Dichlorvos concentrations in the air of houses arising from the use of dichlorvos PVC strips

Trials have been carried out in order to determine the concentrations of dichlorvos that occur in the air of houses when “VAPONA”

1 “VAPONA” is a Shell trade mark.

strips are placed under conditions of normal domestic use. The ten trials were conducted in the U.K., Australia and France in the years 1967 to 1970. Two trials were also carried out in the U.K. with a shorter, slightly thicker product [6.5 in strip (16.5 cm)] of the same basic formulation. Samples of air were taken at regular intervals throughout the 3 or 4 month period of each trial and the samples were analysed for dichlorvos by an enzyme inhibition – ΔpH method. The results from more than 3000 samples of air showed that the great majority of values (97.2%) were 0.1 μg dichlorvos per litre of air or less. Values ranged from less than 0.01 μg/1 to 0.24 μg/l, the higher concentrations being associated with houses closed because of the absence of the householders or with several strips in place in the house, or both. In each trial the dichlorvos concentration in the air rose rapidly and then fell exponentially. In temperate area trials, the concentration was at its highest 1 to 2 weeks after placing the strips, the geometric mean of all the values at this time being 0.04 μg/1 and 3 months after placement the mean concentration was 0.01 μg/1. In the two trials with the 6.5 in (16.5 cm) product, concentrations in air were in one of these no different and in the other slightly lower than from the 10 in (25.4 cm) strip, the rate of decline of the concentrations of dichlorvos being the same in both trials. Observation strongly suggests that ventilation is the most important factor in determining the level of dichlorvos in the air of a room. In the trials in Brisbane, Australia, where houses are constructed to allow a flow of air and where doors and windows are open day and night, concentrations of dichlorvos were low initially and quickly fell below the limit of determination. The effect of increased ambient temperature is to increase the rate of emission of dichlorvos from the strip. However, in general, it seems that the increased ventilation associated with higher temperatures outweighed the increased rate of emission of insecticide since concentrations in air tended to fall with increasing temperature. Some rooms, especially kitchens, are smaller than the volume recommended for placement of strips (30 m³ per strip). However, statistical analysis of the results shows that initial concentrations in kitchens are no higher than in other rooms, and that the rate of decline of concentrations in kitchens is significantly higher than in other rooms.     

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.     

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.     

残留的五种有机磷农药在菜豆烹饪过程中的降解

采用气相色谱法检测了久效磷、毒死蜱、马拉硫磷、对硫磷、敌敌畏5种有机磷农药在菜豆烹饪过程中残留量的变化。结果表明:菜豆经油炸后,除久效磷未降解外,其余农药降解率在37.6%~85.1%之间。油炸时间的长短对敌敌畏降解影响较大,炸5 min时降解率为37.6%,7 min 时降解率为65.2%;油炸时间长短对其余农药的降解均无显著影响。炒的过程中5种农药的降解率在7.6%~56.5%之间;蒸的过程中降解率为23.0%~63.4%;未盖锅盖煮的条件下降解率为39.5%~81.7%,盖锅盖煮后降解率为42.0%~86.4%。在加盖煮10 min后的汤中,各种农药的残留量在0.03~0.50 mg/L 之间。炒过的菜豆再经微波加热2 min后, 5种农药残留量比炒过之后又降解了21.0%~41.5%。     

The fate of the molluscicide N-tritylmorpholine following its use on pastures for the control of liver fluke

The molluscicide N-tritylmorpholine (FRESCON,

1 FRESCON is a Shell trade mark.

trifenmorph) is used for the control of the intermediate snail hosts of fascioliasis in livestock. Laboratory and field studies have been undertaken to establish the fate of the compound following its use on pasture. Radiochemical techniques have been used under laboratory conditions to identify the potential degradation products. The major one has been shown to be triphenylcarbinol. Triphenylcarbinol was detected on pastures treated at 0.4 to 0.5 kg/ha under practical conditions but the residues of it and of the parent molluscicide were generally below 0.3 mg/kg within 8 weeks of the application. On the pasture grass half of the initial deposit of N-tritylmorpholine was lost within 1 to 3 weeks and on soils it was lost within 1 to 4 weeks. Residues could not be detected in the tissues of sheep feeding on the treated pasture. Whilst small residues (0.023 mg/kg or less) were detected in the milk of some cows feeding on the pasture soon after application they were absent (below 0.002 mg/kg) in the milk at 10 days or more from treatment.     

