Determination of Herbicide Residues in Groundwaters Using Liquid/Liquid Extraction and Off-line Purification with Liquid Chromatography-Mass Spectrometry
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摘要: 固相萃取-液相色谱/质谱法是三嗪类和酰胺类除草剂常用的检测方法。本文针对现有分析方法仪器分析时间较长的缺点，以HLB柱为固相萃取柱，二氯甲烷-丙酮混合液(V : V=4 : 1)为洗脱剂，氟罗里硅土柱为净化柱，采用快速液相色谱柱，建立了固相萃取-液相色谱/质谱法快速测定地下水中14种三嗪类和2种酰胺类除草剂的方法。实验考察了固相萃取柱、定量离子扫描时间、富集柱洗脱溶剂、净化柱等因素对三嗪类和酰胺类除草剂测定的影响。通过延长定量离子的扫描时间，可以降低大部分目标化合物的相对标准偏差，提高仪器的稳定性；富集柱洗脱溶剂的极性对目标化合物回收率有较大影响，使用较强极性的二氯甲烷-丙酮(V : V=4 : 1)洗脱剂可以获得较高的目标化合物回收率；采用氟罗里硅土柱对萃取液进行净化，可除去干扰物，降低基体效应的影响。研究结果表明，14种三嗪类除草剂和2种酰胺类除草剂的检出限均小于0.40 μg/L，在低、中、高三种添加浓度下，回收率均满足要求。本方法虽然色谱峰重叠较多，但仪器分析时间为5.10 min，与现有方法的仪器分析时间(15 min以上)相比，分析时间短，检出限低，能够满足日常环境水样中农药残留分析检测的需要。
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关键词:
- 地下水 /
- 三嗪类和酰胺类除草剂 /
- 固相萃取 /
- 液相色谱-质谱法
Abstract: Solid phase extraction-Liquid Chromatography-Mass Spectrometry is a commony method for the determination of triazine and amides herbicides in groundwater. In order to overcome the disadvantage of the long processing time for current analysis procedure and instruments, a new method has been established, which uses HLB solid-phase extraction, elution reagents of methylene chloride-acetone (V : V=4 : 1) and a fluorine florisil column as the purification column. 14 kinds of triazine and 2 amides herbicides in groundwater were measured by Liquid Chromatography-Mass Spectrometry. The influence factors of mass spectrum conditions, solid-phase extraction column, elution solvents and purification columns were studied. Extending the scanning time of quantitative ions can reduce the relative standard deviation for most of the target components, and improve the stability of the instrument. The polarity of elution solvents greatly influences the recoveries of target components. Methylene chloride-acetone (V : V =4 : 1), which is more polar solvent, can obtain higher recoveries. The fluorine florisil column was used to remove interfering substances, reducing the matrix effect. The results show that the detection limits of 14 kinds of triazine herbicide and 2 amide herbicideare are less than 0.40 μg/L. The results are accurate and stable, with the recoveries of all herbicides between 85.8%-103.1% at 0.50 μg/L, and relative standard deviations between 5.2%-8.6%. However, this method has a lot of overlap peaks, but the analysis time is significantly shorter than current methods (5 min compared to 15 min or more), and meets the daily needs of large quantities of water sample testing. -
