收稿日期: 2021-08-03
网络出版日期: 2022-03-11
基金资助
国家科技重大专项(2014ZX07213001)
Test of Various Plasticizers in Groundwater by Using SPME-GC-MS
Received date: 2021-08-03
Online published: 2022-03-11
Supported by
the National Science and Technology Major Project(2014ZX07213001)
水中塑化剂的污染问题已经引起越来越多的关注,关于其测试方法的研究也日益增多,但将不同类别的塑化剂同时进行测试的研究比较少见,且目前大多采用顶空式固相微萃取,难以保证较好的萃取效率和较低的检出限。为此,文中建立了一种浸入式固相微萃取-气相色谱-质谱法(SPME-GC-MS)来测定地下水中11种共两大类别的塑化剂。该方法选用65 μm二乙烯基苯/聚二甲基硅氧烷(DVB/PDMS)萃取纤维,在1 000 r/min的磁力搅拌转速下,于80 ℃萃取50 min,然后将萃取头直接注入GC进样口,于270 ℃下热解析2.5 min,再采用气相色谱-质谱联用仪进行检测,以保留时间和特征离子进行定性,以内标法进行定量。实验结果表明,11种塑化剂在0.1 ~ 2.0 μg/L范围内线性关系良好,相关系数大于0.996,检出限为0.03 ~ 0.06 μg/L,回收率为60.9% ~ 128.0%,相对标准偏差为6.68% ~ 19.00%。文中方法简便可靠,灵敏度高,适用于地下水中邻苯二甲酸酯类和己二酸酯类塑化剂含量的测定。针对塑化剂分析中的空白干扰问题,文中首次从试剂、耗材及仪器维护等各方面进行了详尽的分析,提出了切实可操作的解决方案,有效地降低了分析过程中塑化剂的空白干扰,进一步确保了分析结果的可靠性。
许锐杰, 陈克复, 招蔚弘, 等 . 地下水中多种塑化剂的SPME-GC-MS法测定[J]. 华南理工大学学报(自然科学版), 2022 , 50(8) : 109 -118 . DOI: 10.12141/j.issn.1000-565X.210494
The pollution problem of plasticizers in water has attracted more and more attention, and the research on their testing methods is also increasing, but the research on testing different types of plasticizers at the same time is relatively rare. And most of these studies use headspace solid phase microextraction, which is difficult to ensure good extraction efficiency and low detection limit. Therefore, this paper developed a SPME-GC-MS method to test 11 plasticizers included in two types in groundwater by using immersion solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS). This method used 65 μm DVB/PDMS fiber, and the extraction was carried out at 80 ℃ for 50 min with a constant stirring speed of 1 000 r/min. The fiber was introduced into GC injector port, the extract was desorbed at 270 ℃ for 2.5 min and then detected by GC-MS. Qualitative analysis was performed by using retention time and characteristic ion, and quantitative by internal standard method. The results show that the linearity of 11 plasticizers is good in the range of 0.1 ~ 2.0 μg/L and the correlation coefficients are greater than 0.996; the detection limit is 0.03 ~ 0.06 μg/L; the recovery is 60.9% ~ 128.0%; and the relative standard deviation (RSD) is 6.68% ~ 19.00%. The proposed method is simple, reliable and sensitive, and it’s suitable for the determination of phthalate esters and adipate esters in groundwater. Moreover, aiming at the blank interference in plasticizer analysis, this paper conducted an in-depth study on this difficulty for the first time, carried out a detailed analysis from various aspects such as reagents, consumables and instrument maintenance, and proposed practical and operable solutions, which can effectively reduce the blank interference of plasticizers in the analysis process and further ensure the reliability of the analysis results.
| 1 | DEES J H, GAZOULI M, PAPADOPOULOS V .Effect of monoethylhexyl phthalate on MA-10 leydigtunlorcells[J].Reproductive Toxicology,2001,15(2):171-187. |
| 2 | ECHA .Substances of very high concern[DB/OL].[2021-07-01].. |
| 3 | 丁鹏,赵晓松,刘剑锋 .酞酸酯类化合物(PAEs)研究新进展[J].吉林农业大学学报,1999,21(3):119-123,128. |
| 3 | DING Peng, ZHAO Xiao-song, LIU Jian-feng .Advances in the research of phthalate esters[J].Journal of Jilin Agricultural University,1999,21(3):119-123,128. |
| 4 | 地下水质量标准: [S]. |
| 5 | USEPA .National primary drinking water regulations[DB/OL].[2021-07-01].. |
| 6 | 食品接触材料及制品用添加剂使用标准:2016— [S]. |
| 7 | Union European .Commission regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food[DB/OL].[2021-07-01].. |
| 8 | 水质 邻苯二甲酸二甲(二丁、二辛)酯的测定 液相色谱法: [S]. |
| 9 | 水质 半挥发性有机物的测定 液液萃取-气相色谱/质谱法: [S]. |
| 10 | 生态环境部 .关于征集2021年度国家生态环境监测标准计划项目承担单位的通知[DB/OL].[2021-07-01].. |
| 11 | 戚文炜,朱培瑜,吴薇 .液液萃取/气相色谱法测定环境水样中邻苯二甲酸酯类化合物[J].干旱环境监测,2006,20(4):196-199. |
| 11 | QI Wen-wei, ZHU Pei-yu, WU Wei .Determination of phthalate esters in water by using liquid-liquid extraction/gas chromatography[J].Arid Environmental Monitoring,2006,20(4):196-199. |
