The degradation of diflubenzuron and its chief metabolites in soils. Part II: Fate of 4-chlorophenylurea

The fate of 4-chlorophenylurea in soils was studied with two preparations: one labelled with ¹⁴C in the phenyl ring and the other in the carbonyl group. The initial dose of 1 mg kg^?1 decreased to 50% in about 5 weeks in aerobic sandy clay and in about 16 weeks in anaerobic hydrosoil. Soil treatment with each of the preparations resulted in the release of [¹⁴C]carbon dioxide, pointing to decarbonylation and ring opening. The fraction of non-extractable (soil-bound) radioactivity increased during incubation. Quantities of ring-¹⁴C-labelled and carbonyl-¹⁴C-labelled bound residues differed strongly in the aerobic soil but only slightly in the anaerobic hydrosoil. It is assumed that two sorts of bound residues are formed from 4-chlorophenylurea: one is fairly stable and might consist of bound 4-chloroaniline or its transformation products, whereas the other is presumed to be a degradable derivative of 4-chlorophenylurea.     

Effects of repeated glyphosate applications on soil microbial community composition and the mineralization of glyphosate

Background: Repeated applications may have a greater impact on the soil microbial community than a single application of glyphosate. Experiments were conducted to study the effect of one, two, three, four or five applications of glyphosate on soil microbial community composition and glyphosate mineralization and distribution of ¹⁴C residues in soil. RESULTS: Fatty acid methyl esters (FAMEs) common to gram‐negative bacteria were present in higher concentrations following five applications relative to one, two, three or four applications both 7 and 14 days after application (DAA). Additionally, sequencing of 16S rRNA bacterial genes indicated that the abundance of the gram‐negative Burkholderia spp. was increased following the application of glyphosate. The cumulative percentage ¹⁴C mineralized 14 DAA was reduced when glyphosate was applied 4 or 5 times relative to the amount of ¹⁴C mineralized following one, two or three applications. Incorporation of ¹⁴C residues into soil microbial biomass was greater following five glyphosate applications than following the first application 3 and 7 DAA. CONCLUSION: These studies suggest that the changes in the dissipation or distribution of glyphosate following repeated applications of glyphosate may be related to shifts in the soil microbial community composition. Copyright © 2009 Society of Chemical Industry     

Biodegradation of the herbicide bromoxynil and its plant cell wall bound residues in an agricultural soil

The mineralization and formation of metabolites and nonextractable residues of the herbicide [¹⁴C]bromoxyniloctanoate ([¹⁴C]3,5-dibromo-4-octanoylbenzonitrile) and the corresponding agent substance [¹⁴C]bromoxynil ([¹⁴C]3,5-dibromo-4-hydroxybenzonitrile) was investigated in a soil from an agricultural site in a model experiment. The mineralization of maize cell wall bound bromoxynil residues was also investigated in the agricultural soil material. The mineralization of [¹⁴C]bromoxynil and [¹⁴C]bromoxyniloctanoate in soil within 60 days amounted up to 42 and 49%, respectively. After the experiments, 52% of the originally applied [¹⁴C]bromoxynil and 44% of the [¹⁴C]bromoxyniloctanoate formed nonextractable residues in soil. Plant cell wall bound [¹⁴C]bromoxynil residues were also mineralized to an extent of about 21% within 70 days; the main portion of 76% persisted as nonextractable residues in the soil. In bacterial enrichment cultures and in soil two polar metabolites were observed; one of it could be identified as 3,5-dibromo-4-hydroxybenzoate and the other could be described tentatively as 3,5-dibromo-4-hydroxybenzamide.     

