|
由于农药数目巨多,要求对所有组分完全分离是很困难的。表5列举了使用DB5(ECD,
FTD)分析时组分的重叠图。这里有36种农药在17个重叠位置上产生完全重叠现象。在10个位置上有13种不完全分离农药。表6列举了应用
DB5(ECD, FTD)分析86种农药的流出顺序。该表也指出了当苯硫磷的保留时间被认为是30分钟时各组分对它的相对保留时间。
表5,在DB5柱上不完全分离农药一览表
|
组分
|
不完全分离农药群
|
|
A
|
B
|
C
|
D
|
E
|
F
|
G
|
H
|
I
|
J
|
K
|
L
|
M
|
N
|
O
|
P
|
Q
|
R
|
S
|
T
|
U
|
|
二嗪农
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
?-六六六
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
苯虫威
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
抗蚜威
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
噻草平
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
甲基对硫磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
胺甲萘
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
七氯
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
杀螟硫磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
灭虫威
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
禾草畏
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
虫螨磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
杀草丹
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
马拉息昂
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
艾氏剂
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
倍硫磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
毒死蜱
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
对硫磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
?-毒虫畏
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
环氧七氯
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
除草通
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
啶斑肟-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
克菌丹
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
?-毒虫畏
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氯苯氧基二甲乙基三唑乙醇
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
芬妥胺
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
喹噁磷
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
芬妥胺-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
蚜虫多
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
杨菌胺
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
扫弗特
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氧桥氯甲桥萘
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
P,p’-DDE
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
克瘟散
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
环草定
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
丙环唑-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
P,p’-滴滴涕
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
丙环唑-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氯菊酯-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
双苯三环醇-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氯菊酯-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
哒螨酮
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氯氰菊酯-3
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氯氰菊酯-4
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氟氰戊菊酯-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氟氰戊菊酯-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氟胺氰菊酯-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
氟胺氰菊酯-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
溴氰菊酯-1
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
苄草唑
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
溴氰菊酯-2
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
四溴菊酯
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
表6,在DB5柱上86种农药的相对保留时间
|
序号
|
组分
|
相对保留时间
|
序号
|
组分
|
相对保留时间
|
序号
|
组分
|
相对保留时间
|
|
1
|
甲胺磷
|
7.107
|
35
|
艾氏剂
|
21.477
|
69
|
丙环唑-2
|
28.227
|
|
2
|
敌敌畏
|
7.426
|
36
|
乙霉威
|
21.605
|
70
|
敌菌丹
|
28.847
|
|
3
|
百维灵
|
9.829
|
37
|
倍硫磷
|
21.704
|
71
|
苯硫磷
|
30.000
|
|
4
|
高灭磷
|
10.549
|
38
|
对硫磷
|
21.804
|
72
|
笛高福
|
30.242
|
|
5
|
敌百虫
|
11.143
|
39
|
毒死蜱
|
21.804
|
73
|
伏杀磷
|
31.272
|
|
6
|
异丙威
|
12.710
|
40
|
?-毒虫畏
|
23.007
|
74
|
苯噻草胺
|
31.639
|
|
7
|
丁苯威
|
14.144
|
41
|
环氧七氯
|
23.007
|
75
|
氯氟氰菊酯-1
|
31.720
|
|
8
|
灭克磷
|
14.673
|
42
|
除草通
|
23.007
|
76
|
虫螨眯
|
31.855
|
|
9
|
氯苯胺灵
|
15.011
|
43
|
啶斑肟-1
|
23.148
|
77
|
氯氟氰菊酯-2
|
32.099
|
|
10
|
噁虫威
|
15.462
|
44
|
克菌丹
|
23.229
|
78
|
双苯三唑醇-1
|
33.302
|
|
11
|
?-六氯环己烷
|
16.053
|
45
|
?-毒虫畏
|
23.348
|
79
|
双苯三唑醇-2
|
33.496
|
|
12
|
二甲硫吸磷
|
