Fast gas chromatography for pesticide residues analysis

The importance of method development in the area of pesticide residues analysis is apparent from legislative requirements continuously decreasing the maximum acceptable concentration levels in food and water. This covers also contribution in the science in the field of ultra-trace analysis of organic pollutants in complex mixtures. Analysis time is one of the most important aspects that should be considered in the choice of analytical methods for routine application. With this fact, fast gas chromatography (GC) has acquired a real importance in the pesticide residue analysis. This paper provides an overview of fast GC methods for analysis of pesticide residues in variety of matrices at ultra-trace concentration levels. Emphasis is put on the development in the last 6 years.     

Comparison of sample preparation methods combined with fast gas chromatography-mass spectrometry for ultratrace analysis of pesticide residues in baby food

Four sample preparation techniques were compared for the ultratrace analysis of pesticide residues in baby food: (a) modified Schenck's method based on ACN extraction with SPE cleaning; (b) quick, easy, cheap, effective, rugged, and safe (QuEChERS) method based on ACN extraction and dispersive SPE; (c) modified QuEChERS method which utilizes column-based SPE instead of dispersive SPE; and (d) matrix solid phase dispersion (MSPD). The methods were combined with fast gas chromatographic-mass spectrometric analysis. The effectiveness of clean-up of the final extract was determined by comparison of the chromatograms obtained. Time consumption, laboriousness, demands on glassware and working place, and consumption of chemicals, especially solvents, increase in the following order QuEChERS < modified QuEChERS < MSPD < modified Schenck's method. All methods offer satisfactory analytical characteristics at the concentration levels of 5, 10, and 100 microg/kg in terms of recoveries and repeatability. Recoveries obtained for the modified QuEChERS method were lower than for the original QuEChERS. In general the best LOQs were obtained for the modified Schenck's method. Modified QuEChERS method provides 21-72% better LOQs than the original method.     

Fast gas chromatography for pesticide residues analysis using analyte protectants

Fast GC-MS with narrow-bore columns combined with effective sample preparation technique (QuEChERS method) was used for evaluation of various calibration approaches in pesticide residues analysis. In order to compare the performance of analyte protectants (APs) with matrix-matched standards calibration curves of selected pesticides were searched in terms of linearity of responses, repeatability of measurements and reached limit of quantifications utilizing the following calibration standards in the concentration range 1-500 ng mL(-1)(the equivalent sample concentration 1-500 microg kg(-1)): in neat solvent (acetonitrile) with/without addition of APs, matrix-matched standards with/without addition of APs. For APs results are in a good agreement with matrix-matched standards. To evaluate errors of determination of concentration synthetic samples at concentration level of pesticides 50 ng mL(-1) (50 microg kg(-1)) were analyzed and quantified using the above given standards. For less troublesome pesticides very good estimation of concentration was obtained utilizing APs, while for more troublesome pesticides such as methidathion, malathion, phosalone and deltamethrin significant overestimation reaching up to 80% occurred. According to presented results APs can be advantegously used for "easy" pesticides determination. For "difficult" pesticides an alternative calibration approach is required for samples potentially violating MRLs. An example of real sample measurement is shown. In this paper also the use of internal standards (triphenylphosphate (TPP) and heptachlor (HEPT)) for peak areas normalization is discussed in terms of repeatability of measurements and quantitative data obtained. TPP normalization provided slightly better results than the use of absolute peak areas measurements on the contrary to HEPT.     

Improved analytical procedure for determination of chlorinated pesticide residues in human serum using solid phase disc extraction (SPDE), single-step clean-up and gas chromatography

Summary An improved analytical methodology based on solid-phase disc extraction (SPDE) and a single-step clean-up on Florisil is proposed for a large number of organochlorine pesticide residues in serum. Extraction was performed following denaturation of proteins with formic acid after it was shown that it has no degradation effect on targeted analytes (α, β, γ-HCH isomers, HCB, DDT with its 5 analogues, endrin, aldrin, dieldrin, alachlor; heptachlor, heptachlorepaxide, α, β-endosulphan, endosulphansulphate, methoxychlor and mirex). Determination and quantification were by GC-ECD and GC-MS on two different, analytical capillary-columns using PCNB (pentachlonitrobenzene) and PCB 190 internal standards. Recoveries and limits of detection determined on pooled serum ranged 54–102% (for medium spiking level) and 10–50 pg ml⁻¹ serum respectively. Twenty-one individuals serum samples from the University Hospital of Antwerp were analysed and results were related to the ages of the donors. For compounds not detected by GC-MS, eventual coelution with PCBs in GC-ECD analysis was studied.     

