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.     

Residues of tetrachlorvinphos and its breakdown products on treated crops. I.—Method development

Procedures are described for the analysis of crops for residues of tetrachlorvinphos (Gardona, trans-isomer of dimethyl 1-(2′,4′,5′-trichlorophenyl)-2-chloroyinyl phosphate) insecticide together with methods for the analysis for residues of its isomer and its conjugated and non-conjugated breakdown products. Suitable procedures for the extraction are described together with procedures for the cleanup of the extracts by partition or column chromatography and final analysis down to 0·01 ppm or less by gas-liquid chromatography with electron capture detection.     

Determination of residues of promecarb and its metabolite, 3-methyl-5-isopropylphenol,in cattle

A procedure is described for the colorimetric determination of promecarb as 3-methyl-5-isopropylphenol in tissues using 2,6-dichlorpbenzoquinone-4-chlorimine as the chromogen. Cattle were exposed to either 1, 3, 5 or 8 spray applications of a 0·2% promecarb emulsion at 3-day intervals or were fed promecarb at 2 ppm or 20 ppm daily in the diet for 20 days. All animals were slaughtered 30 h after final exposure. Of the animals in the spraying trial, residues in omental fat ranged from 0·9 ppm to 1·5 ppm promecarb and 0·4 ppm to 1·9 ppm 3-methyl-5-isopropylphenol. Residues in perirenal fat ranged from 0·8 ppm to 1·9 ppm promecarb and 0·9 ppm to 1·6 ppm 3-methyl-5-isopropylphenol. Residues in diaphragm muscle did not exceed 0·06 ppm. In the feeding trial, the maximum residues induced were 2·2 ppm promecarb and 1·4 ppm 3-methyl-5-isopropylphenol in omental fat of an animal fed for 20 days on a diet containing 20 ppm promecarb.     

HERBICIDE RESIDUE DETERMINATIONS AND TAINT TESTS ON FRUIT FROM GOOSEBERRIES TREATED WITH CHLORTHIAMID AND DICHLOBENIL

Fruit harvested from gooseberry plots treated with up to 33·6 kg/ha of chlorthiamid and dichlobenil (applied at two dates) was examined for the presence of residues of 2,6-dichlorobenzonitrile together with the possible metabolites, 2,6-dichlorobenzamide and 2,6-dichlorobenzoic acid. In addition the canned fruit was examined for taint. Residues of 2,6-dichlorobenzonitrile resulting from the application of both herbicides at all rates were below 0·05 ppm. Residues of 2,6-dichlorobenzamide ranged from 0·13 to 0·45 ppm with the greatest residues occurring in fruit from plots treated with the highest amounts of chlorthiamid in March. Fruit from some of the March applications of both herbicides contained residues of up to 0·16 ppm 2,6-dichlorobenzoic acid. No taints were found in the canned fruit.     

Residues of synthetic pyrethroid insecticides on horticultural crops

Foliar applications of synthetic pyrethroids were made to several crops to determine residue levels at various intervals after application. On onions, residues of cypermethrin, permethrin and fenvalerate were negligible > 0.1 mg kg^?1, 7 days after application. On lettuce, residues of fenvalerate and permethrin were 0.8 mg kg^?1. On celery, residues of fenvalerate did not decline and ranged from 0.12 to 0.25 mg kg^?1 during the 14-day period. On green bush-beans, residues of permethrin and cypermethrin did not decline during the 14-day period and ranged from 0.1 to 0.6 mg kg^?1. By day 7, residues of cyfluthrin, cypermethrin, deltamethrin, fenvalerate and permethrin on strawberries were less than the acceptable maximum tolerance of 0.1 mg kg^?1 with the exception of cypermethrin, applied at the rate of 0.14 kg a.i. ha^?1 which gave a residue of 0.14 mg kg^?1.     

