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).     

Artificial recharge of humic ground water

The purpose of this study was to investigate the efficiency of soil in removing natural organic matter from humic ground waters using artificial recharge. The study site, in western Denmark, was a 10,000 ml football field of which 2,000 m2 served as an infiltration field. The impact of the artificial recharge was studied by monitoring the water level and the quality of the underlying shallow aquifer. The humic ground water contained mainly humic adds with an organic carbon (OC) concentration of 100 to 200 mg C L(-1). A total of 5,000 mS of humic ground water were sprinkled onto the infiltration field at an average rate of 4.25 mm h(-1). This resulted in a rise in the water table of the shallow aquifer. The organic matter concentration of the water in the shallow aquifer, however, remained below 2.7 mg C L(-1). The organic matter concentration of the pore water in the unsaturated zone was measured at the end of the experiment. The organic matter concentration of the pore water decreased from 105 mg C L(-1) at 0.5 m to 20 mg C L(-1) at 2.5 m under the infiltration field indicating that the soil removed the organic matter from the humic ground water. From these results we conclude that artificial recharge is a possible method for humic ground water treatment.     

Transport and fate of nitrate in a glacial outwash aquifer in relation to ground water age,land use practices,and redox processes

A combination of ground water modeling, chemical and dissolved gas analyses, and chlorofluorocarbon age dating of water was used to determine the relation between changes in agricultural practices, and NO3- concentrations in ground water of a glacial outwash aquifer in west-central Minnesota. The results revealed a redox zonation throughout the saturated zone with oxygen reduction occurring near the water table, NO3- reduction immediately below it, and then a large zone of ferric iron reduction, with a small area of sulfate (SO4(2-)) reduction and methanogenesis (CH4) near the end of the transsect. Analytical and NETPATH modeling results supported the hypothesis that organic carbon served as the electron donor for the redox reactions. Denitrification rates were quite small, 0.005 to 0.047 mmol NO3- yr(-1), and were limited by the small amounts of organic carbon, 0.01 to 1.45%. In spite of the organic carbon limitation, denitrification was virtually complete because residence time is sufficient to allow even slow processes to reach completion. Ground water sample ages showed that maximum residence times were on the order of 50 to 70 yr. Reconstructed NO3- concentrations, estimated from measured NO3- and dissolved N gas showed that NO3- concentrations have been increasing in the aquifer since the 1940s, and have been above the 714 micromol L(-1) maximum contaminant level at most sites since the mid- to late-1960s. This increase in NO3- has been accompanied by a corresponding increase in agricultural use of fertilizer, identified as the major source of NO3- to the aquifer.     

Field-scale preferential transport of water and chloride tracer by depression-focused recharge

A tracer study was initiated in November 1993 to investigate depression-focused recharge and to monitor solute movement through the vadose zone into the shallow ground water in southeastern North Dakota. Granular potassium chloride (KCl) was surface-applied to two areas overlying subsurface drains and to one area instrumented with soil solution samplers, ground water monitoring wells, time domain reflectometry (TDR) probes, and temperature probes. One of the subsurface drain tracer plots was located on level ground while the other two sites were in small topographic depressions. Formation of ground water mounds beneath the depressions indicated that these areas are recharge sites. The applied Cl- tracer was found to move rapidly to the shallow ground water under the depressional areas after infiltration of spring snowmelt in 1994. Excessive rainfall events were also responsible for focused recharge and the rapid transport of the applied Cl- tracer. Water flow through partially frozen soil at the bottom of the depressions during thaw enhanced preferential movement of the tracer.     

LEAKY ACRES RECHARGE FACILITY: A TEN-YEAR EVALUATION1

From 1971-1980, studies were conducted at Fresno, California, to identify and quantify, where possible, the soil and water chemistry, subsurface geologic, hydrologic, biologic, and operational factors that determine the long term (10-year) effectiveness of basin type artificial ground water recharge through alluvial soils. This paper updates previous findings and refers to publications that describe the geology beneath the basins and regional geology that determine the transmission and storage properties for local ground water management and chemical quality enhancement. High quality irrigation water from the Kings River was used for recharge. Construction and land costs for the present expanded facility 83 ha (205.2 ac) using three parcels of land were $1,457,100. The nine-year annual mean costs for only canal water, maintenance, and operation were $110.42/ha·m ($13.62/ac·ft) based on an average recharge rate of 1338 ha·m/yr (10,848 ac·ft/yr) at 86 percent facility efficiency. The measured end of season recharge rate averaged 14.97 ± 0.24 cm/day. The 10-year mean actual recharge rate based on actual water delivered, total ponded area, and total days of recharge was 12.1 cm/day.     

