Conversion rates of aldicarb and its oxidation products in soils. III. Aldicarb

Aldicarb was incubated in seven soils at 15°C and its loss was well described by first-order kinetics. Rate constants varied between 0.078 day^?1 in a peaty sand to 0.35 day^?1 in a clay loam. The concentration-time relationships for aldicarb, its sulphoxide and its sulphone were approximated by a computation model which was used to analyse the importance of the various consecutive and simultaneous reactions. It was computed that 91 to 100% of the aldicarb would be oxidised to its sulphoxide.     

Conversion rates of aldicarb and its oxidation products in soils. I. Aldicarb sulphone

The rate of loss of aldicarb sulphone was studied in incubation experiments on soils from four plough layers and two deeper layers. In all instances the loss could be described by first-order kinetics in the first period of two to three times half-life. However, in a clay loam soil and a greenhouse soil a faster degradation rate was observed after the first 56 and 112 days of incubation respectively. The half-lives of sulphone in plough layer soils at 15°C ranged from 18 days in a clay loam to 154 days in a peaty sand. Conversion in deeper layers was considerably slower than in the corresponding top layers of the soil profile. In a silty layer at 70 to 90 cm depth the half-life at 15°C was 46 days, whereas in a sand layer at 90–110 cm no clear loss was found during the 294 days of incubation.     

Measured and simulated behaviour of aldicarb and its oxidation products in fallow soils

Aldicarb and its oxidation product aldoxycarb (aldicarb sulphone) were applied separately to columns of fallow, sandy loam soils under field conditions. The breakdown and movement of these compounds were monitored, as was the behaviour of aldicarb sulphoxide and aldoxycarb formed by oxidation of the applied aldicarb. The behaviour of these compounds was simulated by a computer model using laboratory data for adsorption and rates of degradation in soil. The model simulated the observed behaviour reasonably well, although redistribution of chemicals was often more rapid than predicted. Production of aldoxycarb from the sulphoxide was less in the field than was expected from the laboratory incubations. Accumulation of chemicals near the soil surface in dry periods was overestimated, indicating that the processes occurring under these conditions are not well described by the model. About 4 months after application, only aldoxycarb, in small amounts, remained in the soils.     

Movement and conversion of aldicarb and its oxidation products in potato fields

In Spring, the insecticide and nematicide aldicarb in the granular formulation Temik 10G (supplied by Union Carbide) was broadcast on three potato fields and incorporated by rotary cultivation. Ridges were formed by repeated runs with ridging implements. The soil was sampled in layers of 0.1 m up to 0.8 m depth three to four times during the growing season. Aldicarb itself was almost completely converted on a humic sand soil and two loam soils within one month. During the growing season, its sulphoxide and sulphone, which are toxic and are formed by oxidation, were retained mainly in the top 0.3 m of all three soils. Relatively high concentrations were measured only in the top 0.2 m, indicating limited redistribution by leaching.Low to very low contents were found up to 0.8 m depth especially on one of the loam soils where the highest total rainfall was measured from May to October (328 mm). In a humic sand soil, leaching in the furrow was deepter than below the ridge. At the end of the growing season, the sulphoxide plus sulphone corresponded to a mass fraction of 5.7 to 6.7% of the dosage in the two loam soils and to 17% in the humic sand soil. These residues were mainly concentrated in the centre of the ridges.Samenvatting In het voorjaar werd op drie aardappelvelden het insecticide en nematicide aldicarb als Temik 10G breedwerpig toegediend en met een frees ingewerkt. Ruggen werden opgebouwd door herhaalde bewerkingen met aanaardwerktuigen. Gedurende het groeiseizoen werd de grond drie tot viermaal bemonsterd in laagjes van 0,1 m tot op 0,8 m diepte. Aldicarb zelf was binnen een maand bijna geheel omgezet zowel in een humeuze zandgrond als in twee zavelgronden. Gedurende het groeiseizoen bleven het sulfoxide en het sulfon, welke produkten eveneens toxisch zijn en door oxidatie van aldicarb worden gevormd, voornamelijk in de toplaag van 0,3 m bij alle drie gronden. Relatief hoge concentraties werden alleen gemeten in de bovenste 0,2 m, wat wijst op een beperkte herverdeling door uitspoeling.Lage tot zeer lage gehalten werden tot 0,8 m diepte gevonden, met name in één van de zavelgronden waar ook de grootste hoeveelheid neerslag van mei tot oktober (328 mm) werd gemeten. In een humeuze zandgrond was de uitspoeling in de voor groter dan die beneden de rug. Aan het eind van het groeiseizoen kwam de hoeveelheid resterend sulfoxide plus sulfon in de twee zavelgronden overeen met een massafractie van 5,7 tot 6,7% van de dosering en in de humeuze zandgrond met 17%. Deze residuen waren voor het grootste deel geconcentreerd in het centrum van de ruggen.     

