Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).     

Metolachlor persistence in laboratory and field soils under Indian tropical conditions

Abstract

Metolachlor [2‐chloro‐N‐(2‐methoxy‐1‐methylethyl)‐2'‐ethyl‐6'‐methyl acetanilide] dissipation under both field and laboratory conditions were studied during summer season in an Indian soil. Metolachlor was found to have moderate persistence with a half‐life of 27 days in field. The herbicide got leached down to 15–30 cm soil layer and residues were found up to harvest day of the sunflower crop in both 0–15 cm and 15–30 cm soil layers. Metolachlor was found to be more persistent in laboratory studies conducted for 190 days. The rate of degradation was faster in soil under flooded partial anaerobic conditions as compared to aerobic soil with a half‐life of 44.3 days. In aerobic soil, metolachlor was very stable with only 49% dissipation in 130 days. Residues remained in both the soils up to the end of the experimental period of 190 days.     

Metolachlor persistence in laboratory and field soils under Indian tropical conditions

Metolachlor [2-chloro-N-(2-methoxy-1-methylethyl)-2'-ethyl-6'- methyl acetanilide] dissipation under both field and laboratory conditions were studied during summer season in an Indian soil. Metolachlor was found to have moderate persistence with a half-life of 27 days in field. The herbicide got leached down to 15-30 cm soil layer and residues were found up to harvest day of the sunflower crop in both 0-15 cm and 15-30 cm soil layers. Metolachlor was found to be more persistent in laboratory studies conducted for 190 days. The rate of degradation was faster in soil under flooded partial anaerobic conditions as compared to aerobic soil with a half-life of 44.3 days. In aerobic soil, metolachlor was very stable with only 49% dissipation in 130 days. Residues remained in both the soils up to the end of the experimental period of 190 days.     

Leaching of trifluralin,metolachlor, and metribuzin in a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied in field plots located on a Commerce clay loam soil near Baton Rouge, Louisiana at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The half-lives of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth were found to be 54.7 days, 35.8 days and 29.8 days, respectively. The proportion of trifluralin, metolachlor, and metribuzin in the top 0-15 cm soil depth was 94.7%, 86.6%, and 75.4%, respectively of that found in the top 0-60 cm soil depth 30 days after application. Trifluralin concentrations were within a range of 0.026 ng/mL to 0.058 ng/mL in 1 m deep well water, and between 0.007 ng/mL and 0.039 ng/mL in 2 m deep well water over a 62 day period after application. Metolachlor concentrations in the 1 m and 2 m wells ranged from 3.62 ng/mL to 82.32 ng/mL and 8.44 ng/mL to 15.53 ng/mL, respectively. Whereas metribuzin concentrations in the 1 m and 2 m wells ranged from 0.70 ng/mL to 27.75 ng/mL and 1.71 ng/mL to 3.83 ng/mL, respectively. Accordingly, trifluralin was found to be strongly adsorbed on the soil and showed negligible leaching. Although metolachlor and metribuzin were also both readily adsorbed on the soil, their leaching potential was high. As a result, in the clay loam soil studied, metribuzin concentration in groundwater with shallow aquifers is likely to exceed the 10 mg/L US Environmental Protection Agency (EPA) advisory level for drinking water early in the application season, whereas trifluralin and metolachlor concentrations are expected to remain substantially lower than their respective 2 ng/mL and 175 ng/mL EPA advisory levels.     

Aerobic and anaerobic degradation of profluralin and trifluralin

Abstract

The degradation of profluralin [N‐(cyclopropylmethyl)‐α,α,α‐trifluoro‐2,6‐dinitro‐N‐propyl‐]p‐toluidine] and trifluralin (α,α,α‐trifluoro‐2,6‐dinitro‐N,N‐dipropyl‐p‐toluidine) was studied under aerobic and anaerobic soil conditions. Three soils (Goldsboro loamy sand, Cecil loamy sand, Drummer clay loam) were each treated with 1 ppmw herbicide; anaerobic conditions were maintained by flooding. Soil samples were extracted monthly and subjected to TLC analysis. No degradation was detected in sterile controls. Aerobic degradation of both herbicides was greatest in the Cecil loamy sand soil over the entire incubation period. Degradation of profluralin in Cecil soil under aerobic conditions was 86 percent after 4 months with three products detected; 83 percent of the trifluralin was degraded with two products detected. Anaerobic degradation accounted for 72 percent of the profluralin and 78 percent of the trifluralin after 4 months. Degradation of both herbicides increased with incubation time for the first 3 months and decreased slightly thereafter. Generally there was more extensive degradation (percent and in number of products formed) of profluralin than trifluralin under the conditions tested. More degradation products were detected for both herbicides under aerobic conditions than under anaerobic conditions.     

