超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留

陈婷; 张文; 刘光瑞; 朱仁愿; 闫君; 王行智; 戚鹏飞; 陈敏

doi:10.16801/j.issn.1008-7303.2021.0188

超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留

doi: 10.16801/j.issn.1008-7303.2021.0188

1.
兰州市食品药品检验检测研究院，甘肃省种植中药材外源性污染物监测工程研究中心，兰州 730050

基金项目: 甘肃省药品监督管理局青年科技创新项目(2020GSMPA014)；甘肃省市场监督管理局科技计划项目(SSCJG-SP-201910)；国家市场监督管理总局科技计划项目 (2021MK110)

详细信息

通讯作者:
陈婷，125731803@qq.com

中图分类号: TQ450.2；O657.72；X592
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- 被引次数: 0
出版历程
- 收稿日期: 2021-08-23
- 录用日期: 2021-10-29
- 网络出版日期: 2021-12-27
- 刊出日期: 2022-06-10

Rapid screening of 180 pesticide residues in Fructus Citri by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry

1.
Lanzhou Institute for Food and Drug Control, Gansu Engineering Research Center for Monitoring Exogenous Harmful Residues in Traditional Chinese Medicines, Lanzhou 730050, China

Funds: the Youth Science and Technology Innovation Project of the Gansu Medical Products Administration (2020GSMPA014), Science and Technology Planning Project of the Gansu Administration for Market Regulation (SSCJG-SP-201910), Science and Technology Planning Project of the State Administration for Market Regulation (2021MK110).

摘要

摘要: 建立了QuEChERS法结合超高效液相色谱-四极杆-飞行时间质谱 (UPLC-Q-TOF/MS)快速筛查香橼中180种农药多残留的方法。通过优化样品前处理净化方式及保留时间窗口、精确质量数提取窗口和绝对峰面积阈值 (peak filter)等主要检索参数，建立了精确质量数数据库和高分辨碎片离子谱图库，并对筛查方法的定性及定量结果进行了验证。结果表明：在0.005~1 mg/L质量浓度范围内，180种农药在香橼中的线性关系良好( r > 0.99)，其中96.6%的农药筛查限 (SDLs)均低于0.05 mg/kg。在0.02、0.05和0.1 mg/kg 3个添加水平下，180种农药在香橼中的平均回收率分别为58%~129%，68%~131%和66%~132%，相对标准偏差 (RSD)在0.7%~18% (n = 5)之间。该方法利用TOF-MS一级精确质荷比筛查并结合高分辨碎片质谱图确证，提高了多农药残留快速筛查的准确性，有效降低了假阳性率，对中药材香橼中农药残留的日常监测具有普遍适用性。
- 超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF/MS) /
- 香橼 /
- 农药多残留 /
- 快速筛查 /
- 中药材
Abstract: A rapid screening method for multi-residue of 180 pesticides in Fructus Citri was established by QuEChERS combined with ultra-performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry (UPLC-Q-TOF/MS). An accurate mass database and a high-resolution fragment ion spectrum library were established by optimizing the sample preparation and purification, as well as the search parameters such as the accurate mass extraction window, the retention time window and the absolute peak filter. Moreover, the qualitative and quantitative results of the proposed screening method were verified. The results showed that the linear relationship of the 180 pesticides in Fructus Citri was good within the mass concentration range of 0.005-1 mg/L (r > 0.99), and the screening detection limits (SDLs) of 96.6% of the pesticides were below 0.05 mg/kg. The average recoveries at the three spiked levels (0.02, 0.05, 0.1 mg/kg) were 58%-129%, 68%-131% and 66%-132%, respectively, and the relative standard deviation (RSD) was 0.7%-18% (n=5). Using TOF-MS first-level accurate mass-to-charge ratio screening combined with the confirmation of high-resolution fragment mass spectrometry, the proposed method significantly improved the accuracy of rapid screening for multiple pesticide residues, efficiently reduced the false positive rate, and has universal applicability in the daily monitoring of pesticide residues in Chinese medicinal materials of Fructus Citri.
- ultra-performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry /
- Fructus Citri /
- pesticide multi-residue /
- rapid screening /
- traditional Chinese medicine

HTML全文

图 1 不同净化方式对香橼中15种农药回收率的影响

Figure 1. Effects of cleanup sorbent combinations on recoveries of 15 pesticides in Fructus Citri

