Chemical profiling of a 130-year-old manuscript reveals the early use of synthetic lead white correction fluid in ancient China

In practice, correction fluid to mask text errors has been continuously in demand since papers began to be predominantly used since the late fourth century AD in ancient China. However, research on the trajectory of correction fluid composition has been largely overlooked and has not been revealed currently. In this study, a multianalytical approach was used to investigate a thin whiteout layer, used as correction fluids applied in 1890, on a book page from the famous Imperial Encyclopedia (1726 bronze-type repaint version). The results showed that the white layer was composed of hydrocerussite ((PbCO₃)₂·Pb (OH)₂) in mixture with plant oil and a tiny portion of calcium carbonate, which had been applied to conceal the originally printed Chinese characters upon which they were rewritten in preparing photographic negatives for reprinting using photolithography. The analysis results also suggest that lead white was likely domestically made using a local lead ore source by the wet synthetic process. Considering the prolonged use of orpiment (As₂S₃) as a correction fluid ingredient in Chinese tradition, a trajectory to lead white suggests not only advances in pulping and papermaking technology but also a shift in cultural habits and aesthetic psychology in the late Qing Dynasty.     

陕西安康紫阳北五省会馆壁画颜料分析研究

陕西安康紫阳北五省会馆壁画是目前陕西省境内发现的最大的一处建筑壁画,为了解其颜料组成,本工作采用X射线荧光、偏光显微镜、X射线衍射、激光显微拉曼光谱及扫描电镜能谱分析相结合的分析方法,对颜料样品进行了分析。结果表明,北五省会馆壁画除正殿发现一处红色染料外,其他均为无机颜料;红色颜料主要是铅丹、朱砂、铁红;绿色颜料为氯铜矿、石绿、斜氯铜矿;蓝色颜料的主要成分是普鲁士蓝、smalt、石青;黄色颜料为雌黄、铁黄;褐色颜料的主要成分是铁红及铅丹的变色产物二氧化铅;黑色为炭黑;白色颜料主要是铅白,且多使用铅白作为调色颜料。研究结果对于了解清代民间壁画的制作工艺,丰富对陕西建筑壁画的认识具有重要意义。     

Examination of some pigments,grounds and media from Egyptian cartonnage fragments in the Petrie Museum,University College London

A number of cartonnage fragments from the collections of the Petrie Museum, UCL, were examined to identify pigments, media and grounds. The different types of cartonnage made in ancient Egypt are reviewed. Special attention was paid to green pigments, which were shown to be of green earth, or a mixture of Egyptian blue and a yellow, usually goethite or orpiment. Green earth was found in one artefact, dated to the 9th century BC: all other examples were from the Graeco-Roman period. No copper-organometallic greens were present in the examples studied, or Egyptian green, or malachite. Binding media was identified both by ELISA and by GC/MS. A pink colourant was identified as madder, while lead white was used as a white in one example, showing the influence of Roman and Greek pigments on Egyptian art in these later periods. Plant gum, egg, and animal glue were found in different fragments, with mixed media in a few cases. Moganite was found associated with quartz in some preparatory layers by X-ray diffraction, which has not been reported previously as a constituent of ground layers in Egyptian artefacts.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

A Study of Biodeterioration and Chromatic Alterations of Painted and Gilded Mummy Cartonnage at the Saqqara Museum Storeroom,Egypt

Microbial biofilms have developed on the surfaces and within the painted and gilded layers of mummy cartonnage at the Saqqara museum storeroom in Giza, Egypt. SEM–EDX, XRD and FT–IR–ATR techniques were applied to analyse the coloured and gilded materials, ground layer, textile support and binder used for the cartonnage. Aspergillus niger (24.8%), Penicillium chrysogenum (21.5%) and a novel cartonnage‐biodegrading bacterium, Bacillus sonorensis (23.7%), were the most abundant microbes growing over the cartonnage surface. In addition, Aspergillus tamari (15.4%), A. fumigates (8.1%) and Fusarium solani (6.5%) were identified. The pigments comprised Egyptian blue (cuprorivaite), cinnabar (red), orpiment (yellow) and green pigment made from a mixture of cuprorivaite and orpiment. Gold leaf was used for the gilded layer, calcium carbonate and gypsum comprised the ground layer, gum arabic was the binding medium and the fibre base was a fine linen textile. Microbial colonization tests were performed on aged cartonnage replica samples made from linen and pigments of similar composition to ancient pigments found in the cartonnage. Each sample was inoculated separately with A. niger, P. chrysogenum and B. sonorensis. Yellow orpiment samples were the exception, as no colour change was detected after colonization by the examined micro‐organisms.     

敦煌石窟艺术应用颜料的产地之谜

论述了敦煌石窟彩绘艺术颜料的研究背景、科学分析方法和结果。并根据史料所载以及现代科学的实际勘探考察,结合颜料的科学分析,对敦煌石窟艺术所用的朱砂、铅丹、赭石、绛矾、雄黄、雌黄、密陀僧、金粉、金箔、石绿、铜绿、石青、青金石、群青、铅粉、石膏、白垩、云母、二氧化铅等主要矿物质颜料的化学成分、应用及其产地进行了探索。     

Early Islamic pigments at Nishapur,north-eastern Iran: studies on the painted fragments preserved at The Metropolitan Museum of Art

Pigments appearing on ninth–twelfth-century AD-carved stucco, wall painting, and terracotta friezes excavated at Nishapur in north-eastern Iran were investigated by optical reflectance spectroscopy, micro X-ray fluorescence spectrometry (μ-XRF), X-ray diffractometry (XRD), micro-Raman spectroscopy (μ-Raman), and scanning electron microscopy (SEM). Many of the pigments identified including vermilion, red lead, hematite, limonite, carbon black, atacamite, calcite, and gypsum have been identified in previous studies of pigments used in later Islamic periods. However, a series of unusual pigments such as wulfenite, pyromorphite, phoenicochroite, and jarosite were also found in the present study. The association of kaolinite and alunite with limonite and other Fe-bearing yellow pigments points to a local provenance for these pigments. In addition, the presence of orpiment in the vermilion may be indicative that the vermilion was artificially manufactured. These findings suggest that pigment use and manufacturing during the ninth to eleventh centuries in Nishapur was still in a trial-and-error stage and the palette known from the twelfth century onwards had not yet been systematized.     

