食品用纸包装中挥发性有机物的研究
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摘要
食品包装被称作是“特殊食品添加剂”,在一定程度上,食品包装已经成为食品不可分割的重要组成部分。近年来,某些食品包装不符合安全要求,甚至导致危害人体健康的情况颇为突出。
本文利用气相色谱一质谱联用技术(GC—MS),确定了实验条件、实验步骤及数据处理的方法;选取六种市售食品用纸包装袋,检测分析试样包装中可能含有的挥发性有机物及七种目标挥发性有机物(苯、乙苯、邻二甲苯、间／对二甲苯、异丙醇、乙酸丁酯、乙酸乙酯),对检测到的挥发性有机物进行定性定量分析；然后对实验结果进行处理并分析,最后对食品用纸包装材料的安全性进行总结讨论,给出建议和对策。
实验定性结果表明7种挥发性有机物在所检测的食品用纸包装袋中存在很多,苯系物含量较大。另外包装袋中还含有很少量的烷烃类、酮类酯类等物质。检测结果显示,基本上每种包装袋中都含有已醛和D-丙氨酸。
定量分析结果表明,在所检测的六种包装袋中,总的溶剂残留量按照目前国家标准中的规定——溶剂残留总量≤10 mg/m2,其中苯系溶剂残留量≤3mg/m2。均符合标准。而对于肉夹馍包装袋、爆米花包装袋、麦当劳包装袋这三种包装袋中溶剂残留总量虽未超标但量比较大,苯类挥发性有机物的含量也比较大。特别是肉夹馍包装袋,其苯类物质含量经过多次检测得出的平均值为3.145mg/m2超过国家规定。食品用纸包装中,含有这几种有机残留,对人体健康会造成一定的危害,尤以苯系物的含量为卫生和食品监督部门所严格控制。
HS-GC/MS方法具有进样简单、分离效果好、精密度高、适用于沸点较低的痕量物质的定性及定量分析,因此能够满足食品包装中挥发性有机物检测工作的要求。本课题通过实验研究的方法,获得第一手的实验数据,为食品用纸包装安全性后续方面的研究及我国食品包装相关法规的建立提供科学依据。
Food package are considered " kind of special addiitive in food" and to some degree, it has become an important part of food safety. Recently,some package fell short of the standard in food package, even people's health were endangered.
HS-GC/MS was used to inpect possible VOCs and certain VOCs existed in paper package materials.In this paper, firstly, experimental method and conditon was designed,6 food packages was aimed as test sample. VOCs in these packages was determined and qualitative analysis,especially,isopropanol,ethylacetate,benzene,butylactate,ethylbenzene,m/p-xylene,o-xylene.Then,the results were analyzed,and the safety of paper package materials was discussed, Finally, suggestions or advices were given and brought forward.
The results of determining nature showed that almost 7 special VOCs in these packages were found,apart from that,some substance were still found such as hydrocarbon, ester etc.In addition,some hexanal and alanine were also detected.
The results of qualitative analysis indicated that the total quantity of solvent in 6 packages were all in the range of nation standard,which was - the total quantity of solvent must be in the limit of 10 mg/m2,and the total quantity of benzene series must be under 3 mg/m2.But the total quantity of solvent in some packages such as roujiamo, popcorn and Mcdonald's were great, especially the benzene series in the package of roujaim 3.145 mg/m2 have exceeded the rule. If these VOCs were existed in paper package materials for a long time,it will do great harmness to people's health. Consequently, strict control and rigorous surveillance should be enforced to ensure food safety.The origin of these VOCs mainly lies in the usage of certain kinds of printing ink,addictive,bond,etc.
The method of HS-GC/MS has many merits including simple receiving sample, good effect of separating,high exactness,as well as low limit.So it is fitted for the VOCs who have low boiling point and less quantity,All in all, HS-GC/MS fulfill the demand of examination in food package. Through the experiment,first hand data and information were obtained to offer help in research of food package safety. It helps research afterwards and the establishment of rule of law in food safety.
