Influence of application volume on the efficacy of clodinafop-propargyl and fenoxaprop-P-ethyl on oats

The influence of application volume on the efficacy of clodinafop‐propargyl and fenoxaprop‐P‐ethyl on cultivated oats (Avena sativa) was studied in the glasshouse. Both herbicides were more efficacious when applied in 75 L ha^?1 than in 300 L ha^?1, with 11002 and 11006 nozzles respectively. However, when the same two volume rates were created by varying the speed of a 11003 nozzle, clodinafop‐propargyl efficacy was not affected by application volume, whereas fenoxaprop‐P‐ethyl remained more efficacious at 75 L ha^?1. This suggests that in the first experiment, fenoxaprop‐P‐ethyl efficacy was affected by changes in both spray quality and concentration, whereas only the former influenced clodinafop‐propargyl efficacy. The hypothesis that the fenoxaprop‐P‐ethyl formulation was more influenced by concentration than clodinafop‐propargyl was supported by dynamic surface tension studies and measures of active ingredient retention by oat plants. Within the practically relevant concentration range considered, surface activity of clodinafop‐propargyl remained low, with little influence on herbicide retention. In contrast, depending on the concentration, surface activity of fenoxaprop‐P‐ethyl was below or above levels that were critical for its retention. Although these differences may not be as apparent in the field as in the glasshouse, our study certainly indicates that both clodinafop‐propargyl and fenoxaprop‐P‐ethyl are herbicides favoured by low application volumes.     

A new extraction method for benomyl residues in soil and its application in movement and persistence studies

A simple and rapid method for extracting benomyl residues from soils was compared with previous methods. Soil was extracted by shaking for 2 h at room temperature with (1:1) acetone/M aqueous ammonium chloride followed by clean-up by solvent partition and ultraviolet absorption estimation of carbendazim. Recoveries were comparable to those obtained by refluxing with methanolic hydrochloric acid for 4 h, hitherto the most efficient method reported, and were much greater than those obtained by extraction with ethyl acetate or chloroform. The new method gave more tractable extracts than those obtained by refluxing with methanolic hydrochloric acid, which form troublesome metal hydroxide precipitates during clean-up. In field experiments with 2-[¹⁴C]-benomyl and 2-[¹⁴C]-carbendazim, no radioactivity was found more than 25 mm from the soil surface during 10 months after surface application of 1 kg/ha. Carbendazim residues in soils from three field experiments indicated that its persistence is very sensitive to soil pH. The time for 50% loss of initial dose ranged from 26 months at pH 5.5 to less than 3 months at pH 7.2. Biological effectiveness in a crop may therefore depend markedly on differences in soil pH.     

Determination of residues of 1-(2-cyano-2- methoxyiminoacetyl)-3-ethylurea (DPX-3217) by gas-liquid chromatography

Residues of the fungicide 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (DPX-3217) in grapes, potatoes, tomatoes and wine were determined by initial extraction with ethyl acetate, clean-up by liquid-liquid partitioning and adsorption chromatography, and final determination by gas-liquid chromatography with a nitrogen-selective detector. The sensitivity of the method was 0.04 mg kg^?1 based on 50-g samples. Recoveries of the compound added to untreated substrates averaged approximately 92% in the range of 0.04-5.0 mg kg^?1.     

Inheritance of resistance to fenoxaprop‐p‐ethyl in sprangletop (Leptochloa chinensis L. Nees)

Sprangletop (Leptochloa chinensis L. Nees) is a serious grass weed in direct‐seeded rice cropping systems in Thailand. One population of sprangletop, BLC1, was found to be resistant to fenoxaprop‐p‐ethyl at 62‐fold the concentration of a susceptible biotype, SLC1. This study elucidated the inheritance of resistance to fenoxaprop‐p‐ethyl in this sprangletop BLC1 genotype. The reaction to the herbicide at 0.12–2.4 mg ai L^?1 was determined in the seedlings of self‐pollinated resistant BLC1, susceptible SLC1 and SLC1 that had been allowed to cross‐pollinate with BLC1. At 0.24 mg ai L^?1, all the seedlings of SLC1 were killed, while 99% of BLC1 survived, along with 5% of the cross‐pollinated SLC1 seedlings, which were considered to be putative F₁ hybrids. The root and shoot lengths of the F₁ hybrids in 0.24 mg ai L^?1 of fenoxaprop‐p‐ethyl, relative to those in the absence of the herbicide, were close to or the same as the resistant parent, indicating that the resistance is a nearly complete to complete dominant trait. One‐hundred‐and‐forty‐one of the F₂‐derived F₃ families were classified by their response to the herbicide at 0.24 and 0.48 mg ai L^?1 into 39 homozygous susceptible : 72 segregating : 30 homozygous resistant, fitted with a 1:2:1 ratio at χ² = 1.21 and P = 0.56, indicating that the resistance to fenoxaprop‐p‐ethyl in the sprangletop BLC1 genotype is controlled by a single gene.     

