7 4 Vol. 7 No. 4 2016 4 Journal of Food Safety and Quality Apr., 2016-26 陈啟荣 *, 杨明, 梁颖, 朱琳娜, 邵鹏, 范筱京 (,, 100089) 摘要 : 目的 - 26 方法,, 结果,, 26 0.04~1.6 µg/ml 0.005~0.05 mg/kg, 0.015~0.15 mg/kg, 66.6%~125.5%, 0.3%~6.4%(n=5) 结论, 关键词 : ; ; ; Determination of 26 pesticides in tea by gas chromatography-mass spectrometry with multi-walled carbon nanotubes as solid-phase CHEN Qi-Rong *, YANG Ming, LIANG Ying, ZHU Ling-Na, SHAO Peng, FAN Xiao-Jing (Beijing Center for Physical and Chemical Analysis, Beijing Engineering Research Center of Food Safety Analysis, Beijing 100089, China) ABSTRACT: Objective To determine 26 pesticides in tea by solid-phase extraction with multi-walled carbon nanotubes and gas chromatography-mass spectrometry (GC-MS). Methods The sample was extracted with acetonitrile. After purified by multi-walled carbon nanotubes, the sample solution was detected by GC-MS. Results The established method was simple, and could reduce the pesticides decomposition in pretreatment. The calibration curves of 26 pesticides were linear in the range of 0.04~1.6 µg/ml. The limits of detection for 26 pesticides in tea were in the range of 0.005~0.05 mg/kg, and their limits of quantitation were 0.015~0.15 mg/kg. The spiked recoveries of 26 pesticides in tea sample were between 66.6% and 125.5% with relative standard deviations of 0.3%~6.4% (n=5). Conclusion The proposed method is rapid, accurate and sensitive, which is suitable for simultaneous detection of multiple pesticides. KEY WORDS: multi-walled carbon nanotubes; tea; pesticides; gas-chromatography-mass spectrometry 基金项目 : (PXM 2013_178305_000004) Fund: Supported by Beijing Financial Found Project on Creative Engineer Project (PXM 2013_178305_000004) * 通讯作者 : 啟,, E-mail: qrchen@163.com *Corresponding author: CHEN Qi-Rong, Senior Engineer, Beijing Center for Physical and Chemical Analysis, No.27, West Third Ring Road, Haidian District, Beijing 100089, China. E-mail: qrchen@163.com
4 啟, : - 26 1687 1 引言 2 材料与方法, [1], 16, 19 GB 2763-2014 [2], 0.1~20 mg/kg,, GB/T 5009.103 [3], GB/T 5009.19 [4], GB/T 23204 [5], [6-8] [9] [10] [11],,,,, C 18, π π-π,, [12-17] [16] [18,19], [20,21],,,, 26,,,, 2.1 仪器与试剂 Agilent 7890/5975C - ( ); CR22GⅢ ( Hitachi ) α- β- γ- δ- pp - op - pp - pp -, 100 µg/ml, ;, Fisher m-pfc, 10 mg 150 mg 2.2 试验方法 2.2.1 溶液配制 : 8, 0.08 0.16 0.4 0.8 1.6 µg/ml; α-, β- γ-, δ-, pp -, op -, pp -, pp -,,,,,,,,,, 18, 0.04 0.08 0.16 0.4 0.8 µg/ml 2.2.2 样品前处理 1, 200 g,,,, 2 ( ) 5.0 g( 0.001 g), 10 ml,,, 10 ml, 2, 40, 2 ml, 3,,
1688 7,, 2.2.3 气相色谱 - 质谱条件 (1) : HP-5MS (30 m 0.25 mm, 0.25 μm); : 60, 1 min, 30 /min 160, 2 min, 30 /min 300, 10 min; 280 ; :, 1.0 ml/min; (2) (EI) ; 70 ev; 230 ; 280 ;, 5 min, 1, 1 3 结果与分析 3.1 质谱条件优化,,, 26, : 60, 1 min, 30 /min 160, 2 min, 30 /min 300, 10 min; 280 ; :, 1.0 ml/min; 26,, 1 1 Fig. 1 Chromatogram of standard Table 1 表 1 被测农药的测定参数 Detection parameters of target pesticides (min) (m/z) (m/z) 1 5.533 109 145 185 220 2 5.596 94 95 141 126 3 7.524 94 95 136 142 4 11.295 121 75 97 231 5 α- 11.496 219 183 221 254 6 11.970 87 93 125 229 7 β- 12.423 219 181 254 217
