古代壁画颜料变色研究进展
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(1.国家古代壁画与土遗址保护工程技术研究中心(敦煌研究院),甘肃酒泉 736200;2.细胞活动与逆境适应教育部重点实验室(兰州大学),甘肃兰州 730000;3.古代壁画保护国家文物局重点科研基地(敦煌研究院),甘肃酒泉 736200;4.甘肃省敦煌文物保护研究中心(敦煌研究院),甘肃酒泉 736200)

作者简介:

陈雨鑫(1994—),女,2021年博士毕业于日本东京都立大学,馆员,研究方向为文物的生物退化及防护,E-mail: yukiko0312@163.com. 通信作者:武发思(1983—),男,博士,研究馆员,E-mail: wufs@dha.ac.cn

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国家自然科学基金项目(U21A20282;32400140;32060258)资助,国家级青年拔尖人才项目,甘肃省敦煌文物保护研究中心开放课题(GDW2021ZD08)资助


Research progress on the discoloration of ancient mural pigments
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(1. National Research Center for Conservation of Ancient Wall Paintings and Earthen Sites (Dunhuang Academy), Jiuquan 736200, China;2. Key Laboratory of Cell Activities and Stress Adaptations (Lanzhou University), Ministry of Education, Lanzhou 730000, China;3. Key Scientific Research Base for Conservation of Ancient Wall Paintings (Dunhuang Academy), National Cultural Heritage Administration, Jiuquan 736200, China;4. Gansu Provincial Research Center for Conservation of Dunhuang Cultural Heritage (Dunhuang Academy), Jiuquan 736200, China)

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    摘要:

    颜料变色是古代壁画常见病害之一,其中含铅颜料的褪变色问题尤为突出,严重影响到壁画的艺术价值、历史价值和科学价值。长期以来,矿物颜料变色的成因与机制一直是文物保护领域关注的焦点,针对包括含铅颜料在内的变色产物表征与变色过程模拟已有大量研究。本文系统总结了国内外对于古代壁画典型含铅矿物颜料变色的成因研究,提出光照、湿度、微生物,以及壁画表面酸碱性、可溶盐是影响含铅颜料变色的主要因素,并详细分析了铅丹颜料变色过程中涉及的物理学、化学和生物学机制。通过对变色含铅颜料的色彩复原技术的讨论,进一步展望了未来在壁画颜料变色过程及色彩复原领域的重点研究方向。同时,本文对其他常见矿物颜料如红色颜料朱砂、土红,绿色颜料氯铜矿、巴黎绿、舍勒绿,以及蓝色颜料青金石、蓝铜矿等颜料的使用及其褪变色研究进展进行了梳理,明确了赋存环境质量对于颜料色彩保持的重要性。本文可为古代壁画矿物颜料变色现象的科学认知和减缓变色的预防性保护对策制定提供参考依据。

    Abstract:

    As one of the earliest forms of painting in human history, ancient murals are invaluable cultural treasures. They reflect scientific, technological, artistic, and societal developments from different eras, holding immense historical and artistic value. Murals evolved from simple patterns to complex, colorful representations of inner emotions and aspirations, and they provide essential visual evidence for understanding ancient cultures. The use of color in murals also expresses ethnic identity, religious beliefs, social customs, and aesthetic preferences. Pigments are central to mural production. In ancient times, pigments were sourced from natural minerals (e.g., earth red, malachite green), synthetic minerals (e.g., minium, ultramarine), and plant extracts (e.g., indigo, rattan yellow). Among these, inorganic mineral pigments were widely used. However, some mineral pigments—especially lead-based ones—have deteriorated over time, showing discoloration or blackening. Lead-based pigments were historically favored for their vivid hues. Minium (lead tetraoxide, Pb3O4) was among the earliest synthetic pigments, though its color could be influenced by impurities from high-temperature preparation. It is unstable compared to natural mineral pigments. Micro- and non-destructive testing methods have revealed minium use in various cultural relics, many of which have since discolored. This discoloration is primarily due to reactions forming black lead dioxide (β-PbO2) or lead sulfide (PbS). Another lead pigment, lead white, composed of Pb3(OH)2(CO3)2 or PbCO3 are more susceptible to H2S to produce PbS. The discoloration of lead-based pigments is easily affected by light, humidity, microorganisms, and other factors such as acidity-alkalinity and soluble salts of the mural surface. This paper summarizes the relevant physical, chemical, and biological discoloration mechanisms of pigments as follows:1) electron holes are able to be formed inside the pigment after long-term absorption of ultraviolet light energy so that photochemical reactions occur and the valence state change (e.g., Pb3O4→PbO2 or Pb3O4→Pb2+); 2) the combination of higher humidity and pollution gas creates an acidic environment, causing the released H+ to destroy the ionic bond of Pb—O and triggering the disproportionation reaction, which result in the transformation of Pb3O4 to PbO2; 3) microorganisms can quickly grow under suitable temperature and humidity on the mural surface (on the one hand, organic acids and peroxides produced by microbial metabolism can react with pigments, leading to fading or blackening particularly in lead-based pigments; on the other hand, pigments may be absorbed into microbial cells and react with their secretions, altering the microbes’ color, and as these pigmented cells accumulate on the mural surface, they cause further discoloration). To recreate the original appearance of ancient murals, pigment color restoration techniques are essential. High-energy laser technology has emerged as a promising method for this purpose and is becoming a key focus in the field, offering significant potential for future applications. In addition, this article briefly introduces other pigments such as red pigments cinnabar and earth red, green pigments atacamite and Paris green, and blue pigments lapis lazuli and azurite, and briefly summarizes the relevant fading principles and causes, and proposes that environmental quality has a close relationship with maintaining the color of pigments. Therefore, it is of great significance to the long-term preservation of murals to comprehensively monitor the environment, reduce the air pollution, improve the environmental quality, deepen the research on the mechanism of microbial actions on mural pigments, and carry out disease control. Recent conservation strategies for cultural relics in China have shifted from purely remedial efforts to including both remedial and preventive measures. This study aims to provide a scientific basis for understanding pigment discoloration and to guide effective conservation to slow down the discoloration of ancient murals.

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陈雨鑫,苏伯民,冯虎元,李洁,武发思.古代壁画颜料变色研究进展[J].文物保护与考古科学,2025,37(4):169-184.

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  • 收稿日期:2024-01-16
  • 最后修改日期:2025-06-26
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  • 在线发布日期: 2025-08-28
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