Runoff of trifluralin,metolachlor, and metribuzin from a clay loam soil of Louisiana

Trifluralin[2,6-dinitro-N,N-dipropyl-4-(trifluormethyl)benzenamine], metolachlor[2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] and metribuzin[4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)one] were applied as pre-emergent herbicides to soybean plots in Louisiana (LA) at the rate of 1683 g/ha, 2759 g/ha and 609 g/ha, respectively. The concentrations of trifluralin in the runoff water ranged between 0.09 ng/mL and 0.02 ng/mL, which is lower than the 2 ng/mL US Environmental Protection Agency (EPA) advisory level for trifuralin in drinking water. Metolachlor concentrations in the runoff water ranged from 9.0 ng/mL to 221.5 ng/mL, which is both lower and higher than the 175 ng/mL EPA advisory level for metolachlor. Similarly, metribuzin concentrations in the runoff water ranged between 1.5 ng/mL and 56.2 ng/mL, which is also lower and higher than the 10 ng/mL EPA advisory level for metribuzin. Accordingly, from the field plots located on a Commerce clay loam soil in LA, although the concentration of trifluralin in runoff water were substantially lower than the EPA advisory level, metolachlor and metribuzin concentrations are likely to exceed the EPA advisory levels early on in the application season with a subsequent rapid decrease to safe levels. The total loss of trifluralin in runoff water was 0.005% of the applied amount over an 89 day period after application. The total loss of metolachlor and metribuzin in the runoff water was 4.67% and 5.36% of the applied amount, respectively, over a 22 day period after application. As such, there was almost no movement of trifluralin in the runoff water, whereas metolachlor and metribuzin were much more easily moved.     

Degradation of Metribuzin in Two Soil Types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

Persistence of seven pesticides as influenced by soil moisture1

Abstract

Pesticides are often applied in combination, but less‐often is soil persistence measured this way. The present field and laboratory study determined relative persistence of five herbicides and two insecticides, co‐applied, as a function of three soil water contents. Losses were modeled adequately by first‐order dissipation, with no significant improvement by using a two‐compartment model. The order of persistence in a silt loam, at 25% moisture, was carbofuran < cyanazine < metribuzin = alachlor < atrazine < ethoprop < metolachlor (t_½ ranged from 7–91 days). Carbofuran degradation increased greatly from 12–25% soil moisture; atrazine was unaffected by 12–35%, whereas the remaining compounds showed limited increasing loss in wetter soil. Field‐based persistence was more variable, but generally similar to lab rankings.     

Biodegradation of triazine herbicide metribuzin by the strain Bacillus sp. N1

By enrichment culturing of soil contaminated with metribuzin, a highly efficient metribuzin degrading bacterium, Bacillus sp. N1, was isolated. This strain grows using metribuzin at 5.0% (v/v) as the sole nitrogen source in a liquid medium. Optimal metribuzin degradation occurred at a temperature of 30ºC and at pH 7.0. With an initial concentration of 20 mg L^?1, the degradation rate was 73.5% in 120 h. If the initial concentrations were higher than 50 mg L^?1, the biodegradation rates decreased as the metribuzin concentrations increased. When the concentration was 100 mg L^?1, the degradation rate was only 45%. Degradation followed the pesticide degradation kinetic equation at initial concentrations between 5 mg L^?1 and 50 mg L^?1. When the metribuzin contaminated soil was mixed with strain N1 (with the concentration of metribuzin being 20 mg L^?1 and the inoculation rate of 10¹¹ g^?1 dry soil), the degradation rate of the metribuzin was 66.4% in 30 days, while the degradation rate of metribuzin was only 19.4% in the control soil without the strain N1. These results indicate that the strain N1 can significantly increase the degradation rate of metribuzin in contaminated soil.     

