使用液质联用对特香型白酒酿造原料大米中农药残留检测的研究

大米是特香型白酒的酿酒主要原料之一,应用高效液相色谱-质谱联用同时分析大米中噻虫嗪、吡虫啉、啶虫脒、嘧霉铵、甲氨基阿维菌素苯甲酸盐、烯酰吗啉、咪鲜胺、氟啶脲、哒螨灵、嘧菌酯苯醚甲环唑、二甲戊灵、灭幼脲、氟虫腈14种农药残留。液相色谱柱采用AtlantisT3柱,ESI电离,多反映离子监测方式监测。     

超高效液相色谱-串联质谱法测定辣椒及其栽培土壤中烯酰吗啉和唑嘧菌胺

目的建立用于辣椒和土壤中烯酰吗啉和唑嘧菌胺残留检测的超高效液相色谱-串联质谱方法。方法辣椒和土壤样品采用乙腈和水提取,盐析后取上清液,通过优化色谱分离等条件,建立超高效液相色谱-串联质谱方法,结合目标物标准曲线进行定量分析。结果经过3个水平的加标回收率实验,所建立方法的平均回收率在85.2%~97.8%,相对标准偏差0.1%~2.2%(n=5)。烯酰吗啉在辣椒的定量限为0.04mg/kg,在土壤中定量限为0.01 mg/kg;唑嘧菌胺在辣椒和土壤中的定量限均为0.01mg/kg。结论所建立的分析方法操作简便,分离净化效果良好,灵敏度、准确度和精密度均达到农药残留检测要求。     

PSA吸附剂GC-MS法测定蔬菜中的8种农药残留

建立同时测定蔬菜中噻虫嗪、甲霜灵、嘧菌环胺、肟菌酯、戊唑醇、氟环唑、联苯肼酯、吡唑醚菌酯8种农药残留的N-丙基乙二胺-气相色谱质谱(N-propylenediamine-gas chromatography coupled with mass spectrometry,PSA-GGMS)色谱分析方法。样品用乙腈进行超声提取,无水硫酸镁盐析后,提取液经N-丙基乙二胺(N-propylenediamine,PSA)进行分散固相萃取净化,气相色谱质谱(gas chromatography coupled with mass spectrometry,GC-MS)法进行分析,基质内标法定量。结果表明,8种农药的检出限范围为在0.005 mg/kg~0.018 mg/kg,6次进样相对标准偏差小于5%,回收率范围为76.0%~95.3%。试验证明该方法前处理操作简单,快速,可用于蔬菜中多种农药残留的检测。     

高效液相色谱串联质谱法测定蔬菜中苯醚甲环唑的残留量

建立高效液相色谱-串联质谱检测蔬菜中苯醚甲环唑残留的分析方法。样品采用乙腈提取,经石墨碳黑-氨基串联固相萃取(GCB/NH2 SPE)柱净化,液相色谱分离多反应监测模式下测定,外标法定量。结果显示：苯醚甲环唑质量浓度在1～500ng/mL范围内线性关系良好。苯醚甲环唑在不同基质中平均回收率为79.3%～108.0%,相对标准偏差为2.7%～8.5%,检出限为0.001mg/kg。该方法灵敏度高,准确度、精密度好,满足样品测定的定性、定量要求。     

高效液相色谱-串联质谱法测定黄瓜中嘧菌酯残留

目的建立高效液相色谱-串联质谱法测定黄瓜中的嘧菌酯残留量的分析方法。方法样品用乙腈匀浆提取,无水硫酸镁、氯化钠盐析离心,无水硫酸镁、PSA净化,用液相色谱-串联质谱仪测定,外标法定量。结果在选定色谱条件下,嘧菌酯的检出限为1.0×10~(-12)g;在质量浓度0.0025～0.50μg/mL范围内,嘧菌酯的峰面积与浓度呈线性关系,标准曲线方程为:Y=2×10~8X-51888,相关系数r为0.9995;分别在0.005、0.05、0.5 mg/kg 3个添加水平进行添加回收实验,平均回收率为86%～93%,相对标准偏差(relative standard deviation,RSD)为6.0%～7.4%,嘧菌酯在黄瓜中的定量限为0.005mg/kg。结论该方法前处理过程简洁,减少了系统误差,节约了样品处理时间;检测方法灵敏度高,准确度和精密度满足NY/T 788-2018《农作物中农药残留试验准则》的要求,适用于黄瓜中嘧菌酯残留量的检测。     

