气相色谱/质谱法检测灰尘、土壤和沉积物中有机磷酸酯

鹿建霞等

摘 要 本研究对实验过程中可能存在的污染源进行了定性筛查，采用不同的质控措施以降低实验过程中的背景污染。

1 引 言

有机磷酸酯（Organophosphate esters，OPEs）是一类由不同烃类取代基取代磷酸分子上的氢所形成的一类磷酸酯类化合物，其取代基可以是烷烃、芳香烃和卤代烷烃。一般烷烃和芳香烃取代的OPEs常被用作增塑剂，而含卤OPEs则被广泛用作阻燃剂。OPEs由于阻燃性能高，可塑性强， 被广泛应用于许多产品中，如清漆、聚氨酯泡沫、室内装潢和纺织品等[1]。OPEs多以物理方式添加到材料中，因此在材料的生产、使用和废弃处理过程中很容易释放到周围环境中。OPEs的分析方法及环境监测报道最早集中于20 世纪70～90 年代[2，3]，近来随着五溴联苯醚、八溴联苯醚被正式列入斯德哥尔摩公约，作为含溴阻燃剂的替代品OPEs再次受到环境科学家的广泛关注，已在全球范围内的多种环境介质，包括大气、水、土壤和生物体中检测到OPEs[3～10]。与传统持久性有机污染的研究相比，有关OPEs的研究进展缓慢，实验方法的欠缺，依然是制约该类污染物环境行为研究的主要因素之一。

2012年，由Brandsm等发起了OPEs的国际实验室比对，来自9个国家和地区的实验室参加了此次比对[11]，结果表明，当前OPEs分析主要存在两方面困难： （1）由于OPEs用途广泛，测定中的污染物背景干扰已经成为该类化合物分析检测的主要问题，必须有效降低背景污染； （2）对于基质成分复杂的样品，仪器分析前必须采取严格的净化步骤去除基质干扰。常用的净化方法包括凝胶渗透色谱（GPC）净化和固相萃取（SPE）柱净化，其中GPC净化不但费时费力，需要大量溶剂，且净化效果不好。OPEs对强酸强碱都比较敏感，因此以强酸/强碱性吸附材料做填料的SPE也不能应用于这类污染物的分离净化。近年来，以各种硅胶键合材料为吸附填料的SPE小柱断被引入到复杂样品中OPEs的分析[5，7]。

本研究对实验室内可能存在OPEs污染的点源进行了初步分析，在严格的背景污染控制条件下，优化对比了几种不同净化手段对实际样品中OPEs分离净化效果，采用气相色谱/质谱（GC/MS）建立了检测灰尘、土壤和沉积物中7种主要OPEs的分析方法，并应用于实际样品中该类污染物的分析。

2 实验部分

2.1 仪器与试剂

安捷伦7890N联5975C色谱质谱联用仪（美国安捷伦公司）；

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14 Kim J W， Isobe T， Sudaryanto A， Malarvannan G， Chang K H， Muto M， Prudente M， Tanabe S. Environ.Sc. Pollu. Res.， 2013， 20（2）： 812-822

15 Matthews H B， Eustis S L， Haseman J. Toxicol. Sc.， 1993， 20 （4）： 477-485

Analysis of Organophosphate Esters in Dust， Soil and Sediment

Samples Using Gas Chromatography Coupled with Mass Spectrometry

LU JianXia1， JI Wen1， MA ShengTao2， YU ZhiQiang2， WANG Zhao1， LI Han1，

REN GuoFa1， FU JiaMo1，2

1（Institute of Environmental Pollution and Health， School of Environment and Chemical Engineering，

Shanghai University， Shanghai 200444， China）

2（State Key Laboratory of Organic Geochemistry， Guangdong Key Laboratory of Environment and Resources，

Guangzhou Institute of Geochemistry， Chinese Academy of Sciences， Guangzhou 510640， China）

Abstract Background contamination is a major problem in the analysis of organophosphate esters （OPEs）. In this study， the possible sources of OPEs pollution were screened and several different ways were applied to minimize the blank contamination. Under the strict quality control measures， the cleanup efficiency of different solid phase extraction （SPE） was investigated for OPEs in different environmental matrices. A method was developed for the detection of 7 OPEs in dust， soil and sediment samples by gas chromatograph coupled with mass spectrometry （GC/MS）. Target compounds were extracted by hexane：dichloromethane （1∶1， V/V） followed by aminopropyl silica gel SPE column cleanup for dust， and target compounds in soil and sediment were Soxhlet extracted and cleanuped by twostep SPE. The results showed that the aminopropyl silica gel SPE column displayed the best purification performance among the three employed columns. Instrumental detection limits among the 7 OPEs ranged from 2.5 to 25.8 μg/L， and the method limits of quantification （MLOQs） in dust and soil sample ranged from 1.4 to 15.7 ng/g and 0.3 to 2.9 ng/g， respectively. The average recoveries of 7 OPEs in different matrices （dust and soil） at two spiked concentration levels ranged from 67.9% to 117.4%. The proposed method was successfully applied to detect OPEs in different environmental matrices collected in Shanghai.

Keywords Organophosphate flame retardant； Organophosphate esters； Gas chromatograph coupled with mass spectrometry； Soil； Sediment； Dust

（Received 3 December 2013； accepted 21 February 2014）

This work was supported by the National Science Foundation of China （Nos. 21007037， 41273121）， National Program for Water Pollution Control （2009ZX0752800204）， and Shanghai Leading Academic Disciplines （S30109）.

