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1 6 3 Vol. 6 No Journal of Food Safety and Quality Mar., 2015 张 * 亚, 李泽仟, 刘梦娅, 刘建彬, 宋焕禄 (, ) 摘要 : 目的 (SPME) - 5 方法 CAR/DVB/PDMS 5 40 ml, 6 g NaCl, min, 40 min, -, 5 (2- (MIB) 2,4,6- (2,4,6-TCA), (GSM), (IPMP), (IBMP)) 结果 : 65 μm PDMS/CAR/DVB, 30%(m/v), 60, 40 min 5 1~100 ng/l, R 2 >0.971, ng/l, 10% 结论,, 关键词 : ; ; - ; Detection of 5 off-flavors in drinking water by solid phase micro-extraction coupled with gas chromatography-mass spectrometry ZHANG Ya, LI Ze-Qian, LIU Meng-Ya, LIU Jian-Bin, SONG Huan-Lu * (Laboratory of Molecular Sensory Science, Beijing Technology and Business University, Beijing , China) ABSTRACT: Objective To establish a method to detect 5 kinds of trace amounts of volatile odor compounds in drinking water by solid phase micro-extraction (SPME) combined with gas chromatographymass spectrometry. Methods CAR/DVB/PDMS fiber coating was inserted in 40 ml vial with 5 kinds of standard compounds, adding 6 g NaCl, under 80 balancing 20 min, adsorbing 40 min, and 5 kinds of compounds that often causing off-flavor in drinking water, including 2-methylisoborneol (2-MIB), 2,4,6-trichloroanisole (2,4,6-TCA), trans-1,10-dimethyl-trans-9-decalol (Geosmin), 2-isopropyl-3-methoxypyrazine (IPMP) and 2-isobutyl-3-methoxypyrazine (IBMP), were detected by gas chromatography-mass spectrometry. Extraction head, salt amount, extraction temperature and extraction time and other factors were optimized. Results The optimum extraction conditions were listed as follows: 65 μm PDMS/CAR/DVB fiber head, 30% (m/v) the amount of salt, extraction temperature 60, and extraction time 40 min. The 5 kinds of odor compounds showed an excellent linear relationship between 1~100 ng/l, with the correlation coefficient more than 0.971, and the detection limits were 1.0, 1.0, 0.8, 1.0, and 1 ng/l, respectively, and the precision was less than 10%. Conclusion This method is an effective method to detect the odor of drinking water samples, with * 通讯作者 :,, [email protected] *Corresponding author: SONG Huan-Lu, Professor, Beijing Technology and Business University, No.11, Fucheng Road, Haidian District, Beijing , China. [email protected]

2 3, : low detection limit and high sensitivity. KEY WORDS: drinking water; solid phase micro-extraction; gas chromatography-mass spectrometry; off-flavor 1 引言, :,,,, ;, [1],,,,,, [2-7] ;,,,,, [8], 2- (2-methylisoborneol, 2-MIB) 2,4,6- (2,4,6-trichloroanisole, 2,4,6-TCA) (trans-1,10-dimethyl-trans-9-decalol, geosmin, GSM) (2-isopropyl- 3-methoxypyrazine, IPMP) (2-isobutyl-3-methoxypyrazine, IBMP) [1,9-11],, (solid-phase microextraction, SPME) [12-14] 20 90,, [15] 3, 2- β-, [16] 7, [6] (headspace solid-phase microextraction, HS-SPME), (flame ionization detector, FID), - (gas chromatography-mass spectrometer, GC-MS),, μg/l ng/l [17-20], (SPME) 5,,, 2 材料与方法 2.1 材料与试剂 MIB(2- ) Geosmin( ) TCA(2,4,6- ) IBMP( ) IPMP(2- -3 ) 100 mg/l, Sigma-Aldrich ; Hexanes( )>99%, ( ) ; NaCl(, ) 2.2 仪器与设备 7890A/7000B - DB-WAX(30 m 0.25 mm 0.25 μm) ( Agilent );, 65 μm CAR/DVB/PDMS ( Supelco ); (40 ml)( QEC ); (10 μl)( Agilent ); HH-1 ( ); JA5003 ( ) 2.3 实验方法 样品前处理方法 20 g 5 10 mg/l, CAR/PDMS/DVB ( / / ), 40 ml, 6 g NaCl, min,