Confirmed resistance to aryloxyphenoxypropionate herbicides in Phalaris minor populations in Iran

Phalaris minor (littleseed canary grass) is a major weed in wheat fields in some parts of Iran. Diclofop‐methyl, fenoxaprop‐P‐ethyl, and clodinafop‐propargyl are three acetyl coenzyme A carboxylase (ACCase)‐inhibiting herbicides that are commonly used to control this grass in wheat fields. Thirty‐four P. minor populations with suspected resistance to ACCase‐inhibiting herbicides were sampled from wheat fields in the provinces of Fars and Golestan in Iran. The dose–response assays that were conducted under controlled greenhouse conditions indicated that 14 populations were resistant to fenoxaprop‐P‐ethyl, seven populations were resistant to both fenoxaprop‐P‐ethyl and diclofop‐methyl, and three populations were resistant to fenoxaprop‐P‐ethyl, diclofop‐methyl, and clodinafop‐propargyl. These populations showed different levels of resistance to the applied herbicides, compared to the susceptible population. These results suggest that different mechanisms of resistance could be involved. The enzyme assay revealed that the existence of modified ACCase in the three most‐resistant populations (AR, MR4, and SR3) is responsible for the resistance of these populations.     

高效液相色谱法测定噻唑锌在水、土壤及黄瓜中的残留

建立了采用高效液相色谱-二极管阵列检测器（HPLC-DAD）测定水、土壤和黄瓜中噻唑锌残留的方法。在碱性条件下先将噻唑锌转化为噻二唑（AMT）,采用外标法通过测定噻二唑的量来进行噻唑锌的定量分析。样品在40℃恒温振荡条件下,依次经Na2S转化及乙腈提取;过滤后调节混合液pH值至3,经乙酸乙酯液-液分配后,用HPLC-DAD及BDS Hypersil-C18色谱柱,以V（乙腈）:V（0.1%乙酸）=10:90为流动相,在313 nm波长下测定样品中的噻唑锌残留。结果表明:噻二唑在0.10~10 mg/L、噻唑锌在0.20~5.0 mg/L的质量浓度范围内线性关系良好（R2 > 0.999 5）,噻二唑的检出限（LOD）为0.05 mg/L。在0.2、1和5 mg/L添加水平下,噻唑锌在水中的平均回收率为100%~110%,相对标准偏差（RSD）为0.90%~6.4%;在0.05、0.5和5 mg/kg添加水平下,噻唑锌在土壤中的平均回收率为81%~98%,RSD为0.70%~2.8%;在0.05、0.5和2 mg/kg添加水平下,噻唑锌在黄瓜中的平均回收率为95%~102%,RSD为1.3%~4.2%。噻唑锌在水、黄瓜和土壤中的定量限（LOQ）分别为0.03 mg/L、0.05 mg/kg和0.05 mg/kg。本方法简单、准确、可靠,能满足农药残留分析的要求。     

Determination of petroleum oil deposits on Citrus sinensis (L.) Osbeck leaves

Oil deposited on citrus leaves when sprayed with oil-in-water emulsions was measured by gas-liquid chromatography of a hexane/acetone/water/ethyl acetate extract of the leaves. To overcome the problem of decreased recoveries with increased time between spraying and extraction, a refluxing step was included in the procedure followed by Florisil clean-up prior to analysis. Mean oil recoveries of 81% were obtained and, unlike recoveries using published methods, they were independent of time between application and extraction. The method is intended to be used in trials to determine the relationship between spray volume, Chinese wax scale mortality and petroleum oil deposition on citrus leaves sprayed by low-, medium- and high-volume sprayers.     

