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.     

A rapid quantitative bioassay for the determination of biologically available bromacil in soils

A simple rapid bioassay is described for the determination of biologically available bromacil residues in soils. A clear aqueous extract was made from a soil fortified with a known amount of the herbicide, and similar extracts were made from samples of soil taken from plots that had been sprayed with a bromacil formulation at a rate of 4 kg ha⁻¹. Samples of these extracts were added to a suspension of the unicellular green alga Selenastrum capricornutum. The net photosynthetic oxygen production by the alga was then measured using an oxygen electrode. The results were expressed as a percentage of the oxygen production by a control suspension. The concentration of biologically available bromacil was determined by reference to a previously established dose-response curve of the percentage reduction in oxygen production against bromacil concentration. The accuracy of this bioassay was determined by comparing the results with those obtained using capillary gas-liquid chromatography. The results obtained by the two different methods showed good agreement.     

A small-scale method for the determination of pyrethroid insecticide residues in crops and soils

A small-scale method for the determination of pyrethroid insecticide residues in crops and soils is described. Compared with the conventional methods, the overall analysis time is reduced by approximately 60% and solvent usage is reduced by approximately 80% using this approach. Results obtained on a range of crops using the small-scale and conventional methods were in good agreement, and a repeatability study showed that the small-scale approach is unbiased and gives good precision. To date, linseed, tobacco, cotton foliage, cotton seed, wheat grain, sorghum, savoy, cauliflower, cabbage, cucumber, apple, peach, blackcurrant, gooseberry, raspberry and soil samples have been analysed using the method. Good recoveries were obtained with all these matrices.     

Potential safeners for protecting sorghum (Sorghum bicolor (L.) Moench) against chlorsulfuron,fluazifop-butyl and sethoxydim*

In greenhouse studies, the efficacy of the herbicide safeners NA(1,8-naphthalic anhydride), R-25788 (N,N-diallyl-2,2-dichloroacetamide), cyometrinil and CGA-92194 [N-(1,3-dioxolan-2-yl-methoxy)imino-benzeneaceto-nitrile] in protecting grain sorghum (Sorghum bicolor (L.) Moench, cv. ‘Funk G623’) against injury from pre-emergence or early post-emergence applications of the herbicides chlorsulfuron, fluazifop-butyl and sethoxydim was examined. NA as a seed dressing at 0·5 or 1·0% (w/w) was the most effective of the four safeners and offered partial to good protection to sorghum against injury from the lower rates of pre-emergence applications of all three herbicides. R-25788 was totally ineffective as a sorghum protectant against fluazifop-butyl injury but it did antagonize partially the injurious effects of the lower rates of sethoxydim and chlorsulfuron on sorghum. Cyometrinil and CGA-92194 offered partial protection to sorghum against injury from the lowest rate of all herbicides but their efficacy against higher rates of the three herbicides was very limited. None of the four safeners was effective in protecting grain sorghum against injury from post-emergence applications of the three herbicides tested.     

A modified extraction and clean-up procedure for the detection and determination of parathion-methyl and chlorpyrifos residues in tea

Recent advances in methodology and instrumentation have made possible the detection and determination of pesticides at microgram kg-1 (ppb) levels. The sensitivity of a method of analysis depends greatly on the efficient extraction of the pesticide and the subsequent clean-up of the extract. The extract from green tea leaves is a mixture of aroma components, polyphenols and caffeine. The preparation of made tea from green tea leaves adds to this complexity by concentrating these coextractives. Conventional clean-up techniques provide poor recoveries for parathion-methyl and chlorpyrifos from both green tea leaves and made tea. This arises from interference by caffeine during gas chromatography, as it has a similar retention time to the two pesticides and peaks overlap. A modification to the protocol based on a solvent partitioning process using dichloromethane and subsequent washing of the extracts with warm water removed the caffeine, and pigments were removed by column chromatography. Recoveries ranging from 80 to 90% were then obtained for both pesticides.     

