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Existing data in the United States are insufficient for estimating pesticide-treated crop areas at the watershed scale. The objective of this research was to evaluate an approach for estimating simazine usage on corn (Zea mays L.) based on its transport to streams of the Salt River Basin (SRB) of Missouri, USA. Annual loads of total simazine and atrazine (parent + metabolites) were quantified for seven SRB watersheds from 2005 to 2017. Simazine-treated corn area was computed as the total simazine load (g) divided by total atrazine load (g ha-1 ) on a treated area basis; atrazine was used as surrogate in the absence of treated area simazine load data. From 2005 to 2010, an estimated 3.8-31% of the corn area within SRB watersheds was treated with simazine, and four of six watersheds had

Row crop and livestock production contaminate soils and groundwater of the karst aquifers within south-central Kentucky's Pennyroyal Plateau. Transport of atrazine from field application to the epikarstic drainage system beneath a field with active row-crop farming was investigated. The Crumps Cave study site is a shallow autogenic drainage system with a recharge area of ∼1 ha that contains two epikarst drains (WF-1 and WF-2) which were monitored for atrazine, deethylatrazine (DEA), and deisopropylatrazine (DIA) concentrations from January 2011 to May 2012. Atrazine concentrations in both drains did not increase above winter background levels for nearly 2 mo after application when levels suddenly spiked and reached peak concentrations for the study during an event in May 2011. Atrazine, DEA, and DIA were detected in 100% of samples, and metabolites accounted for 54 to 94% of the monthly total loads, except in May 2011. Median dealkylated metabolite/atrazine ratios (DMAR) were ∼5:1 at both sites, and seasonal DMAR patterns corresponded with changes in soil temperature. These data support the hypothesis that a combination of sorption and degradation in the soil column above the epikarst controlled the transport of atrazine and its metabolites. This resulted in delayed atrazine transport after application and prolonged transport of atrazine and its weakly sorbed metabolites to the epikarst aquifer. Management practices that reduce herbicide inputs, such as diverse crop rotations, cover crops, and use of low-rate and strong-sorbing herbicides, would improve groundwater quality in areas of the Corn Belt with intensive row cropping on karst topography.

Veterinary antibiotics (VAs) in manure applied to agricultural lands may change agrichemical degradation by altering soil microbial community structure or function. The objectives of this study were to investigate the influence of two VAs, sulfamethazine (SMZ) and oxytetracycline (OTC), on atrazine (ATZ) degradation, soil microbial enzymatic activity, and phospholipid fatty acid (PLFA) markers. Sandy loam soil with and without 5% swine manure (w/w) was amended with 0 or 500 μg kgC radiolabeled ATZ and with 0, 100, or 1000 μg kg SMZ or OTC and incubated at 25°C in the dark for 96 d. The half-life of ATZ was not significantly affected by VA treatment in the presence or absence of manure; however, the VAs significantly (0.05) inhibited ATZ mineralization in soil without manure (25-50% reduction). Manure amendment decreased ATZ degradation by 22%, reduced ATZ mineralization by 50%, and increased the half-life of ATZ by10 d. The VAs had limited adverse effects on the microbial enzymes β-glucosidase and dehydrogenase in soils with and without manure. In contrast, manure application stimulated dehydrogenase activity and altered chlorinated ATZ metabolite profiles. Concentrations of PLFA markers were reduced by additions of ATZ, manure, OTC, and SMZ; adverse additive effects of combined treatments were noted for arbuscular mycorrhizal fungi and actinobacteria. In this work, the VAs did not influence persistence of the ATZ parent compound or chlorinated ATZ metabolite formation and degradation. However, reduced CO evolved from VA-treated soil suggests an inhibition to the degradation of other ATZ metabolites due to an altered soil microbial community structure.

Nitrogen from agriculture is known to be a primary source of groundwater NO3–N. Research was conducted in a northeastern Missouri watershed to assess the impact of cropping systems on NO3–N for a loess and fractured glacial till aquifer underlying claypan soils. Three cropped fields with 10 yr of similar management were each instrumented with 20 to 25 monitoring wells, 3 to 15 m in depth, in 1991 to 1992. Wells were sampled and analyzed for NO3–N at least annually from 1991 to 2004. Initial NO3–N concentrations were variable, ranging from undetectable to >24 mg L −1 but averaged 7.0 mg L −1 . Groundwater NO3–N was significantly higher in Field 3, probably the result of concurrent applications of manure and N fertilizer before 1980. Overall changes in NO3–N levels in Fields 1 and 2 were generally small; however, NO3–N levels for Field 3 have decreased an average of 0.28 mg L −1 yr −1 . Excessive loading of N into the matrix of the glacial till may have had a long-term impact on NO3–N for this field. Despite the presence of dissolved O2 in the aquifer, evidence of denitrification in some upper-landscape groundwater wells was found. The greatest decreases in NO3–N concentration occurred as groundwater moved through an in-field tree line or through a riparian zone. While overall conclusions were complicated by the long-term impact of past management, the capacity of the till to buffer changes, hydrogeologic variability found among wells, and the activity of biological processes, we conclude that cropping practices during this study did not increase glacial till NO3–N.