Metabolism of [3H]triforine in barley grown in the field: The unbound radioactive residue

Barley was sown and grown normally in an experimental field. At the growth stage J,

1 Growth stage J: during the stem extension stage; second node of stem formed and next-to-last leaf just visible.

the aerial part of the plants was sprayed with an aqueous emulsion of a mixture of triforine and [³H]triforine (uniformly labelled in the piperazine ring) using the recommended dose rate of about 240g triforine ha^?1. The barley was harvested when ripe and the straw and grain were analysed separately. The total radioactivity concentration was 20 times higher in straw than in grain. In straw and grain, 12 and 25% respectively of the total incorporated radioactivity in each of these tissues was methanol soluble. The composition of the methanol-soluble radioactive residue was investigated and was shown to contain triforine and its metabolites which were free and unbound in barley straw and grain. No radioactive piperazine was observed, in spite of the high detection sensitivity for radioactivity. The concentrations of triforine and its identified metabolites in straw and grain respectively (mg kg^?1, relative to the fresh weight of tissue) were: triforine, 0.034 and 0.0018; N-[(2,2,2-trichloro-1-(piperazin-1-yl)ethyl]formamide), 0.009 and 0.0006; iminodiacetic acid, 0.021 and 0.001; glycine, 0.043 and 0.0033. Other radioactive water-soluble and very polar, unidentified compounds were observed, corresponding to advanced metabolic products of triforine.     

Residue distribution of the acaricide coumaphos in honey following application of a new slow-release formulation

Acaricide used in beehives for the control of varroa often leaves residues in bee products. The behaviour and distribution of the acaricide coumaphos in honey following the application of a new slow-release strip formulation (CheckMite+) was assessed. The bee colonies were allowed to build new combs without foundation, and two strips were hung in the brood chamber of each colony for a period of 42 days. The distribution of coumaphos residues in honey in relation to the position of the frame and the duration of treatment was examined by collecting samples from each comb at various time intervals up to 145 days after treatment. In the brood chamber, coumaphos was incorporated into honey from the first day of application, and residues accumulated mainly in combs placed next to strips. In the adjacent combs, residues remained at low concentrations with slight variations. In the honey chamber, residue concentrations on the day of strip removal ranged between 0.006 and 0.020 mg kg(-1), while 79 days after application the concentration of coumaphos residues was below 0.020 mg kg(-1). Residues above the EC fixed maximum residue limit (MRL) of 0.1 mg kg(-1) were measured only in brood chamber honey obtained from those combs placed next to strips. In these samples, 0.060-0.111 mg kg(-1) of coumaphos was detected up to 103 days after strip removal. Coumaphos residues in honey extracted from combs that were placed at the edge of the brood chamber were found below the MRL value, even during the 42 day period of CheckMite+ strip treatment.     

Residues of organochlorine pesticides in broilers from feed fortified with known levels of these compounds

p, p'-DDT, HEOD, endrin, heptachlor epoxide, hexachlorobenzene and lindane were fed in combination to day-old broiler chickens at levels of 0.05, 0.15 and 0.30 part/million in the feed, for a period of about 7 weeks. Birds were killed at regular intervals and samples of abdominal fat and other tissues examined for residues of the chlorinated pesticides by gas-liquid chromatography. The lipid content of each sample was determined and the residue levels calculated for the whole tissue and also for the fat contained in the sample. At the end of the 7 weeks (when in practice broilers are slaughtered) residues were highest for heptachlor epoxide, followed by hexachlorobenzene, HEOD, DDT (total), endrin, and lindane. Heptachlor epoxide residue levels in fat were 13 times the levels in the feed, for lindane the ratio was 3.3. Fat residues of each pesticide reached a plateau level relatively quickly, and these levels were proportional to the fortification rates in the feed. HEOD and p, p'-DDT alone were fed to separate groups of birds. No differences in residue build-up of these compounds were found between these groups and the groups that had received these compounds in combination with the other pesticides. The total amounts of each pesticide in the tissues were reduced when the meat was fried, probably by loss of fat during preparation and frying. For p, p'-DDT and heptachlor epoxide also smaller residue were observed in the remaining fat after frying.     