下载: 全尺寸图片幻灯片

图 2 不同净化方式对香橼中 15种农药响应值的影响

Figure 2. Effects of different purification methods on response values of 15 pesticides in Fructus Citri

下载: 全尺寸图片幻灯片

图 3 不同精确质量数窗口下提取乙螨唑 (m/z = 304.11322) 离子的结果

Figure 3. Extracted ion chromatogram of etoxazole at different mass width (m/z = 304.11322)

下载: 全尺寸图片幻灯片

图 4 检出样品中甲拌磷亚砜的色谱图和质谱图

Figure 4. Chromatogram and mass spectra of phorate sulfoxide in positive sample

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表 1 180种农药的保留时间、基质效应及质谱信息

Table 1. Retention times，matrix effects and mass parameters of 180 pesticides

No.	化合物 Compound	保留时间 Retention time/min	理论质量数Theoretical mass, m/z	实测质量数Measured mass, m/z	产物离子Product ion, m/z	质量数偏差Mass error/ppm	基质效应Matrix effect/%
1	涕灭威 aldicarb^*	4.75	190.0776	190.0780	116.0528, 89.0420	2.1	138
2	莠灭净 ametryn	7.05	227.1205	227.1214	186.0808, 96.0556	4.0	141
3	酰嘧磺隆 amidosulfuron	6.17	369.0413	369.0410	261.0288, 218.0230	−0.8	150
4	灭害威 aminocarb	2.33	208.1212	208.1210	152.1069, 137.0835	−1.0	123
5	环丙嘧啶醇 ancymidol	5.32	256.1212	256.1208	135.0440, 81.0447	−1.6	126
6	莠去通 atraton	4.63	211.1433	211.1430	170.1036, 100.0505	−1.4	99
7	氟氯氰菊酯 cyfluthrin	3.05	173.0468	173.0466	132.0323, 96.0556	−1.2	121
8	保棉磷 azinphos-methyl	9.63	317.0058	317.0062	132.0444, 77.0389	1.3	126
9	苯霜灵 benalaxyl	14.23	325.1678	325.1675	208.1332, 148.1120	−0.9	168
10	麦锈灵 benodanil	8.51	322.9807	322.9811	230.9301, 202.9352	1.2	135
11	地散磷 bensulide	15.32	397.0605	397.0610	218.0304, 158.0270	1.3	138
12	新燕灵 benzoylprop-ethyl	15.36	365.0586	365.0585	320.0239.105.0335	−0.3	169
13	联苯三唑醇 bitertanol	12.88	337.1790	337.1781	99.0804, 70.0399	−2.7	92
14	啶酰菌胺 boscalid	11.26	342.0327	342.0324	271.0865, 139.9898	−0.9	123
15	除草定 bromacil	4.93	260.0160	260.0155	204.9607, 161.9549	−1.9	195
16	溴丁酰草胺 bromobutide	13.92	311.0885	311.0879	194.0175, 119.0855	−1.9	138
17	乙嘧酚磺酸酯 bupirimate	12.96	316.1569	316.1555	317.1641, 272.1063	−4.4	147
18	氟丙嘧草酯 butafenacil^#	14.33	474.0806	474.0804	331.0091, 127.0753	−0.4	136
19	抑草磷 butamifos	16.62	332.0960	332.0954	152.0293, 95.9667	−1.8	133
20	唑草胺 cafenstrole	12.94	350.1413	350.1412	100.0756, 72.0443	−0.3	173
21	环丙酰菌胺 carpropamid	14.77	333.0454	333.0460	139.0309, 81.0698	1.8	107
22	萎锈灵 carboxin	6.63	235.0667	235.0666	208.0426, 143.0161	−0.4	139
23	氯草敏 chloridazon	3.74	221.0356	221.0351	193.0289, 104.0494	−2.3	122
24	氯嘧磺隆 chlorimuron-ethyl	10.92	414.0401	414.0418	186.0060, 83.0239	4.1	128
25	氯磺隆 chlorsulfuron	6.11	357.0299	357.0286	141.0770, 56.0494	−3.6	141
26	异噁草酮 clomazone	8.08	239.0713	239.0709	125.0152, 89.0385	−1.7	144
27	氯甲酰草胺 clomeprop	16.71	323.0480	323.0486	203.0025, 148.0756	1.9	123
28	氯酯磺草胺 cloransulam-methyl	7.87	429.0310	429.0317	398.0120, 306.0184	1.6	136
29	育畜磷 crufomate	10.92	291.0791	291.0784	236.0237, 108.0208	−2.4	147
