摘要
建立了X射线近边吸收光谱法(1sXANES)测定大气颗粒物中无机氯和有机氯形态及含量的分析方法及质量控制体系。在储存环能量为1.5 GeV和光子能量为2.82 keV条件下,利用束流强度在300~150 mA的同步辐射光激发分析无机氯、链烃代有机氯和芳香烃代有机氯标准样品以及≤0.2μm的大气颗粒物样品。通过对标准品谱图的拟合计算,得到该方法无机氯、链烃代有机氯和芳香烃代有机氯最低检出限,分别为5.4,8.7和1.7μg/g。对已知无机氯和有机氯浓度的试样检出率均达到或接近95%,重复测定3-氯丙酸标准品(n=6),得到本方法的相对标准偏差(RSD)为0.9%。应用本方法可以实现定量无损地测定微量样品中氯的形态和含量,对城市大气颗粒物中氯的测定发现,颗粒物中无机氯和芳香烃代有机氯含量分别为110和12 ng/m3,链烃代氯的含量低于检出限。应用本方法对北京某地区大气颗粒物中氯元素形态进行测定,确定氯的主要存在形式是无机氯和芳香烃氯。
An analytical method of X-ray absorption near edge spectrometry(1sXANES) including the quality control for chlorine species in the atmospheric particles was established.The inorganic and aromatic and aliphatic chlorine in the standard and ≤0.2 atmospheric particle samples were analyzed under the conditions of 300-350 synchrotron radiation light beam intensity,storage ring energy of 1.5 GeV and photon energy of 2.82 keV.Calculated by fitting standard spectra,the method detection limits of inorganic,aliphatic and aromatic chlorine were 5.4,8.7 and 1.7 μg/g,respectively.The detectable frequency of atmospheric particle samples was almost 95%.The relative standard deviation(RSD) of repeated measurements of 3-chloro acid standard was 0.9%(n=6).The method was successfully applied to analyze the urban atmospheric particles non-destructively.The contents of inorganic chlorine,aromatic hydrocarbon-substituded organic chlorine in atmospheric ultra-fine particles(≤0.2 μm) were 110 and 12 ng/m3,respectively,while the chain hydrocarbon substituted organic chlorine was not detected.The developed method was applied to the determination of chlorine species concentration in the atmospheric particles.The results showed that the main chlorine species in one place of Beijing were inorganic chlorine and aromatic chlorine.
引文
1 Ramgolam K,Favez O,Cachier H,Gaudichet A,Marano F,Martinon L,Baeza-Squiban A.Particle and Fibre Toxicology,2009,6(10):1-12
2 JIN Xin,CHENG Meng-Tian,WEN Tian-Xue,TANG Gui-Qian,WANG Hui,WANG Yue-Si.Evironmental Chemistry,2012,31(6):783-790金鑫,程萌田,温天雪,唐贵谦,王辉,王跃思.环境化学,2012,31(6):783-790
3 Cho S-H,Tong H,McGee J K,Baldauf R W,Krantz Q T,Gilmour M I.Environmental Health Perspectives,2009,117(11):1682-1689
4 Venier M and Hites R A.Environmental Science&Technology,2010,44(2):618-623
5 Baek S Y,Choi S D,Lee S J and Chang Y S.Environmental Science&Technology,2008,42(19):7336-7340
6 Harner T,Shoeib M,Gouin T,Blanchard P.Environmental Science&Technology,2006,40(17):5333-5339
7 Nicholls C R,Allchin C R,Law R J.Environmental Pollution,2001,114(3):415-430
8 Holmstrand H,Gadomski D,Mandalakis M,Tysklind M,Irvine R,Andersson P,Gustafsson O.Environmental Science&Technology,2006,40(12):3730-3735
9 Shunthirasingham C,Oyiliagu C E,Cao X,Gouin T,Wania F,Lee S C,Pozo K,Harner T,Muir D C G.Journal of Envi-ronmental Monitoring,2010,12(9):1650-1657
10 Angels Olivella M,Caixach J,Pianas C,Oliveras A,Jove P.Chemosphere,2012,86(7):754-758
11 Venier M,Hites R A.Environmental Science&Technology,2010,44(2):618-623
12 Salihovic S,Lampa E,Lindstrom G,Lind L,Lind P M,van Bavel B.Environment International,2012,44:59-67
13 Siddik Cindoruk S,Tasdemir Y.Environ Pollut,2007,148(1):325-333
14 Herrera L C,Potvin M A and Melanson J E.Rapid Communications in Mass Spectrometry,2010,24(18):2745-2752
15 Roosens L,Geeraerts C,Belpaire C,Van Pelt I,Neels H,Covaci A.Environment International,2010,36(5):415-423
16 Xu D D,Dan M,Song Y,Chai Z F and Zhuang G S.Atmospheric Environment,2005,39(22):4119-4128
17 WANG Jian,WENG Jun-Jie,JIA Liang-Yuan,PAN Yang.Chinese J.Anal.Chem.,2012,40(7):1048-1052王健,翁俊桀,贾良元,潘洋.分析化学,2012,40(7):1048-1052
18 GAO Yu-Xi,FENG Wei-Yue,LI Bai,ZHANG Pei-Qun,HE Wei,HUANG Yu-Ying,CHAI Zhi-Fang.Nuclear Techniques,2004,27(3):165-169高愈希,丰伟悦,李柏,章佩群,伟何,黄宇营,柴之芳.核技术,2004,27(3):165-169
19 Golosio B,Simionovici A,Somogyi A,Camerani C,Steenari B M.Journal De Physique Iv,2003,104:647-650
20 WANG Yin-Song,LI Ai-Guo,ZHANG Yuan-Xun,XIE Ya-Ning,LI De-Lu,LI Yan,ZHANG Gui-Lin.Chinese Science Bulletin,2006,51(12):1474-1478王荫淞,李爱国,张元勋,谢亚宁,李德禄,李燕,张桂林.科学通报,2006,51(12):1474-1478
21 Pattanaik S,Huggins F E,Huffman G P,Linak W P,Miller C A.Environmental Science&Technology,2007,41(4):1104-1110
22 Myneni S C.Science,2002,295(5557):1039-1041
23 Nilsson M L,Bengtsson S,Kylin H.Environmental Pollution,2012,163:142-148
24 DAN De-Zhong.Environmental Analytical Chemistry.Beijing:Science Press,2009:20-50但德忠.环境分析化学,北京:科学出版社,2009:20-50