Central Platte region of Nebraska, an area known to have high nitrate-nitrogen (NO3--N) levels, and analyzed for the presence of 13 pesticide residues. Atrazine levels ranged from 0.06 microgram/liter to 3.12 microgram/liter and were correlated to NO3--N concentrations with a coefficient of r = +0.55. Nitrate-nitrogen concentrations were measured as indicators of deep percolation from irrigated lands and ranged from 17.1 mg/liter to 34.3 mg/liter. Alachlor levels ranged from less than 0.01 microgram/liter to 0.71 microgram/liter. The amounts of 2,4-D were indeterminate because of experimental problems. Levels of the herbicides silvex and EPTC were below the limits of detectability. Levels of the organochlorine insecticides endrin, gamma-BHC (lindane), dieldrin, DDT and its primary metabolite DDE, heptachlor and its primary derivative heptachlor epoxide, and methoxychlor were all below the detectable limits of 0.005-0.010 microgram/liter.

Uranium in runoff from the Gulf of Mexico distributive province: anomalous concentrations.

Uranium concentrations in North American rivers are higher than those reported 20 years ago. The increase is attributed to applications to agricultural land of larger amounts of phosphate fertilizer containing appreciable concentrations of uranium. Experiments showing a constant phosphorous-uranium ratio for various types of fertilizers and for the easily solubilized fraction of 0-46-0 fertilizers support this view.