30	氰草津 cyanazine	5.32	240.0890	240.0881	214.0854, 174.0540	−3.7	144
31	氰霜唑 cyazofamid	14.25	324.0448	324.0447	216.0323, 108.0113	−0.3	127
32	环莠隆 cycluron	6.55	198.1732	198.1731	111.1168, 89.0709	−0.5	134
33	环氟菌胺 cyflufenamid	16.71	412.1210	412.1211	295.0864, 241.0383	0.2	123
34	环丙津 cyprazine	6.52	227.0938	227.0935	186.0540, 108.0556	−1.3	123
35	酯菌胺 cyprofuram	7.02	279.0662	279.0668	166.0413, 69.0339	2.2	136
36	敌草净 desmetryn	5.47	213.1048	213.1052	172.0651, 82.0399	1.9	124
37	燕麦敌 diallate	16.83	269.0408	269.0413	228.0011, 128.1069	1.9	159
38	二嗪磷 diazinon	15.20	304.1011	304.1005	249.0454, 169.0793	−2.0	85
39	双氯磺草胺 diclosulam	8.35	404.9865	404.9863	314.0006, 160.9791	−0.5	132
40	苯醚甲环唑 difenoconazole	14.73	405.0647	405.0638	337.0392, 251.0025	−2.2	122
41	敌蝇威 dimetilan^*	3.94	240.1222	240.1220	196.0716, 72.0443	−0.8	163
42	二甲吩草胺 dimethenamid	9.81	275.0747	275.0745	244.0557, 168.0841	−0.7	134
43	双苯酰草胺 diphenamid	8.08	239.1310	239.1313	167.0855, 134.0964	1.3	129
44	肼菌酮 drazoxolon	12.33	237.0305	237.0304	220.0272, 177.0214	−0.4	170
45	氟环唑 epoxiconazole	11.36	329.0731	329.0725	121.0448, 70.0399	−1.8	54
46	戊草丹 esprocarb	17.32	265.1500	265.1504	196.0791, 91.0542	1.5	173
47	甲基胺苯磺隆 ethametsulfuron-methyl	6.53	410.1009	410.1002	196.0829, 142.0723	−1.7	127
48	乙硫苯威砜 ethiofencarb-sulfone	3.60	257.0722	257.0715	107.0491, 77.0385	−2.7	142
49	乙硫苯威亚砜 ethiofencarb-sulfoxide	3.28	241.0773	241.0769	107.0491, 77.0385	−1.7	158
50	乙螨唑 etoxazole	18.28	359.1697	359.1700	304.1132, 141.0146	0.8	149
51	乙嘧硫磷 etrimfos	14.74	292.0647	292.0655	164.0468, 124.9820	2.7	136
52	伐灭磷 famphur	9.53	325.0208	325.0214	280.9701, 217.0082	1.8	130
53	咪唑菌酮 fenamidone	11.04	311.1092	311.1088	236.1182, 165.0481	−1.3	153
54	喹螨醚 fenazaquin	18.55	306.1732	306.1725	161.1324, 105.0698	−2.3	129
55	甲呋酰胺 fenfuram	6.85	201.0790	201.0791	109.0284, 83.0491	0.5	126
56	环酰菌胺 fenhexamid	11.27	301.0636	301.0633	142.0054, 97.1011	−1.0	123
57	苯硫威 fenothiocarb	13.00	253.1137	253.1128	160.0790, 106.0321	−3.6	134
58	噁唑禾草灵 fenoxaprop-ethyl	16.77	361.0717	361.0715	288.0422, 121.0647	−0.6	160
59	苯氧威 fenoxycarb	13.13	301.1314	301.1318	256.0968, 211.0753	1.3	193
60	双氟磺草胺 florasulam	5.99	359.0300	359.0305	296.0753, 129.0384	1.4	207
61	氟环脲 flucycloxuron	17.90	483.1161	483.1165	289.0783, 132.0443	0.8	156
62	氟噻草胺 flufenacet	13.24	363.0665	363.0660	194.0975, 152.0506	−1.4	80
63	氟甲喹 flumequine	5.74	261.0801	261.0809	244.0768, 202.0287	3.1	294
64	唑嘧磺草胺 flumetsulam	4.23	325.0445	325.0440	262.0898, 129.0384	−1.5	143
65	氟吡菌酰胺 fluopyram	12.44	396.0464	396.0470	208.1353, 173.0208	1.5	240
66	乙羧氟草醚 fluoroglycofen-ethyl^#	17.26	447.0333	447.0339	343.9931, 300.0033	1.3	152
67	氟喹唑 fluquinconazole	11.62	375.0090	375.0089	349.0053, 306.9835	−0.3	134
68	氟咯草酮 flurochloridone	13.15	311.0092	311.0088	292.0101, 240.0630	−1.3	221