14 Kim J W， Isobe T， Sudaryanto A， Malarvannan G， Chang K H， Muto M， Prudente M， Tanabe S. Environ.Sc. Pollu. Res.， 2013， 20（2）： 812-822

15 Matthews H B， Eustis S L， Haseman J. Toxicol. Sc.， 1993， 20 （4）： 477-485

Analysis of Organophosphate Esters in Dust， Soil and Sediment

Samples Using Gas Chromatography Coupled with Mass Spectrometry

LU JianXia1， JI Wen1， MA ShengTao2， YU ZhiQiang2， WANG Zhao1， LI Han1，

REN GuoFa1， FU JiaMo1，2

1（Institute of Environmental Pollution and Health， School of Environment and Chemical Engineering，

Shanghai University， Shanghai 200444， China）

2（State Key Laboratory of Organic Geochemistry， Guangdong Key Laboratory of Environment and Resources，

Guangzhou Institute of Geochemistry， Chinese Academy of Sciences， Guangzhou 510640， China）

Abstract Background contamination is a major problem in the analysis of organophosphate esters （OPEs）. In this study， the possible sources of OPEs pollution were screened and several different ways were applied to minimize the blank contamination. Under the strict quality control measures， the cleanup efficiency of different solid phase extraction （SPE） was investigated for OPEs in different environmental matrices. A method was developed for the detection of 7 OPEs in dust， soil and sediment samples by gas chromatograph coupled with mass spectrometry （GC/MS）. Target compounds were extracted by hexane：dichloromethane （1∶1， V/V） followed by aminopropyl silica gel SPE column cleanup for dust， and target compounds in soil and sediment were Soxhlet extracted and cleanuped by twostep SPE. The results showed that the aminopropyl silica gel SPE column displayed the best purification performance among the three employed columns. Instrumental detection limits among the 7 OPEs ranged from 2.5 to 25.8 μg/L， and the method limits of quantification （MLOQs） in dust and soil sample ranged from 1.4 to 15.7 ng/g and 0.3 to 2.9 ng/g， respectively. The average recoveries of 7 OPEs in different matrices （dust and soil） at two spiked concentration levels ranged from 67.9% to 117.4%. The proposed method was successfully applied to detect OPEs in different environmental matrices collected in Shanghai.

Keywords Organophosphate flame retardant； Organophosphate esters； Gas chromatograph coupled with mass spectrometry； Soil； Sediment； Dust

（Received 3 December 2013； accepted 21 February 2014）

This work was supported by the National Science Foundation of China （Nos. 21007037， 41273121）， National Program for Water Pollution Control （2009ZX0752800204）， and Shanghai Leading Academic Disciplines （S30109）.

14 Kim J W， Isobe T， Sudaryanto A， Malarvannan G， Chang K H， Muto M， Prudente M， Tanabe S. Environ.Sc. Pollu. Res.， 2013， 20（2）： 812-822

15 Matthews H B， Eustis S L， Haseman J. Toxicol. Sc.， 1993， 20 （4）： 477-485

Analysis of Organophosphate Esters in Dust， Soil and Sediment

Samples Using Gas Chromatography Coupled with Mass Spectrometry

LU JianXia1， JI Wen1， MA ShengTao2， YU ZhiQiang2， WANG Zhao1， LI Han1，

REN GuoFa1， FU JiaMo1，2

1（Institute of Environmental Pollution and Health， School of Environment and Chemical Engineering，

Shanghai University， Shanghai 200444， China）

2（State Key Laboratory of Organic Geochemistry， Guangdong Key Laboratory of Environment and Resources，

Guangzhou Institute of Geochemistry， Chinese Academy of Sciences， Guangzhou 510640， China）

Abstract Background contamination is a major problem in the analysis of organophosphate esters （OPEs）. In this study， the possible sources of OPEs pollution were screened and several different ways were applied to minimize the blank contamination. Under the strict quality control measures， the cleanup efficiency of different solid phase extraction （SPE） was investigated for OPEs in different environmental matrices. A method was developed for the detection of 7 OPEs in dust， soil and sediment samples by gas chromatograph coupled with mass spectrometry （GC/MS）. Target compounds were extracted by hexane：dichloromethane （1∶1， V/V） followed by aminopropyl silica gel SPE column cleanup for dust， and target compounds in soil and sediment were Soxhlet extracted and cleanuped by twostep SPE. The results showed that the aminopropyl silica gel SPE column displayed the best purification performance among the three employed columns. Instrumental detection limits among the 7 OPEs ranged from 2.5 to 25.8 μg/L， and the method limits of quantification （MLOQs） in dust and soil sample ranged from 1.4 to 15.7 ng/g and 0.3 to 2.9 ng/g， respectively. The average recoveries of 7 OPEs in different matrices （dust and soil） at two spiked concentration levels ranged from 67.9% to 117.4%. The proposed method was successfully applied to detect OPEs in different environmental matrices collected in Shanghai.

Keywords Organophosphate flame retardant； Organophosphate esters； Gas chromatograph coupled with mass spectrometry； Soil； Sediment； Dust

（Received 3 December 2013； accepted 21 February 2014）

This work was supported by the National Science Foundation of China （Nos. 21007037， 41273121）， National Program for Water Pollution Control （2009ZX0752800204）， and Shanghai Leading Academic Disciplines （S30109）.