Prediction of the Fate and Transport Processes of Atrazine in a Reservoir

The fate and transport processes of a toxic chemical such as atrazine, an herbicide, in a reservoir are significantly influenced by hydrodynamic regimes of the reservoir. The two-dimensional (2D) laterally-integrated hydrodynamics and mass transport model, CE-QUAL-W2, was enhanced by incorporating a submodel for toxic contaminants and applied to Saylorville Reservoir, Iowa. The submodel describes the physical, chemical, and biological processes and predicts unsteady vertical and longitudinal distributions of a toxic chemical. The simulation results from the enhanced 2D reservoir model were validated by measured temperatures and atrazine concentrations in the reservoir. Although a strong thermal stratification was not identified from both observed and predicted water temperatures, the spatial variation of atrazine concentrations was largely affected by seasonal flow circulation patterns in the reservoir. In particular, the results showed the effect of flow circulation on spatial distribution of atrazine during summer months as the river flow formed an underflow within the reservoir and resulted in greater concentrations near the surface of the reservoir. Atrazine concentrations in the reservoir peaked around the end of May and early June. A good agreement between predicted and observed times and magnitudes of peak concentrations was obtained. The use of time-variable decay rates of atrazine led to more accurate prediction of atrazine concentrations, while the use of a constant half-life (60 days) over the entire period resulted in a 40% overestimation of peak concentrations. The results provide a better understanding of the fate and transport of atrazine in the reservoir and information useful in the development of reservoir operation strategies with respect to timing, amount, and depth of withdrawal.     

PESTICIDES IN GROUND WATER: DO ATRAZINE METABOLITES MATTER?1

ABSTRACT: Atrazine and atrazine-residue (atrazine + two metabolites - deethylatrazine and deisopropylatrazine) concentrations were examined to determine if consideration of these atrazine metabolites substantially adds to our understanding of the distribution of this pesticide in groundwater of the midcontinental United States. The mean of atrazine.residue concentrations was 53 percent greater than that of atrazine alone for those observations above the detection limit (> 0.05 μg/l). Furthermore, a censored regression analysis using atrazine-residue concentrations revealed significant factors not identified when only atrazine concentrations were used. Thus, knowledge of concentrations of these atrazine metabolites is required to obtain a true estimation of risk of using these aquifers as sources for drinking water, and such knowledge also provides information that ultimately may be important for future management policies designed to reduce atrazine concentrations in ground water.     

A Hierarchical Model for Estimating Long‐Term Trend of Atrazine Concentration in the Surface Water of the Contiguous U.S.

Atrazine is a herbicide frequently detected in both surface and groundwater in the United States (U.S.), but its spatiotemporal distribution and concentration trends have only been analyzed recently at regional or local scales. We employed a Bayesian hierarchical modeling approach to assess spatial and seasonal variation in atrazine concentration trends between 1990 and 2010 for the contiguous U.S. A Markov chain Monte Carlo simulation algorithm was used to address the problem of left‐censored data (i.e., atrazine concentration values below method reporting levels). We observed opposing temporal trends in the northern (flat or decreasing) and southern (increasing) regions of the U.S. This spatial variation in temporal trends can be partially explained by the relative amount of cropland in the region. Flat or decreasing trends in the north are more likely in regions with high cropland coverage while positive trends in the south are more likely in regions with low cropland coverage.     

Measured concentrations of herbicides and model predictions of atrazine fate in the Patuxent River estuary

The environmental fate of herbicides in estuaries is poorly understood. Estuarine physical transport processes and the episodic nature of herbicide release into surface waters complicate interpretation of water concentration measurements and allocation of sources. Water concentrations of herbicides and two triazine degradation products (CIAT [6-amino-2-chloro-4-isopropylamino-s-triazine] and CEAT [6-amino-2-chloro-4-ethylamino-s-triazine]) were measured in surface water from four sites on 40 d from 4 Apr. through 29 July 19% in the Patuxent River estuary, part of the Chesapeake Bay system. Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was most persistent and present in the highest concentrations (maximum = 1.29 microg/L). Metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide], CIAT, CEAT, and simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine) were frequently detected with maximum concentration values of 0.61, 1.1, 0.76, and 0.49 microg/L, respectively. A physical transport model was used to interpret atrazine concentrations in the context of estuarine water transport, giving estimates of in situ degradation rates and total transport. The estimated half-life of atrazine in the turbid, shallow upper estuary was t(1/2) = 20 d, but was much longer (t(1/2) = 100 d) in the deeper lower estuary. Although most (93%) atrazine entered the estuary upstream via the river, simulations suggested additional inputs directly to the lower estuary. The total atrazine load to the estuary from 5 April to 15 July was 71 kg with 48% loss by degradation and 31% exported to the Chesapeake Bay. Atrazine persistence in the estuary is directly related to river flows into the estuary. Low flows will increase atrazine residence time in the upper estuary and increase degradation losses.     

