Uncertainty Evaluation for Measurements of 30 Pesticide Residues in Brassica oleracea by a QuEChERS-Gas Chromatography-Tandem Mass Spectrometry Method
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摘要: 对结球甘蓝中30种农药残留同时测定的QuEChERS-气相色谱三重四级杆串联质谱法进行不确定度评定。结果表明,30种农药在50~250 μg/L的范围内线性关系良好,回归方程相关系数在0.9966~0.9994之间,样品平均回收率在77.46%~114.92%之间,得到30种农药残留在0.05~0.25 mg/kg范围测量结果的扩展不确定度为±0.0098~±0.0606 mg/kg,为结球甘蓝最大残留量临界点附近的结果判定提供了理论依据。
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关键词:
- QuEChERS /
- 气相色谱三重四级杆串联质谱法 /
- 结球甘蓝 /
- 农药残留 /
- 不确定度
Abstract: A QuEChERS sample pretreatment method coupled with gas chromatography-tandem mass spectrometry was established to determine 30 pesticide residues in Brassica oleracea. The results show a good linear relationship for the 30 pesticides in the concentration ranges of 50~250 μg/L, with correlation coefficients between 0.9966 and 0.9994. The average recoveries of this method were in the range of 77.46%~114.92% with the expanded uncertainty between ±0.0098 and ±0.0606. It provides a theoretical basis for determining the results near the critical point of the maximum residue in B. oleracea. -
表 1 农药标准物质配制中所用玻璃量器和可调移液器引入的不确定度
Table 1. Uncertainty associated with glassware and pipette in the process of mixed pesticide reference materials
表 2 农药标准工作液配置中所用玻璃量器和可调移液器引入的不确定度
Table 2. Uncertainty associated with glassware and pipette in the process of standard work-solution
表 3 30种农药在结球甘蓝基质中的质量分析参数和线性回归方程
Table 3. Quality analysis parameters and linear regression equations of 30 pesticides in B. oleracea
编号 农药名称 化学式 CAS NO. 标准物质
原浓度μg/mL相对保
留时间峰形 定量
离子对定性
离子对线性回归方程
Y=a·X+br2 1 灭线磷 C8H19O2PS2 13194-48-4 999.5 0.74 s 322.0/294.0 322.0/202.0 Y=4.0336X-0.3474 0.9978 2 治螟磷 C8H20O5P2S2 3689-24-5 1000 0.78 s 157.8/97.0 157.8/114.0 Y=3.6647X-0.3300 0.9986 3 特丁硫磷 C9H21O2PS3 13071-79-9 1000.4 0.78
0.85ss 231.0/128.9 231.0/174.9 Y=3.6553X-0.1457 0.9981 4 α-六六六 C6H6Cl6 319-84-6 1000 0.79 s 218.9/182.9 218.9/144.9 Y=7.2987X-0.0408 0.9990 5 乐果 C5H12NO3PS2 60-51-5 1000 0.81 s 86.9/47.0 125.0/79.0 Y=3.9660X-0.3898 0.9991 6 β-六六六 C6H6Cl6 319-85-7 1000 0.82 s 218.9/182.9 218.9/144.9 Y=11.390X-0.2015 0.9994 7 γ-六六六 C6H6Cl6 58-89-9 999.6 0.83 s 218.9/182.9 