Movement of metolachlor and terbuthylazine in core and packed soil columns

Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Degradation of Metolachlor in Crude Extract of Aspergillus Flavus

Abstract

Crude enzyme from a soil fungus, Aspergillus flavus, was isolated from a field soil following repeated applications of metolachlor [2-Chloro-N-(methoxy-1-methylethyl)-2′-ethyl-6′-methyl acetanilide]. Metolachlor hydrolysis by the crude enzyme extract was determined by enzyme assay. The tests were performed in phosphate buffer, pH 7.5, and the reaction was carried out at two herbicide concentrations (20 and 100 μg mL^?1) and two crude extract volumes (0.2 and 0.5 mL of the homogenized crude extract mixture). The rate of metolachlor degradation was found faster in samples containing higher volume of crude extract, (T _1/2, 5.7 h) for both concentrations of the herbicide. The activities of enzymes responsible for dechlorination coupled with hydroxylation, N-dealkylation, and breaking of amide linkage were found responsible in the degradation.     

Degradation of metribuzin in two soil types of Lebanon

The degradation of metribuzin [4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one] as influenced by soil type, temperature, humidity, organic fertilizers, soil sterilization, and ultra-violet radiation was studied in two soil types of Lebanon under laboratory conditions. The two soil types were sandy loam and clay. Deamination of metribuzin in the sandy loam soil to its deaminometribuzin (DA) derivative was basically a result of biological activity. In the clay soil the first metabolite diketometribuzin (DK) was a result of oxidative desulfuration, while diketo-deaminometribuzin (DADK) was the product of reductive deamination. The two soils represented major differences in the pesticide transformation processes. Photodecomposition on the soil surface and in aqueous media was also an important process in the degradation of metribuzin. Furthermore, the increase in soil organic matter enhanced degradation.     

The aerobic soil degradation of spinosad ‐ a novel natural insect control agent

Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either ¹⁴C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.     

Fate of autumn-applied metolachlor in a clay loam in the northern U.S. Corn Belt

Application of herbicides in autumn is of interest to land managers who seek to reduce the number of field operations during spring in the northern Corn Belt. A limited number of herbicides, however, posses the physical characteristics that are required to minimize loss from soil over winter. This study examined the fate of one of these herbicides, metolachlor, during three consecutive winters (1994-1995, 1995-1996, and 1996-1997) near Morris, MN. Metolachlor was applied to the top 5 cm of a clay loam that was packed into a 1.8-m long plastic pipe. The pipe was then set inside a larger diameter 1.8-m long plastic pipe that was buried vertically in the field. The gap between the pipes was insulated along the sides and sealed at the top; this configuration allowed collection of leachate and extraction of the smaller diameter pipe while the field soil was frozen. The experimental design was replicated thrice with sample date (date that the smaller diameter pipes were extracted from the field) as the main treatment. Pipes were extracted from the field at least twice during winter and sectioned into 2 cm or larger increments. The soil contained within these sections was then analyzed for metolachlor. Downward movement of metolachlor occurred in the soil profile during the autumn, but only in 1995. This movement was likely caused by exclusion during pore ice formation as the soil froze. At the time of complete soil thaw in spring, the majority of metolachlor was still detected in the zone of application (0-5 cm depth). Some metolachlor, however, was detected 1 to 3 cm below the zone of application in all three years. Downward movement during thaw was due primarily to infiltration of snowmelt and rain. Metolachlor was most vulnerable to degradation during spring, but some loss occurred in autumn prior to freeze-up. This study suggests that autumn-applied metolachlor moves little in a repacked clay loam profile during winter. Further studies are warranted in evaluating movement under a range of soil physical properties and management practices.     

Effects of soil type upon metolachlor losses in subsurface drainage

A field experiment at La Bouzule (Lorraine, France) investigated metolachlor movement to subsurface drains in two soil types, a silt loam and a heavy clay soil, under identical agricultural management practices and climatic conditions. Drainage volumes and concentrations of metolachlor in the soil plough layer and drainwater were monitored after herbicide application from May 1996 to February 1997, and from May to August 1998. Total losses in drainwater were 0.08% and 0.18% of the amount applied to the silt loam compared with 0.59% and 0.41% for the clay soil, in 1996/97 and 1998, respectively. In 1996/97, 32% of total metolachlor loss from the silt loam and 91% from the clay soil occurred during the spring/summer period following treatment. Peak concentrations were 18.5 and 171.6 microg l(-1) for the silt loam and 130.6 and 395.3 microg l(-1) for the clay soil during the spring/summer periods of 1996/97 and 1998, respectively. During the autumn/winter period, concentrations did not exceed 2.2 microg l(-1) for the silt loam and 2.6 microg l(-1) for the clay soil. The experimental results indicate that metolachlor losses in drainwater were primarily caused by preferential flow (macropore flow) which was greater in the clay soil than in the silt loam, and occurring mainly during the spring/summer periods.     