4 啟, : - 26 1689 (min) (m/z) (m/z) 续表 1 8 γ- 12.617 183 219 221 254 9 δ- 13.676 219 181 183 217 10 15.781 277 109 125 260 11 16.325 314 197 258 286 12 16.811 136 230 289 13 16.926 139 141 250 252 14 pp - 20.016 318 316 246 248 15 pp - 21.589 235 237 199 165 16 op - 22.911 235 199 165 17 pp - 23.012 235 199 165 18 24.73 181 165 166 19 25.085 181 209 265 349 20 26.687 181 197 208 21 28.204, 28.467 183 163 165 255 22 29.914, 30.138, 30.229 163 152 181 23 30.269, 30.658 199 157 451 24 31.642 167 181 225 419 25 31.9, 32.043 250 181 252 26 32.748, 33.101 181 172 174 253 3.2 提取溶剂的选择 26, - - 3, -,, ;,,,, ;,, 3.3 净化条件的优化 1.0 µg/ml,,, 1~2,, 3~5 3 4 5,,, 3 3.4 精密度和准确度, 8 0.08~1.6 µg/ml, 0.04~16 µg/ml S/N=3, S/N=10, 2 5,
1690 7 0.3%~6.4%,, 5%, 0.08 0.32 0.80 mg/kg, 5,, 2, 66.6%~125.5%, 0.3%~6.4%,,,, 2, 1, 3 Table 2 表 2 农药标准溶液的回归方程及样品加标回收率 (n=5) Regression equations of standards and their recoveries at different spiked concentrations (n=5) (r 2 ) (mg/kg) (mg/kg) (mg/kg) Y=24980X-615.6 0.998 0.01 0.03 0.08, 0.32, 0.80 83.4, 81.3, 107.4 5.1, 3.8, 4.1 Y=30350X-1992 0.996 0.02 0.06 0.08, 0.32, 0.80 91.2, 102.7, 111.5 3.7, 4.0, 4.6 Y-=1728X-2.23 0.993 0.02 0.06 0.08, 0.32, 0.80 85.9, 90.9, 115.9 1.2, 0.3, 0.5 Y=23880X+145 0.999 0.01 0.03 0.08, 0.32, 0.80 98.4, 94.6, 118.3 3.9, 4.5, 4.2 α- Y=24330X-143 0.999 0.005 0.015 0.08, 0.32, 0.80 90.5, 89.9, 110.6 4.8, 3.9, 6.2 Y=5670X-170 0.991 0.02 0.06 0.08, 0.32, 0.80 84.1, 72.8, 90.9 1.5, 0.5, 1.0 β- Y=19660X-372.3 0.999 0.005 0.015 0.08, 0.32, 0.80 87.2, 86.1, 120.3 4.8, 2.8, 3.2 γ- Y=25400 X -421.6 0.999 0.005 0.015 0.08, 0.32, 0.80 88.9, 83.4, 103.5 0.8, 1.6, 2.3 δ- Y =11780 X -565.2 0.993 0.005 0.015 0.08, 0.32, 0.80 90.2, 86.1, 100.9 1.5, 0.7, 1.6 Y =4307 X -824 0.998 0.01 0.03 0.08, 0.32, 0.80 84.2, 73.9, 123.1 0.9, 1.8, 2.8 Y =12900 X -35.37 0.998 0.01 0.03 0.08, 0.32, 0.80 70.4, 66.6, 99.9 5.1, 4.0, 4.5 Y =27400 X -1.81 0.993 0.01 0.03 0.08, 0.32, 0.80 78.9, 86.1, 109.4 4.2, 3.5, 4.2 Y =77620 X -1970 0.999 0.02 0.06 0.08, 0.32, 0.80 84.1, 72, 115.7 4.2, 0.9, 5.0 pp - Y =37210 X -400.6 0.998 0.01 0.03 0.08, 0.32, 0.80 73.4, 70.3, 117.6 4.6, 3.1, 4.0 pp - Y =156500 X -4585 0.998 0.01 0.03 0.08, 0.32, 0.80 69.4, 72.5, 110.5 3.8, 4.2, 6.4 op - Y =47270 X -1424 0.995 0.01 0.03 0.08, 0.32, 0.80 81.2, 80.2, 109.9 2.9, 3.1, 5.5 pp - Y =15281 X -4215 0.996 0.01 0.03 0.08, 0.32, 0.80 79.0, 81.2, 119.2 3.1, 4.1, 3.8 Y =204500 X -6842 0.997 0.01 0.03 0.08, 0.32, 0.80 79.8, 77.6, 116.3 2.9, 3.5, 4.4 Y =28480 X -1129 0.994 0.01 0.03 0.08, 0.32, 0.80 84.9, 77.2, 106.1 2.9, 2.7, 3.5 Y =30230 X -1463 0.997 0.01 0.03 0.08, 0.32, 0.80 90.4, 88, 118.8 4.1, 2.6, 3.7 Y =17500 X -449.8 0.997 0.02 0.06 0.08, 0.32, 0.80 77.2, 85.2, 116.1 5.3, 3.4, 5.0 Y =7121 X -320.7 0.992 0.01 0.03 0.08, 0.32, 0.80 80.5, 74.1, 102.5 1.9, 2.4, 3.3 Y =19880 X -1107 0.995 0.05 0.15 0.32, 0.80 84.1, 78, 97.5 2.9, 3.1, 4.5 Y =21630 X -9869.8 0.998 0.02 0.06 0.08, 0.32, 0.80 7 1.9, 82, 125.5 1.9, 2.1, 2.4 Y =18540 X -811.8 0.999 0.05 0.15 0.32, 0.80 76.8, 87.5, 94.5 2.8, 1.6, 2.3 Y =14270 X -718.7 0.994 0.05 0.15 0.32, 0.80 82.1, 70.0, 94.7 1.9, 2.3, 1.9
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