69	呋嘧醇 flurprimidol	9.70	312.1086	312.1090	270.0610, 185.0709	1.3	86
70	氟硅唑 flusilazole	12.48	315.1003	315.1004	247.0749, 165.0696	0.3	148
71	氟酰胺 flutolanil	13.08	323.1133	323.1139	262.0662, 173.0197	1.9	86
72	粉唑醇 flutriafol	6.53	301.1027	301.1022	233.0772, 123.0238	−1.7	167
73	氟唑菌酰胺 fluxapyroxad	11.70	381.0901	381.0910	362.0910, 234.0525	2.4	184
74	甲酰氨基嘧磺隆 foramsulfuron	5.12	452.1114	452.1116	255.0427, 182.0560	0.4	145
75	麦穗宁 fuberidazole	3.21	184.0637	184.0633	157.0760, 130.0651	−2.2	149
76	呋霜灵 furalaxyl	9.51	301.1314	301.1310	242.1175, 95.0127	−1.3	178
77	呋线威 furathiocarb	17.43	382.1562	382.1561	252.0682, 195.0474	−0.3	210
78	氯吡嘧磺隆 halosulfuron-methyl	10.01	434.0412	434.0413	221.9729, 182.0560	0.2	137
79	氟吡乙禾灵 haloxyfop-2-ethoxyethyl	17.21	433.0904	433.0908	316.0346, 117.0910	0.9	130
80	氟吡甲禾灵 haloxyfop-methyl	16.41	375.0485	375.0482	316.0346, 272.0084	−0.8	205
81	氯虫酰肼 halofenozide^*	10.64	330.1135	330.1138	138.9945, 105.0334	0.9	123
82	环嗪酮 hexazinone	4.78	252.1586	252.1587	171.0876, 101.0345	0.4	147
83	咪草酸 imazamethabenz-methyl	4.97	288.1474	288.1473	215.0815, 144.0443	−0.3	136
84	亚胺唑 imibenconazole	16.59	409.9927	409.9914	341.9672, 171.0029	−3.2	46
85	唑吡嘧磺隆 imazosulfuron	7.97	412.0357	412.0359	257.9734, 156.0767	0.5	128
86	抗倒胺 inabenfide	7.99	338.0822	338.0820	321.0789, 214.0418	−0.6	123
87	异菌脲 iprodione	12.53	329.0334	329.0337	244.9879, 161.9871	0.9	216
88	丁嗪草酮 isomethiozin	13.53	268.1358	268.1360	200.0852, 130.0433	0.7	188
89	稻瘟灵 isoprothiolane	12.42	290.0647	290.0644	231.0144, 188.9674	−1.0	137
90	异柳磷 isofenphos^*	16.65	345.1164	345.1163	216.9712, 121.0284	−0.3	125
91	异丙隆 isoproturon	6.81	206.1419	206.1415	165.1022, 72.0443	−1.9	153
92	异噁唑草酮 isoxaflutole	4.47	359.0439	359.0440	250.9984, 219.9800	0.3	145
93	特胺灵 karbutilate	5.69	279.1583	279.1581	224.1029, 181.0971	−0.7	132
94	苯噻酰草胺 mefenacet	11.09	298.0776	298.0778	192.0081, 148.0756	0.7	121
95	嘧菌胺 mepanipyrim	11.69	223.1110	223.1117	182.0838, 106.0651	3.1	97
96	灭锈胺 mepronil	12.41	269.1416	269.1412	228.1019, 119.0491	−1.5	203
97	甲霜灵 metalaxyl	6.84	279.1471	279.1478	160.1120, 105.0698	2.5	144
98	甲基苯噻隆 methabenzthiazuron	6.07	221.0623	221.0619	165.0481, 150.0246	−1.8	137
99	甲氧丙净 methoprotryne	6.92	271.1467	271.1469	240.1277, 198.0808	0.7	289
100	溴谷隆 metobromuron	7.20	258.0004	258.0007	227.9892, 169.9599	1.2	57
101	嗪草酮 metribuzin	5.40	214.0888	214.0884	187.1012, 84.0807	−1.9	135
102	绿谷隆 monolinuron	6.74	214.0509	214.0506	183.0319, 126.0100	−1.4	147
103	灭草隆 monuron	5.07	198.0560	198.0569	154.0054, 72.0443	4.5	193
104	腈菌唑 myclobutanil	10.75	288.1142	288.1146	220.0887, 125.0152	1.4	134
105	萘乙酰胺1-naphthyl acetamide	4.57	185.0841	185.0842	141.0699, 115.0542	0.5	90
106	草不隆 neburon	13.32	274.0640	274.0638	187.9664, 88.1120	−0.7	155
