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).     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Simulated fate and transport of metolachlor in the unsaturated zone, Maryland, USA

An unsaturated-zone transport model was used to examine the transport and fate of metolachlor applied to an agricultural site in Maryland, USA. The study site was instrumented to collect data on soil-water content, soil-water potential, ground water levels, major ions, pesticides, and nutrients from the unsaturated zone during 2002-2004. The data set was enhanced with site-specific information describing weather, soils, and agricultural practices. The Root Zone Water Quality Model was used to simulate physical, chemical, and biological processes occurring in the unsaturated zone. Model calibration to bromide tracer concentrations indicated flow occurred through the soil matrix. Simulated recharge rates were within the measured range of values. The pesticide transport model was calibrated to the intensive data collection period (2002-2004), and the calibrated model was then used to simulate the period 1984 through 2004 to examine the impact of sustained agricultural management practices on the concentrations of metolachlor and its degradates at the study site. Simulation results indicated that metolachlor degrades rapidly in the root zone but that the degradates are transported to depth in measurable quantities. Simulations indicated that degradate transport is strongly related to the duration of sustained use of metolachlor and the extent of biodegradation.     

Transport of Escherichia coli in sand columns with constant and changing water contents

Understanding how changes in volumetric water content (theta) affect bacterial adsorption could help reduce transport of pathogenic and indicator bacteria that may be present in infiltrating wastewater. Three flow regimes that simulated infiltration from a household septic system were evaluated: saturated, unsaturated with a constant volumetric water content theta (constant unsaturated flow), and unsaturated with cyclic changes in theta (variable unsaturated flow). Escherichia coli was suspended in artificial sewage (AS) and applied as step inputs to sand columns, with regular interruptions in input for variable unsaturated flow. A transport model was fit to the saturated and constant unsaturated flow breakthrough curves to determine retardation (R), the first-order filtration coefficient (mu), and the maximum outflow relative concentration (Cmax). The total cells transported as a fraction of input (tau) in all three flow regimes was calculated. Constant unsaturated flow resulted in a significantly lower Cmax (0.633) in comparison with saturated flow (0.803, P < or = 0.05), although unsaturated mu (0.0693 h(-1)) was not significantly different from saturated mu (0.0259 h(-1)). Constant unsaturated flow also resulted in a significantly smaller tau (0.617) than saturated (0.806) or variable unsaturated flow (0.734). In variable unsaturated flow, cell concentrations were out of phase with theta--as the column drained, cell concentrations in the outflow increased; and when a pulse of suspension was applied, cell concentrations decreased. Constant unsaturated flow is probably the best for removal of pathogenic bacteria because this regime resulted in lower maximum concentrations of E. coli and greater cell removal, in comparison with saturated and variable unsaturated flow.     

Hydrogeological study of an anti-tank range

The Arnhem Anti-Tank Range (Canadian Forces Base [CFB] Valcartier, Canada, in operation since the 1970s) has been characterized, including the drilling, installation, and characterization of 25 wells and a ground-penetrating radar survey. The observed particular features of this site include highly variable flow velocities (from < 3 to 1200 m/yr) and transient flow regime in the regional aquifer below the contaminant source zone of the impact area, sharp flow direction shifts, discontinuous stratigraphy and a local perched aquifer. A transient ground water flow model permitted us to understand how the complex hydrogeological setting shapes contaminant transport in the regional aquifer. The model explains the highly variable energetic material (EM) concentrations measured in the plume with peaks associated to spring and to a lesser extent to fall recharge events. As a conclusion from this work, the authors suggest that the characterization of contaminant sources on slopes should extend over all seasons to be sure to detect potential transient flow conditions and variable contaminant concentrations.     