Degradation of chlorsulfuron and triasulfuron in alkaline soils under laboratory conditions

The degradation of chlorsulfuron and triasulfuron was investigated in alkaline soils (pH 7.1–9.4) spiked at 40 μg a.i. kg^–1 under laboratory conditions at 25 °C and a moisture content corresponding to 70% field capacity (–33 kPa), using high-performance liquid chromatography. Degradation data for the two herbicides did not follow first-order kinetics, and observed DT₅₀ values in surface soils ranged from 19 to 42 days and from 3 to 24 days for chlorsulfuron and triasulfuron respectively. Disappearance of both chlorsulfuron and triasulfuron was faster in non-sterile than in sterile soil, demonstrating the importance of microbes in the breakdown process. The persistence of chlorsulfuron increased with increasing depth, which can be attributed to the decline in the microbial populations down the profile. The DT₅₀ value for chlorsulfuron at 30–40 cm depth was nearly four times higher than that in the top-soil. The results obtained show that persistence of these herbicides in alkaline surface soils at 25 °C and at a moisture content of 70% field capacity is similar to those reported in other European and North American soils. The study shows that if these herbicides are contained in surface soil layers, the risk of residue carry-over under southern Australian conditions is small. However, the rate of their degradation in alkaline subsoils is very slow, and under conditions conducive to leaching their prolonged persistence in the soil profile is possible.     

Adsorption and degradation of chlorsulfuron and metsulfuron-methyl in soils from different depths

Adsorption and degradation rates of chlorsulfuron and metsulfuron-methyl were measured in soil taken from depths of 0–20, 20–40 and 40–60 cm at eight sites. Adsorption of both herbicides was negatively correlated with soil pH, and positively correlated with soil organic matter content. When two soils with very high organic matter were excluded from the calculations, the correlations with organic matter content were no longer statistically significant but those with soil pH were affected only slightly. Degradation rates of both herbicides generally decreased with increasing depth in the soil and were positively correlated with microbial biomass and negatively correlated with soil pH. The possible significance of the results to persistence of the herbicides in the field is discussed.     

土壤中砜嘧磺隆和氯磺隆残留的光化学荧光分析方法研究

用紫外线照射非荧光特性的砜嘧磺隆和氯磺隆,通过生成具有荧光特性的衍生物,分别研究了其在不同介质中的荧光特性及其影响因子,建立了测定土壤中砜嘧磺隆和氯磺隆残留的光化学荧光分析法(PCF)。结果表明:在2×10-3 mol/L、一定酸碱度(砜嘧磺隆pH 7、氯磺隆pH 12)的十六烷基三甲基氯化铵(CTAC)胶体分散体系中,紫外照射150 s是PCF法测定砜嘧磺 隆和氯磺隆残留的最佳条件,在此条件下砜嘧磺隆和氯磺隆的检出限(LOD)分别为0.7和0.6 μg/kg, 相对标准偏差(RSD)分别为1.7%和2.1%;在黄松田水稻土、黄红壤性水稻土和青紫泥田水稻土3种不同性质的土壤中,砜嘧磺隆和氯磺隆同时测定的平均回收率分别为99.0%±1.0%和98.7%±4.1%、97.6%±1.7%和97.0%±4.7%、96.7 %±2.3%和95.4%±5.5%;所建立的PCF法可有效、快速测定土壤中同时残留的微量砜嘧磺隆和氯磺隆。     