Residues and fate of endosulfan on field-grown pepper and tomato

Endosulfan (Thiodan 3 EC), a mixture of α- and β-isomers, was sprayed on 92-day-old field-grown pepper and tomato at the recommended rate of 0·61 kg AI ha^-1. Plant tissue samples were collected at 1 h to 14 days after application and analysed to determine the content and dissipation rate of endosulfan isomers (α- and β-endosulfan) and the major metabolite, endosulfan sulfate. Analysis of samples was accomplished using gas chromatography-mass selective detection (GC-MSD). The results indicated the formation of endosulfan sulfate as a residue component on the plant tissues and also the relatively higher persistence of the β-isomer as compared to the α-isomer on pepper fruits. The initial total residues (α- and β-endosulfan isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper fruits, the α-isomer, which is the more toxic to mammals, dissipated faster than the less toxic β-isomer. Total residues (α- and β-endosulfan isomers plus the sulfate metabolite) on tomato leaves revealed longer persistence (t_1/2 4·6 days) compared to the total residues detected on pepper leaves (t_1/2 2·0 days) 3–14 days following spraying. Persistence of the β-isomer on pepper fruits was high 3–14 days following spraying compared to on tomato fruits. This long persistence increases risk of exposure of the consumer. In addition, the longer persistence of the total residues on tomato foliage should be considered of importance for timing the safe entry of tomato harvesters due to the high mammalian toxicity of endosulfan. © 1998 Society of Chemical Industry     

Movement of dieldrin through soils: I.—From arable soils into ponds

Dieldrin at a rate of 22–45 kg active ingredient/ha (10–20 times the rate used in practice) was applied to strips, each 1·8–3·6 m wide, 3·6–4·5 m away from the edges of four ponds. There were shallow to steep slopes from the treated strips towards the ponds. Dieldrin was found in small amounts in untreated soil on the surface of the slopes between the treated strips and the ponds but none was found in the pond water. Very small amounts (maximum 0·3 ppm) were found in bottom mud of ponds but not when the dieldrin had been thoroughly incorporated into the treated soil after application. In the experiment where the vertical distribution of dieldrin was studied the largest amount below 15 cm was 1·1 ppm at 81 weeks from application.     

Effects of fluazifop-butyl on shoot growth and rhizome buds of Elymus repens (L.) Gould

A series of glasshouse experiments was conducted to evaluate the activity of fluazifop-butyl, butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy] propionate, against Elymus repens. Foliar applications of doses 0·25–1·0 kg ha^?1 consistently gave better control than did soil applications. The most obvious phytotoxic symptoms were chlorosis and necrosis, beginning with the youngest leaves 5–6 days after spraying, which spread to all leaves within 2 weeks. Translocation was measured by defoliating plants at different times after spraying and assessing regrowth and by evaluating rhizome-bud viability. At low doses (0·125 and 0·25 kg ha^?1) translocation to rhizomes occurred mainly between 6 and 48 h. When fluazifop-butyl was sprayed at a dose range of 0·125–1·0 kg ha^?1, at least 90% of the rhizome buds had accumulated a lethal dose within 72 h of spraying. In another experiment, with a dose of 0·25 kg ha^?1, 31, 72 and 92% of rhizome buds were found to be non-viable when sampled 2, 24 and 48 h respectively after spraying. At 1·0 kg ha^?1 all the buds had accumulated sufficient herbicide to prevent sprouting 48 h after spraying.     

Persistence of dichlobenil in a sandy soil and effects of residues on plant growth

The persistence of dichlobenil following the application of dichlobenil granules was studied in a replicated plot experiment including both surface and incorporated treatments of 8·3 and 16·6 kg/ha ai. Soil analyses showed an initial half-life of about 4 weeks but the persistence increased with time and a year after application the half-life was about 1 year. Incorporation of the granules into the soil markedly increased the persistence of dichlobenil and its metabolite dichlorobenzamide. The most sensitive crop was carrot which was damaged by residues of only 1–2% of the recommended dose. Residues phytotoxic to carrots persisted for 2 years from the 8·3 kg/ha surface application and 5 years from the 18·6 kg/ha incorporated application. Lettuce was also highly sensitive to residues.     