Degradation of fluridone in submersed soils under controlled laboratory conditions

The experimental, aquatic herbicide fluridone (1-methyl-3-phenyl-5-[3-(trifluoromethyl)phenyl]-4(1H)-pyridinone) was degraded in two submersed soils and in the water above those soils to one acidic metabolite (identified as 1,4-dihydro-1-methyl-4-oxo-5-[3-(trifluoromethyl)phenyl]-3-pyridinecarboxylic acid by mass spectrometry). A sandy and a silt loam soil were treated with [¹⁴C]fluridone, immersed in water, and analyzed after 1, 3, 5, 7, 9, and 12 months. Seven to fifteen percent of the ¹⁴C applied to the soils was recovered in the water on each of the various collection dates. The acidic metabolite accounted for 86 to 93% of the radioactivity in the water fraction 7 months after treatment. The metabolite was absorbed strongly by both soils and comprised about 60% of the total ¹⁴C in each soil after 12 months. The remainder of the ¹⁴C in the soils after 12 months was either the parent compound (～30%) or an undefined insoluble residue (～10%).     

Influence of nitrogen fertilisers on the persistence of carbaryl and carbofuran in flooded soils

Ammonium sulphate and urea, but not potassium sulphate, increased the persistence of carbaryl in a flooded laterite soil with a low native nitrogen content (0.04%), but not in an alluvial soil with a higher nitrogen content (0.11%). Thus, NH₄⁺ but not SO₄^2-, contributed to the increased persistence of carbaryl. Likewise, ammonium sulphate increased the persistence of carbofuran in the laterite soil, but not in the alluvial soil. Significant accumulations of 1-naphthol and 2,3-dihydro-2, 2-dimethylbenzofuran-7-ol (‘carbofuran phenol’), in soils treated with carbaryl or carbofuran, suggested hydrolysis as the major pathway of degradation. Treatment of the two soils with ammonium sulphate, urea or potassium sulphate led to a decrease in soil-bound residues and an increase in the respective hydrolysis products, compared with untreated soils. Sorption studies indicated that NH₄⁺ and SO₄^2- compete with carbaryl, 1-naphthol and carbofuran for sorption and exchange sites in the complex soil system. Evolution of [¹⁴C]carbon dioxide from ring-¹⁴C in carbaryl and carbofuran was negligible. Consequently, after 40 days, more than 50% of the ¹⁴C in [¹⁴C]carbaryl and [¹⁴C]carbofuran remained in the soils as hydrolysis products (1-naphthol or 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) plus soil-bound residues.     

Degradation and adsorption of 14C-MCPA in soil—influence of concentration, temperature and moisture content on degradation

MCPA was weakly absorbed in soils with 2.4, 3.0 and 2.9% humus. K_d-values were 0.7, 0.9 and 1.0, respectively. In soil, not previously treated with MCPA, the degradation of 0.05 mg kg^?114C-MCPA followed first-order reaction kinetics whereas degradation of 5 mg kg^?1 was only first-order for 2 weeks; exponentially increasing degradation rates followed indicating enrichment of the soil with MCPA decomposers. Degradation was monitored by evolution of ¹⁴CO₂. The influence of temperature on degradation of MCPA (4 mg kg^?1) could initially be described by Q₁₀ values or by the Arrhenius equation. After 1 day of incubation in two field soils Q₁₀ values were 3.3 and 2.9, respectively, between 0°C and 29°C; the activation energies were 87 and 76 kj mol^?1. Exponentially increasing degradation rates followed with doubling times of about 4.0, 1.8, 1.2 and 0.6 days at 6,10, 15 and 21°C, respectively. After 51 days of incubation, at temperatures between 6°C and 29°C, about 60%¹⁴C was evolved in CO₂ and only traces of MCPA were left in the soil. At 0°C and at 40°C only 1% and 10%¹⁴C, respectively, were evolved as CO₂ after 51 days. ¹⁴C-MCPA (4 mg kg^?1) was incubated at moisture contents from that in air-dried soil to 2.3 times field capacity. Optimum for degradation was from 0.6 to 1.2. field capacity. Degradation was very slow where water contents were below the level of wilting point and was nil in air-dried soil. In wet soil degradation was delayed, but even in water-logged soil (2.3 times field capacity) MCPA was decomposed after 4 to 5 weeks at 10°C.     