107	呋酰胺 ofurace	6.82	281.0819	281.0811	160.1120, 121.0886	−2.8	137
108	坪草丹 orbencarb	14.99	257.0641	257.0639	125.0125, 72.0443	−0.8	136
109	噁霜灵 oxadixyl	5.13	278.1267	278.1266	219.1128, 133.0859	−0.4	62
110	氧化萎锈灵 oxycarboxin	4.54	267.0565	267.0563	175.0059, 83.0127	−0.7	150
111	克草敌 pebulate	15.47	203.1344	203.1347	176.1467, 128.1069	1.5	146
112	五氟磺草胺 penoxsulam	8.15	483.0636	483.0633	326.0872, 195.0750	−0.6	141
113	甲拌磷 phorate	15.79	260.0128	260.0125	142.9384, 75.0263	−1.2	128
114	甲拌磷砜 phorate-Sulfone	8.65	292.0027	292.0033	199.0010, 142.9384	2.2	138
115	甲拌磷亚砜 phorate-Sulfoxide	6.37	276.0077	276.0069	142.9384, 96.9507	−3.0	130
116	氟吡酰草胺 picolinafen	17.18	376.0835	376.0822	238.0462, 145.0259	−3.5	163
117	甲基氟嘧磺隆 primisulfuron-methyl	12.07	468.0363	468.0366	254.0178, 199.0052	0.6	134
118	猛杀威 promecarb	9.93	207.1259	207.1254	151.1117, 109.0647	−2.4	145
119	扑灭通 prometon	5.68	225.1590	225.1593	184.1192, 142.0723	1.3	197
120	扑草净 prometryn	9.25	241.1361	241.1366	200.0964, 158.0495	2.1	174
121	噁草酸 propaquizafop	17.06	443.1248	443.1252	371.0793, 100.0756	0.9	168
122	扑灭津 propazine	8.24	229.1094	229.1093	188.0697, 146.0228	−0.4	170
123	异丙草胺 propisochlor	14.47	283.1339	283.1341	224.0831, 148.1120	0.7	178
124	炔苯酰草胺 propyzamide	11.22	255.0218	255.0211	189.9821, 144.9606	−2.7	197
125	丙氧喹啉 proquinazid	18.43	372.0335	372.0327	330.9938, 288.9382	−2.2	157
126	苄草丹 prosulfocarb	16.67	251.1344	251.1350	128.1069, 91.0542	2.4	138
127	丙硫菌唑 prothioconazole	12.53	343.0313	343.0314	326.0280, 290.0513	0.3	127
128	发硫磷 prothoate	7.97	285.0622	285.0628	142.9384, 96.9507	2.1	141
129	吡唑硫磷 pyraclofos	14.83	360.0464	360.0466	256.9874, 195.0314	0.6	161
130	吡草醚 pyraflufen-ethyl	15.15	412.0205	412.0202	338.9898, 253.0163	−0.7	145
131	唑菌酯 pyraoxystrobin	15.07	205.0859	205.0852	145.0647, 117.0698	−3.4	141
132	磺酰草吡唑 pyrasulfotole	4.34	362.0548	362.0554	250.9984, 113.0709	1.7	139
133	苄草唑 pyrazoxyfen	14.06	402.0538	402.0540	403.0610, 105.0334	0.5	168
134	吡嘧磺隆 pyrazosulfuron-ethyl	9.83	414.0958	414.0954	182.0560, 139.0652	−1.0	105
135	哒嗪硫磷 pyridaphenthion	11.76	340.0647	340.0649	285.0090, 189.0658	0.6	140
136	环酯草醚 pyriftalid	10.68	318.0674	318.0677	269.0379, 179.0161	0.9	153
137	嘧霉胺 pyrimethanil	7.85	199.1110	199.1108	143.0603, 107.0603	−1.0	195
138	嘧硫磷 pyrimitate	14.90	305.0963	305.0966	154.0974, 96.9507	1.0	98
139	吡丙醚 pyriproxyfen	17.59	321.1365	321.1364	185.0597, 96.0443	−0.3	125
140	喹硫磷 quinalphos	14.13	298.0541	298.0537	242.9985, 96.9508	−1.4	103
141	喹氧灵 quinoxyfen	16.93	306.9967	306.9961	272.0272, 196.9788	−2.0	92
142	乙基喹禾灵 quizalofop-ethyl	16.76	372.0877	372.0871	299.0577, 91.0542	−1.6	133
143	吡咪唑 rabenzazole	6.61	212.1062	212.1068	172.0863, 118.0525	2.8	124
144	另丁津 sebuthylazine	8.07	229.1094	229.1091	174.0540, 132.0323	−1.3	272
