土壤中17种有机氯农药残留量的毛细管气相色谱测定法

采用专用索氏提取器、正己烷萃取、Elite-5MS弹性石英毛细柱分离、GC-ECD测定了土壤中17种有机氯农药残留量.方法的检出限为0.4×10-10～2.0×10-10 g,回收率范围在76.0%～108.9%之间,相对标准偏差为0.66%～9.10%.该方法适用于土壤有机氯农药残留量的分析.     

固相萃取-毛细管气相色谱法检测淫羊霍等药用植物有机氯农药残留

建立了淫羊霍等药用植物中六六六及滴滴涕异构体残留量的毛细管气相色谱检测方法。样品采用微量化学法进行提取,固相萃取法净化,以不分流方式进样,用HP 5弹性石英毛细管柱程序升温分离样品,微电子捕获检测器检测,外标法计算其质量分数。结果表明,最小检测量为1.4×10-14～1.2×10-12g,加样平均回收率为92.16%～100.59%,相对标准偏差为0.5%～4.2%。该法各项技术指标均满足农药残留检测的要求。     

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.     

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.     

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.     

同位素稀释气相色谱-质谱法测定土壤/底泥中23种有机氯农药

建立了同位素稀释气相色谱-质谱法(ID-GC-MS))测定土壤/底泥中23种有机氯农药残留的分析方法。样品经干燥、研磨、筛分处理后用250 mL丙酮-正己烷(体积比为1:1)混合溶剂进行索氏提取24 h,再经铜粉、凝胶渗透色谱和弗罗里硅土固相萃取柱净化,最后用DB-5毛细管柱进行分离和电子轰击电离源质谱在选择离子监测模式下进行检测,并用 13C标记同位素稀释内标法定量。实验结果表明,23种化合物的标准曲线的线性相关性良好,线性范围为50～1600 μg/L,同位素内标的回收率范围为60%～110%,相对标准偏差为1.5%～18%;方法的检出限为0.20～10.3 μg/kg。该方法的净化效果较好,定量准确,适用于土壤/底泥这类复杂基质中农药残留的确证分析。     

气相色谱-负化学电离源-飞行时间质谱测定烟草中有机氯农药残留

采用QuEChERS前处理方法,建立了气相色谱-负化学电离源-飞行时间质谱(GC-NCI-TOF-MS)检测烟草中10种有机氯农药残留的分析方法。样品采用乙酸乙酯-正己烷(1 : 1, v/v)溶液提取,提取液经N-丙基乙二胺(PSA)、无水硫酸镁分散固相萃取净化,用GC-NCI-TOF-MS检测分析。根据有机氯化合物特征离子的精确质量数、同位素离子峰簇、碎片离子丰度比和保留时间对目标物定性鉴定,外标法定量。10种有机氯农药的线性关系良好,相关系数 (r²)均大于0.997;相对标准偏差小于6.5%;检出限为0.04~0.80 μ g/kg;加标回收率为77.2%~93.0%。该方法简单快速、灵敏度高、准确性好,适用于烟草中有机氯农药残留的定性分析和定量检测。     

Determination of organochlorine pesticide residues in rice by gas chromatography-mass spectrometry following directly suspended droplet microextraction

A simple and efficient approach as directly suspended droplet microextraction (DSDME) was applied to the determination of organochlorine pesticides in rice prior to analysis by gas chromatography-mass spectrometry (GC-MS). The extraction parameters such as organic solvent type and volume, extraction time, and ion strength were systemically optimized. Furthermore, method linearity, recovery, limits of detections (LODs), and precision were also investigated. The proposed method provided good linearity (R ² = 0.9900–0.9996). LODs determined by GC-MS in selected-ion monitoring (SIM) mode were between 0.0005–0.033 mg/kg. The relative standard deviations (RSDs) varied from 2.0–14.0%, while the enrichment factors were between 221–550. The experimental results suggest that DSDME followed by GC-MS is a simple, sensitive, low-cost and little solvent consumption for the determination of organochlorine pesticides in rice, and has high enrichment factors suitable to trace analysis.     