The role of translocation in selectivity of herbicides with reference to MCPA and MCPB

The distribution of 2.5 mM-[¹⁴C]MCPA

1 MCPA = (2-methyl-4-chlorophenoxyacetic acid).

and [¹⁴C]MCPB

2 MCPB = (4-(2-methyI-4-chlorophenoxy) butyric acid).

formulated as sodium salts with 0.05% tergitol, have been investigated when applied to an isolated leaf/agar block sink system of Vicia faba L. Results are presented which show the effect on absorption and translocation of method of application, age of treatment leaf, treatment period, pretreatment with 5 μM ATP and removal of cuticle wax by chloroform wipe treatment. Significant negative correlations between cuticle wax fixation/translocation and leaf tissue content/translocation were recorded for both compounds, particularly MCPB, suggesting the involvement of both physicochemical and metabolic components in the process of absorption and translocation. The nature of the mechanisms involved was further investigated using isolated cuticle/epidermal systems and tightly-coupled mitochondria isolated from roots of V. faba L. The results suggest that non-movement of MCPB in this species is largely due to its enhanced retention within the cuticle and to the fact that it is a more effective uncoupler of oxidative phosphorylation than MCPA. The importance of these findings in terms of the relative efficiency of translocation of MCPA and MCPB when applied in vivo is discussed.     

Residues of some chlorinated hydrocarbon pesticides in milk and milk products after their addition to the feed of cows

Lactating cows fed 0.05 part/million aldrin, 0.2 part/million γ-BHC and 2.0 parts/million pp'-DDT in their concentrate ration gave detectable residues of dieldrin, γ-BHC, pp'-DDE, pp'-TDE and pp'-DDT in the milk and also aldrin in the butter and cheese. The levels found after 28 days of feeding were not significantly greater than those after 14 days. Subsequent increase of the pesticide content of the feed increased the residue content of the milk, butter and cheese. Only a small percentage of pesticide residue was found in the buttermilk, separated milk and the whey.     

The insecticidal action of some components of wood preservatives

The use of liquid insecticide formulations for prevention and eradication of attack by common wood-boring insects is discussed and some methods of testing and assessing effectiveness described. Gamma-BHC and dieldrin prevent attack when present at 20 g/m³ of softwood while a number of stomach poisons are effective at from 1 to 10 kg/m³. The important part played by the organic solvent in an eradicant formulation is considered. Anobium punctatum in confined spaces can also be controlled by annual use of plastic strips emitting dichlorvos vapour. At 0.015 to 0.05 μg/l in air, dichlorvos virtually prevents initiation or spread of attack by this insect.     

A radiochemical and gas-chromatographic study of the determination of dichlorvos residues in stored grain

An investigation into the extraction of dichlorvos from stored grain and satisfactory storage conditions for samples received for analysis has been carried out using [³²P]-dichlorvos. It has been shown that samples can be effectively stored at —17° C and that methanol can be used for the extractable dichlorvos but does not remove the organophosphorus residue bound to the grain.     

Ursachen unzulässiger Pflanzenschutzmittelrückstände im Strauchbeerenanbau in Baden-Württemberg

In the course of food quality control campaigns on berry fruits (currants, gooseberries and raspberries) in Baden-Württemberg not acceptable residues of plant protection products were detected in a number of cases in 2004 and 2005. In 2005 28 out of 94 samples (30%) were proved to contain residues not allowed in the cultures concerned. In 16 of the samples analysed (17%) residues were above the maximum residue levels. As to the former year 2004 the results were similar. The negative results reported are stated to be due to violating the official registration or the regulations for use of a product, to volume remains in the sprayer as well as to drifts. The residues exceeded the maximum residue level only in cases, where compounds were not registered for use during the residue relevant period. No unacceptable residue levels were found regarding compounds that are admitted for use in the residue relevant period. The Ministry of Agriculture Baden-Württemberg, the plant protection service, growers associations and market organisations reacted to these findings by taking a number of precautionary measures to face the problems of residues in future. In meetings, publications, extension services and in the internet the problems were discussed and producers informed how to avoid them. Berry-growers have to sign declarations binding them to the principles of plant protection. The plant protection stuff and the food control service will intensify their inspection management and will take legal steps in case of violation.     