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.     

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.     

A COMPARISON OF MODELS PREDICTING GROUND WATER LEVELS ON HILLSIDE SLOPES1

ABSTRACT: A comparative study of ground water level predictions on hillside slopes using two models is presented. The models are a simplified mass balance model that has components for evapotran-spiration, recharge, and drainage; and a two-dimensional finite difference model that employs kriging to estimate soil parameters and accounts for non-uniform thickness of the soil layer. These models are representative of a wide range of modeling capabilities and are used to illustrate the sensitivity of ground water level predictions to the sophistication of the modeling techniques. The drainage and recharge components of the two models are evaluated and the importance of unsaturated flow in recharge computations is underscored. Piezometric observations in a small drainage depression on the slope of Kennel Creek Valley in Tongass National Forest, Alaska, were used to evaluate the two models. The results show that, although the predictions differ from the field observations, the simple physically-based mass balance model predicts the ground water levels as well as the two-dimensional model. It is suggested that caution should be exercised in using complex models to validate simpler models.     

EFFECTS OF TOPOGRAPHY AND SOIL PROPERTIES ON RECHARGE AT TWO SITES IN AN AGRICULTURAL FIELD1

ABSTRACT: Field experiments were conducted from 1992 to 1995 to estimate ground water recharge rates at two sites located within a 2.7‐hectare agricultural field. The field lies in a sand plain setting in central Minnesota and is cropped continuously in field corn. The sites are located at a topographically high (upland) site and a topographically low (lowland) site in an effort to quantify the effects of depression focusing of recharge. Three site‐specific methods were used to estimate recharge rates: well hydrograph analysis, chlorofluorocarbon age dating, and an unsaturated zone water balance. All three recharge methods indicated that recharge rates at the lowland site (annual average of all methods of 29 cm) exceeded those at the upland site (annual average of 18 cm). On an annual basis, estimates by the individual methods ranged from 12 to 44 percent of precipitation at the upland site and from 21 to 83 percent at the lowland site. The difference in recharge rates between the sites is primarily attributed to depression focusing of surface water runon at the lowland site. However, two other factors were also important: the presence of thin lamellae at the upland site, and coarser textured soils below a depth of 1.5 m at the lowland site.     

EFFECTS OF ARTIFICIAL RECHARGE ON GROUND WATER QUALITY AND AQUIFER STORAGE RECOVERY1

ABSTRACT: Ground water nitrate contamination and water level decline are common concern in Nebraska. Effects of artificial recharge on ground water quality and aquifer storage recovery (ASR) were studied with spreading basins constructed in the highly agricultural region of the Central Platte, Nebraska. A total of 1.10 million m³ of Platte River water recharged the aquifer through 5000 m² of the recharge basins during 1992, 1993, and 1994. This is equivalent to the quantity needed to completely displace the ground water beneath 34 ha of the local primary aquifer with 13 m thickness and 0.25 porosity. Successful NO₃-N remediation was documented beneath and downgradient of the recharge basins, where NO₃-N declined from 20 to 2 mg L^-1. Ground water atrazine concentrations at the site decreased from 2 to 0.2 mg L^-1 due to recharge. Both NO₃-N and atrazine contamination dramatically improved from concentrations exceeding the maximum contaminant levels to those of drinking water quality. The water table at the site rose rapidly in response to recharge during the early stage then leveled off as infiltration rates declined. At the end of the 1992 recharge season, the water table 12 m downgradient from the basins was elevated 1.36 m above the preproject level; however, at the end of the 1993 recharge season, any increase in the water table from artificial recharge was masked by extremely slow infiltration rates and heavy recharge from precipitation from the wettest growing season in over 100 years. The water table rose 1.37 m during the 1994 recharge season. Resultant ground water quality and ASR improvement from the artificial recharge were measured at 1000 m downgradient and 600 m upgradient from the recharge basins. Constant infiltration rates were not sustained in any of the three years, and rates always decreased with time presumably because of clogging. Scraping the basin floor increased infiltration rates. Using a pulsed recharge to create dry and wet cycles and maintaining low standing water heads in the basins appeared to reduce microbial growth, and therefore enhanced infiltration.     