3 min, min 分析条件 (GC): DB-WAX(30 m 0.25 mm 0.25 μm); 40, 3 min, 5 /min 200, 10 /min min, (He), 1.2 ml/min, 250, psi 1:1 (MS): (electron impact, EI), 70 ev, 280, 230, 150, 3 min, m/z 55~ 化合物鉴定, MassHunter, NIST 08, 800( 1000) 3 结果与分析 3.1 固相微萃取法萃取 5 种异味化合物 GSM( ) 2-MIB(2- ), 20 g 100 mg/l 2,, 萃取纤维头的选择 2 SPME, : DVB/CAR/PDMS CAR/PDMS 2 1,, 离子强度的选择 65 μm PDMS/CAR/DVB 0% 10% 20% 30%, 40% (m:v) NaCl, GSM( ) 2-MIB (2- ) 2,,, 30%, 40%, Duncan s multiple range test (P<0.05), 30% 40%, 30% 萃取温度的选择,, 65 μm PDMS/CAR/DVB, 30%, GSM( ) 2-MIB(2- ) 3, 5 Duncan s multiple range test (P<0.05), Fig. 1 1 MIB-GSM Result of chromatogram comparison of extraction MIB-GSM using two kinds of fiber coating

4 3, : , 65 μm PDMS/DVB/CAR min 4, 40 min 50 min Duncan s multiple range test (P<0.05),, 40 min, 40 min 2 Fig. 2 Peak area changes with amount of salt of two off-flavors 3 Fig. 3 Peak area changes with temperature of two off-flavors,, 60,, 65,, 萃取时间的选择 60 30%(m:v) NaCl 4 Fig. 4 Peak area changes with extraction time of two off-flavors 种异味化合物检测结果 GC-MS 5, (MS), 100 mg/l 6, ng/l,, GC-MS, (S/N=3) 1 Table 1 表 1 5 种嗅味物 GC/MS 参数 相关性系数 线性范围和检出限 GC/MS parameters, correlation coefficients, linear ranges, detection limits of 5 off-flavors /min QI(m/z) SI(m/z) (R 2 ) (ng/l) LOD(ng/L) 2,4,6-TCA ~100 1 IBMP ~100 1 MIB ~100 1 IPMP ~100 1 Geosmin ~

5 972 6 Table 2 表 2 异味物的检测与精密度实验 Detection and precision experiment of off-flavors / (ng/l) RSD(%) 2,4,6-TCA ND ND ND - IBMP ND ND ND - MIB IPMP ND ND ND - Geosmin ND ND ND - : 1, 2, 3, 3 Table 3 表 3 湖水样品检测结果以及回收率 (n=5) Detective results of lake water samples and recovery ( n=5) (ng/l) (ng/l) (ng/l) (%) 2- (MIB) ,4,6- (2,4,6-TCA) (GSM) (IPMP) (IBMP) , 5 1~100 ng/l, R 2 >0.971, 1 ng/l 实际样品检测,,, MIB 30 ng/l, 3.2 精密度实验, (SPME), 3, 2, RSD 10%,,,, GC-MS,, 3.3 样品分析和回收率,,, GC-MS,,, 3 4 结论 SPME, GC-MS, 5,,, SPME,,, 参考文献 [1] Susan Watson, Brian Brownlee, Trwvor Satchwill, et al. Quantitative analysis of trace levels of geosmin and mib in source and drinking water using headspace SPME [J]. Water Res, 2000, 34(10): [2] Nallanthigal Sridhara Chary, Amadeo R, Fernandez-Alba. Determination of volatile organic compounds in drinking and environmental waters [J]. Trend Anal Chem, 2012, 32: [3] Sung YH, Li TY, Huang SD. Analysis of earthy and musty odors in water samples by solid-phase microextraction coupled with