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表 1 流动相梯度洗脱程序
Table 1 Gradient elution program
时间t/min 甲醇+甲酸/% 水+甲酸/% 0.05 10 90 4.00 90 10 5.00 90 10 5.10 10 90 8.00 10 90 8.10 停止 
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表 2 质谱检测条件
Table 2 Measurement conditions of mass spectrometer
目标化合物 定量离子对 定性离子对 去簇电压(CE) 碰撞气能量(DP) 保留时间tR/min 定量离子对碎片1 定性离子碎片2 莠去通 212.1/170.3 212.1/100.2 25 35 55 2.72 扑灭通 226.1/142.1 226.1/184.1 31 25 55 2.98 莠灭净 228.0/186.2 228.0/116.1 27 38 50 3.37 环嗪酮 253.1/170.9 253.1/71.0 20 40 50 3.44 西玛津 202.1/132.1 202.1/124.3 25 25 55 3.64 扑草净 242.2/158.1 242.2/200.1 30 25 55 3.70 氰草津 241.2/241.1 241.2/103.9 25 40 50 3.71 嗪草酮 215.0/187.0 215.0/84.1 25 31 50 3.80 阿特拉津 216.2/174.2 216.2/104.1 23 39 50 4.02 吡草胺 278.0/134.1 278.0/210.1 30 17 25 4.24 扑灭津 230.2/146.2 230.2/188.0 30 26 55 4.37 去乙基阿特拉津 188.0/146.0 188.0/104.1 24 36 80 4.38 特丁津 230.2/174.0 230.2/96.1 25 35 55 4.46 另丁津 230.2/174.1 230.2/104.0 24 40 55 4.47 去异丙基阿特拉津 174.0/104.0 174.0/96.0 34 26 85 4.47 异丙草胺 284.0/224.3 284.0/148.1 13 26 25 5.05
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表 3 固相萃取小柱的回收率对比
Table 3 Comparison of recoveries for different of solid-phase extraction columns
化合物 回收率/% Varian
C18柱CNW
Poly-Sery PSD柱Merck
LiChrolut EN柱Waters
Oasis HLB柱莠去通 71.7 69.8 72.7 78.4 扑灭通 74.6 75.4 79.2 77.8 莠灭净 83.4 82.9 81.8 90.4 环嗪酮 73.8 73.4 77.7 78.0 西玛津 81.9 81.3 65.0 96.2 扑草净 71.6 86.2 85.7 89.4 氰草津 72.2 93.4 73.5 107.8 嗪草酮 81.8 82.7 91.1 95.3 阿特拉津 80.7 80.7 60.1 88.5 吡草胺 80.3 31.9 59.9 87.9 扑灭津 77.2 87.0 101.3 105.3 去乙基阿特拉津 60.3 73.4 63.0 81.8 特丁津 83.3 83.1 85.1 86.8 另丁津 83.4 69.4 79.8 93.5 去异丙基阿特拉津 64.9 62.9 70.2 76.1 异丙草胺 70.1 40.3 49.8 80.9
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表 4 不同洗脱条件对回收率的影响
Table 4 Effect of different elution conditions on the recovery
化合物 回收率/% 正己烷 二氯
甲烷二氯甲烷-丙酮
(体积比4 : 1)二氯甲烷-丙酮
(体积比1 : 4)丙酮 莠去通 62.1 74.2 85.4 82.1 81.9 扑灭通 60.2 72.4 85.7 84.9 83.1 莠灭净 61.3 76.5 87.7 83.4 83.9 环嗪酮 58.4 77.2 85.5 82.9 83.3 西玛津 60.9 76.9 84.9 83.7 84.1 扑草净 59.4 74.2 86.7 88.2 85.4 氰草津 61.3 74.5 85.2 86.8 84.5 嗪草酮 58.6 75.4 86.4 80.5 81.1 阿特拉津 60.6 71.4 86.2 85.5 84.9 吡草胺 48.6 55.4 72.4 85.8 84.9 扑灭津 55.2 73.3 84.7 85.9 85.1 去乙基阿特拉津 60.3 74.9 83.2 84.6 84.5 特丁津 63.8 76.0 86.5 83.4 84.1 另丁津 60.3 78.1 90.6 91.5 92.2 去异丙基阿特拉津 62.9 76.8 84.6 83.8 84.9 异丙草胺 49.2 56.4 71.5 82.3 83.7
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表 5 不同净化条件对回收率的影响
Table 5 Effect of different purification conditions on the recovery
