基于磁性固相萃取剂(MWCNTs/Fe_3O_4)同时测定水中毒死蜱和TCP的方法研究
|
摘要
通过溶剂热还原反应法一步制备了兼具磁性和优良吸附特性的磁性固相萃取剂MWCNTs/Fe_3O_4,对材料的XRD、SEM、VSM的表征分别证实和说明了材料中Fe_3O_4晶型单一,Fe_3O_4成功负载于MWCNTs管束,材料具有良好磁性,将材料分散于水中后也能通过强力磁铁完全回收.实验探究了MWCNTs/Fe_3O_4吸附水中毒死蜱和TCP的平衡时间,适宜的p H和温度,并在此基础上优化MWCNTs/Fe_3O_4磁固相萃取条件,以实现对水中毒死蜱、TCP的高效富集,其中包括适宜的材料用量、洗脱剂的种类、洗脱体积和温度的确定等,以此建立了一种磁固相萃取联合HPLC同时测定水样中毒死蜱和TCP的分析方法.该方法对水样中不同质量浓度添加的毒死蜱和TCP回收率分别是83.2%~91.7%与93.5%~97.1%,相对标准偏差分别是3.2%~7.4%与1.1%~4.6%,日内、日间精密度均小于10%,该方法对水样中毒死蜱和TCP定量限分别是2.5与1.5μg/L.利用该方法测定实际水样,并进行不同质量浓度的加标实验,仍能实现对毒死蜱和TCP回收率范围为88.9%~98.1%,且相对标准偏差均小于8%,说明本方法对水中杂质有一定抗干扰能力,适用于实际水样的检测.
The magnetic solidphase extraction agent MWCNTs/Fe_3O_4 with both magnetic and excellent adsorption properties was prepared by solvothermal reduction reaction. The XRD,SEM and VSM characterization of the materials were confirmed and demonstrated respectively. The Fe_3O_4 crystal single,Fe_3O_4 successfully loaded in the MWCNTs tube bundle,the material has a good magnetic,the material is dispersed in the water can also be fully recovered by the powerful magnet. The equilibrium time,suitable p H and temperature of chlorpyrifos and TCP in MWCNTs/Fe_3O_4 adsorbed water were investigated. Based on this,the MWCNTs/Fe_3O_4 magnetic solid phase extraction conditions were optimized to achieve the efficient enrichment of chlorpyrifos and TCP in water. The amount of material,elution volume and temperature were determined. A method of simultaneous determination of chlorpyrifos and TCP in water samples was established by magnetic solid phase extraction( SPE) combined with HPLC. The recoveries of chlorpyrifos and TCP were 83.2% ~ 91.7% and 93.5% ~ 97.1%,respectively. The relative standard deviations were 3.2% ~ 7.4% and 1.1% ~ 4.6%,respectively. The limits of quantification were 2. 5 and 1. 5 μg/L,respectively. The recoveries of chlorpyrifos and TCP were 88. 9% ~ 98.1%,and the relative standard deviations were less than 8%,which indicated that the method was effective for the presence of impurities in the water and suitable for the real water sample detection.
The magnetic solidphase extraction agent MWCNTs/Fe_3O_4 with both magnetic and excellent adsorption properties was prepared by solvothermal reduction reaction. The XRD,SEM and VSM characterization of the materials were confirmed and demonstrated respectively. The Fe_3O_4 crystal single,Fe_3O_4 successfully loaded in the MWCNTs tube bundle,the material has a good magnetic,the material is dispersed in the water can also be fully recovered by the powerful magnet. The equilibrium time,suitable p H and temperature of chlorpyrifos and TCP in MWCNTs/Fe_3O_4 adsorbed water were investigated. Based on this,the MWCNTs/Fe_3O_4 magnetic solid phase extraction conditions were optimized to achieve the efficient enrichment of chlorpyrifos and TCP in water. The amount of material,elution volume and temperature were determined. A method of simultaneous determination of chlorpyrifos and TCP in water samples was established by magnetic solid phase extraction( SPE) combined with HPLC. The recoveries of chlorpyrifos and TCP were 83.2% ~ 91.7% and 93.5% ~ 97.1%,respectively. The relative standard deviations were 3.2% ~ 7.4% and 1.1% ~ 4.6%,respectively. The limits of quantification were 2. 5 and 1. 5 μg/L,respectively. The recoveries of chlorpyrifos and TCP were 88. 9% ~ 98.1%,and the relative standard deviations were less than 8%,which indicated that the method was effective for the presence of impurities in the water and suitable for the real water sample detection.
引文
[1]郭瑞峰,黄彬彬,杨晓伟,等.毒死蜱-聚乳酸微球的制备及其性能评价[J].农药学学报,2011,13(4):409-414.
[2]刘腾飞,邓金花,周峰杰,等.毒死蜱在土壤中的降解及分析研究进展[J].中国农学通报,2014,30(9):26-34.
[3]葛志荣.食品中农业化学品残留限量[M].北京:中国标准出版社,2006:16-1581.
