Anaerobic degradation of vinyl chloride in aquifer microcosms

The anaerobic degradation potential at a chloroethene-contaminated site was investigated by operating two anoxic column aquifer microcosms enriched in iron(III). One column was fed with vinyl chloride (VC) only (column A) and one with VC and acetate (column B). In column A, after about 600 pore volume exchanges (PVEs), VC started to disappear and reached almost zero VC recovery in the effluent after 1000 PVEs. No formation of ethene was observed. In column B, effluent VC was almost always only a fraction of influent VC. Formation of ethene was observed after 800 PVEs and started to become an important degradation product after 1550 PVEs. However, ethene was never observed in stoichiometric amounts compared with disappeared VC. The average stable isotope enrichment factor for VC disappearance in column A was determined to be -4.3‰. In column B, the isotope enrichment factor shifted from -10.7 to -18.5‰ concurrent with an increase in ethene production. Batch microcosms inoculated with column material showed similar isotope enrichment factors as the column microcosms. These results indicated that two degradation processes occurred, one in column A and two in parallel in column B with increasing importance of reductive dechlorination with time. This study suggests that in addition to reductive dechlorination, other degradation processes such as anaerobic oxidation should be taken into account when evaluating natural attenuation of VC and that isotope analysis can help to differentiate between different pathways of VC removal.     

Field history and dissipation of atrazine and metolachlor in Colorado

Farmers in eastern Colorado have commented that atrazine does not provide the length of weed control that they expected in fields that have received multiple applications of the herbicide. Multiple laboratory studies suggest that atrazine dissipates more rapidly in soils with a history of atrazine use compared with soils that had not been treated with the herbicide and this could be related to the above observation. Field and laboratory studies were conducted to determine the rate of dissipation of atrazine and metolachlor in fields in Colorado. The published half-lives of atrazine and metolachlor are 60 and 56 d, respectively. In the field studies, the half-lives of atrazine and metolachlor in the top 15 cm of the soil ranged between 3.5 and 7.2 d and 17.9 and 18.8 d, respectively. In laboratory studies, the half-life of atrazine varied from 1.4 to 19.8 d with the shortest half-life occurring in soils which had been treated with atrazine for at least 5 yr. The longest half-life was in a soil that had never received atrazine. The half-life of metolachlor in these same soils varied from 10.6 to 28.2 d. There was no apparent relationship between the half-life of metolachlor and the half-life of atrazine in the laboratory studies. These results confirm farmers' observation of the shorter residual activity of atrazine in Colorado fields receiving atrazine over multiple years.     

Runoff and drainage losses of atrazine, metribuzin, and metolachlor in three water management systems

Rainfall can transport herbicides from agricultural land to surface waters, where they become an environmental concern. Tile drainage can benefit crop production by removing excess soil water but tile drainage may also aggravate herbicide and nutrient movement into surface waters. Water management of tile drains after planting may reduce tile drainage and thereby reduce herbicide losses to surface water. To test this hypothesis we calculated the loss of three herbicides from a field with three water management systems: free drainage (D), controlled drainage (CD), and controlled drainage with subsurface irrigation (CDS). The effect of water management systems on the dissipation of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one), and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] in soil was also monitored. Less herbicide was lost by surface runoff from the D and CD treatments than from CDS. The CDS treatment increased surface runoff, which transported more herbicide than that from D or CD treatments. In one year, the time for metribuzin residue to dissipate to half its initial value was shorter for CDS (33 d) than for D (43 d) and CD (46 d). The half-life of atrazine and metolachlor were not affected by water management. Controlled drainage with subsurface irrigation may increase herbicide loss through increased surface runoff when excessive rain is received soon after herbicide application. However, increasing soil water content in CDS may decrease herbicide persistence, resulting in less residual herbicide available for aqueous transport.     

