Chinese Journal of Chromatography ›› 2022, Vol. 40 ›› Issue (4): 313-322.DOI: 10.3724/SP.J.1123.2021.08014
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Received:
2021-08-16
Online:
2022-04-08
Published:
2021-11-12
Contact:
WEI Dan
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CLC Number:
WEI Dan, GUO Ming. Simultaneous determination of 76 pesticide residues in the traditional Chinese medicine by magnetic hydrophilic-lipophilic-balanced materials assisted matrix solid phase dispersion extraction-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(4): 313-322.
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URL: https://www.chrom-china.com/EN/10.3724/SP.J.1123.2021.08014
No. | Analyte | CAS No. | tR/min | Precursor ion (m/z) | Product ion (m/z) | Fragment voltage/V | Collision energy/V | |
---|---|---|---|---|---|---|---|---|
1 | cyromazine (灭蝇胺) | 66215-27-8 | 1.364 | 167.0 | 85.0 | 120 | 25 | |
2 | carbendazol (多菌灵) | 10605-21-7 | 2.218 | 192.1 | 160.1 | 80 | 15 | |
3 | atraton (莠去通) | 1610-17-9 | 3.498 | 212.2 | 170.2 | 120 | 15 | |
4 | desmetryn (敌草净) | 1014-69-3 | 4.027 | 214.1 | 172.1 | 120 | 15 | |
5 | prometon (扑灭通) | 1610-18-0 | 4.067 | 226.2 | 142.0 | 120 | 20 | |
6 | terbuthylon (特丁通) | 33693-04-8 | 4.152 | 226.2 | 170.1 | 120 | 15 | |
7 | imazalil (抑霉唑) | 35554-44-0 | 4.785 | 297.0 | 159.0 | 120 | 20 | |
8 | flumazenil (除草定) | 314-40-9 | 4.804 | 261.0 | 205.0 | 80 | 10 | |
9 | cyprazine (环丙津) | 22936-86-3 | 4.915 | 228.2 | 186.1 | 120 | 15 | |
10 | ametryn (莠灭净) | 834-12-8 | 4.915 | 228.2 | 186.0 | 120 | 20 | |
11 | monuron (灭草隆) | 150-68-5 | 4.933 | 199.0 | 72.0 | 120 | 15 | |
12 | dichlorovos (敌敌畏) | 62-73-7 | 5.166 | 221.0 | 109.0 | 120 | 15 | |
13 | carbofuran (克百威) | 1563-66-2 | 5.795 | 222.3 | 165.1 | 120 | 5 | |
14 | chlorotoluron (绿麦隆) | 15545-48-9 | 6.064 | 213.1 | 72.0 | 80 | 25 | |
15 | diuron (敌草隆) | 330-54-1 | 6.256 | 233.1 | 72.0 | 120 | 20 | |
16 | fluometuron (伏草隆) | 2164-17-2 | 6.256 | 233.1 | 72.0 | 120 | 20 | |
17 | terbutryn (特丁净) | 886-50-0 | 6.263 | 242.2 | 186.1 | 120 | 15 | |
18 | phorate-sulfoxide (甲拌磷亚砜) | 3-6-2588 | 6.289 | 277.0 | 143.0 | 100 | 15 | |
19 | rabenzazol (吡咪唑) | 40341-04-6 | 6.316 | 213.2 | 172.0 | 120 | 25 | |
20 | atrazine (莠去津) | 1912-24-9 | 6.333 | 216.0 | 174.2 | 120 | 15 | |
21 | flutriafol (粉唑醇) | 76674-21-0 | 6.362 | 302.1 | 70.0 | 120 | 15 | |
22 | colophonate (噻唑硫磷) | 98886-44-3 | 6.380 | 284.1 | 228.1 | 80 | 5 | |
