液液提取-固相萃取-高效液相色谱-串联质谱测定人体血液中16种有机磷酸酯

doi:10.3724/SP.J.1123.2020.07033

色谱 ›› 2021, Vol. 39 ›› Issue (1): 69-76.DOI: 10.3724/SP.J.1123.2020.07033

液液提取-固相萃取-高效液相色谱-串联质谱测定人体血液中16种有机磷酸酯

侯敏敏¹^,², 史亚利¹^,²^,^*(), 蔡亚岐¹^,²

1.中国科学院生态环境研究中心, 环境化学与生态毒理学国家重点实验室, 北京 100083
2.中国科学院大学, 北京 100049

收稿日期:2020-07-29 出版日期:2021-01-08 发布日期:2020-12-20
通讯作者: 史亚利
作者简介:

史亚利: 博士,副研究员,中国科学院生态环境研究中心,环境化学与生态毒理学国家重点实验室。主要从事环境污染物的色谱-质谱分析方法及其环境存在、迁移转化、归趋以及人体暴露的相关研究,近几年重点关注的污染物有全氟/多氟化合物(PFASs)、有机磷酸酯(OPEs)和高氯酸等,在相关研究中取得了一系列创新性成果。先后主持或参与国家自然科学基金、国家重大水专项、国家重点研发计划、国家环保公益性行业科研专项等多项国家课题,2017 年获得国家自然科学基金委优秀青年基金的资助。曾获得中国分析测试协会科学与技术奖(CAIA奖)一等奖和二等奖各一项。目前在Environ Sci Technol, Anal Chem, Environ Int等国际学术期刊上发表SCI论文70余篇,累积他引次数4500余次,参与编写专著2部。现任《色谱》和《分析测试学报》青年编委、“中国仪器仪表学会分析仪器分会”离子色谱专业委员会委员。*Tel:(010)62849676,E-mail:shiyali@rcees.ac.cn.
基金资助:
国家自然科学基金(21722705);国家自然科学基金(21677154);国家自然科学基金(21621064)

Determination of 16 organophosphate esters in human blood by high performance liquid chromatography-tandem mass spectrometry combined with liquid-liquid extraction and solid phase extraction

HOU Minmin¹^,², SHI Yali¹^,²^,^*(), CAI Yaqi¹^,²

1. State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100083, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-07-29 Online:2021-01-08 Published:2020-12-20
Contact: SHI Yali
Supported by:
National Natural Science Foundation of China(21722705);National Natural Science Foundation of China(21677154);National Natural Science Foundation of China(21621064)

摘要/Abstract

摘要：

人体体液中有机磷酸酯(OPEs)浓度的测定对于了解人体OPEs的暴露水平以及评估人体健康风险具有重要意义。然而,目前的研究大多数集中于尿液中OPEs代谢物含量的分析测定,将其作为人体OPEs暴露的生物标志物,而对人体血液中OPEs的分析研究较少,仅有的少量研究涉及的OPEs种类有限。该研究在优化前处理过程(固相萃取,SPE)和色谱分离的基础上,建立了人体血液中16种OPEs的超高效液相色谱-串联质谱(UPLC-MS-MS)测定方法。血液样品经过乙腈摇床萃取后,经ENVI-18 SPE小柱净化,然后采用Acquity UPLC BEH C18色谱柱,以甲醇/5 mmol/L的乙酸铵水溶液为流动相进行梯度洗脱对目标物进行分离,最后进行LC-MS/MS测定。质谱分析采用电喷雾正离子模式电离,多重反应监测模式测定,内标法定量。在优化的检测条件下,16种OPEs的检出限为0.0038~0.882 ng/mL。除磷酸三甲酯(TMP)外,其余15种OPEs在3个浓度水平的血液基质加标回收率为53.1%~126%,相对标准偏差为0.15%~12.6%。样品的基质效应检测发现,4种OPEs存在明显的基质抑制,选用合适的同位素内标进行定量,可以部分消除基质影响。该方法样品前处理简单,灵敏度高,适用于人体血液样品中OPEs阻燃剂的测定。15个人体血液样本分析结果表明,OPEs的总浓度范围为1.50~7.99 ng/mL,其中8种OPEs的检出率均高于50%,磷酸三异丁酯(TiBP)、磷酸三(2-氯乙基)酯(TCEP)和磷酸三(1-氯-2-丙基)磷酸酯(TCIPP)为主要的OPEs,表明人体存在较为普遍的OPEs暴露,应该引起关注。