Sorption and degradation of alachlor and metolachlor in ground water using green sands

Reactive barriers are used for in situ treatment of contaminated ground water. Waste green sand, a by-product of gray-iron foundries that contains iron particles and organic carbon, was evaluated in this study as a low-cost reactive material for treating ground water contaminated with the herbicides alachlor [2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide] and metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide]. Batch and column tests were conducted with 11 green sands to determine transport parameters and reaction rate constants for the herbicides. Similar Fe-normalized rate constants (K(SA)) were obtained from the batch and column tests. The K(SA) values obtained for green sand iron were also found to be comparable with or slightly higher than K(SA) values for Peerless iron, a common reactive medium used in reactive barriers. Partition coefficients ranging between 3.6 and 50.2 L/kg were obtained for alachlor and between 1.0 and 54.8 L/kg for metolachlor, indicating that the organic carbon and clay in green sands can significantly retard the movement of the herbicides. Partition coefficients obtained from the batch and column tests were similar (+/-25%), but the batch tests typically yielded higher partition coefficients for green sands exhibiting greater sorption. Calculations made using transport parameters from the column tests indicate that a 1-m-thick reactive barrier will result in a 10-fold reduction in concentration of alachlor and metolachlor for seepage velocities less than 0.1 m/d provided the green sand contains at least 2% iron. This level of reduction generally is sufficient to reduce alachlor and metolachlor concentrations below maximum contaminant levels in the United States.     

Anionic polyacrylamide effects on soil sorption and desorption of metolachlor,atrazine, 2,4-D,and picloram

Polyacrylamide (PAM) treatment of irrigation water is a growing conservation technology in irrigated agriculture in recent years. There is a concern regarding the environmental impact of PAM after its application. The effects of anionic PAM on the sorption characteristics of four widely used herbicides (metolachlor, atrazine, 2,4-D, and picloram) on two natural soils were assessed in batch equilibrium experiments. Results showed that PAM treatment kinetically reduced the sorption rate of all herbicides, possibly due to the slower diffusion of herbicide molecules into interior sorption sites of soil particles that were covered and/or cemented together by PAM. The equilibrium sorption and desorption amounts of nonionic herbicides (metolachlor and atrazine) were essentially unaffected by anionic PAM, even under a high PAM application rate, while the sorption amounts of anionic herbicides (2,4-D and picloram) were slightly decreased and their desorption amounts increased little. The impact mechanisms of PAM were related to the molecular characteristics of PAM and herbicides. The negative effects of PAM on the sorption of anionic herbicides are possibly caused by the enhancement of electrostatic repulsion by presorbed anionic PAM and competition for sorption sites. However, steric hindrance of the large PAM molecule weakens its influence on herbicide sorption on interior sorption sites of soil particles, which probably leads to the small interference on herbicide sorption, even under high application rates.     

Adsorption and desorption of metolachlor and metolachlor metabolites in vegetated filter strip and cultivated soil

Previous studies have indicated that dissolved-phase metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide] transported in surface runoff is retained by vegetative filter strips to a greater degree than either metolachlor oxanilic acid 12-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxo-acetic acid] (OA) or metolachlor ethanesulfonic acid [2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl-1)amino]-2-oxoethanesul-fonic acid] (ESA), two primary metabolites of metolachlor. Adsorption-desorption of ESA and OA in vegetated filter strip soil (VFSS) has not been evaluated, yet these data are required to assess the mobility of these compounds in VFSS. The objective of this experiment was to compare metolachlor, ESA, and OA adsorption and desorption parameters between VFSS and cultivated soil (CS). Adsorption and desorption isotherms were determined using the batch equilibrium procedure. With the exception of a 1.7-fold increase in organic carbon content in the VFSS, the evaluated chemical and physical properties of the soils were similar. Sorption coefficients for metolachlor were 88% higher in VFSS than in CS. In contrast, sorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, sorption coefficients for ESA and OA were at least 79% lower in both soils. Metolachlor desorption coefficients were 59% higher in the VFSS than in the CS. Desorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, desorption coefficients for ESA and OA were at least 66% lower in both soils. These data indicate that the mobility of ESA and OA will be greater than metolachlor in both soils. However, higher organic carbon content in VFSS relative to CS may limit the subsequent transport of metolachlor from the vegetated filter strip.     