Conversion and leaching of aldicarb in soil columns

Aldicarb was applied to soil columns in the laboratory which were leached by artificial rainfall. Concentrations of aldicarb, its sulphoxide and its sulphone in the effluent were measured by gas-liquid chromatography. The measured results were analysed in some detail using a computation model. Aldicarb and its oxidation products were very mobile in soil, a fact which could be well described after introducing very low sorption coefficients in the computation model. Aldicarb itself was converted at a high rate following first order kinetics (half-life about 2 days). The best approximations obtained for the rate constant of sulphoxide conversion in two soils were about 0.03 and 0.06/day respectively (half-lives 23 and 12 days). Only a rather wide range of possible values could be obtained for the rate at which sulphone was decomposed.     

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.     

Leaching of aldicarb and thiofanox,and their uptake in soils by sugarbeet plants

The leaching of aldicarb and thiofanox in soils (sandy loam, silt loam and sandy clay loam), and their uptake by sugarbeet plants were studied. Three irrigation levels were maintained: half, normal and double dose. The residues were determined as the sum of the insecticidal metabolites (parent compound + sulphoxide+ sulphone) for both pesticides. Leaching was greatly influenced by the amount of water added and the soil type. Under normal conditions, leaching seemed to proceed very slowly, keeping the chemicals available for uptake by the root systems for a long time. The concentration of insecticide in the leaves was highest in beets grown on sandy loam and lowest in those grown on sandy clay loam. The quantity of irrigation did not influence the residue concentration in the leaves greatly, although its influence was obvious on the total residue present (μg per plant). Increasing the water dose always resulted in a higher total residue, and a greater plant weight. The breakdown in the soils was directly related to the water dose. The experiments show that thiofanox was more stable than aldicarb and was taken up by sugarbeet to a greater extent.     

The fate of the herbicide chlortoluron and its possible degradation products in soils

Chlortoluron hadàhalf-tire in soil of 4–6 weeks. The only metabolite identified was monomethyl chlortoluron, half-life 8 weeks. 3-Chloro-4-methylphenylurea hadàsimilar half-life but was not detected in soils treated with chlortoluron or monomethyl chlortoluron suggesting that 3-chloro-4-methylaniline was formed directly from monomethyl chlortoluron. This aniline hadàhalf-life of 1–2 days in soil, initial concentrations above 5 ppm yielding dimers and trimers predominantly C — N linked. Neither the aniline nor polymeric products were detected in chlortoluron treated soils, presumably because slow formation of the aniline was followed by rapid degradation which kept concentration low.     

Transformation of aldicarb sulfoxide and aldicarb sulfone in four water-saturated sandy subsoils

The transformation of aldicarb sulfoxide and aldicarb sulfone was studied in incubations with water-saturated subsoils under simulated field conditions at 10°C. The subsoils were collected at four locations from beneath the water table at a depth of 2.5 to 3.5 m. In three of the subsoils, the half-life of sulfoxide, incubated at concentrations of 0.14-0.17 mg litre^?1, ranged from 0.7 to 2.8 years. At higher concentrations (8-13 mg litre^?1), its half-life ranged from 3.4 to 6.4 years. At the lower concentration, a large fraction of sulfoxide was transformed into sulfone. The rates of transformation of the sulfone at the lower concentration in the three subsoils corresponded to half-lives of 3.3 to 8.1 years, but in only one subsoil was a significant transformation rate (half-life 6.7 years) measured at the higher concentration during the 2.3-year incubation period. The half-lives at the lower concentrations were more like those in field studies, and perhaps would still underestimate transformation rates under field conditions. After a year, 2.5-15% of the higher sulfoxide and sulfone doses had been trapped as [¹⁴C] carbon dioxide. In the fourth subsoil, with more anaerobic conditions, the half-life of sulfoxide at both concentrations was less than 0.02 year and that of sulfone was about 0.04 year. Four or five radio-labelled transformation products could be traced in this subsoil and about half of the dose of both compounds was trapped as [¹⁴C] carbon dioxide.     

