The determination and study of residues of flamprop-isopropyl in soil

Residue analytical studies are reported on soils from trial sites in the UK and France following applications of flamprop-isopropyl ( I ) to growing crops. The analytical procedure developed allowed the determination of I and its hydrolysis product N-benzoyl-N-(3-chloro-4-fluorophenyl)-DL -alanine ( II ). The residues in the soil often increased during some weeks after application due to transfer of I from the crop to the soil, so that measurement of the initial half-life of I in soil was unusually difficult. However, it was probably within the range 4–20 weeks. Both I and II were detected in field soils, but neither compound was persistent in soil and normally little or no carry-over of residues occurred from one season to the next, although greater persistence was found in one Kentish trial.     

A sensitive method for the determination of residues of N,N'-Bis(1,3,4-thiadiazol-2-yl)methanediamine in rice

A sensitive method for the isolation, clean-up and thin-layer chromatographic semi-quantitative determination of residues of N,N'-bis(1,3,4-thiadiazol-2-yl)methanediamine ( II ) in rice is reported. The residue from II in rice was found to be its degradation product 1,3,4-thiadiazol-2-ylamine ( I ). The mean recovery by this method was 85%, and the lowest limit of determination was 0.01 mg kg^?f. Using this proposed technique, the residues of I and II in various field-treated rice samples were studied.     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. II. Prognose möglicher Folgekulturen bei Atrazinrükständen im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. II. Prediction of the phytotoxicity of atrazine residues to following crops Total and plant-available atrazine residues in the top 10 cm soil were measured 120 days after application of 3 kg ai ha^?1 to maize (Zea mays L.) at three sites in Rumania. At one site, similar measurements were made 3?5 years after application of 100 kg ai ha^?1. Plant-available atrazine residues were estimated by extraction of soil samples with water, and by bioassay using Brassica rapa as the test plant. It was calculated that between 30 and 120μg atrazine 1^?1 was potentially available to plants in the different soils. Dose-response relationships for atrazine and the most important rotational crops with maize in Rumania—sunflower, winter wheat, soybean and flax—were determined in hydroponic culture using herbicide concentrations corresponding with the plant-available fractions measured in the different soils. ED₅₀ values were determined by probit analysis and the results showed that sunflower (ED₅₀, 22μg 1^?1) was the most sensitive crop, and soybean (ED₅₀, 78μg 1^?1) was the least. The residual phytotoxicity of atrazine to succeeding crops in the different soils was predicted using the appropriate availability and phytotoxicity data, and the results showed good agreement with those observed. The results suggest that measurements of plant-available herbicide residues afford a rapid method of assessing possible phytotoxicity to following crops.     

Analysis of soils for diclofop-methyl and diclofop

A method is described for the analysis of soils for residues of the herbicide diclofop-methyl, methyl (RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate, and its breakdown product diclofop, (RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid. Diclofop-methyl undergoes hydrolysis in the soil to diclofop, which also has herbicidal activity. A procedure, using a 1% phosphoric acid solution for extraction purposes, has been developed and gives good recoveries of both diclofop-methyl and diclofop at the 0.5 and 0.05 mg kg^?1 levels. After methylation, gas-liquid chromatography with electron-capture detection is used to determine total residue concentrations.     

The behaviour of residues of flamprop-isopropyl and its breakdown products in barley

Residue data are reported for flamprop-isopropyl ( I ) in barley grain and straw samples following applications of the herbicide to crops grown in eight countries. The samples were analysed for I and its hydrolysis product N-benzoyl-N-(3-chloro-4-fluorophenyl)-DL -alanine ( II ). Following recommended applications (normally 1 kg ha^?1 at Feekes scale G-I/J), residues of I and II in the grain were low (90% were <0.02 mg kg^?1 for I , 86% were <0.06 mg kg^?1 for II , levels which were essentially the limits of determination). Residues in straw were higher and more variable, but again 63 and 77% of samples were below 1 mg kg^?1 for I and II , respectively.     