23 | N,N-diethyl-3-methylbenzamide (避蚊胺) | 134-62-3 | 6.637 | 192.2 | 119.0 | 100 | 15 | |
24 | fenfuram (甲呋酰胺) | 58810-48-3 | 6.640 | 282.1 | 160.2 | 120 | 20 | |
25 | metalaxyl-M (精甲霜灵) | 70630-17-0 | 6.683 | 280.1 | 192.1 | 100 | 15 | |
26 | metalaxyl (甲霜灵) | 57837-19-1 | 6.683 | 280.1 | 192.2 | 120 | 15 | |
27 | azaconazole (戊环唑) | 60207-31-0 | 6.723 | 300.1 | 231.1 | 100 | 15 | |
28 | metobromuron (溴谷隆) | 3060-89-7 | 7.036 | 259.0 | 170.1 | 80 | 15 | |
29 | methyl paraoxon (甲基对氧磷) | 311-45-5 | 7.061 | 276.2 | 220.1 | 100 | 10 | |
30 | dimethametryn (阔草净) | 22936-75-0 | 7.337 | 256.2 | 186.1 | 140 | 20 | |
31 | fensulphothion (丰索磷) | 115-90-2 | 7.357 | 309.0 | 157.1 | 120 | 25 | |
32 | metazachlor (吡唑草胺) | 67129-08-2 | 7.475 | 278.1 | 134.1 | 80 | 20 | |
33 | cotofor (杀草净) | 4147-51-7 | 7.479 | 256.1 | 144.1 | 140 | 30 | |
34 | diphenamid (双苯酰草胺) | 957-51-7 | 7.871 | 240.1 | 134.1 | 120 | 20 | |
35 | propanil (敌稗) | 709-98-8 | 8.042 | 218.0 | 162.1 | 120 | 15 | |
36 | dichlofenthion (虫线磷) | 297-97-2 | 8.045 | 249.1 | 97.0 | 80 | 30 | |
37 | propazine (扑灭津) | 139-40-2 | 8.099 | 229.9 | 146.1 | 120 | 20 | |
38 | triadimenol (三唑醇) | 55219-65-3 | 8.471 | 296.1 | 70.0 | 80 | 10 | |
39 | paclobutrazol (多效唑) | 76738-62-0 | 8.623 | 294.2 | 70.0 | 100 | 15 | |
40 | terbuthylazine (特丁津) | 5915-41-3 | 8.761 | 230.1 | 174.1 | 120 | 15 | |
41 | fenobucarb (仲丁威) | 3766-81-2 | 8.812 | 208.2 | 95.0 | 80 | 10 | |
42 | lorox (利谷隆) | 330-55-2 | 9.127 | 249.0 | 160.1 | 100 | 15 | |
43 | phenmedipham (甜菜宁) | 13684-63-4 | 9.242 | 301.1 | 168.1 | 80 | 5 | |
44 | tiancaian (甜菜胺) | 13684-56-5 | 9.276 | 301.2 | 182.1 | 80 | 5 | |
45 | flusilazole (氟硅唑) | 85509-19-9 | 10.462 | 321.1 | 119.0 | 100 | 25 | |
46 | pyriftalid (环酯草醚) | 135186-78-6 | 10.521 | 319.0 | 139.1 | 140 | 35 | |
47 | cyproconazole (环丙唑醇) | 94361-06-5 | 10.541 | 292.1 | 70.0 | 120 | 15 | |
48 | uniconazole (烯效唑) | 83657-22-1 | 10.541 | 292.1 | 70.1 | 120 | 30 | |
49 | myclobutanil (腈菌唑) | 88671-89-0 | 10.542 | 289.1 | 125.0 | 120 | 20 | |
50 | ruelene (育畜磷) | 299-86-5 | 10.717 | 292.1 | 236.0 | 120 | 20 | |
51 | ethoprophos (灭线磷) | 13194-48-4 | 10.861 | 243.1 | 173.0 | 120 | 10 | |
52 | pyridaphethione (哒嗪硫磷) | 119-12-0 | 11.608 | 341.1 | 189.2 | 120 | 20 | |
No. | Analyte | CAS No. | tR/min | Precursor ion (m/z) | Product ion (m/z) | Fragment voltage/V | Collision energy/V | |
53 | terbufos sulfone (特丁磷砜) | 56070-16-7 | 11.612 | 321.2 | 171.1 | 80 | 5 | |
