超高效液相色谱-串联质谱法检测婴儿米粉中11种有机磷阻燃剂

王溪; 凌映茹; 张昊; 吉文亮

doi:10.13386/j.issn1002-0306.2021110236

超高效液相色谱-串联质谱法检测婴儿米粉中11种有机磷阻燃剂

doi: 10.13386/j.issn1002-0306.2021110236

江苏省疾病预防控制中心，江苏南京 210009

基金项目: 淮安市突发公共卫生事件应急检测重点实验室开放课题（ETPHI-K-04）；江苏省医学重点学科（ZDXKA2016008）。

详细信息

作者简介:
王溪（1990−），女，硕士，主管技师，研究方向：食品、化妆品、消毒产品理化检验，E-mail：wangxi_sanjia@163.com

中图分类号: TS201
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出版历程
- 收稿日期: 2021-11-19
- 网络出版日期: 2022-07-17

Determination of 11 Kinds of Organophosphorus Flame Retardants in Baby Rice Cereal by Ultra-high Performance Liquid Chromatography-tandem Mass Spectrometry

Jiangsu Provincial Center for Disease Control and Prevention, Nanjing 210009, China

摘要

摘要: 采用超高效液相色谱-串联质谱技术，建立婴儿米粉中11种有机磷阻燃剂的检测方法。样品用0.5%甲酸乙腈溶液超声提取，提取液经分散固相萃取吸附剂净化，聚四氟乙烯滤膜过滤后上机检测，5 mmol/L甲酸铵的水溶液和乙腈为流动相梯度洗脱，目标化合物在ACQUITY UPLC^® BEH C₁₈ 色谱柱（100 mm×2.1 mm，1.7 μm）上实现分离，在电喷雾正离子扫描模式下进行多反应监测（MRM），外标法定量。通过优化色谱条件，11种有机磷阻燃剂均达到了基线分离。11种有机磷阻燃剂在0.5~100 μg/L（磷酸三辛酯0.05~10 μg/L）范围内线性关系良好，相关系数r均大于0.994。检出限（3S/N）为0.003~0.926 μg/kg，定量限（10S/N）为0.01~2.78 μg/kg。婴儿米粉中低、中、高3个添加浓度水平的加标回收率为63.2%~113.4%，相对标准偏差（n=6）均小于10%。运用建立的方法分析了4种婴儿米粉，磷酸三苯酯的检出率高达100%，其中一份米粉检出了磷酸三正丁酯和磷酸三（2-氯丙基）酯。该方法简单可靠、灵敏度高、重现性好，覆盖的有机磷阻燃剂种类多，适用于婴儿米粉中痕量有机磷阻燃剂的检测。
- 超高效液相色谱-串联质谱 /
- 有机磷阻燃剂 /
- 婴儿米粉 /
- 痕量
Abstract: A method for the determination of 11 organophosphorus flame retardants in baby rice flour was established by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were extracted by 0.5% formic acid acetonitrile solution by ultrasound. The extracted solution was purified by dispersive solid phase extraction packing and filtered by polytetrafluoroethylene membrane and detected by UPLC-MS/MS. Gradient elution was carried out with 5 mmol/L ammonium formate and acetonitrile. The target compounds were separated by ACQUITY UPLC^® BEH C₁₈ column (100 mm×2.1 mm, 1.7 μm), and multiple response monitoring (MRM) was conducted in the positive electrospray ionization mode. The external standard method was used for quantification. By optimizing chromatographic conditions, all the 11 kinds of organophosphorus flame retardants achieved baseline separation. The 11 kinds of organophosphorus flame retardants had a good linear relationship in the range of 0.5~100 μg/L (Tris (2-ethylhexyl) phosphate 0.05~10 μg/L) with correlation coefficient r>0.994. The limits of detection (3S/N) were 0.003~0.926 μg/kg and the limits of quantitation (10S/N) were 0.01~2.78 μg/kg. The average recoveries at three spiked levels (low, medium and high) were 63.2%~113.4% with the relative standard deviations all less than 10% (n=6). Four kinds of baby rice cereal were analyzed by the established method and the detection rate of triphenyl phosphate (TPhP) was up to 100%. Tributyl phosphate (TnBP) and tris (2-chloroisopropyl) phosphate (TCPP) were also detected in one of the samples. The method could be used for the determination of trace organophosphorus flame retardants in baby rice flour cereal with accurate and reliable results.
- ultra-high performance liquid chromatography-tandem mass spectrometry /
- organophosphorus flame retardants /
- baby rice cereal /
- trace amount.

