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.     

Metabolic fate of bioxone in cotton

The metabolic fate of the ¹⁴C-labeled herbicide, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione (bioxone), in cotton (Gossypium hirsutum L. “Acala 4-42-77”) was studied using thin-layer chromatography, autoradiography, and counting. Bioxone-¹⁴C was readily metabolized by cotton tissue to 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU) and 1-(3,4-dichlorophenyl)urea (DCPU). Leaf discs metabolized bioxone-¹⁴C rapidly; 12 hr posttreatment, 65% of the ¹⁴C in methanol extracts was in forms other than intact herbicide. Excised leaves treated through the petiole with either heterocyclic ring-labeled or phenyl ring-labeled herbicide contained little bioxone-¹⁴C after 1 day; DCPMU was formed early then decreased with time. DCPU accounted for 55–70% of the ¹⁴C in excised leaves 3 days posttreatment. In intact plants treated via the roots, the herbicide was rapidly metabolized in the roots to DCPMU and DCPU; little or no intact herbicide was translocated to the leaves. Little radioactivity accumulated in the roots with time; the radioactivity in the leaves accounted for 80–90% of the methanol-soluble ¹⁴C 47 days posttreatment. Most of the ¹⁴C in the leaves was recovered as DCPU (50–60%) and unidentified polar metabolite(s) which remained at the origin of the thin-layer plates (30–40%). The percentage of radioactivity which remained in cotton residue after methanol extraction increased with time. Digestion of the plant residues with the proteolytic enzyme pronase indicated that some of the nonextractable ¹⁴C may be DCPMU and DCPU complexed with proteins. Similar metabolic patterns were noted after treatment with either heterocyclic ring-labeled or phenyl ring-labeled bioxone-¹⁴C. Generally, bioxone was metabolized to DCPMU which in turn was demethylated to DCPU. The herbicide and DCPMU were 20 times as toxic as DCPU to oat (Avena sativa L.), a susceptible species.     

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.     

Radiochemical distribution and decline studies with bromoxynil octanoate in wheat

Bromoxynil octanoate labelled with ¹⁴C in the ring or in the cyano-group was applied to wheat seedlings at the two-leaf or fully-tillered stage and at rates equivalent to up to 16 oz a.i./acre. The plants were grown either in environmental chambers under controlled conditions for up to 28 days, or outdoors under field conditions for various periods up to harvest. Initially, elimination of radioactivity occurred more rapidly with bromoxynil-cyano-[¹⁴C]-octanoate than with bromoxynil-ring-[¹⁴C]-octanoate, indicating metabolic attack on the cyano group. Under outdoor conditions with ring-[¹⁴C]-herbicide applied at the two-leaf stage, only 12% of the radioactivity was retained after 28 days, principally in the treated leaves. When application was made at fully-tillered stage, about 33% of the ¹⁴C was retained after 56 days, almost entirely in the treated senescent leaves at the base of the plant. There was very little translocation of the herbicide or of any major metabolite. The level of radioactivity in harvested grain and in straw more than 7.5 cm above the ground was very low, even after very late application of ring-[¹⁴C]-labelled herbicide. The amount of bromoxynil octanoate, together with any metabolite retaining part of the aromatic ring, did not collectively exceed the equivalent of approx. 0.01 parts/million bromoxynil octanoate.     

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%).     

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.     