关键词: 固相萃取, 液液提取, 高效液相色谱-串联质谱, 有机磷酸酯, 人体血液

Abstract:

Measurement of organophosphate esters (OPEs) in human body fluids is important for understanding human internal exposure to OPEs and for assessing related health risks. Most of the current studies have focused on the determination of OPE metabolites in human urine, as OPEs are readily metabolized into their diester or hydroxylated forms in the human body. However, given the existence of one metabolite across multiple OPEs or multiple metabolites of one OPE, as well as the low metabolic rates of several OPEs in in vitro studies, the reliability of urinary OPE metabolites as biomarkers for specific OPEs is needs to be treated with caution.Human blood is a matrix that is in contact with all body organs and tissues, and the blood levels of compounds may better represent the doses that reach target tissues. Currently, only a few studies have investigated the occurrence of OPEs in human blood by different analytical methods, and the variety of OPEs considered is limited. In this study, a method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous determination of 16 OPEs in human blood, and the extraction efficiency of the solid phase extraction (SPE) column for OPEs was verified. To human blood samples, 10 ng of an internal standard was added, followed by mixing and aging for 30 min. The samples were extracted three times with acetonitrile using a shaker, and then purified on ENVI-18 cartridges with acetonitrile containing 25% dichloromethane as the eluent. Finally, the OPEs were analyzed by high performance liquid chromatography-tandem mass spectrometry. After optimization of the analytical column and mobile phases, the analytes were separated on a BEH C18 column (100 mm×2.1 mm, 1.7 μm) by gradient elution using methanol and 5 mmol/L ammonium acetate in water as the mobile phase. Then, the analytes were ionized in electrospray ionization positive (ESI⁺) mode and detected in the multiple reaction monitoring (MRM) mode. The mass spectral parameters, including the precursor ion, product ion, declustering potential, entrance potential, and collision cell exit potential, were optimized. The results were quantified by the internal standard method. The limits of detection (LOD, S/N=3) of the OPEs were in the range of 0.0038-0.882 ng/mL. The calibration curves for the 16 OPEs showed good linear relationships in the range of 0.1-50 ng/mL, and the correlation coefficients were >0.995. The extraction efficiency of the ENVI-18 column for the 16 OPEs was validated, and the average recoveries of the target compounds were 54.6%-104%. The average recoveries (n=3) of 15 OPEs, except trimethyl phosphate (TMP), in whole blood at three spiked levels were in the range of 53.1%-126%, and the relative standard deviations (RSDs) were in the range of 0.15%-12.6%. The average recoveries of six internal standards were in the range of 66.8%-91.6% except for TMP-d9 (39.1%), with RSDs of 3.52%-6.85%. The average matrix effects of the OPEs in whole blood were 56.4%-103.0%. Significant matrix effects were found for resorcinol bis(diphenyl phosphate) (RDP) (75.8%±1.4%), trimethylphenyl phosphate (TMPP) (68.4%±1.0%), 2-ethylhexyl di-phenyl phosphate (EHDPP) (56.4%±12.4%), and bisphenol-A bis(diphenyl phosphate) (BABP) (58.5%±0.4%). However, these effects could be corrected by similar signal suppressions of the corresponding internal standard (TPHP-d15, 77.4%±7.5%). This method is simple, highly sensitive, and suitable for the determination of OPEs in human blood. Fifteen human whole blood samples were collected to quantify the 16 OPEs using the developed method. The total concentrations of the OPEs ranged from 1.50 to 7.99 ng/mL. The detection frequencies of eight OPEs were higher than 50%. Tri-iso-butyl phosphate (TiBP), tri(2-chloroethyl) phosphate (TCEP), and tri(1-chloro-2-propyl) phosphate (TCIPP) were the dominant OPEs, with median concentrations of 0.813, 0.764, and 0.690 ng/mL, respectively. These results indicated widespread human exposure to OPEs, which should be of concern.

Key words: solid phase extraction (SPE), liquid-liquid extraction (LLE), high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), organophosphate ester, human blood

中图分类号:

O658

侯敏敏, 史亚利, 蔡亚岐. 液液提取-固相萃取-高效液相色谱-串联质谱测定人体血液中16种有机磷酸酯[J]. 色谱, 2021, 39(1): 69-76.