6 3, : gas chromatography/ion trap mass spectrometry [J]. Talanta, 2005, 65: [4] Yu JW, An W, Cao N, et al. Quantitative method to determine the regional drinking water odorant regulation goals based on odor sensitivity distribution: Illustrated using 2-MIB [J]. J Environ Sci, 2014, 05: 003. [5],,. LFSA -GC [J]., 2002, 15(1): 1 2. Jiang HT, Han YP, Gao TY. Off-flavor in water using LFSA-GC technology [J]. Jiangsu Environ Sci Technol, 2002, 15(1): 1 2. [6],,. HS-SPME-GC [J]., 2007, 23(2): Zhang XH, Wang ZJ, Xiang XJ. Determination of the typical odor substance using HS-SPME-GC method [J]. China W Wastewater, 2007, 23(2): [7],, [J]., 2013, 29(4): Shen F, Li R, Su XY, et al. Detection of GSM and MIB in drinking water using solid phase micro extraction combined with gas chromatography-mass chromatography [J]. Environ Monitor China, 2013, 29(4): [8] Keita Saito, Kota Okamura, Hiroyuki Kataoka. Determination of musty odorants, 2-methylisoborneol and geosmin in environmental water by headspace solid-phase microextraction and gas chromatography mass spectrometry [J]. J Chromatogr A, 2008, 1186: [9] Steven L, Jeanne ML, Paul VZ, et al. Rapid analysis of geosmin and 2-methylisoborneol in water using solid phase micro extraction procedures [J]. Water Res, 1998, 32(7): [10] Deng XW, Liang GD, Chen J, et al. Simultaneous determination of eight common odors in natural water body using automatic purge and trap coupled to gas chromatography with mass spectrometry [J]. J Chromatogr A, 2011, 1218: [11] Zhang LF, Hu RK, Yang ZG. Simultaneous picogram determination of earthy-musty odorous compounds in water using solid-phase microextraction and gas chromatography mass spectrometry coupled with initial cool programmable temperature vaporizer inlet [J]. J Chromatogr A, 2005, 1098: [12] Jorge R, Maria L, Carmen GJ, et al. Development of a solid-phase microextraction gas chromatography tandem mass spectrometry method for the analysis of chlorinated toluenes in environmental waters [J]. J Chromatogr A, 2009, 1216: [13] Chen XC, Luo Q, Yuan SG, et al. Simultaneous determination of ten taste and odor compounds in drinking water by solid-phase microextraction combined with gas chromatography-mass spectrometry [J]. J Environ Sci, 2013, 25(11): [14] Vadoud HN, Leslie B, Janusz P. Fast analysis of volatile organic compounds and disinfection by-products in drinking water using solid-phase microextraction gas chromatography/time of flight mass spectrometry [J]. J Chromatogr A, 2008, 1201: [15],,,. - - [J]., 2005, 33(8): Li L, Song LR, Gan NQ, et al. Headspace solid phase micro extraction combined with gas chromatography-mass spectrometry to detect odorous compounds in water [J]. Chin J Anal Chem, 2005, 33(8): [16],,, [J]., 2009, (6): Zhang QJ, Guo ZP, Li MZ, et al. Headspace solid phase micro extraction combined with gas chromatography-mass spectrometry to detect seven kinds of nitrosamine compounds [J]. Chin J Health Lab Technol, 2009, (6): [17] Anu M, Egil TG, Tanja L, et al. An overview of the methods used in the characterisation of natural organic matter (NOM) in relation to drinking water treatment [J]. Chemosphere, 2011, 83: [18] Antonopouloua M, Evgenidou E, Lambropoulou D, et al. A review on advanced oxidation processes for the removal of taste and odor compounds from aqueous media [J]. Water Res, 2014, 53: [19] Anu Matilainen, Mika Sillanpää. Removal of natural organic matter from drinking water by advanced oxidation processes [J]. Chemosphere, 2010, 80: [20] Rangesh S, George AS. Treatment of taste and odor causing compounds 2-methyl isoborneol and geosmin in drinking water: A critical review [J]. J Environ Sci, 2011, 23(1): 作者简介 ( 责任编辑 : 杨翠娜 ) 张亚, 硕士研究生, 主要研究方向为食品风味化学 [email protected] 宋焕禄, 教授, 主要研究方向为食品风味化学 [email protected]