54 | pretilachlor (丙草胺) | 51218-49-6 | 12.289 | 316.1 | 247.1 | 120 | 15 | |
55 | penconazole (戊菌唑) | 66246-88-6 | 12.334 | 284.1 | 70.0 | 120 | 15 | |
56 | iprobenfos (异稻瘟净) | 26087-47-8 | 12.342 | 289.1 | 91.0 | 80 | 25 | |
57 | alachlor (甲草胺) | 15972-60-8 | 12.494 | 270.2 | 238.2 | 80 | 10 | |
58 | isazofos (氯唑磷) | 42509-80-8 | 12.752 | 314.1 | 162.1 | 100 | 10 | |
59 | flutolanil (氟酰胺) | 66332-96-5 | 12.903 | 324.2 | 262.1 | 30 | 25 | |
60 | diniconazole (烯唑醇) | 83657-24-3 | 12.968 | 326.1 | 70.0 | 120 | 25 | |
61 | azinphos (嘧硫磷) | 5221-49-8 | 13.147 | 306.1 | 170.2 | 120 | 20 | |
62 | buprofezin (噻嗪酮) | 69327-76-0 | 13.347 | 306.2 | 201.0 | 120 | 15 | |
63 | diazinon (二嗪磷) | 333-41-5 | 13.470 | 311.1 | 283.0 | 100 | 10 | |
64 | mecarbam (灭蚜磷) | 2595-54-2 | 13.727 | 330.0 | 227.0 | 80 | 5 | |
65 | tebufenozide (虫酰肼) | 112410-23-8 | 13.942 | 297.0 | 133.0 | 80 | 15 | |
66 | pirimiphos-ethyl (乙嘧硫磷) | 38260-54-7 | 14.569 | 293.1 | 125.0 | 80 | 20 | |
67 | pirimiphos-methyl (甲基嘧啶磷) | 29232-93-7 | 14.592 | 306.2 | 164.0 | 120 | 20 | |
68 | cadusafos (硫线磷) | 95465-99-9 | 14.621 | 271.1 | 159.1 | 80 | 10 | |
69 | triallate (野麦畏) | 2303-17-5 | 14.860 | 305.0 | 169.1 | 160 | 20 | |
70 | fonofos (地虫硫磷) | 944-22-9 | 15.240 | 247.1 | 109.0 | 80 | 15 | |
71 | vernolate (灭草敌) | 1929-77-7 | 15.291 | 204.2 | 128.2 | 100 | 10 | |
72 | dehydro barnidipine (治螟磷) | 3689-24-5 | 15.765 | 323.0 | 171.1 | 120 | 10 | |
73 | ediphenphos (敌瘟磷) | 17109-49-8 | 16.185 | 312.1 | 252.1 | 100 | 15 | |
74 | pyrimitate (嘧啶磷) | 23505-41-1 | 17.139 | 334.2 | 198.2 | 120 | 20 | |
75 | S-bioallethrin (烯丙菊酯) | 584-79-2 | 17.284 | 303.2 | 135.1 | 60 | 10 | |
76 | tebupirimfos (丁基嘧啶磷) | 96182-53-5 | 17.425 | 319.1 | 277.1 | 120 | 10 |
Table 1 MS parameters for the 76 pesticides
No. | Analyte | CAS No. | tR/min | Precursor ion (m/z) | Product ion (m/z) | Fragment voltage/V | Collision energy/V | |
---|---|---|---|---|---|---|---|---|
1 | cyromazine (灭蝇胺) | 66215-27-8 | 1.364 | 167.0 | 85.0 | 120 | 25 | |
2 | carbendazol (多菌灵) | 10605-21-7 | 2.218 | 192.1 | 160.1 | 80 | 15 | |
3 | atraton (莠去通) | 1610-17-9 | 3.498 | 212.2 | 170.2 | 120 | 15 | |
4 | desmetryn (敌草净) | 1014-69-3 | 4.027 | 214.1 | 172.1 | 120 | 15 | |
5 | prometon (扑灭通) | 1610-18-0 | 4.067 | 226.2 | 142.0 | 120 | 20 | |
6 | terbuthylon (特丁通) | 33693-04-8 | 4.152 | 226.2 | 170.1 | 120 | 15 | |
7 | imazalil (抑霉唑) | 35554-44-0 | 4.785 | 297.0 | 159.0 | 120 | 20 | |
8 | flumazenil (除草定) | 314-40-9 | 4.804 | 261.0 | 205.0 | 80 | 10 | |