超声波提取-固相萃取净化-气相色谱法分析烟草中拟除虫菊酯类农药及氟节胺残留

建立了超声波提取-固相萃取净化-气相色谱联用测定烟草中多种拟除虫菊酯类农药及氟节胺残留量的方法。与现行标准方法相比,本方法前处理简单、快速、有机溶剂消耗量少,且增加了分析目标物的数量。8种拟除虫菊酯类农药及氟节胺在0.1、0.5和1μg/g三个加标水平的回收率为86%～111%,相对标准偏差为0.2%～4.1%,满足当前烟草农药残留的检测要求。     

Fast solid phase extraction of polychlorobiphenyls and chlorinated pesticide residues from mussels using sep-pak cartridges

Summary A rapid method for the determination of chlorinated pesticides and polychlorinated biphenyls in mussels (Mytilus sp.) is reported. The mussel sample is homogenized and extracted with acetonitrile. The organic solution is concentrated and successively diluted with distilled water solution (12 g L⁻¹ NaCl). The organic compounds from water solution are adsorbed onto a NH₂ Sep-Pak cartridge. The clean-up step, in which the polychlorobiphenyls and chiorinated pesticides are separated in different eluates, is achieved by passing 25 mL of a 40% methanol aqueous solution through the NH₂ Sep-Pak and the C₁₈ Sep-Pak cartridges connected in series. The polychloroblphenyls are desorbed from the NH₂ Sep-Pak cartridge whilst the chlorinated peslicides are recovered from the C₁₈ Sep-Pak cartridge. In the separation of polychlorobiphenyls from the chlorinated pesticides tested in this work, only aldrin, hepatachlor and 4,4′-DDD are partially adsorbed with the polychlorobiphenyls onto the NH₂ Sep-Pak cartridge. The average recovery is ≥95.0% with a relative standard deviation ≤5.0%. The limits of detection for different pesticides and polychlorobiphenyl congeners are 0.01 and 0.008 μg Kg⁻¹. The final determination is carried out by capillary gas chromatography with ECD.     

固相萃取-气相色谱法测定茶叶中残留的92种农药

建立了茶叶中92种农药多残留的气相色谱分析方法。茶叶样品用乙腈一次性提取后,有机磷类农药经Envi-Carb固相小柱净化,用10 mL乙腈-甲苯(体积比为3∶1)洗脱剂淋洗,气相色谱-火焰光度检测器(GC-FPD)检测;有机氯类和拟除虫菊酯类农药经串联Envi-Carb和NH2固相小柱净化,用5 mL乙腈-甲苯(体积比为3∶1)洗脱剂淋洗,GC-电子捕获检测器(ECD)检测。采用外标法定量。添加回收试验的结果表明:92种农药的平均回收率为80.3%～117.1%,相对标准偏差为1.5%～9.8%。方法的检出限为0.0025～0.10 mg/kg。该方法的灵敏度、准确度和精密度均符合农药残留测定的技术要求。     

Automated capillary gas chromatographic analysis of pesticide residues in food

A method for multiresidue pesticide analysis in food is described. After a conventional clean-up, gas chromatographic analysis is performed in a gas chromatograph equipped with two fused-silica capillary columns coated with methylsilicone SP 2100 and methylphenylsilicone OV-17. The effluent from each column is split to electron-capture and nitrogen-phosphorus detectors, which are connected to a dual channel integrator. Therefore, from each gas chromatographic run parallel records of signals from the two detectors are obtained. Calibration of the system is carried out for the SP 2100 column with three test mixtures covering all pesticides. Additionally, four internal standards are included, two responding to the electron-capture detector and the other two to the nitrogen-phosphorus detector. Automated analysis is performed with test mixtures and food samples on the SP 2100 column overnight as a screening procedure. After selection of positive samples a confirmatory test and quantitation are carried out manually applying appropriate test mixtures according to the results of the screening runs.     