Spatial variability of atrazine and metolachlor dissipation on dryland no-tillage crop fields in Colorado

An area of interest in precision farming is variable-rate application of herbicides to optimize herbicide use efficiency and minimize negative off-site and non-target effects. Site-specific weed management based on field scale management zones derived from soil characteristics known to affect soil-applied herbicide efficacy could alleviate challenges posed by post-emergence precision weed management. Two commonly used soil-applied herbicides in dryland corn (Zea mays L.) production are atrazine and metolachlor. Accelerated dissipation of atrazine has been discovered recently in irrigated corn fields in eastern Colorado. The objectives of this study were (i) to compare the rates of dissipation of atrazine and metolachlor across different soil zones from three dryland no-tillage fields under laboratory incubation conditions and (ii) to determine if rapid dissipation of atrazine and/or metolachlor occurred in dryland soils. Herbicide dissipation was evaluated at time points between 0 and 35 d after soil treatment using a toluene extraction procedure with GC/MS analysis. Differential rates of atrazine and metolachlor dissipation occurred between two soil zones on two of three fields evaluated. Accelerated atrazine dissipation occurred in soil from all fields of this study, with half-lives ranging from 1.8 to 3.2 d in the laboratory. The rapid atrazine dissipation rates were likely attributed to the history of atrazine use on all fields investigated in this study. Metolachlor dissipation was not considered accelerated and exhibited half-lives ranging from 9.0 to 10.7 d in the laboratory.     

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.     

Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water

Mesotrione is a carotenoid biosynthesis-inhibiting herbicide labeled for pre-emergence and postemergence weed control in corn production. Understanding the factors that influence the dissipation of mesotrione in soil and in the plant-available water (PAW) is important for the environmental fate assessment and optimal weed management practices. The present research investigated the role of soil properties and microbial activities on the interrelated sorption and degradation processes of mesotrione in four soils by direct measurements of PAW. We found that mesotrione bound to the soils time dependently, with approximately 14 d to reach equilibrium. The 24-h batch-slurry equilibrium experiments provided the sorption partition coefficient ranging from 0.26 to 3.53 L kg(-1), depending on soil organic carbon and pH. The dissipation of mesotrione in the soil-bound phase was primarily attributed to desorption to the PAW. Degradation in the PAW was rapid and primarily dependent on microbial actions, with half-degradation time (DT(50)) <3 d in all four soils tested. The rapid degradation in the PAW became rate limited by sorption as more available molecules were depleted in the soil pore water, resulting in a more slowed overall process for the total soil-water system (DT(50) <26 d). The dissipation of mesotrione in the PAW was due to microbial metabolism and time-dependent sorption to the soils. A coupled kinetics model calibrated with the data from the laboratory centrifugation technique provided an effective approach to investigate the interrelated processes of sorption and degradation in realistic soil moisture conditions.     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.     

Atrazine dissipation in s-triazine-adapted and nonadapted soil from Colorado and Mississippi: implications of enhanced degradation on atrazine fate and transport parameters

Soil bacteria have developed novel metabolic abilities resulting in enhanced atrazine degradation. Consequently, there is a need to evaluate the effects of enhanced degradation on parameters used to model atrazine fate and transport. The objectives of this study were (i) to screen Colorado (CO) and Mississippi (MS) atrazine-adapted and non-adapted soil for genes that code for enzymes able to rapidly catabolize atrazine and (ii) to compare atrazine persistence, Q(10), beta, and metabolite profiles between adapted and non-adapted soils. The atzABC and/or trzN genes were detected only in adapted soil. Atrazine's average half-life in adapted soil was 10-fold lower than that of the non-adapted soil and 18-fold lower than the USEPA estimate of 3 to 4 mo. Q(10) was greater in adapted soil. No difference in beta was observed between soils. The accumulation and persistence of mono-N-dealkylated metabolites was lower in adapted soil; conversely, under suboptimal moisture levels in CO adapted soil, hydroxyatrazine concentrations exceeded 30% of the parent compounds' initial mass. Results indicate that (i) enhanced atrazine degradation and atzABC and/or trzN genes are likely widespread across the Western and Southern corn-growing regions of the USA; (ii) persistence of atrazine and its mono-N-dealkylated metabolites is significantly reduced in adapted soil; (iii) hydroxyatrazine can be a major degradation product in adapted soil; and (iv) fate, transport, and risk assessment models that assume historic atrazine degradation pathways and persistence estimates will likely overpredict the compounds' transport potential in adapted soil.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

Organic manure and urea effect on metolachlor transport through packed soil columns

