基于气相色谱-四级杆串联飞行时间质谱联用法测定积雪中28种多氯联苯

doi:10.7522/j.issn.1000-0240.2023.0020

摘要/Abstract

摘要：

多氯联苯（PCBs）是一类典型持久性有机污染物（POPs），在环境中长期存留并通过多种环境介质进行远距离迁移，对环境安全及人类健康具有严重危害。已有研究表明PCBs在大气中广泛存在，但在积雪中PCBs的浓度极低，大量积雪样品采集给分析研究带来困难。为了探究积雪中PCBs的含量及分布特征，本研究首先建立了基于气相色谱-四级杆串联飞行时间质谱（GC-QTOF/MS）测定积雪中28种PCBs的方法，利用优化高分辨气质联用仪参数，在较少样品量（1~2 L）情况下实现积雪中PCBs的定量分析。通过比较PCBs在不同离子源下的定性定量参数，最终发现电子轰击离子源最优，并进一步对发射电流进行优化，提高了仪器灵敏度。结果表明：28种PCBs标准样品在0.05~10 μg·L^-1浓度范围内线性关系良好，相关系数为0.993~0.999；在低、中、高三种不同浓度水平下，28种PCBs回收率为60.2%~103.2%，相对标准偏差为0.9%~14.0%（n=3）；方法检出限为1.01~2.92 pg·L^-1，可满足实际样品分析检测的需求，为进一步分析积雪中污染物分布特征提供了依据。此外，通过对我国东北典型地区积雪中PCBs的分析发现，积雪中PCBs以五、六氯联苯为主要组成，含量较高的PCB单体为PCB81、128、126及169，结合已有研究初步推断积雪中PCBs的污染除与PCB历史生产、残留有关外，还与燃烧与热工业过程等有关。

关键词: GC-QTOF/MS, 积雪, 多氯联苯

Abstract:

Polychlorinated biphenyls （PCBs） are typical components of persistent organic pollutants （POPs） with long-term retention， bioaccumulation， semi-volatility and high toxicity. PCBs can exist in the environment for a long time and migrate over long distances through a variety of environmental media， which result in serious threaten to environmental safety and human health. Snow is considered an almost ideal depositing medium for assessing atmospheric deposition. Previous studies have shown that PCBs exist widely in the atmosphere， but the concentration of PCBs in snow is extremely low， and the collection of a large number of snow samples brings difficulties to analysis and research. In order to explore the content and distribution characteristics of PCBs in snow， this study first established a method for the determination of 28 PCB congeners in snow based on gas chromatography-quadrupole time-of-flight mass spectrometry （GC-QTOF/MS）. The quantitative analysis of PCBs in snow was achieved with a small sample volume （1~2 L） by optimizing the parameters of high-resolution GC-MS. By comparing the qualitative and quantitative parameters of PCBs under different ion sources， it was finally found that the electron bombardment ion source was optimal， and the emission current was further optimized to improve the sensitivity of the instrument. The results showed that the PCBs standard samples had a good linear relationship within the concentration of 0.05~10 μg·L^-1， and the correlation coefficient was in the range of 0.993~0.999. At three spiked levels， the recoveries of PCBs were 60.2%~103.2%， the relative standard deviations were 0.9%~14.0% （n=3）， and the detection limit of the method was 1.01~2.92 pg·L^-1. This method can be applied to the analysis of snow samples， which provides a basis for further analysis of the distribution characteristics of pollutants in snow. In addition， through the analysis of PCBs in snow in typical areas of Northeast China， it was found that PCBs in snow were mainly composed of pentachlorobiphenyl and hexachlorobiphenyl， and the PCB monomers with higher content were PCB81， 128， 126 and 169. The study preliminarily concluded that the pollution of PCBs in snow is not only related to the historical production and residues of PCBs， but also related to combustion and thermal industrial processes.