The metabolic behavior of chlorotoluron in wheat and soil

The degradation of chlorotoluron, 1-(3-chloro-4-methylphenyl)-3,3-dimethylurea, was investigated in laboratory and field-grown wheat and soil. Thin-layer cochromatography and, partially, derivatization and mass spectroscopy were used to elucidate the structures of the metabolites. Wheat treated with 4-methyl[¹⁴C]-phenyl-labeled chlorotoluron rapidly metabolized the herbicide using two independent mechanisms: (I) oxidation of the 4-methylphenyl group to yield 4-hydroxy-methylphenyl and 4-carboxyphenyl derivatives; and (II) N-demethylation. Mechanism (I) clearly predominated over mechanism (II). Young wheat degraded the herbicide mainly to 4-hydroxy-methylphenyl derivatives with only a small fraction being additionally N-monodemethylated. Most of both metabolites was conjugated, most probably, with glucose. In straw and grains of mature field-grown summer wheat treated postemergence with labeled chlorotoluron at a rate corresponding to 2 kg active ingredient/hectare 2.8 ppm and 0.12 ppm radioactivity equivalent to chlorotoluron were found, respectively. About 50% of this terminal radioactivity was nonextractable by organic solvents. No chlorotoluron or its N-demethylated derivatives were present in either plant part. About 40% of the radioactivity in straw consisted of 4-carboxyphenyl derivatives half of which were N-mono- or didemethylated. The rest of the terminal radioactivity was mainly in form of the 4-hydroxymethylphenyl derivative of chlorotoluron. Less than 20% of the soluble metabolites was present as conjugates. In soil mechanism (II) exceeded mechanism (I). At harvest of the wheat the 0.4 ppm radioactivity of the 0- to 30-cm soil layer was composed of 43% chlorotoluron, 36% N-mono- and 3% N-didemethylated chlorotoluron, as well as 13% 4-carboxyphenyl derivatives partly N-demethylated.     

Behavior of 14C oryzalin in soil and plants

Radiochemical studies of field soil treated with ¹⁴C oryzalin (3,5-dinitro-N⁴,N⁴-dipropylsulfanilamide) indicated that the compound was readily degradable. One year after soil treatment with oryzalin, 45% of the original radioactivity had dissipated, 25% was extractable, and 30% was “soil bound”. The extractable fraction contained oryzalin and several degradation products, some of which were isolated and identified. No single degradation product accounted for more than 3% of the applied oryzalin. The “soil-bound” radioactivity was extractable with hot alkali. No significant radioactive residues were detectable in either seed or forage of soybean and wheat plants. No specific metabolites of oryzalin were identified in soybean plants. Trace amounts of radioactivity found in plant tissue appeared to be associated with the various plant constituents.     

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%.     

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.     

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 ioxynil to CO2 in soil

Degradation of ioxynil (4-hydroxy-3,5-diiodobenzonitrile) to CO₂ was detected in a clay loam, high organic matter content soil. The majority of radioactivity was recovered as ¹⁴CO₂ from both ring-labeled and cyano-labeled ioxynil; however, ¹⁴CO₂ was always released from cyano-labeled ioxynil at a much faster initial rate. No ¹⁴CO₂ was released in treated sterile soil, either aerobically or anaerobically. Production of ¹⁴CO₂ from cyanolabeled and ring-labeled ioxynil was greatly inhibited by HgCl₂ (10^?5M), and p-chloromercuribenzoate (5 × 10^?5M), but slightly inhibited by ferricyanide (10^?4M). No ¹⁴CO₂ was evolved from ring-labeled ioxynil under anaerobic conditions. These observations indicated that the degradation of ioxynil to CO₂ in soil was a microbial action and was oxygen dependent. This is consistent with the known mechanism of oxygenases in degrading benzene rings. Anaerobically, a small amount of ¹⁴CO₂ was released from cyano-labeled ioxynil. Thin-layer chromatographic analyses of the culture supernatant revealed that 3,5-diiodo-4-hydroxybenzamide and 3,5-diiodo-4-hydroxybenzoic acid were intermediate metabolites.     