9 | cyprazine (环丙津) | 22936-86-3 | 4.915 | 228.2 | 186.1 | 120 | 15 | |
10 | ametryn (莠灭净) | 834-12-8 | 4.915 | 228.2 | 186.0 | 120 | 20 | |
11 | monuron (灭草隆) | 150-68-5 | 4.933 | 199.0 | 72.0 | 120 | 15 | |
12 | dichlorovos (敌敌畏) | 62-73-7 | 5.166 | 221.0 | 109.0 | 120 | 15 | |
13 | carbofuran (克百威) | 1563-66-2 | 5.795 | 222.3 | 165.1 | 120 | 5 | |
14 | chlorotoluron (绿麦隆) | 15545-48-9 | 6.064 | 213.1 | 72.0 | 80 | 25 | |
15 | diuron (敌草隆) | 330-54-1 | 6.256 | 233.1 | 72.0 | 120 | 20 | |
16 | fluometuron (伏草隆) | 2164-17-2 | 6.256 | 233.1 | 72.0 | 120 | 20 | |
17 | terbutryn (特丁净) | 886-50-0 | 6.263 | 242.2 | 186.1 | 120 | 15 | |
18 | phorate-sulfoxide (甲拌磷亚砜) | 3-6-2588 | 6.289 | 277.0 | 143.0 | 100 | 15 | |
19 | rabenzazol (吡咪唑) | 40341-04-6 | 6.316 | 213.2 | 172.0 | 120 | 25 | |
20 | atrazine (莠去津) | 1912-24-9 | 6.333 | 216.0 | 174.2 | 120 | 15 | |
21 | flutriafol (粉唑醇) | 76674-21-0 | 6.362 | 302.1 | 70.0 | 120 | 15 | |
22 | colophonate (噻唑硫磷) | 98886-44-3 | 6.380 | 284.1 | 228.1 | 80 | 5 | |
23 | N,N-diethyl-3-methylbenzamide (避蚊胺) | 134-62-3 | 6.637 | 192.2 | 119.0 | 100 | 15 | |
24 | fenfuram (甲呋酰胺) | 58810-48-3 | 6.640 | 282.1 | 160.2 | 120 | 20 | |
25 | metalaxyl-M (精甲霜灵) | 70630-17-0 | 6.683 | 280.1 | 192.1 | 100 | 15 | |
26 | metalaxyl (甲霜灵) | 57837-19-1 | 6.683 | 280.1 | 192.2 | 120 | 15 | |
27 | azaconazole (戊环唑) | 60207-31-0 | 6.723 | 300.1 | 231.1 | 100 | 15 | |
28 | metobromuron (溴谷隆) | 3060-89-7 | 7.036 | 259.0 | 170.1 | 80 | 15 | |
29 | methyl paraoxon (甲基对氧磷) | 311-45-5 | 7.061 | 276.2 | 220.1 | 100 | 10 | |
30 | dimethametryn (阔草净) | 22936-75-0 | 7.337 | 256.2 | 186.1 | 140 | 20 | |
31 | fensulphothion (丰索磷) | 115-90-2 | 7.357 | 309.0 | 157.1 | 120 | 25 | |
32 | metazachlor (吡唑草胺) | 67129-08-2 | 7.475 | 278.1 | 134.1 | 80 | 20 | |
33 | cotofor (杀草净) | 4147-51-7 | 7.479 | 256.1 | 144.1 | 140 | 30 | |
34 | diphenamid (双苯酰草胺) | 957-51-7 | 7.871 | 240.1 | 134.1 | 120 | 20 | |
35 | propanil (敌稗) | 709-98-8 | 8.042 | 218.0 | 162.1 | 120 | 15 | |
36 | dichlofenthion (虫线磷) | 297-97-2 | 8.045 | 249.1 | 97.0 | 80 | 30 | |
37 | propazine (扑灭津) | 139-40-2 | 8.099 | 229.9 | 146.1 | 120 | 20 | |
38 | triadimenol (三唑醇) | 55219-65-3 | 8.471 | 296.1 | 70.0 | 80 | 10 | |
39 | paclobutrazol (多效唑) | 76738-62-0 | 8.623 | 294.2 | 70.0 | 100 | 15 | |
40 | terbuthylazine (特丁津) | 5915-41-3 | 8.761 | 230.1 | 174.1 | 120 | 15 | |
41 | fenobucarb (仲丁威) | 3766-81-2 | 8.812 | 208.2 | 95.0 | 80 | 10 | |