RESIDUAL ACTIVITY OF PARAQUAT IN SOILS II. ADSORPTION AND DESORPTION

Glasshouse studies showed that low doses of paraquat inhibited the germination of Lolium perenne L. broadcast directly onto the paraquat-sprayed surfaces of a sphagnum and a peat soil, but that higher doses were necessary to produce phytotoxic symptoms on mineral soils, a compost and a loam. On all soils residual activity increased rapidly with increasing dose once the minimum phytotoxic dose was reached. On a sandy soil, residual activity increased almost linearly from the lowest to the highest dose applied. At 9·0, 4·5 and 2·24 kg/ha phytotoxicity on a compost was not affected by changes in the volume of application, but at 1·68 kg/ha and lower, reducing the volume from 562 1/ha to 281 and 112 1/ha resulted in increased phytotoxicity. Phytotoxic residues were eluted from paraquat-treated compost surfaces by percolating de-ionized water up soil columns but residual activity was not removed from the eluted surfaces. Surface irrigation of paraquat-treated surfaces with water previously percolated through columns of untreated soil reduced residual activity by 45%.     

THE PERSISTENCE AND PENETRATION OF LARGE DOSES OF SIMAZINE IN UNCROPPED SOIL

Summary. The residues remaining in the soil from repeated annual application of simazine at 2–8, 5–6, and 22–4 kg/ha to uncropped plots on a loam soil were measured by chemical or bioassay methods at various intervals after treatment.
The total simazine residue present 12 months after the last of three treatments with 2–8 kg/ha and 8 months after the last of five treatments with 5–6 kg/ha was less than 10% of the annual dose. This rapid decomposition is considered consistent with the soil and climatic conditions. In contrast a much larger residue (a mean value of 1·7 kg/ha) was found on plots sampled 21/2 years after the last of two annual applications of simazine at 22·4 kg/ha and the reduction in the amount of residue during the next 12 months was only of the order of 25%.
In all treatments the highest concentration of simazine was found in the surface layers of the soil but measurable residues were detected to 60 cm depth, 31/2 years after the last 22·4 kg/ha application.
There was considerable variation in the total residues recovered between replicate plots and between different positions on the same plots in all treatments regardless of the depth of the sample. The possible causes of this variation are discussed.
Persistance et pénétration de fortes doses de simazine dans un sol non cultivé     

Residues of chlorpyrifos in various crops II. Residues after field treatments

Five agricultural crops were treated with OO-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate (chlorpyrifos) granular or emulsifiable concentrate formulations at dosages from 0.5 to 6.0 kg (a.i.)/ha and at different periods before harvest. Chlorpyrifos residues were determined by gas chromatography after extraction and sweep co-distillation clean-up. Low residue levels were found. The average values in lettuce were 0.046 and 0.070 part/million, in sugar beet leaves 0.037 to 0.128 part/million and roots <0.005 to 0.038 part/million; no chlorpyrifos was detected in carrots, potatoes and cured tobacco leaves at the limit of the method (0.005 part/million).     

Correspondence

Abstract

Twenty-seven different herbicides were tested at the AUB Agricultural Research and Education Center in the Beqa'a, Lebanon, to determine their effects on weeds in wheat, barley, maize, onion and sugar beet. Each herbicide was tested at three different rates as pre-emergence and post-emergence applications. Unweeded and hand-weeded check plots were included. Data on yield, quality and other agronomic characteristics of the crops tested were recorded.

Concentrations of 1,000 and 10,000 ppm of 2, 4–D caused a significant decrease in the height and grain yield of wheat and barley when sprayed at the 3-leaf stage. At the 5-leaf stage, injury to wheat and barley occurred only when sprayed at 10,000 ppm, whereas an increase in the grain yield was obtained at 1,000 ppm of 2, 4–D acid equivalent (1 kg a.i./ha).

Pre-emergence treatments of atrazine and simazine at 2.5 kg a.i./ha caused a significant increase in the forage and grain yields of maize as compared to unweeded check plots. Wheat, oats, vetch and sugar beet were injured when planted after triazine-treated maize, whereas onions and soyabeans were tolerant. Other promising herbicides tested on maize were C 3095 (N–3–trifluoromethylphenyl–N'–methyl–N'–methoxyurea) and BV– 201 (1–(3′, 4′–dichlorophenyl)–3–methylpyrrolidin–2–one) applied as a pre-emergence spray at 1 and 2 kg/ha respectively.