Application of organic manure (OM) amendments and nitrogen fertilizers can affect the sorption and movement of pesticides in soil. This study summarizes the sorption and leaching of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl) acetamide] in soils after cow (Bos taurus) manure (2.5 and 5.0%) and urea (60 and 120 kg N ha(-1)) amendments in batch and column experiments. Both cow manure and urea applications increased metolachlor sorption in soils. The values of the Freundlich adsorption parameter K(r)(1/n) for treatments T0, T1 (OM), and T2 (OM) were 2.31, 3.32, and 3.96 in Soil 1; 2.02, 2.77, and 3.32 in Soil 2; and 1.10, 1.46, and 2.02 in Soil 3, respectively. Similarly, K(f)(1/n) values for treatment T1 (urea) and T2 (urea) were 2.37 and 2.84 in Soil 1; 2.16 and 2.83 in Soil 2; and 1.50 and 1.70 in Soil 3, respectively. Column leaching studies using Soil 1 indicated that OM application drastically reduced the metolachlor leaching losses from 50% (natural soil) to < 1.0% (5.0% OM amendment). Likewise, urea application also decreased metolachlor mobility and leaching losses in columns treated with 60 and 120 kg N ha(-1) urea were 33 and 20%, respectively. The reduction in the metolachlor leaching losses was achieved through the increase in the sorption capability of the OM- and urea-amended soil. Therefore, coapplication of metolachlor with cow manure or urea fertilizers will not enhance metolachlor mobility and reduces metolachlor leaching losses in low-organic-matter soil.     

Pyrene degradation in forest humus microcosms with or without pine and its mycorrhizal fungus

The mineralization potential of forest humus and the self-cleaning potential of a boreal coniferous forest environment for polycyclic aromatic hydrocarbon (PAH) compounds was studied using a model ecosystem of acid forest humus (pH = 3.6) and pyrene as the model compound. The matrix was natural humus or humus mixed with oil-polluted soil in the presence and absence of Scots pine (Pinus sylvestris L.) and its mycorrhizal fungus (Paxillus involutus). The rates of pyrene mineralization in the microcosms with humus implants (without pine) were initially insignificant but increased from Day 64 onward to 47 microg kg(-1) d(-1) and further to 144 microg kg(-1) d(-1) after Day 105. In the pine-planted humus microcosms the rate of mineralization also increased, reaching 28 microg kg(-1) d(-1) after Day 105. The 14CO2 emission was already considerable in nonplanted microcosms containing oily soil at Day 21 and the pyrene mineralization continued throughout the study. The pyrene was converted to CO2 at rates of 0.07 and 0.6 microg kg(-1) d(-1) in the oily-soil implanted microcosms with and without pine, respectively. When the probable assimilation of 14CO2 by the pine and ground vegetation was taken into account the most efficient microcosm mineralized 20% of the 91.2 mg kg(-1) pyrene in 180 d. The presence of pine and its mycorrhizal fungus had no statistically significant effect on mineralization yields. The rates of pyrene mineralization observed in this study for forest humus exceeded the total annual deposition rate of PAHs in southern Finland. This indicates that accumulation in forest soil is not to be expected.     

Modeling concentration-dependent sorption-desorption hysteresis of atrazine in a loam soil

Nonequilibrium sorption plays an active role in the transport of organic contaminants in soil. We applied a two-stage, one-rate model (2S1R) and a new, nonlinear variant (2S1RN) of this model to examine the effects of wastewater irrigation on the sorption kinetics of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) in soil. The models were applied to previously published sorption-desorption data sets, which showed pronounced deviations between sorption curves and desorption curves (sorption-desorption hysteresis). Moreover, the slopes of the desorption curves decreased with decreasing concentration. Different treatments had been used, and two experimental time steps (2 and 14 d) were used. Treatments considered were lipid removal, fulvic and humic acid removal, and untreated soil. The 2S1R model was unable to reproduce the observed type of hysteresis, but the 2S1RN model, which assumes that the sorption-desorption process follows a power function relationship, was able to reproduce the observed type of hysteresis. Visually, applying the new model improved the model fits in all test cases. Statistically, as tested by an extra sum of squares analysis, the new model performed significantly better in 50% of all test cases. According to an example simulation, the choice of the sorption model has a considerable impact on the prediction of atrazine transport in soil.     