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图 1 11种OPFRs标准溶液的提取离子流图

Figure 1. Extracted ion chromatograms of 11 kinds of OPFRs standard solutions

注： TEHP浓度为2 μg/L，其余标准液浓度为20 μg/L。

下载: 全尺寸图片幻灯片

图 2 程序空白提取液过不同滤膜时TEP的检出情况

Figure 2. Detection of TEP when blank extract passed through different filter membrane

注：A：空白提取液不过滤膜；B：空白提取液过尼龙滤膜；C：空白提取液过再生纤维素滤膜；D：空白提取液过PTFE滤膜。

下载: 全尺寸图片幻灯片

图 3 不同溶剂的提取效率

Figure 3. Extraction efficiency of different solvents

注：A：0.5%甲酸乙腈；B：4:1乙腈丙酮；C：乙腈。

下载: 全尺寸图片幻灯片

图 4 不同净化管对OPFRs提取效率的影响

Figure 4. Effect of different purification pipes on extraction efficiency of OPFRs

注：A、B、C分别对应A管、B管、C管。

下载: 全尺寸图片幻灯片

表 1 流动相梯度洗脱程序

Table 1. Gradient elution program for mobile phase

时间（min）	A相（%）	B相（%）
0	80	20
8	35	65
9	0	100
12	0	100
13	80	20
14	80	20

下载: 导出CSV

表 2 目标化合物质谱参数

Table 2. Mass spectrometry parameters for the target OPFRs

化合物	CAS号	保留时间（min）	母离子（m/z）	子离子（m/z）	锥孔电压（V）	碰撞能量（eV）
TEP	78-40-0	2.92	183.1	99.0^*/127.0	20	16/12
TiPP	513-02-0	5.39	225.1	99.0^*/141.0	20	16/9
TnPP	513-08-6	6.11	225.1	99.0^*/141.0	20	16/9
TiBP	126-71-6	8.86	267.1	99.0^*/155.0	20	17/10
TnBP	126-73-8	8.98	267.1	99.0^*/155.0	20	17/10
TCEP	115-96-8	4.67	287.0	99.0^*/124.9	20	22/22
TPhP	115-86-6	8.85	327.1	77.0/152.0^*	20	40/35
TCPP	13674-84-5	6.77	328.1	99.0^*/174.9	20	18/12
TBOEP	78-51-3	9.49	399.3	199.0/299.0^*	20	15/12
TDCPP	13674-87-8	8.47	431.0	98.7^*/320.8	20	22/11
TEHP	78-42-2	12.13	435.3	99.0^*/323.2	20	14/7
注：“*”为定量离子

下载: 导出CSV

表 3 不同溶剂中OPFRs的响应

Table 3. Response of OPFRs in different solvents

斜率	TEP	TiPP	TnPP	TiBP	TnBP	TCEP	TPhP	TCPP	TBOEP	TDCPP	TEHP
甲醇	4.9×10⁵	2.3×10⁵	6.0×10⁵	3.2×10⁵	4.0×10⁵	9.0×10³	3.0×10⁴	8.5×10³	1.7×10⁵	620.2	8.5×10⁵
80%甲醇	4.7×10⁵	3.1×10⁵	9.7×10⁵	3.4×10⁵	4.9×10⁵	1.0×10⁴	4.6×10⁴	1.1×10⁴	2.1×10⁵	839.1	1.2×10⁶

下载: 导出CSV

表 4 11种OPFRs的检出限、定量限、线性相关系数及线性方程

Table 4. LOD, LOQ, linear correlation coefficient and linear equation of 11 kinds of OPFRs

标准品	线性范围（μg/L）	线性方程	相关系数r	LOD （μg/kg）	LOQ （μg/kg）
TEP	0.5～100	y=384599.2x+257374.6	0.9997	0.667	2.00
TiPP	0.5～100	y=347665.9x−33966.8	0.9999	0.111	0.33
TnPP	0.5～100	y=598665.0x+38063.0	0.9997	0.074	0.22
TiBP	0.5～100	y=335398.2x+218614.4	0.9993	0.042	0.13
TnBP	0.5～100	y=467942.4x+188062.6	0.9999	0.035	0.10
TCEP	0.5～100	y=7415.2x+971.5	0.9998	0.926	2.78
TPhP	0.5～100	y=41675.4x+1812.3	0.9995	0.093	0.28
TCPP	0.5～100	y=8378.9x+16408.4	0.9991	0.667	2.00
TBOEP	0.5～100	y=177095.2x+55890.3	0.9998	0.010	0.03
TDCPP	0.5～100	y=737.7x+1667.8	0.9964	0.556	1.67
TEHP	0.05～10	y=1621194.8x+415578.8	0.9947	0.003	0.01

下载: 导出CSV

表 5 婴儿米粉中OPFRs的加标回收率及相对标准偏差（n=6）

Table 5. Recovery rate and relative standard deviation of OPFRs in babyrice cereal (n=6)

标准品	加标量（μg/kg）
	10		100		500
	回收率（%）	RSD（%）	回收率（%）	RSD（%）	回收率（%）	RSD（%）
TEP	65.5	5.6	85.8	2.1	92.4	6.9
TiPP	63.2	2.4	87.7	3.6	97.8	1.7
TnPP	68.8	6.3	94.0	3.8	100.8	4.5
TiBP	86.8	7.2	99.8	3.4	103.2	4.4
TnBP	81.3	9.8	99.5	5.1	106.0	5.9
TCEP	74.6	8.6	91.3	3.4	97.9	3.6
TPhP	95.4	8.3	93.7	9.2	95.2	7.4
TCPP	81.4	3.2	94.1	6.9	100.4	6.3
TBOEP	101.2	8.4	105.5	7.7	113.4	3.6
TDCPP	79.4	4.1	99.7	9.4	102.8	6.1
	0.1		10		50
	回收率（%）	RSD（%）	回收率（%）	RSD（%）	回收率（%）	RSD（%）
TEHP	69.0	7.5	76.4	3.8	74.3	3.8

下载: 导出CSV

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