Degradation of the herbicide benzoylprop-ethyl in soil

The degradation of [¹⁴C] benzoyl prop ethyl (SUFFIX,^a ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate) in four soils has been studied under laboratory conditions. The major degradation product of benzoylprop ethyl at up to 4 months after treatment was its corresponding carboxylic acid (II). On further storage this compound became firmly bound to soil before it underwent a slow debenzoylation process which led to the formation of a number of products including N-3,4-dichlorophenylalanine (IV), benzoic acid, 3,4-dichloroaniline (DCA), which was mainly present complexed with humic acids, and other polar products. Although these polar products were not identified, they were probably degradation products of DCA, since they were also formed when DCA was added to soil. No 3,3′,4,4′-tetrachloroazobenzene (TCAB) was detected in any of the soils at limits of detectability ranging from 0.01-0.001 parts/million. Since N-3,4-dichlorophenylalanine (IV) and 3,4-dichloroaniline were transient degradation products of benzoylprop ethyl, the metabolism in soil of radiolabelled samples of these compounds was also studied. In these laboratory experiments the persistence of the herbicide increased as the organic matter content of the soil increased and the time for depletion of half of the applied benzoylprop ethyl varied from 1 week in sandy loam and clay loam soils to 12 weeks in a peat soil.     

Residualwirkung von Chlortriazin-Herbiziden im Boden an drei rumänischen Standorten. I. Prognose der Persistenz von Simazin und Atrazin im Boden

Residual effects of chlorotriazine herbicides in soil at three Rumanian sites. I. Prediction of the persistence of simazine and atrazine Persistence of simazine and atrazine in the top 10 cm soil was measured at three sites in Rumania with variations in climate and soil conditions. Both herbicides were applied at 1 and 3 kg ai ha^?1 to uncropped plots and to plots cropped with maize (Zea mays L.). Rates of residue decline were independent of application rate and crop cover but varied between sites. The time for 50% loss of atrazine varied from 36 to 68 days and that of simazine from 48 to 70 days. Laboratory studies were made with atrazine to characterize degradation rates under standard conditions and to measure adsorption and leaching behaviour in the different soils. Weather records for the periods of the field experiments were used in conjunction with appropriate constants derived from the laboratory results, or from data in the literature, in a computer program to simulate persistence in the field. Results from the model were in reasonable agreement with the observed soil residues although there was a tendency to overestimate rates of loss on some occasions. The results suggest that the model of persistence was sufficiently accurate for practical purposes, and that its use could preclude the need for extensive analytical measurements of residues.     

The breakdown of the triazine herbicide cyanazine in soils and maize

Radioisotope techniques have been used to study the breakdown products that are formed from the herbicide cyanazine ( BLADEX )^a, 2-chloro-4-(1-cyano-1-methylethyl-amino)-6-ethylamino-1,3,5-triazine, in soils and in maize grown in the soils under indoor conditions. In soils of different types cyanazine broke down mainly by conversion of the nitrile group to amide ( II ) and then to an acid ( III ) followed by hydrolysis of the ring chlorine to hydroxyl ( IV ). Dealkylation reactions occurred to only a limited extent in soils. In maize plants grown in treated soils the hydrolysis products, the amide ( II ) and the hydroxy acid ( IV ) were detected as well as appreciable quantities of products ( VI ) and ( VIII ) formed from these by loss of the N-ethyl group. In plants the hydroxy acids ( IV ) and ( VIII ) were present in the free form and there was also evidence for conjugates which were not identified but could be converted to these hydroxy acids, ( IV ) and ( VIII ), on treatment with acids. In these indoor studies the major residues appear to be the hydroxy acid ( IV ) in soils and ( IV ) and its dealkylated analogue ( VIII ) in plants grown in treated soils. These compounds are not herbicides and are of a low order of toxicity to mammals.     