A rapid sensitive bioassay for determination of paraquat and diquat in water

The change in cell-membrane permeability as indicated by leakage of electrolytes from treated fronds of Lemna minor was the criterion used to detect the presence of diquat and paraquat in solution. The minimum herbicide concentrations that could be detected ranged from 1.8 and 1.7 μg/ml diquat and paraquat cation respectively after 3 h treatment to 0.00018 and 0.000017 μg/ml after 72 h. Paraquat was more active than diquat in all treatments. Increase in cell-membrane permeability occurred without the appearance of injury such as, chlorosis or bleaching of fronds. Light was necessary for these herbicides to alter cell-membrane permeability, though a little herbicidal activity could be detected after 48 h in the dark at concentrations above 0.17μg/ml. Un test biologique rapide et sensible pour la recherche du paraquat et du diquat dans l'eau Des modifications de la perméabilité de la membrane cellulaire, révélées par la déperdition d'électrolytes à partir de frondes de Lemna minor, ont été utilisées comme critères pour révéler la prèsence de diquat et de paraquat dans des solutions. Les concentrations minimales d'herbicides qui ont pu être décelées se sont situées entre 1,8 μg/ml et 1,7 μg/ml des cations diquat et paraquat respectivement, apres 3 heures de traitement, jusquà 0,00018 et 0,000017 μg/ml après 72 heures. Le paraquat s'est montré plus actif que le diquat dans tous les traitements. Un accroissement de la perméabilité cellulaire s'est produit sans qu'il soit apparu de dégâts tels que la chlorose ou le blanchissement des frondes. La lumière a été nécessaire pour que ces herbicides altèrent la perméabilité de la membrane cellulaire, bien qu'une faible activité herbicide ait pu être décelée après 48 heures à l'obscurité, à des concentrations supérieures à 0,17 μg/ml. Ein schneller und empindlicher Biotest für den Nachweis von Paraquat und Deiquat in Wasser Veränderungen in der Permeabilität der Zellmembran in Form des Austretens von Elektrolyten aus behandelten Wedeln von Lemna minor wurden als Kriterium für den Nachweis von Deiquat und Paraquat in wässeriger Lösung benutzt. Die geringsten Herbizidkonzentrationen, die festgestellt werden konnten, lagen nach 3 h nach der Applikation bei 1,8 und 1,7 μg/ml Deiquatbzw. Paraquat-Kation und nach 72 h bei 0,00018 und 0,000017 (μg/ml). In allen Behandlungen war Paraquat wirksamer als Deiquat. Der Anstieg in der Zellmembran-Per-meabilität war nichi mit äusseren Symptomen wie Chlorose oder Ausbleichen der Wedel verbunden. Für die Herbizidbedingte Veränderung der Zellmembran-Permeabilität war Licht notwendig, doch konnte auch eine geringfügige Herbizidwirkung nach einer 48-h-Dunkelperiode bei Konzenlrationen > 0,17 μg/ml festgestellt werden.     

Phytotoxic persistence and microbiological effects of chlorsulfuron and metsulfuron in Finnish soils

