水中磺胺类、喹诺酮类、四环素类抗生素残留的测定
图1 固相萃取方法流程
表1 流动相梯度表
步骤 | 总时间 | 流速(mL/min) | A(0.1%甲酸水溶液)% | B(甲醇)% |
1 | 0 | 0.4 | 90 | 10 |
2 | 3.50 | 0.4 | 70 | 30 |
3 | 4.50 | 0.4 | 70 | 30 |
4 | 6.40 | 0.4 | 25 | 75 |
5 | 6.50 | 0.4 | 5 | 95 |
6 | 8.20 | 0.4 | 5 | 95 |
7 | 8.21 | 0.4 | 90 | 10 |
8 | 9.50 | 0.4 | 90 | 10 |
图2 35种抗生素色谱图
图3 自来水样品谱图
图4样品加标色谱图
表2 35 种抗生素线性数据
序号 | 目标物 | 标准方程 | R2 |
1 | 磺胺甲氧哒嗪 | y=3717.132546x-3986.91331 | 0.9991 |
2 | 磺胺嘧啶 | y=10777.22676x+6.81909e4 | 0.995 |
3 | 磺胺二甲基异嘧啶 | y=20081.94273x+3.25382e5 | 0.996 |
4 | 磺胺吡啶 | y=10437.58816x+648.27812 | 0.996 |
5 | 磺胺噻唑 | y=11139.53177x-23012.14273 | 0.997 |
6 | 磺胺甲氧嘧啶 | y=11724.36084x+9.81426e4 | 0.993 |
7 | 磺胺二甲嘧啶 | y=7454.71601x+5.57874e4 | 0.9991 |
8 | 磺胺甲噻二唑 | y=7059.57922x+6.83213e4 | 0.993 |
9 | 磺胺苄氧嘧啶 | y=18311.70455x+3.91436e5 | 0.9991 |
10 | 磺胺对甲氧嘧啶 | y=4982.71401x+6090.07390 | 0.998 |
11 | 磺胺氯哒嗪 | y=11844.92493x+10815.02366 | 0.997 |
12 | 磺胺甲基异唑 | y=6838.04479x-16374.61503 | 0.996 |
13 | 磺胺间甲氧嘧啶 | y=4323.77874x+5464.06251 | 0.9991 |
14 | 磺胺异恶唑 | y=3340.45952x-6087.42436 | 0.9993 |
15 | 磺胺邻二甲氧嘧啶 | y=19800.03116x+2.20808e5 | 0.994 |
16 | 苯甲酰磺胺 | y=4905.65699x+12808.94002 | 0.998 |
17 | 磺胺苯吡唑 | y=4566.04380x+17396.37504 | 0.993 |
18 | 磺胺间二甲氧嘧啶 | y=5.55167e4x+2384.42877 | 0.995 |
19 | 磺胺喹恶啉 | y=4872.96043x-21692.49629 | 0.995 |
20 | 磺胺硝苯 | y=372.28825x+2190.77162 | 0.9992 |
21 | 磺胺氯吡嗪 | y=3429.09757x-347.31111 | 0.995 |
22 | 恶喹酸 | y=4995.27914x+981.63610 | 0.997 |
23 | 氟甲喹 | y=6924.80502x+872.70823 | 0.992 |
24 | 诺氟沙星 | y=1607.77377x-11812.39856 | 0.993 |
25 | 环丙沙星 | y=9424.46807x-22274.57193 | 0.9996 |
26 | 培氟沙星 | y=3943.01048x-3.01304e4 | 0.992 |
27 | 西诺沙星 | y=8409.86961x-8780.22485 | 0.9999 |
28 | 盐酸洛美沙星 | y=3719.92954x+4268.19484 | 0.996 |
29 | 恩喏沙星 | y=3703.37371x-6300.18486 | 0.998 |
30 | 氧氟沙星 | y=3149.46624x+900.49497 | 0.998 |
31 | 盐酸沙拉沙星 | y=10344.51319x+5.37140e4 | 0.994 |
32 | 盐酸二氟沙星 | y=2211.31423x+663.63872 | 0.993 |
33 | 萘啶酸 | y=4096.66699x+774.07341 | 0.992 |
34 | 四环素 | y=1345.50678x-8239.23361 | 0.998 |
35 | 土霉素 | y=157.65579x-1595.60701 | 0.992 |
表3 自来水加标回收率结果
化合物 | 加标浓度
| 加标回收率/% | 均值 | RSD | ||||||||
ng/L
| 1 | 2 | 3 | 4 | 5 | 6 | % | % | ||||
磺胺甲氧 | 200 | 81.4 | 85.4 | 85.4 | 77.7 | 85.9 | 95.2 | 85.2 | 6.9 | |||
磺胺嘧啶 | 200 | 88.2 | 79.5 | 88.8 | 85.8 | 87.5 | 80.6 | 85.1 | 4.7 | |||
磺胺二甲 | 200 | 85.8 | 92.5 | 85.8 | 84.5 | 81.7 | 88.5 | 86.5 | 4.3 | |||