218.9/144.9 Y=11.646X-0.2092 0.9991 8 嘧霉胺 C12H13N3 53112-28-0 1000.1 0.84 s 198.0/183.1 198.0/118.0 Y=8.7587X-0.1487 0.9985 9 二嗪磷 C12H21N2O3PS 333-41-5 1000 0.85 s 137.1/64.0 137.1/54.0 Y=6.1515X-0.4485 0.9990 10 δ-六六六 C6H6Cl6 319-86-8 999.6 0.86 s 218.9/182.9 218.9/144.9 Y=10.834X-0.0335 0.9990 11 乙烯菌核利 C12H9Cl2NO3 50471-44-8 1000.3 0.90 s 285.0/212.0 285.0/178.0 Y=2.5305X-0.0555 0.9988 12 甲霜灵 C15H21NO4 57837-19-1 1001.3 0.92 s 234.0/146.1 220.0/192.1 Y=4.0273X-0.1046 0.9990 13 倍硫磷 C10H15O3PS2 55-38-9 998.6 0.96
1.11ss 278.0/109.0 278.0/169.0 Y=3.1731X-0.3345 0.9981 14 毒死蜱 C9H11Cl3NO3PS 2921-88-2 1000.1 0.96 s 313.9/257.9 313.9/285.9 Y=7.1595X-0.9022 0.9991 15 三氯杀螨醇 C14H9Cl5O 115-32-2 1000.9 0.96 s 250.4/139.0 138.5/111.1 Y=3.9511X-0.3335 0.9993 16 三唑酮 C14H16ClN3O3 43121-43-3 1001.7 0.96 s 208.1/181.0 208.1/111.0 Y=6.3477X-0.5737 0.9989 环氧七氯B C10H5Cl7O 1024-57-3 100.2 1.00 s 352.8/316.9 352.8/262.9 17 腐霉利 C13H11Cl2NO2 32809-16-8 1001.6 1.02 s 283.1/96.0 283.1/66.0 Y=8.1053X-0.1385 0.9990 18 丙溴磷 C11H15BrClO3PS 41198-08-7 1000.8 1.06 s 207.9/63.0 338.8/268.7 Y=3.4557X-0.3029 0.9985 19 腈菌唑 C15H17ClN4 88671-89-0 1003 1.08 s 179.2/125.1 179.2/90.0 Y=17.868X-1.3815 0.9986 20 p,p’-滴滴伊 C14H8Cl4 72-55-9 999.6 1.08 s 246.0/176.0 246.0/211.0 Y=3.1806X-0.0970 0.9989 21 噁霜灵 C14H18N2O4 77732-09-3 1000 1.12 s 163.1/132.1 163.1/117.1 Y=11.114X-0.7019 0.9988 22 丙环唑 C15H17Cl2N3O2 60207-90-1 999.7 1.15
1.16ss 172.7/74.0 172.7/145.0 Y=14.550X-0.4316 0.9989 23 p,p’-滴滴涕 C14H9Cl5 50-29-3 999.7 1.16 s 235.0/165.0 235.0/199.0 Y=0.8983X-0.0017 0.9988 24 甲氰菊酯 C22H23NO3 39515-41-8 1000.2 1.22 s 264.9/210.0 207.9/181.0 Y=3.8120X-0.7619 0.9983 25 高效
氯氟氰菊酯C23H19ClF3NO3 91465-08-6 1000.4 1.26
1.27ss 196.9/161.0 196.9/141.0 Y=3.3438X-0.6818 0.9991 26 氯菊酯 C21H20Cl2O3 52645-53-1 1000.2 1.31
1.32ss 183.1/168.1 183.1/165.1 Y=7.9767X-0.7958 0.9990 27 蝇毒磷 C14H16ClNO5PS 56-72-4 1000.2 1.33 s 210.0/182.0 361.9/109.0 Y=3.3130X-0.6636 0.9980 28 氟氯氰菊酯 C22H18Cl2FNO3 68359-37-5 1003.8 1.36 m 199.1/170.1 226.1/206.1 Y=1.6943X-0.2698 0.9988 29 氰戊菊酯 C25H22ClNO3 51630-58-1 1000.8 1.43
1.44ss 167..0/125.1 224.9/119.0 Y=6.4967X-1.6811 0.9966 30 溴氰菊酯 C22H19Br2NO3 52918-63-5 1000 1.46 ss 250.7/172.0 252.9/93.0 Y=1.0216X-0.1686 0.9976 注:s表示1个单峰,ss表示2个单峰,m表示多重峰。 表 4 结球甘蓝中30种农药允许误差Urel(cal)