The persistence and movement of chlorsulfuron and metsulfuron in Finnish sandy, clay and organic soils were studied with onion bioassays. Field plots grown with barley were sprayed with 4 and 12 g a.i. ha^?1 Chlorsulfuron and metsulfuron persisted and leached to nearly the same extent. They persisted longer in the sandy soils than in the other soils, and leaching was also deeper in the sandy soils. The phytotoxicity of the 4 g a.i. ha^?1 dose persisted in the 0–5 cm layer of all soils for 1 month on average. The residues tended to leach deeper than 5 cm and, in some cases, were recovered up to 1 year after application. The phytotoxicity of the dose of 12 g a.i. ha^?1 persisted for at least 1 month and generally for 1 year. Residues of this dose were found in the 0–5, 5–15 and 15–25 cm layers, and in clay, mostly in the 0–15 cm layer. Significant growth stimulation in bioassays was common 1–2 years after application in the 5–15 and 15–25 cm layers of sandy soils. Chlorsulfuron and metsulfuron generally had only a very small effect on microbial dehydrogenase and nitrification activities. Persistance et effets microbiologiques du chlorsulfuron et du metsulfuron dans des sols finlandais La persistance et le mouvement du chlorsulfuron et du metsulfuron dans des sols sableux, argileux et humiferes de Finlande ont ete etudies l'aide d'essais biologiques utilisant l'oignon. Des parcelles semees en orge ont ete traitees a raison de 4 et 12 g m.a. ha. La persistance et le lessivage du chlorsulfuron et du metsulfuron etaient similaires. Us persistaient plus longtemps dans les sols sableux que dans les autres et le lessivage y etait plus important. La plupart du temps, la phytotoxicite de la dose 4 g m.a. ha^?1 persistait pendant un mois dans la couche 0–5 cm. Les residus tendaient a etre lessives plus profondement que 5 cm et dans certains cas etaient detects 1 an apres l'application. La phytotoxicite de la dose 12 g m.a. ha^?1 persistail pendant au moins un mois et generalement pendant an. Les residus de cette dose etaient retrouves dans les couches 0–5, 5–15 et 15–25 cm et dans le sol argileux principalement dans le couche 0–15 cm. Des stimulations de croissance significatives, detectees par des essais biologiques, etaient communement observees 1–2 ans apres Tapplication dans les couches 5–15 et 15–25 cm des sols sableux. Le chlorsulfuron, et le metsulfuron la plupart du temps, n'avaient qu'un tres faible effet sur les activites microbiennes deshydrogenase et de nitrification. Persistenz und mikrobiologische Wirkungen von Chlorsulfuron und Metsulfuron in finnischen Boden Die Persistenz und Einwaschung von Chlorsulfuron und Metsulfuron in finnischen Sand-. Lehm- und organischen Boden wurden mit Zwiebel-Biotests untersucht. In Gerstenbestanden hatten die beiden Herbizide nach Anwendung von 4 und 12 g A.S. ha^?1 ungefahr gleiche Persistenz und Einwaschung, die in den Sandboden starker als in den anderen waren. Die Phytotoxizitat blieb in alien Boden bis 5 cm Tiefe nach Anwendung von 4 g A.S. ha^?1 fur rund 1 Monat erhalten. Herbizidruckstande traten auch tiefer als 5 cm auf und lieBen sich in einigen Fallen bis zu 1 Jahr nach der Anwendung nachweisen. Bei der Dosis von 12 g A.S. ha^?1 blieb die Phytotoxizitat mindestens 1 Monat und im allgemeinen 1 Jahr lang erhalten. Bei dieser Dosierung wurden Ruckstande in 0 bis 5,5 bis 15 sowie 15 bis 25 cm Tiefe und in Tonboden uberwiegend in 0 bis 15 cm Tiefe gefunden. In den Biotests wurde allgemein eine signifikante Wuchsforderung bei Bodenproben aus 5 bis 15 und 15 bis 25 cm Tiefe aus Sandboden 1 bis 2 Jahre nach der Herbizidapplikation beobachtet. Beide Herbizide hatten nur eine sehr geringe Wirkung auf die mikrobielle Dehydrogenase- Aktivitat und Nitrifikation.     

Method for the determination of butachlor residues in water,soil and rice

A method is described for the analysis of water, soil and crops for residues of the herbicide butachlor. Residues were extracted with acetone + light petroleum distillate. The extracts were concentrated and purified on a chromatographic column containing aluminum oxide, silver–aluminum oxide and Florisil. Finally, they were quantitated by gas chromatography using an electron-capture detector. The detection limits of various samples were between 0.001 and 0.015 mg kg^?1. The average recoveries ranged from 79.4 to 104.6%.     

A bioassay technique to study the leaching behaviour of sulfonylurea herbicides in different soils

