元素分析-同位素比质谱法与液相色谱-同位素比质谱法测定乙醇中δ~(13)C值
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摘要
目的研制木薯乙醇和玉米乙醇中碳同位素标准物质,探讨碳同位素准确定值技术。方法定值分别采用元素分析-稳定同位素比质谱法(elemental analyzer-isotope ratio mass spectrometry, EA-IRMS)和液相色谱-稳定同位素比质谱法(liquid chromatography-isotope ratio mass spectrometry, LC-IRMS)。LC-IRMS分析过程中,将标准物质BCR657分别与待测样品和标准物质BCR660混合,可以实现对乙醇和蔗糖δ~(13)C值的同时测定。结果LC-IRMS方法验证结果显示使用该方法检测的标准物质BCR660的测量值在标准值的不确定度范围内,证明了混合检测方法的可行性。使用E_n值核查法对2种检测方法检测得到的乙醇样品δ~(13)C值进行检验,|E_(ncassava)|=0.952,|Enmaize|=0.551,En值均小于1,证明2种检测方法所测结果等效一致。结论该方法不但有利于对乙醇进行多方法定值,且弥补了气相色谱-稳定同位素比质谱法(gas chromatography-isotope ratio mass spectrometry, GC-IRMS)标准物质有限的缺陷。本研究建立的分析技术和研制的标准物质可用于食品真实性鉴别。
Objective To develop the carbon isotope reference materials in cassava ethanol and maize ethanol,and explore the accurate certification technology for carbon isotope. Methods Certification was conducted by the combination of elemental analyzer-isotope ratio mass spectrometry(EA-IRMS) and liquid chromatography-isotope ratio mass spectrometry(LC-IRMS). In LC-IRMS, CRM BCR657 was mixed with the sample and CRM BCR660,respectively, which could perform simultaneous determination of δ~(13) C in both ethanol and sucrose. Results The determined results in BCR660 were within the uncertainty range, which verified the feasibility of simultaneous determination of ethanol and sugar by LC-IRMS. The δ~(13) C values of ethanol samples determined with EA-IRMS and LC-IRMS were inspected with En method, which showed that |Encassava|=0.952, |Enmaize|=0.551, respectively.Both values were less than 1, which implied that the methods agreed with each other well. Conclusion These methods are not only beneficial to the determination of ethanol by multi-methods, but also make up for the limited defect of GC-IRMS(gas chromatography-isotope ratio mass spectrometry) by supplying reference materials. Based on the techniques, new carbon isotope reference materials are developed for GC-IRMS, further, this technique and reference materials will helpful for food authenticity.
Objective To develop the carbon isotope reference materials in cassava ethanol and maize ethanol,and explore the accurate certification technology for carbon isotope. Methods Certification was conducted by the combination of elemental analyzer-isotope ratio mass spectrometry(EA-IRMS) and liquid chromatography-isotope ratio mass spectrometry(LC-IRMS). In LC-IRMS, CRM BCR657 was mixed with the sample and CRM BCR660,respectively, which could perform simultaneous determination of δ~(13) C in both ethanol and sucrose. Results The determined results in BCR660 were within the uncertainty range, which verified the feasibility of simultaneous determination of ethanol and sugar by LC-IRMS. The δ~(13) C values of ethanol samples determined with EA-IRMS and LC-IRMS were inspected with En method, which showed that |Encassava|=0.952, |Enmaize|=0.551, respectively.Both values were less than 1, which implied that the methods agreed with each other well. Conclusion These methods are not only beneficial to the determination of ethanol by multi-methods, but also make up for the limited defect of GC-IRMS(gas chromatography-isotope ratio mass spectrometry) by supplying reference materials. Based on the techniques, new carbon isotope reference materials are developed for GC-IRMS, further, this technique and reference materials will helpful for food authenticity.
引文
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[19]李学民,贾光群,曹彦忠,等.液相色谱-同位素比质谱法同时测定葡萄酒中甘油和乙醇的δ13C值[J].色谱,2013,31(12):1201-1205.Li XM,Jia GQ,Cao YZ,et al.Simultaneous determination ofδ13C values of glycerol and ethanol in wine by liquid chromatography coupled with isotope ratio mass spectrometry[J].Chin J Chromatogr,2013,31(12):1201-1205.
[2]车明秀,胡明燕,刘睿,等.葡萄酒真伪鉴别技术研究进展[J].中国酿造,2018,37(10):5-8.Che MX,Hu MY,Liu R,et al.Research progress on identification technology of wine authenticity[J].China Brew,2018,37(10):5-8.
[3]Goldner MC,Zamora MC.Sensory characterization of vitis vinifera CV.Malbec wines from seven viticulture regions of argentina[J].J Sens Stud,2007,22(5):520-532.
