Determination of the amide herbicides in milk using dispersive liquid-liquid microextraction prior to GC-MS
-
摘要:目的
实现牛奶中农药残留快速、准确的分析检测，更好地监督牛奶的食品安全问题.
方法采用分散液液微萃取技术(DLLME)作为前处理方法，气相色谱-质谱联用(GC-MS)作为色谱分析仪器，建立了牛奶中4种酰胺类除草剂(甲草胺、乙草胺、丙草胺和异丙甲草胺)的残留分析方法.
结果和结论对影响萃取效率的因素进行了分析和优化，最终选取40 μL四氯化碳作为萃取剂，1 000 μL甲醇作为分散剂，提取时间设置为1.0 min.在最优的试验条件下，4种酰胺类除草剂质量浓度在0.05~5.00 mg·L-1范围内均具有良好的线性相关，相关系数≥0.997 8.该方法灵敏度高，检出限在0.8~1.4 μg·L-1(S/N=3)范围内.该方法应用于实际牛奶样品的检测，4种目标物的平均添加回收率为67.0%~105.7%，相对标准偏差(RSD)为1.6%~8.3%.
Abstract:ObjectiveTo supervise the food safety problem in milk and achieve a rapid and accurate determination of pesticide residues in milk.
MethodIn this paper, a simple, sensitive and environment friendly dispersive liquid-liquid microextraction (DLLME) technique coupled with gas chromatography-mass spectrometry (GC-MS) was established for the extraction and determination of four amide herbicides (alachlor, acetochlor, pretilachlor, and metolachlor) in milk samples.
Result and conclusionThe factors that affected extraction efficiency were studied and optimized. Eventually, 40 μL carbon tetrachloride was used as the extractant, 1 000 μL methanol was chosen as the dispersant and the extraction time was set to 1.0 min. Under the optimum conditions, the good linearity was exhibited from 0.05 to 5.00 mg·L-1 herbicide, with the correlation coefficient being more than 0.997 8. The method had a high sensitivity, and the limits of detection (S/N=3) of the four amide herbicides ranged from 0.8 to 1.4 μg·L-1. The recoveries of the target analytes from milk samples were found between 67.0% and 105.7%, and the relative standard deviations (RSD) varied from 1.6% to 8.3%. The method can be successfully applied for the analysis of amide herbicides in real milk samples.
-
-
![]()
图 1 4种酰胺类除草剂在1.00 mg·L-1时的标准样品色谱图
1:乙草胺；2:甲草胺；3:异丙甲草胺；4:丙草胺.
Figure 1. Typical chromatography of 1.00 mg·L-1 mix standards amide herbicides
![]()
图 3 萃取剂体积对萃取效率的影响
Figure 3. Effect of extraction solvent volume on the extraction efficiency
![]()
图 5 分散剂体积对萃取效率的影响
Figure 5. Effect of dispersive solvent volume on the extraction efficiency
![]()
图 7 盐质量浓度对萃取效率的影响
Figure 7. Effect of salt mass concentration on the extraction efficiency
![]()
图 9 牛奶样品添加4种酰胺类农药(0.1 mg·L-1)色谱图
1:乙草胺；2:甲草胺；3:异丙甲草胺；4:丙草胺
Figure 9. Chromatogram of milk samples spiked with amide herbicides at each concentration of 0.1 mg·L-1 obtained by using DLLME-GC/MS
表 1 4种酰胺类除草剂的保留时间和特征离子
Table 1 The retention time and characteristic ions of four amide herbicides
下载: 导出CSV
表 2 方法的线性、相关系数、检出限
Table 2 Linearity, correlation coefficients, and limit of detection of the method
下载: 导出CSV
表 3 4种酰胺类除草剂在牛奶样品中的添加回收率和相对标准偏差
Table 3 Recoveries and relative standard deviations of four amide herbicides in milk samples
下载: 导出CSV
表 4 不同方法对酰胺类除草剂分析测定的比较
Table 4 Comparisons of DLLME-GC-MS with other methods for the extraction and determination of amide herbicides
下载: 导出CSV
-
[1] 盛姣, 柏连阳, 刘祥英.酰胺类除草剂及其安全剂研究进展[J].江西植保, 2005, 28(4): 163-165. doi: 10.3969/j.issn.2095-3704.2005.04.007 [2] 张一宾.酰胺类除草剂的全球市场、品种及发展趋向[J].现代农药, 2011, 10(1): 41-43. doi: 10.3969/j.issn.1671-5284.2011.01.012 [3] COLEMAN S, LINDERMAN R, HODGSON E, et al. Comparative metabolism of chloroacetamide herbicides and selected metabolites in human and rat liver microsomes[J]. Environ Health Perspect, 2000, 108(12): 1151-1157. http://cn.bing.com/academic/profile?id=b460f06ff7ad9681ebfef23eb056cbd9&encoded=0&v=paper_preview&mkt=zh-cn