HOU Minmin, SHI Yali, CAI Yaqi. Determination of 16 organophosphate esters in human blood by high performance liquid chromatography-tandem mass spectrometry combined with liquid-liquid extraction and solid phase extraction[J]. Chinese Journal of Chromatography, 2021, 39(1): 69-76.

图/表 6

参考文献

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Compound	Abbreviation	Formula	M_r	CAS No.
Trimethyl phosphate	TMP	C₃H₉O₄P	140.08	512-56-1
Triethyl phosphate	TEP	C₆H₁₅O₄P	182.16	78-40-0
Tripropyl phosphate	TPrP	C₉H₂₁O₄P	224.23	513-08-06
Tri-n-butyl phosphate	TnBP	C₁₂H₂₇O₄P	266.31	126-73-8
Tri-iso-butyl phosphate	TiBP	C₁₂H₂₇O₄P	266.31	126-71-6
Tris(2-ethylhexyl) phosphate	TEHP	C₂₄H₅₁O₄P	434.63	78-42-2
Tri(2-butoxyethyl) phosphate	TBOEP	C₁₈H₃₉O₇P	398.47	78-51-3
Tri(1-chloro-2-propyl) phosphate	TCIPP	C₉H₁₈Cl₃O₄P	327.57	13674-84-5
Tri(2-chloroethyl) phosphate	TCEP	C₆H₁₂Cl₃O₄P	285.49	115-96-8
Tri(1,3-dichloro-2-propyl) phosphate	TDCPP	C₉H₁₅Cl₆O₄P	430.90	13674-87-8
Tri-phenyl phosphate	TPHP	C₁₈H₁₅O₄P	326.28	115-86-6
Trimethylphenyl phosphate	TMPP	C₂₁H₂₁O₄P	368.36	563-04-2
Cresyl diphenyl phosphate	CDPP	C₁₉H₁₇O₄P	340.31	26444-49-5
2-Ethylhexyl di-phenyl phosphate	EHDPP	C₂₀H₂₇O₄P	362.41	1241-94-7
Resorcinol bis(diphenyl phosphate)	RDP	C₃₀H₂₄O₈P₂	574.45	57583-54-7
Bisphenol-A bis(diphenyl phosphate)	BABP	C₃₉H₃₄O₈P₂	692.63	5945-33-5

Compound	Abbreviation	Formula	M_r	CAS No.
Trimethyl phosphate	TMP	C₃H₉O₄P	140.08	512-56-1
Triethyl phosphate	TEP	C₆H₁₅O₄P	182.16	78-40-0
Tripropyl phosphate	TPrP	C₉H₂₁O₄P	224.23	513-08-06
Tri-n-butyl phosphate	TnBP	C₁₂H₂₇O₄P	266.31	126-73-8
Tri-iso-butyl phosphate	TiBP	C₁₂H₂₇O₄P	266.31	126-71-6
Tris(2-ethylhexyl) phosphate	TEHP	C₂₄H₅₁O₄P	434.63	78-42-2
Tri(2-butoxyethyl) phosphate	TBOEP	C₁₈H₃₉O₇P	398.47	78-51-3
Tri(1-chloro-2-propyl) phosphate	TCIPP	C₉H₁₈Cl₃O₄P	327.57	13674-84-5
Tri(2-chloroethyl) phosphate	TCEP	C₆H₁₂Cl₃O₄P	285.49	115-96-8
Tri(1,3-dichloro-2-propyl) phosphate	TDCPP	C₉H₁₅Cl₆O₄P	430.90	13674-87-8
Tri-phenyl phosphate	TPHP	C₁₈H₁₅O₄P	326.28	115-86-6
Trimethylphenyl phosphate	TMPP	C₂₁H₂₁O₄P	368.36	563-04-2
Cresyl diphenyl phosphate	CDPP	C₁₉H₁₇O₄P	340.31	26444-49-5
2-Ethylhexyl di-phenyl phosphate	EHDPP	C₂₀H₂₇O₄P	362.41	1241-94-7
Resorcinol bis(diphenyl phosphate)	RDP	C₃₀H₂₄O₈P₂	574.45	57583-54-7
Bisphenol-A bis(diphenyl phosphate)	BABP	C₃₉H₃₄O₈P₂	692.63	5945-33-5