Chlorpyrifos residue levels in avian food items following applications of a commercial EC formulation to alfalfa and citrus

Two 10-day field residue studies were conducted to measure the amount of chlorpyrifos residue found in typical avian food following applications of a commercial 480 g liter(-1) EC (Lorsban 4E) at 1.1 kg AI ha(-1) (1 lb AI acre(-1)) to alfalfa and at 2.3 kg Al ha(-1) (2.0 lb AI acre(-1)) to citrus. Avian food items used in these studies included: crickets (Acheta domestica (L)), earthworms (Lumbricus terrestris L), darkling ground beetle larvae (Tenebrio molitor L), seed heads (Triticum sp), and naturally occurring flying and ground-dwelling insects. The studies incorporated a design involving three main study plots placed within larger treated areas of an alfalfa crop and a mature orange grove. The three main study plots represented three replications and each contained four sub-plots. One sub-plot, on each study plot, was sampled on day 0 (2-h post-application), day 1, day 5 and day 10 post-application. Chlorpyrifos residues were present in all avian food sampled following the application; however, residue levels were lower than estimated residue values typically used by the US EPA to establish expected environmental concentration (EEC) used in screening assessments of risk to terrestrial wildlife.     

超高效液相色谱法检测啶虫脒在工厂化双孢蘑菇栽培中的残留

采用超高效液相色谱法(UPLC-PDA)测定了双孢蘑菇及其覆土和培养料中啶虫脒的残留量,研究了啶虫脒在工厂化双孢蘑菇栽培中的残留规律。样品以乙腈提取,分散固相萃取净化,超高效液相色谱测定。结果表明:在0.02~3mg/kg3个添加水平下,啶虫脒在双孢蘑菇、覆土和培养料3种基质中的平均添加回收率为81%~97%,相对标准偏差(RSD)为5.7%~9.6%。在不同施药水平下,啶虫脒在覆土和培养料中的消解动态均符合一级动力学指数方程,平均半衰期分别为34和23d。覆土单独施药后啶虫脒会向培养料迁移,培养料内的啶虫脒残留量总体先升高后降低。随覆土或培养料中啶虫脒施药剂量的增加,双孢蘑菇中啶虫脒的残留量随之增加,当啶虫脒在覆土或培养料中的施药量有效成分在10~250mg/kg之间时,双孢蘑菇子实体中啶虫脒的残留量在0.03~2.6mg/kg之间,且第一潮、第二潮和第三潮菇间残留量存在显著差异。同一处理剂量下,覆土单独施药后蘑菇中啶虫脒的残留量显著高于培养料单独施药后蘑菇中的残留量。     

西北春小麦和麦田土壤中15种常用农药残留的检测

为掌握西北春小麦和麦田土壤的农药残留污染状况,在调研和总结分析了西北春小麦的病、虫、草害发生和防治措施基础上,采集了我国西北地区甘肃、青海、宁夏的9个春小麦产区的小麦籽粒和麦田土壤样品。针对春小麦病虫草害防治中常用的农药,使用HPLC-MS/MS和GC-MS方法,测定了吡虫啉、高效氯氰菊酯、辛硫磷、毒死蜱等4种杀虫剂,三唑酮及其代谢物三唑醇、戊唑醇、多菌灵、三环唑、苯醚甲环唑等6种杀菌剂,精噁唑禾草灵、苯磺隆、2,4-滴丁酯、炔草酯及其代谢物炔草酸等5种除草剂,共15种农药及代谢物在小麦籽粒和麦田土壤中的残留量。通过与小麦中农药残留限量相比较,评价了西北春小麦的食品安全。结果显示,仅在采自甘肃金昌的小麦籽粒样品中检出了戊唑醇,且未超过最大残留限量,在其他样品中均未检出15种农药的残留,表明西北春小麦和麦田土壤的农药安全性均较高。本研究为掌握小麦籽粒的农药残留和麦田土壤的农药污染情况提供了研究数据,为进一步指导西北春小麦的绿色无公害病虫害防治提供了参考。     

Hydrolysis of the triazine herbicide,cyanazine

The hydrolysis of cyanazine

1 Cyanazine is the proposed common name for the herbicide sold under the Shell registered trade name BLADEX.

(2-chloro-4-cyanoisopropylamino-6-ethylamino-1,3,5-triazine) has been studied using ¹⁴C-ring labelled compound over a temperature range of 25° to 75 °C and over a range of pH values from 1.5 to 12. The activation energies and the activation entropy changes during hydrolysis showed there was a different mechanism under acid and alkaline conditions. The only product identified after hydrolysis in acid solutions was 2-hydroxy-4-carboxyisopropylamino-6-ethylamino-1,3,5-triazine. In alkaline solution the same hydroxy-acid was the end-product, but 2-chloro-4-amidoisopropylamino-6-ethylamino-1,3,5-triazine was isolated as an intermediate. The variation of the specific rate constants with temperature for hydrolytic catalysis by H⁺, OH^? was determined, thus enabling the hydrolytic half-life of cyanazine to be calculated at any pH and temperature.     