气相色谱质谱法检测土壤中4种嘧啶类杀虫剂

建立一种QuEChERS提取,气相色谱三重四级杆质谱测定土壤中嘧菌环胺、乙嘧酚、嘧螨酯和嘧霉胺4种嘧啶类杀虫剂残留的分析方法。土壤样品过筛后,用正己烷丙酮溶液(体积比1∶1)提取,提取液转移至QuEChERS净化管(1.2 g MgSO_4, 500 mg PSA和500 mg C_(18))净化,取10 mL净化液氮吹至近干,残渣用丙酮定容1 mL,气相色谱质谱检测和确证,外标法定量。4种嘧啶类杀菌剂在0.02～2.0μg/m L质量浓度范围内线性关系良好,相关系数均大于0.995;检出限如下:嘧菌环胺0.004 6 mg/kg,乙嘧酚0.004 0 mg/kg,嘧螨酯0.007 2 mg/kg,嘧霉胺0.007 0 mg/kg。4种嘧啶类杀虫剂3个不同浓度点(0.05, 0.1和1.0μg/m L)的样品平均加标回收率在89.3%～101.1%之间;精密度相对标准偏差在5.0%以内(n=6)。该方法具有前处理简单、快速、灵敏、准确,适用于嘧啶类杀虫剂残留的监测。     

QuEChERS-超高效液相色谱-串联质谱法同时检测辣椒中5种杀菌剂残留

建立QuEChERS-超高效液相色谱-串联质谱法同时检测鲜食辣椒中多菌灵、甲基硫菌灵、烯酰吗啉、嘧菌酯和苯醚甲环唑5种杀菌剂的分析方法。方法 样品经2.0%乙酸乙腈提取分离, 50 mg C18和20 mg GCB净化, 采用超高效液相色谱-串联质谱法检测, 基质外标法定量。结果 5种杀菌剂在0.01~1.00 mg/L质量浓度范围内, 峰面积与对应的质量浓度间线性关系良好, 相关系数均大于0.989; 5种杀菌剂在0.01、0.1和1.0 mg/kg添加水平下的平均回收率为74%~105%, 相对标准偏差为2.07%~9.61% (n=5), 方法定量限均为 0.01 mg/kg。贵州辣椒中5种杀菌剂的残留量为<0.01-0.092 mg/kg。结论 本方法满足农药残留检测分析要求, 适用于5种农药在鲜食辣椒中的多残留准确定性和定量分析以及市场监督抽查等。实际样品检测显示5种杀菌剂在贵州辣椒上的使用是安全的, 不会产生相关膳食风险与危害, 不影响出口贸易。     

高效液相色谱-串联质谱法测定进出口食品中十三吗啉残留

建立一种快速、灵敏的测定进出口食品中十三吗啉残留量的高效液相色谱- 串联质谱(LC-MS-MS)方法,并已在选定的多种基质的检测中证明是有效的。采用乙酸乙酯对样品中十三吗啉残留进行提取。提取液经ENVI-Carb/LC-NH2 柱固相萃取(花生采用GPC 净化)净化后,用液相色谱- 串联质谱联用仪检测,外标法定量。实验结果表明,该方法的线性范围为2.5～100ng/ml,线性相关系数为0.9995,检测限为2.5ng/ml,在添加浓度10～100ng/g 范围内,十三吗啉的平均回收率在80.2%～101.8% 之间,相对标准偏差在5.71%～10.50% 之间(n=6)。实验证明该方法具有操作简便、快速、结果准确、检测限低等特点,能够满足日本肯定列表及欧盟等发达国家的限量检测要求。     

4种小作物中嘧菌酯残留量的检测及膳食风险评估

目的建立超高效液相色谱-串联质谱联用法检测4种小作物(茄子、苦瓜、葱和蕹菜)中嘧菌酯残留的分析方法,探明嘧菌酯在4种小作物中的残留特性和使用安全性。方法样品经乙腈提取,QuEChERS方法净化,在电喷雾正离子(electrospray positive ion,ESI+)模式下,用UPLC-MS/MS采用多反应监测(multiple reaction monitoring,MRM)模式检测。结果嘧菌酯在0.001～2 mg/L浓度范围内溶剂标准曲线和空白基质匹配标准曲线均有良好线性,相关系数在0.9989～1之间。在0.01～20 mg/kg添加水平内平均回收率为73.5%～109.7%,相对标准差(relative standard deviation,RSD)为1.5%～8.9%,方法的检出限(limits of detection,LOD)为0.001 mg/L,最低检测浓度(limits of quantification,LOQ)为0.01 mg/kg。25%嘧菌酯水分散粒剂在4种小作物中的半衰期分别为3.9、2.7、4.6和2.5 d;连续多次施药10 d后在茄子和苦瓜中残留量最大值分别为0.015 mg/kg和0.018 mg/kg;连续多次施药14 d后在葱和蕹菜中残留量最大值分别为1.43 mg/kg和0.450 mg/kg;膳食风险商值(risk quotient,RQ)为0.0002～0.0959,均低于1。结论该方法简便、快速、灵敏度高,能有效克服杂质干扰,膳食风险结果表明使用25%嘧菌酯水分散粒剂防治蔬菜病害风险较小,相对安全。     