In situ bioremediation of an underground diesel fuel spill: A case history

In the winter months of 1983, approximately 1000 gallons of diesel fuel had flowed along an asphalt parking lot of a commercial establishment towards a surface drain near an open creek. Investigations led to the discovery of an underground storage tank leaking diesel fuel. Exploratory borings showed that contamination was near the surface horizon and the capillary zone of the water table. Hydrocarbon quantities ranged up to 1500 mg/kg of soil. The plume continued to move in an eastward direction toward the surface water of the creek. A laboratory study indicated relatively high numbers of hydrocarbon-oxidizing organisms relative to glucose-utilizing microorganisms in the unsaturated vadose zone. Bioreclamation was initiated in April 1984 by injecting nutrients (nitrogen and phosphorus) and hydrogen peroxide and terminated in October 1984 upon no detection (<1 mg/kg) of hydrocarbons. A verification boring within the vicinity of the contaminated plume confirmed that residual contamination had attained background levels. The monitoring program was terminated in January 1987.     

PARAMETER ESTIMATES FOR A GROUND WATER MODEL1

ABSTRACT: This paper presents a parameter sensitivity study of a two-dimensional flow and transport model of a contaminated site. Hydrogeological and site data from previous investigations were used for calibration. The USGS contaminant transport model (MOC) was used. After flow calibration to establish a reference model, parameters were varied to examine the effect each had on predictions of a contaminant plume. Hydrogeological parameters and a step size parameter were incrementally varied individually. Each result was compared to the reference model output to evaluate changes in concentration values and contaminant plume configuration. The study indicated that a generally predictable trend can be established for some parameters not affected by pumping or similar high stresses. Ranges were identified to relate concentration error or plume change to the amount of parameter error. Some parameter perturbations produced distorted model responses at high stress locations. Porosity and anisotropy were found to be the most influential of the model parameters studied on the plume predictions. (KEY TERMS: ground water hydrology; hydrogeology; pollution modeling; water quality; model calibration.)     

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 μg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.     

Sampling silica and ferrihydrite colloids with fiberglass wicks under unsaturated conditions

The suitability of passive capillary samplers (PCAPS) for collection of representative colloid samples under partially saturated conditions was evaluated by investigating the transport of negatively and positively charged colloids in fiberglass wicks. A synthetic pore water solution was used to suspend silica microspheres (330 nm in diameter) and ferrihydrite (172 nm in diameter) for transport experiments on fiberglass wicks. Breakthrough curves were collected for three unsaturated flow rates with silica microspheres and one unsaturated flow rate with ferrihydrite colloids. A moisture characteristic curve, relating tensiometer measurements of matric potential to moisture content, was developed for the fiberglass wick. Results indicate that retention of the silica and the ferrihydrite on the wick occurred; that is, the wicks did not facilitate quantitative sampling of the colloids. For silica microspheres, 90% of the colloids were transmitted through the wicks. For ferrihydrite, 80 to 90% of the colloids were transmitted. The mechanisms responsible for the retention of the colloids on the fiberglass wicks appeared to be physicochemical attachment and not thin-film, triple-phase entrapment, or mechanical straining. Visualization of pathways by iron staining indicates that flow is preferential at the center of twisted bundles of filaments. Although axial preferential flow in PCAPS may enhance their hydraulic suitability for sampling mobile colloids, we conclude that without specific preparation to reduce attachment or retention, fiberglass wicks should only be used for qualitative sampling of pore water colloids.     

Integrated environmental monitoring and simulation system for use as a management decision support tool in urban areas

Leachates are generated as a result of water or other liquid passing through waste at a landfill site. These contaminated liquids originate from a number of sources, including the water produced during the decomposition of the waste as well as rain-fall which penetrates the waste and dissolves the material with which it comes into contact. The penetration of the rain-water depends on the nature of the landfill (e.g. surface characteristics, type and quantity of vegetation, gradient of layers, etc). The uncontrolled infiltration of leachate into the vadose (unsaturated) zone and finally into the saturated zone (groundwater) is considered to be the most serious environmental impact of a landfill. In the present paper the water flow and the pollutant transport characteristics of the Ano Liosia Landfill site in Athens (Greece) were simulated by creating a model of groundwater flows and contaminant transport. A methodology for the model is presented. The model was then integrated into the Ecosim system which is a prototype funded by the EU, (Directorate General XIII: Telematics and Environment). This is an integrated environmental monitoring and modeling system, which supports the management of environmental planning in urban areas.     