Determination of dominant biogeochemical processes in a contaminated aquifer-wetland system using multivariate statistical analysis

Determining the processes governing aqueous biogeochemistry in a wetland hydrologically linked to an underlying contaminated aquifer is challenging due to the complex exchange between the systems and their distinct responses to changes in precipitation, recharge, and biological activities. To evaluate temporal and spatial processes in the wetland-aquifer system, water samples were collected using cm-scale multi-chambered passive diffusion samplers (peepers) to span the wetland-aquifer interface over a period of 3 yr. Samples were analyzed for major cations and anions, methane, and a suite of organic acids resulting in a large dataset of over 8000 points, which was evaluated using multivariate statistics. Principal component analysis (PCA) was chosen with the purpose of exploring the sources of variation in the dataset to expose related variables and provide insight into the biogeochemical processes that control the water chemistry of the system. Factor scores computed from PCA were mapped by date and depth. Patterns observed suggest that (i) fermentation is the process controlling the greatest variability in the dataset and it peaks in May; (ii) iron and sulfate reduction were the dominant terminal electron-accepting processes in the system and were associated with fermentation but had more complex seasonal variability than fermentation; (iii) methanogenesis was also important and associated with bacterial utilization of minerals as a source of electron acceptors (e.g., barite BaSO(4)); and (iv) seasonal hydrological patterns (wet and dry periods) control the availability of electron acceptors through the reoxidation of reduced iron-sulfur species enhancing iron and sulfate reduction.     

Understanding long-term baseflow water quality trends using a synoptic survey of the ground water-surface water interface, central Wisconsin

The relationship between stream water quality and landscape activities is difficult to evaluate where the principal source of stream flow is ground water seepage because the average travel time from ground water recharge areas to stream discharge positions can be on the order of decades. We tested the idea that past and future baseflow water quality can be predicted based on a synoptic survey of ground water recharge age-dates (based on chlorofluorocarbon [CFC] measurements) and water quality measurements obtained at the ground water-surface water interface. In this study we (i) characterize the discharge-weighted age distribution and water quality of ground water seepage into the Little Plover River (LPR); (ii) use this information to backcast and forecast baseflow NO(3)(-) concentrations; and (iii) evaluate NO(3)(-) backcasts against historical baseflow data (1960 to 2000). The discharge-weighted apparent CFC age of ground water seepage into the LPR was 23.7 (+/-7) yr. Baseflow backcasts matched the four decade rise of baseflow NO(3)(-) from 2 to 8 mg L(-1). Baseflow forecasts included three scenarios. Scenario A projects the historical rise of NO(3)(-) in the LPR basin's ground water recharge through 2050. Scenario B projects a leveling off of NO(3)(-) in ground water recharge in the year 2000. Scenario C projects a leveling off in the year 1985. Under Scenario A, LPR baseflow NO(3)(-) will increase steadily from 8 to 19 mg L(-1) between 2000 and 2050. Under scenarios B and C baseflow NO(3)(-) will plateau at 13 mg L(-1) in 2030 and at 10 mg L(-1) in 2010, respectively. The approach developed in this study can be used to (i) reconstruct historical baseflow water quality patterns in the absence of long-term monitoring data and (ii) project the effects of potential management decision on future water quality.     

Herbicide loading to shallow ground water beneath Nebraska's Management Systems Evaluation Area

Better management practices can counter deterioration of ground water quality. From 1991 through 1996 the influence of improved irrigation practices on ground water pesticide contamination was assessed at the Nebraska Management Systems Evaluation Area. Three 13.4-ha corn (Zea mays L.) fields were studied: a conventional furrow-irrigated field, a surge-irrigated field and a center pivot-irrigated field, and a center pivot-irrigated alfalfa (Medicago sativa L.) field. The corn fields received one identical banded application of Bicep (atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] + metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamidel) annually; the alfalfa field was untreated. Ground water samples were collected three times annually from 16 depths of 31 multilevel samplers. Six years of sample data indicated that a greater than 50% reduction in irrigation water on the corn management fields lowered average atrazine concentrations in the upper 1.5 m of the aquifer downgradient of the corn fields from approximately 5.5 to <0.5 microg L(-1). Increases in deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to atrazine molar ratios indicated that reducing water applications enhanced microbial degradation of atrazine in soil zones. The occurrence of peak herbicide loading in ground water was unpredictable but usually was associated with heavy precipitation within days of herbicide application. Focused recharge of storm runoff that ponded in the surge-irrigated field drainage ditch, in the upgradient road ditch, and at the downgradient end of the conventionally irrigated field was a major mechanism for vertical transport. Sprinkler irrigation technology limited areas for focused recharge and promoted significantly more soil microbial degradation of atrazine than furrow irrigation techniques and, thereby, improved ground water quality.     