固相萃取-气相色谱法同时检测草莓中13种农药残留

目的建立一种固相萃取-毛细管柱气相色谱方法,可以同时检测草莓中常用的13种农药残留,包括百菌清、腐霉利、粉唑醇、腈菌唑、醚菌酯、苯醚甲环唑、烯酰吗啉等7种杀菌剂,毒死蜱、三氟氯氰菊酯、哒螨灵、氰戊菊酯等4种杀虫剂及莠去津、乙草胺等2种除草剂。方法草莓样品20 g匀浆后,经乙腈50 mL提取,NH_2固相萃取柱净化,HP-5毛细管气相色谱柱进行分离,GC-ECD进行定性及定量分析。结果 13种农药残留的色谱图分离效果良好,线性相关系数均大于0.996,方法检出限在0.01 mg/kg~0.5 mg/kg之间。13种农药的添加水平为0.01 mg/kg~2 mg/kg,回收试验表明该方法平均回收率在70.5%~114.5%之间,相对标准偏差在2.17%~6.85%之间。结论该方法简单、快速、灵敏、净化效果好、回收率高,适合草莓中多种农药残留的检测和安全监控。通过对50份草莓样品进行检测,检出百菌清、乙草胺、毒死蜱、粉唑醇、醚菌酯、烯酰吗啉6种农药。     

Simultaneous determination of five penicillins in muscle,liver and kidney from slaughtered animals using liquid chromatography coupled with electrospray ionization tandem mass spectrometry

A simple and rapid method for the simultaneous determination of five penicillins (ampicillin, penicillin G, penicillin V, oxacillin and cloxacillin) in muscle, liver and kidney tissues using high-performance liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS/MS) was developed. Mass spectral acquisition was done in the negative ion mode by applying selected reaction monitoring (SRM). The five penicillins were extracted with water, and the extracted solution was cleaned up on a C18 cartridge. Phenethicillin was added as an internal standard, and the extract was diluted with water for injection into the LC-ESI-MS/MS. The recoveries of the five penicillins were in the range of 77.3-99.8% from muscle, liver and kidney fortified at 10-250 ng/g. The detection limits for ampicillin were 6 ng/g in muscle and kidney and 15 ng/g in liver. For penicillin G and penicillin V, the detection limits were 2 ng/g in muscle and kidney and 5 ng/g in liver. For oxacillin and cloxacillin, the detection limits were 4 ng/g in muscle and kidney and 10 ng/g in liver. Twenty-three muscle, fourteen liver and twenty-two kidney samples from the markets were analyzed by this method. No penicillins were detected in any sample.     

Determination of hyoscyamine and scopolamine in serum and urine of humans by liquid chromatography with tandem mass spectrometry

A simple method was developed for the analysis of hyoscyamine and scopolamine in human serum and urine using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Hyoscyamine and scopolamine in serum and urine were cleaned up with an Oasis HLB cartridge and a PSA cartridge. The LC separation was carried out on an ODS column, using linear gradient elution with 5 mmol/L IPCC-MS3-methanol as the mobile phase. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of hyoscyamine and scopolamine were 86.0-105% from human serum and urine fortified at 0.2 ng/mL and 10 ng/mL. The detection limits of hyoscyamine and scopolamine were 0.02 ng/mL. Four serum and three urine samples of humans poisoned by eating Datura innoxia Mill. were analyzed by this method. Hyoscyamine and scopolamine were detected at the levels of 0.45-3.5 ng/mL in all serum samples and 170-670 ng/mL in all urine samples.     