化合物 回收率/% 净化前 氟罗里硅土柱 硅胶柱 莠去通 136.7 81.1 81.1 扑灭通 158.2 78.1 73.3 莠灭净 146.2 104.1 92.6 环嗪酮 134.5 92.7 95.6 西玛津 138.0 102.0 95.6 扑草净 135.7 113.3 89.3 氰草津 130.0 106.4 85.2 嗪草酮 147.2 98.7 110.2 阿特拉津 138.2 115.1 84.3 吡草胺 150.0 108.0 122.5 扑灭津 148.2 108.7 119.0 去乙基阿特拉津 139.1 87.6 81.1 特丁津 137.2 102.2 101.2 另丁津 138.1 106.5 117.4 去异丙基阿特拉津 140.2 85.6 78.5 异丙草胺 148.6 114.2 130.1
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表 6 两种扫描方式下目标化合物的相对标准偏差对比
Table 6 Comparison of relative standard deviation for the target compounds with two scanning modes
化合物 RSD/% 定量定性离子的
扫描时间相同定量定性离子的
扫描时间不同莠去通 6.3 3.5 扑灭通 5.2 3.6 莠灭净 4.8 2.8 环嗪酮 4.9 4.4 西玛津 4.9 4.1 扑草净 3.6 4.0 氰草津 4.4 3.8 嗪草酮 4.6 3.8 阿特拉津 5.5 5.0 吡草胺 8.2 5.0 扑灭津 4.1 4.4 去乙基阿特拉津 5.8 5.0 特丁津 5.8 4.0 另丁津 6.8 4.9 去异丙基阿特拉津 6.9 5.8 异丙草胺 8.5 5.4
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表 7 目标化合物的准确度、精密度和检出限(加标浓度为0.50 μg/L )
Table 7 Accuracy,precision and detection limit for the target compounds (spiked concentration of 0.50 μg/L)
化合物 平均检出浓度
ρ/(μg·L-1)标准偏差/
(μg·L-1)平均回收率
/%RSD/% 检出限/
(μg·L-1)莠去通 0.47 0.02 93.3 4.4 0.21 扑灭通 0.43 0.02 89.4 5.2 0.23 莠灭净 0.45 0.02 101.1 4.1 0.21 环嗪酮 0.43 0.03 90.5 5.9 0.27 西玛津 0.45 0.02 93.7 4.8 0.22 扑草净 0.48 0.02 94.5 4.7 0.22 氰草津 0.45 0.02 93.7 5.2 0.24 嗪草酮 0.44 0.03 95.9 6.2 0.30 阿特拉津 0.48 0.02 96.4 4.5 0.22 吡草胺 0.45 0.04 102.5 7.1 0.36 扑灭津 0.45 0.03 100.3 5.7 0.29 去乙基阿特拉津 0.43 0.03 97.8 6.3 0.31 特丁津 0.52 0.03 95.1 5.5 0.26 另丁津 0.50 0.03 96.3 5.7 0.27 去异丙基阿特拉津 0.49 0.03 98.6 6.8 0.34 异丙草胺 0.43 0.03 92.8 7.2 0.33
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表 8 目标化合物的准确度和精密度(加标浓度为1.50 μg/L )
Table 8 Accuracy and precision for the target compounds (spiked concentration of 1.50 μg/L)
化合物 平均检出浓度
ρ/(μg·L-1)标准偏差/
(μg·L-1)平均回收率/% RSD/% 莠去通 1.34 0.07 89.4 5.3 扑灭通 1.30 0.08 86.4 5.8 莠灭净 1.35 0.06 90.1 4.3 环嗪酮 1.36 0.08 90.4 5.7 西玛津 1.34 0.08 89.4 5.6 扑草净 1.35 0.08 90.1 5.7 氰草津 1.44 0.08 96.2 5.2 嗪草酮 1.47 0.08 97.9 5.2 阿特拉津 1.51 0.06 100.5 4.3 吡草胺 1.29 0.08 86.2 6.4 扑灭津 1.40 0.08 93.3 5.7 去乙基阿特拉津 1.32 0.06 87.8 4.8 特丁津 1.40 0.08 93.1 5.7 另丁津 1.35 0.06 90.3 4.5 去异丙基阿特拉津 1.43 0.07 95.6 5.2 异丙草胺 1.21 0.08 80.8 6.5
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表 9 目标化合物的准确度和精密度(加标浓度为5.00 μg/L )
Table 9 Accuracy and precision for the target compounds (spiked concentration of 5.00 μg/L)
化合物 平均检出浓度
ρ/(μg·L-1)标准偏差/
(μg·L-1)平均回收率/% RSD/% 莠去通 4.68 0.29 93.6 0.2 扑灭通 4.82 0.23 96.4 0.3 莠灭净 4.61 0.28 92.2 0.2 环嗪酮 5.14 0.29 102.8 0.3 西玛津 5.20 0.22 104.0 0.2 扑草净 4.52 0.26 90.3 0.3 氰草津 4.76 0.23 95.1 0.2 嗪草酮 4.55 0.24 91.0 0.2 阿特拉津 4.48 0.25 89.5 0.2 吡草胺 4.66 0.27 93.2 0.3 扑灭津 4.67 0.24 93.3 0.3 去乙基阿特拉津 4.46 0.27 89.2 0.2 特丁津 5.18 0.25 103.5 0.3 另丁津 5.02 0.28 100.3 0.3 去异丙基阿特拉津 4.73 0.26 94.6 0.3 异丙草胺 4.69 0.28 93.7 0.3