Long-term monitoring data from agricultural watersheds are needed to determine if efforts to reduce nutrient transport from crop and pasture land have been effective. Goodwater Creek Experimental Watershed (GCEW), located in northeastern Missouri, is a high-runoff-potential watershed dominated by claypan soils. The objectives of this study were to: (i) summarize dissolved NH-N, NO-N, and PO-P flow-weighted concentrations (FWC), daily loads, and yields (unit area loads) in GCEW from 1992 to 2010; (ii) assess time trends and relationships between precipitation, land use, and fertilizer inputs and nutrient transport; and (iii) provide context to the GCEW data by comparisons with other Corn Belt watersheds. Significant declines in annual and quarterly FWCs and yields occurred for all three nutrient species during the study, and the decreases were most evident for NO-N. Substantial decreases in first- and fourth-quarter NO-N FWCs and daily loads and modest decreases in first-quarter PO-P daily loads were observed. Declines in NO-N and PO-P transport were attributed to decreased winter wheat ( L.) and increased corn ( L.) production that shifted fertilizer application from fall to spring as well as to improved management, such as increased use of incorporation. Regression models and correlation analyses indicated that precipitation, land use, and fertilizer inputs were critical factors controlling transport. Within the Mississippi River Basin, NO-N yields in GCEW were much lower than in tile-drained areas, but PO-P yields were among the highest in the basin. Overall, results demonstrated that reductions in fall-applied fertilizer and improved fertilizer management reduced N and P transport in GCEW.

Goodwater Creek Experimental Watershed (GCEW) has been the focus area of a long-term effort to document the extent of and to understand the factors controlling herbicide transport. We document the datasets generated in the 20-yr-long research effort to study the transport of herbicides to surface and groundwater in the GCEW. This long-term effort was augmented with a spatially broad effort within the Central Mississippi River Basin encompassing 12 related claypan watersheds in the Salt River Basin, two cave streams on the fringe of the Central Claypan Areas in the Bonne Femme watershed, and 95 streams in northern Missouri and southern Iowa. Details of the analytical methods, periods of record, number of samples, study locations, and means of accessing these data are provided. In addition, a brief overview of significant findings is presented. A key finding was that near-surface restrictive soil layers, such as argillic horizons of smectitic mineralogy, result in greater herbicide transport than soils with high percolation and low clay content. Because of this, streams in the claypan soil watersheds of northeastern Missouri have exceptionally high herbicide concentrations and relative loads compared with other areas of the Corn Belt.

Multiple species vegetative buffer strips (VBSs) have been recommended as a cost-effective approach to mitigate agrochemical transport in surface runoff derived from agronomic operations, while at the same time offering a broader range of long-term ecological and environmental benefits. However, the effect of VBS designs and species composition on reducing herbicide and veterinary antibiotic transport has not been well documented. An experiment consisting of three VBS designs and one continuous cultivated fallow control replicated in triplicate was conducted to assess effectiveness in reducing herbicide and antibiotic transport for claypan soils. The three VBS designs include (i) tall fescue, (ii) tall fescue with a switchgrass hedge barrier, and (iii) native vegetation (largely eastern gamagrass). Rainfall simulation was used to create uniform antecedent soil moisture content in the plots and to generate runoff. Our results suggested that all VBS significantly reduced the transport of dissolved and sediment-bound atrazine, metolachlor, and glyphosate in surface runoff by 58 to 72%. Four to 8 m of any tested VBS reduced dissolved sulfamethazine transport in the surface runoff by more than 70%. The tall fescue VBS was overall most effective at reducing dissolved tylosin and enrofloxacin transport in the runoff (>75%). The developed exponential regression models can be used to predict expected field-scale results and provide design criteria for effective field implementation of grass buffers. Our study has demonstrated that an optimized VBS design may achieve desired agrochemical reductions and minimize acreage removed from crop production.

