秦始皇兵马俑彩绘胶料的气相色谱-质谱联用分析
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摘要
采用气相色谱-质谱联用技术,结合C4柱固相萃取、氨水超声辅助萃取、离子交换树脂净化以及微波辅助水解/皂化等步骤,建立了对同一个文物样品进行蛋白、脂肪酸和糖类物质分析的方法。利用此方法分析了秦始皇兵马俑彩绘所使用胶料中的氨基酸、脂肪酸和糖类物质,结果表明,秦俑彩绘样品使用的胶料为蛋白类物质,但残留量较低(仅有0.89‰)。通过样品胶料的氨基酸组成特点,即均含有动物胶的特征氨基酸羟基脯氨酸,以及甘氨酸、谷氨酸及脯氨酸的相对含量,结合因子分析,判断7件文物样品的胶料为蛋类与动物胶的混合物, 2件为动物胶与奶类的混合物, 1件为动物胶、奶类和蛋类的三元混合物。本研究结果表明,秦俑彩绘制作时的胶料选择可能并没有严格一致的规定,当前秦俑彩绘易于脱落的另一重要原因是胶料残留量少,出土后应立即进行加固处理。
For analysis and identification of binding media used in the polychrome of Qin Shihuang Terracotta and Horses, gas chromatography-mass spectrometry combined with pretreatments such as solid phase extraction, ultrasonic assisted extraction, ion exchange resin purification and microwave-assisted hydrolysis was used for amino acids analysis, fatty acids analysis and saccharides analysis. By comparing the protein amounts, ester amounts and polysaccharide amounts in the samples, it was found that only the protein binding media was used in Terracotta and Horses of Qin Shihuang. The residue of protein was very low(only 0.89‰ in weight). According to the features of hydroxyproline, glycine, glutamic acid and proline in binder and principle component analysis, it could be confirmed that the binder of seven samples were the mixture of animal glue and egg, two samples were the mixture of animal glue and casein, and one sample was the mixture of casein, egg and animal glue. From the analysis results, it was inferred that there might be not strict and consistent regulations about the usage of binding media in Terracotta and Horses in Qin dynasty. And for the Qin Shihuang Terracotta and Horses, the low amount of binding media residue was another important reason of color decoration falling off. So the Terracotta and Horses should be consolidated immediately after excavation.
For analysis and identification of binding media used in the polychrome of Qin Shihuang Terracotta and Horses, gas chromatography-mass spectrometry combined with pretreatments such as solid phase extraction, ultrasonic assisted extraction, ion exchange resin purification and microwave-assisted hydrolysis was used for amino acids analysis, fatty acids analysis and saccharides analysis. By comparing the protein amounts, ester amounts and polysaccharide amounts in the samples, it was found that only the protein binding media was used in Terracotta and Horses of Qin Shihuang. The residue of protein was very low(only 0.89‰ in weight). According to the features of hydroxyproline, glycine, glutamic acid and proline in binder and principle component analysis, it could be confirmed that the binder of seven samples were the mixture of animal glue and egg, two samples were the mixture of animal glue and casein, and one sample was the mixture of casein, egg and animal glue. From the analysis results, it was inferred that there might be not strict and consistent regulations about the usage of binding media in Terracotta and Horses in Qin dynasty. And for the Qin Shihuang Terracotta and Horses, the low amount of binding media residue was another important reason of color decoration falling off. So the Terracotta and Horses should be consolidated immediately after excavation.
引文
1 HE Shi-Min,CHEN Hai-Dong,RONG Bo,ZHOU Tie,ZHANG Hui,ZHANG Bing-Jian.Sciences of Conservation and Archaeology.,2014,(4):14-24何诗敏,陈海栋,容波,周铁,张晖,张秉坚.文物保护与考古科学,2014,(4):14-24
2 ZHAO Zhen,XIAO Wei-Guo,XIA Ju-Xian,ZHANG Tian-Zhu,XU Wei-Hong,LIU Qun.Cultural Relics,2015,(9):4-38赵震,肖卫国,夏居宪,张天柱,许卫红,刘群.文物,2015,(9):4-38
3 SHEN Yang.China Cultural Heritage,2014,(3):94-101沈阳.中国文化遗产,2014,(3):94-101
4 WU Chen,WANG Li-Qin,YANG Lu,MA Zhen-Zhen.Chinese J.Anal.Chem.,2013,41(11):1773-1779吴晨,王丽琴,杨璐,马珍珍.分析化学,2013,41(11):1773-1779
5 YAN Hong-Tao,AN Jing-Jing,ZHOU Tie,RONG Bo,XIA Yin.Journal of Analytical Science,2012,28(5):708-714闫宏涛,安晶晶,周铁,容波,夏寅.分析科学学报,2012,28(5):708-714
