Determination of extractable and non-extractable radioactivity from prairie soils treated with carboxyl- and ring-labelled [14C]2,4-D

Ring- and carboxyl-labelled [¹⁴C]2,4-D were incubated under laboratory conditions, at the 2 g/g level, in a heavy clay, sandy loam, and clay loam at 85% of field capacity and 20 1C. The soils were extracted at regular intervals for 35 days with aqaeous acidic acetonitrile, and analysed for [¹⁴C]2,4-D and possible radioactive degradation products. Following solvent extraction, a portion of the soil residues were combusted in oxygen to determine unextracted radioactivity as [¹⁴C]carbon dioxide. The remaining soil residues were then treated with aqueous sodium hydroxide, and the radioactivity associated with the fulvic and humic soil components determined. In all soils there was a rapid decrease in the amounts of extractable radioacitivity, with only 5% of that applied being recoverable after 35 days. All recoverable radioactivity was attributable to [¹⁴C]2,4-D, and no [¹⁴C]-containing degradation products were observed. This loss of extractable radioactivity was accompanied by an increase in non-extractable radioactivity. Approximately 15% of the applied radioactivity, derived from carboxyl-labelled [¹⁴C]2,4-D, and 30% from the ring-labelled [¹⁴C]2,4-D was associated with the soil in a non-extractable form, after 35 days of incubation. After 35 days, less than 5% of the radioactivity from the carboxyl-labelled herbicide, and less than 10% of the ringlabelled material, was associated with the fulvic components derived from the three soils. Less than 5% of the applied radioactivities were identifiable with any of the humic acid components. It was considered that during the incubation [¹⁴C]2,4-D did not become bound or conjugated to soil components, and that non-extractable radioactivity associated with the three soil types resulted from incorporation of radioactive degradation products, such as [¹⁴C]carbon dioxide, into soil organic matter.     

Degradation of the herbicide flamprop-methyl in soil

The degradation of the wild oat herbicide flamprop-methyl [methyl DL -N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate] in four soils has been studied under laboratory conditions using ¹⁴C-1abelled samples. The flamprop-methyl underwent degradation more rapidly than its analogue flamprop-isopropyl. However, similar degradation products were formed, namely the corresponding carboxylic acid and 3-chloro-4-fluoroaniline. The latter compound occurred mainly as ‘bound’ forms although evidence was obtained of limited ring-opening to give [¹⁴C]carbon dioxide. The time for depletion of 50% of the applied herbicide was approximately 1-2 weeks in sandy loam, clay and medium loam soils and 2-3 weeks in a peat soil.     

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.     

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%).     

Degradation of the herbicide flamprop-isopropyl in soil under laboratory conditions

The degradation of the wild-oat herbicide flamprop-isopropyl, [isopropyl (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate], in four soils has been examined under laboratory conditions with sampling times of up to 45 weeks after treatment. The major degradation product of [¹⁴C]flamprop-isopropyl in all soils at up to 10 weeks after treatment was the carboxylic acid (±)-N-benzoyl-N-(3-chloro-4-fluorophenyl)alanine. This compound in turn underwent degradation by loss of the benzoyl group and the propionic acid moiety, with evolution of [¹⁴C]carbon dioxide to form 3-chloro-4-fluoroaniline (CFA). The CFA was formed slowly in soil and occurred mainly as a bound form. There was evidence to show that the CFA was subsequently converted into other polar products. The time for depletion of 50% of the applied herbicide was approximately 10 weeks in sandy loam and medium loam soils, 11 weeks in a clay loam soil and 23 weeks in a peat soil.     

Degradation of the pyrethroid cypermethrin NRDC 149 (±)-α-cyano-3-phenoxybenzyl (±)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and the respective cis-(NRDC 160) and trans- (NRDC 159) isomers in soils

The degradation of the pyrethroid insecticide cypermethrin and the geometric isomers NRDC 160 (cis-) and NRDC 159 (trans-) in three soils has been studied under laboratory conditions. Samples of the insecticides labelled separately with ¹⁴C in the cyclopropyl and benzyl rings were used. The rate of degradation was most rapid on sandy clay and sandy loam soils, 50% of the NRDC 160 and NRDC 159 applied to both soils being decomposed in 4 weeks and 2 weeks respectively. The major degradative route in all soils was hydrolysis of the ester linkage leading to the formation of 3-phenoxybenzoic acid and 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid; soil treated with the cis-isomer (NRDC 160) was found to contain both cis- and trans-isomer forms of the cyclopropanecarboxylic acid. Further degradation of these carboxylic acids was evident since ¹⁴CO₂ was released from cyclopropyl- and benzyllabelled cypermethrin in amounts equivalent to 24 and 38% of the applied radioactivity over a 22 week period. A minor degradative route was ring-hydroxylation of the insecticide to give an α-cyano-3-(4-hydroxyphenoxy)benzyl ester followed by hydrolysis of the ester bond. Under waterlogged conditions the rate of hydrolysis of cypermethrin on sandy loam soil was slower than under aerobic conditions and 3-phenoxybenzoic acid accumulated in the anaerobic soil.     