Changes in the concentrations of isoproturon and its degradation products in soil and soil solution during incubation at two temperatures

Changes in the concentrations of [¹⁴C]carbonyl-isoproturon and its degradation products in a clay-loam soil and in soil solution during incubation at 11°C and 18°C for 6 weeks, were measured following solvent extraction and soil solution sampling with glass microfibre filters. During herbicide degradation, ¹⁴CO₂ was released (up to 20%) and unextractable radioactivity increased (up to 30%). Monomethyl isoproturon was the main metabolite in soil followed by metabolite X₅ (possibly hydroxy di-des-methyl isoproturon). Isoproturon and monomethyl isoproturon were mainly adsorbed by soil whereas metabolite X₅ was found mainly in the soil solution. Isoproturon concentrations declined in both soil and soil solution, but the percentage of the residual herbicide dissolved in the soil solution decreased from 26 to 15%. At low temperature, herbicide degradation occurred more slowly, and the degradation products were generally less abundant. However metabolite X₅ was present at unexpectedly high levels, particularly in the soil solution. Evolution de l'isoproturon et de ses produits dégradation dans le sol et la solution du sol pendant l'incubation de Vherbicide a deux temperatures. L'évolution de l'isoproturon (marqué au ¹⁴C sur le carbonyle) et de ses produits de dégradation dans un sol argilo-limoneux et dans la solution du sol est suivie pendant 6 sêmaines d'incubation de l'herbicide à 11 et 18°C. Pour ce faire, la solution du sol est échantillonnée au moyen de filtres en fibres de verre et les composés sont extraits du sol par des solvants. Au cours de la dégradation, du ¹⁴CO₂ est libéré (jusqu'à 20%) et la radioactivité non extraite s'accroit (jusqu'à 30%). L'isoproturon monométhyle est le principal métabolite dans le sol suivi du metabolite X5 (probablement le dérivé hydroxy didéméthylé). L'isoproturon et son dérivé monométhyle sont surtout adsorbés par le sol alors que le métabolite X5 est surtout en solution. La quantite d'iso-proturon diminue simultanemént dans le sol et la solution du sol mais la fraction dissoute de l'herbicide residuel décroit de 26 à 15%. A basse température, la dégradation de l'herbicide est plus lente et les produits de dégradation sont généralement moins abondants à l'exception notable du métabolite X⁵ qui est présent a un niveau élevé, en particulier dans la solution du sol. Veränderung der Konzentration von Isoproturon und seiner Abbauprodukte im Boden und in der Bodenlösung bei Inkubation Veränderung der Konzentration von [¹⁴C]-Car-bonyl-Isoproturon und seiner Abbauprodukte in einem Lehmboden und in der Bodenlösung wurden nach 6 Wochen Inkubation bei 11 und 18°C und Extraktion bzw. Probennahme durch Glasmikrofaserfilter gemessen. Während des Herbizidabbaus wurden bis zu 20 % der Radioaktivität als ¹⁴CO2 freigesetzt, und die nichtextrahierbare Radioaktivität nahm zu (bis zu 30 %). Monomethyl-Isoproturon war der Hauptmetabolit, gefolgt vom Metabolit X₅ (möglicherweise Hydroxy-didesmethyl-Isoproturon). Isoproturon und Monomethyl-Isoproturon waren weitgehend an Bodenpartikeln adsorbiert, während der Metabolit X₅ vorwiegend in der Bodenlösung gefunden wurde. Die Isoproturon-Konzentrationen nahmen sowohl im Boden als auch in der Bodenlösung ab, aber der Anteil des Herbizidrückstands in der Bodenlösung ging von 26 auf 15 % zurück. Bei der niedrigen Temperatur wurde das Herbizid langsamer abgebaut, und die Menge der Abbauprodukte war allgemein geringer. Der Metabolit X₅ lag jedoch in unerwartet hoher Menge vor, besonders in der Bodenlösung.     