本文利用气相色谱一质谱联用技术(GC—MS),确定了实验条件、实验步骤及数据处理的方法;选取六种市售食品用纸包装袋,检测分析试样包装中可能含有的挥发性有机物及七种目标挥发性有机物(苯、乙苯、邻二甲苯、间／对二甲苯、异丙醇、乙酸丁酯、乙酸乙酯),对检测到的挥发性有机物进行定性定量分析；然后对实验结果进行处理并分析,最后对食品用纸包装材料的安全性进行总结讨论,给出建议和对策。
实验定性结果表明7种挥发性有机物在所检测的食品用纸包装袋中存在很多,苯系物含量较大。另外包装袋中还含有很少量的烷烃类、酮类酯类等物质。检测结果显示,基本上每种包装袋中都含有已醛和D-丙氨酸。
定量分析结果表明,在所检测的六种包装袋中,总的溶剂残留量按照目前国家标准中的规定——溶剂残留总量≤10 mg/m2,其中苯系溶剂残留量≤3mg/m2。均符合标准。而对于肉夹馍包装袋、爆米花包装袋、麦当劳包装袋这三种包装袋中溶剂残留总量虽未超标但量比较大,苯类挥发性有机物的含量也比较大。特别是肉夹馍包装袋,其苯类物质含量经过多次检测得出的平均值为3.145mg/m2超过国家规定。食品用纸包装中,含有这几种有机残留,对人体健康会造成一定的危害,尤以苯系物的含量为卫生和食品监督部门所严格控制。
HS-GC/MS方法具有进样简单、分离效果好、精密度高、适用于沸点较低的痕量物质的定性及定量分析,因此能够满足食品包装中挥发性有机物检测工作的要求。本课题通过实验研究的方法,获得第一手的实验数据,为食品用纸包装安全性后续方面的研究及我国食品包装相关法规的建立提供科学依据。
Food package are considered " kind of special addiitive in food" and to some degree, it has become an important part of food safety. Recently,some package fell short of the standard in food package, even people's health were endangered.
HS-GC/MS was used to inpect possible VOCs and certain VOCs existed in paper package materials.In this paper, firstly, experimental method and conditon was designed,6 food packages was aimed as test sample. VOCs in these packages was determined and qualitative analysis,especially,isopropanol,ethylacetate,benzene,butylactate,ethylbenzene,m/p-xylene,o-xylene.Then,the results were analyzed,and the safety of paper package materials was discussed, Finally, suggestions or advices were given and brought forward.
The results of determining nature showed that almost 7 special VOCs in these packages were found,apart from that,some substance were still found such as hydrocarbon, ester etc.In addition,some hexanal and alanine were also detected.
The results of qualitative analysis indicated that the total quantity of solvent in 6 packages were all in the range of nation standard,which was - the total quantity of solvent must be in the limit of 10 mg/m2,and the total quantity of benzene series must be under 3 mg/m2.But the total quantity of solvent in some packages such as roujiamo, popcorn and Mcdonald's were great, especially the benzene series in the package of roujaim 3.145 mg/m2 have exceeded the rule. If these VOCs were existed in paper package materials for a long time,it will do great harmness to people's health. Consequently, strict control and rigorous surveillance should be enforced to ensure food safety.The origin of these VOCs mainly lies in the usage of certain kinds of printing ink,addictive,bond,etc.
The method of HS-GC/MS has many merits including simple receiving sample, good effect of separating,high exactness,as well as low limit.So it is fitted for the VOCs who have low boiling point and less quantity,All in all, HS-GC/MS fulfill the demand of examination in food package. Through the experiment,first hand data and information were obtained to offer help in research of food package safety. It helps research afterwards and the establishment of rule of law in food safety.
引文
[1]顶空固相微萃取—气相色谱法测定环境中挥发性有机物-中国公共卫生-刘红河黎源倩
[2]李忠 蒋次清.顶空气相色谱法测定卷烟材料中的溶剂残留[J].烟草科学研究,2003,(4)：77-79.
[3]谢焰 浦俊卿.顶空-气相色谱法测定卷烟商标纸中的挥发性有机化合物(VOCs)[C].中国烟草学会工业专业委员会.2004中烟烟草化学学组年会暨学术研讨会论文集[C].2004.166-175.
[4]汪正范.色谱定性与定量[M].北京：化学工业出版社,2003.179-180.
[5]申书昌,张维兵,崔力行.色谱,2000,18(6)：571-573
[6]汤桦,雷根虎,李鹏,孔详虹,何学文.色谱,2003,21(2)：178-180
[7]王卫.药品中有机溶剂残留量及其测定[J].天津药学,2001,13(6)：13
[8]吴丽苹,陈浩然.关于食品包装卫生要求的检测[J].科技信息,2007(20)：548.
[9]GB/T 9685-2003,食品溶剂、包装材料用助剂使用卫生标准[S].北京：中国标准出版社,2004.
[10]胡兴军.关注食品包装安全[J].中国食品,2007(2)：54-55.
[11]张黎明.我国食品包装安全问题的现状与分析[J].中国包装,2007(2).