[4] 高晓昇, 张艳, 王松雪, 等.牛奶中拟除虫菊酯类农药残留检测:QuEChERS-气相色谱分析方法的研究与建立[J].中国奶牛, 2010 (8): 56-60. doi: 10.3969/j.issn.1004-4264.2010.08.020 [5] 陈虹, 韩勇, 钟明, 等.水样中几种酰胺类除草剂的SPE-GC/ECD法检测[J].化学试剂, 2010, 32(4): 325-327. doi: 10.3969/j.issn.0258-3283.2010.04.012 [6] 李建中, 储晓刚, 蔡会霞, 等.高效液相色谱法同时测定大豆中12种酰胺类除草剂的残留量[J].色谱, 2006, 24(6): 585-588. doi: 10.3321/j.issn:1000-8713.2006.06.011 [7] 周瑶敏, 熊艳, 袁林峰, 等.分散固相萃取法快速测定大米中的酰胺类除草剂[J].中国粮油学报, 2010, 25(8): 113-116. http://d.old.wanfangdata.com.cn/Periodical/zglyxb201008025 [8] 沈伟健, 徐锦忠, 杨雯筌, 等.两种离子源技术气相色谱-质谱法检测茶叶中酰胺类除草剂的残留量[J].色谱, 2007, 25(5): 753-757. doi: 10.3321/j.issn:1000-8713.2007.05.028 [9] REZAEE M, ASSADI Y, MILANI HOSSEINI M R, et al. Determination of organic compounds in water using dispersive liquid-liquid microextraction[J]. J Chromatogr A, 2006, 1116(1/2): 1-9. http://d.old.wanfangdata.com.cn/Conference/8395795
[10] ZHAO R S, DIAO C P, CHEN Q F, et al. Sensitive determination of amide herbicides in environmental water samples by a combination of solid-phase extraction and dispersive liquid-liquid microextraction prior to GC-MS[J]. J Sep Sci, 2009, 32(7): 1069-1074. doi: 10.1002/jssc.v32:7
[11] 白沙沙, 李芝, 臧晓欢, 等.磁性石墨烯固相萃取-分散液液微萃取-气相色谱法测定水和绿茶中酰胺类除草剂残留[J].分析化学, 2013, 41(8): 1177-1182. http://d.old.wanfangdata.com.cn/Periodical/fxhx201308008 [12] 王鹤, 陈忠林, 沈吉敏, 等.液液微萃取/气相色谱法速检水中四种酰胺类除草剂[J].中国给水排水, 2011, 27(12): 90-93. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgjsps201112025 [13] CAMPILLO N, VIÑAS P, FÉREZ-MELGAREJO G, et al. Dispersive liquid-liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry[J]. J Chromatogr A, 2013, 1282: 20-26. doi: 10.1016/j.chroma.2013.01.086
[14] FARAJZADEH M A, DJOZAN D, MOGADDAM M R, et al. Extraction and preconcentration technique for triazole pesticides from cow milk using dispersive liquid-liquid microextraction followed by GC-FID and GC-MS determinations[J]. J Sep Sci, 2011, 34(11): 1309-1316. doi: 10.1002/jssc.v34.11
[15] GAO S Q, YANG X, YU W, et al. Ultrasound-assisted Ionic liquid/Lonic liquid-dispersive liquid-liquid microextraction for the determination of sulfonamides in infant formula milk powder using high-performance liquid chromatography[J]. Talanta, 2012, 99: 875-882. doi: 10.1016/j.talanta.2012.07.050
[16] YIANTZI E, PSILLAKIS E, TYROVOLA K, et al. Vortex-assisted liquid-liquid microextraction of octylphenol, nonylphenol and bisphenol-A[J]. Talanta, 2010, 80(5): 2057-2062. doi: 10.1016/j.talanta.2009.11.005
[17] XU X Q, YANG H H, WANG L, et al. Analysis of chloroacetanilide herbicides in water samples by solid-phase microextraction coupled with gas chromatography-mass spectrometry[J]. Anal Chim Acta, 2007, 591(1): 87-96. doi: 10.1016/j.aca.2007.03.044
-
期刊类型引用(4)
1. 张馨悦，王超，王庆杰，康可新，李贵蓉，刘立晶. 玉米苗期行间除草二级对行装置设计与试验. 农业机械学报. 2025(04): 42-51+60 . 
百度学术
2. 何创新，巩蕾，苗中华，韩科立，郝付平，韩增德. 基于平行轨迹导航的采棉机自动对行控制方法. 农业机械学报. 2024(06): 34-41 . 百度学术
3. 苏鹏鉴，马海琴，叶俊明. 基于无人系统的智能视觉控制算法研究. 电子测量技术. 2024(09): 93-97 . 百度学术
4. 张晓龙，易克传，姜春霞，凃何平，郭子明. 基于四连杆机构自动对行装置的设计与仿真. 东莞理工学院学报. 2024(05): 110-116 . 百度学术
其他类型引用(0)
计量
- 文章访问数: 1690
- HTML全文浏览量: 3
- PDF下载量: 1518
- 被引次数: 4
