甲苯增强高气压光电离-飞行时间质谱高灵敏快速测量酚类化合物
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摘要
酚类化合物在环境中污染危害大,具有慢性毒性、致癌性、致突变性,严重威胁人类生命健康。常规的离线检测方法检测酚类化合物的预处理过程复杂,且分析过程繁琐耗时,因此,亟需发展高灵敏、快速的检测方法。本研究基于真空紫外(VUV)氪气(Kr)放电灯研制了一种新型甲苯增强高气压光电离(TE-HPPI)源,并将此电离源与飞行时间质谱(TOFMS)相结合用于酚类化合物的快速分析。在高气压条件下,通过甲苯试剂离子与待测物分子之间发生电荷转移反应电离的方式,检测0.5μg/L的苯酚、3-甲酚、2-氯酚,2,4-二氯酚和2,4,6-三氯酚的灵敏度分别提高14.8、2.68、2.47、2.33和2.30倍,且电离过程不受样品湿度的影响。针对液体样品中的酚类化合物,设计了一种动态鼓泡吹扫进样法直接进样检测,无需复杂前处理过程。在1 min内对苯酚、3-甲酚、2-氯酚,2,4-二氯酚和2,4,6-三氯酚的气相检出限分别达到0. 24、1. 43、0. 42、19. 8及29.1 ng/L,液相色谱检出限分别达到4.87、3.60、0.21、1.50和4.32μg/L。将此仪器成功应用于污水处理厂的污泥悬浮液中5种酚类化合物的测量,结果表明,本仪器具有灵敏度高、分析速度快、谱图简单、易于解析等优点,在环境污染物快速筛查和在线监测方面具有良好的应用前景。
Phenolic compounds are toxic and difficult to be degraded,and can cause serious pollution to the environment. Conventional off-line detection methods for phenolic compounds mostly require complicated and time-consuming pretreatment process. Therefore,it is an urgent need to develop a method for highly sensitive and rapid measurement of phenolic compounds. In this work, a novel toluene enhanced-high pressure photoionization (TE-HPPI) source,based on a vacuum ultraviolet (VUV) lamp filling with krypton (Kr)gas,was developed for rapid detection of phenolic compounds by time-of-flight mass spectrometry (TOFMS).By introducing toluene as the reagent molecule and elevating the ion source pressure,the detection sensitivities for 0. 5 μg/L phenol,3-methylphenol,2-chlorophenol,2,4-dichlorophenol and 2,4,6-trichloropenol were improved by 14. 8,2. 68,2. 47,2. 33 and 2. 30 times,respectively. The ionization process of phenolic compounds was not affected by sample humidity. A dynamic bubbling and purging inlet method was employed to measure phenolic compounds in liquid samples without any pretreatment process. The limits of detection(LODs) of phenol,3-methylphenol,2-chlorophenol,2,4-dichlorophenol and 2,4,6-trichloropenol in gas phase within 1 min were down to 0.24,1.43,0.42,19.8 and 29.1 ng/L,respectively,while the LODs were4.87,3.60,0. 21,1. 50 and 4. 32 μg/L in solution,respectively. The method was successfully applied for analyzing phenolic compounds in sludge suspension from sewage treatment plants. The capability of high sensitivity,fast analysis,few fragmentation and simple spectrum interpretation have made the TE-HPPITOFMS as a promising tool in rapid detection and online monitoring of phenolic pollutants.
Phenolic compounds are toxic and difficult to be degraded,and can cause serious pollution to the environment. Conventional off-line detection methods for phenolic compounds mostly require complicated and time-consuming pretreatment process. Therefore,it is an urgent need to develop a method for highly sensitive and rapid measurement of phenolic compounds. In this work, a novel toluene enhanced-high pressure photoionization (TE-HPPI) source,based on a vacuum ultraviolet (VUV) lamp filling with krypton (Kr)gas,was developed for rapid detection of phenolic compounds by time-of-flight mass spectrometry (TOFMS).By introducing toluene as the reagent molecule and elevating the ion source pressure,the detection sensitivities for 0. 5 μg/L phenol,3-methylphenol,2-chlorophenol,2,4-dichlorophenol and 2,4,6-trichloropenol were improved by 14. 8,2. 68,2. 47,2. 33 and 2. 30 times,respectively. The ionization process of phenolic compounds was not affected by sample humidity. A dynamic bubbling and purging inlet method was employed to measure phenolic compounds in liquid samples without any pretreatment process. The limits of detection(LODs) of phenol,3-methylphenol,2-chlorophenol,2,4-dichlorophenol and 2,4,6-trichloropenol in gas phase within 1 min were down to 0.24,1.43,0.42,19.8 and 29.1 ng/L,respectively,while the LODs were4.87,3.60,0. 21,1. 50 and 4. 32 μg/L in solution,respectively. The method was successfully applied for analyzing phenolic compounds in sludge suspension from sewage treatment plants. The capability of high sensitivity,fast analysis,few fragmentation and simple spectrum interpretation have made the TE-HPPITOFMS as a promising tool in rapid detection and online monitoring of phenolic pollutants.