A sound multi-species vegetation buffer design should incorporate the species that facilitate rapid degradation and sequestration of deposited herbicides in the buffer. A field lysimeter study with six different ground covers (bare ground, orchardgrass, tall fescue, timothy, smooth bromegrass, and switchgrass) was established to assess the bioremediation capacity of five forage species to enhance atrazine (ATR) dissipation in the environment via plant uptake and degradation and detoxification in the rhizosphere. Results suggested that the majority of the applied ATR remained in the soil and only a relatively small fraction of herbicide leached to leachates (

Many challenges currently facing agriculture require long-term data on landscape-scale hydrologic responses to weather, such as from the Goodwater Creek Experimental Watershed (GCEW), located in northeastern Missouri, USA. This watershed is prone to surface runoff despite shallow slopes, as a result of a significant smectitic clay layer 30 to 50 cm deep that restricts downward flow of water and gives rise to a periodic perched water table. This paper is the first in a series that documents the database developed from GCEW. The objectives of this paper are to (i) establish the context of long-term data and the federal infrastructure that provides it, (ii) describe the GCEW/ Central Mississippi River Basin (CMRB) establishment and the geophysical and anthropogenic context, (iii) summarize in brief the collected research results published using data from within GCEW, (iv) describe the series of papers this work introduces, and (v) identify knowledge gaps and research needs. The rationale for the collection derives from converging trends in data from long-term research, integration of multiple disciplines, and increasing public awareness of increasingly larger problems. The outcome of those trends includes being selected as the CMRB site in the USDA-ARS Long-Term Agro-Ecosystem Research (LTAR) network. Research needs include quantifying watershed scale fluxes of N, P, K, sediment, and energy, accounting for fluxes involving forest, livestock, and anthropogenic sources, scaling from near-term point-scale results to increasingly long and broad scales, and considering whole-system interactions. This special section informs the scientific community about this database and provides support for its future use in research to solve natural resource problems important to US agricultural, environmental, and science policy.

In situ methods for estimating water quality parameters would facilitate efforts in spatial and temporal monitoring, and optical reflectance sensing has shown potential in this regard, particularly for chlorophyll, suspended sediment, and turbidity. The objective of this research was to develop and evaluate relationships between hyperspectral remote sensing and lake water quality parameters—chlorophyll, turbidity, and N and P species. Proximal hyperspectral water reflectance data were obtained on seven sampling dates for multiple arms of Mark Twain Lake, a large man-made reservoir in northeastern Missouri. Aerial hyperspectral data were also obtained on two dates. Water samples were collected and analyzed in the laboratory for chlorophyll, nutrients, and turbidity. Previously reported reflectance indices and full-spectrum (i.e., partial least squares regression) methods were used to develop relationships between spectral and water quality data. With the exception of dissolved NH3, all measured water quality parameters were strongly related (R 2 ≥ 0.7) to proximal reflectance across all measurement dates. Aerial hyperspectral sensing was somewhat less accurate than proximal sensing for the two measurement dates where both were obtained. Although full-spectrum calibrations were more accurate for chlorophyll and turbidity than results from previously reported models, those previous models performed better for an independent test set. Because extrapolation of estimation models to dates other than those used to calibrate the model greatly increased estimation error for some parameters, collection of calibration samples at each sensing date would be required for the most accurate remote sensing estimates of water quality.

The spatial and temporal variability of herbicides during the growing season were studied on a 35-ha watershed located in the cIaypan soil region of north-central Missouri. Soil samples were collected from the 0- to 5-em soil depth in 1993, and 0- to 5-, 5- to 10-, and 10totS-em soil depths in 1995 and analyzed for atrazine (2-chloro-4ethylamino-6-isopropylamino-s-triazine) and alachlor (2-chloro-N-(2, 6-diethl-N-(methoxymethyl) acetanilide) concentrations. The effects of rainfall, topography, soil pH, cation exchange capacity (CEC), and organic matter (OM) content on the spatial distribution of herbicides were evaluated. There was no spatial dependency between samples taken immediately after herbicide application; however, spatial dependency was observed in the following sampling periods. During the year