Analyte	Precursor ion (m/z)	Product ion (m/z)	Declustering potential (DP)/V	Entrance potential (EP)/V	Collision cell exit potential (CXP)/V
TMP	141.1	109.1^*	60	22	10
		79.0	60	29	6
TEP	183.0	99.0^*	54	24	7
		81.0	60	50	8
TPrP	225.4	99.0^*	60	22	7
		141	60	24	10
TnBP	267.4	99.0^*	60	20	10
		155	60	12	10
TiBP	267.4	99.0^*	60	20	10
		155	60	12	10
TEHP	435.3	99.0^*	140	22	9
		113.1	120	16	8
TBOEP	399.3	299.3^*	95	19	10
		199.0	95	21	10
TCIPP	327.0	99.0^*	70	30	10
	329.1	99.0	70	28	10
TCEP	285.0	63.0^*	80	42	10
		99.2	75	30	10
TDCPP	431.1	98.9^*	85	35	9
		208.9	84	20	8
TPHP	327.1	152.0^*	130	42	11
		77.1	130	65	7
TMPP	369.2	166.1^*	147	37	11
		90.9	147	61	8
CDPP	341.1	152.1^*	135	40	10
		165.1	135	40	10
EHDPP	363.2	76.9^*	70	71	7
		251.0	72	12	9
RDP	575.2	419.2^*	190	46	15
		481.1	183	46	15
BABP	693.2	367.0^*	200	45	15
		693.3	200	12	15
TMP-d9	150.1	83.1	90	31	7
TEP-d15	198.1	101.9	65	27	8
TPrP-d21	246.4	102	120	25	9
TCEP-d12	299.1	102	75	30	6
TnBP-d27	294.4	101.9	140	25	10
TPHP-d15	342.3	160	135	47	10
TCIPP-d18	345.1	101.9	75	30	8

Analyte	Precursor ion (m/z)	Product ion (m/z)	Declustering potential (DP)/V	Entrance potential (EP)/V	Collision cell exit potential (CXP)/V
TMP	141.1	109.1^*	60	22	10
		79.0	60	29	6
TEP	183.0	99.0^*	54	24	7
		81.0	60	50	8
TPrP	225.4	99.0^*	60	22	7
		141	60	24	10
TnBP	267.4	99.0^*	60	20	10
		155	60	12	10
TiBP	267.4	99.0^*	60	20	10
		155	60	12	10
TEHP	435.3	99.0^*	140	22	9
		113.1	120	16	8
TBOEP	399.3	299.3^*	95	19	10
		199.0	95	21	10
TCIPP	327.0	99.0^*	70	30	10
	329.1	99.0	70	28	10
TCEP	285.0	63.0^*	80	42	10
		99.2	75	30	10
TDCPP	431.1	98.9^*	85	35	9
		208.9	84	20	8
TPHP	327.1	152.0^*	130	42	11
		77.1	130	65	7
TMPP	369.2	166.1^*	147	37	11
		90.9	147	61	8
CDPP	341.1	152.1^*	135	40	10
		165.1	135	40	10
EHDPP	363.2	76.9^*	70	71	7
		251.0	72	12	9
RDP	575.2	419.2^*	190	46	15
		481.1	183	46	15
BABP	693.2	367.0^*	200	45	15
		693.3	200	12	15
TMP-d9	150.1	83.1	90	31	7
TEP-d15	198.1	101.9	65	27	8
TPrP-d21	246.4	102	120	25	9
TCEP-d12	299.1	102	75	30	6
TnBP-d27	294.4	101.9	140	25	10
TPHP-d15	342.3	160	135	47	10
TCIPP-d18	345.1	101.9	75	30	8

Analyte	Recoveries/%				RSD/%
Analyte	1	2	3	Mean	RSD/%
TMP	52.7	59.3	51.6	54.6	4.2
TEP	63.0	68.8	67.3	66.3	3.0
TPrP	79.5	79.5	84.3	81.1	2.7
TnBP	76.2	77.2	80.5	78.0	2.3
TiBP	77.6	80.3	78.5	78.8	1.4
TEHP	73.3	78.8	74.9	75.7	2.8
TBOEP	81.4	89.3	94.9	88.5	6.8
TCEP	80.8	88.1	73.7	80.9	7.2
TCIPP	87.9	91.5	87.9	89.1	2.1
TDCPP	66.3	74.8	70.8	70.6	4.2
TPHP	82.6	83.0	81.4	82.3	0.8
EHDPP	69.7	90.5	81.8	80.7	10
TMPP	76.8	83.0	82.6	80.8	3.5
CDPP	101	106	104	104	2.6
RDP	85.1	92.0	92.3	89.8	4.1
BABP	79.1	82.3	89.2	83.5	5.1