Table 4. The Urel(cal) values of 30 pesticides in B. oleracea
编号 项目
农药名称$ {\bar X}_{0} $ Xi Yi Urel(cal) X1 X2 X3 X4 X5 Y1 Y2 Y3 Y4 Y5 1 灭线磷 1.2101 0.4810 0.9750 1.4915 2.0270 2.5020 1.6355 3.5926 5.6595 7.7952 9.6872 0.0164 2 治螟磷 1.1674 0.4920 0.9647 1.4865 2.0345 2.5035 1.5165 3.2177 5.1117 7.0944 8.7899 0.0169 3 特丁硫磷 1.251 0.4840 0.9730 1.5050 2.0405 2.4835 1.5836 3.3689 5.3290 7.2953 8.9226 0.0036 4 α-六六六 1.0543 0.4995 0.9850 1.5005 2.0335 2.4825 3.5393 7.0900 10.8771 14.7755 18.0595 0.0003 5 乐果 1.6698 0.4795 0.9660 1.5255 1.9910 2.5165 1.5704 3.4660 5.6557 7.4771 9.5274 0.0147 6 β-六六六 1.3162 0.4970 0.9787 1.5025 2.0310 2.4870 5.3608 10.8545 16.8533 22.8890 28.0982 0.0023 7 γ-六六六 1.2019 0.5010 0.9793 1.5010 2.0180 2.4970 5.5115 11.0945 17.2071 23.2458 28.8496 0.0028 8 嘧霉胺 1.3243 0.4845 0.9877 1.5080 2.0345 2.4780 4.0219 8.4303 13.0143 17.6424 21.5333 0.0016 9 二嗪磷 1.2881 0.4865 0.9730 1.4970 2.0315 2.4955 2.5955 5.5472 8.7443 12.0036 14.8293 0.0167 10 δ-六六六 1.2636 0.5025 0.9803 1.5075 2.0325 2.4805 5.3206 10.5043 16.2486 21.9528 26.8177 0.0002 11 乙烯菌核利 1.3051 0.4915 0.9803 1.5000 2.0380 2.4830 1.1609 2.3997 3.7232 5.0906 6.2212 0.0008 12 甲霜灵 1.3525 0.4915 0.9790 1.5025 2.0245 2.4930 1.8311 3.7937 5.9192 8.0288 9.9246 0.0017 13 倍硫磷 1.8467 0.4830 0.9647 1.4920 2.0390 2.4980 1.2500 2.7465 4.3988 6.1086 7.5400 0.0125 14 毒死蜱 1.3517 0.4865 0.9607 1.4845 2.0175 2.5215 2.7224 6.0389 9.7299 13.4731 17.0072 0.0534 15 三氯杀螨醇 1.3879 0.4905 0.9733 1.4950 1.9960 2.5240 1.6457 3.5234 5.5661 7.5235 9.5838 0.0131 16 三唑酮 1.3001 0.4850 0.9670 1.5005 2.0265 2.5010 2.5828 5.5957 8.9440 12.2397 15.2101 0.0258 17 腐霉利 1.3336 0.4985 0.9763 1.5060 2.0295 2.4870 3.8158 7.6922 12.0143 16.2780 19.9995 0.0016 18 丙溴磷 1.4467 0.4820 0.9617 1.5140 2.0380 2.4880 1.3990 3.0302 4.9222 6.7105 8.2448 0.0119 19 腈菌唑 1.3381 0.4745 0.9767 1.5085 2.0295 2.4905 7.2632 16.0907 25.5241 34.7452 42.8876 0.0523 20 p,p’-滴滴伊 1.2919 0.5130 0.9783 1.4700 2.0120 2.5185 1.5109 2.9841 4.5434 6.2651 7.8726 0.0020 21 噁霜灵 1.3019 0.4890 0.9723 1.5025 2.0295 2.4935 4.8021 10.1099 15.9721 21.7830 26.8885 0.0226 22 丙环唑 1.3532 0.4950 0.9667 1.5270 