TRANSPORT AND FATE OF ATRAZINE IN MIDWESTERN RIPARIAN BUFFER STRIPS1

ABSTRACT: The fate of pesticides entering the Riparian Buffer Strips (RBS) has not been well documented. This study compared the transport and fate of atrazine in soil of three‐, five‐, and nine‐year‐old switchgrass (Panicum virgatum L.) RBS to that in adjacent soils cropped to a corn‐soybean rotation or a grass‐alfalfa pasture. Undisturbed soil columns were collected from the RBS and cropped areas within the Bear Creek watershed, near Roland, Iowa. Atrazine and bromide breakthrough curves obtained using intact soil columns under saturated conditions were described by a two‐region, mobile‐immobile transport model. Preferential flow of bromide and atrazine was evident in five‐and nine‐year‐old RBS soil, but there was little difference in transport characteristics between these two RBS soils and the adjacent cropped soils. There was a trend towards an increase in dispersion coefficients between the five‐and nine‐year‐old RBS sites, which suggests an increased degree of preferential flow with increasing RBS age. Despite similar texture and organic C contents, atrazine sorption was significantly greater in RBS soil than the adjacent cropped soil. Cropped soil degraded atrazine faster than the RBS soil. The rapid degradation of atrazine in the corn‐soybean soil adjacent to the five‐year‐old RBS (atrazine half‐life of 19 days) appeared to be due to a larger population of atrazine‐degrading microorganisms. Atrazine‐degrading microorganisms in the corn‐soybean soil were 50,940 cells g^‐1 soil compared with 2,970 cells g^‐4 soil in 5‐year‐old RBS soil which resulted in 60 percent mineralization of [¹⁴C‐UL‐atrazine] in the corn‐soybean soil.     

FACTORS AFFECTING HERBICIDE YIELDS IN THE CHESAPEAKE BAY WATERSHED,JUNE 19941

ABSTRACT: Median concentrations and instantaneous yields of alachlor, metolachlor, atrazine, cyanazine, and simazine were generally highest at sites in the Lower Susquehanna River Basin and in agricultural subbasins. Instantaneous herbicide yields are related to land use, hydrogeologic setting, streamflow yield, and agricultural row cropping practices. The significance of these relations may be affected by the interdependence of the factors. The percentage of basin area planted in corn is the most influential factor in the prediction of herbicide yield. Instantaneous yields of all five herbicides measured in June 1994 related poorly to averaged 1990–94 herbicide use. Annually averaged herbicide-use data are too general to use as a predictor for short-term herbicide yields. An evaluation of factors affecting herbicide yields could be refined with more-current land use and land cover information and a more accurate estimate of the percentage of basin area planted in corn. Factors related to herbicide yields can be used to predict herbicide yields in other basins within the Chesapeake Bay watershed and to develop an estimate of herbicide loads to Chesapeake Bay.     

Atrazine sorption-desorption hysteresis by sugarcane mulch residue

Sorption and desorption kinetics are essential components for modeling the movement and retention of applied agricultural chemicals in soils and the fraction of chemicals susceptible to runoff. In this study, we investigated the retention characteristics of sugarcane (Saccharum spp. hybrid) mulch residue for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) based on studies of sorption-desorption kinetics. A sorption kinetic batch method was used to quantify retention of the mulch residue for a wide range of atrazine concentrations and reaction times. Desorption was performed following 504 h of sorption using successive dilutions, followed by methanol extraction. Atrazine retention by the mulch residue was well described using a linear model where the partitioning coefficient (K(d)) increased with reaction time from 10.40 to 23.4 cm3 g(-1) after 2 and 504 h, respectively. Values for mulch residue K(d) were an order of magnitude higher than those found for Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquepts) where the sugarcane crop was grown. A kinetic multireaction model was successful in describing sorption behavior with reaction time. The model was equally successful in describing observed hysteretic atrazine behavior during desorption for all input concentrations. The model was concentration independent where one set of model parameters, which was derived from all batch results, was valid for the entire atrazine concentration range. Average atrazine recovery following six successive desorption steps were 63.67 +/- 4.38% of the amount adsorbed. Moreover, a hysteresis coefficient based on the difference in the area between sorption and desorption isotherms was capable of quantifying hysteresis of desorption isotherms.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