USE OF SOIL MOISTURE PROBES TO ESTIMATE GROUND WATER RECHARGE AT AN OIL SPILL SITE1

Soil moisture data collected using an automated data logging system were used to estimate ground water recharge at a crude oil spill research site near Bemidji, Minnesota. Three different soil moisture probes were tested in the laboratory as well as the field conditions of limited power supply and extreme weather typical of northern Minnesota: a self‐contained reflectometer probe, and two time domain reflectometry (TDR) probes, 30 and 50 cm long. Recharge was estimated using an unsaturated zone water balance method. Recharge estimates for 1999 using the laboratory calibrations were 13 to 30 percent greater than estimates based on the factory calibrations. Recharge indicated by the self‐contained probes was 170 percent to 210 percent greater than the estimates for the TDR probes regardless of calibration method. Results indicate that the anomalously large recharge estimates for the self‐contained probes are not the result of inaccurate measurements of volumetric moisture content, but result from the presence of crude oil, or borehole leakage. Of the probes tested, the 50 cm long TDR probe yielded recharge estimates that compared most favorably to estimates based on a method utilizing water table fluctuations. Recharge rates for this probe represented 24 to 27 percent of 1999 precipitation. Recharge based on the 30 cm long horizontal TDR probes was 29 to 37 percent of 1999 precipitation. By comparison, recharge based on the water table fluctuation method represented about 29 percent of precipitation.     

WATER QUALITY BENEATH URBAN RUNOFF WATER MANAGEMENT BASINS1

ABSTRACT: The chemical impact of urban runoff water on water quality beneath five retention/recharge basins was investigated as part of the US EPA's Nationwide Urban Runoff Program in Fresno, California. Soil water percolating through alluvium soils and the ground water at the top of the water table were sampled with ceramic/Teflon vacuum water extractors at depths up to 26 m during the two-year investigation. Inorganic and organic pollutants are present in the runoff water delivered to the basins. No significant contamination of percolating soil water or ground water underlying any of the five retention/recharge basins has occurred for constituents monitored in the study. The oldest basins was constructed in 1962. The concentration of selected trace elements in the ground water samples was similar to the levels reported in the regional ground water. None of the pesticides or other organic priority pollutants, for which water samples were analyzed, was s̊ detected except diazinon which was found in trace amounts (0.3 μg/L or less) in only three soil water samples. These results are important to the continued conservation of storm water and the development of a best management practice for storm-water management using retention/recharge basins in a semi-arid climate.     

FROZEN SOIL IMPACT ON GROUND WATER‐SURFACE WATER INTERACTION1

ABSTRACT: Ground water and surface water interaction in the prairie pothole region of the United States and Canada is seasonally dominated by the presence of thick, frozen soil layers that affect infiltration. During a spring thaw, the subsoil may remain frozen, preventing infiltration. The impact of the frozen soil layer on the timing of infiltration of depressional‐focused recharge to the ground water is not clearly understood. The objective of this paper is to relate changes in the water table during spring to changes in frost depth and soil water content. A depression and adjacent upland study site were instrumented with CRREL‐type frost tubes, neutron probe access tubes, and ground water monitoring wells. Increases in water table levels in a depression occurred before the frost layer decomposed and infiltrating water quickly formed a recharge mound. Water table responses at the upland site took place as two events. The first event was a gradual rise, probably caused by the lateral dissemination of the recharge mound. The second rise was a rapid rise coinciding with the decomposition of the soil frost layer. Because of the accumulation of surface water in depressions, agricultural practices that remove water from a field can affect water resources management by limiting the addition of water recharge to unconfmed ground water.     