The behaviour of residues of benzoylprop-ethyl and its breakdown products in wheat

Samples of wheat grain and straw have been analysed from trials with the wild oat herbicide benzoylprop-ethyl ( I ) in several countries. Following recommended commercial treatments (application of 1.0–1.6 kg ha^?1 at Feekes growth stage G-J), total residues of I and its hydrolysis product N-benzoyl-N-(3,4-dichlorophenyl)-DL - alanine (free and conjugated) were low and in the majority of instances they were < 0.01 mg kg^?1 in samples of grain from the UK, although rather higher residues were detected in some grain samples from other countries. Residues in straw were higher, but normally did not exceed 2 mg kg^?1, and were rather variable, possibly as a result of differences in agricultural practice.     

The breakdown of the triazine herbicide cyanazine in wheat and potatoes grown under indoor conditions in treated soils

The breakdown of the triazine herbicide cyanazine (“BLADEX”,^a 2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine) has been studied in spring and winter wheat and potatoes grown under indoor conditions in soils treated at planting with up to 1.5 kg/ha of the radiolabelled herbicide. Breakdown products were mainly those formed by hydrolysis of the cyano group to give an amide ( II ) and an acid ( III ) followed by hydrolysis of the chlorine to hydroxyl ( IV ). De-N-alkylation reactions also occurred although these were less evident in soils. In wheat the chloro acid ( VII ) formed by the des-ethylation of ( III ) was more evident than in previous studies with maize. In all of the crops at harvest the residues were mainly of the hydroxy acids ( IV ) and ( VIII ); ( IV ) 2-hydroxy-4-(1-carboxy-1-methylethylamino)-6-ethyl-amino-1,3,5-triazine; ( VIII ) 2-hydroxy-4-(1-carboxy-1-methylethylamino)-6-amino-1,3,5-triazine, respectively. In potatoes and spring wheat they were present in both free and conjugated forms whereas in winter wheat they were almost entirely in conjugated forms. The compounds (IV) and (VIII) are of a low order of toxicity to animals and are not herbicidal. They are unlikely to present a residue hazard if present in field crops.     

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.     

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.     

Fate of metsulfuron-methyl in soils in relation to pedo-climatic conditions

The dependence of the behaviour of metsulfuron-methyl on soil pH was confirmed during incubations under controlled laboratory conditions with two French soils used for wheat cropping. The fate of [¹⁴C] residues from [triazine-¹⁴C]metsulfuron-methyl was studied by combining different experimen-tal conditions: soil pH (8·1 and 5·2), temperature (28 and 10°C), soil moisture (90 and 50% of soil water holding capacity) and microbial activity (sterile and non-sterile conditions). Metsulfuron-methyl degradation was mainly influenced by soil pH and temperature. The metsulfuron-methyl half-life varied from five days in the acidic soil to 69 days in the alkaline soil. Under sterile conditions, the half-life increased in alkaline soil to 139 days but was not changed in the acidic soil. Metsulfuron-methyl degradation mainly resulted in the formation of the amino-triazine. In the acidic soil, degradation was characterised by rapid hydrolysis giving two specific unidentified metabolites, not detected during incubations in the alkaline soil. Bound residues formation and metsulfuron-methyl mineralisation were highly correlated. The extent of bound residue formation increased when soil water content decreased and was maximal [48 (±4)% of the applied metsulfuron-methyl after 98 incubation days] in the acidic soil at 50% of the water holding capacity and 28°C. Otherwise, bound residues represented between 13 and 32% of the initial radioactivity. © 1998 SCI     