SUSPENDED SEDIMENT AND TURBIDITY FOLLOWING ROAD CONSTRUCTION AND LOGGING IN WESTERN MONTANA1

ABSTRACT: Forest management activities in a second order drainage basin increased suspended sediment yields 7.7 fold in the first year following road construction, and two-fold following logging in the second year. Sediment supply limitations resulted in poor correlations between sediment concentrations with discharge. Sediment transport was strongly hysteretic, with the highest sediment concentrations occurring on the rising limbs of snowmelt hydrographs and individual peaks. In addition to discharge, hydrograph characteristics such as limb, dQ/dt, and the product of dQ/dt and limb aided in explaining variability of observed sediment concentrations. Sediment-turbidity relationships were strongly discharge dependent, reflecting the changing composition of the suspended load with stream power and sediment supplies.     

Alachlor and bentazone losses from subsurface drainage of two soils

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is frequently detected at high concentrations in ground water. Bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] plus alachlor (2-chloro-2',6'-diethyl-N-methoxymethylacetanilide) is a potential herbicide combination used as a substitute for atrazine. Thus, the objective of this study was to assess the environmental risk of this blend. Drainage water contamination by bentazone and alachlor was assessed in silty clay (Vertic Eutrochrept) and silt loam (Aquic Hapludalf) soils under the same management and climatic conditions. Drainage volumes and concentrations of alachlor and bentazone were monitored after application. Herbicides first arrived at the drains after less than 1 cm of net drainage. This is consistent with preferential flow and suggests that about 3% of the pore volume was active in rapid transport. During the monitoring periods, bentazone losses were higher (0.11-2.40% of the applied amount) than alachlor losses (0.00-0.28%) in the drains of the silty clay and silt loam. The rank order of herbicide mass losses corresponded with the rank order of herbicide adsorption coefficients. More herbicide residues were detected in drainage from the silty clay, probably due to preferential flow and more intensive drainage in this soil than the silt loam. Surprisingly, herbicide losses were higher in the drains of both soils in the drier of the two study years. This could be explained by the time intervals between the treatments and first drainage events, which were longer in the wetter year. Results suggest that the drainage phases occurred by preferential flow in the spring-summer period, with correspondingly fast leaching of herbicides, and by matrix flow during the fall-winter period, with slower herbicide migration.     

ATRAZINE AND METOLACHLOR OCCURRENCE IN SHALLOW GROUND WATER OF THE UNITED STATES, 1993 TO 1995: RELATIONS TO EXPLANATORY FACTORS1

ABSTRACT: Since 1991, the U.S. Geological Survey has been conducting the National Water Quality Assessment (NAWQA) Program to determine the quality of the Nation's water resources. In an effort to obtain a better understanding of why pesticides are found in shallow ground water on a national scale, a set of factors likely to affect the fate and transport of two herbicides in the subsurface were examined. Atrazine and metolachlor were selected for this discussion because they were among the most frequently detected pesticides in ground water during the first phase of the NAWQA Program (1993 to 1995), and each was the most frequently detected compound in its chemical class (triazines and acetanilides, respectively). The factors that most strongly correlated with the frequencies of atrazine detection in shallow ground‐water networks were those that provided either: (1) an indication of the potential susceptibility of ground water to atrazine contamination, or (2) an indication of relative ground‐water age. The factors most closely related to the frequencies of metolachlor detection in ground water, however, were those that estimated or indicated the intensity of the agricultural use of metolachlor. This difference is probably the result of detailed use estimates for these compounds being available only for agricultural settings. While atrazine use is relatively extensive in nonagricultural settings, in addition to its widespread agricultural use, metolachlor is used almost exclusively for agricultural purposes. As a result, estimates of agricultural applications provide a less reliable indication of total chemical use for atrazine than for metolachlor. A multivariate analysis demonstrated that the factors of interest explained about 50 percent of the variance in atrazine and metolachlor detection frequencies among the NAWQA land‐use studies examined. The inclusion of other factors related to pesticide fate and transport in ground water, or improvements in the quality and accuracy of the data employed for the factors examined, may help explain more of the remaining variance in the frequencies of atrazine and metolachlor detection.     