16.294
|
46
|
芬妥胺
|
23.447
|
80
|
氯菊酯-1
|
33.499
|
|
13
|
乐果
|
16.547
|
47
|
唑菌醇
|
23.447
|
81
|
氯菊酯-2
|
33.745
|
|
14
|
噻节因
|
16.903
|
48
|
喹噁磷
|
23.447
|
82
|
哒螨酮
|
33.745
|
|
15
|
?-六氯环己烷
|
17.080
|
49
|
灭满猛
|
23.764
|
83
|
抗倒胺
|
34.073
|
|
16
|
?-六氯环己烷
|
17.336
|
50
|
啶斑肟-2
|
24.159
|
84
|
氟氯氰菊酯-1
|
34.682
|
|
17
|
特丁磷
|
17.615
|
51
|
蚜虫多
|
24.159
|
85
|
氟氯氰菊酯-2
|
34.860
|
|
18
|
二嗪农
|
18.077
|
52
|
杨菌胺
|
24.159
|
86
|
氟氯氰菊酯-3
|
35.019
|
|
19
|
?-六氯环己烷
|
18.240
|
53
|
望佳多
|
24.911
|
87
|
氟氯氰菊酯-4
|
35.091
|
|
20
|
氧嘧啶磷
|
18.721
|
54
|
丙硫磷
|
25.030
|
88
|
氯氰菊酯-1
|
35.290
|
|
21
|
苯虫威
|
19.114
|
55
|
扫弗特
|
25.299
|
89
|
氯氰菊酯-2
|
35.482
|
|
22
|
抗蚜威
|
19.114
|
56
|
狄氏剂
|
25.299
|
90
|
氯氰菊酯-3
|
35.636
|
|
23
|
赛克津
|
19.583
|
57
|
P,p’-滴滴伊
|
25.299
|
91
|
氯氰菊酯-4
|
35.718
|
|
24
|
噻草平
|
19.788
|
58
|
腈菌唑
|
25.510
|
92
|
氟氰戊菊酯-1
|
35.718
|
|
25
|
甲基对硫磷
|
19.798
|
59
|
异狄氏剂
|
26.083
|
93
|
氟氰戊菊酯-2
|
36.100
|
|
26
|
胺甲萘
|
20.022
|
60
|
杀螨酯
|
26.459
|
94
|
杀灭菊酯-1
|
37.082
|
|
27
|
七氯
|
20.157
|
61
|
丰索磷
|
26.562
|
95
|
杀灭菊酯-2
|
37.495
|
|
28
|
杀螟硫磷
|
20.960
|
62
|
P,p’-滴滴涕
|
26.791
|
96
|
氟胺氰菊酯-1
|
37.495
|
|
29
|
灭虫威
|
20.960
|
63
|
O,p’-滴滴涕
|
26.925
|
97
|
氟胺氰菊酯-2
|
37.613
|
|
30
|
禾草畏
|
21.097
|
64
|
纹达克
|
7.250
|
98
|
苄草唑
|
38.138
|
|
31
|
虫螨磷
|
21.097
|
65
|
环草定
|
27.863
|
99
|
溴氰菊酯-1
|
38.138
|
|
32
|
抑菌灵
|
21.236
|
66
|
克瘟散
|
27.863
|
100
|
溴氰菊酯-2
|
38.520
|
|
33
|
杀草丹
|
21.354
|
67
|
丙环唑-1
|
27.995
|
101
|
四溴菊酯
|
38.520
|
|
34
|
马拉息昂
|
21.477
|
68
|
p,p’-滴滴涕
|
28.158
|
( 苯硫磷=30
)
|
3.1.3 DB17研究
使用中等极性的DB17(50%苯基50%聚甲基硅氧烷,与OV-17相当)分析。
应用DB17柱(30×0.25)和火焰热离子化检测器对68种农药分析的结果见图5,图B-D为A的扩展部分。进样量为1?l,组分随升温程序从
50-280℃逐一流出。同时,使用压力程序增加流出速率。图6为使用电子俘获检测器的68种农药的分析图,图B-D为A的扩展部分。进样量为1?
l,组分随梯度升温程序从50-280℃逐一流出。同时,使用压力程序增加流出速率。

色谱柱:DB17(30m×0.25,0.25?m)
载气:He(150kPa)
柱温: 50℃(1mim)→20℃/min→120℃→5℃/min→280℃
进样方式:冷柱头进样
|
检测器的温度:300℃
检测器:FTD
OCI温度:50℃(0.1mim)→150℃/min→280℃
压力程序:150kPa (1mim)→5kPa/min→350kPa |
| Fig.5 86种农药在DB17上分离FTD检测的色谱图 |

色谱柱:DB17(30m×0.25,0.25?m)
载气:He(150kPa)
柱温: 50℃(1mim)→20℃/min→120℃→5℃/min→280℃
进样方式:无分流进样(1min)
|
检测器的温度:300℃
检测器:ECD
进样温度:280℃ |
| Fig.6 86种农药在DB17上分离ECD检测的色谱图 |
由于农药数目巨多,要求对所有组分完全分离是很困难的。表7列举了使用DB17(ECD,
FTD)分析时组分的重叠图。这里有37种农药在17个重叠位置上产生完全重叠现象。在13个位置上有20种不完全分离农药。表8列举了应用
DB17(ECD, FTD)分析86种农药的出顺序。该表也指出了当苯硫磷的保留时间被认为是30分钟时各组分对它的相对保留时间。
表7,在DB17柱上不完全分离农药一览表
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组分
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不完全分离农药群
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A
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B
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C
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D
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E
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F
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G
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H
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I
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J
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K
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L
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M
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N
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O
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P
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Q
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R
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S
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T
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U
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V
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W
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丁苯威
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氯苯胺灵
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甲基乙拌磷
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特丁磷
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噁虫威
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二嗪农
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?-六六六
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