超声辅助提取-高效液相色谱-电感耦合等离子体质谱法分析食品中水溶性铬价态
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摘要
目的建立一种超声辅助提取-高效液相色谱分离-电感耦合等离子体质谱联用法(high performance liquid chromatography-inductively coupled plasma mass spectrometry,HPLC-ICP-MS)测定食品中水溶性铬价态的分析方法。方法样品经乙二胺四乙酸二钠(ethylenediaminetetraacetic acid disodium salt, EDTA-2Na)-硝酸铵混合溶液提取后,含蛋白质的样品加入铁氰化钾和乙酸锌溶液沉淀蛋白质,0.45μm微孔滤膜过滤后备用。样品经离子交换柱分离,ICP-MS检测。结果 Cr(Ⅲ)和Cr(Ⅵ)在0.5～50ng/mL的范围内呈线性关系,大米和鸡蛋样品在0.025、0.05和2.0 mg/kg添加水平下的回收率为76.8%～117.0%;土豆在0.025、0.05和1.0 mg/kg添加水平下回收率为84.7%～108.2%;牛奶在0.025、0.05、0.6 mg/kg添加水平下回收率为75.1%～103.8%; 2种价态的铬的检出限均为10μg/kg。结论该方法快速、准确、灵敏,适合用于多种食品中可溶性铬价态分析检测。
Objective To establish a method for determination of water soluble chromium valence in foods by high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS) with ultrasound assisted extraction. Methods Samples were extracted with ethylenediaminetetraacetic acid disodium salt(EDTA-2Na)-ammonium nitrate mixture solvent. Protein-containing sample was added to potassium ferricyanide and zinc acetate solution to precipitate protein, and filtered through a 0.45 μm microporous membrane. The sample was separated by ion exchange column and detected by ICP-MS. Results Cr(Ⅲ) and Cr(Ⅵ) were linear in the range of 0.5-50 ng/mL. The recoveries of rice and egg samples at 3 spiked levels(0.025, 0.05 and 2.0 mg/kg) were 76.8%-117.0%. The recoveries of potatoes at 3 spiked levels(0.025, 0.05 and 1.0 mg/kg) were 84.7%-108.2%. The recovery rates of milk at 3 spiked levels(0.025, 0.05, 0.6 mg/kg) were 75.1%-103.8%. The detection limit of the two valence states of chromium is 10 μg/kg. The detection limit of chromium in both valence states was 10 μg/kg. Conclusion This method is fast, accurate and sensitive, which is suitable for the analysis and determination of soluble chromium in various foods.
Objective To establish a method for determination of water soluble chromium valence in foods by high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS) with ultrasound assisted extraction. Methods Samples were extracted with ethylenediaminetetraacetic acid disodium salt(EDTA-2Na)-ammonium nitrate mixture solvent. Protein-containing sample was added to potassium ferricyanide and zinc acetate solution to precipitate protein, and filtered through a 0.45 μm microporous membrane. The sample was separated by ion exchange column and detected by ICP-MS. Results Cr(Ⅲ) and Cr(Ⅵ) were linear in the range of 0.5-50 ng/mL. The recoveries of rice and egg samples at 3 spiked levels(0.025, 0.05 and 2.0 mg/kg) were 76.8%-117.0%. The recoveries of potatoes at 3 spiked levels(0.025, 0.05 and 1.0 mg/kg) were 84.7%-108.2%. The recovery rates of milk at 3 spiked levels(0.025, 0.05, 0.6 mg/kg) were 75.1%-103.8%. The detection limit of the two valence states of chromium is 10 μg/kg. The detection limit of chromium in both valence states was 10 μg/kg. Conclusion This method is fast, accurate and sensitive, which is suitable for the analysis and determination of soluble chromium in various foods.
引文
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[14]王林裴,郑亚哲,彭新然.HPLC-ICP-MS法测定水产动物及其制品中5种砷形态的含量[J].食品与机械,2017,33(11):61-66.Wang LP,Zheng YZ,Peng XR.Determination of five arsenic species in aquatic animals and their products by high performance liquid chromatography and inductively coupled plasma mass spectrometry[J].Food Mach,2017,33(11):61-66.
[15]吕海燕,曹小云,钟冠男.HPLC-ICPMS测定海鱼中六种砷形态方法探讨[J].河南预防医学杂质,2018,29(8):594-597.Lv HY,Cao XY,Zhong GN.Simultaneous determination of six arsenic species in marine fishes by HPLC-ICPMS[J].Henan J Prev Med,2018,29(8):594f597.
[16]鲁照玲,胡红云,姚洪.HPLC-ICPMS对环境样品中Cr(Ⅲ)和Cr(Ⅵ)分析研究[J].环境科学与技术,2012(s2):230-233.Lu ZL,Hu HY,Yao H.Study on Speciation analysis of Cr(Ⅲ)&(Ⅵ)in environmental samples by high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry[J].Environ Sci Technol,2018,29(8):594-597.
[2]Wang YS,Pan ZY,Lang JM,et al.Bioleaching of chromium from tannery sludge by indigenous acidithiobacillusthiooxidans[J].Hazard Mater,2007,(147):319-324.