The role of ferrous ions in the rapid degradation of oxamyl,methomyl and aldicarb in anaerobic soils

The carbamoyloxime pesticides methomyl, oxamyl and aldicarb, together with the oxidation products of aldicarb, are known to break down much more rapidly in certain anaerobic subsoils than in the aerobic topsoils from the same site. Ferrous ions have now been shown to be involved in this reaction. Oxamyl was degraded in aqueous solutions at 30°C containing 250 μg ml^?1 Fe²⁺ with a half-life of about 10 h, independent of pH in the range of 5.65–7.66; the observed products of this reaction were N,N-dimethyl-l-cyanoformamide and methanethiol. These same products, rather than the oximino hydrolysis product observed from degradation in aerobic soils, were rapidly and quantitatively formed from oxamyl in suspensions of anaerobic reduced subsoils (Fe²⁺ concentration 27–41 μg ml^?1 soil water), but oxamyl was rather stable in water-saturated Vredepeel subsoil (Fe²⁺ concentration 0.65 μg ml^?1) in which the redox potential was much higher. Methomyl behaved similarly. The rates of reaction in the suspensions of anaerobic subsoils were greater than expected from the concentrations of Fe²⁺ in the soil water, but most of the Fe²⁺ present in soil was bound to the soil particles by cation exchange and this bound Fe²⁺ may have participated. Breakdown of aldicarb was accelerated both in solutions of Fe²⁺ and in the suspensions of anaerobic reduced subsoils, though the rate enhancement was less than observed with methomyl and oxamyl; 2-methyl-2-methylthiopropionitrile and 2-methyl-2-methylthiopropionaldehyde were the observed products from aldicarb in anaerobic soil but only the former was produced in Fe²⁺ solutions; the corresponding nitriles and aldehydes were also yielded by aldicarb sulphoxide and aldicarb sulphone in the anaerobic, reduced subsoils.     

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.     

Residues of aldicarb and its main metabolites in the leaves of sugar beet plants

The residues of aldicarb and of its main metabolites (aldoxycarb, 2-mesyl-2-methylpropionitrile, and 2-mesyl-2-methylpropan-1-ol) were measured, by a gas-liquid chromatographic procedure, in the leaves of ripe sugar beet plants from cultures made by several farmers. The sugar beet plants had been grown in normal fields and treated at sowing with aldicarb at the usual rate of 1 kg ha^?1 in the form of ‘Temik’, the commercial formulation of aldicarb which contains 10% by weight of aldicarb. The samples of sugar beet plants were taken from three fields of different soil types. The residue concentrations, ranged in order of soil type, were: sandy loam > silt loam > clay.     

Assessment of leaching potential of aldicarb and its metabolites using laboratory studies

The metabolites of pesticides can contaminate groundwater and pose a risk to human health when this water is used for drinking. This paper reports the results of a laboratory study on aldicarb and its main metabolites, aldicarb sulfone and aldicarb sulfoxide. Aldicarb and its metabolites showed K_oc values (6–31) which were lower than that of atrazine (55), indicating that they are very mobile in soil. They are less persistent than atrazine (DT₅₀ = 25 days), with DT₅₀ values from less than 1 day and up to 12 days. Aldicarb behaved as a non‐leacher, whereas its metabolites clearly showed the characteristics of leachers. Aged residue leaching experiments showed that aldicarb can occur at high concentrations in the leachate, together with its two metabolites. The leachate composition depends on the incubation time of the parent compound. Aldicarb and its metabolites can form various mixtures in groundwater on the basis of the time elapsing between the application of the insecticide and the first significant rainfall. This study confirms the characteristics of contaminants of aldicarb and especially its metabolites, as reported in the literature. © 2001 Society of Chemical Industry     

Potential enhancement of degradation of the nematicides aldicarb,oxamyl and fosthiazate in UK agricultural soils through repeated applications

BACKGROUND: The potential for enhanced degradation of the carbamoyloxime nematicides aldicarb and oxamyl and the organophosphate fosthiazate was investigated in 35 UK agricultural soils. Under laboratory conditions, soil samples received three successive applications of nematicide at 25 day intervals. RESULTS: The second and third applications of aldicarb were degraded at a faster rate than the first application in six of the 15 aldicarb‐treated soils, and a further three soils demonstrated rapid degradation of all three applications. High organic matter content and low pH had an inhibitory effect on the rate of aldicarb degradation. Rapid degradation was observed in nine out of the ten soils treated with oxamyl. In contrast, none of the fosthiazate‐treated soils demonstrated enhanced degradation. CONCLUSION: The potential for enhanced degradation of aldicarb and oxamyl was demonstrated in nine out of 15 and nine out of ten soils respectively that had previously been treated with these active substances. Degradation of fosthiazate occurred at a much slower rate, with no evidence of enhanced degradation. Fosthiazate may provide a useful alternative in cases where the efficacy of aldicarb and oxamyl has been reduced as a result of enhanced degradation. Copyright © 2009 Society of Chemical Industry     

The analysis of crops and soils for the triazine herbicide cyanazine and some of its degradation products. I. Development of method

Radiochemical techniques have been used to develop efficient procedures for the extraction of residues of cyanazine herbicide [‘BLADEX’,

1 BLADEX and FORTROL are Shell registered Trade Marks.

^a ‘FORTROL’,^a 2-chloro-4-(1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-triazine] and its metabolites 2-chloro-4-(1-carbamoyl-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-carbamoyl-1-methylethylamino)-6-amino-1,3,5-triazine ( VI ) from crops and soils. Partition and column chromatographic techniques have been established for the purification of the extracts. The full analytical procedure is described and the final determination of all four compounds is by g.l.c. with electron capture detection with blank values for field samples generally 0.02 part/million and with good recoveries.     