Spatial distribution of enhanced atrazine degradation across northeastern Colorado cropping systems

Reports of enhanced atrazine degradation and reduced residual weed control have increased in recent years, sparking interest in identifying factors contributing to enhanced atrazine degradation. The objectives of this study were to (i) assess the spatial distribution of enhanced atrazine degradation in 45 commercial farm fields in northeastern Colorado (Kit Carson, Larimer, Logan, Morgan, Phillips, and Yuma counties) where selected cultural management practices and soil bio-chemo-physical properties were quantified; (ii) utilize Classification and Regression Tree (CART) Analysis to identify cultural management practices and (or) soil bio-chemophysical attributes that are associated with enhanced atrazine degradation; and (iii) translate our CART Analysis into a model that predicts relative atrazine degradation rate (rapid, moderate, or slow) as a function of known management practices and (or) soil properties. Enhanced atrazine degradation was widespread within a 300-km radius across northeastern Colorado, with approximately 44% of the fields demonstrating rapid atrazine degradation activity (laboratory-based dissipation time halflife [DT50] < 3 d). The most rapid degradation rates occurred in fields that received the most frequent atrazine applications. Classification and Regression Tree Analysis resulted in a prediction model that correctly classified soils with rapid atrazine DT50 80% of the time and soils with slow degradation (DT50 > 8 d) 62.5% of the time. Significant factors were recent atrazine use history, soil pH, and organic matter content. The presence/absence of atzC polymerase chain reaction (PCR) product was not a significant predictor variable for atrazine DT50. In conclusion, enhanced atrazine degradation is widespread in northeastern Colorado. If producers know their atrazine use history, soil pH, and OM content, they should be able to identify fields exhibiting enhanced atrazine degradation using our CART Model.     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.     

EPA worst case water microcosms for testing phage biocontrol of Salmonella

A microplate method was developed as a tool to test phages for their ability to control Salmonella in aqueous environments. The method used EPA (U.S. Environmental Protection Agency) worst case water (WCW) in 96-well plates. The WCW provided a consistent and relatively simple defined turbid aqueous matrix, high in total organic carbon (TOC) and total dissolved salts (TDS), to simulate swine lagoon effluent, without the inconvenience of malodor and confounding effects from other biological factors. The WCW was originally defined to simulate high turbidity and organic matter in water for testing point-of-use filtration devices. Use of WCW to simulate lagoon effluent for phage testing is a new and innovative application of this matrix. Control of physical and chemical parameters (TOC, TDS, turbidity, temperature, and pH) allowed precise evaluation of microbiological parameters (Salmonella and phages). In a typical application, wells containing WCW were loaded with Salmonella enterica susp. enterica serovar Typhimurium (ATCC14028) and treated with phages alone and in cocktail combinations. Mean Salmonella inactivation rates (k, where the lower the value, the greater the inactivation) of phage treatments ranged from -0.32 to -1.60 versus -0.004 for Salmonella controls. Mean log(10) reductions (the lower the value, the greater the reduction) of Salmonella phage treatments were -1.60 for phage PR04-1, -2.14 for phage PR37-96, and -2.14 for both phages in a sequential cocktail, versus -0.08 for Salmonella controls. The WCW microcosm system was an effective tool for evaluating the biocontrol potential of Salmonella phages.     

Modeling of sorption and biodegradation of parathion and its metabolite paraoxon in soil

To investigate the distribution of parathion [O,O-diethyl O-(4-nitrophenyl) phosphorothioate] and its highly toxic metabolite paraoxon [O,O-diethyl O-(4-nitrophenyl)phosphate] between the soluble and sorbed pools in the soil, batch experiments were conducted to evaluate the rate of adsorption and desorption of 14C-labeled parathion and paraoxon in soil. The mineralization and degradation of these products were also investigated during a 56-d experiment under controlled laboratory conditions. Adsorption patterns indicated initial fast adsorption reactions occurring within 4 h for both parathion and paraoxon. We also observed the formation of nonextractable residues. The paraoxon was more intensively degraded than the parathion, and production of p-nitrophenol and other metabolites was observed. A kinetic model was developed to describe the sorption and biodegradation rates of parathion, taking into account the production, retention, and biodegradation of paraoxon, the main metabolite of parathion. After fitting the parameters of the model we made a simulation of the kinetics of the appearance and disappearance of paraoxon. From the simulation we predicted a quantity of metabolite in the liquid phase amounting to 1% of the quantity of parathion initially applied. This is in agreement with the experimental data.