Herbicide Transport in Goodwater Creek ExperimentalWatershed: I. Long‐Term Research on Atrazine1

Lerch, R.N., E.J. Sadler, K.A. Sudduth, C. Baffaut, and N.R. Kitchen, 2010. Herbicide Transport in Goodwater Creek Experimental Watershed: I. Long‐Term Research on Atrazine. Journal of the American Water Resources Association (JAWRA) 1‐15. DOI: 10.1111/j.1752‐1688.2010.00503.x Abstract: Atrazine continues to be the herbicide of greatest concern relative to contamination of surface waters in the United States (U.S.). The objectives of this study were to analyze trends in atrazine concentration and load in Goodwater Creek Experimental Watershed (GCEW) from 1992 to 2006, and to conduct a retrospective assessment of the potential aquatic ecosystem impacts caused by atrazine contamination. Located within the Central Claypan Region of northeastern Missouri, GCEW encompasses 72.5 km² of predominantly agricultural land uses, with an average of 21% of the watershed in corn and sorghum. Flow‐weighted runoff and weekly base‐flow grab samples were collected at the outlet to GCEW and analyzed for atrazine. Cumulative frequency diagrams and linear regression analyses generally showed no significant time trends for atrazine concentration or load. Relative annual loads varied from 0.56 to 14% of the applied atrazine, with a median of 5.9%. A cumulative vulnerability index, which takes into account the interactions between herbicide application, surface runoff events, and atrazine dissipation kinetics, explained 63% of the variation in annual atrazine loads. Based on criteria established by the U.S. Environmental Protection Agency, atrazine reached concentrations considered harmful to aquatic ecosystems in 10 of 15 years. Because of its vulnerability, atrazine registrants will be required to work with farmers in GCEW to implement practices that reduce atrazine transport.     

WALNUT CREEK WATERSHED MONITORING PROJECT,IOWA MONITORING WATER QUALITY IN RESPONSE TO PRAIRIE RESTORATION1

ABSTRACT: Land use and surface water data for nitrogen and pesticides (1995 to 1997) are reported for the Walnut Creek Watershed Monitoring Project, Jasper County Iowa. The Walnut Creek project was established in 1995 as a nonpoint source monitoring program in relation to watershed habitat restoration and agricultural management changes implemented at the Neal Smith National Wildlife Refuge by the U.S. Fish and Wildlife Service. The monitoring project utilizes a paired‐watershed approach (Walnut and Squaw creeks) as well as upstream/downstream comparisons on Walnut for analysis and tracking of trends. From 1992 to 1997, 13.4 percent of the watershed was converted from row crop to native prairie in the Walnut Creek watershed. Including another 6 percent of watershed farmed on a cash‐rent basis, land use changes have been implemented on 19.4 percent of the watershed by the USFWS. Nitrogen and pesticide applications were reduced an estimated 18 percent and 28 percent in the watershed from land use changes. Atrazine was detected most often in surface water with frequencies of detection ranging from 76–86 percent. No significant differences were noted in atrazine concentrations between Walnut and Squaw Creek. Nitrate‐N concentrations measured in both watersheds were similar; both basins showed a similar pattern of detection and an overall reduction in nitrate‐N concentrations from upstream to downstream monitoring sites. Water quality improvements are suggested by nitrate‐N and chloride ratios less than one in the Walnut Creek watershed and low nitrate‐N concentrations measured in the subbasin of Walnut Creek containing the greatest amount of land use changes. Atrazine and nitrate‐N concentrations from the lower portion of the Walnut Creek watershed (including the prairie restoration area) may be decreasing in relation to the upstream untreated component of the watershed. The frequencies of pesticide detections and mean nitrate‐N concentrations appear related to the percentage of row crop in the basins and subbasins. Although some results are encouraging, definitive water quality improvements have not been observed during the first three years of monitoring. Possible reasons include: (1) more time is needed to adequately detect changes; (2) the size of the watershed is too large to detect improvements; (3) land use changes are not located in the area of the watershed where they would have greatest effect; or (4) water quality improvements have occurred but have been missed by the project monitoring design. Longer‐term monitoring will allow better evaluation of the impact of restoration activities on water quality.     

Tillage system, application rate, and extreme event effects on herbicide losses in surface runoff

