凝固漂浮有机液滴-分散液液微萃取结合高效液相色谱法同时测定地表水中多环芳烃和酞酸酯

引用本文: 袁继委, 王金成, 徐威力, 徐方曦, 卢宪波. 凝固漂浮有机液滴-分散液液微萃取结合高效液相色谱法同时测定地表水中多环芳烃和酞酸酯[J]. 色谱, 2020, 38(11): 1308-1315. doi: 10.3724/SP.J.1123.2020.01020 shu

Citation: YUAN Jiwei, WANG Jincheng, XU Weili, XU Fangxi, LU Xianbo. Simultaneous determination of polycyclic aromatic hydrocarbons and phthalate esters in surface water by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by high performance liquid chromatography[J]. Chinese Journal of Chromatography, 2020, 38(11): 1308-1315. doi: 10.3724/SP.J.1123.2020.01020 shu

凝固漂浮有机液滴-分散液液微萃取结合高效液相色谱法同时测定地表水中多环芳烃和酞酸酯

1.
台州市环境监测中心站, 浙江台州 318000;
2.
中国科学院大连化学物理研究所, 辽宁大连 116023
基金项目:
辽宁省自然科学基金（2019-MS-317）.

摘要: 多环芳烃和酞酸酯是国际公认的优控污染物，因此准确快速地测定水中多环芳烃和酞酸酯非常重要。凝固漂浮有机液滴-分散液液微萃取（DLLME-SFO）是一种简便、快速、环境友好、灵敏度高的样品前处理技术。采用DLLME-SFO同时测定地表水中多环芳烃和酞酸酯的分析方法鲜有报道。该文采用凝固漂浮有机液滴-分散液液微萃取富集技术，结合高效液相色谱紫外/荧光法，建立了同时测定地表水中16种多环芳烃和6种酞酸酯的分析方法。考察优化了影响萃取效率的主要因素，包括萃取剂的种类和用量、分散剂的种类和用量、萃取时间和离子强度等。优化后的萃取实验条件为：5.0 mL水样，10 μL十二醇为萃取溶剂，500 μL甲醇为分散溶剂，涡旋振荡时间2 min，氯化钠用量0.2 g。目标化合物经多环芳烃专用色谱柱（SUPELCOSIL^TM LC-PAH，150 mm×4.6 mm，5 μm）结合乙腈-水梯度洗脱分离，16种多环芳烃除苊烯外采用荧光检测，苊烯和6种酞酸酯采用紫外检测，外标法定量。结果表明，22种目标化合物的基质加标回收率为60.2%~113.5%，相对标准偏差为1.9%~14.3%；多环芳烃和酞酸酯的检出限分别为0.002~0.07 μg/L和0.2~2.2 μg/L；多环芳烃和酞酸酯的定量限分别为0.006~0.23 μg/L和0.8~7.4 μg/L。该方法简便、快速，环境友好，灵敏度高，可用于地表水中多环芳烃和酞酸酯的快速分析检测。

关键词:

English

Simultaneous determination of polycyclic aromatic hydrocarbons and phthalate esters in surface water by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by high performance liquid chromatography

1.
Taizhou Environmental Monitoring Center Station, Taizhou 318000, China;
2.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Received Date: 02 March 2020
Fund Project:
Liaoning Natural Science Foundation (No. 2019-MS-317).

Abstract: Polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs) are internationally recognized as priority pollutants; hence, it is important to monitor their concentrations in the environment. However, the low concentrations of PAHs and PAEs in surface water make the direct and sensitive determination of these compounds by instrumental methods difficult. Therefore, the development of an accurate and rapid sample pretreating method for the determination of PAHs and PAEs in water has always been the goal of environmental scientists. Dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) is a simple, rapid, low-cost, sensitive, and environmentally friendly method. Methods based on DLLME-SFO for the simultaneous determination of PAHs and PAEs in surface water have rarely been reported. In this study, a novel DLLME-SFO method was developed for the simultaneous determination of 16 PAHs and 6 PAEs in surface water samples. To optimize the extraction efficiency for the target compounds, various parameters, including the types and volumes of extractants and dispersants, ionic strength, and extraction time, were investigated. First, 1-undecanol (melting point:19℃) and 1-dodecanol (melting point:24℃) were selected as extractive solvents, and their extraction efficiency was investigated. The results showed that 1-dodecanol had better extraction efficiency. The melting point of 1-undecanol was relatively low, and the droplets that solidified during the experiment were easy to melt and break, which led to the low recovery rate of extraction. Then, the effect of the volume (10, 20, 30, 40, 50 μL) of 1-dodecanol was investigated, and the extraction efficiency of the target compounds was found to decrease with increasing volume of 1-dodecanol. Second, the effect of four dispersive solvents (methanol, ethanol, acetonitrile, and acetone) on the extraction efficiencies was studied. The extraction efficiencies of the target compounds were the highest when methanol was used as the dispersant; hence, the effect of different volumes of methanol on the extraction efficiency was further examined. When the volume of methanol was less than 500 μL, the contact area between the extraction solvent and the water phase increased with increasing methanol volume, and the extraction efficiency increased. However, when the volume of methanol was more than 500 μL, the excessive dispersant increased the solubility of the target compound in the water phase, which led to a decrease in the extraction efficiency. Finally, the effects of salt addition and vortex oscillation time on the extraction efficiency were probed. The experimental results indicated that the extraction efficiency increased with an increase in the quantity of NaCl. When the NaCl quantity was greater than 0.2 g, there was no notable change in the extraction efficiency. Vortex oscillation could accelerate the establishment of the extraction equilibrium, and the extraction efficiency reached a stable state when the vortex oscillation time was more than 2 min. According to the abovementioned results, the optimized DLLME-SFO conditions were established as follows:for 5.0 mL water samples, 10 μL of 1-dodecanol was chosen as the extraction solvent, 500 μL of methanol was used as the dispersive solvent, the vortex oscillation extraction time was 2 min, and the NaCl quantity was 0.2 g. The target compounds were analyzed by high-performance liquid chromatography. Separation of the PAHs and PAEs was achieved on a SUPELCOSIL^TM LC-PAH column (150 mm×4.6 mm, 5 μm) with acetonitrile-water as the mobile phase using a gradient elution program. Fifteen PAHs were detected using a fluorescence detector, and six PAEs and acenaphthylene were detected by an ultraviolet detector. Quantitative determination was achieved by the external standard method. This method was successfully validated for the analyses of the 16 PAHs and 6 PAEs in two types of water samples (tap water and river water). The average recoveries of the target compounds were 60.2%-113.5%, and the corresponding relative standard deviations (RSDs, n=3) were 1.9%-14.3%. The limits of detection (LODs, S/N=3) ranged from 0.002 μg/L to 0.07 μg/L for the PAHs and from 0.2 μg/L to 2.2 μg/L for the PAEs. The limits of quantification (LOQs, S/N=10) ranged from 0.006 μg/L to 0.23 μg/L for the PAHs and from 0.8 μg/L to 7.4 μg/L for PAEs. The proposed method is simple, fast, low-cost, and environmentally friendly, and it is suitable for the rapid determination of trace PAHs and PAEs in surface water samples.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

凝固漂浮有机液滴-分散液液微萃取结合高效液相色谱法同时测定地表水中多环芳烃和酞酸酯

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Simultaneous determination of polycyclic aromatic hydrocarbons and phthalate esters in surface water by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by high performance liquid chromatography

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