Solid-phase microextraction for organochlorine pesticide residues analysis in Chinese herbal formulations

Solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used to determine pesticide residues in Chinese herbal formulations. Fibers coated with a 100-microm film thickness of poly(dimethylsiloxane) was used to extract 19 organochlorine pesticides (OCPs). The pesticides in the study consisted of alpha-, beta-, gamma-and delta-hexachlorocyclohexane, p,p'-DDD, p,p'-DDE, p,p'-DDT, o,p'-DDT, aldrin, dieldrin, endrin, endrin aldehyde, endrin ketone, endosulfan (I, II and sulfate), heptachlor, heptachlor epoxide, and methoxychlor. The optimal experimental procedures for the adsorption and desorption of pesticides were evaluated. The linearity was obtained with a precision below 11% RSD for the studied pesticides expect endosulfan sulfate (21%) in a wide range from 1 to 200 ng/g. Detection limits were reached at below ng/g levels. Heptachlor epoxide was determined at a calculated limit of 0.03 ng/g. Comparison between SPME and Soxhlet extraction showed that SPME has a less than one order detection limit for residue pesticide determination. The proposed method was tested by analyzing herbal formulations from a local market for OCP multiresidues. Some residues studied were detected in the analyzed samples. The results demonstrate the suitability of the SPME-GC-MS approach for the analysis of multi-residue OCPs in Chinese herbal formulations.     

Rapid determination of organochlorine pesticide residues in feeds by capillary gas chromatography

A simple micro-method is described for determination of 15 organochlorine pesticide residues in mixed feeds. Clean-up of the petroleum ether extract is by basic alumina minicolumn chromatography and quantitative identification is by capillary gas chromatography with electron capture detection. Cyanopropyl-polysiloxane chemically bonded fused silica capillary columns have been used to perform high resolution analyses in short time as well as to overcome possible interferences by PCBs. Recovery, repeatability, and detection limits of the proposed procedure are checked and results are also reported for non random samples of 180 feeds collected in Italy.     

黄瓜中敌敌畏残留的快速分析

构建了一种十六烷基三甲基溴化铵/植物酯酶修饰玻碳电极测定敌敌畏的方法,植物酯酶可使乙酸-1-萘酯水解为1-萘酚,敌敌畏使植物酯酶的活性降低,根据1-萘酚氧化峰电流峰值的降低值,可对敌敌畏进行定量分析.在最优条件下,敌敌畏的线性范围为1.0×10~(-9)～1.0×10~(-5) mol·L~(-1),检出限为3.0×10~(-10) mol·L~(-1).     

Determination of fluoroquinolone residues in poultry muscle in Portugal

A total of 98 poultry samples, including chicken and turkey muscle, were analysed, using a sensitive and reliable analytical method based on liquid chromatography (LC) with spectrofluorimetric detection, for simultaneous determination of four fluoroquinolone (FQ) antibiotics, namely enrofloxacin (ENRO), ciprofloxacin (CIPRO), norfloxacin (NOR), and sarafloxacin (SARA). The method involved extraction with 0.15 mol L⁻¹ HCl and clean-up by solid-phase extraction using Oasis HLB cartridges. Chromatographic separation was carried out on a C₁₈ TSK gel column, in isocratic mode, with 0.025 mol L⁻¹ H₃PO₄ solution, adjusted to pH 3.0 with tetrabutylammonium hydroxide-methanol (78:22) as mobile phase. Good linearity over the investigated concentration range was observed, with mean values of correlation coefficients higher than 0.9989 for all the analytes studied. The limits of quantification (LOQ), expressed as the lowest fortification level with acceptable precision were 15 μg kg⁻¹ for ENRO, CIPRO, and NOR, and 30 μg kg⁻¹ for SARA; these values are in compliance with requirements for monitoring of maximum residues levels (MRLs). Overall recoveries from spiked samples ranged from 80% to 92% with relative standard deviations (RSD) lower than 6.1%. Of the chicken and turkey samples analysed, 44.2% and 37.8%, respectively, were contaminated. The levels found in the analysed poultry samples, collected from markets of Oporto and Coimbra, located in the north and central zones of Portugal, respectively, were lower than 114.2 and 87.6 μg kg⁻¹ in chicken and turkey muscle samples, respectively. One positive chicken sample was contaminated with ENRO at levels higher than the MRL.     

加速溶剂萃取-气相色谱-负化学源质谱法测定茶叶中有机氯和拟除虫菊酯类农药残留量

建立了茶叶中13种有机氯和10种拟除虫菊酯农药残留量的气相色谱-负化学离子源.质谱(GC-NCl-MS)分析方法.茶叶样品用V(丙酮):V(CH2Cl2)=1:1混合液作提取剂经加速溶剂萃取,提取液经凝胶色谱净化除去大部分的色素、脂类和蜡质,再经活性炭-氨基(Carb-NH2)复合小柱和Florisil小柱净化后,用GC-NCl-MS的选择离子监测方式(SIM)进行定性和定量分析.添加50μg/kg 浓度水平时,农药回收率在45.6%～112.4%之间,相对标准偏差在0.57%～10.1%之间;方法的检出限(3倍信噪比)在0.05～10.0μg/kg之间.方法适用于出口茶叶农残检测实际工作.     

Comparison of solvent extraction and solid-phase extraction for the determination of organochlorine pesticide residues in water.