Key words: GC-QTOF/MS, snow cover, polychlorinated biphenyls

中图分类号:

P426.63⁺5

郝琳瑶, 步小敏, 牟臻, 浦伟, 王鑫, 付晓丽. 基于气相色谱-四级杆串联飞行时间质谱联用法测定积雪中28种多氯联苯[J]. 冰川冻土, 2023, 45(1): 267-276.

Linyao HAO, Xiaomin BU, Zhen MU, Wei PU, Xin WANG, Xiaoli FU. Determination of 28 kinds of polychlorinated biphenyls in snow based on gas chromatography-quadrupole tandem time-of-flight mass spectrometry[J]. Journal of Glaciology and Geocryology, 2023, 45(1): 267-276.

图/表 9

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参考文献 38

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化合物	保留时间/min	定性离子（m/z）	定量离子（m/z）	定量内标化合物
PCB8	9.973	223.9975/152.0629	221.9999	PCB77-d6
PCB18	11.051	257.9571/186.0236	255.9602	PCB77-d6
PCB28	12.437	257.9575/186.0237	255.9606	PCB77-d6
PCB52	13.468	219.9843/289.9212	291.9183	PCB77-d6
PCB44	14.071	219.9840/289.9211	291.9180	PCB77-d6
PCB66	15.473	219.9841/289.9214	291.9184	PCB77-d6
PCB101	16.266	253.9445/327.8767	325.8791	PCB77-d6
PCB81	17.172	219.9837/289.9208	291.9177	PCB77-d6
PCB77	17.520	219.9836/289.9212	291.9179	PCB77-d6
PCB123	18.237	253.9445/327.8764	325.8794	PCB77-d6
PCB118	18.369	253.9447/327.8760	325.8791	PCB77-d6
PCB114	18.696	255.9417/323.8823	325.8790	PCB77-d6
PCB153	19.117	289.9023/361.8374	359.8402	PCB77-d6
PCB105	19.205	253.9446/327.8765	325.8796	PCB77-d6
PCB138	20.010	289.9018/361.8373	359.8397	PCB156-d3
PCB126	20.364	253.9437/323.8816	325.8789	PCB156-d3
PCB187	20.526	323.8632/395.7982	393.8010	PCB156-d3
PCB128	20.894	361.8375/289.9021	359.8400	PCB156-d3
PCB167	21.025	289.9023/361.8375	359.8402	PCB156-d3
PCB156	21.750	289.9015/361.8368	359.8397	PCB156-d3
PCB157	21.908	289.9021/361.8374	359.8401	PCB156-d3
PCB180	22.319	323.8629/395.7975	393.8007	PCB156-d3
PCB169	23.058	289.9023/361.8376	359.8406	PCB156-d3
PCB170	23.253	323.8636/395.7990	393.8013	PCB156-d3
PCB189	24.281	323.8638/395.7989	393.8019	PCB156-d3
PCB195	24.686	357.8249/427.7629	429.7597	PCB156-d3
PCB206	26.600	461.7248/391.7865	463.7207	PCB156-d3
PCB209	27.588	499.6798/427.7436	497.6825	PCB156-d3