The adsorption and degradation of glyphosate in five Hawaiian sugarcane soils*

The rate of aerobic evolution of ¹⁴CO₂ from ¹⁴C-glyphosate labelled in the methylphosphonyl carbon, varied 100-fold within a group of five Hawaiian sugarcane soils. The rate depended inversely on the degree of soil binding, probably associated with the phosphonic acid moiety, and to a less certain extent on soil pH and soil organic matter. After an initial rapid degradation, the rate of ¹⁴CO₂ evolution in three soils reached a constant at 16–21 days which continued to the 60-day termination. The other two soils showed a continually decreasing rate throughout. Two soils released over 50% of the labelled carbon in 60 days, a third released 35%, while the remaining soils released 1.2 and 0.8% respectively. Labelled carbon in the soils after 60 days consisted of glyphosate and one metabolite, aminomethyl-phosphonic acid, with glyphosate predominating in high fixing soils. The ¹⁴C could be extracted almost completely with NaOH solution, and remained mainly in solution after acidification.     

The degradation of methazole in soil. II. Studies with methazole,methazole degradation products and diuron

[¹⁴C]-Labelled methazole, 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), and diuron were incubated in soil at 20°C and field capacity soil moisture content. Decomposition followed first-order kinetics; half-lives for degradation of these four compounds were 2.4, 144, 30 and 108 days respectively. The amount of DCPMU and DCPU that could be extracted decreased with time and the decrease was accompanied by the generation of an equivalent amount of ¹⁴CO₂. This was not so in the studies with diuron and methazole, however, and the decrease in the concentrations of radioactivity extracted from soil treated with these compounds could not be entirely accounted for as carbon dioxide. It is concluded that the unextractable radiochemical that was present was DCPMU. Methazole appeared to be degraded through DCPMU to 3,4-dichloroaniline (DCA) with the production of only traces of DCPU.     

Uptake,distribution and metabolic fate of 3H-triforine in plants. II. Long-term experiments

Uptake of ³H-triforine by tomato and barley seedlings from soil with a high organic matter content was much less efficient than from aqueous suspensions, even though the period of exposure was much longer—at least 1 week (“long-term treatment”) vs 1 day (“short-term treatment”). After transplanting to fresh soil, part of the label in the roots was lost probably by desorption. Distribution of label in tomato shoots was as irregular as after short-term treatment; label was virtually confined to the leaves which expanded before about 14 days after cessation of the treatment. In shoots of barley seedlings which were pretreated in an aqueous suspension of ³H-triforine for 1 day before being subjected to a long-term soil treatment, almost all radioactivity present could be ascribed to uptake during the pretreatment phase. The distribution pattern strongly resembled that obtained after short-term treatment, hardly any label being found in leaves which unfolded after the pretreatment phase. Rates of conversion of ³H-triforine in barley shoots depended to some extent on whether or not seedlings were transplanted to fresh soil after 1 week.     

Degradation and adsorption of carbendazim and 2-aminobenzimidazole in soil

Increasing adsorption of [¹⁴C]-labelled carbendazim in soil took place within a few weeks of incubation and was greatest in soil with a high organic matter content. Carbendazim was slowly decomposed in soil, mainly by soil microorganisms. After 250 days of incubation in two unsterilised soils, 13 and 5% respectively of added [¹⁴C]-carbendazim was recovered compared with 70 and 50% respectively from sterile soils; 4–8% of added carbendazim was recovered as 2-aminobenzimidazole (2-AB) from both unsterilised and sterile soil. After 270 days' incubation, 33 and 9% of ¹⁴C was recovered as ¹⁴CO₂ from soil supplied with [¹⁴C]-carbendazim (20 and 100 mg/kg) respectively. Degradation started more rapidly when carbendazim was added to soil preincubated with the fungicide but the degradation rate was very low in all cases, indicating that the compound is a poor microbial energy source and that the degradation is a co-metabolic process. 2-AB was found as a degradation product although it appeared to be unstable in soil, decomposing rapidly after a lag period of about 3 weeks; small amounts remained in the soil for several months, however, presumably adsorbed on soil particles.     