A bioassay procedure is described for quantitative determination of sulfonylurea herbicides in water and for studying their leaching behaviour in soils. Sunflower (Helianthus annuus L.) was found a more susceptible bioassay species than turnip (Brassica rapa L.) or lentil (Lens culinaris Medic.). The limit of quantitative detection (EC₃₀) in soil leachates was 0.12 μg 1^?1 for triasulfuron and 0.15 μg 1^?1 for metsulfuron-methyl. Leaching experiments were carried out by uniformly packing the soil in glass columns corresponding to its natural bulk density and applying simulated irrigation of 50 mm day^?1 with leachate water from untreated soil columns. Results obtained by measuring fresh weights of the true leaves of sunflowers in soil leachates showed that metsulfuron-methyl was much more mobile than triasulfuron in two soils with different sorption capacity. The BBA soil with low sorptive capacity showed very little retardation of both herbicides in the columns. The Horotiu soil with high sorptive capacity retarded triasulfuron for a long period, even under high flow conditions. Une technique d'essai biologique pour étudier l'aptitu.de au lessivage des herbicides sul-fony-lurées dans des différents sols Un protocole d'essai biologique est décrit pour la détermination quantitative des herbicides sulfonylurées dans l'eau, et pour l'étude de leur lessivage dans les sols. Le tournesol (Helianthus annuus) a été reconnu comme une espèce pour l'essai biologique plus sensible que le navet (Brassica rapa) ou la lentille (Lens culinaris). La limite de détection quantitative (EC₃₀) dans le lessivat du sol a été 0,12 μg 1^?1 pour le triasulfuron et 0,15 μg 1^?1 pour le metsulfuron methyl. Des études de lessivage ont été con-duites en mettant unifomément du sol dans des colonnes de verre de façon équivalente à la densité naturelle dans le sol et en appliquant une irrigation simulée de 50 mm jour^?1 avec de l'eau d'un lessivat de sol non traité. Les résult ats obtenus en mesurant le poids frais des feuilles vraies de tournesol dans les lessivats de sol ont montré que le metsulfuron-methyl était beau-coup plus mobile que le triasulfuron dans les 2 sols de capacités d'adsorption différentes. Le sol BBA avec une capacité d'adsorption faible a entraiîné un faible ralentissement des 2 herbicides dans les colonnes. Le sol Horotiu avec une capacité d'adsorption élevée a retardé le triasulfuron pendant une longue période, même sous des conditions de fortes précipitations. Biotestmethode zur Bestimmung des Ein-waschungsverhaltens von Sulfonyl-Harnstoff-herbiziden in unterschiedlich sorptiven Böden Eine Biotestmethode zum quantitativen Nach-weis von Sulfonyl-Harnstoffherbiziden in Was-serproben zur Bestimmung des Einwaschungs-verhaltens wurde entwickelt. Sonnenblume (Helianthus annuus L.) war unter den geprüf-ten Testpflanzen wesentlich empfindlicher als Herbstrübe (Brassica rapa L.) oder Linse (Lens culinaris Medic.). Als empfindlichste Meßgröße erwiesen sich die Echten Laubblätter der Sonnenblume. Die Nachweisgrenzen (EC₃₀-Werte) in Bodenperkolatwasser lagen bei 0,12 μg 1^?1 für Triasulfuron und 0,15 μg l^?1 für Metsulf-uron-methyl. Die Einwaschungsversuche wurden in Glassäulen durchgeführt, wobei die Böden gleichmäßig entsprechend ihrer Lagerungsdichte gepackt wurden. Die Beregnung erfolgte mit 50 mm Perkolat/Tag, das von nicht mit Herbiziden behandelten Säulenversuchen vorab gewonnen wurde. In beiden, unterschiedlich sorptiven, Böden zeigte Met-sulfuron-methyl eine stärkere Einwaschung als Triasulfuron. Im schwach sorptiven BBA-Boden wurden beide Wirkstoffe kaum retardiert, während Triasulfuron im stark sorptiven Horotiu-Boden über einen langen Zeitraum, auch unter den extremen Flußraten, zurückgehalten wurde.     

A colorimetric method for the determination of eight carbamate insecticide residues

A simple, quick and reliable method is described for the colorimetric estimation of residues of eight carbamate insecticides. The method is applicable to carbamates which on hydrolysis yield phenols with free para-positions suitable for coupling with a diazo reagent to yield coloured solutions. Optimum conditions for the development and measurement of the colour are described. Analytical data including graphs and some results from mud-bricks and cloth are presented to show the wide applicability of the method.     