42 | lorox (利谷隆) | 330-55-2 | 9.127 | 249.0 | 160.1 | 100 | 15 | |
43 | phenmedipham (甜菜宁) | 13684-63-4 | 9.242 | 301.1 | 168.1 | 80 | 5 | |
44 | tiancaian (甜菜胺) | 13684-56-5 | 9.276 | 301.2 | 182.1 | 80 | 5 | |
45 | flusilazole (氟硅唑) | 85509-19-9 | 10.462 | 321.1 | 119.0 | 100 | 25 | |
46 | pyriftalid (环酯草醚) | 135186-78-6 | 10.521 | 319.0 | 139.1 | 140 | 35 | |
47 | cyproconazole (环丙唑醇) | 94361-06-5 | 10.541 | 292.1 | 70.0 | 120 | 15 | |
48 | uniconazole (烯效唑) | 83657-22-1 | 10.541 | 292.1 | 70.1 | 120 | 30 | |
49 | myclobutanil (腈菌唑) | 88671-89-0 | 10.542 | 289.1 | 125.0 | 120 | 20 | |
50 | ruelene (育畜磷) | 299-86-5 | 10.717 | 292.1 | 236.0 | 120 | 20 | |
51 | ethoprophos (灭线磷) | 13194-48-4 | 10.861 | 243.1 | 173.0 | 120 | 10 | |
52 | pyridaphethione (哒嗪硫磷) | 119-12-0 | 11.608 | 341.1 | 189.2 | 120 | 20 | |
No. | Analyte | CAS No. | tR/min | Precursor ion (m/z) | Product ion (m/z) | Fragment voltage/V | Collision energy/V | |
53 | terbufos sulfone (特丁磷砜) | 56070-16-7 | 11.612 | 321.2 | 171.1 | 80 | 5 | |
54 | pretilachlor (丙草胺) | 51218-49-6 | 12.289 | 316.1 | 247.1 | 120 | 15 | |
55 | penconazole (戊菌唑) | 66246-88-6 | 12.334 | 284.1 | 70.0 | 120 | 15 | |
56 | iprobenfos (异稻瘟净) | 26087-47-8 | 12.342 | 289.1 | 91.0 | 80 | 25 | |
57 | alachlor (甲草胺) | 15972-60-8 | 12.494 | 270.2 | 238.2 | 80 | 10 | |
58 | isazofos (氯唑磷) | 42509-80-8 | 12.752 | 314.1 | 162.1 | 100 | 10 | |
59 | flutolanil (氟酰胺) | 66332-96-5 | 12.903 | 324.2 | 262.1 | 30 | 25 | |
60 | diniconazole (烯唑醇) | 83657-24-3 | 12.968 | 326.1 | 70.0 | 120 | 25 | |
61 | azinphos (嘧硫磷) | 5221-49-8 | 13.147 | 306.1 | 170.2 | 120 | 20 | |
62 | buprofezin (噻嗪酮) | 69327-76-0 | 13.347 | 306.2 | 201.0 | 120 | 15 | |
63 | diazinon (二嗪磷) | 333-41-5 | 13.470 | 311.1 | 283.0 | 100 | 10 | |
64 | mecarbam (灭蚜磷) | 2595-54-2 | 13.727 | 330.0 | 227.0 | 80 | 5 | |
65 | tebufenozide (虫酰肼) | 112410-23-8 | 13.942 | 297.0 | 133.0 | 80 | 15 | |
66 | pirimiphos-ethyl (乙嘧硫磷) | 38260-54-7 | 14.569 | 293.1 | 125.0 | 80 | 20 | |
67 | pirimiphos-methyl (甲基嘧啶磷) | 29232-93-7 | 14.592 | 306.2 | 164.0 | 120 | 20 | |
68 | cadusafos (硫线磷) | 95465-99-9 | 14.621 | 271.1 | 159.1 | 80 | 10 | |
69 | triallate (野麦畏) | 2303-17-5 | 14.860 | 305.0 | 169.1 | 160 | 20 | |
70 | fonofos (地虫硫磷) | 944-22-9 | 15.240 | 247.1 | 109.0 | 80 | 15 | |
71 | vernolate (灭草敌) | 1929-77-7 | 15.291 | 204.2 | 128.2 | 100 | 10 | |
72 | dehydro barnidipine (治螟磷) | 3689-24-5 | 15.765 | 323.0 | 171.1 | 120 | 10 | |