Aerobic Metabolism of Flupropacil in Sandy Loam Soil

The aerobic soil metabolism of [¹⁴C]flupropacil (isopropyl 2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoate) was determined in microbially active, sieved (2-mm) sandy loam soil with a soil moisture content of 75% at 1/3 bar. The soil was treated with [¹⁴C]flupropacil at 0·5 mg kg⁻¹ (twice the field use rate) and placed in incubation flasks connected to a series of traps (50 g litre⁻¹ NaOH, 0·5M H₂SO₄, ethylene glycol) and incubated at 25(±1)°C. Soil was sampled at 0, 3, 9, 20, 30, 48, 76, 120, 181 and 238 days of aerobic incubation. Volatiles were collected once every two weeks and on the day of soil sampling. Flupropacil metabolized with a half-life of 79 days under aerobic conditions. The major metabolite was flupropacil acid which accounted for up to 69·1% of the initially applied radioactivity at Day 238. Each of the two minor metabolites detected at the end of the study accounted for less than 0·5%. One of the minor metabolites was identified as C4242 acid (2-chloro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoic acid). Only a negligible portion (less than 0·3%) of the applied flupropacil was mineralized to [¹⁴C]carbon dioxide. Extractable radioactivity ranged from 78·9% to 95·5%, with bound residues accounting for 3·2%–23·4%. The material balance ranged from 91·6% to 104·4%.     

Influence of application methods on the degradation of permethrin in laboratory,soil aerobic metabolism studies

The effects of application rate, volume, solvent and soil moisture content on the kinetics of mineralization and degradation, of [¹⁴C] permethrin have been studied in a sandy loam soil under standard laboratory conditions. During the incubation period, up to 32 days, the temperature and moisture level of the soil were controlled. Apart from the effects of application rate, which have been widely reported, application volume had the most significant effect on mineralization rate and T_1/2. [¹⁴C]Permethrin, at a level of a 1 mg kg^?1 in the soil, applied in 100 μl of methanol, resulted in the evolution of 14% of the applied radiochemical as [¹⁴C] carbon dioxide over 30 days. The same level applied in 1000 μl mineralized at a faster rate, with 30% [¹⁴C]carbon dioxide evolved over 30 days. The test chemical applied to soil in methanol mineralized at a significantly faster rate than a similar concentration applied in ethanol. There was no significant difference when comparing applications made using acetonitrile with those using methanol or ethanol. The addition of formulation ingredients resulted in little or no variation in mineralisation rate compared to an equivalent application volume of methanol/water.     

Factors affecting the activity of ethephon in stimulating seed germination of Striga hermonthica (Del.) Benth.

Ethephon (2-chloroethylphosphonic acid), which generates ethylene, stimulated the germination of pre-conditioned seeds of Striga hermonthica when it was added to the alkaline Gezira clay soil at concentrations of 2.5 to 30 mg kg^?1. As little as 5 min contact with treated soil was enough to stimulate germination. Ethephon in soil did not cause germination of unconditioned seeds for periods of up to 12 days and also had an adverse effect on seed germination when such seeds were given a second ethephon exposure after a storage period which was adequate, in untreated soil, to give the necessary pre-conditioning. Ethephon activity persisted in air-dry soil but declined over a 14 day period in moist soil. In the field ethephon at 0.6 to 4.8 kg ha^?1 decreased the number of Striga shoots and increased sorghum height and flowering.     

The degradation of diflubenzuron and its chief metabolites in soils. Part I: Hydrolytic cleavage of diflubenzuron

[¹⁴C]Diflubenzuron is readily degraded in various agricultural soils and in hydro-soil; 50% of the applied dose of 1 mg kg⁻¹ was metabolised in 2 days or less. The chief products of hydrolysis were identified as 4-chlorophenylurea and 2, 6-difluorobenzoic acid. A part of the radioactivity, increasing with incubation time, could not be extracted. Release from the soil of [¹⁴C]carbon dioxide, derived from both labelled phenyl rings, points to the ultimate mineralisation of diflubenzuron.     

