Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content

Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils.     

Runoff and dissolved organic carbon loss from a paired-watershed study of three adjacent agricultural Watersheds

Organic matter plays several important roles in the biogeochemistry of terrestrial and aquatic ecosystems including the mobilization and transport of nutrients and pollutants. Cropping, tillage practices and vegetative buffer strip installation affect losses of dissolved organic carbon (DOC). While many studies show reductions in pollutant export from agroecosystems where vegetative buffers have been implemented, buffer strips may be a source of DOC and contribute to surface water pollution. Using a paired-watershed approach, the objectives of this study were to determine the effect of grass and agroforestry buffers on runoff and DOC loss, compare runoff and DOC losses between the growing and fallow seasons, and investigate crop effects on runoff and DOC losses. The study design consisted of three small agricultural Watersheds in a no-till, maize-soybean rotation located in the claypan region of northeast Missouri, USA; one watershed was planted with grass buffer strips, one with agroforestry buffer strips, and one unaltered watershed served as the control. Runoff and DOC loss were measured during a six-year calibration period (1991–1997) prior to buffer installation and for a nine-year treatment period (1997–2006). The grass buffer strips significantly decreased runoff by 8.4% (p = 0.015) during the treatment period while the agroforestry buffer system exhibited no significant change in runoff (p = 0.207). Loss of DOC was not significantly affected by grass or agroforestry buffer installation (p = 0.535 and p = 0.246, respectively). Additionally, no significant difference in runoff or DOC loss was found between crops (maize and soybean) or between seasons (growing and fallow). Overall, this study indicates that grass buffer systems are effective at reducing runoff and that DOC contamination of surface waters is not exacerbated by either type of vegetative buffer strip.     

Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay

Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots, respectively. When the initial irrigation was delayed for 24h, irrespective of antecedent moisture conditions, a 30% reduction in aldicarb degradation occurred. This study illustrates the deeper transport of pesticides and their increased persistence when applied to initially dry soils.     

Vegetative Buffer Strips for Reducing Herbicide Transport in Runoff: Effects of Buffer Width,Vegetation, and Season

The effectiveness of vegetative buffer strips (VBS) for reducing herbicide transport has not been well documented for runoff prone soils. A multi‐year plot‐scale study was conducted on an eroded claypan soil with the following objectives: (1) assess the effects of buffer width, vegetation, and season on runoff transport of atrazine (ATR), metolachlor (MET), and glyphosate; (2) develop VBS design criteria for herbicides; and (3) compare differences in soil quality among vegetation treatments. Rainfall simulation was used to create uniform antecedent soil water content and to generate runoff. Vegetation treatment and buffer width impacted herbicide loads much more than season. Grass treatments reduced herbicide loads by 19‐28% and sediment loads by 67% compared to the control. Grass treatments increased retention of dissolved‐phase herbicides by both infiltration and adsorption, but adsorption accounted for the greatest proportion of retained herbicide load. This latter finding indicated VBS can be effective on poorly drained soils or when the source to buffer area ratio is high. Grass treatments modestly improved surface soil quality 8‐13 years after establishment, with significant increases in organic C, total N, and ATR and MET sorption compared to continuously tilled control. Herbicide loads as a function of buffer width were well described by first‐order decay models which indicated VBS can provide significant load reductions under anticipated field conditions.     

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.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides

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.