Rate of microbial degradation of high concentrations of α-hexachlorocyclohexane in soil under aerobic and anaerobic conditions

A case study was carried out to determine the bio-degradability of α-HCH in waste dumps polluted with HCH-isomers. Polluted soil was homogenized through a 2 mm sieve. The degradation of α-HCH (5300 mg kg^?1) occurred under anaerobic as well as under aerobic conditions; the concentration decreased in 20 weeks with 35% and 55% respectively. Addition of glucose, glutamic acid and peptone to the polluted soil hardly affected the degradation rate of α-HCH.     

Effects of the antimicrobial agent sulfamethazine on metolachlor persistence and sorption in soil

Recent monitoring investigations have shown that antimicrobial agents used in veterinary medicine can cause non-point source contamination of soils through manure spreading. In the present study, the effect of the antimicrobial agent sulfamethazine (sulfadimidine) on degradation and sorption of the herbicide metolachlor in a sandy loam soil was studied. In soil samples treated with sulfamethazine at two concentrations (15 and 150 microg kg(-1) soil), metolachlor persistence was not different than of that observed in untreated samples. These results were supported by the absence of effects of both sulfamethazine concentration levels on the size of the culturable soil bacteria population. Equilibrating soil samples with metolachlor solutions containing equivalent sulfamethazine concentrations did not lead to any significant effects on metolachlor sorption, suggesting that, under the conditions of the present experiment, sulfamethazine did not affect metolachlor bioavailability in soil. This laboratory investigation showed that concentrations of sulfamethazine in the microg kg(-1) range did not cause significant effects on metolachlor degradation and sorption thus not affecting the main processes ruling its environmental fate in soil.     

Reduced Downward Mobility of Metolachlor and Metribuzin from Surfactant-Modified Clays

The study aims to prepare the organoclay complexes of metolachlor and metribuzin so as to reduce their downward mobility in soil profile. The organoclays were preadsorbed with phenyltrimethylammonium (PTMA) (50% of cation exchange capacity [CEC]) and hexadecyltrimethylammonium (HDTMA) (100% of CEC). Four metolachlor formulations, two for each organoclay, were prepared having 1% and 2% load of herbicide and were called PTMA-Metol-1%, PTMA-Metol-2%, HDTMA-Metol-1% and HDTMA-Metol-2%. Two metribuzin formulations were prepared and were called PTMA-Metri-1% and HDTMA-Metri-1%. Soil column leaching experiment showed that compared to their commercially available formulations, organoclay complexes were effective in reducing the downward mobility of both herbicides. Organoclay complexes of metolachlor and metribuzin prepared using PTMA-Montmorillonite performed better than the HDTMA-Montmorillonite complexes.     

Biodegradation of endosulfan-contaminated soil in a pilot-scale reactor-bioaugmented with mixed bacterial culture

A novel mixed bacterial culture was enriched from an endosulfan (6, 7, 8, 9, 10, 10 – hexachloro-1, 5, 5a, 6, 9, 9a-hexahydro-6, 9-methano-2, 3, 4-benzo (e) dioxathiepin-3-oxide) processing industrial surface soil. The cultures were successful in the degradation of aqueous phase endosulfan in both aerobic and anaerobic conditions. Using the cultures, endosulfan degradation in silty gravel with sand (GM) was examined via pilot scale reactor at an endosulfan concentration of 0.78 ± 0.01 mg g^{? 1} of soil, and optimized moisture content of 40 ± 1%. During operation, vertical spatial variability in endosulfan degradation was observed within the reactor. At the end of 56 days, maximum endosulfan degradation efficiency of 78 ± 0.2% and 86.91 ± 0.2% was observed in the top and bottom portion of the reactor, respectively. Both aerobic and anaerobic conditions were observed within the reactor. However, endosulfan degradation was predominant in anaerobic condition and the total protein concentration in the reactor was declined progressively down the soil depth. Throughout the study, no known intermediate metabolites of endosulfan reported by previous researchers were observed.