A new method is described for the analysis of atrazine and four of its degradation products (desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine) in water. This method uses solid-phase extraction on a graphitized carbon black cartridge, derivatization of the eluate with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), and analysis by gas chromatography/mass spectrometry (GC/MS). This method was used to analyze lysimeter samples collected from a field in central Indiana in 1994 and 1995. Atrazine and its degradation products were transported rapidly through the vadose zone. Maximum values of atrazine ranged from 2.61 to 8.44 μg/L and occurred from 15 to 57 days after application. Maximum concentrations of the degradation products occurred from 11 to 140 days after atrazine application. The degradation products were more persistent than atrazine in pore water. Desethylatrazine was the dominant degradation product detected in the first year, and didealkylatrazine was the dominant degradation product detected in the second year. Concentrations of atrazine and the degradation products sorbed onto soil were estimated; maximum concentrations ranged from 7.3 to 24 μg/kg for atrazine and were less than 5 μg/kg for all degradation products. Degradation of atrazine and transport of all five compounds were simulated by the vadose zone flow model LEACHM. LEACHM was run as a Darcian-flow model and as a non-Darcian-flow model.

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.

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4‐mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated‐zone computer model (LEACHM).

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