固相萃取-气相色谱-质谱联用法测定蔬菜中烯肟菌胺的残留及其裂解机理

建立了蔬菜中烯肟菌胺残留量的固相萃取-气相色谱-质谱联用（SPE-GC-MS）分析方法;对烯肟菌胺的裂解机理进行了探讨;确定了测试分析的定性离子和定量离子。样品采用乙酸乙酯高速分散提取,以无水硫酸镁、硅胶和石墨化炭黑（GCB）为混合填料进行固相萃取净化,气相色谱-质谱联用仪在选择离子扫描（SIM）模式下进行检测,基质匹配标准溶液外标法定量。结果显示:烯肟菌胺在0.02~1 mg/L内,标准溶液的峰面积与质量浓度呈良好的线性关系（r>0.999）;在0.02~0.2 mg/kg添加水平下,烯肟菌胺的平均回收率为94%~99%,相对标准偏差（RSD,n=6）为2.3%~2.9%;方法的检出限（LOD）（S/N=3）为0.006 mg/kg,定量限（LOQ）（S/N=10）为0.02 mg/kg。     

Measurement of simazine residues in chickpeas,Cicer arietinum,by gas–liquid chromatography

A method is described for the measurement of simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine] residues in chickpeas (Cicer arietinum). Ground chickpea samples were extracted with dichloromethane, followed by clean-up on alumina. Gas-liquid chromatography using metribuzin [4-amino- 6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one] as internal standard with thermionic detection was used to quantify simazine residues. The limit of detection was 0.02 mg kg^?1 and the recoveries of simazine from chickpea samples (0.1–4 mg kg-1) averaged 92%.     

气相色谱-电子捕获检测器法测定柑桔和土壤中苯丁锡的残留

建立了采用气相色谱-电子捕获检测器(GC-ECD)测定柑桔和土壤中苯丁锡残留量的分析方法。样品经乙腈提取,浓盐酸衍生化,中性氧化铝柱净化。结果表明:在0.5~5.0 mg/kg添加水平范围内,苯丁锡的平均添加回收率为92% ~98%,相对标准偏差(RSD)为5.8% ~8.7%(n=5)。方法的最小检出量(MDL)为1×10-10g,苯丁锡在桔肉、桔皮、全果和土壤4种基质中的定量限(LOQ)均为0.5 mg/kg。该方法杂质干扰少,准确性及灵敏度满足农药残留检测要求,对检测硬件要求低,适用于柑桔和土壤中苯丁锡残留的分析。消解动态试验结果表明,苯丁锡在柑桔和土壤中的消解半衰期分别为9~14 d和9~11 d,属易降解农药。     

The determination of abamectin from soil and animal tissue by supercritical fluid extraction and fluorescence detection

The insecticide abamectin is extracted from soil and animal tissue by supercritical fluid extraction. Supercritical carbon dioxide modified with 9% 2-methoxyethanol extracted abamectin from soil samples at levels up to 11 ng g^?1 with greater than 80% efficiency. Recovery at fortification levels of 5 ng g^?1 were obtainable without the need for clean-up. Abamectin was also easily extracted from animal tissue at levels of 22ng g^?1 without interfering coextractives. Extracted abamectin was determined by liquid chromatography of a fluorescent derivative.     

高效液相色谱法测定甘蔗及土壤中环嗪酮的残留量

建立了高效液相色谱法(HPLC)测定甘蔗及土壤中环嗪酮残留量的方法。甘蔗样品以氯仿提取,经中性氧化铝柱层析净化,HPLC法测定;土壤样品以乙酸乙酯-甲醇(体积比9∶ 1)混合溶剂提取,HPLC法测定;甘蔗和土壤中环嗪酮的最低检测浓度(LOQ)分别为0.02 mg/kg 和0.04 mg/kg;在0.04~0.4 mg/kg添加水平内,土壤中环嗪酮的回收率为79.4% ~86.1%;在0.02~0.5 mg/kg添加水平内,甘蔗中环嗪酮的回收率为84.1% ~95.7%;相对标准偏差均低于6.1%。     