Bromoxynil degradation in a Mississippi silt loam soil

BACKGROUND: The objectives of these laboratory experiments were: (1) to assess bromoxynil sorption, mineralization, bound residue formation and extractable residue persistence in a Dundee silt loam collected from 0–2 cm and 2–10 cm depths under continuous conventional tillage and no‐tillage; (2) to assess the effects of autoclaving on bromoxynil mineralization and bound residue formation; (3) to determine the partitioning of non‐extractable residues; and (4) to ascertain the effects of bromoxynil concentration on extractable and bound residues and metabolite formation. RESULTS: Bromoxynil K_d values ranged from 0.7 to 1.4 L kg^?1 and were positively correlated with soil organic carbon. Cumulative mineralization (38.5% ± 1.5), bound residue formation (46.5% ± 0.5) and persistence of extractable residues (T_1/2 < 1 day) in non‐autoclaved soils were independent of tillage and depth. Autoclaving decreased mineralization and bound residue formation 257‐fold and 6.0‐fold respectively. Bromoxynil persistence in soil was rate independent (T_1/2 < 1 day), and the majority of non‐extractable residues (87%) were associated with the humic acid fraction of soil organic matter. CONCLUSIONS: Irrespective of tillage or depth, bromoxynil half‐life in native soil is less than 1 day owing to rapid incorporation of the herbicide into non‐extractable residues. Bound residue formation is governed principally by biochemical metabolite formation and primarily associated with soil humic acids that are moderately bioavailable for mineralization. These data indicate that the risk of off‐site transport of bromoxynil residues is low owing to rapid incorporation into non‐extractable residues. Published 2009 by John Wiley & Sons, Ltd     

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.     

The fate of the herbicide benzoylprop-ethyl in crops grown in treated soils

The herbicide benzoylprop-ethyl (SUFFIX,^a ethyl (±)-2-(N-benzoyl-3,4-dichloro-anilino) propionate) is applied post-emergence for the control of wild oats (Avena spp.) in wheat. During application some falls onto the soil and in the present work the possible uptake of residues from the soil, particularly by rotation crops has been studied using radioisotope techniques under indoor and outdoor conditions. Soil application at 1 kg/ha gave lower residues in wheat in the year of application than were found in previous studies using overall foliar-soil application. In the radiochemical experiments soil residues did persist into the following year, but residues in potatoes and wheat grown in these soils, although generally below the limit of determination (0.005 mg/kg), were occasionally just above this level (0.006 mg/kg). On the results of the present work, residues in rotational crops from soils treated in the previous year are unlikely to reach the limits of normal analytical determination.     

The analysis of crops and soils for the triazine herbicide cyanazine and some of its degradation products. II. Results

Crops and soils from field trials in 1967–1970 in several countries have been analysed for residues of the triazine herbicide cyanazine (‘BLADEX’

1 Shell Registered Trade Mark.

^a or ‘FORTROL’^a' 2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine) and for its degradation products 2-chloro-4-(1-carbarmoyl-1-methylethylamino)-6-ethylamino-1,3,5-triazine ( II ), 2-chloro-4-(1-cyano-1-methylethylamino)-6-amino-1,3,5-triazine ( V ) and 2-chloro-4-(1-carbonyl-1-methylethylamino)-6-amino-1,3,5-triazine ( VI ). The time for the concentration of cyanazine in soils to fall to half the initial value was in the range 1.3 to 5 weeks with a mean value of 2.4 weeks. The rate of loss was not affected by sparse crop cover and there was some indication that the rate was greater under moist soil conditions. Residues of up to 0.5 part/million of ( II ) and up to 0.08 part/million of ( VI ) were detected in soils at 4 weeks from cyanazine application at 2 kg/ha. The residues of cyanazine and the degradation products declined rapidly and were 0.07 part/million or less at 16 weeks from treatment. Repeated annual applications did not lead to a detectable build up of residues in soil. Neither residues of cyanazine nor those of ( II ), ( V ) or ( VI ) could be detected in a wide range of crops harvested from soil treated in accordance with the likely recommendations and the limits of detectability were 0.01 to 0.04 part/million.     