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杨炜春,王琪全,刘维屏.除草剂莠去津(atrazine)在土壤-水环境中的吸附及其机理[J].环境科学,2000,21(4): 94-97. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=0&CurRec=1&recid=&FileName=HJKZ200004022&DbName=CJFD2000&DbCode=CJFQ&pr= 赵兰,骆世明,黎华寿,贺鸿志,陈桂葵,秦俊豪.不同浓度下四种除草剂对福寿螺和坑螺的生态毒理效应[J].生态学报,2011,31(19): 5720-5727. http://www.cnki.com.cn/Article/CJFDTOTAL-STXB201119035.htm 廖人宽,杨培岭,任树梅,程闯胜,李云开.农用除草剂对土壤保水剂吸液性能的影响[J].农业工程学报,2013,29(4): 125-132. http://www.cnki.com.cn/Article/CJFDTOTAL-NYGU201304017.htm Klanova J, Matyiewiczova N, Macka Z, Prosek P, Laska K, Klan P. Persistent organic pollutants in soils and sediments from James Ross Island, Antarctica [J].Environmental Pollution,2008,152: 416-423. http://www.sciencedirect.com/science/article/pii/S100107421060633X 吴珍,刘慧,黄咸雨.液液萃取对邻苯二甲酸酯单体稳定碳同位素比值分馏的影响初探[J].岩矿测试,2012,31(6): 1028-1032. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120622&flag=1 饶竹,谢原利,陈巍.液液萃取-固相萃取富集地下水中毒杀芬的对比研究[J].岩矿测试,2012,31(4): 653-659. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120418&flag=1 徐静,肖珊珊,董伟峰,隋凯,曹际娟,刁文婷,张静.两次液液萃取-气相色谱-质谱联用法测定动物肝脏中左旋咪唑残留[J].色谱,2012,30(9): 922-925. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=4&CurRec=1&recid=&FileName=SPZZ201209012&DbName=CJFD2012&DbCode=CJFQ&pr= 丁明,钟冬莲,汤富彬,方伟.固相萃取-高效液相色谱-串联质谱联用测定竹笋中残留的7种杀虫剂农药[J].色谱,2013,31(2): 117-121. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=8&CurRec=1&recid=&FileName=SPZZ201302004&DbName=CJFD2013&DbCode=CJFQ&pr= Takashi M, Ayato K, Katsuhisa H.Development of sup-ercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments [J]. Chemosphere, 2008, 70(4): 648-655. http://www.sciencedirect.com/science/article/pii/S0045653507008557 袁圣柳,李晓锋,姜晓满,张海霞,郑少奎.自动固相萃取-高效液相色谱串联质谱法测定生活污水中13种抗精神病药物[J].分析化学,2013,41(1): 49-56. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=12&CurRec=1&recid=&FileName=FXHX201301010&DbName=CJFD2013&DbCode=CJFQ&pr= 秦明友,张新申,康莉,陈刚才,杨清玲.全自动固相萃取分子筛脱水气质联用法测定水中多氯联苯[J].分析化学,2013,41(1): 76-82. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201301014.htm 黄运瑞,周庆祥.固相萃取吸附剂的研究进展[J].冶金分析,2012,32(12): 22-28. doi: 10.3969/j.issn.1000-7571.2012.12.004 李俊,肖雅雯,王震,赵为武.加速溶剂萃取-气相色谱/质谱法同时测定土壤中拟除虫菊酯类等18种农药残留[J].岩矿测试,2011,30(5): 590-595. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110513&flag=1 陈卫明,李庆霞,张芳,何小辉,张勤.加速溶剂萃取-气相色谱/气相色谱-质谱法测定土壤中7种多氯联苯[J].岩矿测试,2011,30(1): 33-39. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110107&flag=1 Ken L, Michael L, Merv F, Maria L. Accelerated solvent extraction (ASE) of environmental organic compounds in soils using a modified supercritical fluid extractor [J]. Journal of Hazardous Materials, 2003, 102(1): 93-104. http://www.sciencedirect.com/science/article/pii/S0304389403002048 刘文长,陶文靖,程丽亚,余兴,田旻,黄勤,李胜生.超声提取-固相萃取小柱净化-气相色谱法测定土壤中14种有机氯农药[J].岩矿测试,2009,28(6): 541-544. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20090608&flag=1 李琴,黄云,唐琴秀.快速溶剂提取-气相色谱法测定土壤中19种多氯联苯单体[J].环境监测管理与技术,2008,20(6): 37-39. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=16&CurRec=1&recid=&FileName=HJJS200806013&DbName=CJFD2008&DbCode=CJFQ&pr= 李庆霞,刘亚轩,陈卫明,张勤.微波萃取-气相色谱/气相色谱-质谱法测定土壤中18种有机氯农药[J].岩矿测试,2010,29(2): 118-122. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20100206&flag=1 张勇,薛昆鹏,何美,陈再洁,吴虹,赵岳星.固相萃取/超高效液相色谱法测定龙胆泻肝丸中栀子苷、龙胆苦苷与黄芩苷[J].分析测试学报,2013,32(1): 122-126. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201301024.htm 黄毅,饶竹,刘艳,刘晨,郭晓辰.超高效液相色谱法直接快速测定环境水样中硝基苯和苯胺[J].岩矿测试,2012, 31(4): 666-671. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120420&flag=1 Wu T, Wang C, Wang X, Xiao H Q, Ma Q, Zhang Q.Comparison of UPLC and HPLC for analysis of 12 phthalates [J]. Chromatographia, 2008, 68: 803-806. doi: 10.1365/s10337-008-0788-y Batt A L, Kostich M S, Lazorchak J M.Analysis of ecologically relevant pharmaceuticals in wastewater and surface water using selective solid-phase extraction and UPLC-MS/MS [J].Analytical Chemistry,2008,80(13): 5021-5030. doi: 10.1021/ac800066n 储晓刚,雍炜,凌云,仇雯荔,姚惠源.超高效液相色谱-电喷雾串联质谱法同时测定大豆中107种除草剂残留[J].分析化学,2008, 36(3): 325-329. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=20&CurRec=1&recid=&FileName=FXHX200803012&DbName=CJFD2008&DbCode=CJFQ&pr= Rainville P D, Stumphf C L, Shockcor J P, Plumb R S, Nicholson J K.Novel application of reversed-phase UPLC-oaTOF-MS for lipid analysis in complex biological mixtures: A new tool for lipidomics [J].Journal of Proteome Research, 2007, 6(2): 552-558. doi: 10.1021/pr060611b 路国慧,沈亚婷,何俊,袁帆,杨永亮,饶竹.高效液相色谱-串联质谱法测定黄河河口段水中全氟化合物的初步研究[J].岩矿测试,2012,31(1): 147-153. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120121&flag=1 王道玮,赵世民,金伟,沈秋莹,胡平,黄斌,潘学军.加速溶剂萃取-固相萃取净化-气相色谱/质谱法测定沉积物中多氯联苯和多环芳烃[J].分析化学, 2013, 41(6): 861-868. http://epub.cnki.net/kns/detail/detail.aspx?QueryID=24&CurRec=1&recid=&FileName=FXHX201306012&DbName=CJFD2013&DbCode=CJFQ&pr= 祁彦,占春瑞,张新忠,杨强.高效液相色谱法测定大豆中13种三嗪类除草剂多残留量[J]. 分析化学,2006,34(6):787-790. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX200606010.htm
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