6 3 Vol. 6 No. 3 2015 3 Journal of Food Safety and Quality Mar., 2015 张 * 亚, 李泽仟, 刘梦娅, 刘建彬, 宋焕禄 (, 100048) 摘要 : 目的 (SPME) - 5 方法 CAR/DVB/PDMS 5 40 ml, 6 g NaCl, 80 20 min, 40 min, -, 5 (2- (MIB) 2,4,6- (2,4,6-TCA), (GSM), 2- -3- (IPMP), 2- -3- (IBMP)) 结果 : 65 μm PDMS/CAR/DVB, 30%(m/v), 60, 40 min 5 1~100 ng/l, R 2 >0.971, 1.0 1.0 0.8 1.0 1.0 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 100048, 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 :,, E-mail: songhl@th.btbu.edu.cn *Corresponding author: SONG Huan-Lu, Professor, Beijing Technology and Business University, No.11, Fucheng Road, Haidian District, Beijing 100048, China. E-mail: songhl@th.btbu.edu.cn
3, : - 5 969 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- -3- (2-isopropyl- 3-methoxypyrazine, IPMP) 2- -3- (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(2- -3- ) 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 2.3.1 样品前处理方法 20 g 5 10 mg/l, CAR/PDMS/DVB ( / / ), 40 ml, 6 g NaCl, 80 20 min,
970 6 40 min, - - 250 5 min 2.3.2 分析条件 (GC): DB-WAX(30 m 0.25 mm 0.25 μm); 40, 3 min, 5 /min 200, 10 /min 230 3 min, (He), 1.2 ml/min, 250, 14.87 psi 1:1 (MS): (electron impact, EI), 70 ev, 280, 230, 150, 3 min, m/z 55~500 2.3.3 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,, 3.1.1 萃取纤维头的选择 2 SPME, : DVB/CAR/PDMS CAR/PDMS 2 1,, 3.1.2 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% 3.1.3 萃取温度的选择,, 65 μm PDMS/CAR/DVB, 30%, 40 50 60 65 70 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
3, : - 5 971, 65 μm PDMS/DVB/CAR 2 20 30 40 50 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,, 60 3.1.4 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 3.1.5 5 种异味化合物检测结果 GC-MS 5, (MS), 100 mg/l 6, 100 50 20 10 5 1 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 28.792 195 209 197 0.998 1~100 1 IBMP 21.843 124 151 94 0.997 1~100 1 MIB 23.695 95 57 93 0.990 1~100 1 IPMP 19.324 137 152 124 0.991 1~100 1 Geosmin 29.168 112 97 207 0.971 1~100 0.8
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) 1 2 3 RSD(%) 2,4,6-TCA ND ND ND - IBMP ND ND ND - MIB 30 30 35 9 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) 80.6 90.0 165.8 94.0 2,4,6- (2,4,6-TCA) 100.2 90.0 179.5 89.3 (GSM) 24.5 20.0 42.3 91.0 2- -3- (IPMP) 16.2 20.0 30.0 85.2 2- -3- (IBMP) 22.4 20.0 39.8 88.3 1, 5 1~100 ng/l, R 2 >0.971, 1 ng/l 3.1.6 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): 2818 2828. [2] Nallanthigal Sridhara Chary, Amadeo R, Fernandez-Alba. Determination of volatile organic compounds in drinking and environmental waters [J]. Trend Anal Chem, 2012, 32: 60 75 [3] Sung YH, Li TY, Huang SD. Analysis of earthy and musty odors in water samples by solid-phase microextraction coupled with
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