QuEChERS-高效液相色谱串联质谱法测定甜橙中哒螨灵和螺螨酯

[目的]建立了甜橙全果、果肉、果皮、果渣、橙汁和精油等6项基质中哒螨灵和螺螨酯的QuEChERS-高效液相色谱-串联质谱分析检测方法(HPLC-MS/MS)。[方法]甜橙样品经乙腈提取,PSA、GCB、MgSO4净化,高效液相色谱-串联质谱仪配备电喷雾正离子多反应监测(MRM),外标法定量。[结果]甜橙6种基质通过此分析检测方法,哒螨灵和螺螨酯在0.001~1.25 mg/L质量浓度范围线性相关系数不小于0.9965,3个加标水平(0.01、0.5、5 mg/kg)下哒螨灵回收率为81%~93%,RSD为0.5%~6.5%,螺螨酯回收率为81%~99%,RSD为0.5%~7.9%。[结论]该方法简单、方便、灵敏度、准确度高,覆盖甜橙全项样品基质,可适用于大批量样品快速分析。     

Determination of flonicamid and its metabolites in bell pepper using ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (Orbitrap)

The development and validation of a method to determine flonicamid and its metabolites as TFNA (4-trifluoromethylnicotinic acid), TFNG (N-(4-trifluoromethylnicotinoyl) glycine) and TFNA-AM (4-trifluoromethylnicotinamide) in bell pepper samples by ultra-high-performance liquid chromatography coupled to Orbitrap mass spectrometry (UHPLC-Orbitrap-MS) was performed. A fast and simple extraction procedure with acidified acetonitrile and salts (magnesium sulfate and sodium chloride) was used. The methodology was validated, checking for specificity, recovery, precision, limits of detection (LODs) and limits of quantification (LOQs). The recoveries ranged from 84% to 98%, and precisions were lower than 17%. Finally, LODs ranged from 1 µg kg^–1 (flonicamid) to 6 µg kg^–1 (TFNA-AM), while LOQs ranged from 10 µg kg^–1 (flonicamid) to 30 µg kg^–1 (TFNA-AM). Bell pepper samples were analysed and concentrations up to 98 µg kg^–1 (flonicamid) were detected, although the sum of flonicamid and metabolites did not exceed the maximum residue limit (MRL) set by the European Union.     

Determination of organochlorine pesticides in shrimp by gas chromatography–mass spectrometry using a modified QuEChERS approach

Pacific white shrimp (Litopenaeus vannamei) collected during dry and rainy seasons from three different states in Malaysia were analyzed for nine organochlorine pesticides (OCPs) (α-HCH, β-HCH, γ-HCH, δ-HCH, trans-chlordane, cis-chlordane, p,p′-DDE, p,p′-DDD and p,p′-DDT) using QuEChERS sample preparation method and GC–MS SIM with split/splitless injection mode. The efficiency of combination of primary and secondary amine (PSA) and octadecyl (C18) at 25 mg of PSA and 25 mg of C18 per mL of shrimp extract as the clean-up sorbent to remove matrix interferences was evaluated. By combining PSA and C18, matrix interferences such as gamma-tocopherol and cholesterol were not able to be eliminated. Good separation and high recoveries which ranged from 90 to 105% with associated RSD < 15% were obtained for all OCPs at 3–75 ng/g. No significant difference in recoveries due to seasonal variation for studied OCPs, except for α-HCH, β-HCH, δ-HCH and p,p′-DDT were obtained. The limits of detection and quantification ranged from 0.3 to 4.5 ng/g and 3 to 15 ng/g, respectively. The linearity for matrix matched standard calibrations was >0.99.     

Monitoring survey of patulin in a variety of fruit-based products using a sensitive UHPLC–MS/MS analytical procedure

The mycotoxin patulin is known to be the predominant natural contaminant of apples, apple-based products and a variety of other fruits. Because of its high incidence and harmful health effects, patulin is included with mycotoxins, which are strictly monitored. In this study, a sensitive and reliable ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS) method was developed and validated for determination of patulin in a variety of fruit matrices. A combination of the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) procedure along with a solid phase extraction (SPE) clean-up strategy enabled an effective removal of sample matrix and pre-concentration of patulin. This resulted in low limits of quantification ranging from 1 to 2.5 μg/kg, depending on fruit type. In our study, quantification of patulin was based on a stable isotope dilution assay (SIDA) using ¹³C₇-patulin as the internal standard. Data showed that the procedure described, in combination with neat solvent internal calibration, can be used for accurate quantification of patulin regardless the type of fruit. Although the SIDA method allowed omission of matrix-matched calibration, matrix-effects were estimated in order to assess suppression of the patulin signal caused by a variety of fruit samples. The method was fully validated for apples, apple baby food, apple juice, peaches, strawberries and blueberries. The recovery values were in the range from 92 to 109%. Repeatability of the method was below 10% for all tested matrices. The method was applied to the monitoring of patulin in 135 samples of fresh fruits and fruit products and can also be used as an efficient tool for routine monitoring of this contaminant in a variety of fruit-based foods.     