引文
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4 HJ 676-2013,Water Quality-Determination of Phenolic Compounds Liquid Extraction Gas Chromatography.National Standards of the People's Republic of China水质酚类化合物的测定液液萃取/气相色谱法.中华人民共和国国家标准.HJ 676-2013
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15 Butcher D J.Microchem.J.,1999,62(3):354-362
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19 Wang Y,Hua L,Jiang J C,Xie Y Y,Hou K Y,Li Q Y,Wu C X,Li H Y.Anal.Chim.Acta,2018,1008:74-81
20 Jiang J C,Wang Y,Hou K Y,Hua L,Chen P,Liu W,Xie Y Y,Li H Y.Anal.Chem.,2016,88(10):5028-5032
21 Kauppila T J,Kersten H,Benter T.J.Am.Soc.Mass Spectrom.,2014,25(11):1870-1881
22 Liu C Y,Zhu Y A,Zhou Z Y,Yang J Z,Qi F,Pan Y.Anal.Chim.Acta,2015,891(2):203-210
23 Yang B,Zhang H X,Shu J N,Ma P K,Zhang P,Huang J Y,Li Z,Xu C.Anal.Chem.,2018,90(2):1301-1308
24 Kauppila T J,Syage J A,Benter T.Mass Spectrom.Rev.,2017,36(3):377-378
25 Sidheswaran M,Chen W H,Chang A,Miller R,Cohn S,Sullivan D,Fisk J W,Kumagai K,Destaillats H.Environ.Sci.Technol.,2013,47(10):5336-5343
26 Newsome G A,Ackerman L K,Johnson K J.Anal.Chem.,2014,86(24):11977-11980
2 EPA U S.National Recommended Water Quality Criteria.Clean Water Act,2009
3 GB 5058.3-2007,Identification Standards for Hazardous Wastes-Identification for Extraction Toxicity.National Standards of the People's Republic of China危险废物鉴别标准浸出毒性鉴别.中华人民共和国国家标准.GB 5085.3-2007
4 HJ 676-2013,Water Quality-Determination of Phenolic Compounds Liquid Extraction Gas Chromatography.National Standards of the People's Republic of China水质酚类化合物的测定液液萃取/气相色谱法.中华人民共和国国家标准.HJ 676-2013
5 Shen S F,Chang Z D,Liu H Z.Sep.Purif.Technol.,2006,49(3):217-222
6 Djozan D,Bahar S.Chromatographia,2003,58(9-10):637-642
7 Rodil R,Quintana J B,Basaglia G,Pietrogrande M C,Cela R.Chromatographia,2010,1217(41):6428-6435
8 WU Jing,CUI Hua-Peng,HOU Ke-Yong,WU Qing-Hao,HUA Lei,CHEN Ping,ZHAO Wu-Duo,JU Bang-Yu,LI Lin,QU Ling-Bo,LI Hai-Yang.Journal of Chinese Mass Spectrometry Society,2010,31(6):321-325吴婧,崔华鹏,侯可勇,吴庆浩,花磊,陈平,赵无垛,鞠帮玉,李林,屈凌波,李海洋.质谱学报,2010,31(6):321-325
9 Raza A,Ansari T M.J.Pharm.Sci.,2018,31(1):153-157
10 Mateos R,Espartero J L,Trujillo M,Rios J J,Leon C M,Alcudia F,Cert A.J.Agric.Food Chem.,2001,49(5):2185-2192
11 Xing H Z,Wang X,Chen X F,Wang M L,Zhao R S.J.Sep.Sci.,2015,38(8):1419-1425
12 Jordan A,Haidacher S,Hanel G,Hartungen E,Herbig J,Mark L,Schottkowsky R,Seehauser H,Sulzer P,Mark T D.Int.J.Mass Spectrom.,2009,286(1):32-38
13 Reyesvillegas E,Bannan T,Breton L M,Mehra A,Priestley M,Percival C,Coe H,Allan J D.Environ.Sci.Technol.,2018:5308-5318
14 Shi Z W,Jin L J,Zhou Y,Li H,Li Y,Hu H Q.Fuel,2018,227:386-393
15 Butcher D J.Microchem.J.,1999,62(3):354-362
16 Hanley L,Zimmermann R.Anal.Chem.,2009,81(11):4174-4182
17 Sears L J,Campbell J A,Grimsrud E P.Biomed.Enviren.Mass Spectrom.,1987,14(8):401-415
18 Wang Y,Jiang J C,Hua L,Hou K Y,Xie Y Y,Chen P,Liu W,Li Q Y,Wang S,Li H Y.Anal.Chem.,2016,88(18):9047-9055
19 Wang Y,Hua L,Jiang J C,Xie Y Y,Hou K Y,Li Q Y,Wu C X,Li H Y.Anal.Chim.Acta,2018,1008:74-81
20 Jiang J C,Wang Y,Hou K Y,Hua L,Chen P,Liu W,Xie Y Y,Li H Y.Anal.Chem.,2016,88(10):5028-5032
21 Kauppila T J,Kersten H,Benter T.J.Am.Soc.Mass Spectrom.,2014,25(11):1870-1881
22 Liu C Y,Zhu Y A,Zhou Z Y,Yang J Z,Qi F,Pan Y.Anal.Chim.Acta,2015,891(2):203-210
23 Yang B,Zhang H X,Shu J N,Ma P K,Zhang P,Huang J Y,Li Z,Xu C.Anal.Chem.,2018,90(2):1301-1308
24 Kauppila T J,Syage J A,Benter T.Mass Spectrom.Rev.,2017,36(3):377-378
25 Sidheswaran M,Chen W H,Chang A,Miller R,Cohn S,Sullivan D,Fisk J W,Kumagai K,Destaillats H.Environ.Sci.Technol.,2013,47(10):5336-5343
26 Newsome G A,Ackerman L K,Johnson K J.Anal.Chem.,2014,86(24):11977-11980