Pre-planting treatment of EPTC and pre-emergence treatment of pebulate at 2 kg/ha gave a slight increase in the yield of roots of sugar beet. BV–201 and BV–207 (1–(3–chloro–4–methylphenyl)–3–methylpyrrolidin–2–one) were phytotoxic to beet.

In onions, nitrofen, BV–201 and BV–207 at 1–2 kg/ha were promising as pre-emergence and post-emergence sprays. DNOC and dinoseb at 1.5 kg/ha and ioxynil at 0.5 kg/ha sprayed post-emergence increased the yield of onions significantly over the check. No significant effects of these herbicides were observed on the bulb index, moisture content and total soluble solids of onions.     

百菌清和福美双在蘑菇上的残留研究

建立了杀菌剂30%菇丰(12%百菌清和18%福美双)可湿性粉剂在蘑菇中的残留分析方法,并用该方法研究了其在蘑菇中的消解动态和最终残留。样品分别经GC-ECD和HPLC-UV检测。方法的添加回收率分别为90.19%~99.11%和73.94%~86.47%;变异系数分别为0.9%~3.2%和2.6%~15.8%;最小检出量分别为1×10-12g和6×10-9g;最低检测浓度分别为0.01和0.3mg/kg。田间残留动态试验结果表明,百菌清和福美双在蘑菇中的半衰期分别为2.5d和4.2h。在最高推荐剂量(1 800g/hm2)和推荐剂量2倍的条件下,施药12次,施药后第5d,蘑菇中百菌清残留量高于我国规定的MRL值(1mg/kg);而施药后2d福美双残留量已低于MRL值(3mg/kg)。试验结果表明,百菌清不适于在蘑菇中使用,而福美双则可以使用。     

Residues of atrazine, simazine, linuron and diuron after repeated annual applications in a peach orchard

Annual applications of the herbicides atrazine, simazine, linuron and diuron at 45 kg/ha were made to the same plots for 9 consecutive years from 1963 to 1971 in a peach (Prunus persica (L.) Batsch.) orchard located on sandy loam soil near Harrow, Ontario. Soil samples from these plots were collected in late October for the last 3 years (1969–1971) and trees were cut down in December, 1969. Herbicide residues were determined by bioassays based on the fresh and dry weight of oats (Avena sativa L.) and in one year results were confirmed by chemical analysis. Significant accumulation of herbicides was not observed. The maximum residue levels measured in October over the 3 years of sampling were 7′3 kg/ha for diuron, 3–8 kg/ha for linuron, 1–6 kg/ha for simazine and 04 kg/ha for atrazine in the top 15 cm of the soil profile. Simazine and atrazine showed a rapid decrease in amount after treatment but diuron and linuron were degraded more slowly. Measurable residues of all herbicides were confined to the upper 15 cm of the soil profile and the majority of herbicide remained in the 0–5-cm soil layer. Oats were planted in the orchard plots from 1972 to 1974 to follow the disappearance of the herbicides. All herbicides caused highly significant yield decreases in 1972, atrazine causing the least (38%) and diuron the greatest (86%) reductions. Diuron reduced the yield of oats in 1973 and caused a highly significant decrease in the weight of young oat plants in 1974.     

Response of spring cereal crops to soil residues of ethofumesate*

For evaluation of soil residues of ethofumseate [(±)2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl-methylsulphonate], spring barley (Hordeum vulgare L.) and spring wheat (Triticum aestivum L.) were sown in soil planted 11 months previously with sugar-beet (Beta vulgaris L.) and previously treated with band or broad-cast applications of the herbicide at rates of 1.68-4.48 kg/ha. The height of barley and wheat was suppressed only where ethofumesate was applied broadcast and the soil was not ploughed after sugar-beet harvest. Three months after sowing, the 4.48 kg/ha rate suppressed the height of barley 18% and wheat 34%. In another experiment, barley grew normally on soil treated the previous year with pre-planting and post-emergence applications of ethofumesate where ploughing followed sugar-beet harvest. For all treatments, yields of straw and grain were not significantly lower than those of the untreated check plots. The dissipation of ethofumesate 24 weeks after application to sugar-beet was 89–100% when applied on a band compared to 85-95% when applied broadcast.     