145	仲丁通 secbumeton	5.60	225.1590	225.1587	170.1036, 142.0723	−1.3	153
146	去乙基另丁津 sebuthylazine-desethyl	4.59	201.0781	201.0782	146.0228, 104.0010	0.5	90
147	西玛津 simazine	5.11	201.0781	201.0788	174.0540, 124.0869	3.5	162
148	西玛通 simeton	3.69	197.1277	197.1275	170.1036, 128.0818	−1.0	142
149	西草净 simetryn	5.53	213.1048	213.1044	124.0868, 96.0556	−1.9	174
150	螺螨酯 spirodiclofen	19.08	410.1052	410.1058	313.0392, 71.0855	1.5	145
151	螺虫乙酯 spirotetramat	10.48	373.1889	373.1885	302.1751, 216.0990	−1.1	137
152	菜草畏 sulfallate	14.77	223.0256	223.0255	188.0562, 116.0528	−0.4	173
153	氟啶虫胺腈 sulfoxaflor	4.68	277.0497	277.0499	174.0524, 105.0117	0.7	135
154	硫丙磷 sulprofos	18.11	322.0285	322.0288	218.9697, 139.0212	0.9	144
155	吡螨胺 tebufenpyrad	16.79	333.1608	333.1610	278.1054, 147.1168	0.6	136
156	牧草胺 tebutam	12.54	233.1780	233.1782	192.1382, 91.0542	0.9	167
157	丁噻隆 tebuthiuron	4.66	228.1045	228.1044	172.0903, 116.0276	−0.4	157
158	双硫磷 temephos^#	17.85	465.9897	465.9899	341.0065, 124.9820	0.4	162
159	特草灵 terbucarb	15.93	277.2042	277.2048	222.1488, 166.0862	2.2	142
160	特丁通 terbumeton	5.94	225.1590	225.1597	170.1036, 142.0723	3.1	129
161	氧特丁硫磷砜 terbufos-oxon-sulfone	5.29	304.0568	304.0556	174.9283, 109.0049	−3.9	127
162	特丁津 terbuthylazine	8.94	229.1094	229.1088	174.0540, 132.0323	−2.6	136
163	杀虫威 tetrachlorvinphos	12.81	363.8993	363.8988	238.8982, 127.0155	−1.4	130
164	四氟醚唑 tetraconazole	11.97	371.0215	371.0211	184.9919, 158.9762	−1.1	143
165	噻吩草胺 thenylchlor	13.11	323.0747	323.0745	288.1053, 127.0212	−0.6	172
166	噻氟隆 thiazafluron	5.21	240.0293	240.0299	184.0150, 74.0059	2.5	139
167	禾草丹 thiobencarb	15.32	257.0641	257.0643	125.0152, 72.0443	0.8	133
168	硫双威 thiodicarb	5.89	354.0490	354.0485	107.9902, 88.0188	−1.4	135
169	虫线磷 thionazin	8.24	248.0385	248.0387	192.9831, 153.0133	0.8	129
170	仲草丹 tiocarbazil	18.40	279.1657	279.1662	224.1103, 91.0542	1.8	150
171	甲基立枯磷 tolclofos-mehyl	15.79	299.9544	299.9548	174.9710, 124.9820	1.3	68
172	唑虫酰胺 tolfenpyrad	17.04	383.1401	383.1411	197.0960, 145.0527	2.6	139
173	抑芽唑 triapenthenol	11.56	263.1998	263.1995	109.1011, 70.0399	−1.1	133
174	醚苯磺隆 triasulfuron	6.16	401.0561	401.0560	218.9858, 167.0536	−0.2	133
175	草达津 trietazine	11.61	229.1094	229.1091	202.0854, 132.0323	−1.3	134
176	氟菌唑 triflumizole	15.17	345.0856	345.0857	278.0553, 73.0647	0.3	154
177	氟胺磺隆 triflusulfuron-methyl	12.08	492.1039	492.1046	264.0698, 238.0907	1.4	200
178	3,4,5-混杀威 3,4,5-trimethacarb	7.37	193.1103	193.1109	137.0961, 122.0726	3.1	116
179	烯效唑 uniconazole	10.73	291.1138	291.1139	125.0152, 70.0399	0.3	139
180	苯酰菌胺 zoxamide	15.09	335.0247	335.0241	186.9711, 158.9762	−1.8	126
注：加合离子形式中，^表示[M + Na]⁺；^#表示[M + NH₄]⁺；未标注的表示[M + H]⁺。Note: Adduct ion form, ^means[M + Na]⁺; ^#means [M + NH₄]⁺; not marked means [M + H]⁺.

