新疆汉代羊毛织物染料的飞行时间二次离子质谱表征

O657.63; 汉代女性干尸着鲜艳的红-蓝-浅黄三色羊毛纤维编制的华丽服饰,本研究以织物片段作为研究样本,主要采用飞行时间二次离子质谱(TOF-SIMS)法对其染料进行表征.离子成像与高质量分辨数据显示:红色纤维表面产生汞同位素离子(202Hg+和199Hg+)、汞-硫离子(HgS+,m/z 234)、硫同位素离子(32S-和34S-)等,指示其染料属于天然无机矿物朱砂(HgS);蓝色纤维则出现目标化合物的准分子离子m/z 263([M+H]+),以及合理的碎片离子系列,如m/z 235(C15H11N2O+)和m/z 247(C16H11N2O+)等,指示其呈色来自经典天然植物有机染料靛蓝...

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Published in质谱学报 Vol. 45; no. 3; pp. 386 - 395
Main Authors 刘婕, 陈相龙, 梁汉东, 铁偲, 李展平
Format Journal Article
LanguageChinese
Published 煤炭精细勘探与智能开发全国重点实验室,北京 100083 01.05.2024
中国矿业大学(北京)地球科学与测绘工程学院,北京 100083%中国社会科学院考古研究所,北京 100101%煤炭精细勘探与智能开发全国重点实验室,北京 100083%清华大学化学系,有机光电子与分子工程教育部重点实验室,北京 100084
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ISSN1004-2997
DOI10.7538/zpxb.2024.1009

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Abstract O657.63; 汉代女性干尸着鲜艳的红-蓝-浅黄三色羊毛纤维编制的华丽服饰,本研究以织物片段作为研究样本,主要采用飞行时间二次离子质谱(TOF-SIMS)法对其染料进行表征.离子成像与高质量分辨数据显示:红色纤维表面产生汞同位素离子(202Hg+和199Hg+)、汞-硫离子(HgS+,m/z 234)、硫同位素离子(32S-和34S-)等,指示其染料属于天然无机矿物朱砂(HgS);蓝色纤维则出现目标化合物的准分子离子m/z 263([M+H]+),以及合理的碎片离子系列,如m/z 235(C15H11N2O+)和m/z 247(C16H11N2O+)等,指示其呈色来自经典天然植物有机染料靛蓝(C16H10N2O2,分子质量 262.074 2);浅黄纤维未检出有机染料(如姜黄)或无机染料(如铁黄),其呈色可能是白色羊毛自然老化陈旧所致.本工作表明,擅长微区原位与超高灵敏度检测的TOF-SIMS法既适用于有机染料分析,也适用于无机染料分析,该方法有望在考古和博物馆馆藏相关研究中获得广泛应用.
AbstractList O657.63; 汉代女性干尸着鲜艳的红-蓝-浅黄三色羊毛纤维编制的华丽服饰,本研究以织物片段作为研究样本,主要采用飞行时间二次离子质谱(TOF-SIMS)法对其染料进行表征.离子成像与高质量分辨数据显示:红色纤维表面产生汞同位素离子(202Hg+和199Hg+)、汞-硫离子(HgS+,m/z 234)、硫同位素离子(32S-和34S-)等,指示其染料属于天然无机矿物朱砂(HgS);蓝色纤维则出现目标化合物的准分子离子m/z 263([M+H]+),以及合理的碎片离子系列,如m/z 235(C15H11N2O+)和m/z 247(C16H11N2O+)等,指示其呈色来自经典天然植物有机染料靛蓝(C16H10N2O2,分子质量 262.074 2);浅黄纤维未检出有机染料(如姜黄)或无机染料(如铁黄),其呈色可能是白色羊毛自然老化陈旧所致.本工作表明,擅长微区原位与超高灵敏度检测的TOF-SIMS法既适用于有机染料分析,也适用于无机染料分析,该方法有望在考古和博物馆馆藏相关研究中获得广泛应用.
Abstract_FL In Xinjiang,China,a female corpse dating back to the Han Dynasty was discovered adorned in splendid attire crafted from wool fibers dyed in vibrant shades of red,blue,and light yellow.This study utilized fabric fragments as research specimens to analyze the dyes present,primarily employing time of flight secondary ion mass spectrometry(TOF-SIMS),in conjunction with optical microscopy,ultra-high performance liquid chromatography-high resolution mass spectrometry(UPLC-HRMS)and a mercury vapor analyzer for precise characterization.The TOF-SIMS analysis revealed the presence of mercury isotopic ions(202Hg+ and 199Hg+),mercury-sulfur ions(HgS+,m/z 234),sulfur isotopic ions(32S-and 34S-)on the surface of the red fiber samples.These findings suggest the utilization of cinnabar(HgS),a naturally occurring inorganic mineral dye,in the red fibers.Moreover,mercury content measurements indicated a significant enrichment of mercury in the red fibers,with the Hg content of 84 ng/g,markedly higher than the average Hg content of other fibers,which stood at 31 ng/g.Analysis of the blue fiber samples detected the quasi-molecular ion m/z 263([M+H]+)and a series of reasonable fragment ions,such as m/z 235(C15H11N2O+)and m/z 247(C16H11N2O+),indicative of the presence of indigo,a natural plant-based organic dye.UPLC-HRMS analysis further confirmed the presence of indigo in the blue fabric samples,providing cross-validation of the dye used.The light yellow fiber samples did not yield detections of common organic dyes like turmeric or inorganic pigments such as iron-yellow(Fe2O3H2O).The yellow hue observed in these fibers may be attributed to the natural aging of the original white wool,remaining undyed.Additionally,granular water-soluble inorganic ions such as NaCl,carbonate,and sulfate were detected within the yellow fabric samples.This study underscores the efficacy of the TOF-SIMS method for in-situ microanalysis and ultra-high sensitivity detection,rendering it is suitable for the analysis of both organic dye and inorganic dye.Moreover,TOF-SIMS will be widely used in archaeological and museum collections related research.
Author 梁汉东
陈相龙
铁偲
李展平
刘婕
AuthorAffiliation 煤炭精细勘探与智能开发全国重点实验室,北京 100083;中国矿业大学(北京)地球科学与测绘工程学院,北京 100083%中国社会科学院考古研究所,北京 100101%煤炭精细勘探与智能开发全国重点实验室,北京 100083%清华大学化学系,有机光电子与分子工程教育部重点实验室,北京 100084
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Author_FL TIE Cai
LI Zhan-ping
LIU Jie
CHEN Xiang-long
LIANG Han-dong
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DocumentTitle_FL Characterization of Dyes for Han Dynasty Wool Fabrics in Xinjiang by Time-of-Flight Secondary Ion Mass Spectrometry
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Keywords Han Dynasty
无机
fabric
汉代
飞行时间二次离子质谱(TOF-SIMS)
time of flight secondary ion mass spectrometry(TOF-SIMS)
染料
dyes
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有机
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中国矿业大学(北京)地球科学与测绘工程学院,北京 100083%中国社会科学院考古研究所,北京 100101%煤炭精细勘探与智能开发全国重点实验室,北京 100083%清华大学化学系,有机光电子与分子工程教育部重点实验室,北京 100084
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Snippet O657.63; 汉代女性干尸着鲜艳的红-蓝-浅黄三色羊毛纤维编制的华丽服饰,本研究以织物片段作为研究样本,主要采用飞行时间二次离子质谱(TOF-SIMS)法对其染料进行表征.离子成...
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Title 新疆汉代羊毛织物染料的飞行时间二次离子质谱表征
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