Elucidating veterinary antibiotic interactions with soil is important for assessing and mitigating possible environmental hazards. The objectives of this study were to investigate the effects of vegetative management, soil properties, and1000 Da dissolved organic matter (DOM) on sulfamethazine (SMZ) behavior in soil. Sorption experiments were performed over a range of SMZ concentrations (2.5-50 μmol L) using samples from three soils (Armstrong, Huntington, and Menfro), each planted to one of three vegetation treatments: agroforestry buffers strips (ABS), grass buffer strips (GBS), and row crops (RC). Our results show that SMZ sorption isotherms are well fitted by the Freundlich isotherm model (log = 0.44-0.93; Freundlich nonlinearity parameter = 0.59-0.79). Further investigation of solid-to-solution distribution coefficients () demonstrated that vegetative management significantly (0.05) influences SMZ sorption (ABSGBSRC). Multiple linear regression analyses indicated that organic carbon (OC) content, pH, and initial SMZ concentration were important properties controlling SMZ sorption. Study of the two most contrasting soils in our sample set revealed that increasing solution pH (pH 6.0-7.5) reduced SMZ sorption to the Armstrong GBS soil, but little pH effect was observed for the Huntington GBS soil containing 50% kaolinite in the clay fraction. The presence of DOM (150 mg L OC) had little significant effect on the Freundlich nonlinearity parameter; however, DOM slightly reduced SMZ values overall. Our results support the use of vegetative buffers to mitigate veterinary antibiotic loss from agroecosystems, provide guidance for properly managing vegetative buffer strips to increase SMZ sorption, and enhance understanding of SMZ sorption to soil.

The efficacy of vegetative buffer strips (VBS) in removing herbicides deposited from surface runoff is related to the ability of plant species to promote rapid herbicide degradation. A growth chamber study was conducted to compare C-atrazine (ATR) degradation profiles in soil rhizospheres from different forage grasses and correlate ATR degradation rates and profiles with microbial activity using three soil enzymes. The plant treatments included: (i) orchardgrass ( L.), (ii) smooth bromegrass ( Leyss.), (iii) tall fescue ( Schreb.), (iv) Illinois bundle flower (), (v) perennial ryegrass ( L.), (vi) switchgrass ( L.), and (vii) eastern gamagrass (). Soil without plants was used as the control. The results suggested that all plant species significantly enhanced ATR degradation by 84 to 260% compared with the control, but eastern gamagrass showed the highest capability for promoting biodegradation of ATR in the rhizosphere. More than 90% of ATR was degraded in the eastern gamagrass rhizosphere compared with 24% in the control. Dealkylation of atrazine strongly correlated with increased enzymatic activities of β-glucosidase (GLU) ( = 0.96), dehydrogenase (DHG) ( = 0.842), and fluorescein diacetate (FDA) hydrolysis ( = 0.702). The incorporation of forage species, particularly eastern gamagrass, into VBS designs will significantly promote the degradation of ATR transported into the VBS by surface runoff. Microbial parameters widely used for assessment of soil quality, e.g., DHG and GLU activities, are promising tools for evaluating the overall degradation potential of various vegetative buffer designs for ATR remediation.

Isoxaflutole is a preemergence herbicide that has been marketed as a substitute for atrazine. It is rapidly transformed to a more stable and soluble diketonitrile degradate (DKN) after field application and can further degrade to a benzoic acid degradate (BA) within soil. However, no previous research has been conducted to investigate DKN and BA sorption to metal oxide minerals. The primary objective of this research was to elucidate the interactions of DKN and BA with synthetic hydrous aluminum and iron oxides (HAO and HFO, respectively) to understand how variably charged minerals may influence adsorption of these compounds in soil. The herbicide degradates did adsorb to HAO and HFO, and the data were well described by the Freundlich model (R2 > 0.91), with Nvalues ranging from 0.89 to 1.2. Adsorption isotherms and Kd values demonstrate that BA is adsorbed to HFO to a greater extent than other degradate-mineral combinations that were studied. The degree of hysteresis between adsorption/desorption isotherms was characterized as slight (hysteresis index values < 1.7), suggesting weak DKN and BA retention to HFO and HAO oxide surfaces. Degradate adsorption was observed to greatly diminish as suspension pH increased. Attenuated total reflectance-Fourier transform infrared spectra show no evidence that DKN or BA adsorb to mineral surfaces as inner-sphere complexes under hydrated conditions. Instead DKN and BA adsorb to positively charged metal oxide surfaces as outer-sphere or diffuse ion swarm complexes via electrostatic attraction. This research indicates that metal oxides may serve as important retardants for DKN and BA migration through acidic soils enriched with aluminum and iron oxides.