Nitrate movement in shallow ground water from swine-lagoon-effluent spray fields managed under current application regulations

Rapid increases in the swine (Sus scrofa domestica) population in the 1990s and associated potential for nitrate N pollution of surface waters led the state of North Carolina to adopt stringent waste management regulations in 1993. Our objectives were to characterize (i) nitrate N movement from waste application fields (WAFs) in shallow ground water, and (ii) soil, hydrologic, and biological factors influencing the amount of nitrate N in the adjacent stream. A ground water monitoring study was conducted for 36 mo on a swine farm managed under new regulations. Water table contours and lack of vertical gradients indicated horizontal flow over most of the site. Nitrate N concentrations in water from shallow wells in WAFs averaged 30 +/- 19 mg L(-1) and delta15N ratios for nitrate N were between +20 and +25 per mil. Nitrate N concentration decreased from field-edge to streamside wells by 22 to 99%. Measurement of delta18O and delta15N enrichment of nitrate in ground water throughout the WAF-riparian system indicated that denitrification has not caused significant 15N enrichment of nitrate. Over a 24-mo period, delta15N ratios for nitrate N in the stream approached delta15N ratios for nitrate N in ground water beneath WAFs indicating delivery of some waste-derived nitrate N to the stream in shallow ground water. Nitrate N concentrations in the stream were relatively low, averaging 1 mg L(-1). Dilution of high nitrate N water in shallow horizontal flow paths with low nitrate N water from deeper horizontal flow paths at or near the stream, some denitrification as ground water discharges through the stream bottom, and some denitrification in riparian zone contributed to this low nitrate N concentration.     

Solute movement through an allophanic soil

Allophanic soils are widespread around the world, but little research has been done on their transport properties. This study reveals the effect of two soil water potential heads and two water-flow regimes of continuous and intermittent flow on solute transport through undisturbed soil columns of Horotiu silt loam (Typic Hapludand), an allophanic soil. Two different methods--breakthrough curves (BTCs) and time domain reflectometry (TDR)--were employed to determine the extent of preferential solute transport in the topsoil. The TDR data were also used to look at the depth dependence of the transport properties. The convection-dispersion equation (CDE) with the appropriate boundary conditions adequately described the movement of both Br and Cl under the various flow conditions. Although no preferential flow was found under the imposed unsaturated flow conditions, the flow of water and transport of solute became more uniform with depth. The results show that both Br and Cl are retarded in this allophanic soil. Retardation values range from 1.5 to 1.9, and, as the TDR data showed, increase from the depth of 5.0 to 10.0 cm. Intermittent leaching results showed that there was no effect on solute concentrations in the leachate following no-flow periods. This suggests that water and solute transport in this soil were either relatively uniform or that transverse mixing during flow was already fast enough to eliminate concentration gradients between regions of different "mobility."     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Nitrogen fluxes through unsaturated zones in five agricultural settings across the United States

The main physical and chemical controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Indiana, Maryland, Nebraska, and Washington from 2004 to 2005. Sites included irrigated and nonirrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 1 to 22 m. Chemical analyses of water from lysimeters and shallow wells indicate that advective transport of nitrate is the dominant process affecting the flux of N below the root zone. Vertical profiles of (i) nitrogen species, (ii) stable isotopes of nitrogen and oxygen, and (iii) oxygen, N, and argon in unsaturated zone air and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. As a result, physical factors, such as N application rate, water inputs, and evapotranspiration, control the differences in concentrations among the sites. Concentrations of N in shallow lysimeters exhibit seasonal variation, whereas concentrations in lysimeters deeper than a few meters are relatively stable. Based on concentration and recharge estimates, fluxes of N through the deep unsaturated zone range from 7 to 99 kg ha(-1) yr(-1). Vertical fluxes of N in ground water are lower due to spatial and historical changes in N inputs. High N fluxes are associated with coarse sediments and high N application rates.     