Translocation and degradation of pyrazosulfuron-ethyl in rice soil

BACKGROUND: Pyrazosulfuron‐ethyl {ethyl 5‐[(4,6‐dimethoxypyrimidin‐2‐ylcarbamoyl)‐sulfamoyl]‐1‐methylpyrazole‐4‐carboxylate} is a new rice herbicide belonging to the sulfonylurea group. This study reports the translocation of ¹⁴C‐pyrazosulfuron‐ethyl to rice plants and its degradation in rice‐planted and unplanted soil. RESULTS: Pyrazosulfuron‐ethyl did not show any appreciable translocation to rice shoots, as ¹⁴C‐activity translocated to the aerial portion never exceeded 1% of the initially applied ¹⁴C‐activity over a 25 day period. Results suggested that the dissipation of pyrazosulfuron‐ethyl from soils followed first‐order kinetics with a half‐life of 5.5 and 6.9 days in rice‐planted and unplanted soils respectively. HPLC analysis of the organic extract of soil samples showed the formation of three metabolites, namely ethyl 5‐(aminosulfonyl)‐1‐methyl‐1‐H‐pyrazole‐4‐carboxylate, 5‐[({[(4,6‐dimethoxy‐2 pyrimidinyl)‐amino]‐carbonyl} amino)‐sulfonyl]‐1‐methyl‐1H‐pyrazole‐4‐carboxylic acid and 2‐amino‐4,6‐dimethoxy pyrimidine, in both rice‐planted and unplanted soils. CONCLUSION: The study indicates that pyrazosulfuron‐ethyl was a short‐lived compound in the soil and was degraded relatively faster in rice‐planted soil than in unplanted soil. The herbicide did not show any appreciable translocation to rice plants. Copyright © 2011 Society of Chemical Industry     

Degradation of [14C]Terbuthylazine and [14C]Atrazine in Laboratory Soil Microcosms

The degradation and formation of major chlorinated metabolites of terbuthylazine and atrazine in three soils (loamy clay, calcareous clay and high clay) were studied in laboratory experiments using molecules labelled with ¹⁴C on the s-triazine ring. Soil microcosms were treated with the equivalent of 1 kg ha^-1 of herbicide and incubated in the dark for 45 days at 20(±1)°C. The quantity of [¹⁴C]carbon dioxide evolved in the soils treated with atrazine was negligible and could not be attributed to mineralization of the parent molecule. The mineralization of terbuthylazine accounted for 0·9–1·2% of the initial radioactivity. In the soils studied, the extrapolated half-lives varied from 88 to 116 days for terbuthylazine and 66 to 105 days for atrazine, with no significant differences for the three soils and the two molecules. The deethyl metabolites of the two s-triazines and the deisopropyl-atrazine metabolite appeared during the incubation in the three soils. The completely dealkylated metabolite was not detected in any of the soils. After 45 days of incubation, the non-extractable soil residues for the high clay, loamy clay and calcareous clay soils represented for terbuthylazine, 33·5, 38·3 and 43·1% and for atrazine, 19·8, 20·8 and 22·3% of the initial radioactivity. © 1997 SCI.     

The degradation of dinitramine (N3,N3-diethyl 2,4-dinitro-6-trifluoromethyl-m-phenylenediamine) in soil

Radioactive dinitramine (1) was incorporated at $\text{1}\text{2}$ Ib/acre (0.6 ppm) in Anaheim silty loam soil and its degradation studied over an 8-month period. For both specifically—¹⁴CF₃ and -Ring-UL-[¹⁴C] labeled (1), only ca. 20% of the radioactivity was lost from the incorporated zone. Mehanol- or acetonitrile-extractable radioactivity decreased rapidly over the initial 60 days reaching 20% after 244 days. Two compounds were isolated and characterized as (1), 0.05 ppm, and 6-amino-1-ethyl-2-methyl-7-nitro-5-trifluoromethylbenzimidazole (2), 0.06 ppm. Two other compounds were tentatively identified by TLC as monodealkylated dinitramine (3), 0.01 ppm, and 6-amino-2-methyl-7-nitro-5-trifluoromethylbenzimidazole (4), 0.01 ppm, Sodium hydroxide (10%) and anionic surfactant (10%) were effective in removing up to 50% of the residual bound radioactivity (i.e., nonacetonitrile extractable), while dimethylamine (25%) released 26%; extraction by acid was less effective.     

