加速溶剂萃取/气相色谱-三重四极杆质谱测定土壤中8种得克隆类化合物
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摘要
建立了加速溶剂萃取(ASE)/气相色谱-三重四极串联质谱(GC-MS/MS)测定土壤中灭蚁灵、顺式得克隆、反式得克隆、得克隆602、得克隆603、得克隆604及反式得克隆脱氯产物(anti-Cl10DP、anti-Cl11DP) 8种超痕量新型高氯代阻燃剂的分析方法。样品经ASE在120℃条件下使用正己烷-丙酮(体积比1∶1)混合溶剂提取,石墨碳黑在线净化、GCB/PSA固相萃取柱进一步净化,采用质谱多反应监测(MRM)模式检测。结果显示,方法线性范围为3个数量级,8个目标物在低、中、高3个浓度水平土壤基质中的加标回收率为93. 8%～107%、84. 7%～101%、99. 0%～108%,相对标准偏差为5. 1%～13%、5. 2%～8. 3%、4. 3%～6. 6%,方法检出限为0. 17～11. 0 pg/g。将该方法应用于京杭大运河沿线部分城区、农村表层土壤中8种得克隆类化合物测定,发现顺式得克隆、反式得克隆、得克隆602和灭蚁灵4种目标物检出率较高,可达35. 0%以上,其中得克隆产地淮安市土壤中顺式得克隆和反式得克隆最高含量分别达到6. 50 ng/g和24. 4 ng/g。
An analytical method of gas chromatography-triple quadrupole mass spectrometry with accelerated solvent extraction( ASE) was established for the determination of 8 kinds of super-trace high chlorinated flame retardants dechloranes in surface soil,including mirex,syn-declorane,anti-declorane,declorane 602,declorane 603,declorane 604,anti-Cl10 DP and anti-Cl11 DP. Soil samples were extracted by ASE with hexane-acetone( 1 ∶ 1,by volume) mixed solvent at 120 ℃,then online purified with graphitized carbon black and followed by GCB/PSA solid-phase extraction column clean-up. The extract was analyzed by GC-MS/MS in MRM mode. The spike recoveries of the method for 8 target compounds in soil at low,medium and high levels ranged from 93. 8% to 107%,84. 7% to 101% and 99. 0% to 108% with the relative standard deviations of 5. 1%-13%,5. 2%-8. 3% and 4. 3%-6. 6%, respectively. The detection limits were in the range of 0. 17-11. 0 pg/g. This method was applied in the analysis on the surface soil samples from some urban and rural areas along the Beijing-Hangzhou Grande Canale. Results showed that the detection rates for 4 compounds i. e. syn-declorane,anti-declorane,declorane 602 and mirex were higher than the others,in which the highest rate reached up to 35. 0%,and the highest concentrations of syn-declorane,anti-declorane in Huai' an were 6. 50 ng/g and 24. 4 ng/g,respectively.
An analytical method of gas chromatography-triple quadrupole mass spectrometry with accelerated solvent extraction( ASE) was established for the determination of 8 kinds of super-trace high chlorinated flame retardants dechloranes in surface soil,including mirex,syn-declorane,anti-declorane,declorane 602,declorane 603,declorane 604,anti-Cl10 DP and anti-Cl11 DP. Soil samples were extracted by ASE with hexane-acetone( 1 ∶ 1,by volume) mixed solvent at 120 ℃,then online purified with graphitized carbon black and followed by GCB/PSA solid-phase extraction column clean-up. The extract was analyzed by GC-MS/MS in MRM mode. The spike recoveries of the method for 8 target compounds in soil at low,medium and high levels ranged from 93. 8% to 107%,84. 7% to 101% and 99. 0% to 108% with the relative standard deviations of 5. 1%-13%,5. 2%-8. 3% and 4. 3%-6. 6%, respectively. The detection limits were in the range of 0. 17-11. 0 pg/g. This method was applied in the analysis on the surface soil samples from some urban and rural areas along the Beijing-Hangzhou Grande Canale. Results showed that the detection rates for 4 compounds i. e. syn-declorane,anti-declorane,declorane 602 and mirex were higher than the others,in which the highest rate reached up to 35. 0%,and the highest concentrations of syn-declorane,anti-declorane in Huai' an were 6. 50 ng/g and 24. 4 ng/g,respectively.
引文
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[2] Moller A,Xie Z Y,Caba A,Sturm R,Ebinghaus R. Atmos. Environ.,2012,46:346-353.
[3] Na G S,Wei W,Zhou S Y,Gao H,Ma X D,Qiu L N,Ge L K,Bao C G,Yao Z W. J. Environ. Sci.,2015,28:8-13.
[4] Liu H H,Hu Y J,Luo P,Bao L J,Qiu J W,Leung K M Y,Zheng E Y. Environ. Sci. Technol.,2014,48:8465-8473.
[5] Cao Z G, Xu F C, Covaci A, Wu M, Wang H Z, Yu G, Wang B, Deng S B, Huang J, Wang X Y.Environ. Sci. Technol.,2014,48:8839-8846.
[6] Zhang L J,Ji F N,Li M,Cui Y B,Wu B. J. Hazard. Mater.,2014,273:239-246.
[7] Fromme H,Cequier E,Kim J T,Hanssen L,Hilger B,Thomsen C,Chang Y S,Volkel W. Environ. Int.,2015,85:292-298.
[8] Chen K H,Zheng J,Yan X,Yu L H,Luo X J,Peng X W,Yu Y J,Yang Z Y,Mai B X. Chemosphere,2015,123:43-47.
[9] Kakimoto K,Nagayoshi H,Akutsu K,Konishi Y,Kajimura K,Hayakawa K,Toriba A. Environ. Sci. Pollut. Res.,2015,22:14600-14605.
[10] Li Y,Yu L H,Wang J S,Wu J P,Mai B X,Dai J Y. Chemosphere,2013,90:2149-2156.
[11] Gong N,Shao K S,Jia H L,Zhang H,Zhao L,Jiang T,Sun Y Q. Mar. Environ. Sci.(巩宁,邵魁双,贾宏亮,张浩,赵磊,姜涛,孙野青.海洋环境科学),2013,32(5):674-678.
[12] Yan X,Zheng J,Chen K H,Yang J Z,Luo X J,Yu L H,Chen S J,Mai B X,Yang Z Y. Environ. Int.,2012,49:31-37.
[13] Shen L,Reiner E J,Helm P A,Marvin C H,Hill B,Zhang X M,Macpherson K A,Kolic T M,Tomy G T,BrindleI D. Environ. Sci. Technol.,2011,45:3333-3340.
[14] Zhang Y,Wu J P,Luo X J,Wang J,Chen S J,Mai B X. Environ. Pollut.,2011,159:3647-3652.
[15] Kang H,Moon H B,Choi K. Chemosphere,2016,146:226-232.
[16] Dou J,Jin Y J,Li Y,Wu B,Li M. Chemosphere,2015,135:462-466.
[17] Candidate List of Substances of Very High Concern for Authorisation.[2018-6-27]. https://echa. europa. eu/web/guest/candidate-list-table.
[18] Wang D G,Yang M,Qi H,Sverko E,Ma W L,Li Y F,Alaee M,Reiner E J,Shen L. Environ. Sci. Technol.,2010,44(17):6608-6613.
[19] Wang B,Iino F,Huang J,Lu Y,Yu G,Morita M. Chemosphere,2010,80:1285-1290.