2.0080 2.4985 6.5993 13.4663 21.6686 28.7128 35.8769 0.0077 23 p,p’-滴滴涕 1.2679 0.4935 0.9807 1.5150 2.0630 2.4540 0.4413 0.8861 1.3732 1.8723 2.2287 0 24 甲氰菊酯 1.3435 0.4740 0.9483 1.4715 2.0175 2.5395 1.1942 2.9321 4.8668 6.8783 8.8018 0.0705 25 高效氯氟氰菊酯 1.3314 0.4735 0.9517 1.4695 2.0035 2.5500 1.0345 2.5727 4.2515 5.9757 7.7387 0.0649 26 氯菊酯 1.363 0.4755 0.9823 1.4810 2.0170 2.5135 3.1148 7.0825 11.0134 15.2234 19.1260 0.0373 27 蝇毒磷 1.4527 0.4660 0.9530 1.5005 1.9680 2.5605 1.0071 2.5601 4.3187 5.8178 7.7148 0.0567 28 氟氯氰菊酯 1.3201 0.4735 0.9630 1.4820 2.0090 2.5310 0.5855 1.3893 2.2472 3.1166 3.9771 0.0203 29 氰戊菊酯 1.3165 0.4800 0.9310 1.4675 1.9720 2.5870 2.2508 5.8645 10.2811 14.3591 19.3109 0.0428 30 溴氰菊酯 1.2009 0.4860 0.9560 1.4815 1.9775 2.5585 0.3633 0.8346 1.3662 1.8658 2.4508 0.0132 表 5 样品提取和净化中所用玻璃量器和可调移液器引入的不确定度
Table 5. Uncertainty associated with glassware and pipette in the process of extraction and purification
表 6 结球甘蓝中30种农药添加测定回收率结果
Table 6. The determination P % results of 30 pesticides in B. oleracea
编号 添加水平
农药名称回收率P % Urel(rpt) 0.05 mg/kg 0.1 mg/kg 0.15 mg/kg 0.2 mg/kg 0.25 mg/kg $ {\bar p} $ 1 灭线磷 88.20 92.20 89.90 85.50 80.07 78.07 82.65 82.55 75.32 75.44 82.41 0.0216 2 治螟磷 90.20 92.60 86.00 81.30 81.93 81.07 80.45 79.55 69.36 68.32 80.79 0.0289 3 特丁硫磷 94.80 94.40 91.40 86.30 82.53 79.60 85.45 85.75 79.00 78.24 82.87 0.0248 4 α-六六六 71.40 69.60 80.60 72.40 73.73 70.20 73.70 74.05 64.68 63.08 77.46 0.0315 5 乐果 109.40 119.80 116.90 108.00 109.20 105.53 110.50 108.75 115.68 112.20 105.72 0.0217 6 β-六六六 95.60 95.60 96.80 90.00 81.33 77.47 91.25 89.25 87.40 86.44 86.67 0.0235 7 γ-六六六 82.40 81.00 89.40 81.60 79.73 76.13 84.00 83.20 76.76 75.64 80.44 0.0158 8 嘧霉胺 94.00 98.40 95.30 88.30 81.20 78.27 91.75 90.25 88.12 88.40 87.70 0.0218 9 二嗪磷 94.80 95.80 93.00 87.40 84.27 79.53 89.30 87.10 84.12 81.44 85.60 0.0209 10 δ-六六六 90.40 87.60 92.40 84.30 78.53 76.13 87.70 86.75 84.40 82.40 83.39 0.0192 11 乙烯菌核利 96.00 93.40 92.00 84.80 81.07 80.13 88.25 88.75 88.44 86.68 87.54 0.0175 12 甲霜灵 104.20 104.20 103.70 93.70 87.07 83.87 87.90 87.50 89.60 87.88 90.76 0.0276 13 倍硫磷 117.20 120.40 125.90 120.00 116.00 110.93 126.95 126.35 128.52 125.48 114.92 0.0242 14 毒死蜱 