| 12 | 吴鹏,於香湘,缪建军 .小体积液液萃取气相色谱-质谱法测定水体中邻苯二甲酸酯[J].分析科学学报,2013(1):139-142. |
| 12 | WU Peng, YU Xiang-xiang, Jian-jun MIU .Determination of phthalate esters in waters by small volume liquid-liquid extraction combined with gas chromatography-mass spectrometry[J].Journal of Analytical Science,2013(1):139-142. |
| 13 | 戴树桂,张东梅,张仁江,等 .固相萃取技术预富集环境水样中邻苯二甲酸酯[J].环境科学,2000,21(2):66-69. |
| 13 | DAI Shugui, ZHANG Dongmei, ZHANG Renjiang,et al .Preconcentration of phthalate esters in environmental water samples by solid phase extraction[J].Environmental Science,2000,21(2):66-69. |
| 14 | 贾宁,许恒智,胡亚丽,等 .固相萃取-气相色谱法测定北京市水样中的邻苯二甲酸酯[J].分析试验室,2005,24(11):18-21. |
| 14 | JIA Ning, XU Heng-zhi, HU Ya-li,et al .Determination of the phthalates in water samples in Beijing city by solid-phase extraction and gas chromatography[J].Chinese Journal of Analysis Laboratory,2005,24(11):18-21. |
| 15 | 马燕玲,陈令新,丁养军,等 .超声辅助分散液液微萃取-高效液相色谱测定水样中的4种邻苯二甲酸酯类增塑剂[J].色谱,2013,31(2):155-161. |
| 15 | MA Yanling, CHEN Lingxin, DING Yangjun,et al .Simultaneous determination of four phthalate esters in water samples using ultrasound-assisted dispersive liquid-liquid microextraction coupled with high performance liquid chromatography[J].Chinese Journal of Chromatography,2013,31(2):155-161. |
| 16 | 窦筱艳,王静,孙静,等 .高效液相色谱-三重四级杆/复合线性离子阱质谱法测定饮用水中22种邻苯二甲酸酯[J].中国环境监测,2020,36(4):132-138. |
| 16 | DOU Xiaoyan, WANG Jing, SUN Jing,et al .Determination of 22 phthalate esters in drinking water by liquid chromatography-triple quadrupole linear ion trap mass spectrometry[J].Environmental Monitoring in China,2020,36(4):132-138. |
| 17 | 张军,张丹,彭华,等 .固相微萃取-气相色谱法测定水中酞酸酯类化合物[J].中国环境监测,2015(4):91-94. |
| 17 | ZHANG Jun, ZHANG Dan, PENG Hua,et al .Determination of phthalate esters in water by solid-phase microextraction and gas chromatography[J].Environmental Monitoring in China,2015(4):91-94. |
| 18 | 陈海东,鲜啟鸣,邹惠仙,等 .固相微萃取气相色谱法(SPME-GC)测定水体中邻苯二甲酸酯[J].分析试验室,2006,25(3):32-36. |
| 18 | CHEN Hai-dong, XIAN Qi-ming, ZOU Hui-xian,et al .Application of solid-phase microextraction and gas chromatography to the analysis of phthalic acid esters in water[J].Chinese Journal of Analysis Laboratory,2006,25(3):32-36. |
| 19 | 王超英,李碧芳,李攻科 .固相微萃取/高效液相色谱联用分析水样中邻苯二甲酸酯[J].分析测试学报,2005,24(5):35-38. |
| 19 | WANG Chao-ying, LI Bi-fang, LI Gong-ke .Determination of phthalate esters in water samples by solid-phase microextraction and high performance liquid chromatography[J].Journal of Instrumental Analysis,2005,24(5):35-38. |
| 20 | 张潜,高舸,王炼,等 .自动固相微萃取-气相色谱/串联质谱法测定饮用水中11种邻苯二甲酸酯[J].中国卫生检验杂志,2013(7):1641-1644. |
| 20 | ZHANG Qian, GAO Ge, WANG Lian,et al .Determination of eleven phthalate esters in drinking water by automated solid phase microextraction coupled with gas chromatography-triple quadrupole mass spectrometry[J].Chinese Journal of Health Laboratory Technology,2013(7):1641-1644. |
| 21 | PEALVER A, POCURULL E, BORRULL F,et al .Comparison of different fibers for the solid-phase microextraction of phthalate esters from water[J].Journal of Chromatography A,2001,922(1/2):377-384. |
| 22 | PENALVER A, POCURULL E, BORRULL F,et al .Determination of phthalate esters in water samples by solid-phase microextraction and gas chromatography with mass spectrometric detection[J].Journal of Chromatography A,2000,872:191-201. |
| 23 | 龚丽雯,卫才银,李京会 .顶空固相微萃取气相色谱法测定水中多种增塑剂[J].广东化工,2005,32(10):59-62,77. |
| 23 | GONG Liwen, WEI Caiyin, LI Jinghui .Determination of plasticizers in water by headspace solid-phase microextraction coupled with gas chromatogrphy[J].Guangdong Chemical Industry,2005,32(10):59-62,77. |
| 24 | 张伟亚,王成云,杨左军 .顶空固相微萃取气相色谱-质谱单离子监测法测定水中的多种己二酸酯[J].分析试验室,2004,23(4):77-80. |
| 24 | ZHANG Wei-ya, WANG Cheng-yun, YANG Zuo-jun .Determination of adipate in water with headspace solid-phase microextraction and single ion monitoring gas chromatography-mass spectrometry[J].Chinese Journal of Analysis Laboratory,2004,23(4):77-80. |
| 25 | 地下水环境监测技术规范: [S]. |
| 26 | 环境监测分析方法标准制定技术导则: [S]. |
| 27 | 水质高锰酸盐指数的测定: [S]. |
/
| 〈 |
|
〉 |