[4]Yang Y,Jin GJ,Wang XJ,et al.Chemical profiles and aroma contribution of terpene compounds in Meili grape and wine[J].Food Chem,2019,(284):155-161.
[5]张晶莹,魏彦锋,梁红敏,等.指纹图谱技术在葡萄及葡萄酒研究上的应用[J].中外葡萄与葡萄酒,2019,(1):57-63.Zhang JY,Wei YF,Liang HM,et al.Application of fingerprint technique in grape and wine research[J].Sino-Overseas Grap Evine Wine,2019,(1):57-63.
[6]郭海霞,王涛,刘洋,等.基于可见-近红外光谱技术的葡萄酒真伪鉴别的研究[J].光谱学与光谱分析,2011,31(12):3269-3272.Guo HX,Wang T,Liu Y,et al.Study on recognition of the true or false red wine based on visible-near infrared spectroscopy[J].Spectrosc Spect Anal,2011,31(12):3269-3272.
[7]Moncayo S,Rosales JD,Izquierdo-Hornillos R,et al.Classification of red wine based on its protected designation of origin(PDO)using laser-induced breakdown spectroscopy(LIBS)[J].Talanta,2016,(158):185-191.
[8]Coetzee PP,Jaarsveld FPV,Vanhaecke F.Intraregional classification of wine via ICP-MS elemental fingerprinting[J].Food Chem,2014,164C(3):485-492.
[9]Geana I,Iordache A,Ionete R,et al.Geographical origin identification of Romanian wines by ICP-MS elemental analysis[J].Food Chem,2013,138(2-3):1125-1134.
[10]Santos CEID,Silva LRMD,Boufleur LA,et al.Elemental characterisation of Cabernet Sauvignon wines using particle-induced X-ray emission(PIXE)[J].Food Chem,2010,121(1):244-250.
[11]李斯屿.干红葡萄酒酚类代谢组学技术构建及应用[D].北京:中国农业大学,2018.Li SY.Establishment and application of dry red wine phenolic metabolomic technology[D].Beijing:China Agriculture University,2018.
[12]Dong H,Xiao KJ,Xian YP,et al.Authenticity determination of honeys with non-extractable proteins by means of elemental analyzer(EA)and liquid chromatography(LC)coupled to isotope ratio mass spectroscopy(IRMS)[J].Food Chem,2018,240(1):717-724.
[13]费晓庆,沈崇钰,吴斌,等.元素分析-碳同位素比值质谱法在蜂王浆掺假鉴定中的应用[J].质谱学报,2014,35(2):144-148.Fei XQ,Shen CY,Wu B,et al.Detection of royal jelly adulteration using elemental analyzer-carbon isotope ratio mass spectrometry[J].J Chin Mass Spectr Soc,35(2):144-148.
[14]Matteo P,Mauro P,Roberto P,et al.The use of stable isotope ratio analysis to characterise saw palmetto extract[J].Food Chem,2019,(274):26-34.
[15]谭孟茹,林宏,沈崇渝,等.元素分析-碳同位素比值质谱法在酿造酱油掺假鉴别中的应用[J].质谱学报,2015,4(36):334-340.Tan MR,Lin H,Shen CY,et al.Detection of fermented soy sauce adulteration using elemental analyzer-carbon isotope ratio mass spectrometry[J].J Chin Mass Spectr Soc,2015,4(36):334-340.
[16]陶宏兵.碳氧稳定同位素技术在葡萄酒真实性的研究与应用[D].南宁:广西大学,2014.Tao HB.Application and research of carbon and oxygen stable isotope in the authenticity of wine[D].Nanning:Guangxi University,2014.
[17]Schlesier K,Fauhl-Hassek C,Forina M,et al.Characterisation and determination of the geographical origin of wines[J].Eur Food Res Technol,2009,230(1):1-13.
[18]吴昊,谢丽琪,靳保辉,等.气相色谱-燃烧-同位素比率质谱法测定葡萄酒中5种挥发性组分的碳同位素比值及其在产地溯源中的应用[J].分析化学,2015,43(3):344-349.Wu H,Xie LQ,Jin BH,et al.Gas chromatography-combustion-isotope ratio mass spectrometry for determination of five volatile components in wine and its application in geographical origin traceability[J].Chin J Anal Chem,2015,43(3):344-349.
[19]李学民,贾光群,曹彦忠,等.液相色谱-同位素比质谱法同时测定葡萄酒中甘油和乙醇的δ13C值[J].色谱,2013,31(12):1201-1205.Li XM,Jia GQ,Cao YZ,et al.Simultaneous determination ofδ13C values of glycerol and ethanol in wine by liquid chromatography coupled with isotope ratio mass spectrometry[J].Chin J Chromatogr,2013,31(12):1201-1205.