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表 2 香橼样品定性筛查结果

Table 2. Qualitative screening results of Fructus Citri sample

No.	化合物 Compound	理论质量数 Theoretical mass, m/z	质量数偏差 Mass error/ppm	保留时间 Retention time/min	保留时间偏差 Retention time error/min	匹配得分 Score
1	环莠隆 cycluron	198.17321	1.51	6.676	−0.182	83.85
2	氟甲喹 flumequine	261.08012	−5.31	5.786	0.219	60.77
3	氟氯氰菊酯 cyfluthrin	215.09377	3.6	6.53	−0.036	73.46
4	西玛津 simazine	201.07812	0.49	5.123	0.089	56.39
5	灭害威 aminocarb	208.12118	1.09	2.204	0.138	56.91
6	苯醚甲环唑 difenoconazole	405.0647	−2.01	14.817	0.009	95.44
7	氟环唑 epoxiconazole	329.07312	−3.82	11.491	−0.17	54.81
8	甲拌磷砜 phorate-Sulfone	292.00266	−4.93	8.647	0.006	91.53
9	甲拌磷亚砜 phorate-sulfoxide	276.00774	−2.67	6.366	−0.109	80.49

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表 3 实际样品检测结果

Table 3. Sample test results

样品序号 Sample No.	检出农药 Detected pesticide	残留量 Residue/(mg/kg)		相对误差 Relative error/%
样品序号 Sample No.	检出农药 Detected pesticide	UPLC-Q-TOF/MS	LC-MS/MS	相对误差 Relative error/%
3	苯醚甲环唑 difenoconazole	0.0042	0.0035	18.2
	乙螨唑 etoxazole	0.0098	0.0082	17.8
7	环莠隆 cycluron	0.0109	0.0106	2.8
	氟氯氰菊酯 cyfluthrin	0.0075	0.0081	7.7
20	氟环唑 epoxiconazole	0.0052	0.0063	19.1
	唑虫酰胺 tolfenpyrad	0.0087	0.0069	23.1
	氟环脲 flucycloxuron	0.0123	0.0156	23.7
29	氟啶虫胺腈 sulfoxaflor^*	0.5062	0.4985	1.5
	二嗪磷 diazinon	0.0062	0.0075	19.0
36	稻瘟灵 isoprothiolane	0.0055	0.0063	13.6
	异菌脲 iprodione	0.0070	0.0068	2.9
	二嗪磷 diazinon	0.0018	0.0021	15.4
42	甲拌磷砜 phorate-sulfone^*	0.0607	0.0589	3.0
	甲拌磷亚砜 phorate-sulfoxide^*	0.1988	0.1725	14.2
	甲呋酰胺 fenfuram	0.0033	0.0029	12.9
48	环莠隆 cycluron	0.0066	0.0057	14.6
	苯醚甲环唑 difenoconazole	0.0118	0.0098	18.5
注：^表示检出该农药含量超出MRL值。Note: ^ means the pesticide content exceeds the MRL value.

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