样品前处理QuEChERS法及新型吸附材料在水产品中抗生素残留分析中的应用进展

抗生素的不合理使用，给水产品带来了一系列的潜在食用安全风险。品种繁多且残留痕量的抗生素也为食品安全检测带来了新的挑战，发展准确、快速、简便、高效且安全的前处理方法尤为重要。QuEChERS法作为一种新型样品前处理技术，现已逐渐应用到水产品抗生素残留检测中，并可实现较好的回收率。由于水产品中蛋白质和脂类含量高，样品基质复杂，使用经典QuEChERS法无法满足抗生素分析需求，改良其提取方法和净化方法是保证分析结果的关键。本文综述QuEChERS法原理特点，总结归纳其在针对水产品抗生素分析上的主要方法改良手段，并就近十年来改良QuEChERS法在水产品抗生素残留分析中的应用进行文献归纳，同时介绍新型吸附材料在该领域的使用，为探索新的净化方式提供参考，以期帮助检测人员持续优化改进QuEChERS法，推动和扩大QuEChERS法在水产品抗生素残留分析中的应用范围。     

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。     

QuEChERS-GC/MS检测地表水中5种常见塑化剂

建立了一种地表水中5种常见邻苯二甲酸酯类塑化剂的QuEChERS净化、气相色谱-质谱联用法(GC-MS)的分析测定方法。样品经QuEChERS(PSA+Mg2SO4)脱水除杂后,加入叔丁基甲醚-乙腈提取,GC-MS法测定,外标法定量。5种塑化剂在10~1000μg/L范围内线性良好(r0.998),方法最低检出限(LOD)为0.10~0.18 mg/kg,方法定量下限(LOQ)在0.3~0.7 mg/kg之间,2个加标水平的回收率为97.1%~107.4%,相对标准偏差(RSD,n=6)小于8%。该方法具有净化效果好、定量准确的特点,适用于地表水中多种邻苯二甲酸酯类塑化剂的快速检测。     

The effects of oxygenation aeration treatment on dissipation behaviors of tricaine mesylate in carp (Cyprinus carpio) muscle and water

Tricaine mesylate (MS-222) is one of the most used anesthetics in fish. It can be absorbed by the human body via food consumption, with related detriments to human health. In this study, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed for the determination of MS-222 in carp muscle and water samples using liquid chromatography-tandem mass spectrometry (LC-MS/MS). For cleanup procedure, multiplug filtration cleanup (m-PFC) method with n-Hexane delipidation was adopted. The extraction solvent, cleanup methods and sorbents were optimized. All method validation parameters were in the acceptable range. The dissipation behavior study was followed by the method development. Firstly, the anesthesia dose and time were optimized in application study. Secondly, carps were revived for different period of time with (experimental group) and without (control group) the oxygenation aeration treatment to compare the dissipation rate of MS-222. After being anesthetized for 6 h at 50 mg/L and 12 h of elimination, the concentrations of MS-222 in crap muscle and water of experimental group was lower than those of control group. After 36 h of elimination under oxygenation aeration, over 90% of MS-222 was dissipated in carp muscle. The results showed that the half-life of MS-222 in carp muscle was 6.2 h. The findings suggested that the commonly-used oxygenation aeration treatment in aquaculture production had potential effects in accelerating the dissipation of MS-222 in carp and water. In this study, three days of withdrawal period was recommended in carps after MS-222 administration under oxygenation aeration.     

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.     

Multiple mycotoxin co-occurrence in maize grown in three agro-ecological zones of Tanzania

In this study, the co-occurrence of multiple mycotoxins in maize kernels collected from 300 households' stores in three agro-ecological zones in Tanzania was evaluated by using ultra high performance liquid chromatography/time-of-flight mass spectrometry (TOFMS) with a QuEChERS-based procedure as sample treatment. This method was validated for the analysis of the main eleven mycotoxins of health concern that can occur in maize: aflatoxin B₁ (AFB₁), aflatoxin B₂ (AFB₂), aflatoxin G₁ (AFG₁), aflatoxin G₂ (AFG₂), ochratoxin A (OTA), deoxynivalenol (DON), fumonisin B₁ (FB₁), fumonisin B₂ (FB₂), HT-2 toxin, T-2 toxin and zearalenone (ZEN). From each zone one major maize producing district for home consumption was chosen and 20 villages for each district were randomly selected for sampling. All mycotoxins of health concern, except for T-2 toxin, were detected in the maize samples. Particularly high levels of AFB₁ (50%; 3–1,081 μg kg⁻¹), FB₁ (73%; 16–18,184 μg kg⁻¹), FB₂ (48%; 178–38,217 μg kg⁻¹) and DON (63%; 68–2,196 μg kg⁻¹) were observed. Some samples exceeded the maximum limits set in Tanzania for aflatoxins or in European regulations for other mycotoxins in unprocessed maize. Eighty seven percent of samples were contaminated with more than one mycotoxin, with 45% of samples co-contaminated by carcinogenic mycotoxins, aflatoxins and fumonisins. Significant differences in contamination pattern were observed among the three agro-ecological zones. The high incidence and at high levels (for some) of these mycotoxins in maize may have serious implications on the health of the consumers since maize constitute the staple food of most Tanzanian population. Effective strategies targeting more than one mycotoxin are encouraged to reduce contamination of maize with mycotoxins.     

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.     

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.     

Rapid screening and quantification of multi-class multi-residue veterinary drugs in royal jelly by ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry

A simple and rapid multi-class multi-residue analytical method was developed for the screening and quantification of veterinary drugs in royal jelly by ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS). A total of 90 veterinary drugs investigated belonged to more than 14 families such as lincomycins, macrolides, sulfonamides, quinolones, tetracyclines, β-agonists, β-lactams, sedatives, β-receptor antagonists, sex hormones, glucocorticoids, nitroimidazoles, benzimidazoles, nitrofurans, and the others. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure was used for the sample preparation without solid-phase extraction step. The linearity, sensitivity, accuracy, repeatability, and reproducibility of the method were fully validated. The response of the detector was linear for each target compounds in wide concentration range (at least, two orders of magnitude) with correlation coefficient (R²) of 0.9921–0.9999. The range of the limit of quantification for these compounds in the royal jelly ranged from 0.21 to 20 μg/kg. The repeatability and reproducibility were in the range of 3.01–11.6% and 5.97–14.9%, respectively. The average recoveries ranged from 70.21 to 120.1% with relative standard deviation of 1.77–9.90% at three concentration levels. For the screening method, the data of the precursor and product ions of the target analytes were simultaneously acquired under the All Ions MS/MS mode in a single run. A homemade database including the elemental composition, accurate masses, retention time, isotopic pattern data of the target ions the characteristic in-source fragment ions was utilized for the confirmation and identification of the target compounds. The applicability of the screening method was verified by applying to real royal jelly samples, and certain veterinary drugs were detected in some cases.