Differences in microbial biomass,organic carbon,and dye sorption between flow and no-flow regions of unsaturated soil

Transport models in which the liquid phase is partitioned between conducting and nonconducting regions allow the possibility that degradation and sorption are different in these regions. However, there is little information on biological or chemical differences between conducting and nonconducting regions of the soil matrix. Previous work by the authors on Br transport through unsaturated, intact soil cores of Dundee silty clay loam (fine-silty, mixed, active, thermic Typic Endoaqualf) indicated non-equilibrium conditions that could be well-described by a two-region model. Fitted parameters indicated little solute transfer between flow regions, suggesting that dye movement in unsaturated soil might delineate conducting and nonconducting regions of this soil. Steady-state, unsaturated flow was established in intact cores (10 by 30 cm) of the Dundee soil, then Br and erioglaucine dye were displaced through these cores. The soil cores were then sectioned into 5-cm segments and stained soil was separated from unstained soil. Microbial biomass C, organic C, and dye sorption K(D) (= g(sorbed) kg(-1)soil/g L(-1)) values for stained and unstained soil were determined. Stained soil had higher microbial biomass C but generally lower organic C and lower affinity for dye sorption than unstained soil from the same depth increment. Fraction of immobile water, dispersion, and mass transfer between conducting and nonconducting regions were consistent with previous results.     

Modeling effluent distribution and nitrate transport through an on-site wastewater system

Properly functioning on-site wastewater systems (OWS) are an integral component of the wastewater system infrastructure necessary to renovate wastewater before it reaches surface or ground waters. There are a large number of factors, including soil hydraulic properties, effluent quality and dispersal, and system design, that affect OWS function. The ability to evaluate these factors using a simulation model would improve the capability to determine the impact of wastewater application on the subsurface soil environment. An existing subsurface drip irrigation system (SDIS) dosed with sequential batch reactor effluent (SBRE) was used in this study. This system has the potential to solve soil and site problems that limit OWS and to reduce the potential for environmental degradation. Soil water potentials (Psi(s)) and nitrate (NO(3)) migration were simulated at 55- and 120-cm depths within and downslope of the SDIS using a two-dimensional code in HYDRUS-3D. Results show that the average measured Psi(s) were -121 and -319 cm, whereas simulated values were -121 and -322 cm at 55- and 120-cm depths, respectively, indicating unsaturated conditions. Average measured NO(3) concentrations were 0.248 and 0.176 mmol N L(-1), whereas simulated values were 0.237 and 0.152 mmol N L(-1) at 55- and 120-cm depths, respectively. Observed unsaturated conditions decreased the potential for NO(3) to migrate in more concentrated plumes away from the SDIS. The agreement (high R(2) values approximately 0.97) between the measured and simulated Psi(s) and NO(3) concentrations indicate that HYDRUS-3D adequately simulated SBRE flow and NO(3) transport through the soil domain under a range of environmental and effluent application conditions.     

Effect of soil properties on saturated and unsaturated virus transport through columns

Viruses from contaminant sources can be transported through porous media to drinking water wells. The objective of this study was to investigate inactivation and sorption of viruses during saturated and unsaturated transport in different soils. Bacteriophages phiX174 and MS-2, and Br- tracer in a phosphate-buffered saline solution were introduced into saturated and unsaturated soil columns as a step function under constant flow rate and hydraulic conditions. Results showed that significantly greater virus removal occurred in the unsaturated columns than in the saturated columns in the two soils containing high metal oxides content. However, the increase in virus retention under unsaturated conditions was not significant in two other soils having high phosphorus and calcium contents and high pH, and in another soil with high organic matter content. The results imply that the extent of water content effect on inactivation and sorption of viruses can range from significant to minimal depending on the properties of the transport medium. We found that the presence of in situ metal oxides was a significant factor responsible for virus sorption and inactivation. Therefore, soils with high metal oxides content may have the potential to be used as hydrological barriers in preventing microbial contamination in the subsurface environments. We also found that the water content effect on virus removal and inactivation strongly depended on solid properties of the testing medium.     