There are many challenges in the accurate quantification of bacterial genes, such as the atrazine-degrading enzyme antA from Pseudomonas sp. strain ADP, from soil samples. We compared four quantitative methods for enumeration of atrazine-degrading bacteria in rhizosphere environments and utilized the optimal probe-based real-time polymerase chain reaction (PCR)-based method in an ongoing bioremediation experiment to monitor atzA copy number over time. We compared three quantitative PCR (qPCR) based methods--quantitative competitive PCR and two real-time qPCR methods--to traditional dilution-plate counting techniques. The optimal real-time qPCR assay was then used to monitor atzA copy number over time in the robust atrazine-degrading Pseudomonas sp. strain ADP-spiked rhizosphere environment. The use of sensitive and reliable probe-based real-time qPCRs for the enumeration of bacterial catabolic genes allows for their detection from soil samples and monitoring of potential degradative populations over time. The addition of arrazine-biodegrading bacteria into arrazine-contaminated sites to remove entrapped atrazine is a promising approach for mitigating atrazine pollution and its metabolites. The methodology contained herein will allow for optimal monitoring of atzA in rhizosphere soil with or without the addition of biodegradative Pseudomonas sp. strain ADP of bacteria.

The extraction and quantitation of sewage sludge proteins is a prerequisite to evaluating their role as labile C and N sources in sludge amended soil. The objective of this study was to develop extraction methodology for the routine quantitation of sewage sludge proteins. Seven sewage sludges were obtained and prepared by oven drying at 55 o C followed by extensive grinding and mixing to produce homogeneous samples

The characterization of sewage sludge proteins is necessary to better understand their degradation by microbial populations when sludges are utilized for land application. The objective of this study was to characterize the molecular weights of extractable sewage sludge proteins by dialysis partitioning and polyacrylamide gel electrophoretic (PAGE) separation. Sewage sludges obtained from seven municipalities were extracted using H 2 O and 1 M NaOH followed by purification and concentration to facilitate molecular weight determinations

The detection of veterinary antibiotics (VAs) in drinking water resources resulting from manure disposal operations has raised public health concerns. Previous studies have demonstrated the benefits of using multispecies vegetated buffer strips (VBS) to reduce agrichemical transport from agroecosystems. However, VA fate and subsequent effects of VAs on microbial activities in the root zone ofVBS have not been well documented. A growth chamber study was conducted to investigate dissipation of two commonly administered VAs, sulfamethazine (SMZ) and tetracycline (TC), and the relationship between VA dissipation and soil enzyme activities in the root zone of selected plant species. Switchgrass, eastern gammagrass, orchardgrass, and a hybrid poplar tree were grown in pots containing a Mexico silt loam/sand mixture for 3 mo, followed by plant biomass removal and collection of root zone soil. Radiolabeled (3H) SMZ or TC was applied to the soils and samples were incubated in the dark for 5 wk. Among the plant species studied, hybrid poplar showed enhanced capability for promoting SMZ dissipation. The half-lives of SMZ in soil planted to the poplar tree were significantly reduced by the enhanced enzymatic activity. Comparison of soil enzymatic activities between the antibiotic treatments revealed that fluorescein diacetate hydrolytic and glucosaminidase enzyme activities were significantly lower in TC-treated soils than in SMZ-treated soils. The beta-glucosidase activities were similar between the two VA treatments. Correlation analyses showed that the half-life of SMZ in the soil was negatively correlated with enzymatic activity. Enhanced SMZ dissipation in soil planted to hybrid poplar suggests that incorporation of this plant species in VBS may mitigate deleterious effects of SMZ in the environment.

A field lysimeter study with bare ground and five different ground covers was established to evaluate the effect of forage grasses on the fate and transport of two herbicides in leachate. The herbicides were atrazine (ATR; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and isoxaflutole [IXF; 5-cyclopropyl-4-(2-methylsulfonyl-4-trifluormethyl-benzoyl)isoxazole], which has the commercial name Balance (Aventis Crop Science, Strasbourg, France). The ground covers included orchardgrass (Dactylis glomerata L.), smooth bromegrass (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), timothy (Phleum pratense L.), and switchgrass (Panicum virgatum L.). The results suggested that the total IXF (parent + metabolites) showed higher mobility than ATR and its metabolites. Differences in the timing of transport reflected the rapid degradation of IXF to the more soluble, stable, and biologically active diketonitrile (DKN) metabolite in the system. Although grass treatments did not promote the hydrolysis of DKN, they significantly reduced its transport in the leachate through enhanced evapotranspiration. Grass treatments significantly enhanced ATR degradation in the leachates and soils, especially through N dealkylation, but they did not reduce total ATR transported in the leachate. Leachate from the orchardgrass lysimeters contained the highest proportion of ATR metabolites (64.2%). Timothy and smooth bromegrass treatments also displayed a significant increase in ATR metabolites in leachate. Grass-treated lysimeters showed higher microbial biomass carbon than bare ground. For ATR treatments, the proportion of metabolites in the leachate strongly correlated with the elevated soil microbial biomass carbon in forage treatments. In contrast, DKN degradation was poorly correlated with soil microbial biomass carbon, suggesting that DKN degradation is an abiotic process.