Simultaneous gas chromatographic determination of chlorpyrifos and its impurity sulfotep in liquid pesticide formulations

An analytical method for simultaneous determination of the active substance (chlorpyrifos) and its relevant impurity (sulfotep) in commercial pesticide formulations has been developed and validated. The proposed method entails extraction of the analytes from samples by sonication with acetone and analysis by gas chromatography-flame ionization detection (GC-FID). The proposed method was characterized by satisfactory accuracy and precision. The repeatability expressed as relative standard deviation (RSD) was lower than the acceptable values calculated from the modified Horwitz equation whereas individual recoveries were in the range of 98–102% and 80–120% for chlorpyrifos and sulfotep, respectively. The limit of quantification (LOQ) for the impurity (sulfotep) was 0.003 mg mL^?1 corresponding to the maximum permitted level according to Food and Agricultural Organization of the United Nations (FAO) specifications for the active substance (chlorpyrifos) being 3 g kg^?1 of the chlorpyrifos content found. The main advantage of the proposed method was a considerable reduction in the analysis time since both analytes were determined based on a single injection into the GC-FID. Analysis of real samples of commercial pesticide formulations confirmed fitness-for-purpose of the proposed method.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

气相色谱/质谱测定苯酚丙酮生产废水中半挥发性有机物

建立了用二氯甲烷液液萃取对苯酚丙酮生产废水进行预处理,气相色谱/质谱法同时测定废水中半挥发性有毒有机物异丁酸、异丙苯、α-甲基苯乙烯、2-苯基丙醛、苯乙酮、2-苯基-2-丙醇、α-甲基苯甲醇、苯酚和苯甲酸等的定性定量分析方法。色谱条件为:DB-17MS型色谱柱,程序升温,进样量为1μL,质量选择检测器(MSD)。实验结果表明,该色谱条件对苯酚丙酮生产废水中各半挥发性组分具有较好的分离效果。而对9种组分的最低检出限均低于0.04mg/L,精密度实验相对标准偏差2.14%～5.15%,实际水样的加标回收率稳定。苯酚丙酮生产废水中的主要污染物为2-苯基-2-丙醇,其次为苯酚、异丁酸和异丙苯。     

顶空气相色谱测试水中苯系混合物在不同材料上的吸附行为

设计了正交实验对5种材料吸附模拟废水中苯系混合物(苯、甲苯、二甲苯)的条件进行优化,CD02硅藻土与X型纳米分子筛以2∶1(质量比)进行复合后,对苯系混合物去除效果最好.采用顶空气相色谱法测定8种不同材料对水中苯系混合物的去除情况,结果表明复合材料对苯系混合物具有良好的去除效果,仅次于活性炭.复合材料在pH为7、搅拌时间为25 min、用量为1.8g/L时,对苯系混合物质量浓度为4.0 mg/L模拟废水的平均去除率为87.56％.经过4次再生后,复合材料的再生率仍高达84.90％,对苯系混合物的平均去除率为91.49％.     

混合表面活性剂-浊点萃取法测定沉积物中多环芳烃的含量

以混合型表面活性剂（十二烷基硫酸钠（SDS）和对叔辛基苯基聚己二醇醚（Triton X-114））为萃取剂,采用浊点萃取法萃取沉积物中的15种多环芳烃（PAHs）,并利用HPLC技术测定15种PAHs的含量。实验结果表明,当混合型表面活性剂的加入量 3％（w）、混合型表面活性剂中SDS含量 50%（φ）、Na2SO4含量 8％（w）、萃取温度 60 ℃、超声萃取时间 10 min 时,15种PAHs的线性关系良好,r=0.998 9~0.999 7,检出限0.4~8.2 μg/L,加标回收率71.22%~97.36%,相对标准偏差0.92%~4.36%（n=6）。     

Application of indoxacarb for managing shoot and fruit borer of eggplant (Solanum melongena L.) and its decontamination

Indoxacarb was applied at 75 and 150 g a.i. ha^{? 1} for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg^{? 1} and 3.64–3.68 mg kg^{? 1} from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg^{? 1}) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg^{? 1} thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO₄) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g^{? 1} spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.     

Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River,Brazil

The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Simultaneous analysis of thiabendazole,carbendazim and 2-aminobenzimidazole in concentrated fruit juices by liquid chromatography after a single mix-mode solid-phase extraction cleanup

A method using liquid chromatography and a single mix-mode solid-phase extraction cleanup for the simultaneous analysis of thiabendazole [2-(1,3-thiazol-4-yl)-1H-benzoimidazole], carbendazim [(methyl N-(1H-benzoimidazol-2-yl)-carbamate)] and 2-aminobenzimidazole (1H-benzimidazol-2-amine) in concentrated fruit juices is described. The three fungicides were isolated from the samples and concentrated by solid-phase extraction on Oasis MCX cartridges. The determination was performed by liquid chromatography with a diode array, detecting at 288 nm. In this method, the average recoveries from blank control juice samples spiked in a concentration range of 0.01–0.10 mg/kg were in the range of 81–95%, with relative standard deviations below 8%. Detection limits and limits of quantification were 4 μ g/kg and 10 μ g/kg, respectively, for each fungicide. Real juice samples were analyzed by the proposed method. The results were compared to those from liquid chromatography-tandem mass spectrometry.