92.60 100.40 92.90 87.90 85.53 83.20 92.40 92.10 91.20 89.72 89.59 0.0163 15 三氯杀螨醇 98.00 94.80 96.50 90.70 88.40 81.67 94.15 95.20 95.00 93.20 90.23 0.0182 16 三唑酮 94.20 96.20 94.50 87.50 79.53 77.80 88.50 88.25 87.40 85.96 87.12 0.0210 17 腐霉利 99.80 98.20 94.90 87.70 83.07 79.93 89.75 89.15 91.28 88.60 90.13 0.0206 18 丙溴磷 100.20 105.80 96.70 90.70 89.40 90.20 99.85 98.40 99.28 96.88 93.99 0.0191 19 腈菌唑 100.60 102.20 98.70 92.60 81.60 78.60 89.95 89.55 90.36 88.08 87.52 0.0296 20 p,p’-滴滴伊 88.20 82.00 95.70 88.00 85.00 71.53 89.30 90.25 88.28 83.40 83.87 0.0245 21 噁霜灵 101.40 100.80 100.00 92.60 84.87 82.00 82.20 81.05 87.12 85.44 89.03 0.0279 22 丙环唑 105.20 103.60 98.00 94.00 82.33 78.80 91.00 91.35 91.28 88.88 89.28 0.0302 23 p,p’-滴滴涕 71.00 77.20 89.80 81.40 79.67 75.80 89.45 86.55 86.64 88.32 81.30 0.0246 24 甲氰菊酯 91.60 96.60 91.20 86.20 81.20 80.07 90.10 90.50 95.08 92.48 89.87 0.0183 25 高效氯氟氰菊酯 92.20 99.60 89.00 85.00 80.53 78.07 89.75 87.65 93.80 93.72 87.54 0.0228 26 氯菊酯 85.60 91.60 90.80 86.10 84.33 79.33 93.25 92.65 97.28 94.80 87.26 0.0208 27 蝇毒磷 94.80 102.80 106.00 96.20 88.80 86.67 97.10 96.00 101.12 99.80 93.78 0.0218 28 氟氯氰菊酯 97.60 100.00 92.00 87.30 78.93 79.27 87.90 85.40 92.08 91.16 86.47 0.0260 29 氰戊菊酯 93.40 99.20 86.30 82.30 76.20 74.47 86.60 86.25 96.32 95.64 85.49 0.0308 30 溴氰菊酯 85.40 86.40 86.80 77.10 70.13 72.13 80.10 76.40 85.92 83.96 80.81 0.0231 表 7 结球甘蓝中30种农药残留的合成不确定度
Table 7. The statistics on the relative standard uncertainty of 30 pesticides in B. oleracea
编号 来源农药名称 标准储备液
配制Urel(C)标准工作溶液配
制和测定Urel(S)样品前处
理Urel(R)分析仪器测
定Urel(E)合成不确定
度Urel(Z)1 灭线磷 8.73% 1.95% 2.39% 3.95% 10.07% 2 治螟磷 8.73% 2.00% 3.07% 3.95% 10.26% 3 特丁硫磷 8.73% 1.12% 2.68% 3.95% 10.01% 4 α-六六六 8.73% 1.06% 3.31% 3.95% 10.19% 5 乐果 8.73% 1.81% 2.40% 3.95% 10.04% 6 β-六六六 8.73% 1.08% 2.56% 3.95% 9.98% 7 γ-六六六 8.73% 1.10% 1.88% 3.95% 9.83% 8 嘧霉胺 8.73% 1.07% 2.41% 3.95% 9.94% 9 二嗪磷 8.73% 1.98% 2.33% 3.95% 10.06% 10 δ-六六六 8.73% 1.06% 2.18% 3.95% 9.88% 11 乙烯菌核利 8.73% 1.06% 2.03% 3.95% 9.85% 12 甲霜灵 8.73% 1.07% 2.94% 3.95% 10.08% 13 倍硫磷 8.73% 1.64% 2.63% 3.95% 10.03% 14 毒死蜱 8.73% 5.44% 1.92% 3.95% 11.18% 15 三氯杀螨醇 8.73% 1.69% 2.09% 3.95% 9.95% 16 三唑酮 8.73% 2.79% 2.34% 3.95% 10.25% 17 腐霉利 