A comparative study of carbofuran metabolism in treated and untreated soils

Soils which have been pretreated with carbofuran can degrade the insecticide more rapidly than untreated soils, with a consequent loss of efficacy. In laboratory studies, soils pretreated with carbofuran were found to degrade the chemical more rapidly than soils which were not so pretreated. When pretreated soils were sterilised, the rate of carbofuran degradation was much reduced, indicating that most of it was due to microbial action. Incubation of pretreated soil with [phenyl-U-¹⁴C]carbofuran led to the rapid disappearance of the parent compound (3 % left after seven days). Most of the ¹⁴C was accounted for as bound residue after seven days, whilst smaller amounts were recovered as carbon dioxide, 3-hydroxycarbofuran, 3-ketocarbofuran, and an unknown metabolite. Incubation of pretreated soil with [carbonyl-¹⁴C]carbofuran led to rapid loss of the parent compound and the recovery of 73% of ¹⁴C as carbon dioxide by five days. Most of the bound ¹⁴C (>90%) arising from [phenyl-U-¹⁴C]carbofuran treatment of pretreated soil was extracted by 1 M sodium hydroxide and about half of the extracted ¹⁴C was precipitated with ‘humic acids’ after acidification. These and other results suggest that the major metabolic route for carbofuran in pretreated soils involves hydrolysis of the ester bond leading to (1) release of carbofuran phenol which rapidly binds to soil organic matter and, (2) release of the carbonyl moiety which quickly degrades to generate carbon dioxide.     

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     

Persistence studies with the herbicide sethoxydim in prairie soils

The persistence of [¹⁴C]sethoxydim (2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexene-1-one) at the 2 μg g^?1 level was studied under laboratory conditions in three soils at 20°C and 85% of their field capacity moistures. Following extraction of the soils with methanol, the herbicide remaining was determined using radiochemical techniques. Loss of radioactivity was more rapid on moist clay loam and sandy loam, where the half-lives were 12 days, than on heavy clay in which the half-life was 26 days. Loss of radioactivity from air-dried soils (15% of field capacity) was negligible with over 94% of the applied activity being recovered after 28 days. The persistence of sethoxydim at a rate of 1 kg ha^?1 was investigated under field conditions using small plots at three prairie locations for 3 successive years. Using an oat-root bioassay procedure, no residues were detected in the 0–10 cm depths of any soils, any year, in September following May treatments.     

Mineralization of [14C] glyphosate and its plant-associated residues in arable soils originating from different farming systems

The biomineralization of [¹⁴C]glyphosate, both in the free state and as ¹⁴C-residues associated with soybean cell-wall material, was studied in soil samples from four different agricultural farming systems. After 26 days, [¹⁴C]carbon dioxide production from free glyphosate accounted for 34–51% of the applied radiocarbon, and 45–55% was recovered from plant-associated residues. For three soils, the cumulative [¹⁴C]carbon dioxide production from free glyphosate was positively correlated with soil microbial biomass, determined by substrate-induced heat output measurement and by total adenylate content. The fourth soil, originating from a former hop plantation, and containing high concentrations of copper from long-term fungicide applications, did not fit this correlation but showed a significantly higher [¹⁴C]carbon dioxide production per unit of microbial biomass. Although the cumulative [¹⁴C]carbon dioxide production from plant-associated ¹⁴C-residues after 26 days was as high as from the free compound, it was not correlated with the soil microbial biomass. This indicates that the biodegradation of plant-associated herbicide residues, in contrast to that of the free compound, involves different degradation processes. These encompass either additional steps to degrade the plant matrix, presumably performed by different soil organisms, or fewer degradation steps since the plant-associated herbicide residues are likely to consist mainly of easily degradable metabolites. Moreover, the bioavailability of plant-associated pesticide residues seems to be dominated by the type and strength of their fixation in the plant matrix. ©1997 SCI     

Soil persistence studies with bromoxynil, propanil and [14C]dicamba in herbicidal mixtures