LC-ESI-MS/MS analysis of phosphodiesterase-5 inhibitors and their analogues in foods and dietary supplements in Korea

A number of 188 food and dietary supplement samples were collected from 2009 to the first half of 2013 in Korean online and offline stores. A method to identify phosphodiesterase-5 (PDE-5) inhibitors and their analogues using liquid chromatography-electrospray ionisation-mass spectrometry/mass spectrometry (LC-ESI-MS/MS) was validated. Limit of detection and limit of quantitation of liquid-type and solid-type negative samples ranged from 0.05 to 3.33 ng/mL or ng/g and from 0.15 to 10.00 ng/mL or ng/g, respectively. Recoveries ranged from 83% to 112%. Nineteen PDE-5 inhibitors and their analogues were detected, with tadalafil group compounds being the most frequently observed (53.0%), followed by the sildenafil group (42.5%). Tadalafil concentrations ranged from 0.08 to 138.69 mg/g. Compounds were most frequently detected in capsules (in 40 of 80 adulterated samples). To protect public health and food safety, appropriate monitoring of PDE-5 inhibitors and their analogues in foods and dietary supplements is recommended.     

超高效液相色谱-四极杆/飞行时间质谱检测猪肉和牛肉中30 种食源性兴奋剂类药物残留

建立猪肉和牛肉中30 种食源性兴奋剂的超高效液相色谱-四极杆/飞行时间质谱的快速筛查和确证方法。样品经37 ℃酶解16 h,体积分数1.0%甲酸-乙腈溶液提取后,经PRiME-HLB通过式固相萃取小柱净化,用Waters XBridge BEH C18柱分离,在飞行时间质谱模式和数据依赖扫描串联质谱模式对目标物进行检测,通过一次数据采集,可同时完成化合物的定性筛查和确证。结果表明：30 种食源性兴奋剂的精确质量数偏差小于5.0×10－6,在0.5～100.0 ng/mL范围内线性良好,相关系数大于0.998 0。检出限范围为0.1～2.0 μg/kg;定量限范围为0.2～4.0 μg/kg。方法回收率范围为77.99%～109.2%,相对标准偏差为0.29%～9.68%（n=6）。该方法有效提高了食源性兴奋剂检测的效率和准确度,具有较强的实用价值。     

Determination of tetrodotoxin in puffer-fish tissues, and in serum and urine of intoxicated humans by liquid chromatography with tandem mass spectrometry

A simple and rapid method was developed for the analysis of tetrodotoxin in puffer-fish tissues, and in serum and urine of humans poisoned after consuming puffer-fish, by means of high-performance liquid chromatography with tandem mass spectrometry (LC/MS/MS). Tetrodotoxin was extracted with 2% acetic acid. The extracted solution from puffer-fish tissues was diluted with water, and the extracted solution from human serum and urine was cleaned up by LC/MS/MS with a methacrylate-styrenedivinylbenzene cartridge. The LC separation was performed on a C18 column (50 mm x 2.1 mm i.d.) using 10 mmol/L IPCC-MS7-methanol (65 : 35) as the mobile phase at a flow rate of 0.2 mL/min. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of tetrodotoxin were 79-90% from puffer-fish tissues fortified at 0.1 microg/g and 1 microg/g, and 93-101% from human serum and urine fortified at 0.5 ng/mL and 5 ng/mL. The detection limits of tetrodotoxin were 0.01 microg/g in puffer-fish tissues and 0.1 ng/mL in human serum and urine. Thirty samples of puffer-fish from wholesale markets, and 7 serum and 5 urine samples of humans poisoned after consuming puffer-fish were analyzed by this method. Tetrodotoxin was detected in all puffer-fish tissues, and all serum and urine samples at the levels of 0.04-140 microg/g, 0.9-1.8 ng/mL and 15-150 ng/mL, respectively.     

养殖水中孔雀石绿、隐色孔雀石绿、结晶紫、 隐色结晶紫、亚甲基蓝残留量的测定

目的建立一种高效液相色谱-串联质谱同时测定养殖水体中孔雀石绿、结晶紫及其代谢物和亚甲基蓝残留量的方法。方法将水样用盐酸羟胺-对甲苯磺酸溶液和乙腈提取,二氯甲烷萃取2次后浓缩,用1 mL乙腈-5 mmol/L乙酸铵(1:1,V:V)定容。以乙腈-5 mmol/L乙酸铵(85:15,V:V)混合溶液为流动相进行色谱分离,然后进入串联质谱仪,选用电喷雾离子源,在正离子、多反应监测扫描模式下进行定性,孔雀石绿和结晶紫通过内标法定量,亚甲基蓝通过外标法定量。结果在优化条件下,孔雀石绿、隐色孔雀石绿、结晶紫、隐色结晶紫在0.025~0.600 ng/mL浓度范围内,亚甲基蓝在0.05~1 ng/mL浓度范围内均满足线性关系,相关系数r0.99,方法检出限为0.2 ng/mL。加标浓度在0.2~2.0 ng/mL时,孔雀石绿、隐色孔雀石绿、结晶紫、隐色结晶紫和亚甲基蓝的平均回收率均在70%~110%之间,相对标准偏差均在10%以内。结论该方法简单快速、灵敏度高、前处理成本低、重现性好、回收率高,适用于同时检测养殖水体中孔雀石绿、隐色孔雀石绿、结晶紫、隐色结晶紫、亚甲基蓝残留量。     

