“华光礁Ⅰ号”沉船木材降解评价及硫铁化合物分析
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(海南省博物馆,海南海口 570203)

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包春磊(1979—),男,2009年毕业于华南理工大学材料学专业,博士,研究员,研究方向为文物科技保护和南海文化遗产保护研究,E-mail: chunleibao2002@163.com

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2019年海南省基础与应用基础研究计划(自然科学领域)高层次人才项目基金资助(2019RC362)


Evaluation of wood degradation and analysis of sulfur and iron compounds of the Huaguangjiao Ⅰ shipwreck
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(Hainan Provincial Museum, Haikou 570203, China)

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    摘要:

    含有硫和铁化合物的有机材质文物在海洋长期浸泡过程中会受到生物、化学等方面的侵蚀,发掘出水后从低氧的海洋环境到有氧的空气,这些化合物就会变得不稳定,可能会引发文物化学劣化,从而降低有机质文物的机械稳定性。目前世界上打捞出水的古代沉船大多为木质有机质材料,最著名的就是瑞典斯德哥尔摩的“瓦萨(Vasa)”号和英国朴次茅斯“玛丽·玫瑰(Mary Rose)”号沉船,船体木材由于积累了海洋中硫酸盐还原菌转化的还原硫化合物以及来自船体腐蚀铁螺栓的铁离子(Ⅱ)从而劣化。据研究,数吨的还原态硫化物聚集在瑞典Vasa号战舰船身的木材中,280吨的船体中大约有2吨的硫或硫酸存在。中国“华光礁Ⅰ号”南宋沉船船货有大量铁器,制造船只的过程中又嵌入了大量铁钉用于加固船体,这些铁质物出水前后都会对木质船体形成隐患。为了对“华光礁Ⅰ号”沉船进行保护,根据实际情况选择一批样品对船体现状进行科学评估,为下一步制定保护方案提供依据。 通过对“华光礁Ⅰ号”船体选取一定数量的样品分析其含水率,并通过红外光谱仪(FTIR)、离子色谱仪(IC)、元素分析仪、等离子发射光谱仪(ICP)、X射线衍射仪(XRD),分别对木材样品的分子结构变化、化学组分、离子含量、物相构成等进行分析,评估其现状情况。通过分析,发现“华光礁Ⅰ号”松木构件与正常现代松木含水率相比普遍较高,平均含水率为447.9%,与泉州湾宋代海船船体木材300%的含水率、宁波“小白礁Ⅰ号”船体木材210%含水率相比,“华光礁Ⅰ号”船体构件降解比较严重。“华光礁Ⅰ号”饱水考古木材1%NaOH的抽取物含量远高于现代木材,总纤维素平均含量仅占现代木材的27%,说明纤维素和半纤维素已被严重降解;木质素含量有所增加,灰分平均含量为现代松木的68倍。从红外光谱看出,“华光礁Ⅰ号”考古木材与现代松木相比木材化学成分和结构发生了变化,半纤维素严重流失,纤维素分子链有部分降解,分子链结晶结构遭到破坏。“华光礁Ⅰ号”木材浸泡液中硫酸根离子浓度较高。ICP测试结果中铁离子含量很高,说明木材内无机化合物中主要含铁,结合浸泡液较高的硫酸根浓度说明船体内铁硫化合物还没有清除干净。XRD结果证实表明了铁硫化合物黄铁矿(FeS2)以及针铁矿、硫酸盐的在船体中的存在。 相比于其他文献,本研究的“华光礁Ⅰ号”沉船是目前热带地区出水的文物,高温高盐的热带气候下海洋出水含硫铁化合物的木质文物的保护及保存都是一个挑战,也是一个崭新的课题。通过对“华光礁Ⅰ号”沉船构件现状进行的科学评估,沉船保存情况不容乐观,木材糟朽程度和破坏程度均非常严重,这是文物保护工作者必须面临和解决的关键问题。

    Abstract:

