高效液相色谱-串联质谱法测定肉类中的氯酸盐和高氯酸盐

于艳丽; 李杰

doi:10.13386/j.issn1002-0306.2022060254

高效液相色谱-串联质谱法测定肉类中的氯酸盐和高氯酸盐

doi: 10.13386/j.issn1002-0306.2022060254

于艳丽^1, ,,
李杰²

1.
上海杉达学院，上海 201209
2.
上海德诺产品检测有限公司，上海 200436

基金项目: 上海杉达学院科研基金项目（2022YB05）。

详细信息

作者简介:
于艳丽（1982−），女，硕士，副教授，研究方向：食品安全检测，E-mail：ylyu@sandau.edu.cn

通讯作者:
于艳丽（1982−），女，硕士，副教授，研究方向：食品安全检测，E-mail：ylyu@sandau.edu.cn

中图分类号: TS207.3
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- 被引次数: 0
出版历程
- 收稿日期: 2022-06-28
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-06-01

Determination of Chlorate and Perchlorate Amounts in Meat by High Performance Liquid Chromatography-Tandem Mass Spectrometry

YU Yanli^{1
, ,},
LI Jie²

1.
Shanghai Sanda University, Shanghai 201209, China
2.
Shanghai Denuo Product Service Co., Ltd., Shanghai 200436, China

摘要

摘要: 建立了高效液相色谱-串联质谱法同时测定肉类中氯酸盐和高氯酸盐的分析方法。样品经乙腈-水（13:7，V:V）提取后离心，上清液经PRiME HLB固相萃取柱净化，Acclaim Trinity P1复合离子交换柱分离，以乙腈及20 mmol/L乙酸铵为流动相进行梯度洗脱，串联质谱分析中采用电喷雾正离子源和多反应监测模式，内标法定量。结果表明，氯酸盐和高氯酸盐分别在2～200.0 ng/mL、1～100.0 ng/mL范围内呈现良好线性关系，决定系数分别为0.9983和0.9998，方法的定量限分别为2.0、1.0 μg/kg。氯酸盐和高氯酸盐分别在三种肉类四个添加水平6.0、20、40、200 μg/kg和3.0、10、20、100 μg/kg的加标回收率为91.0%～105.7%和94.2%～110.5%，相对标准偏差为1.8%～9.7%和0.7%～9.4%。本方法具有操作简单、灵敏度高、稳定性好等优点，可很好地满足肉中氯酸盐、高氯酸盐的检测。
- 氯酸盐 /
- 高氯酸盐 /
- 高效液相色谱-串联质谱法 /
- 肉类
Abstract: A method for simultaneous determination of chlorate and perchlorate amounts in meat by high performance liquid chromatography-tandem mass spectrometry was developed. Samples were extracted with acetonitrile/water (13:7, V:V ) and centrifuged. The obtained supernatants were purified on a PRiME HLB solid phase extraction column, followed by an Acclaim Trinity P1 ion exchange column with the gradient elution of acetonitrile and 20 mmol/L ammonium acetate as the mobile phase to afford chlorate and perchlorate. MS/MS was performed in ESI⁺ and multiple reaction monitoring mode with an internal standard for quantification. The results showed chlorate and perchlorate had calibration curves with good linearity in the ranges of 2~200.0 ng/mL and 1~100.0 ng/mL respectively, with corresponding correlation coefficients being 0.9983 and 0.9998. The detection limits of the method were 2.0 and 1.0 μg/kg, respectively. The recovery rates of chlorate and perchlorate were 91.0%~105.7% and 94.2%~110.5% respectively, at the addition levels of 6.0, 20, 40, 200 μg/kg, and 3.0, 10, 20, 100 μg/kg. The relative standard deviations for chlorate and perchlorate were 1.8%~9.7% and 0.7%~9.4% respectively. This method would be easy to use and has high detection sensitivity and good stability, and could well meet the requirements of determining chlorate and perchlorate amounts in meat.
- chlorate /
- perchlorate /
- high performance liquid chromatography-tandem mass spectrometry /
- meat

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图 1 空白基质加标样品色谱图

Figure 1. Chromatograms of a blank matrix spiked sample

下载: 全尺寸图片幻灯片

图 2 阳性样品的色谱图

Figure 2. Chromatograms of a positive sample

下载: 全尺寸图片幻灯片

表 1 氯酸根离子、高氯酸根离子及其内标的质谱参数

Table 1. MS parameters of chlorate, perchlorate and their internal standard

化合物	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）
氯酸根离子	83.0^*	67.0^*	94	25
氯酸根离子	85.0	69.0	80	25
高氯酸根离子	99.0^*	83.0^*	136	30
高氯酸根离子	101.0	85.0	80	29
氯酸根离子内标	89.0^*	71.0^*	80	25
高氯酸根离子内标	107.0^*	89.0^*	136	30
注：“*”为定量离子。

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表 2 不同体积比乙腈-水提取后氯酸根离子和高氯酸根离子及其内标的回收率

Table 2. Recovery rates of chlorate, perchlorate and their internal standard extracted with acetonitrile-water at different volume ratios

乙腈-水体积比（V:V）	回收率（%）
乙腈-水体积比（V:V）	氯酸根离子	氯酸根离子内标	高氯酸根离子	高氯酸根离子内标
11:9	45.71	84.65	98.20	94.21
13:7	103.04	105.47	102.27	102.47
15:5	83.97	90.79	104.89	103.17

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表 3 氯酸根离子和高氯酸根离子线性范围、线性回归方程、决定系数、检出限和定量限

Table 3. Linear range, linear equation, determination coefficient, detection limit and quantitative limit of chlorate and perchlorate

化合物	线性范围（ng/mL）	线性方程	决定系数（R²）	检出限（μg/kg）	定量限（μg/kg）
氯酸根离子	2～200.0	y=0.119132x+ 0.060179	0.9983	0.6	2.0
高氯酸根离子	1～100.0	y=0.334560x+ 0.101939	0.9998	0.3	1.0

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表 4 肉类样品加标回收率（n=6）

Table 4. Spiked recoveries of meat samples (n=6)

样品	氯酸盐			高氯酸盐
样品	加标浓度 (μg/kg)	平均回收率(%)	RSD (%)	加标浓度 (μg/kg)	平均回收率(%)	RSD (%)
猪肉	6.0	91.0	8.0	3.0	98.3	4.9
	20	98.3	1.9	10	99.3	2.1
	40	96.0	3.0	20	106.0	0.7
	200	105.7	1.8	100	106.9	0.9
鸡肉	6.0	96.1	7.1	3.0	102.2	9.4
	20	96.4	6.8	10	94.6	5.0
	40	95.6	4.3	20	96.7	1.6
	200	101.4	3.1	100	94.2	1.5
鸭肉	6.0	97.7	9.7	3.0	94.9	7.4
	20	91.3	5.2	10	110.5	4.9
	40	96.5	5.3	20	108.9	2.9
	200	101.1	3.3	100	104.7	1.2

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