Simultaneous determination of quinolones in foods by LC/MS/MS

A simple method was developed for the simultaneous determination of seven quinolones (enoxacin, ofloxacin, ciprofloxacin, danofloxacin, lomefloxacin, enrofloxacin and sarafloxacin) in foods using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The seven quinolones were extracted with acetonitrile containing 0.2% formic acid, and the extracted solution was cleaned up on a C18 cartridge. The extract was diluted with 5 mmol/L IPCC-MS3 for injection into the LC-ESI-MS/MS. The LC separation was carried out on an ODS column with gradient elution of 5 mmol/L IPCC-MS3-acetonitrile as the mobile phase. Mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of the seven quinolones were mostly greater than 60% from foods fortified at 10 ng/g. The detection limits in foods were 2 ng/g for enoxacin and ciprofloxacin, and 1 ng/g for the other drugs. Twenty cattle muscle, 7 swine muscle, 9 chicken muscle, 16 milk, 19 prawn and 20 broiled eel samples from retail markets were analyzed by this method. Enrofloxacin and its metabolite ciprofloxacin were detected in 9 broiled eel at the level of trace (tr)-34 ng/g and tr-10 ng/g, respectively.     

高效液相色谱-串联质谱法测定儿童奶酪中的三聚氰胺

基于QuEChERS快速前处理方法,建立了一种由高效液相色谱-串联质谱法准确测定儿童奶酪中三聚氰胺的快速检测方法.试验结果表明,用该方法检测三聚氰胺,在20 ng/mL～200 ng/mL范围内,三聚氰胺质量浓度与峰面积有良好的线性关系,相关系数R2为0.999 1,方法定量限为20μg/kg.添加水平为100μg/k...     

LC-MS/MS Determination of Organophosphorus Pesticide Residues in Coconut Water

A simple and specific analytical method based on solid phase extraction (SPE), and liquid chromatography–electrospray ionization–tandem mass spectrometry (LC-ESI-MS/MS) operated in multipule reaction monitoring (MRM) mode with dynamic time segment acquisition windows, was developed to determine organophosphorus pesticide residues (acephate, monocrotophos, dimethoate, malaoxon, dichlorvos, malathion, phenthoate, parathion-ethyl, chlorfenvinfos, quinalphos, diazinon, phosalone, profenofos, ethion, chlorpyrifos) in tender coconut water. The method was observed to be linear with lower limit of detections ranged from 0.1 to 1.5 ng/mL (measured at S/N ratio 5:1) and limit of qunatitation 0.5 to 2.0 ng/mL (measured at S/N ratio 10:1) for all studied pesticides. The intra- and inter-day assay accuracies calculated at four concentration levels in six replicates (n?=?6) were in the range of 80 % to 115 % with relative standard deviations (RSD) below 15 %. The percentage recoveries of all the analysed pesticides were in the range of 86.8 % to 107.6 % and the calculated RSD values were below 12 %. The developed method was applied to determine pesticide residues in natural tender coconut water samples. The results showed the presence of malathion ranging from 24 to 45 ng/L concentrations in some natural tender coconut water samples collected from various local market places in and around Hyderabad, Andhra Pradesh, India.     

Simultaneous determination of pesticide residues in crops by liquid chromatography with tandem mass spectrometry

A simultaneous method using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was developed for the determination of pesticide residues in crops. Mass spectral acquisition was performed in the positive mode by applying multiple reaction monitoring. In LC separation, an Atlantis dC18 Column was used with acetic acid-ammonium acetate-acetonitrile as the mobile phase. Pesticide residues in crops were extracted with acetone, and cleaned up by liquid-liquid separation with saturated salt solution and hexane, followed by an ENVI-Carb cartridge. The quantification limits of compounds in crops were below 5 ng/g. Eighty compounds were obtained with recoveries ranging from 60 to 130% at the level of 50 ng/g with RSD (%) of less than 15%. Fifty crop samples were analyzed by the developed method. Seven pesticide residues were detected in nine crops.