磺胺吡啶 | 200 | 80.4 | 92.9 | 79.9 | 94.6 | 99.9 | 77.7 | 87.6 | 10.7 | |||
磺胺噻唑 | 200 | 92.3 | 91.9 | 84.8 | 87.6 | 97.3 | 98.0 | 92.0 | 5.7 | |||
磺胺甲氧 | 200 | 90.7 | 76.4 | 88.5 | 96.0 | 75.7 | 94.0 | 86.8 | 10.1 | |||
磺胺二甲 | 200 | 82.8 | 86.6 | 82.9 | 84.8 | 91.1 | 77.3 | 84.3 | 5.4 | |||
磺胺甲噻 | 200 | 86.0 | 89.3 | 86.7 | 86.7 | 91.0 | 87.8 | 87.9 | 2.1 | |||
磺胺苄氧 | 200 | 87.1 | 94.0 | 100.4 | 87.1 | 95.8 | 93.8 | 93.0 | 5.6 | |||
磺胺对甲 | 200 | 99.0 | 86.4 | 92.8 | 97.6 | 95.0 | 92.3 | 93.8 | 4.8 | |||
磺胺氯哒 | 200 | 81.9 | 81.2 | 91.0 | 88.8 | 83.8 | 85.2 | 85.3 | 4.5 | |||
磺胺甲基 | 200 | 78.5 | 94.1 | 87.6 | 91.2 | 82.6 | 86.1 | 86.7 | 6.5 | |||
磺胺间甲 | 200 | 91.7 | 83.5 | 83.8 | 83.0 | 81.6 | 85.7 | 84.9 | 4.2 | |||
磺胺异恶 | 200 | 92.3 | 83.2 | 81.4 | 81.8 | 86.1 | 87.1 | 85.3 | 4.8 | |||
磺胺邻二 | 200 | 83.0 | 87.3 | 83.9 | 77.4 | 85.4 | 79.7 | 82.8 | 4.4 | |||
苯甲酰磺 | 200 | 88.8 | 86.9 | 95.4 | 79.5 | 87.5 | 81.0 | 86.5 | 6.6 | |||
磺胺苯吡 | 200 | 87.9 | 85.2 | 79.7 | 88.3 | 87.3 | 76.6 | 84.2 | 5.8 | |||
磺胺间二 | 200 | 93.8 | 98.4 | 94.1 | 89.2 | 80.8 | 78.1 | 89.1 | 9.1 | |||
磺胺喹恶 | 200 | 83.4 | 83.0 | 85.3 | 82.9 | 81.7 | 83.2 | 83.2 | 1.4 | |||
磺胺硝苯 | 200 | 66.8 | 76.4 | 64.4 | 78.3 | 67.7 | 74.1 | 71.3 | 8.0 | |||
磺胺氯吡 | 200 | 92.7 | 95.2 | 89.5 | 88.0 | 79.8 | 82.3 | 87.9 | 6.8 | |||
恶喹酸 | 200 | 103.2 | 101.5 | 107.5 | 101.1 | 88.8 | 99.7 | 100.3 | 6.2 | |||
氟甲喹 | 200 | 69.3 | 69.1 | 74.4 | 71.3 | 71.4 | 68.3 | 70.6 | 3.2 | |||
诺氟沙星 | 200 | 99.4 | 97.8 | 84.2 | 95.9 | 95.5 | 82.4 | 92.5 | 7.9 | |||
环丙沙星 | 200 | 104.4 | 103.7 | 97.6 | 106.1 | 103.7 | 103.5 | 103.2 | 2.8 | |||
培氟沙星 | 200 | 79.8 | 96.7 | 91.6 | 96.9 | 82.1 | 84.5 | 88.6 | 8.4 | |||
西诺沙星 | 200 | 90.5 | 87.1 | 86.5 | 80.8 | 86.5 | 85.5 | 86.2 | 3.6 | |||
盐酸洛美 | 200 | 78.7 | 84.6 | 89.4 | 83.2 | 77.2 | 80.4 | 82.3 | 5.4 | |||
恩喏沙星 | 200 | 97.0 | 92.4 | 95.3 | 97.2 | 94.8 | 93.5 | 95.0 | 2.0 | |||
氧氟沙星 | 200 | 95.2 | 99.7 | 94.7 | 98.4 | 96.4 | 102.5 | 97.8 | 3.0 | |||
盐酸沙拉 | 200 | 95.0 | 94.6 | 98.9 | 93.6 | 97.0 | 98.7 | 96.3 | 2.3 | |||
盐酸二氟 | 200 | 92.9 | 105.6 | 93.8 | 103.2 | 96.0 | 102.4 | 99.0 | 5.4 | |||
萘啶酸 | 200 | 78.6 | 74.7 | 77.3 | 84.9 | 69.7 | 72.4 | 76.2 | 7.0 | |||
四环素 | 200 | 70.9 | 71.8 | 75.0 | 74.1 | 71.3 | 72.4 | 72.6 | 2.3 | |||
土霉素 | 200 | 84.3 | 86.2 | 80.0 | 85.4 | 90.1 | 90.3 | 86.1 | 4.5 |