饱水古木材难溶盐分析
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摘要
为研究饱水古木材中难溶盐的成分和分布,基于电感耦合等离子体光谱、X射线衍射以及显微共聚焦激光拉曼等分析手段对出土出水饱水古木材表面和纵向横向不同取样深度的元素含量和分布、表面凝结物以及纵向横向切面颗粒物的物相进行了分析。分析结果表明饱水古木材含有大量的Fe、S和Ca元素,包含这三种元素的凝结物主要由难溶盐和不溶物组成。难溶盐主要分为两大类,一类为钙盐(包括硫酸盐、碳酸盐和磷酸盐等),一类为硫铁化合物(包括硫铁矿、黄铁矿、磁黄铁矿等);不溶物包括各类铁氧化物(如针铁矿、纤铁矿、赤铁矿和水合氧化铁)以及硫单质等。难溶盐分析结果有助于有针对性地对饱水古木材难溶盐尤其是对古木材危害比较大难溶盐进行预防控制和有效脱除。
In our study, we analyzed the elemental content and distribution on the surface and at different sampling depths longitudinally and transversely, the phases of the sediments on the surface and the particles on the longitudinal and transverse sections of waterlogged archaeological wood, using inductively coupled plasma(ICP) spectrometry, X-ray diffraction(XRD) and micro-confocal laser Raman spectrometry. The results show that waterlogged archaeological wood is rich in the elements, iron(Fe), sulfur(S) and calcium(Ca), and that the sediments containing these three elements are mainly composed of insoluble salts and other insoluble substances. The insoluble salts are mainly divided into two categories, namely, calcium salts(including sulfate, carbonate and phosphate), and iron sulfides(including troilite, pyrite and pyrrhotite). The other insoluble substances include various types of iron oxides(such as goethite, hematite and lepidocrocite, hydrated ferric oxide) and elemental sulfur, etc. The analytical results for these insoluble salts contribute to an understanding of the preventive control and effective removal of insoluble salts on or in waterlogged archaeological wood, especially those seriously harmful to the waterlogged archaeological wood.
In our study, we analyzed the elemental content and distribution on the surface and at different sampling depths longitudinally and transversely, the phases of the sediments on the surface and the particles on the longitudinal and transverse sections of waterlogged archaeological wood, using inductively coupled plasma(ICP) spectrometry, X-ray diffraction(XRD) and micro-confocal laser Raman spectrometry. The results show that waterlogged archaeological wood is rich in the elements, iron(Fe), sulfur(S) and calcium(Ca), and that the sediments containing these three elements are mainly composed of insoluble salts and other insoluble substances. The insoluble salts are mainly divided into two categories, namely, calcium salts(including sulfate, carbonate and phosphate), and iron sulfides(including troilite, pyrite and pyrrhotite). The other insoluble substances include various types of iron oxides(such as goethite, hematite and lepidocrocite, hydrated ferric oxide) and elemental sulfur, etc. The analytical results for these insoluble salts contribute to an understanding of the preventive control and effective removal of insoluble salts on or in waterlogged archaeological wood, especially those seriously harmful to the waterlogged archaeological wood.
引文
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[12] DONALD E C.Reactive iron in marine sediments[J].Geochimica et Cosmochimica Acta,1989,53:619-632.
[13] LARRASOANA J C,ROBERTS A P,MUSGRAVE R J,et al.Diagenetic formation of greigite and pyrrhotite in gas hydrate marine sedimentary system[J].Earth and Planetary Science Letters,2007,261(3-4):350-366.
[2] MAGNUS S,FARIDEH J,INGMAR P,et al.Acidity and salt precipitation on the Vasa:the sulfur problem[C]//Proceedings 8th ICOM-CC WOAM Conference,Stockholm,2001:67-89.
[3] MAGNUS S,FARIDEH J,EMILIANA D,et al.Sulfur accumulation in the timbers of King Henry VIII’s warship Mary Rose:A pathway in the sulfur cycle of conservation concern[J].Proceedings of National Academy Sciences USA,2005,102(40):14165-14170.
[4] WETHERALL K M,MOSS R M,JONES A M,et al.Sulfur and iron speciation in recently recovered timbers of the Mary Rose revealed via X-ray absorption spectroscopy[J].Journal of Archaeological Science,2008,35(5):1317-1328.
[5] CéLINE R,KHOI T,ELODIE G,et al.Study of Fe(II) sulphides in waterlogged archaeological wood[J].Studies in Conservation,2013,58(4):297-307.
[6] GUNNAR A,INGMAR P.Analysis of acids and degradation products related to iron and sulfur in the Swedish warship Vasa[J].Holzforschung,2008,62:694-703.
[7] YVONNE F,FARIDEH J,EMILIANA D R,et al.Sulfur and iron analyses of marine archaeological wood in shipwrecks from the Baltic Sea and Scandinavian waters[J].Journal of Archaeological Science,2012,39:2521-2532.
[8] YVONNE F,MAGNUS S.Sulfur and iron in shipwrecks cause conservation concerns[J].Chemical Society Review,2006,35:399-415.
[9] 沈大娲,葛琴雅,杨淼,等.海洋出水木质文物保护中的硫铁化合物问题[J].文物保护与考古科学,2013,25(1):82-88.SHEN Dawa,GE Qinya,YANG Miao,et al.Iron sulfide in the conservation of marine archaeological wood[J].Sciences of Conservation and Archaeology,2013,25(1):82-88.
[10] 马丹,郑幼明.“华光礁一号”南宋沉船船板中硫铁化合物分析[J].文物保护与考古科学,2012,24(3):84-89.MA Dan,ZHENG Youming.Analysis of the iron sulfides in the shipwrecks Huaguang Reef I of the Southern Song Dynasty[J].Sciences of Conservation and Archaeology,2012,24(3):84-89.
[11] 张治国,李乃胜,田兴玲,等.宁波“小白礁I号”清代木质沉船中硫铁化合物脱除技术研究[J].文物保护与考古科学,2014,26(4):30-38.ZHANG Zhiguo,LI Naisheng,TIAN Xingling,et al.Research on the removal of the iron sulfides in the Qing Dynasty marine shipwreck,Ningbo Xiaobaijiao No.1[J].Sciences of Conservation and Archaeology,2014,26(4):30-38.
[12] DONALD E C.Reactive iron in marine sediments[J].Geochimica et Cosmochimica Acta,1989,53:619-632.
[13] LARRASOANA J C,ROBERTS A P,MUSGRAVE R J,et al.Diagenetic formation of greigite and pyrrhotite in gas hydrate marine sedimentary system[J].Earth and Planetary Science Letters,2007,261(3-4):350-366.