Preferential flow estimates to an agricultural tile drain with implications for glyphosate transport

Agricultural subsurface drains, commonly referred to as tile drains, are potentially significant pathways for the movement of fertilizers and pesticides to streams and ditches in much of the Midwest. Preferential flow in the unsaturated zone provides a route for water and solutes to bypass the soil matrix and reach tile drains faster than predicted by traditional displacement theory. This paper uses chloride concentrations to estimate preferential flow contributions to a tile drain during two storms in May 2004. Chloride, a conservative anion, was selected as the tracer because of differences in chloride concentrations between the two sources of water to the tile drain, preferential and matrix flow. A strong correlation between specific conductance and chloride concentration provided a mechanism to estimate chloride concentrations in the tile drain throughout the storm hydrographs. A simple mixing analysis was used to identify the preferential flow component of the storm hydrograph. During two storms, preferential flow contributed 11 and 51% of total storm tile drain flow; the peak contributions, 40 and 81%, coincided with the peak tile drain flow. Positive relations between glyphosate [N-(phosphonomethyl)glycine] concentrations and preferential flow for the two storms suggest that preferential flow is an important transport pathway to the tile drain.     

A Method for Designing Detection Monitoring Networks in Layered Aquifers with Non-uniform Flow

An integer programming method was devised to locate detection monitoring wells in layered aquifers. The method is applicable to aquifers with non-uniform groundwater flow, and it does not require that a compliance boundary be linear or perpendicular to the direction(s) of groundwater flow. In each layer, monitoring sites are defined along curvilinear transects that parallel equipotential lines. The model can be formulated to allocate wells to the transect with the highest detection efficiency, or to establish multiple lines of defense against contaminant migrating to a compliance boundary. Detection efficiencies of alternative monitoring transects are calculated from parameters obtained via numerical modeling of contaminant transport. These parameters include the narrowest plume that could traverse a monitoring transect, and the zone width of potential contaminant migration at the transect. Problem formulations are compact, and computational requirements are low relative to alternative approaches for designing detection monitoring networks in aquifers. An application to a glacial outwash aquifer demonstrates the utility of the method.     

Water movement within the unsaturated zone in four agricultural areas of the United States

Millions of tons of agricultural fertilizer and pesticides are applied annually in the USA. Due to the potential for these chemicals to migrate to groundwater, a study was conducted in 2004 using field data to calculate water budgets, rates of groundwater recharge and times of water travel through the unsaturated zone and to identify factors that influence these phenomena. Precipitation was the only water input at sites in Indiana and Maryland; irrigation accounted for about 80% of total water input at sites in California and Washington. Recharge at the Indiana site (47.5 cm) and at the Maryland site (31.5 cm) were equivalent to 51 and 32%, respectively, of annual precipitation and occurred between growing seasons. Recharge at the California site (42.3 cm) and Washington site (11.9 cm) occurred in response to irrigation events and was about 29 and 13% of total water input, respectively. Average residence time of water in the unsaturated zone, calculated using a piston-flow approach, ranged from less than 1 yr at the Indiana site to more than 8 yr at the Washington site. Results of bromide tracer tests indicate that at three of the four sites, a fraction of the water applied at land surface may have traveled to the water table in less than 1 yr. The timing and intensity of precipitation and irrigation were the dominant factors controlling recharge, suggesting that the time of the year at which chemicals are applied may be important for chemical transport through the unsaturated zone.