Pyrethroid insecticide residues on vegetable crops

Pyrethroid insecticides were applied on various vegetable crops as foliar treatments to determine dissipation rates. On Chinese broccoli (Guy Lon), Chinese mustard (Pak Choi) and Chinese cabbage (Kasumi, napa), fenvalerate was persistent with residues of 0.10, 0.14 and 0.11 mg kg-1, respectively, by day 21. Cypermethrin residues on head lettuce were below 0.1 mg kg-1 by day 10 but on the leafier romaine and endive varieties it was more persistent and required 14-19 days to dissipate below this concentration. After three applications, residues of cypermethrin in harvested carrots and of permethrin in eggplant were not detected on the day of application. On asparagus, deltamethrin and cypermethrin residues declined to less than 0.1 mg kg-1 by days 1 and 2, respectively; permethrin was more persistent, requiring more than 2 days to decline to less than 0.1 mg kg-1. Deltamethrin on dry (cooking) and Spanish onions was not detected on the day of application. On tomatoes, the concentration of permethrin was 0.093 mg kg-1 on the day of application and declined to about 0.05 mg kg-1 after 2-4 days. In general, permethrin, cypermethrin and deltamethrin residues declined to acceptable concentrations within an acceptable pre-harvest interval. Fenvalerate may be too persistent on these speciality crops unless a maximum residue limit > 0.1 mg kg-1 is permitted.     

Residues of the algicide endothal in water,soil and rice,after paddy field applications

In order to obtain residue data from the application of the algicide endothal in Italian rice paddy fields, two experiments were carried out using a 50 g kg^?1 granular formulation in a small pond and the same granular and two liquid formulations in actual paddy fields of the Italian rice growing area. Endothal decay in the pond water was very rapid, reaching residue levels of 0·01-1·02 mg litre^?1 in two days and 0·004-0·01 mg litre^?1 at the third day. The muddy soil of the pond was free from measurable endothal residues( <0·02 mg kg^?1). In the paddy-field waters, the endothal decay was slower, with an average half-life time of 3·3 days, independently of the type of formulation. The actual residues in water after 6 days ranged from 0·3 to 1·3 mg litre^?1 according to the initial amount of product applied, and, consequently, to the initial concentration in water. Rice samples collected at the normal harvest time from the two paddy fields, treated with three different formulations, showed no endothal residue at the minimum detectable level of 0·01 mg kg^?1.     

Residues of Mecoprop in Post-emergence-Treated Wheat and Oat

The dissipation of mecoprop in wheat (Triticum aestivum L.) and oat (Avena sativa L.) was monitored over a growing season following post-emergence application of the dimethylamine salt of mecoprop to each crop at 1·1 kg ha^?1. Residues of mecoprop, as its methyl ester, were determined gas chromatographically using electrolytic conductivity detection. Initial residues in wheat (119 (±20) mg kg^?1) and oat (95·3 (± 10·0) mg kg^?1) on the day of application (four-leaf stage of wheat and four- to five-leaf stage of oat) decreased to 0·1 to 0·2 mg kg^?1, respectively, within six weeks. Residues were non-detectable in the mature seed of both crops. Recoveries of mecoprop were in the order of 90% from the green tissue and seed of both crops fortified at 0·05 mg kg^?1.     

Residues in carrots treated with linuron

Investigations have been carried out on residues of linuron and its breakdown products in carrots sprayed with Jinuron at 1, 2, or 4 kg a.i./ha, 0, 19, 28, 36 or 60 days after sowing (up to 57 days before harvesting). The extracted residues were separated into three fractions by liquid-liquid partitioning: (a) linuron, (b) 3-(3,4-dichlorophenyi)-l-methoxyurea, 3-(3,4-dichlorophenyl)-l-methylurea, 3,4-di-chlorophenylurea and (c) 3,4-dichloroaniline. The compounds in each fraction were hydrolysed and the iodine derivative 1,2-dichloro-4-iodobenzene was formed by a Sandmeyer reaction between 3,4-dichloroaniline and iodide ion, followed by gas chromatography with electron capture detector. Only 5-13% of the extract-able residues were breakdown products. Most of the detectable residue (87-95%) was identified as linuron. The relative proportions of linuron and breakdown products in carrots at the time of harvest were not affected by the time of spraying or the interval between treatment and harvest.