DEGRADATION OF BROMOXYNIL IN REGINA HEAVY CLAY*

A spectrophotometric method was developed to detect bromoxynil in Regina heavy clay, and the breakdown under different temperature and moisture conditions was studied. At rates equivalent to 14 kg/ha, over 50% of the applied bromoxynil was degraded in 2 weeks at 25°C and at moisture levels in excess of the wilting point. Losses at 18°C were slightly slower. Little breakdown occurred in sterile soil, indicating that microbial degradation could be an important factor contributing to bromoxynil breakdown under field conditions. Paper and thin-layer chromatographic techniques were used to isolate and identify soil degradation products. In addition to the parent compound small amounts of 3,5-dibromo-4-hydroxybenzamide and 3,5-dibromo-4-hydroxybenzoic acid were detected.     

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.     

Studies on the mode of action of asulam,aminotriazole and glyphosate in Equisetum arvense L. (field horsetail). I: The uptake and translocation of [14c]asulam, [14C]aminotriazole and [14C]glyphosate

The uptake and translocation of [¹⁴C]asulam (methyl 4-aminophenyl-sulphonylcarbamate), [¹⁴C]aminotriazole (1-H-1,2,4-triazol-3-ylamine) and [¹⁴C]glyphosate (N-(phosphonomethyl)glycine) were assessed in Equisetum arvense L. (field horsetail), a weed of mainly horticultural situations. Under controlled-environment conditions, 21°C day/18°C night and 70% r. h., the test herbicides were applied to 2-month-old and 2-year-old plants. Seven days following the application of 0.07-0.09 °Ci (1.14mg) of the test herbicides to young E. arvense, the accumulation of ¹⁴C-label (as percentage of applied radioactivity) in the treated shoots, untreated apical and basal shoots was as follows: [¹⁴C]asulam, 13.2, 0.18 and 1.02%; [¹⁴C] aminotriazole, 67.2, 3.65 and 1-91%; [¹⁴C]glyphosate, 35.9, 0.06 and 0.11%. The equivalent mean values for the accumulation of ¹⁴C-label in 2-year-old E. arvense were [¹⁴C]asulam, 12.0, 1-15 and 1.74%; [¹⁴C]aminotriazole, 58.6, 9.44 and 4.12%; [¹⁴C]glyphosate, 33.1, 0.79 and 2.32%. In the latter experiment, test plants received 0.25-0.30 °Ci (4mg) of herbicide, they were assessed after a 14-day period and the experiment was carried out at 3-week intervals between 2 June and 25 August on outdoor-grown plants. Irrespective of test herbicide or time of application, very low levels of ¹⁴C-label accumulated in the rhizome system. Only 0.2% of the applied radioactivity was recovered in 2-year-old plants and 0.4% in 2-month-old plants. In the young plants [¹⁴C]asulam accumulated greater amounts and concentrations of ¹⁴C-label in the rhizome apices and nodes than [¹⁴C]aminotriazole or [¹⁴C]glyphosate treatments. Inadequate control of E. arvense under field conditions may be due to limited basipetal translocation and accumulation of the test herbicides in the rhizome apices and nodes.     

Metabolism of isopropyl carbanilate (propham) in alfalfa grown in nutrient solution

Alfalfa plants, Moapa variety, were grown in nutrient solution containing isopropylring-[¹⁴C] carbanilate (43.8 μCi/liter propham). After 8 days, 41.2% of the radioactivity initially added to the nutrient culture was recovered; 10.9% of this was from shoots, 3.4% from roots and 26.9% from nutrient medium. Nonextracted residues accounted for 23% of the radioactivity in shoots and 62% of that in roots. The parent herbicide constituted 53 and 38% of the radioactivity extracted from shoots and roots, respectively. The balance of extracted ¹⁴C was polar metabolites which were purified and subjected to enzymatic and acid hydrolysis. Four aglycones were isolated, three of which were purified by thin-layer chromatography and characterized by mass spectrometry. The principal aglycones were: isopropyl-2-hydroxycarbanilate, isopropyl-4-hydroxycarbanilate, and 1-hydroxy-2-propylcarbanilate. The fourth aglycone was not identified.