73 | ediphenphos (敌瘟磷) | 17109-49-8 | 16.185 | 312.1 | 252.1 | 100 | 15 | |
74 | pyrimitate (嘧啶磷) | 23505-41-1 | 17.139 | 334.2 | 198.2 | 120 | 20 | |
75 | S-bioallethrin (烯丙菊酯) | 584-79-2 | 17.284 | 303.2 | 135.1 | 60 | 10 | |
76 | tebupirimfos (丁基嘧啶磷) | 96182-53-5 | 17.425 | 319.1 | 277.1 | 120 | 10 |
Fig. 1 Characterization results for Fe3O4@PLS and Fe3O4 a. SEM micrographs; b. X-rays diffraction patterns; c. Fourier transform-infrared spectra. PLS: macroporous copolymer of divinyl benzene (DVB) and N-vinyl pyrrolidone (NVP).
Fig. 2 Effect of different extraction parameters on the recoveries of the 76 pesticides a. amount of magnetic material; b. grinding adsorption time; c. volume fraction of methanol in rinsing agent; d. type of eluent solvent; e. volume of eluent solvent; f. elution time. ME: methanol; ME-0.1% FA: methanol containing 0.1% formic acid; ACN: acetonitrile; ACN-0.1% FA: acetonitrile containing 0.1% formic acid.
Sample | Method | Adsorbent | Analytes | Amount of sample | Amount of adsorbent | LOQ | Ref. | ||
---|---|---|---|---|---|---|---|---|---|
Water | SPE-HPLC-MS/MS | Cleanrt®-PEP SPE column | 18 pesticides | 300 mL | 500 | mg | 10 | ng/L | [10] |
Bayberry | Pass-through SPE- | PRiME HLB SPE column | 29 pesticides | 5 g | 200 | mg | 6.0 | μg/kg | [11] |
UPLC-MS/MS | |||||||||
Commercial | DLLME-UPLC-MS/MS | PSA | 6 pesticides | 4 g | 1.5 | g | 0.06-0.10 | μg/kg | [13] |
herbal tea | |||||||||
Herb tea | QuECHERS-HPLC-MS/MS | C18+PSA+GCB | 77 pesticides | 2 g | 1.05 | g | 3.3-33.3 | μg/kg | [14] |
TCMs | MMSPD-HPLC-MS/MS | Fe3O4@PLS | 76 pesticides | 10 mg | 10 | mg | 1.7-20.7 | μg/kg | this work |
Table 2 Comparison of the proposed method with some other methods
Sample | Method | Adsorbent | Analytes | Amount of sample | Amount of adsorbent | LOQ | Ref. | ||
---|---|---|---|---|---|---|---|---|---|
Water | SPE-HPLC-MS/MS | Cleanrt®-PEP SPE column | 18 pesticides | 300 mL | 500 | mg | 10 | ng/L | [10] |
Bayberry | Pass-through SPE- | PRiME HLB SPE column | 29 pesticides | 5 g | 200 | mg | 6.0 | μg/kg | [11] |
UPLC-MS/MS | |||||||||
Commercial | DLLME-UPLC-MS/MS | PSA | 6 pesticides | 4 g | 1.5 | g | 0.06-0.10 | μg/kg | [13] |
herbal tea | |||||||||
Herb tea | QuECHERS-HPLC-MS/MS | C18+PSA+GCB | 77 pesticides | 2 g | 1.05 | g | 3.3-33.3 | μg/kg | [14] |
TCMs | MMSPD-HPLC-MS/MS | Fe3O4@PLS | 76 pesticides | 10 mg | 10 | mg | 1.7-20.7 | μg/kg | this work |
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