Detection of Colletotrichum coccodes and Helminthosporium solani in soils by bioassay

The sensitivity of a bioassay in detecting soil inoculum of Colletotrichum coccodes and Helminthosporium solani was examined using potato minitubers and microplants. Tests were conducted on soils which were collected from fields in which the interval after a previous potato crop differed, and which were also artificially infested with conidia or microsclerotia. For C. coccodes , determining plant infection based on the occurrence of infected roots after 9–12 weeks was a sensitive method for detecting and quantifying the amount of inoculum in soil. Infestations of less than 0·4 microsclerotia per g soil were detected in artificially infested soils. A semiselective medium, developed for isolating C. gloeosporioides from pepper, detected soil infestations by C. coccodes as low as nine conidia or one microsclerotium per g soil in artificially infested soil. For H. solani , infection on minitubers was a sensitive measure, with soil inoculum of fewer than 10 conidia per g soil being detected. Soil infestation could be quantified by assessing the percentage surface area of minitubers covered by sporulating lesions, which was strongly related to the amount of soil infestation. The results of these bioassay tests were compared with published results for real-time quantitative PCR assays on the same soils. The two methods were in good agreement in artificially infested soils, but the bioassay appeared to be more sensitive with naturally infested soils.     

吡虫啉在金银花及土壤中的残留动态研究

采用HPLC DAD方法对吡虫啉在金银花及土壤中的残留动态进行研究。该方法最小检出量为0.021 2 ng,样品添加回收率为80.9%~ 84.6%,变异系数为7.74%~ 18.15%。研究结果表明：吡虫啉在金银花和土壤中的半衰期分别为1.52~ 4.65、11.07~ 19.09 d。建议金银花中吡虫啉的最大残留限量（MRL）为3.0 mg/kg;10%吡虫啉可湿性粉剂防治金银花蚜虫,用药量为30 g/hm2（有效成分）,采用喷雾的施药方法,在每茬花中最多施药2次,安全施药间隔期为7 d。     

A rapid high-pressure liquid chromatographic method for the determination of carbaryl residues in wheat grain

Carbaryl residues in wheat grain have been determined in methanol extracts using normal-phase high-pressure liquid chromatography (h. p. l. c.) with ultraviolet detection. A single-injection, clean-up and analysis technique was used to allow more rapid analysis of samples after extraction. A detection limit of 0.1 mg kg^?1 in a 50 g sample of wheat was achieved. Recoveries of 86% at the 1 mg kg^?1 level and 90-99% at the 5 mg kg^?1 level were obtained for fortified grain samples. Methanol was found to be a superior extractant for carbaryl from wheat when compared with hexane, acetone and dichloromethane. Twelve samples containing aged carbaryl residues were analysed by the h. p. l. c. technique and by a colorimetric procedure which allowed statistical analysis of errors. For the h. p. l. c. method (excluding sampling error), a relative standard deviation of 4.4% was obtained.     

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.     

超高效液相色谱-串联四级杆质谱联用法测定水果中多效唑、氯吡脲和咪鲜胺的残留

建立了超高效液相色谱-串联四级杆质谱(UPLC-MS/MS)法同时分析西瓜、杨梅中多效唑、氯吡脲和咪鲜胺3种农药残留的方法。样品经乙腈提取后用氨基固相萃取柱净化,反相液相色谱分离,采用三重四级杆串联质谱检测,用基质匹配标准品的外标法定量。结果表明:在添加水平为0.05～0.2 mg/kg范围时,西瓜中多效唑、氯吡脲和咪鲜胺的平均添加回收率分别为85.4%～99.4%、85.6%～98.7%和88.8%～100.3%,相对标准偏差(RSD)分别为2.7%～4.0%、2.5%～3.6%和2.3%～4.6%;杨梅中多效唑、氯吡脲、咪鲜胺的平均添加回收率分别为84.3%～99.3%、84.6%～98.2%和83.6%～99.2%, RSD 分别为2.4%～4.5%、2.9%～3.7%和2.2%～3.9%。该方法对两种水果中3种农药的检出限 (LOD)均为0.5 μg/kg,定量限(LOQ)均为1.7 μg/kg。方法灵敏度高、操作简便、定量准确、测定浓度范围宽,可用于多效唑、氯吡脲、咪鲜胺在西瓜、杨梅等水果中的残留分析。