6 Hu W J,Zhang K,Zhang H,Zhang B J,Rong B.J.Cult.Her.,2015,16(2):244-248
7 AN Jing-Jing,YAN Hong-Tao.Chinese Science Bulletin.,2013,58(3):211-217安晶晶,闫宏涛.科学通报,2013,58(3):211-217
8 ZHOU Rui-Ze,ZHOU Ya,MAO Ting,JIANG Jie.Chinese Journal of Chromatography,2018,36(1):43-50周瑞泽,周雅,毛婷,姜洁.色谱,2018,36(1):43-50
9 Degano I,La Nasa J,Ghelardi E,Modugno F,Colombini M P.Talanta,2016,161:62-70
10 Namdar D,Shoval S,Amrani A,van den Brink E C M,Kirzner D,Beeri R.J.Archaeol.Sci.Rep.,2017,12:726-733
11 Serefidou M,Bracci S,Tapete D,Andreotti A,Biondi L,Colombini M P.Microchem.J.,2016,127:187-198
12 Leila B,Antonella T,Marco T,Finizia A,Luigi P,Angela A,Roberto V.Archaeol.Anthropol.Sci.,2017,9:591-602
13 Research Group on Protection Technology of Qin Terra-cotta Warriors Painting.Journal of Chinese Lacquer,2005,(1):7-16秦俑彩绘保护技术研究课题组.中国生漆,2005,(1):7-16
14 Bonaduce I,Blaensdorf C,Dietemann P,Colombini M P.J.Cult.Her.,2008,9(1):103-108
15 Yan H T,An J J,Zhou T,Xia Y,Rong B.Chin.Sci.Bull.,2014,59(21):2574-2581
16 Skoog D A,West D M,Holler F J,Crouch S R.Fundamentals of Analytical Chemistry 9th ed.Belmont:Thomson Brooks Cole,2013:187
17 Colombini MP,Modugno F,Gamberini M C.Anal.Bioanal.Chem.,2011,401(6):1847-1860
18 Colombini M P,Modugno F,Menicagli E,Fuoco R,Giacomelli A.Microchem.J.,2000,67:291-300
19 YANG Lu,WANG Li-Qin,HUANG Jian-Hua,MA Tao,LI Xiao-Xxi.Chinese J.Anal.Chem.,2010,38(7):1044-1047杨璐,王丽琴,黄建华,马涛,李晓溪.分析化学,2010,38(7):1044-1047
20 Ma Z Z,Yan J,Zhao X C,Wang L Q,Yang L.J.Cult.Her.,2017,24:171-174
21 Dallongeville S,Garnier N,Rolando C,Tokarski C.Chem.Rev.,2016,116(1):2-79
22 Tomasini E,Rodríguez D C,Gómez B A,de Faria D L A,Landa C R,Siracusano G.Microchem.J.,2016,128:172-180
2 ZHAO Zhen,XIAO Wei-Guo,XIA Ju-Xian,ZHANG Tian-Zhu,XU Wei-Hong,LIU Qun.Cultural Relics,2015,(9):4-38赵震,肖卫国,夏居宪,张天柱,许卫红,刘群.文物,2015,(9):4-38
3 SHEN Yang.China Cultural Heritage,2014,(3):94-101沈阳.中国文化遗产,2014,(3):94-101
4 WU Chen,WANG Li-Qin,YANG Lu,MA Zhen-Zhen.Chinese J.Anal.Chem.,2013,41(11):1773-1779吴晨,王丽琴,杨璐,马珍珍.分析化学,2013,41(11):1773-1779
5 YAN Hong-Tao,AN Jing-Jing,ZHOU Tie,RONG Bo,XIA Yin.Journal of Analytical Science,2012,28(5):708-714闫宏涛,安晶晶,周铁,容波,夏寅.分析科学学报,2012,28(5):708-714
6 Hu W J,Zhang K,Zhang H,Zhang B J,Rong B.J.Cult.Her.,2015,16(2):244-248
7 AN Jing-Jing,YAN Hong-Tao.Chinese Science Bulletin.,2013,58(3):211-217安晶晶,闫宏涛.科学通报,2013,58(3):211-217
8 ZHOU Rui-Ze,ZHOU Ya,MAO Ting,JIANG Jie.Chinese Journal of Chromatography,2018,36(1):43-50周瑞泽,周雅,毛婷,姜洁.色谱,2018,36(1):43-50
9 Degano I,La Nasa J,Ghelardi E,Modugno F,Colombini M P.Talanta,2016,161:62-70
10 Namdar D,Shoval S,Amrani A,van den Brink E C M,Kirzner D,Beeri R.J.Archaeol.Sci.Rep.,2017,12:726-733
11 Serefidou M,Bracci S,Tapete D,Andreotti A,Biondi L,Colombini M P.Microchem.J.,2016,127:187-198
12 Leila B,Antonella T,Marco T,Finizia A,Luigi P,Angela A,Roberto V.Archaeol.Anthropol.Sci.,2017,9:591-602
13 Research Group on Protection Technology of Qin Terra-cotta Warriors Painting.Journal of Chinese Lacquer,2005,(1):7-16秦俑彩绘保护技术研究课题组.中国生漆,2005,(1):7-16
14 Bonaduce I,Blaensdorf C,Dietemann P,Colombini M P.J.Cult.Her.,2008,9(1):103-108
15 Yan H T,An J J,Zhou T,Xia Y,Rong B.Chin.Sci.Bull.,2014,59(21):2574-2581
16 Skoog D A,West D M,Holler F J,Crouch S R.Fundamentals of Analytical Chemistry 9th ed.Belmont:Thomson Brooks Cole,2013:187
17 Colombini MP,Modugno F,Gamberini M C.Anal.Bioanal.Chem.,2011,401(6):1847-1860
18 Colombini M P,Modugno F,Menicagli E,Fuoco R,Giacomelli A.Microchem.J.,2000,67:291-300
19 YANG Lu,WANG Li-Qin,HUANG Jian-Hua,MA Tao,LI Xiao-Xxi.Chinese J.Anal.Chem.,2010,38(7):1044-1047杨璐,王丽琴,黄建华,马涛,李晓溪.分析化学,2010,38(7):1044-1047
20 Ma Z Z,Yan J,Zhao X C,Wang L Q,Yang L.J.Cult.Her.,2017,24:171-174
21 Dallongeville S,Garnier N,Rolando C,Tokarski C.Chem.Rev.,2016,116(1):2-79
22 Tomasini E,Rodríguez D C,Gómez B A,de Faria D L A,Landa C R,Siracusano G.Microchem.J.,2016,128:172-180