加速溶剂萃取-固相萃取净化-气相色谱-串联质谱法检测茶叶中9种拟除虫菊酯类农药残留

建立了加速溶剂萃取（ASE）-固相萃取净化（SPE）-气相色谱-串联质谱（GC-MS/MS）同时测定茶叶中9种拟除虫菊酯类农药残留的方法。ASE萃取溶剂为丙酮-正己烷（1：1,v/v）,萃取温度为100℃,萃取压力为10 MPa,加热时间为3 min,静态萃取时间为5 min,循环1次,冲洗体积为40%萃取池体积,氮气吹扫100 s。萃取结束后用Cleanert TPT固相萃取柱净化,净化液浓缩定容后,采用GC-MS/MS测定,外标法定量。9种拟除虫菊酯类农药在2~1000 μg/L范围内呈现良好的线性关系,相关系数（r²）均大于0.99,方法检出限为0.2~4.5 μg/kg,定量限为0.8~15.0 μg/kg。在绿茶、红茶空白基质中做加标回收试验,添加水平为0.02、0.1、0.4 mg/kg以及定量限水平,得到的平均回收率为69.87%~110.0%,相对标准偏差（RSD）为0.7%~11.2%。该方法背景干扰低、灵敏度高、重现性好、回收率稳定,适用于茶叶中拟除虫菊酯类农药残留量的检测。     

Determination of organochlorine pesticide residues by solid phase extraction and dual-column HRGC

Organochlorine pesticide residues have been extracted from samples of animal feed by a solid phase extraction clean-up procedure using an octadecyl-bonded column. The proposed method gave recoveries ranging from 70 to 100 % for ppb levels of the fifteeen pesticides studied. Analytes were identified by dual-column capillary gas chromatography employing DB-1 and DB-1701 columns in parallel; identities were confirmed by calculation of retention indexes with the cubic spline interpolation method.     

Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination

Pesticides are widely utilized at various stages of cultivation and during postharvest storage to protect plants against a range of pests and/or to provide quality preservation. Reliable confirmatory methods are required to monitor pesticide residues in baby foods and to ensure the safety of baby food supply. This review covers methods in which pesticide residues have been determined in baby food by the use of a wide range of chromatographic techniques after various sample preparation steps. The main attention is paid to the evaluation and improvement of sample extraction and clean-up methods (liquid extraction, solid-phase extraction (SPE), dispersive SPE (DSPE), microextraction procedures, matrix solid-phase dispersion (MSPD) and supercritical fluid extraction (SFE)) considering low concentration levels of pesticide residues in baby food resulting from stringent European Union (EU) legislation. Instrumental aspects together with the matrix effects significantly contributing to the most important parameters considered in pesticide residues analysis of baby food--limits of detection (LODs) and limits of quantification (LOQs) were included within the scope of this overview. Paper involves also monitoring studies.     

Determination of organochlorine pesticide residues in foods using solid-phase extraction clean-up cartridges

Fourteen organochlorine pesticide residues in fatty foods were determined using a simple and rapid procedure based on solid-phase extraction (SPE) clean-up cartridges with octadecyl (C18)-bonded porous silica, a tandem C18 and Florisil column, Alumina-N and Florisil. A Florisil cartridge eluted with 12 ml petroleum ether-ethyl ether (95 + 5) was the most efficient clean-up procedure capable of eliminating the matrix interference and satisfying the agreed acceptable recovery for the large numbers of organochlorine pesticides in nine kinds of foods having different fat contents. Average recoveries of organochlorine pesticides in shellfish, fish and meats ranged from 77 to 105%, 84 to 98% and 85 to 107%, respectively. In addition, analysis of a certified Standard Reference Material (SRM 1945) verified the satisfactory performance of Florisil clean-up cartridge. This SPE method not only yielded comparable results for nonfatty foods, but also provided a reliable separation and quantification of organochlorine pesticides for analyzing a large number of foods with a wide range of fat content.     

Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography and mini-silica gel-column chromatography

A new extraction and partition step was introduced into the well established multi-residue method of Specht and Tillkes (DFG method S 19) replacing dichloromethane by ethyl acetate/cyclohexane (1+1). In addition, more simple working conditions were obtained. Results of fortification experiments with organochlorine, organophosphorus and organonitrogen pesticides showed good agreement with those obtained by the formerly published method.     

Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography and mini-silica gel-column chromatography

A new extraction and partition step was introduced into the well established multi-residue method of Specht and Tillkes (DFG method S 19) replacing dichloromethane by ethyl acetate/cyclohexane (1+1). In addition, more simple working conditions were obtained. Results of fortification experiments with organochlorine, organophosphorus and organonitrogen pesticides showed good agreement with those obtained by the formerly published method.     

Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography and mini-silica gel-column chromatography

Zusammenfassung Es wird eine Methode für die gaschromatographische Bestimmung von 11 herbiciden Phenoxyalkancarbonsäuren sowie deren Ester und Konjugate in Pflanzenmaterial beschrieben. Nach alkalischer Hydrolyse werden die Säuren aus dem angesäuerten Hydrolysat durch Aceton/Wasser/Dichlormethan-Verteilung extrahiert. Der Extrakt wird über Gel-Chromatographie an Bio Beads S-X3 und eine Säure/Base-Ausschüttelung gereinigt. Die Säuren werden mit Methanol/Schwefelsäure verestert. Die gaschromatographische Bestimmung erfolgt massenfragmentographisch als Methylester. 2,4-D, 2,4-DB, Dichlorprop, Diclofop-methyl, Fenoprop und 2,4,5-T können gas-chromatographisch auch mit dem Elektroneneinfangdetektor bestimmt werden, wenn die Methylesterlösungen an einer Mini-Kieselgel-Säule nachgereinigt werden.

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Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography and mini-silica gel-column chromatography4. Communication. gas-chromatographic determination of 11 herbicidal phenoxyalkyl acids and their esters

Summary A method is described for the gas-chromatographic determination of 11 herbicidal phenoxyalkyl acids, their esters and conjugates in plant material. The method includes alkaline hydrolysis, extraction of the acids by aceton/water/dichloromethane partition, gel permeation Chromatography, acid/base distribution, methylation with methanol/sulphuric acid and detection by gas-chromatography/mass fragmentography. 2,4-D, 2,4-DB, dichlorprop, diclofop methyl, fenoprop and 2,4,5-T can likewise be detected by electron-capture gas-chromatography after additional clean-up of the methyl ester solutions by minisilica gel-column Chromatography.

1. Mitt.: Organochlor-Pflanzenbehandlungsmittel in Tabak und Tabakerzeugnissen. Beitr. Tabakforsch. Int. 10, 73–79 (1979). 2. Mitt.: Bestimmung der Fungizide Bitertanol, Fluotrimazol, Fuberidazol, Imazalil, Rabenzazole, Triadimefon und Triadimenol in Pflanzen und Boden. Pflanzenschutz-Nachrichten Bayer 33, 61–85 (1980). 3. Mitt.: Methode zur Aufarbeitung von Lebensmitteln und Futtermitteln pflanzlicher und tierischer Herkunft für die Multirückstandsbestimmung lipoid- und wasserlöslicher Pflanzenbehandlungsmittel. Fresenius Z. Anal. Chem. 301, 300–307 (1980)     

Determination of organochlorine pesticide residues in honey, applying solid phase extraction with RP-C18 material

In this study, a new clean up method was developed for the routine multiresidue determination of organochlorine pesticide residues in honey. The analytical procedure requires sample extraction with methanol, followed by a clean up step through a C18 Sep-Pak cartridge. Finally, pesticides are eluted with hexane. The determination of organochlorine pesticide residues was performed by capillary gas chromatography with electron capture detection. The mean recoveries of 18 organochlorine pesticides were estimated at various concentrations and found very efficient in most cases. The detection limits were found to be between 0.05 and 0.20 microgram kg-1.     