    Organic cultural relics containing sulfur and iron compounds will be subject to biological and chemical erosion during long-term immersion in the ocean. After excavation, these compounds will become unstable in the transition from a low-oxygen marine environment to aerobic air, which may lead to reduction of the mechanical stability of organic cultural relics and their chemical deterioration. At present, most of the ancient shipwrecks salvaged in the world are made of wooden organic materials, among which the most famous are the Vasa in Stockholm, Sweden and the Mary Rose in Portsmouth, England, with their hull wood degraded due to the accumulation of reduced sulfur compounds transformed by sulfate-reducing bacteria in the sea and iron ions (Ⅱ) from corroded iron bolts on the hulls. According to research, several tons of reduced sulfides have accumulated in the hull wood of the Vasa, and about two tons of sulfur or sulfuric acid exists in a hull weighing 280 tons. China’s Huaguangjiao Ⅰ shipwreck of the Southern Song Dynasty has large amounts of ironware. In the process of ship manufacturing, a large number of iron nails were embedded to strengthen the hull. These iron objects may pose hidden dangers to the wooden hull before and after the excavation. In order to protect the Huaguangjiao Ⅰ shipwreck, a batch of samples was selected according to the actual situation to scientifically evaluate the status of the hull, so as to provide a basis for formulating the protection scheme in the next step. In this study, several samples were selected from the hull of Huaguangjiao Ⅰ to determine its moisture content; the molecular structure changes, chemical components, ion content and phase composition of wood samples were analyzed using a Fourier transform infrared spectrometer (FTIR), an ion chromatograph (IC), an element analyzer, an inductively coupled plasma optical emission spectrometer (ICP-OES) and an X-ray diffractometer (XRD) to evaluate its current situation. Through these analyses, it was found that, with an average moisture content of 447.9%, the moisture content of its pine components is generally higher than that of normal modern pine wood. Compared with the hull wood of a Song Dynasty shipwreck (300% moisture content) in Quanzhou Bay and that of Xiaobaijiao Ⅰ(210% moisture content) in Ningbo, the hull components of Huaguangjiao Ⅰ suffer more serious degradation. The extract content by 1% NaOH from Huaguangjiao Ⅰ water-saturated archaeological wood is much higher than that from modern wood, and its average content of total cellulose accounts for only 27% of that of modern wood, indicating that cellulose and hemicellulose have been seriously degraded. The lignin content is increased, and the average ash content is 68 times that of modern pine. It can be seen from the infrared spectrum that compared with modern pine wood, the chemical composition and structure of the archaeological wood of Huaguangjiao Ⅰ have been changed, the hemicellulose has been seriously lost, the cellulose molecular chain has been partially degraded, and the molecular chain crystal structure has been damaged. The concentration of sulfate ion in a wood-soaking solution of Huaguangjiao Ⅰ is high. The content of iron ion according to ICP-OES test results is very high, indicating that the inorganic compounds in wood are mainly iron. In combination with the high concentration of sulfate ion in the soaking solution, this indicates that the iron and sulfur compounds in the hull have not been removed. XRD results confirm the existence of iron and sulfur compounds—pyrite (FeS2), goethite and sulfate in the hull. According to the literature, the Huaguangjiao Ⅰ shipwreck is a cultural relic found in a tropical area. The conservation and preservation of sulfur- and iron-containing wooden cultural relics salvaged from a warm and salty tropical sea is not only a challenge, but also a new topic. Based on scientific evaluation of the current situation of the Huaguangjiao Ⅰ shipwreck components, it is hard to be optimistic about preservation of the shipwreck, as the degree of wood decay and damage is very serious. This is the key problem that cultural relic conservators must face and solve.

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包春磊.“华光礁Ⅰ号”沉船木材降解评价及硫铁化合物分析[J].文物保护与考古科学,2021,33(5):60-70.

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  • 收稿日期:2020-02-17
  • 最后修改日期:2020-04-28
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  • 在线发布日期: 2021-10-27
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