Conservation tillage can reduce soil loss; however, the residual herbicides normally used to control weeds are often detected in surface runoff at high levels, particularly if runoff-producing storms occur shortly after application. Therefore, we measured losses of alachlor, atrazine, linuron, and metribuzin from seven small (0.45-0.79-ha) watersheds for 9 yr (1993-2001) to investigate whether a reduced-input system for corn (Zea mays L.) and soybean [Glycine max (L.) Merr.] production with light disking, cultivation, and half-rate herbicide applications could reduce losses compared with chisel and no-till. As a percentage of application, annual losses were highest for all herbicides for no-till and similar for chisel and reduced-input. Atrazine was the most frequently detected herbicide and yearly flow-weighted concentrations exceeded the drinking water standard of 3 microg L(-1) in 20 out of 27 watershed years that it was applied. Averaged for 9 corn yr, yearly flow-weighted atrazine concentrations were 26.3, 9.6, and 8.3 microg L(-1) for no-till, chisel, and reduced-input, respectively. Similarly, flow-weighted concentrations of alachlor exceeded the drinking water standard of 2 microg L(-1) in 23 out of 54 application years and in all treatments. Thus, while banding and half-rate applications as part of a reduced-input management practice reduced herbicide loss, concentrations of some herbicides may still be a concern. For all watersheds, 60 to 99% of herbicide loss was due to the five largest transport events during the 9-yr period. Thus, regardless of tillage practice, a small number of runoff events, usually shortly after herbicide application, dominated herbicide transport.     

Behavior of 14C-atrazine in Argentinean topsoils under different cropping managements

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) behavior was studied in four surface soils during incubations in laboratory conditions. Soils were chosen in relation to their cropping management (tillage and no tillage) and crop rotation system (continuous soybean [Glycine mar (L.) Merr.] and maize (Zea mays L.)-soybean rotation). A natural soil under brushwood was sampled as a reference. Atrazine use in field conditions was associated with maize cropping, thus only one soil received atrazine every other year. Atrazine behavior was characterized through the balance of 14C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction, and the nonextractable bound residues. Soil organic matter capacity to form bound residues was characterized using soil size fractionation. Accelerated atrazine mineralization was only observed in the soil receiving atrazine in field conditions. Atrazine application every other year was enough to develop a microflora adapted to triazine ring mineralization. Bound residue formation was rapid and increased with soil organic matter content. The coarsest soil size fractions (2000-200 and 200-50 microm) containing the nonhumified organic matter presented the highest capacity to form bound residues. No effect of tillage system was observed, probably because of the uniform sampling depth at 20 cm, hiding the stratification pattern of soil organic matter in non-tilled soils.     

EFFECTS OF LAND COVER AND GEOLOGY ON STREAM CHEMISTRY IN WATERSHEDS OF CHESAPEAKE BAY1

ABSTRACT: We measured the base‐flow stream chemistry in all the major physiographic provinces of the Chesapeake Bay drainage basin. The spatial variation of stream chemistry was closely related to differences in geology and land cover among the sampled watersheds. Some stream chemistry variables were strongly affected by geological settings in the watersheds while others were more influenced by land cover. The effects of land cover differed among chemical constituents and regions. Concentrations of Ca²⁺, Mg²⁺, pH, total alkalinity, and conductivity were mainly functions of carbonate bedrock, especially in the Great Valley. Nitrate‐N and total dissolved N were closely related to cropland and increased as the percentage of cropland increased. The rate of increase varied from region to region with the highest in the Piedmont. Na⁺ and Cl^? were mainly affected by the percentage of developed area in a watershed, especially in the Coastal Plain and Piedmont. We observed no significant effects of region or land cover on species of phosphorus because samples were collected under base flow conditions and only dissolved forms were measured. Dissolved silicate (DSi) was not related to any other water chemistry variables. DSi increased as developed area decreased and cropland increased in the Coastal Plain, but these patterns were reversed in the Piedmont. There was no consistent pattern in the spatial variation of land cover effects on the reduced forms of N, dissolved organic P, dissolved organic matter, and K⁺.     

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.     

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

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 micromol 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).     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.     

NONPOINT SOURCE DISCHARGES OF NUTRIENTS FROM PIEDMONT WATERSHEDS OF CHESAPEAKE BAY1

ABSTRACT: We measured annual discharges of water, sediments, and nutrients from 10 watersheds with differing proportions of agricultural lands in the Piedmont physiographic province of the Chesapeake Bay drainage. Flow-weighted mean concentrations of total N, nitrate, and dissolved silicate in watershed discharges were correlated with the proportion of cropland in the watershed. In contrast, concentrations of P species did not correlate with cropland. Organic P and C correlated with the concentration of suspended particles, which differed among watersheds. Thus, the ratio of N:P:Si in discharges differed greatly among watersheds, potentially affecting N, P or Si limitation of phytoplankton growth in the receiving waters. Simple regression models of N discharge versus the percentage of cropland suggest that croplands discharge 29–42 kg N ha^-1 yr^-1 and other lands discharge 1.2–5.8 kg N ha^-1 yr^-1. We estimated net anthropogenic input of N to croplands and other lands using county level data on agriculture and N deposition from the atmosphere. For most of the study watersheds, N discharge amounted to less than half of the net anthropogenic N.