Robert N. Lerch

Hydroxylated atrazine degradation products in a small Missouri stream

This research assessed the occurrence of hydroxylated atrazine degradation products (HADPs) in streamwater from Goodwater Creek watershed in the claypan soil region of northeastern Missouri. Streamwater was sampled weekly from June 1992 to December 1994 at a V-notch weir used to measure streamflow for this 7250-ha watershed. Filtered water samples were prepared by cation exchange solid-phase extraction and analyzed for hydroxyatrazine (HA), deethylhydroxyatrazine (DEHA), and deisopropylhydroxyatrazine (DIHA) by high-performance liquid chromatography with UV detection. HADPs were confirmed by mass spectrometry and an alternative HPLC/UV method. Frequency of HADP detection was 100% for HA, 25% for DEHA, and 6% for DIHA. Concentrations ranged from 0.18 to 5.7 μg L -1 for HA, from <0.12 to 1.9 μg L -1 for DEHA, and from <0.12 to 0.72 μg L -1 for DIHA. These results establish that HADPs can contaminate surface water and that HA contamination of surface water is a significant fate pathway for atrazine in this watershed.

Bioremediation of atrazine-contaminated soil by forage grasses: transformation, uptake, and detoxification.

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 (<15%) or was taken up by plants (<4%). Biological degradation or chemical hydroxylation of soil ATR was enhanced by 20 to 45% in forage treatment compared with the control. Of the ATR residues remaining in soil, switchgrass degraded more than 80% to less toxic metabolites, with 47% of these residues converted to the less mobile hydroxylated metabolites 25 d after application. The strong correlation between the degradation of N-dealkylated ATR metabolites and the increased microbial biomass carbon in forage treatments suggested that enhanced biological degradation in the rhizosphere was facilitated by the forages. Hydroxylated ATR degradation products were the predominant ATR metabolites in the tissues of switchgrass and tall fescue. In contrast, the N-dealkylated metabolites were the major degradation products found in the other cool-season species. The difference in metabolite patterns between the warm- and cool-season species demonstrated their contrasting detoxification mechanisms, which also related to their tolerance to ATR exposure. Based on this study, switchgrass is recommended for use in riparian buffers designed to reduce ATR toxicity and mobility due to its high tolerance and strong degradation capacity.

Reducing herbicides and veterinary antibiotics losses from agroecosystems using vegetative buffers.

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.

Stimulated Rhizodegradation of Atrazine by Selected Plant Species

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.

Long-term agroecosystem research in the central Mississippi river basin: goodwater creek experimental watershed and regional nutrient water quality data.

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.

Streambank erosion in two watersheds of the Central Claypan Region of Missouri, United States

This study was undertaken to assess the importance of streambank erosion to the total in-stream sediment of two agricultural watersheds within the Central Claypan Areas. The objective of this research was to determine the effect of stream order, adjacent land use, and season on streambank erosion rates. Thirty-four study sites were established in 2007 and 2008 within Crooked and Otter Creek watersheds, two claypan watersheds located in northeastern Missouri. At each site, field assessments of severely to very severely eroding bank length were determined along 300 to 400 m (984 to 1,312 ft) stream reaches. A factorial experimental design was implemented with four land uses (crop, forest, pasture, and riparian forest), three seasons, and three stream orders (1st, 2nd, and 3rd). Each treatment was replicated three times for each stream order, except for the cropped 3rd order treatment as only one suitable treatment site could be found. Streambank erosion was measured using erosion pins, which were installed in randomly assigned plots that included at least 20% of the eroded bank length within each site. The effect of different seasons was assessed by measuring the length of the exposed pins three times per year (March, July, and November). The bulk density and carbon and nitrogen content of bank material were also determined. Sediment loss rates showed that season and the three-way interaction between season, land use, and stream order were highly significant. Erosion rates were consistently higher in the winter months than spring/summer and fall seasons; however, the significant three-way interaction precluded a simple interpretation of the seasonal effect. Soil nutrient concentration data showed that forest sites had significantly lower C and N concentrations than other land uses. At the watershed scale, bank sediment accounted for 79% to 96% of the total in-stream sediment and 21% to 24% of the total N exported from the study area. These results indicate that streambanks are the dominant source of sediment and a significant source of N in these streams. Therefore, improved management of riparian areas to decrease streambank erosion would result in significant water quality improvement in streams of the Central Claypan Areas in northeastern Missouri.

Sulfamethazine Sorption to Soil: Vegetative Management, pH, and Dissolved Organic Matter Effects.

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, and >1000 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 (ABS > GBS > RC). 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.

Analysis of Hydroxylated Atrazine Degradation Products in Soils

Abstract Hydroxylated atrazine degradation products (HADPs) have been shown to persist in soils and contaminate surface waters throughout the Midwestern United States, yet expedient analytical methods for their determination in soils are lacking. The developed method employs a mixed-mode extractant [3:1 0.5M KH2PO4, pH 7.5:CH3CN, v/v] designed to disrupt the two primary mechanisms of HADP sorption to soils: cation exchange and hydrophobic interactions. Strong anion exchange solid-phase extraction (SPE) is used for sample clean-up followed by isolation and concentration using strong cation exchange SPE. HADPs were quantitated by LC/MS/MS and LC/UV. Method recoveries were determined by spiking 14C-HADPs into three soils with lengthy atrazine use histories. Recoveries ranged from 74–81% for 14C-hydroxyatrazine (HA), 79–88% for 14C-deethlhydroxyatrazine (DEHA), and 64–77% for 14C-deisopropylhydroxyatrazine (DIHA). HADP soil concentrations ranged from 66.9–178 μ kg−1 for HA, 8.99–40.9 μg kg−1 for DEHA, and 5.27–16.2 μg kg−1 for DIHA. Utilization of the mixed-mode procedure, in conjunction with existing methodologies for analysis of atrazine and its chlorinated metabolites, enables a more complete and accurate quantitation of all the major stable atrazine residues in soiis. HADPs comprised an average of 91% of the total atrazine residues in three agricultural surface soils, with HA the major constituent present in all soils. These data indicate that repeated atrazine use results in HADPs as the predominant atrazine residues in surface soils.

Long-Term Agroecosystem Research in the Central Mississippi River Basin: Dissolved Nitrogen and Phosphorus Transport in a High-Runoff-Potential Watershed

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.

Nutrient Sources and Transport from the Goodwater Creek Experimental Watershed

The Goodwater Creek watershed has been monitored for flow since 1971 and for dissolved nutrients since 1991 for 3 nested watersheds (12.1, 31.5 and 73.0 km2 drainage area). This watershed includes row crop land (76%), grassland (14%), woodland (6%) and a small town at the upper end (4%). The objectives of this paper are to analyze nutrient loadings at the 3 gauging stations from 1991 to 2004. Daily, monthly and annual loadings and flow-weighted concentrations of ammonium-nitrogen, nitrate-nitrogen, dissolved phosphorus and atrazine were calculated and analyzed using the non parametric tests for differences, homogeneity, and trends. Atrazine was included in the analysis as one compound not implicated with point source discharges in the watershed. Dissolved phosphorus and ammonium-nitrogen concentrations and loads at the upstream weir were significantly greater than those at the two downstream weirs, which suggest wastewater was a potential source of these nutrients. Possible explanations for these differences were drawn from our knowledge of the watershed and tested with a SWAT model of the watershed. These findings provide insight to what should be included in a complete analysis of the nutrient sources in the watershed and how stream processes affect nutrient loadings.