Sorption–desorption of 'aged' isoxaflutole and diketonitrile degradate in soil

Isoxaflutole is a relatively new herbicide used for weed control in maize. The objective of this research was to increase the understanding of the behaviour and environmental fate of isoxaflutole and its diketonitrile (DKN) degradate in soil, including determination of the strength of sorption to soil and whether sorption is affected by ageing. In sandy loam (SL) and silty clay (SiCl) soils, ¹⁴C‐isoxaflutole was found to dissipate rapidly after application to soil; recovery ranged from ～42% to 68% at week 0, and recovery had decreased to <10% at week 12. Decreases in ¹⁴C isoxaflutole residues over time in SL and SiCl soils are consistent with hydrolysis of isoxaflutole and formation of bound DKN residues in the soil. DKN recovery from freshly treated SiCl and SL soils was 41% to 52%. After a 12‐week incubation in SL soil at pH 7.1 and 8.0, recoveries were similar, ～40%. However, at week 12 in SL soil pH 5.7, DKN recovery decreased to ～28%. DKN recovery in SiCl soil at week 12 was <10%. Increases in sorption of DKN in SL at pH 5.7 and SiCl soil over time indicate that the DKN degradate is tightly bound to the soil and sorption is affected by soil pH and soil type. Sorption of ¹⁴C‐DKN in the SiCl soil more than doubled with ageing compared with the lower K_d sorption coefficient values of the SL soils. In the SiCl soil at time 0, the K_d was 0.6; at 1 week, K_d increased to 2; and at the end of the 12‐week incubation period, K_d was 4.5. This strong binding of DKN to the soil may be due to chelate formation in the interlayer of the clay.     

The behavior of clomazone in the soil environment

BACKGROUND: Clomazone is a herbicide used to control broadleaf weeds and grasses. Clomazone use in agriculturally important crops and forests for weed control has increased and is a potential water contaminant given its high water solubility (1100 µg mL^?1). Soil sorption is an environmental fate parameter that may limit its movement to water systems. The authors used model rice and forest soils of California to test clomazone sorption affinity, capacity, desorption, interaction with soil organic matter and behavior with black carbon. RESULTS: Sorption of clomazone to the major organic matter fraction of soil, humic acid (HA) (K_d = 29–87 L kg^?1), was greater than to whole soils (K_d = 2.3–11 L kg^?1). Increased isotherm non‐linearity was observed for the whole soils (N = 0.831–0.893) when compared with the humic acids (N = 0.954–0.999). Desorption isotherm results showed hysteresis, which was greatest at the lowest solution concentration of 0.067 µg mL^?1 for all whole soils and HA extracts. Aliphatic carbon content appeared to contribute to increased isotherm linearity. CONCLUSION: The results indicate that clomazone does not sorb appreciably to sandy or clay soils. Its sorption affinity and capacity is greater in humic acid, and consequently clomazone has difficulty desorbing from soil organic matter. Sorption appears to follow processes explained by the dual‐mode model, the presence of fire residues (black carbon) and a recently proposed sorption mechanism. Copyright © 2009 Society of Chemical Industry     

异噁唑草酮在土壤表面光解及在土壤中的降解和淋溶特性

为合理评估除草剂异唑草酮的环境风险，在实验室模拟条件下，研究了异唑草酮在土壤 (红壤土)表面光解以及在不同质地土壤 (潮土、水稻土和红壤土) 中的降解和淋溶特性。结果表明:异唑草酮在土壤表面的光解遵循一级反应动力学方程c_t = 4.23e–0.008t (r = 0.937)，半衰期为82.5 h；其在潮土、水稻土和红壤土中的降解均符合一级动力学方程，好氧条件下，异唑草酮在3种土壤中的降解半衰期分别为10.5、43.3和139 h，厌氧条件下的降解半衰期分别为19.4、18.4和158 h；其在潮土、水稻土和红壤土中的淋溶系数 (R_f) 分别为0.417 0、0.083 3和0.083 3。研究表明:异唑草酮在土壤表面光解速率较慢，而在土壤中好氧及厌氧条件下降解速率均较快，残留期短；其在土壤中淋溶性较弱，不易对周围环境及地下水造成污染风险。