QuEChERS提取与气相色谱-电子捕获检测器串联测定茶叶中12种农药残留

建立了Qu ECh ERS提取与气相色谱-电子捕获检测器串联测定茶叶中12种农药残留的方法。试样经一种Qu EChERS方法进行前处理,经GC-ECD检测,基质外标法定量。当农药的添加级别范围在0.05~0.5 mg/kg时,平均回收率为71.6%~109.0%,相对标准偏差(RSDs)为0.29%~11.21%;线性范围为0.05~1μg/m L,最低检出量(LODs)为0.5×10~(-12)~26.1×10~(-12)g,最低检出浓度(LOQs)为0.006~0.05 mg/kg。该方法的准确度、精密度和灵敏度均达到了农药残留检测的要求,可以检测随机在市场上买来的茶叶中多种农药残留情况。     

超高效合相色谱-串联质谱法测定口含烟中对羟基苯甲酸酯

建立了QuEChERS-超高效合相色谱-串联质谱法（UPC²-MS/MS）测定口含烟中对羟基苯甲酸酯类防腐剂。采用乙腈提取,基质分散固相萃取净化,UPC^{2 TM} HSS C18 SB色谱柱（3.0 mm×100 mm×1.8 μm）分离,内标法定量。优化后的对羟基苯甲酸酯的合相色谱分离条件为：主要流动相为CO₂,改性剂为甲醇-异丙醇混合溶液（V/V,1∶1）,系统流速1.5 mL/min,离子化辅助溶剂（补偿溶剂）为0.1%甲酸-甲醇溶液,动态备压1.03×10⁷ Pa,柱温55 ℃,可在3 min内完成单个样品分析。4种成分的线性范围均为0.5~5.0 mg/kg;在低、中、高加标水平下,方法的平均回收率为94.6%~105.6%,相对标准偏差小于5%。实际样品测定结果表明,单个成分的含量和多种成分的总含量均小于10 mg/kg,低于GB 2760-2014对于此类防腐剂在食品中添加限量的要求。该方法环境友好、高效、准确,适用于口含烟中对羟基苯甲酸酯类物质的测定。     

渝东北地区食品中典型酰胺醇类抗生素残留快速检测及风险评估

目的 建立食品中典型酰胺醇类抗生素残留的快速检测方法并对该类药物在渝东北地区的残留污染风险进行评估。方法 采用乙腈萃取食品基质中残留的酰胺醇类抗生素, QuEChERS法进行净化,超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)分析检测;同时应用层次分析法(analytic hierarchy process, AHP)对渝东北地区食品中酰胺醇类药物残留的污染风险进行评估。结果 Qu ECh ERS-UPLC-MS/MS检测技术精确度高,氯霉素、氟苯尼考和甲砜霉素在0.15～50.00μg/kg浓度范围内的线性相关系数均大于0.999,在0.15～50.00μg/kg浓度水平范围内的回收率分别为85.2%～100.9%、76.7%～90.6%、85.3%～96.7%,精密度均小于15%,检出限为0.10μg/kg,定量限为0.15μg/kg。求解AHP模型可知,渝东北地区酰胺醇类药物残留的食品污染风险程度为:氟苯尼考>甲砜霉素>氯霉素。其中,...     

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...     

超高效液相色谱-串联质谱法测定果蔬汁类及其饮料中22种镰刀菌属毒素

目的 建立果蔬汁类及其饮料中22种镰刀菌属毒素的超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)检测的实验方法。方法 样品经水和乙腈提取,QuEChERS净化,氮吹至近干,1 mL 80%乙腈水(体积分数)复溶,以乙腈和0.1%甲酸水(2mmol/L甲酸铵)为流动相,经ACQUITY UPLC CSH Phenyl-Hexyl 反相柱梯度分离,UPLC-MS/MS在正、负离子模式下多反应监测,基质配制外标法定量。结果 22种镰刀菌属毒素在线性范围内,相关系数平方(R2)均大于0.985,回收率在66.6%-119.1%之间,相对标准偏差在2.64%-14.96%之间。结论 该方法具有前处理方式简单、分析时间短、灵敏度好、准确度高、杂质干扰小等特点,可以用于果蔬汁类及其饮料中22种镰刀菌属毒素的检测。     

超高压液相色谱-高分辨质谱快速筛查和确证食用贝类中多种原多甲藻酸贝类毒素

建立超高压液相色谱-高分辨质谱快速筛查和确证贻贝、牡蛎、蚌类、扇贝等食用贝类及其制品中3 种天然形式的原多甲藻酸贝类毒素的检测方法。样品中的原多甲藻酸采用乙腈-水体系均质提取,应用改进型QuEChERS技术净化,在乙腈-水（含5 mmol/L醋酸铵和0.1%甲酸）体系经Acquity HSS T3柱（150 mm×2.1 mm,1.8 μm）梯度洗脱,实现了3 种原多甲藻酸贝类毒素的基线分离。该方法基于电喷雾正离子模式,采用高分辨质谱一级全扫描和数据依赖扫描,对食用贝类及其制品样品中的原多甲藻酸贝类毒素进行检测。3 种贝类毒素的定量限均为10 μg/kg（RSN＞10）;在10～500 μg/L范围内线性关系良好,相关系数（R2）均大于0.99。应用该方法对国内外多个地区的贝类产品进行了筛查及确证,其中部分样品检出原多甲藻酸贝类毒素。该方法灵敏度高,重复性好,操作简便、快捷,适用于食用贝类及其制品中多种原多甲藻酸贝类毒素的筛查分析。