Mode of action of the systemic fungicides furalaxyl,metalaxyl and ofurace

The systemic fungicides furalaxyl, metalaxyl and ofurace,

1 Ofurace is the proposed BSI and ISO common name for α-(2-chloro-N-2,6-xylylacetamido)-γ-butyrolactone.

used to control diseases caused by phycomycetes, were extremely active in vitro against Pythium ultimum, Phytophthora nicotianae and Phytophthora palmivora. Sporangia production was reduced more than mycelial growth but germination of sporangia and zoospores was relatively unaffected. Less than 1% of the metalaxyl or furalaxyl, present in media at the ED₅₀ for hyphal growth, was firmly absorbed by Phyt. palmivora mycelium; uptake was against a concentration gradient and was characterised by a rapid accumulation followed by a more gradual release. Respiration and wall synthesis were not inhibited, whilst membrane permeability was unaffected. Lipid patterns were altered but these changes were probably of secondary importance. The fungicides inhibited protein and nucleic acid synthesis; RNA production was particularly affected. There was some evidence of a reduction in nuclear division. The primary effect of furalaxyl and metalaxyl probably involves impaired biosynthesis of RNA so that mitosis is inhibited; ofurace may act in the same way.     

Residues of the carbamate acaricide, 3-methyl-5-isopropylphenyl-N(n-butanoyl)-N-methylcarbamate (promacyl) and two metabolites in the tissues and milk of cattle

In order to assess some of the residue characteristics of the experimental carbamate acaricide, 3-methyl-5-isopropylphenyl-N-(n-butanoyl-)-N-methylcarbamate (promacyl) a 0.2 % aqueous emulsion was applied to cattle in a series of five trials and in a sixth, the technical product was added to the feed of stalled cattle. A method of analysis involving the formation of a derivative suitable for gas chromatographic analysis on electron capture detection mode was developed. Separate estimations of levels of the parent compound and the metabolites, 3-methyl-5-isopropylphenyl -N-methylcarbamate and 3-methyl-5- isopropylphenol, were carried out on fatty tissues and butterfat but for non-fatty tissues “total” levels, which were a combined estimate of 3-methyl-5-isopropylphenol itself and all substances hydrolysable to it, were estimated and quoted as Promacyl. The highest group average level of the parent compound was 0.9 part/million in fatty tissues 24 h after the last of 8 applications at 3 day intervals. In a single spray trial the maximum group average of 0.7 part/million in fatty tissues 24 h after treatment fell to 0.2 part/million after 5 days. Residues in butterfat, 7 h after a single dermal application showed a maximum level of 1.2 parts/million and this declined to 0.1 part/million on the seventh day after treatment. “Total” residues in non-fatty tissues were of the order of 1/10 those found in fatty tissues.     

丁虫腈在玉米和土壤中的残留及消解动态

建立了丁虫腈在土壤、玉米植株及玉米籽粒中残留的气相色谱分析方法。玉米植株和籽粒样品用乙腈提取,经Oasis HLB固相萃取柱净化;土壤样品用丙酮提取,经液-液萃取净化,气相色谱-电子捕获检测器(GC-ECD)检测,外标法定量。结果表明:在0.01、0.05和0.5 mg/kg 3个添加水平下,丁虫腈的回收率为80%~86%,相对标准偏差(RSD)为5.1%~8.0%;其在土壤、玉米植株及籽粒中的定量限(LOQ)均为0.01 mg/kg。采用所建立的方法对丁虫腈在玉米和土壤中的残留及消解动态进行研究的结果表明:丁虫腈在土壤和玉米植株中的半衰期分别为6.77和2.44 d。采用5%的丁虫腈乳油按推荐高剂量(有效成分)37.5 g/hm2及其1.5倍该剂量(56.25 g/hm2)于玉米苗后茎叶初期施药1次,在玉米乳熟期和成熟期时,玉米籽粒中丁虫腈的最终残留量均低于定量限;玉米收获时(距施药90 d),籽粒中丁虫腈的残留量均低于参考的MRL值(0.02 mg/kg,氟虫腈在谷物中的最大残留限量)。