顶空固相微萃取-气相色谱质谱法同时检测白酒中多种挥发性有机污染物
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摘要
目的建立白酒中33种挥发性有机污染物(VOCs)同时测定的顶空固相微萃取-气相色谱质谱检测方法。方法将白酒的酒精度稀释成12%,取7 ml放入20 ml的顶空瓶,以DVB/CAR/PDMS为萃取纤维在25℃条件下萃取10min后,在200℃的气相色谱进样口中解吸3 min,解吸出来的VOCs随1 ml/min的载气在VF-624MS毛细管柱内得到分离,并进入四级杆质谱检测。结果在优化后的顶空固相微萃取条件下,33种VOCs得到了较好的分离,各物质线性相关系数均大于0. 99,不同水平的加标回收率在81. 2%～106. 6%之间,相对标准偏差均小于9%。仪器检出限和定量限分别在0. 001μg/L～0. 101μg/L和0. 004μg/L～0. 336μg/L之间。检测发现,15个白酒样品中共检出5种VOCs,甲苯的检出率及平均浓度均最高(86. 7%,137. 45μg/L),其次为苯乙烯,其平均检出浓度为63. 12μg/L。结论该方法适用于白酒中多种VOCs的同时、灵敏、准确地测定。白酒中存在多种VOCs的污染。
Objective To develop an analytical method for simultaneous determination of 33 VOCs in white spirit by headspace solid phase micro-extraction( HS-SPME) coupled with gas chromatography-mass spectrometry( GC-MS). Methods White spirit was diluted to 12% alcohol,and then 7 ml was transferred into a 20 ml glass bottle for HS-SPME. HS-SPME conditions included extraction fiber( DVB/CAR/PDMS),extraction temperature( 25℃) and extraction time( 10 min). After extraction,DVB/CAR/PDMS fiber was inserted into the injection port of gas chromatography under conditions of 200℃ for 3min. Then the desorbed VOCs were separated by VF-624 capillary column and detected by quadrupole mass spectrometer. Results The correction coefficients of VOCs were all larger than 0. 99. The recoveries explored at different levels were between 81. 2% and 106. 6%. And the precisions were less than 9%. The limits of detection and the limits of quantitation were 0. 001 μg/L-0. 101 μg/L and 0. 004 μg/L-0. 336 μg/L,respectively. Contamination profiles of VOCs in 15 white spirits were acquired,and 5 kinds of VOCs were found. The detection rate and mean concentration of toluene were both the highest( 86. 7%,137. 45 μg/L),followed by styrene,with the mean concentration of 63. 12 μg/L. Conclusion This method is suitable for simultaneous,sensitive and accurate determination of VOCs in white spirit. There are many kinds of VOCs pollution in white spirit.
Objective To develop an analytical method for simultaneous determination of 33 VOCs in white spirit by headspace solid phase micro-extraction( HS-SPME) coupled with gas chromatography-mass spectrometry( GC-MS). Methods White spirit was diluted to 12% alcohol,and then 7 ml was transferred into a 20 ml glass bottle for HS-SPME. HS-SPME conditions included extraction fiber( DVB/CAR/PDMS),extraction temperature( 25℃) and extraction time( 10 min). After extraction,DVB/CAR/PDMS fiber was inserted into the injection port of gas chromatography under conditions of 200℃ for 3min. Then the desorbed VOCs were separated by VF-624 capillary column and detected by quadrupole mass spectrometer. Results The correction coefficients of VOCs were all larger than 0. 99. The recoveries explored at different levels were between 81. 2% and 106. 6%. And the precisions were less than 9%. The limits of detection and the limits of quantitation were 0. 001 μg/L-0. 101 μg/L and 0. 004 μg/L-0. 336 μg/L,respectively. Contamination profiles of VOCs in 15 white spirits were acquired,and 5 kinds of VOCs were found. The detection rate and mean concentration of toluene were both the highest( 86. 7%,137. 45 μg/L),followed by styrene,with the mean concentration of 63. 12 μg/L. Conclusion This method is suitable for simultaneous,sensitive and accurate determination of VOCs in white spirit. There are many kinds of VOCs pollution in white spirit.
引文
[1]中国酒业协会. 2017中国白酒行业分析[EB/OL].[2018-11-22]. http://www. cada. cc/Item/75. aspx.