化合物	线性范围/（μg·L^-1）	回归方程	相关系数r	检出限/（pg·L^-1）	定量限/（pg·L^-1）
PCB8	0.05~10	y=2.7556x-0.000941	0.997	1.35	4.04
PCB18	0.05~10	y=1.5747x-0.000721	0.999	1.47	4.41
PCB28	0.05~10	y=1.8056x+0.000102	0.995	1.15	3.45
PCB44	0.05~10	y=1.0643x-0.000407	0.997	1.33	4.00
PCB52	0.05~10	y=1.2568x-0.000302	0.996	1.33	3.98
PCB66	0.05~10	y=1.2814x+0.000001	0.995	2.14	6.41
PCB77	0.05~10	y=0.9433x-0.000044	0.994	1.11	3.33
PCB81	0.05~10	y=0.8777x-0.000739	0.996	1.99	5.98
PCB101	0.05~10	y=0.8170x-0.000273	0.995	2.34	7.03
PCB105	0.05~10	y=0.6669x-0.000550	0.995	1.89	5.67
PCB114	0.05~10	y=0.7190x-0.000245	0.996	1.08	3.25
PCB118	0.05~10	y=0.7100x-0.000015	0.996	1.15	3.45
PCB123	0.05~10	y=0.7321x-0.000052	0.995	1.04	3.13
PCB126	0.05~10	y=1.0730x-0.000649	0.995	1.09	3.26
PCB128	0.05~10	y=0.8469x+0.000078	0.994	1.01	3.04
PCB138	0.05~10	y=1.1128x-0.000506	0.997	2.35	7.04
PCB153	0.05~10	y=0.5086x-0.000358	0.996	1.02	3.05
PCB156	0.05~10	y=0.8552x-0.000506	0.995	1.53	4.60
PCB157	0.05~10	y=0.8804x-0.000553	0.996	2.35	7.05
PCB167	0.05~10	y=0.9421x-0.000545	0.994	2.30	6.91
PCB169	0.05~10	y=0.4831x+0.000119	0.994	2.45	7.34
PCB170	0.05~10	y=0.4228x+0.000009	0.996	2.27	6.81
PCB180	0.05~10	y=0.5110x-0.000082	0.994	2.47	7.40
PCB187	0.05~10	y=0.9182x-0.000414	0.996	1.21	3.64
PCB189	0.05~10	y=0.3526x+0.000331	0.996	2.23	6.68
PCB195	0.05~10	y=0.3373x+0.000038	0.997	2.41	7.23
PCB206	0.05~10	y=0.1916x+0.000197	0.993	2.91	8.73
PCB209	0.05~10	y=0.2541x+0.001522	0.994	2.92	8.75

化合物	加标水平
	0.2 μg·L^-1		1 μg·L^-1		10 μg·L^-1
	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
TCMX	50.6	5.7	53.7	3.9	48.2	6.4
PCB8	74.3	5.8	66.4	2.0	64.3	8.9
PCB18	68.1	7.5	60.5	2.7	60.2	9.9
PCB28	86.9	5.4	81.1	5.7	71.7	7.9
PCB44	75.4	13.1	65.6	0.9	63.5	5.3
PCB52	75.0	9.0	65.9	5.9	62.4	5.7
PCB66	93.6	6.7	88.4	7.9	70.1	3.1
PCB77	85.3	12.6	88.8	6.0	72.5	4.4
PCB81	100.4	8.2	95.4	4.7	72.6	3.4
PCB101	90.0	10.4	79.1	6.0	68.1	1.6
PCB105	96.0	12.0	94.0	5.6	71.8	2.1
PCB114	86.9	7.9	86.8	9.2	70.8	1.2
PCB118	92.4	9.2	83.8	8.7	72.4	4.0
PCB123	98.5	7.8	85.1	7.7	72.8	3.1
PCB126	105.8	12.1	78.0	9.2	72.5	13.2
PCB128	85.3	11.6	75.5	4.3	77.3	10.8
PCB138	91.9	11.7	92.7	11.1	76.1	4.3
PCB153	82.5	7.0	77.4	2.6	68.9	0.9
PCB156	98.8	13.7	70.0	5.0	74.5	7.8
PCB157	86.8	7.2	85.7	9.3	73.8	5.4
PCB167	65.2	4.5	71.6	6.5	74.2	9.3
PCB169	85.2	9.8	103.2	11.9	84.1	8.2
PCB170	81.1	4.8	83.9	8.9	78.3	2.6
PCB180	81.7	9.0	71.2	2.8	74.2	7.3
PCB187	88.1	5.4	64.5	7.3	66.4	12.9
PCB189	89.9	7.4	84.0	6.4	83.1	7.0
PCB195	83.0	9.1	71.6	9.8	81.1	1.5
PCB206	68.8	6.3	68.2	4.7	77.8	10.3
PCB209	68.6	12.4	66.0	3.0	76.4	0.3

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