采用超高效液相色谱串联四级杆飞行时间质谱法测定茶叶中的草甘膦和草铵膦,探讨衍生条件、净化方法和质谱参数对茶叶中草甘膦和草铵膦含量的影响。结果表明,样品经纯水超声辅助提取,混合型阳离子交换反相吸附固相萃取柱净化,净化液加入到pH 10.0的硼酸盐缓冲液中,并加入9-芴甲氧羰酰氯乙腈溶液进行衍生化处理2 h,过0.22 μm微孔滤膜,经超高效液相色谱BEH C18柱分离,用2 mmol/L乙酸铵水溶液(含体积分数0.1%甲酸)和乙腈为流动相梯度洗脱,采用四级杆串联飞行时间高分辨质谱仪电喷雾正离子准多反应监测模式检测,外标法定量。草甘膦和草铵膦分别在质量浓度1.25~400和0.25~160 μg/L呈良好的线性关系(R＞0.99),其检测限分别为4.0和1.34 μg/kg。在低、中、高(定量限的2、10和40倍)3个添加水平时,草甘膦的加标回收率为88%~103%,草铵膦的加标回收率为93%~99%,相对标准偏差均<5%。该方法分析速度快、净化效果好、杂质干扰小、回收率高、重复性好,适用于茶叶类样品中草甘膦和草铵膦残留量的测定。
Determination of glyphosate and glyphosate in tea was carried out by ultra-high performance liquid chromatography-tandem quadrupole time of flight mass spectrometry. Effects of derivation conditions, purification methods and mass spectrometry parameters on the determination of glyphosate and glyphosate in tea were investigated. The results showed that the samples were extracted with pure water enhanced by ultrasound, purified on solid phase extraction column packing mixed cation exchange reversed-phase adsorbent. The purified solution was added into borate buffer solution with pH 10.0 and the derivatization with 9-fluorene methoxycarbonyl chloride acetonitrile solution was carried out for 2 h, then filtered through 0.22 μm microporous membrane. The separation was carried out on an ultra-high performance liquid chromatography BEH C18 column with 2 mmol/L ammonium acetate aqueous solution (containing 0.1% formic acid, V/V) and acetonitrile as mobile phase gradient elution. The targets were detected by quadrupole tandem time-of flight mass spectrometer with electrospray positive ion pseudo-multiple reaction monitoring mode and quantified by external standard method. Glyphosate and glufosinate showed good linearity in the range of 1.25-400 μg/L and 0.25-160 μg/L, respectively (R>0.99). The limits of detection of this method for glyphosate and glufosinate were 4.0 μg/kg, 1.34 μg/kg, respectively. At low, medium and high (2, 10 and 40 times of limits of quantification) supplemental levels, the recoveries of glyphosate ranged from 88% to 103% with relative standard deviations lower than 5%, and glufosinate ranged from 93% to 99% with relative standard deviations lower than 5%. This method is suitable for the determination of glyphosate and glyphosate residues in tea samples with fast analysis speed, good purification effect, low interference from impurities, high recovery rate and good repeatability.
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