[3]Arun KS,Carlos C,Herminia I,et al.Chromium toxicity in plants[J].Environ Int,2005,7,31(5):739-753.
[4]覃莎.浊点萃取-火焰原子吸收光谱法在重金属铬、铅、镉价态分析的应用[J].当代化工研究,2016,(12):39-40.Qin S.Application of cloud point extraction-flame atomic absorption spectrometry method in the analysis of heavy metal chrome,lead and cadmium form[J].Chenm Int,2016,(12):39-40.
[5]范华均,曲波.茶汤及河水中铬的价态分析[J].分析科学学报,1995,11(1):37-41.Fan HJ,Qu B.Speciation analysis of chromium in tea soup and river water[J].J Anal Sci,1995,11(1):37-41.
[6]喻德忠,汪国庆,艾军.纳米级氧化铝的制备及其对铬的价态分析[J].武汉工程大学学报,2012,34(1):10-13.Yu DZ,Wang GQ,Ai J.Preparation of nanometer-sized aluminum oxide and it speciation analysis of chromium[J].J Wuhan Inst Technol,2012,34(1):10-13.
[7]冉丽敏,刘曙,杨勇,等.离子液体微萃取-硝酸反萃取结合电感耦合等离子体质谱法用于铬元素的价态分析[J].理化检验-化学分册,2017,53(9):1094-1098.Ran LM,Liu S,Yang Y,et al.ICP-MS combined with ionic liquid microextraction and back-extraction of nitric acid for speciation analysis of chromium[J].PTCA(Part B:Chem Anal),2017,53(9):1094-1098.
[8]陈明丽,赵亚男,王建华.固载化离子液体用于Cr(VI)的吸附及铬价态分析的研究[J].分析化学,2009,37(增刊):A012.Chen ML,Zhao YN,Wang JH.Adsorption of Cr(VI)and analysis of chromium valence state by immobilized ionic liquids[J].Chin J Anal Chem,2009,37(Supplement):A012.
[9]陈晓燕,冯亚丹,杨旭日,等.HPLC-ICP-MS联用技术应用于海产品中铬价态的分析[J].分析化学,2009,37(增刊):D189.Chen XY,Feng YD,Yang XR,et al.Analysis of chromium valence state in Marine products by HPLC-ICP-MS combined technology[J].Chin JAnal Chem,2009,37(Supplement):D189.
[10]李登科,范国樑,姚鹤鸣,等.HPLC-ICP-MS联用技术用于烟草中铬的价态分析研究[J].中国烟草学报,2016,22(2):1-7.Li DK,Fan GL,Yao HM,et al.Analysis of chromium speciation in tobacco by HPL-ICP-MS[J].Acta Tabacaria Sinica,2016,22(2):1-7.
[11]陈德勋,李玉珍.环境水样中铬价态分析方法研究[J].岩矿测试,1999,18(3):171-15.Chen DX,Li YZ.Speciation analysis of chromium in environmental water samples[J].Rock Miner Anal,1999,18(3):171-175.
[12]池泉,史建波,梅俊,等.石墨炉原子吸收光谱法测定土壤中可交换Cr(III)和Cr(VI)[J].分析试验室,2002,21(2):63-67.Chi Q,Shi JB,Mei J,et al.Determination of exchangeable Cr(III)and Cr(VI)in soil by graphite furnace atomic absorption spectrometry[J].Anal Lab,2002,21(2):63-67.
[13]赵彤,周慧敏,于利军,等.微波萃取HPLC-ICP-MS法测定稻米中砷的形态[J].食品研究与开发,2016,37(17):124-126.Zhao T,Zhou HM,Yu LJ,et al.Determination for arsenic species in rice by microwave extraction HPLC-ICP-MS[J].Food Res Dev,2016,37(17):124-126.
[14]王林裴,郑亚哲,彭新然.HPLC-ICP-MS法测定水产动物及其制品中5种砷形态的含量[J].食品与机械,2017,33(11):61-66.Wang LP,Zheng YZ,Peng XR.Determination of five arsenic species in aquatic animals and their products by high performance liquid chromatography and inductively coupled plasma mass spectrometry[J].Food Mach,2017,33(11):61-66.
[15]吕海燕,曹小云,钟冠男.HPLC-ICPMS测定海鱼中六种砷形态方法探讨[J].河南预防医学杂质,2018,29(8):594-597.Lv HY,Cao XY,Zhong GN.Simultaneous determination of six arsenic species in marine fishes by HPLC-ICPMS[J].Henan J Prev Med,2018,29(8):594f597.
[16]鲁照玲,胡红云,姚洪.HPLC-ICPMS对环境样品中Cr(Ⅲ)和Cr(Ⅵ)分析研究[J].环境科学与技术,2012(s2):230-233.Lu ZL,Hu HY,Yao H.Study on Speciation analysis of Cr(Ⅲ)&(Ⅵ)in environmental samples by high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry[J].Environ Sci Technol,2018,29(8):594-597.