食品与环境样本中有机氯农药残留的净化技术研究进展

在查阅大量相关文献并结合作者自身研究工作经验的基础上,根据介质中干扰物的种类和特点,按照不同介质进行分类,重点介绍了填充柱、固相萃取、凝胶色谱、磺化和基质固相分散等净化技术在检测分析水、土壤、沉积物、茶叶、中药以及脂肪性样本中有机氯农药残留中的应用。认为将净化技术与提取技术或分析技术有效结合,提高样品净化效率及整体分析速度将是未来净化技术的主要发展趋势。     

土壤和水体中20种除草剂的气相色谱-质谱法多残留分析

建立了土壤和水体中20种除草剂残留的气相色谱-质谱(GC-MS)分析方法。土壤样本通过乙腈提取,Florisil固相萃取柱净化,V(石油醚):V(乙酸乙酯)=9:1洗脱,GC-MS测定;水体样本用C18固相萃取柱进行富集和净化,以V(甲醇):V(乙酸乙酯)=1:1洗脱,GC-MS测定。20种除草剂在土壤和水体中的平均添加回收率分别为72%～109%和77%～113%,相对标准偏差(RSD)分别在0.15%～16.5%和0.45%～16.3%之间,方法定量限(LOQ)在土壤中为0.01 mg/kg,在水体中为0.1 μg/L。用所建方法可同时检测土壤和水中20种常用除草剂,方法净化效果好、灵敏度高、重现性好、简便快速。     

Cross‐resistance patterns to acetyl coenzyme A carboxylase (ACCase) inhibitors associated with different ACCase mutations in Beckmannia syzigachne

Beckmannia syzigachne (American sloughgrass) is a competitive grass weed found in China. Fenoxaprop‐P‐ethyl is widely used for control of this species in China. Resistance to fenoxaprop‐P‐ethyl in B. syzigachne has been reported to be conferred by an isoleucine(Ile)‐1781‐leucine(Leu) substitution in the gene encoding the herbicide target, acetyl‐CoA carboxylase (ACCase). In this study, three mutations were detected by derived cleaved amplified polymorphic sequence (dCAPS) method in fenoxaprop‐P‐ethyl‐resistant B. syzigachne populations: Ile‐1781‐Leu in population JCWL‐R, Ile‐2041‐Asn in JCJT‐R and Gly‐2096‐Ala in JYJD‐R. The data indicated they were genetically homogeneous (homozygous mutant) at the ACCase locus. The use of cytochrome P450 inhibitors was shown to slightly reduce the GR₅₀ value of fenoxaprop‐P‐ethyl‐resistant populations, from which we inferred a combination of target‐site resistance (TSR) and non‐target‐site resistance (NTSR) was involved in fenoxaprop‐P‐ethyl‐resistance. We characterised the cross‐resistance patterns to ACCase inhibitors in B. syzigachne. The plants in the JCWL‐R population were highly resistant to all tested APPs (aryloxyphen‐oxypropionates), sethoxydim and pinoxaden, and moderately resistant to clethodim. The plants in the JCJT‐R population were highly resistant to fluazifop‐P‐butyl, clodinafop‐propargyl, cyhalofop‐butyl, metamifop and pinoxaden; moderately resistant to haloxyfop‐R‐methyl, quizalofop‐P‐ethyl and sethoxydim; and sensitive to clethodim. The plants in the JYJD‐R population were highly resistant to clodinafop‐propargyl, metamifop and pinoxaden; moderately resistant to haloxyfop‐R‐methyl, cyhalofop‐butyl, quizalofop‐P‐ethyl, fluazifop‐P‐butyl and sethoxydim; and sensitive to clethodim. If resistance to ACCase inhibitors is present in B. syzigachne populations in the field, then our results indicate that clethodim should be used. While we demonstrated the cross‐resistance patterns of TSR resulting from three mutations in B. syzigachne, we also demonstrated that NTSR plays a role in resistance, which will complicate weed management.     

