超声萃取-高效液相色谱-串联质谱法测定土壤中三种硝基酚类化合物

乔淞汾; 秦冲; 刘爱琴; 安彩秀; 刘安; 杨利娟; 孙凯茜; 冉卓

doi:10.15898/j.ykcs.202303170036

超声萃取-高效液相色谱-串联质谱法测定土壤中三种硝基酚类化合物

1.
河北省地质实验测试中心，河北省矿产资源与生态环境监测重点实验室，河北保定 071052

基金项目: 河北省地质矿产勘查开发局科技项目“土壤中酚类化合物分析方法研究”(13000023P0069B4101215)

详细信息

作者简介: 乔淞汾，硕士，工程师，主要从事地质实验测试工作。E-mail：1535722404@qq.com

通讯作者: 刘安，硕士，工程师，主要从事地质实验测试工作。E-mail： 357296414@qq.com。

中图分类号: O657.72；O657.63；S151.95

收稿日期: 2023-03-17

修回日期: 2023-06-04

录用日期: 2023-08-07

刊出日期: 2024-05-31

Determination of Three Nitrophenol Compounds in Soil by Ultrasonic Extraction-High Performance Liquid Chromatography-Mass Spectrometry

1.
Hebei Research Center for Geoanalysis, Hebei Key Laboratory of Mineral Resources and Ecological Environment Monitoring, Baoding 071052, China

More Information

Corresponding author: LIU An, 357296414@qq.com

Received Date: 17 March 2023

Revised Date: 04 June 2023

Accepted Date: 07 August 2023

Publish Date: 31 May 2024

摘要

摘要:
硝基酚类化合物作为一类有机化工原料，具有高毒性和致癌性，可通过空气、水传播进入土壤造成污染，危害人类健康。以往采用气相色谱法和气相色谱-质谱法直接测定硝基酚类化合物，存在色谱灵敏度低、峰形差等问题。为提高灵敏度，通常需要对硝基酚类化合物进行衍生化处理，但衍生化方法步骤繁琐耗时。为实现土壤中硝基酚类化合物的快速准确分析，本文建立了超声萃取-高效液相色谱-串联质谱法分析土壤中三种硝基酚类化合物的方法。用二氯甲烷-正己烷(2∶1，V/V)混合溶剂超声萃取土壤中硝基酚类化合物，在超声萃取液中加入强碱性水溶液(pH＞12)，将下层有机相除去。将水溶液调至酸性(pH＜2)后，用二氯甲烷-乙酸乙酯(4∶1，V/V)混合溶剂萃取三种硝基酚类化合物。萃取液浓缩后用10%乙腈-水溶液定容至10.0mL，高效液相色谱-串联质谱仪测定，外标法定量。性能评价的结果表明方法精密度(RSD＜10%，n=6)和准确度都可以满足测定要求，三种硝基酚类化合物的方法检出限为0.1～0.2μg/kg，加标回收率为61.7%～90.8%。本方法具有前处理简单、检出限低等优点，可应用于土壤中硝基酚类化合物的测定和评估。
- 硝基酚类化合物 /
- 土壤 /
- 超声萃取 /
- 二氯甲烷-正己烷 /
- 高效液相色谱-串联质谱法
Abstract:
As important organic chemical raw materials, nitrophenol compounds have high toxicity and carcinogenicity, which can be transmitted into soil through air and water, causing pollution and endangering human health. In the past, nitrophenol compounds in soil were usually determined by gas chromatography and gas chromatography-mass spectrometry. The derivatization was usually required to improve the sensitivity, which was time-consuming and cumbersome. To achieve a rapid and accurate analysis of the three nitrophenol compounds in soil, a method of ultrasonic extraction-high performance liquid chromatography-mass spectrometry (HPLC-MS) was established. The nitrophenol compounds in soil were extracted by ultrasonic extraction with dichloromethane/n-hexane (2∶1, V/V), and a strong alkaline aqueous solution (pH>12) was added to the ultrasonic extraction solution to remove the underlying organic phase. After the aqueous solution was adjusted to acidity (pH<2), three nitrophenol compounds were extracted with dichloromethane-ethyl acetate (4∶1, V/V). The extraction solution was concentrated and diluted to 10.0mL with 10% acetonitrile aqueous solution, and then determined by HPLC-MS. The RSDs of three nitrophenol compounds were less than 10.0%, detection limits were 0.1−0.2μg/kg, and the recoveries were 61.7%−90.8%. This method has the advantages of simple pretreatment and low detection limit, and can be applied to the determination and evaluation of nitrophenol compounds in soil.
- nitrophenol compounds /
- soil /
- ultra-sonic extraction /
- dichloromethane n-hexane /
- high performance liquid chromatography-mass spectrometry

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图 1 三种硝基酚类化合物标准溶液的总离子流图

Figure 1.

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图 2 不同实验条件下三种硝基酚类化合物的回收率对比

Figure 2.

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表 1 三种硝基酚类化合物的质谱参数

Table 1. Parameters of mass spectrometry for the determination of three nitrophenol compounds.

硝基酚类化合物	母离子 m/z	去簇电压 (V)	子离子1 碰撞能 (V)	子离子2 碰撞能 (V)
2，6-二硝基酚	183.0	−71	79.0/−30	64.1/−30
2，4-二硝基酚	183.0	−112	108.9/−30	123.0/−22
4-硝基酚	137.9	−70	46.1/−48	91.9/−26

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表 2 三种硝基酚化合物的线性回归方程、相关系数、方法检出限、精密度和加标回收率

Table 2. Linear regression equations, correlation coefficients, method detection limits, precision and spiked recoveries (n=6) of three nitrophenol compounds.

硝基酚化合物	线性回归方程	相关系数 (r)	检出限 (µg/kg)	HJ703—2014 检出限 (µg/kg)	液相色谱法^［29］检出限 (µg/kg)	气相色谱- 质谱法^［20］检出限 (µg/kg)	加标浓度 2μg/kg (n=6)		加标浓度 5μg/kg (n=6)		加标浓度 20μg/kg (n=6)
硝基酚化合物	线性回归方程	相关系数 (r)	检出限 (µg/kg)	HJ703—2014 检出限 (µg/kg)	液相色谱法^［29］检出限 (µg/kg)	气相色谱- 质谱法^［20］检出限 (µg/kg)	回收率 (%)	RSD (%)	回收率 (%)	RSD (%)	回收率 (%)	RSD (%)
2，6-二硝基酚	y=21742x−9327	0.9997	0.1	−	−	−	61.7	5.4	70.3	4.4	68.5	4.6
2，4-二硝基酚	y=539061x−151658	0.9992	0.2	80	−	1.47	73.2	5.9	90.8	3.8	79.5	3.5
4-硝基酚	y=307087x−20313	0.9999	0.1	40	20	3.95	62.9	7.6	73.2	3.5	63.2	4.4
注：“−”表示该方法未涉及此化合物。

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