Fusarium solani f.sp.cucurbitae andF. oxysporum f.sp.niveum inoculum densities in tunisian soils and their effect on watermelon seedlings

Populations ofFusarium solani f.sp.cucurbitae (Fsc) andFusarium oxysporum f.sp.niveum (Fon) in naturally infested soil of watermelon fields were counted by the soil dilution method with subsequent pathogenicity tests. Inoculum density varied within the same region from one field to another, ranging between 9 and 1600 CFU g^?1 soil forFsc and from 0 to 200 CFU g^?1 soil forFon. Fusarium crown- and root-rot-diseased seedlings were observed in most soils (93%); however, Fusarium wilt was observed in only 34% of soil samples. The disease incidence on cv. ‘Giza’ (Y) increased significantly with inoculum density in the soil (X) (P<0.001). ForFsc, the relationship between inoculum density and disease incidence was characterized by the equation Y=0.0005X+0.165 (R²=0.67). ForFon, the equation was Y=0.003X?0.0014 (R²=0.88). Based on these equations, the estimated inoculum densities required to cause 50% disease incidence (DI₅₀) on cv. Giza plants was 670 and 171 CFU g^?1 soil forFsc andFon, respectively.     

Aerobic soil metabolism of metsulfuron-methyl

A laboratory study was conducted to determine the degradation rates and identify major metabolites of the herbicide metsulfuron-methyl in sterile and non-sterile aerobic soils in the dark at 20°C. Both [phenyl-U-¹⁴C]- and [triazine-2-¹⁴C]metsulfuron-methyl were used. The soil was treated with [¹⁴C]metsulfuron-methyl (0.1 mg kg⁻¹) and incubated in flow-through systems for one year. The degradation rate constants, DT₅₀, and DT₉₀ were obtained based on the first-order and biphasic models. The DT₅₀ (time required for 50% of applied chemical to degrade) for metsulfuron-methyl, estimated using a biphasic model, was approximately 10 days (9–11 days, 95% confidence limits) in the non-sterile soil and 20 days (12–32 days, 95% confidence limits) in the sterile soil. One-year cumulative carbon dioxide accounted for approximately 48% and 23% of the applied radioactivity in the [phenyl-U-¹⁴C] and [triazine-2-¹⁴C]metsulfuron-methyl systems, respectively. Seven metabolites were identified by HPLC or LC/MS with synthetic standards. The degradation pathways included O-demethylation, cleavage of the sulfonylurea bridge, and triazine ring opening. The triazine ring-opened products were methyl 2-[[[[[[[(acetylamino)carbohyl]amino]carbonyl]amino] carbonyl]-amino]sulfonyl]benzoate in the sterile soil and methyl 2-[[[[[amino[(aminocarbonyl)imino]methyl] amino]carbonyl]amino]sulfonyl]benzoate in the non-sterile soil, indicating that different pathways were operable. © 1999 Society of Chemical Industry     

Degradation of mecoprop at different concentrations in surface and sub-surface soil

Biodegradation of [ring-¹⁴C] mecoprop (2-(4-chloro-2-methylphenoxy)propionic acid) was determined in surface and sub-surface soil at concentrations of 0·0005, 0·05, 0·5, 5, 50, 500, 5000 and 25000 mg kg^-1. The kinetics of mineralisation were evaluated from the mineralisation rates as a function of time and by non-linear regression analysis. In the sub-surface soil, degradation was 6–8 times slower than in surface soil, but the shape of the curves was the same in both layers. At concentrations between 0·0005 and 0·5 mg kg^-1, in both surface and sub-surface soil, degradation was initially zero-order followed by first-order kinetics. At 5 to 500 mg kg^-1 in surface soil and 5 to 50 mg kg^-1 in sub-surface soil the degradation rate was initially either constant or decreasing followed by exponential degradation indicating increasing populations of mecoprop decomposers in the soil. At 5000 and 25000 mg kg^-1 in the surface soil and at 500, 5000 and 25000 mg kg^-1 in the sub-surface soil, the degradation was negligible, as determined by the percentage [¹⁴C] carbon dioxide evolved. By non-linear regression, the three-half order model was found to describe the mineralisation. © 1998 SCI     