液液提取-固相萃取-高效液相色谱-串联质谱测定人体血液中16种有机磷酸酯

Determination of 16 organophosphate esters in human blood by high performance liquid chromatography-tandem mass spectrometry combined with liquid-liquid extraction and solid phase extraction

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Metrics

Analyte	Spiked 2 ng/mL		Spiked 20 ng/mL		Spiked 40 ng/mL		LOD/(ng/mL)
Analyte	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%	LOD/(ng/mL)
TMP	30.6	2.2	33.3	1.0	37.3	6.0	0.83
TEP	72.6	5.7	70.6	6.6	71.1	3.8	0.17
TPrP	82.2	1.9	78.5	1.4	70.8	1.4	0.038
TnBP	88.1	7.6	78.6	3.0	71.0	2.9	0.042
TiBP	79.9	12.3	70.6	8.4	77.3	10.4	0.020
TEHP	63.6	7.9	53.1	12.3	72.7	12.6	0.070
TBOEP	85.9	4.9	84.3	5.7	77.8	3.0	0.015
TCIPP	72.1	4.7	79.9	4.2	74.2	2.9	0.26
TCEP	79.4	3.5	71.6	7.0	70.8	1.4	0.26
TDCPP	64.9	8.9	70.6	4.2	74.3	1.8	0.15
TPHP	75.4	1.0	77.1	10.4	75.7	4.5	0.15
TMPP	60.2	1.4	65.2	0.71	65.5	0.15	0.028
CDPP	126	12.1	114	5.2	111	6.5	0.88
EHDPP	58.1	2.2	55.0	6.8	68.5	3.6	0.034
RDP	69.1	4.7	62.1	4.7	64.1	2.0	0.024
BABP	63.5	8.6	67.6	3.7	63.5	3.9	0.0038

No.	TMP	TEP	TPrP	TnBP	TiBP	TEHP	TBOEP	TPHP	EHDPP	CDPP	TMPP	BABP	RDP	TCEP	TCIPP	TDCPP	∑₁₆OPE
1	-	0.160	-	-	0.235	-	0.793	0.462	0.485	-	-	0.029	-	2.490	0.290	-	4.94
2	-	-	-	-	0.960	-	-	0.332	-	-	-	-	-	1.378	0.590	-	3.26
3	-	-	-	-	0.378	0.115	-	0.335	0.165	-	-	-	-	2.415	0.415	-	3.82
4	-	-	-	-	-	0.178	-	0.392	0.153	-	-	-	-	-	1.615	-	2.34
5	-	-	-	-	0.953	0.290	0.245	0.390	0.230	-	-	0.023	-	0.298	0.765	0.460	3.65
6	-	-	-	0.225	-	0.398	0.185	0.270	0.155	-	-	-	-	0.523	-	-	1.76
7	-	-	-	0.218	0.920	0.138	-	-	0.048	-	-	-	0.132	-	0.240	-	1.69
8	-	0.118	-	-	0.365	0.163	0.238	0.252	0.070	-	-	-	-	-	0.640	-	1.85
9	-	-	-	0.673	1.413	-	-	0.485	0.123	-	-	-	-	-	1.440	-	4.13
10	-	0.263	-	1.173	1.488	0.375	0.713	0.330	0.128	0.795	-	-	-	0.708	2.015	-	7.99
11	-	-	-	0.538	0.803	-	1.010	0.910	0.280	-	-	-	-	0.820	2.140	-	6.50
12	-	0.115	-	0.200	0.313	0.878	0.750	0.151	0.210	-	-	0.006	-	-	0.165	-	2.79
13	-	-	-	1.505	1.693	0.363	0.410	-	0.325	-	-	0.007	-	0.628	2.365	0.538	7.83
14	-	-	-	-	0.270	-	0.153	0.335	-	-	-	0.005	-	-	0.740	-	1.50
15	-	-	-	0.230	0.813	0.365	0.598	-	0.383	-	-	-	-	-	0.415	-	2.80

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