The persistence of bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), [¹⁴C]dicamba (3,6-dichloro-2-methoxybenzoic-7-¹⁴C acid) and propanil [N-(3,4-dichlorophenyl)propionamide] at rates equivalent to 1 kg ha^?1, were studied under laboratory conditions in a clay loam, a heavy clay and a sandy loam at 85% of field capacity and at 20±1°C, both singly and in the presence of herbicides normally applied with these chemicals as tank-mix or split-mix components. The degradation of bromoxynil was rapid with over 90% breakdown occurring within a week in the heavy clay and sandy-loam soils, while in the clay-loam approximately 80% of the bromoxynil had broken down after 7 days. In all three soils degradation was unaffected by the presence of asulam, diclofop-methyl, flamprop-methyl, MCPA, metribuzin or propanil. Propanil underwent rapid degradation in all soil treatments, with over 95% of the applied propanil being dissipated within 7 days. There were no noticeable effects on propanil degradation resulting from applications of asulam, barban, bromoxynil, dicamba, MCPA, MCPB, metribuzin or 2,4-D. The breakdown of [¹⁴C]dicamba in a particular soil was unaffected by being applied alone or in the presence of diclofop-methyl, flampropmethyl, MCPA, metribuzin, propanil or 2,4-D. The times for 50% of the applied dicamba to be degraded were approximately 16 days in both the clay loam and sandy loam, and about 50 days in the heavy clay.     

Influence of soil pH and contents of organic carbon and clay on the volatilization of [14C]fenpropimorph after application to bare soil

The behaviour of the morpholine fungicide fenpropimorph applied to soil was investigated in a laboratory chamber. The volatility and metabolism of a ¹⁴C-labelled fenpropimorph formulation (Corbel^®) was studied after application to three soils (sandy loam, loamy clay and loamy sand), simulating a four-day weather scenario in the volatilization chamber. Additional experiments were conducted under standard climatic conditions over a period of 24 h using sandy soils with different pH values. The results of the first experiments showed that most of the radioactivity applied remained in the soils as unchanged fenpropimorph four days after application. In the experiments with the sandy loam and loamy clay, less than 5% of the applied radioactivity was removed by volatilization whereas 11·4% volatilized from the surface of the loamy sand. The comparatively higher volatilization of the fungicide from the loamy sand was confirmed by the later experiments indicating that higher soil pH favoured volatilization of [¹⁴C]fenpropimorph from sandy soils. Thus 5·6% (pH 5·0), 18·9% (pH 5·8) and 28·3% (pH 6·6) of the radioactivity applied volatilized within one day after application. The overall recoveries were between 93·8% and 111·3% in these experiments. © 1998 SCI     

Soil persistence studies with [14C]MCPA in combination with other herbicides and pesticides

The persistence of [¹⁴C]MCPA at a rate equivalent to 1 kg ha^?1 was studied under laboratory conditions in a clay loam, heavy clay and sandy loam at 85% of field capacity moisture and 20±1°C both alone and in the presence of tri-allate, trifluralin, tri-allate and trifluralin, malathion, Vitaflow DB, malathion and Vitaflow DB, bromoxynil, bromoxynil and asulam, bromoxynil and difenzoquat, dicamba, dicamba and mecoprop, linuron, MCPB, metribuzin, propanil, TCA, benzoylprop-ethyl, diclofop-methyl, and flamprop-methyl. Except in the soils treated with asulam, the half-lives of [¹⁴C]MCPA in all three soil types were similar, being approximately 13±1 days, thus indicating that none of the other chemicals studied adversely affected the soil degradation of MCPA. In the asulam treated soils, the half-lives of the MCPA were about 3 days longer than in non-asulam treated soils; the effect was most marked in the clay loam.     

Availability and biodegradation of metribuzin in alluvial soils as affected by temperature and soil properties

Herbicide degradation in soils is highly temperature‐dependent. Laboratory incubations and field experiments are usually conducted with soils from the temperate climatic zone. Few data are available for cold conditions and the validation of approaches to correct the degradation rate at low temperatures representative of Nordic environments is scarce. Laboratory incubation studies were conducted at 5, 15 and 28°C to compare the influence of temperature on the dissipation of metribuzin in silt/sandy loam soils in southern and northern Norway and in a sandy loam soil under temperate climate in France. Using ¹⁴C‐labelled metribuzin, sorption and biodegradation were studied over an incubation period of 49 days. Metribuzin mineralisation and total soil organic carbon mineralisation rates showed a positive temperature response in all soils. Metribuzin mineralisation was low, but metabolites were formed and their abundance depended on temperature conditions. The rate of dissipation of ¹⁴C‐metribuzin from soil pore water was strongly dependent on temperature. In Nordic soils with low organic content, metribuzin sorption is rather weak and biodegradation is the most important process controlling its mobility and persistence.     