Aerobic soil metabolism of flupyrazofos

To elucidate the fate of flupyrazofos [O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphorothionate] in soil, an aerobic soil metabolism study was carried out for 60 days with [¹⁴C]flupyrazofos applied at a concentration of 0·38 μg g^-1 to a loamy soil. The material balance ranged from 103·5% to 86·9% and the half-life of [¹⁴C]flupyrazofos was calculated to be 13·6 days. The metabolites identified during the study were 1-phenyl-3-trifluoromethyl-5-hydroxypyrazole (PTMHP) and O,O-diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphate (flupyrazofos oxon), with maximum levels of 9·8% and 1·6% of applied radiocarbon, respectively. Evolved [¹⁴C]carbon dioxide accounted for up to 5·3% of applied radiocarbon and no volatile products were detected during the study. Non-extractable ¹⁴C-residue reached 31·6% of applied material at 60 days after treatment and radiocarbon was distributed almost evenly in humin, humic acid and fulvic acid fraction. © 1998 Society of Chemical Industry     

Leaching of Alachlor from Alginate-Encapsulated Controlled-Release Formulations

The mobility of alachlor from alginate-encapsulated controlled-release (CR) formulations was investigated in two contrasting soil profiles. Two CR formulations of alachlor were prepared with the following components (1) base—sodium alginate+kaolin+‘Tween’ 20 (1+10+0·5 by mass) and (2) base+40 g kg⁻¹ linseed oil. These were compared to technical grade alachlor and to a commercial alachlor EC formulation (‘Lasso’ 4EC). All herbicide treatments were labeled with [¹⁴C]alachlor and were applied to duplicate soil columns that were composed of a surface and a subsoil horizon. Each horizon was packed to a depth of 12·5 cm, giving a total column length of 25 cm. The columns were leached with 21 cm (420 ml) to 30 cm (600 ml) of 0·01M calcium chloride for a period of 7 to 10 days. Alachlor leaching from the EC formulations was the same as that from the technical material in both soils: 33% in the Evesboro and 10% in the Conover soil. The CR-Oil formulation leached 4 and 2% of the applied [¹⁴C]alachlor, compared to 12 and 3% for the CR-N formulation for the Evesboro and Conover soils, respectively. The CR-Oil formulation also increased the amount of [¹⁴C]alachlor retained in the soil surface horizon (105–114%), compared to CR-N (39–45%), technical material (14–23%) and EC (12–17%).     

Fate of [14C]diflubenzuron on cotton and in soil

Aqueous suspensions and oil emulsions of a commercial [¹⁴C]diflubenzuron (N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide) formulation (Dimilin W-25) remained on the leaf surface of greenhouse-treated plant tissues. Absorption, translocation, and metabolism of the [¹⁴C]diflubenzuron were not significant. Less than 0.05% of the applied ¹⁴C was found in newly developed plant tissues 28 days after spray treatment. [¹⁴C]Diflubenzuron was degraded in soil. After 91 days, biometer flask studies showed that 28% of the ¹⁴C incorporated into the soil as [¹⁴C]diflubenzuron was recovered as ¹⁴CO₂. Major dichloromethane-soluble soil residues were identified as unreacted [¹⁴C]diflubenzuron and [¹⁴C]4-chlorophenylurea. A minor unknown degradation product cochromatographed with 2,6-difluorobenzoic acid. Insoluble ¹⁴C-residues increased with time and represented 67.8% of the residual ¹⁴C in the soil 89 days after treatment. Cotton plants grown for 89 days in [¹⁴C]diflubenzuron-treated soil contained only 3% of the ¹⁴C applied to the soil. Small quantities of acetonitrile-soluble [¹⁴C]4-chlorophenylurea were isolated from the foliar tissues. Root tissues contained small amounts of [¹⁴C]diflubenzuron and trace quantities of a minor ¹⁴C-product that chromotographed similarly to 2,6-difluorobenzoic acid. Most of the ¹⁴C in the plant tissues (84–93%) was associated with an insoluble residue fraction 89 days after treatment.