8.73% 1.07% 2.30% 3.95% 9.91% 18 丙溴磷 8.73% 1.59% 2.17% 3.95% 9.95% 19 腈菌唑 8.73% 5.34% 3.13% 3.95% 11.41% 20 p,p’-滴滴伊 8.73% 1.08% 2.66% 3.95% 10.00% 21 噁霜灵 8.73% 2.49% 2.97% 3.95% 10.29% 22 丙环唑 8.73% 1.31% 3.19% 3.95% 10.18% 23 p,p’-滴滴涕 8.73% 1.06% 2.66% 3.95% 10.00% 24 甲氰菊酯 8.73% 7.13% 2.10% 3.95% 12.13% 25 高效氯氟氰菊酯 8.73% 6.58% 2.50% 3.95% 11.89% 26 氯菊酯 8.73% 3.88% 2.32% 3.95% 10.59% 27 蝇毒磷 8.73% 5.76% 2.41% 3.95% 11.44% 28 氟氯氰菊酯 8.73% 2.29% 2.79% 3.95% 10.24% 29 氰戊菊酯 8.73% 4.41% 3.25% 3.95% 11.04% 30 溴氰菊酯 8.73% 1.69% 2.53% 3.95% 10.05% 表 8 结球甘蓝中30种农药残留的扩展不确定度
Table 8. The relative standard expanded uncertainty of 30 pesticides in B. oleracea
编号 类别
农药名称U 0.05 mg/kg 0.1 mg/kg 0.15 mg/kg 0.2 mg/kg 0.25 mg/kg 1 灭线磷 ±0.0101 ±0.0201 ±0.0302 ±0.0403 ±0.0503 2 治螟磷 ±0.0103 ±0.0205 ±0.0308 ±0.0410 ±0.0513 3 特丁硫磷 ±0.0100 ±0.0200 ±0.0300 ±0.0401 ±0.0501 4 α-六六六 ±0.0102 ±0.0204 ±0.0306 ±0.0408 ±0.0510 5 乐果 ±0.0100 ±0.0201 ±0.0301 ±0.0402 ±0.0502 6 β-六六六 ±0.0100 ±0.0200 ±0.0299 ±0.0399 ±0.0499 7 γ-六六六 ±0.0098 ±0.0197 ±0.0295 ±0.0393 ±0.0491 8 嘧霉胺 ±0.0099 ±0.0199 ±0.0298 ±0.0398 ±0.0497 9 二嗪磷 ±0.0101 ±0.0201 ±0.0302 ±0.0402 ±0.0503 10 δ-六六六 ±0.0099 ±0.0198 ±0.0297 ±0.0395 ±0.0494 11 乙烯菌核利 ±0.0099 ±0.0197 ±0.0296 ±0.0394 ±0.0493 12 甲霜灵 ±0.0101 ±0.0202 ±0.0302 ±0.0403 ±0.0504 13 倍硫磷 ±0.0100 ±0.0201 ±0.0301 ±0.0401 ±0.0501 14 毒死蜱 ±0.0112 ±0.0224 ±0.0336 ±0.0447 ±0.0559 15 三氯杀螨醇 ±0.0100 ±0.0199 ±0.0299 ±0.0398 ±0.0498 16 三唑酮 ±0.0103 ±0.0205 ±0.0308 ±0.0410 ±0.0513 17 腐霉利 ±0.0099 ±0.0198 ±0.0297 ±0.0396 ±0.0496 18 丙溴磷 ±0.0100 ±0.0199 ±0.0299 ±0.0398 ±0.0498 19 腈菌唑 ±0.0114 ±0.0228 ±0.0342 ±0.0456 ±0.0570 20 p,p’-滴滴伊 ±0.0100 ±0.0200 ±0.0300 ±0.0400 ±0.0500 21 噁霜灵 ±0.0103 ±0.0206 ±0.0309 ±0.0412 ±0.0515 22 丙环唑 ±0.0102 ±0.0204 ±0.0306 ±0.0407 ±0.0509 23 p,p’-滴滴涕 ±0.0100 ±0.0200 ±0.0300 ±0.0400 ±0.0500 24 甲氰菊酯 ±0.0121 ±0.0243 ±0.0364 ±0.0485 ±0.0606 25 高效氯氟氰菊酯 ±0.0119 ±0.0238 ±0.0357 ±0.0476 ±0.0594 26 氯菊酯 ±0.0106 ±0.0212 ±0.0318 ±0.0424 ±0.0530 27 蝇毒磷 ±0.0114 ±0.0229 ±0.0343 ±0.0457 ±0.0572 28 氟氯氰菊酯 ±0.0102 ±0.0205 ±0.0307 ±0.0410 ±0.0512 29 氰戊菊酯 ±0.0110 ±0.0221 ±0.0331 ±0.0441 ±0.0552 30 溴氰菊酯 ±0.0101 ±0.0201 ±0.0302 ±0.0402 ±0.0503 -
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