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[9]黄旭锋,闫海阔,姚林江,等.吹扫捕集-快速气相色谱-质谱联用法测定水中54种挥发性有机物[J].环境工程学报,2015,9(4):2014-2020.
[10]王永华,徐福留.顶空气相色谱法测定水中挥发性有机污染物[J].湖泊科学,2010,22(6):910-915.
[11] Pino JA,Queris O. Analysis of volatile compounds of pineapple wine using solid-phase microextraction techniques[J]. Food Chemistry,2010,122(4):1241-1246.
[12] Ramirez N,Cuadras A,Rovira E,et al. Comparative study of solvent extraction and thermal desorption methods for determining a wide range of volatile organic compounds in ambient air[J]. Talanta,2010,82(2):719-727.
[13] Robinson AL,Mueller M,Heymann HA,et al. Effect of simulated shipping conditions on sensory attributes and volatile composition of commercial white and red wines[J]. American Journal of Enology andViticulture,2010,61(3):337-347.
[14] Ye NS,Zhang LQ,Gu XX. Discrimination of green teas from different geographical origins by using HS-SPME/GC-MS and pattern recognition methods[J]. Food Analytical Methods,2012,5(4):856-860.
[15] Pecoraino G,Scalici L,Avellone GA,et al. Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry(SPME/GC/MS)[J]. Water Research,2008,42(14):3563-3577.
[2] Styger G,Prior B,Bauer FF. Wine flavor and aroma[J]. Journal of Industrial Microbiology&Biotechnology,2011,38(9):1145-1159.
[3] Yucesoy D,Ozen B. Authentication of a Turkish traditional aniseed flavoured distilled spirit,raki[J]. Food Chemistry,2013,141(2):1461-1465.
[4] Metafa M, Economou A. Chemometrical development and comprehensive validation of a solid phase microextraction/gas chromatography-mass spectrometry methodology for the determination of important free and bound primary aromatics in Greek wines[J]. Journal of Chromatography A,2013,1305:244-258.
[5] Gilman JB,Lerner BM,Kuster WC,et al. Source signature of volatile organic compounds from oil and natural gas operations in northeastern Colorado[J]. Environmental Science&Technology,2013,47(3):1297-1305.
[6] Altomare DF,Di Lena M,Porcelli F,et al. Exhaled volatile organic compounds identify patients with colorectal cancer[J]. British Journal of Surgery,2013,100(1):144-151.
[7] Van Leeuwen JG,Wijma HJ,Floor RJ,et al. Directed evolution strategies for enantiocomplementary haloalkane dehalogenases:from chemical waste to enantiopure building blocks[J]. ChemBioChem,2012,13(1):137-148.
[8] Cermak JH,Stephenson GL,Birkholz DA,et al. Toxicity of petroleum hydrocarbon distillates to soil organisms[J].Environmental Toxicology and Chemistry,2010,29(12):2685-2694.
[9]黄旭锋,闫海阔,姚林江,等.吹扫捕集-快速气相色谱-质谱联用法测定水中54种挥发性有机物[J].环境工程学报,2015,9(4):2014-2020.
[10]王永华,徐福留.顶空气相色谱法测定水中挥发性有机污染物[J].湖泊科学,2010,22(6):910-915.
[11] Pino JA,Queris O. Analysis of volatile compounds of pineapple wine using solid-phase microextraction techniques[J]. Food Chemistry,2010,122(4):1241-1246.
[12] Ramirez N,Cuadras A,Rovira E,et al. Comparative study of solvent extraction and thermal desorption methods for determining a wide range of volatile organic compounds in ambient air[J]. Talanta,2010,82(2):719-727.
[13] Robinson AL,Mueller M,Heymann HA,et al. Effect of simulated shipping conditions on sensory attributes and volatile composition of commercial white and red wines[J]. American Journal of Enology andViticulture,2010,61(3):337-347.
[14] Ye NS,Zhang LQ,Gu XX. Discrimination of green teas from different geographical origins by using HS-SPME/GC-MS and pattern recognition methods[J]. Food Analytical Methods,2012,5(4):856-860.
[15] Pecoraino G,Scalici L,Avellone GA,et al. Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry(SPME/GC/MS)[J]. Water Research,2008,42(14):3563-3577.