Persistence of pyrazosulfuron in rice-field and laboratory soil under Indian tropical conditions

BACKGROUND: Pyrazosulfuron ethyl, a new rice herbicide belonging to the sulfonylurea group, has recently been registered in India for weed control in rice crops. Many field experiments revealed the bioefficacy of this herbicide; however, no information is available on the persistence of this herbicide in paddy soil under Indian tropical conditions. Therefore, a field experiment was undertaken to investigate the fate of pyrazosulfuron ethyl in soil and water of rice fields. Persistence studies were also carried out under laboratory conditions in sterile and non‐sterile soil to evaluate the microbial contribution to degradation. RESULTS: High‐performance liquid chromatography (HPLC) of pyrazosulfuron ethyl gave a single sharp peak at 3.41 min. The instrument detection limit (IDL) for pyrazosulfuron ethyl by HPLC was 0.1 µg mL^?1, with a sensitivity of 2 ng. The estimated method detection limit (EMDL) was 0.001 µg mL^?1 and 0.002 µg g^?1 for water and soil respectively. Two applications at an interval of 10 days gave good weed control. The herbicide residues dissipated faster in water than in soil. In the present study, with a field‐soil pH of 8.2 and an organic matter content of 0.5%, the pyrazosulfuron ethyl residues dissipated with a half‐life of 5.4 and 0.9 days in soil and water respectively. Dissipation followed first‐order kinetics. Under laboratory conditions, degradation of pyrazosulfuron ethyl was faster in non‐sterile soil (t_1/2 = 9.7 days) than in sterile soil (t_1/2 = 16.9 days). CONCLUSION: Pyrazosulfuron ethyl is a short‐lived molecule, and it dissipated rapidly in field soil and water. The faster degradation of pyrazosulfuron in non‐sterile soil than in sterile soil indicated microbial degradation of this herbicide. Copyright © 2012 Society of Chemical Industry     

莠去津在土壤及作物中残留量测定

本文建立了一种土壤和作物中痕量莠去津的高效液相色谱分析方法,比较了超声波提取与振荡提取的回收率,研究了弗罗里硅土净化效果。以甲醇：水（８０／２０,Ｖ／Ｖ）为流动相,检测波长２３５ｎｍ,在ＯＤＳ柱上实现了莠去津与杂质的良好分离。方法简单,分析速度快,测定费用低,检测限为２４ｎｇ／ｇ,回收率为９５％～９７％。     

Enzyme immunoassay for atrazine analysis in water and soil

Enzyme immunoassay (EIA) has been tested for the detection of atrazine in soil and water. EIA kits and atrazine-fortified samples were received from the International Atomic Energy Agency. Atrazine concentrations of about 0·01 μg litre^-1 could be detected and the central detection point was found at about 0·15 μg litre^-1 which is a reasonably sensitive region for atrazine. A validation study with spiked local water samples yielded acceptable results. No treatment was required for water samples. Extraction of atrazine from soil was done by simple shaking with methanol without any clean-up steps. Detection limits of 1×10^-2 μg litre^-1 for water and 5×10^-3 μg kg^-1 for soil were achieved. © 1998 SCI.     

超高效液相色谱-串联质谱法分析氟虫双酰胺在稻田生态系统中的消解动态

应用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了氟虫双酰胺(NNI-0001)及其代谢产物(NNI-des)在土壤和田水中的残留检测方法。样品采用乙腈提取,乙二胺-N-丙基硅烷吸附剂(PSA)净化,UPLC-MS/MS检测。氟虫双酰胺及其代谢产物NNI-des在土壤和田水中的最低检测浓度分别为0.002 mg/kg和0.001 mg/L,最小检出量分别为1.2×10-13和3.1×10-14 g。在土壤和田水中的添加水平为0.001~1 mg/kg(mg/L)条件下,氟虫双酰胺及其代谢产物NNI-des的平均回收率在78.2%~108.2%之间,相对标准偏差在8.2%~15.3%之间。消解动态试验结果表明,氟虫双酰胺在土壤和田水中的半衰期分别为1.0和 5.4 d。施药21 d后,消解率均在85%以上,属易降解农药。     

Determination of permethrin by gas–liquid chromatography with electron capture detection

A method was developed for determining permethrin in potatoes. The insecticide was extracted with acetone and hexane, and partitioned into ethyl acetate. The extract was purified on a column containing a mixture of alumina, “Florisil” and silica gel plus a layer of activated charcoal mixed with cellulose. Analysis was by gas-liquid chromatography with electron-capture detection. Recovery from fortified potatoes ranged from 78 to 91% at 0.01 mg/kg and 98 to 107% at 1.0 mg/kg. The method appears to be applicable to other crops; a trial run on fortified bean leaves gave 80% recovery at 0.1 mg/kg.