[12]吴春明.奶粉包装溶剂残留问题探源[J].中国包装工业,2007(12)：40-42.
[13]赵世亮.食品包装残留溶剂知多少[J].中国包装工业,2007(12)：43-44.
[14]杨炳海.浅析烟标异味的来源及控制[J].印刷世界,2005(9)：6-7.
[15]郭紫明,李艳春,蒋腊梅,董道竹,樊华,刘斌.烟用包装材料中挥发性有机物VOCs的定性分析[J].湖南农业大学学报(自然科学版),2006(3)：248-250.
[16]朱勇,王志伟,王雷.化学物在食品和包装系统中分配系数的一种近似处理[J].包装工程,2006(27)：15-16.
[17]刘玉敏,路庆华,庄明珠,赖奕坚,马钢,朱新远.静态顶空/气相色谱-质谱联用快速测定茶粉中残留溶剂[J].分析测试学报,2007(26)：122-124.
[18]廖远熹,程志红,王昊阳,郭寅龙,邵应男.静态顶空气相色谱-质谱联用鉴别硫黄熏制的柴胡[J].中国中药杂志,2005(30)：1909-1911.
[19]董永智,盛志艺,周仕禄,彭莹,阮晓明.卷烟商标残留成分的顶空-GC/MS分析[J].烟草科技,2006(10)：49-52.
[20]廖远熹,王昊阳,郭寅龙,邵应男.中药柴胡挥发性成分的静态顶空-气相色谱-质谱分析[J].质谱学报,2005(26)：187-192.
[21]彭姗姗,文飞食品包装风险分析及防范 [J]包装工程,2006,273：222-2251
[22]姚卫蓉.食品包装污染物研究进展 [J]现代食品科技,2005,211：150-1531
[23]P. Maneesin. GC-MS and electronic nose analysis on off-flavor components in HDPE containers and correlation with sensory evaluation[D]. Michigan State University,2001:1-167.
[24]袁振华 食品包装村料中化学物向食品迁移和安全评估 [J]浙江预防医学,1999 1129-311
[25]王克利,李明元 固相萃取HPLC-PDA测定罐装食品中双酚 A[J]口岸卫生控制,2002,64：43-431
[26]王志伟,孙彬青,刘志刚.包装材料化学物迁移研究[J].包装工程,2004(25)：14.
[27]孙彬青,王志伟,刘志刚.包装材料化学物迁移研究[J].包装工程,2004(25)：14.
[28]陈志锋,潘健伟,储晓刚,唐英章.塑料食品包装材料中有毒有害化学残留物及分析方法[J].食品与机械,2006(22)：3-7.
[29]刘志刚,王志伟.塑料包装材料化学物向食品迁移的模型研究进展[J].高分子材料科学与工程,2007(23)：19-23.
[30]D. Thompson, S. J. Parry, R. Benzing. The validation of a method for determining the migration of trace elements from food packaging materials into food[J]. Journal of Radioanalytical and Nuclear Chemistry,1997(217):147-150.
[31]S. Biedermann-Brem, M. Biedermann, K. Fiselier, K. Grob. Compositional GC-FID analysis of the additives to PVC focusing on the gaskets of lids for glass jars[J]. Food Addit Contam.,2005(22):1274-1284.
[32]L. Coulier, F. R. Kaal, M. Tienstra, T. Hankemeier. Identification and quantification of (polymeric) hindered-amine light stabilizers in polymers using pyrolysis-gas chromatography-mass spectrometry and liquid chromatography-ultraviolet absorbance detection-evaporative light scattering detection[J]. J. Chromatogr A.,2005,1062(2):227-238.
[33]Rainer Buchalla, Christian Boess, Klaus Werner Bogl. Analysis fo volatile radiolysis products in gamma-irradiated LDPE and polypropylene films by thermal desorption-gas chromatography-mass spectrometry[J]. Applied Radiation and Isotopes,2000(52):251-269.
[2]李忠 蒋次清.顶空气相色谱法测定卷烟材料中的溶剂残留[J].烟草科学研究,2003,(4)：77-79.
[3]谢焰 浦俊卿.顶空-气相色谱法测定卷烟商标纸中的挥发性有机化合物(VOCs)[C].中国烟草学会工业专业委员会.2004中烟烟草化学学组年会暨学术研讨会论文集[C].2004.166-175.
[4]汪正范.色谱定性与定量[M].北京：化学工业出版社,2003.179-180.