苦皮滕素Ⅴ在土壤中的消解动态及降解产物

为指导苦皮藤素制剂的科学合理使用,采用高效液相色谱-电喷雾多级串联质谱技术(HPLC-ESI-MS/MS)研究了苦皮藤素V在4种土壤中的消解动态及其降解产物。结果表明:苦皮藤素V在江西红土和陕西黄土中消解缓慢,90 d的消解率仅为68.0%和65.0%;在黑龙江黑土和天津碱土中消解相对较快,90 d时消解率分别为84.9%和95.1%。苦皮藤素V在4种土壤中的主要降解产物为一系列在其C-1、C-2和C-8位发生酯键水解而形成的3-羟基、4-羟基及5-羟基的二氢沉香呋喃多元酯。     

Residues of tetrachlorvinphos and its breakdown products on treated crops. II.—Residues on apples

Apples treated with tetrachlorvinphos (Gardona, trans-isomer of dimethyl 1-(2′,4′,5′-trichloropheny1)-2-chlorovinyl phosphate) insecticide under field conditions in several countries in 1965, 1966 and 1967 have been analysed at intervals after treatment for residues of tetrachlorvinphos itself, its cis-isomer and seven potential breakdown products. Residues of up to 10 ppm of tetrachlorvinphos were detected immediately after the last of three applications of tetrachlorvinphos (diluted to 0.16% active material). The initial half-life of the tetrachlorvinphos was on average about 0.5 weeks under U.K. conditions and only 10% of the tetrachlorvinphos remained unchanged at 2 weeks after application. The overall chemical persistence of the wettable powder formulation was not significantly different from that of the emulsifiable concentrate formulation. Within 8 weeks of the application the residues were mainly of tetrachlorvinphos itself, its cis-isomer and the alcohol 1-(2′,4′-5′-trichlorophenyl)ethan-l-ol, in free and sugar-conjugated forms. The residues of the conjugates of this alcohol (up to 0.92 ppm) were generally present in higher concentration at 6-8 weeks after the application than were the residues of the other components. Whilst residues of other breakdown products were detected on the apples their individual residues were below 0.05 ppm and generally below 0.01 ppm at 6 weeks or more after the last of several applications of tetrachlorvinphos.     

The distribution of aldicarb and its metabolites between Lumbricus terrestris,water and soil

Aldicarb is taken up by earthworms from aqueous solution to give concentrations in the worms comparable to that in the external aqueous solutions. Uptake from waterlogged soils is similar, but much less aldicarb is taken up from drier soils. Aldicarb sulphoxide [2-methyl-2-(methylsulphinylpropionaldehyde O-methylcar-bamoyloxime], aldoxycarb and oxamyl are poorly taken up, giving concentrations in the worm of about 5% of the external aqueous concentration. In worms, aldicarb is rapidly converted to the sulphoxide which has a half-life in worms of 19 h at 15°C, and 50 h at 5°C.     

The degradation of aldicarb and oxamyl in soil

The breakdown of oxamyl was studied in three downland chalk soils, a peat loam, a sandy loam, and the same sandy loam modified by adding peat. The kinetics of aldicarb degradation via its sulphoxide and aldoxycarb (aldicarb sulphone) were also studied in these two sandy loam soils. All the reactions followed first-order kinetics, the reaction being faster in the original than in the modified sandy loam. Rates of reaction were slower at low moisture contents, and decreased markedly when the temperature was reduced from 10 to 5°C though less so than from 15 to 10°C.     

Development of methods for the analysis of crops and soils for residues of benzoylprop-ethyl and its breakdown products

Methods are described for the analysis of residues of the herbicide benzoylpropethyl, ethyl (±)-2-[ N-(3,4-dichlorophenyl)benzamido]propionate, and its breakdown product, (±)-2-[ N-(3,4-dichlorophenyl)benzamido]propionic acid, in wheat and soil. In wheat the acid degradation product conjugates with plant sugars and the present paper includes methods for determination of these residues either separately or as a combined residue with unconjugated acid. Efficient extraction procedures have been developed together with partition and column chromatographic techniques for purification of extracts. The full analytical procedures are described and the final determinations are by g.1.c. with electron capture detection with blank values for field samples in the range 0.01–0.05 mg/kg. Good recoveries were obtained. Radiochemical techniques have been used to verify the extraction and subsequent procedures in the methods.