Relation Between Flow and Temporal Variations of Nitrate and Pesticides in Two Karst Springs in Northern Alabama1

Abstract: Two karst springs in the Mississippian Carbonate Aquifer of northern Alabama were sampled between March 1999 and March 2001 to characterize the variability in concentration of nitrate, pesticides, selected pesticide degradates, water temperature, and inorganic constituents. Water temperature and inorganic ion data for McGeehee Spring indicate that this spring represents a shallow flow system with a relatively short average ground‐water residence time. Water issuing from the larger of the two springs, Meridianville Spring, maintained a constant temperature, and inorganic ion data indicate that this water represents a deeper flow system having a longer average ground‐water residence time than McGeehee Spring. Although water‐quality data indicate differing short‐term responses to rainfall at the two springs, the seasonal variation of nitrate and pesticide concentrations generally is similar for the two springs. With the exception of pesticides detected at low concentrations, the coefficient of variation for most constituent concentrations was less than that of flow at both springs, with greater variability in concentration at McGeehee Spring. Degradates of the herbicides atrazine and fluometuron were detected at concentrations comparable to or greater than the parent pesticides. Decreases in concentration of the principal degradate of fluometuron from about July to November indicate that the degradation rate may decrease as fluometuron (demethylfluometuron) moves deeper into the soil after application. Data collected during the study show that from about November to March when recharge rates increase, nitrate and residual pesticides in the soil, unsaturated zone, and storage within the aquifer are transported to the spring discharges. Because of the increase in recharge, fluometuron loads discharged from the springs during the winter were comparable to loads discharged at the springs during the growing season.     

Soil property control of biogeochemical processes beneath two subtropical stormwater infiltration basins

Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath two stormwater infiltration basins in north-central Florida. Differences are related to soil textural properties that deeply link hydroclimatic conditions with soil moisture variations in a humid, subtropical climate. During 2008, shallow groundwater beneath the basin with predominantly clayey soils (median, 41% silt+clay) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg L and decreases in nitrate nitrogen (NO-N) from 2.7 mg L to <0.016 mg L, followed by manganese and iron reduction, sulfate reduction, and methanogenesis. In contrast, beneath the basin with predominantly sandy soils (median, 2% silt+clay), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen, 5.0-7.8 mg L), resulting in NO-N of 1.3 to 3.3 mg L in shallow groundwater. Enrichment of δN and δO of NO combined with water chemistry data indicates denitrification beneath the clayey basin and relatively conservative NO transport beneath the sandy basin. Soil-extractable NO-N was significantly lower and the copper-containing nitrite reductase gene density was significantly higher beneath the clayey basin. Differences in moisture retention capacity between fine- and coarse-textured soils resulted in median volumetric gas-phase contents of 0.04 beneath the clayey basin and 0.19 beneath the sandy basin, inhibiting surface/subsurface oxygen exchange beneath the clayey basin. Results can inform development of soil amendments to maintain elevated moisture content in shallow soils of stormwater infiltration basins, which can be incorporated in improved best management practices to mitigate NO impacts.     

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.     

Seasonal dynamics of denitrification along topohydrosequences in three different riparian wetlands

We investigated the seasonal patterns of denitrification rates and potentials in soil profiles along the topohydrosequence formed at the upland-wetland interface in three riparian wetlands with different vegetation cover (i.e., forest, understory vegetation, and grass). Denitrification was measured using the acetylene inhibition method on soil cores and slurries, which provided a means of comparing the relative activity of this process in different locations. We evaluated, on a seasonal basis, the respective importance of the vegetative cover and the hydromorphic gradient as factors limiting denitrification. Regardless of the season, vegetation type, or lateral position along each topohydrosequence in the riparian wetlands, strong significant gradients of both in situ and potential denitrification rates were measured within a soil profile. Results confirm that the upper organic soil horizon is the most active, when in contact with the ground water. In deeper soil horizons, denitrification activity was low (from 0.004 to 0.5 mg N kg(-1) dry soil d(-1)), but contributed significantly to the reduction of ground water NO3- load along the riparian ground water flowpath (from 9.32 to 0.98 mg NO3-N L(-1)). Along the soil topohydrosequence, the denitrifying community of the upper soil horizons did not vary significantly on a seasonal basis despite the large seasonal ground water fluctuations. Along each topohydrosequence, the denitrification-limiting factor gradually shifted from anaerobiosis to NO3- supply. In situ denitrification rates in the forested, understory vegetation and grass sites were not significantly different. This result emphasizes the importance of the topography of the valley rather than the vegetation cover in controlling denitrification activity in riparian wetlands.