Solid-phase extraction (SPE) of organochlorine pesticide residues from environmental water samples was evaluated using octadecyl (C18)-bonded porous silica. The efficiency of SPE of these pesticide residues from reagent water samples at 1-5 micrograms dm-3 levels was compared with those obtained by solvent extraction with hexane and Freon TF (trichlorotrifluoroethane). Average recoveries exceeding 80% for these organochlorine pesticides were obtained via the SPE method using small cartridges containing 100 mg of 40 microns C18-bonded porous silica. The average recovery by solvent extraction with hexane and Freon TF exceeded 90% in both instances. It was concluded that the recoveries and precision for the SPE of organochlorine pesticides were poorer than those for the solvent extraction method. Organochlorine pesticide residue levels in environmental water samples from two major rivers flowing through predominantly rice-growing areas were monitored by gas chromatography using the solvent extraction method with hexane. Exceptionally high levels of organochlorine pesticide residues such as BHC, DDT, heptachlor, endosulfan and dieldrin were found in these water samples.     

Kuwait's total diet study: dietary intake of organochlorine, carbamate, benzimidazole and phenylurea pesticide residues

The State of Kuwait in cooperation with the U.S. Food and Drug Administration (FDA) conducted a Total Diet Study (TDS) to estimate intakes of pesticide residues by the population. The levels of organochlorine (OC) pesticides, carbamates, benzimidazoles, and phenylureas in the TDS core list are reported here. The TDS core list was established through a national food consumption survey. All food items (140 for the Kuwaiti adult) were prepared as eaten and analyzed for the pesticides mentioned above. The FDA's multiresidue methods in Volume I of the Pesticide Analytical Manual were used in gas, liquid, and gel permeation chromatographic analyses. Only vegetable and fruit samples contained pesticide residues (mg/kg), including the carbamates 1-naphthol (1.4) and 3H-carbofuran (0.94) in carrots; the OC pesticide vinclozolin (0.47), 3H-carbofuran (0.66), and fenuron (0.6) in kiwi fruit; the OC pesticide procymidone (0.32) and carbendazim (0.5) in grapes; 3H-carbofuran (5.0) in apricots; the OC pesticides captan (0.013) and thiabendazole (0.63) in pears; captan (0.035) in plums; and carbendazim (0.4) in mandarin oranges. The levels of 3H-carbofuran found in both apricots and kiwi fruit exceeded the maximum residue limits (MRLs) of the Food and Agriculture Organization/World Health Organization (FAO/WHO) of the United Nations. The daily intakes of pesticides by the different population groups are discussed in light of the FAO/WHO acceptable daily intakes.     

微波辅助萃取法测定烟草中有机氯类农药残留量

建立了一种微波辅助萃取-固相萃取净化测定烟草中17种有机氯类农药残留量的新方法. 样品用V(正己烷):V(乙酸乙酯)＝1:1提取, 提取液经Florisil固相萃取柱净化后, 采用气相色谱-电子捕获检测器(GC-μECD)进行检测. 17种有机氯农药的0.01、 0.05 mg/kg和0.5 mg/kg加标回收率均在82%以上, RSD在0.11%～8.2%之间, 能满足当前烟草中有机氯农药残留的检测要求.     

土壤中多种有机氯及拟除虫菊酯类农药的GC-ECD测定

气相色谱法同时测定土壤中多种有机氯及拟除虫菊酯类农药。对土壤的分析结果：有机氯农药的检出限0．001～0、003μg／mL，拟除虫菊酯类农药检出限0.008～0．02μg／mL，线性相关系数0．9978～0．9999。用y（石油醚）：V（丙酮）=3：1超声波提取，有机氯农药回收率94．2％～124．0％，相对标准偏差为3．3％～8．8％（n=5）；拟除虫菊酯类农药回收率95．2％～118．3％，相对标准偏差为5．7％～7．1％（n=5）；方法适用于土壤样品中农药残留测定。     

Determination of organochlorine pesticide residues in fatty foods: a critical review on the analytical methods and their testing capabilities

Organochlorine pesticide (OCP) residues in foods have been of concern for several decades. However, the analysis of some of the OCPs and their metabolites or derivatives, such as endrin aldehyde, endrin ketone, nonachlor, etc. in fatty foods (including foods of animal and plant origin), was not commonly included in routine monitoring programme. Recently, the Stockholm Convention introduced nine plus one new persistent organic pollutants (POPs) that included chlordecone and some other OCPs. Is there a method available that can analyze both traditional OCPs, together with their metabolites and derivatives in fatty foods? Furthermore, is there a suitable method that can monitor OCPs and the newly added POPs including chlordecone in fatty foods together in a pot? This review aims to provide some background information to answer these questions.