[5]申书昌,张维兵,崔力行.色谱,2000,18(6)：571-573
[6]汤桦,雷根虎,李鹏,孔详虹,何学文.色谱,2003,21(2)：178-180
[7]王卫.药品中有机溶剂残留量及其测定[J].天津药学,2001,13(6)：13
[8]吴丽苹,陈浩然.关于食品包装卫生要求的检测[J].科技信息,2007(20)：548.
[9]GB/T 9685-2003,食品溶剂、包装材料用助剂使用卫生标准[S].北京：中国标准出版社,2004.
[10]胡兴军.关注食品包装安全[J].中国食品,2007(2)：54-55.
[11]张黎明.我国食品包装安全问题的现状与分析[J].中国包装,2007(2).
[12]吴春明.奶粉包装溶剂残留问题探源[J].中国包装工业,2007(12)：40-42.
[13]赵世亮.食品包装残留溶剂知多少[J].中国包装工业,2007(12)：43-44.
[14]杨炳海.浅析烟标异味的来源及控制[J].印刷世界,2005(9)：6-7.
[15]郭紫明,李艳春,蒋腊梅,董道竹,樊华,刘斌.烟用包装材料中挥发性有机物VOCs的定性分析[J].湖南农业大学学报(自然科学版),2006(3)：248-250.
[16]朱勇,王志伟,王雷.化学物在食品和包装系统中分配系数的一种近似处理[J].包装工程,2006(27)：15-16.
[17]刘玉敏,路庆华,庄明珠,赖奕坚,马钢,朱新远.静态顶空/气相色谱-质谱联用快速测定茶粉中残留溶剂[J].分析测试学报,2007(26)：122-124.
[18]廖远熹,程志红,王昊阳,郭寅龙,邵应男.静态顶空气相色谱-质谱联用鉴别硫黄熏制的柴胡[J].中国中药杂志,2005(30)：1909-1911.
[19]董永智,盛志艺,周仕禄,彭莹,阮晓明.卷烟商标残留成分的顶空-GC/MS分析[J].烟草科技,2006(10)：49-52.
[20]廖远熹,王昊阳,郭寅龙,邵应男.中药柴胡挥发性成分的静态顶空-气相色谱-质谱分析[J].质谱学报,2005(26)：187-192.
[21]彭姗姗,文飞食品包装风险分析及防范 [J]包装工程,2006,273：222-2251
[22]姚卫蓉.食品包装污染物研究进展 [J]现代食品科技,2005,211：150-1531
[23]P. Maneesin. GC-MS and electronic nose analysis on off-flavor components in HDPE containers and correlation with sensory evaluation[D]. Michigan State University,2001:1-167.
[24]袁振华 食品包装村料中化学物向食品迁移和安全评估 [J]浙江预防医学,1999 1129-311
[25]王克利,李明元 固相萃取HPLC-PDA测定罐装食品中双酚 A[J]口岸卫生控制,2002,64：43-431
[26]王志伟,孙彬青,刘志刚.包装材料化学物迁移研究[J].包装工程,2004(25)：14.
[27]孙彬青,王志伟,刘志刚.包装材料化学物迁移研究[J].包装工程,2004(25)：14.
[28]陈志锋,潘健伟,储晓刚,唐英章.塑料食品包装材料中有毒有害化学残留物及分析方法[J].食品与机械,2006(22)：3-7.
[29]刘志刚,王志伟.塑料包装材料化学物向食品迁移的模型研究进展[J].高分子材料科学与工程,2007(23)：19-23.
[30]D. Thompson, S. J. Parry, R. Benzing. The validation of a method for determining the migration of trace elements from food packaging materials into food[J]. Journal of Radioanalytical and Nuclear Chemistry,1997(217):147-150.
[31]S. Biedermann-Brem, M. Biedermann, K. Fiselier, K. Grob. Compositional GC-FID analysis of the additives to PVC focusing on the gaskets of lids for glass jars[J]. Food Addit Contam.,2005(22):1274-1284.
[32]L. Coulier, F. R. Kaal, M. Tienstra, T. Hankemeier. Identification and quantification of (polymeric) hindered-amine light stabilizers in polymers using pyrolysis-gas chromatography-mass spectrometry and liquid chromatography-ultraviolet absorbance detection-evaporative light scattering detection[J]. J. Chromatogr A.,2005,1062(2):227-238.
[33]Rainer Buchalla, Christian Boess, Klaus Werner Bogl. Analysis fo volatile radiolysis products in gamma-irradiated LDPE and polypropylene films by thermal desorption-gas chromatography-mass spectrometry[J]. Applied Radiation and Isotopes,2000(52):251-269.