[4]韩畅,朱鲁生,王军,等.HPLC测定水体中毒死蜱及其有毒降解产物TCP[J].农业环境科学学报,2009,28(7):1552-1556.
[5]蔡玺晨.分散固相萃取-HPLC-QTOF/MS法测定水中农药残留的研究[D].苏州:苏州科技学院,2014.
[6]潘胜东,叶美君,金米聪.磁性固相萃取在食品安全检测中的应用进展[J].理化检验:化学分册,2015,51(3):416-424.
[7]朱建国,李培武,张文,等.磁固相萃取/气相色谱-串联质谱法测定花生中多种农药残留[J].分析测试学报,2016,35(9):1087-1093.
[8]DENG X J,GUO Q J,CHEN X P,et al.Rapid and effective clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography-mass spectrometry[J].Food Chemistry,2014,39(145):853-858.
[9]WU Q H,ZHAO G Y,FENG C.Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from water samples[J].J Chromatography,2011,A19(44):7936-7942.
[10]GUAN Y,JIANG C,HU C,et al.Preparation of multi-walled carbon nanotubes functionalized magnetic particles by sol-gel technology and its alication in extraction of estrogens[J].Talanta,2010,83(2):337-343.
[11]付佳.溶剂热法制备纳米四氧化三铁研究[D].西安:西安建筑科技大学,2007.
[12]XIONG J F,ZHOU G M,GUAN Z,et al.Determination of chlorpyrifos and its main degradation product TCP in water samples by dispersive liquid-liquid microextraction based on solidfication of floating organic droplet combined with high-performance liquid chromatography liquidchromatogramance liquid chromatography[J].J Liquid Chromatography&Related Technologies,2014,37(11):1499-1512.
[13]孙宝利,曾希柏.高效液相色谱法同时测定土壤中毒死蜱残留及其有毒代谢物3,5,6-TCP[J].分析试验室,2011,30(8):19-22.
[14]秦烨.磁性石墨烯固相萃取-HPLC-MS/MS在水产品药残检测中的应用研究[D].杭州:浙江工商大学,2016.
[15]王娜,孙娟,石利利.超高效液相色谱-串联质谱法测定人尿中毒死蜱的主要代谢产物3,5,6-三氯-2-吡啶醇[J].色谱,2013,31(9):903-907.
[2]刘腾飞,邓金花,周峰杰,等.毒死蜱在土壤中的降解及分析研究进展[J].中国农学通报,2014,30(9):26-34.
[3]葛志荣.食品中农业化学品残留限量[M].北京:中国标准出版社,2006:16-1581.
[4]韩畅,朱鲁生,王军,等.HPLC测定水体中毒死蜱及其有毒降解产物TCP[J].农业环境科学学报,2009,28(7):1552-1556.
[5]蔡玺晨.分散固相萃取-HPLC-QTOF/MS法测定水中农药残留的研究[D].苏州:苏州科技学院,2014.
[6]潘胜东,叶美君,金米聪.磁性固相萃取在食品安全检测中的应用进展[J].理化检验:化学分册,2015,51(3):416-424.
[7]朱建国,李培武,张文,等.磁固相萃取/气相色谱-串联质谱法测定花生中多种农药残留[J].分析测试学报,2016,35(9):1087-1093.
[8]DENG X J,GUO Q J,CHEN X P,et al.Rapid and effective clean-up based on magnetic multiwalled carbon nanotubes for the determination of pesticide residues in tea by gas chromatography-mass spectrometry[J].Food Chemistry,2014,39(145):853-858.
[9]WU Q H,ZHAO G Y,FENG C.Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from water samples[J].J Chromatography,2011,A19(44):7936-7942.
[10]GUAN Y,JIANG C,HU C,et al.Preparation of multi-walled carbon nanotubes functionalized magnetic particles by sol-gel technology and its alication in extraction of estrogens[J].Talanta,2010,83(2):337-343.
[11]付佳.溶剂热法制备纳米四氧化三铁研究[D].西安:西安建筑科技大学,2007.
[12]XIONG J F,ZHOU G M,GUAN Z,et al.Determination of chlorpyrifos and its main degradation product TCP in water samples by dispersive liquid-liquid microextraction based on solidfication of floating organic droplet combined with high-performance liquid chromatography liquidchromatogramance liquid chromatography[J].J Liquid Chromatography&Related Technologies,2014,37(11):1499-1512.
[13]孙宝利,曾希柏.高效液相色谱法同时测定土壤中毒死蜱残留及其有毒代谢物3,5,6-TCP[J].分析试验室,2011,30(8):19-22.
[14]秦烨.磁性石墨烯固相萃取-HPLC-MS/MS在水产品药残检测中的应用研究[D].杭州:浙江工商大学,2016.
[15]王娜,孙娟,石利利.超高效液相色谱-串联质谱法测定人尿中毒死蜱的主要代谢产物3,5,6-三氯-2-吡啶醇[J].色谱,2013,31(9):903-907.