Metabolism of amitrole in apple: II. Bound residues from mature fruits

Significant radioactivity detected in mature fruits, harvested from apple trees (Malus domestica Borkh., cv. ‘Golden Delicious’ and ‘Gloster’) that were soiltreated with [3,5-¹⁴C]amitrole, remained in the insoluble plant material after exhaustive extraction. These bound residues were solubilized with a mixture of pectinases and cellulases. Thus, separation and characterization of carbohydrates and xenobiotic moieties released during this procedure became possible. A part of the radiolabel was incorporated into natural products, indicating degradation of the applied amitrole and reassimilation of [¹⁴C] carbon dioxide.     

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.     

The microbial biodegradation of paraquat in soil

The microbial degradation of [¹⁴C]paraquat using cultures from two agricultural soils was investigated. The experiments were carried out in the absence of light, under aerobic conditions. Degradation was rapid, with 50% mineralisation to [¹⁴C]carbon dioxide occurring within three weeks. HPLC, capillary electrophoresis and mass spectroscopy confirmed that the majority (>85%) of the remaining radiochemical in solution was [¹⁴C]oxalic acid, and that no paraquat remained.     

Microbial aspects of atrazine biodegradation in relation to history of soil treatment

Among 15 soils with different cropping practices, seven which had an history of repeated atrazine applications showed accelerated degradation of this herbicide. By contrast, grassland or agricultural soils with no recorded atrazine application, at least for the last three years, had a low degradation potential. No direct relation was found between the rate of atrazine mineralisation and the size of the microbial biomass. In adapted soils, the amounts of extractable residues were lowered and the very high percentages of radioactivity from [ring-¹⁴C]atrazine recovered as [¹⁴C]carbon dioxide demonstrated that N-dealkylation and deamidation were the only processes for micro-organisms to derive carbon and energy for heterotrophic growth. Kinetics of microbial ¹⁴C accumulation revealed that atrazine ring carbon could be incorporated by direct oxidative condensation with structural components of the bacterial or fungal cell whereas side-chain carbon was preferentially used for biosynthesis of new protoplasmic cell material, as confirmed by the high turnover rate of radiolabelled microbial components. From the determination of the Michaelis–Menten parameters, V_m and K_m in the presence of different selective biocides, it was possible to conclude that fungi were probably less active in atrazine degradation than bacteria and that over years the microbial atrazine-degrading community showed an increased efficiency. © 1999 Society of Chemical Industry     

Laboratory studies on formation of bound residues and degradation of propiconazole in soils

Laboratory studies on the formation of bound residues and on the degradation of the triazole fungicide propiconazole were conducted in two different soils. Soils treated with 14C-propiconazole were incubated at 22 degrees C and extracted exhaustively with a solvent at each sampling date until no further propiconazole was extracted. The solvent-extractable residues were used to measure propiconazole remaining in the soil, and the extracted soils were used to investigate bound residues of propiconazole. Mineralization of propiconazole was investigated by measuring [14C]carbon dioxide evolved from the soil samples. Formation of bound residues of propiconazole was higher in silty clay loam soil than in sandy loam soil, giving approximately 38 and 23% of the applied 14C, respectively. In contrast, the rates of degradation and mineralization of propiconazole were lower in silty clay loam soil than in sandy loam soil. Decreased extractability of the 14C residues with incubation time was observed with increased formation of bound residues. When the propiconazole remaining in the solvent-extractable residues was quantitatively measured by high-pressure liquid chromatographic analysis, the half-life value in sandy loam soil was about 315 days, while the half-life in silty clay loam soil exceeded the duration of the 1 year experimental period. Increased formation of bound residues was observed as propiconazole degraded with incubation time, suggesting that degradation products are involved in the formation of bound residues. Our study suggests that the formation of bound residues of propiconazole contributes to the persistence of this fungicide in soil.     

The degradation of diflubenzuron and its chief metabolites in soils. Part III. Fate of 2,6-difluorobenzoic acid

2,6-Difluorobenzoic acid, one of the two primary diflubenzuron metabolites, is rapidly and completely degraded in soil. Times to 50% disappearance were 9 and 12 days in two agricultural soils. [¹⁴C]Carbon dioxide was an ultimate product of the ring-¹⁴C-labelled compound. A part of the radioactivity, increasing with time to one third of the applied dose of 1 mg kg^?1, could not be extracted from the soil.