Analyses of pesticide residues in fruit-based baby food by liquid chromatography/electrospray ionization time-of-flight mass spectrometry

A liquid chromatography/electrospray ionization time-of-flight mass spectrometry (LC/ESI-TOFMS) method has been developed for the determination of 12 pesticides (namely, carbendazim, thiabendazole, imazalil, tridemorph, triadimefon, bitertanol, prochloraz, flutriafol, myclobutanil, iprodione, diphenylamine and procymidone) in fruit-based baby food (multi-fruit jars and juices intended for infant consumption). The developed method consists of a sample treatment step based on liquid-liquid extraction using acetonitrile, followed by a clean-up step based on dispersive solid-phase extraction (SPE) with a primary-secondary amine (PSA). Multi-fruit and apple juices were processed by a SPE procedure using Oasis HLB cartridges. Subsequent identification and quantitation was accomplished by LC/ESI-TOFMS analysis: the confirmation of the target pesticides was based on accurate mass measurements of selected ions (protonated molecules ([M+H]+) and fragment ions). Confirmation studies were accomplished at low concentration levels (10 microg kg-1) and accuracy errors lower than 2 ppm were obtained in most cases. Baby food extracts spiked at 10 microg kg-1 fortification level yielded average recoveries in the range 78-105% with relative standard deviations less than 10% for most of the analytes. Limits of detection (LODs) were between 0.1 and 4 microg kg-1 depending on the pesticide studied. Finally, the proposed method was applied to a total of 33 baby food samples from Spain and the United Kingdom. Although imazalil, thiabendazole and carbendazim were detected in a high number--over 60%- of baby food samples, none of the samples tested were found to be above the 0.01 mg kg-1 EU standard.     

Rapid analysis of multiple pesticide residues in fruit-based baby food using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry

A rapid method using programmed temperature vaporiser injection-low-pressure gas chromatography-high-resolution time-of-flight mass spectrometry (PTV-LP-GC-HR-TOF-MS) for the analysis of multiple pesticide residues in fruit-based baby food was developed. The fast and inexpensive buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction method and "conventional" approach that employs ethyl acetate extraction followed by gel permeation chromatography (GPC) cleanup were employed for sample preparation. A PTV injector in solvent venting mode was used to reduce volume of acetonitrile and acetic acid (from the buffered QuEChERS extracts) that caused higher column bleed without their elimination. Otherwise, the time-to-digital converter would become saturated in HR-TOF-MS. For fast GC separation allowing analysis of 100 analytes within a 7 min runtime, both a high temperature programming rate and vacuum conditions in a megabore GC column were employed. The use of HR-TOF-MS allowed the unbiased identification and reliable quantification of target analytes through the application of a narrow mass window (0.02 Da) for extracting analyte ions and the availability of full spectral information even at very low levels. With only a few exceptions, the lowest calibration levels for the pesticides tested were 相似文献   

Fast temperature programming in routine analysis of multiple pesticide residues in food matrices

Flash gas chromatographic (GC) analysis of 15 organophosphorus pesticides commonly occurring in food crops was performed using the Thermedics Detection EZ Flash upgrade kit installed in the oven of a HP 5890 Series II Plus gas chromatograph. The temperature program and splitless time period were the main parameters to be optimized. In the first set of experiments wheat matrix-matched standards were analyzed both by: (i) the flash GC technique (resistive heating of a 5 m capillary column), and (ii) the conventional GC technique (moderate oven temperature programming of a 30 m capillary column). Using the flash GC technique, the analysis time was reduced by a factor of more than 10 compared to the conventional GC technique. Dramatically improved detectability of analytes was achieved due to much narrower peak widths. The flash GC technique was compared with another approach to faster GC analysis employing a 5 m column and fast temperature programming with a conventional GC oven. In comparison with this alternative, in the case of flash GC significantly better retention time repeatability was observed. The other superiority of resistive heating is very rapid cooling down (i.e., equilibration to the initial conditions) which contributes to the increased sample throughput.