Some results on mean tidal structure and day-to-day variability over Arecibo

A long series of monthly 36 h observations, plus a series of observations at the same local time each day over two months at Arecibo, have been analyzed for tidal structure and variability. Some of the results are as follows. (1) A diurnal tide with vertical structure similar to that of the S_1,1 mode dominates the wind field up to heights of the order of 110 km over Arecibo. A semidiurnal oscillation dominates above that height. For non-winter conditions the semidiurnal oscillation in the 80–200 km region closely resembles the S_2,2 mode, though there is the possibility of contributions from higher order modes in the 100–120 km region. (2) Larger semidiurnal amplitudes are observed in the lower thermosphere for winter conditions. The data appears roughly consistent with Bernard's (1979) hypothesis that S_2,2, S_2,4 and S_2,5 modes are thermally excited, with the S_2,4 and S_2,5 modes out of phase in the meteor region in summer and in phase in winter. (3) The day-to-day variability of the tides is at least half the amplitude of the mean oscillations. The maximum wind variability was observed to occur in the 100–110 km region where the diurnal tide is strongly dissipated. (4) The day-to-day deviations in the wind and temperature oscillations from a long term mean at one local time tend to be wave-like structures which are generally correlated from day to day. The structures tend to move upwards, i.e., appear at a later local time, from day to day.     

RESEARCH ON THE PIGMENTS FROM PAINTED CERAMICS EXCAVATED FROM THE YANGQIAOPAN TOMBS OF THE LATE HAN DYNASTY (48 BC – AD 25)

The analysis of pigments on painted ceramics excavated from the Yangqiaopan Tombs of the late Western Han Dynasty was undertaken using optical microscopy (OM), micro‐Raman spectroscopy (μ‐RS), scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM–EDS), X‐ray diffraction (XRD) and Fourier‐transform infrared spectroscopy spectra (FTIR). The pigments were identified as red lead (Pb₃O₄), carbon (C), malachite [Cu₂CO₃(OH)₂], Chinese purple (BaCuSi₂O₆) and illite {[K,H₃O]Al₂Si₃AlO₁₀(OH)₂}. Fibrous materials were observed in some pigment samples. When observed by SEM, one showed a large amount of fibre in solidified gum, which indicated that gum of ramie could have been used as the binding medium to make the pigment particles adhere together. These results provide significant insights into the characteristics of these pigments in the Qin and Han Dynasties.     

MICRO‐RAMAN SPECTROSCOPY CHARACTERIZATION OF DELLA ROBBIA GLAZES*

Micro‐Raman spectroscopy and the laser‐induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that ions in a lead silicate matrix, called ‘lead ultramarine’, could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004 ). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser‐induced micro‐crystallization.     

铅丹、朱砂及其混合物紫外光致变色的电化学及光谱研究

铅丹(Pb₃O₄)和朱砂(HgS)是古代壁画和彩绘上常用的红色颜料,它们的变色是文物保护工作者、策展人和艺术史学家长期关注的问题。但由于其所处环境复杂,影响因素众多,这些颜料的变色机理的研究较为困难。为了探究紫外光照对这些颜料的影响,采用电化学方法和控制环境的紫外老化模拟实验研究了铅丹、朱砂及其混合物的光降解过程,并利用拉曼光谱和X射线光电子能谱(XPS)对实验样品进行分析。电化学实验中铅丹受405 nm激光照射出现还原电流,朱砂出现氧化电流。紫外老化实验确认了铅丹在光照下的还原反应,反应产物为碳酸铅(PbCO₃)和碱式碳酸铅[Pb₃(CO₃)₂(OH)₂]。因此,光照会引起铅丹发生还原反应,引起朱砂发生氧化反应,两种颜料表现出典型的半导体性质。另外,光化学反应动力学结果显示,掺杂朱砂可能会加快铅丹的光降解过程。     

Spectral characteristics of magnetic storm-induced F-region scintillations extending into daytime

Magnetic storm-induced F-region scintillations extending into daytime were recorded over Bombay, situated near the anomaly crest region in India, on 12 November 1991. The scintillations at 244 MHz using the radio beacon onboard FLEETSAT (73°E), lasted till 1312 h IST (77.5°E). Observations at Trivandrum, situated close to the magnetic equator also show strong daytime scintillations lasting till 1030 h. The scintillation event followed a sudden commencement at 1748 h UT (2318 h IST) on 11 November 1991 and the ionosonde observations, both over Ahmedabad in the anomaly crest region and Kodaikanal near the magnetic equator, show large upward drift of about 50 m s⁻¹ around 0300 h IST. The scintillation index S₄, autocorrelation function and power spectra have been computed from the digital data recorded at Bombay. The time variation of S₄ shows large fluctuations with a periodicity of about half an hour. The 50% decorrelation time of the signal fluctuations is of the order of seconds. The spectral index n, of the temporal power spectra, where P(F)αF⁻ⁿ, varies between 1.5 and 5.0, with a mean value of 3.0, and shows a dependence on the S₄ index. These features are similar to those reported for night time scintillations recorded over Ahmedabad.     

新疆阿斯塔那唐墓出土彩塑的制作工艺和颜料分析

新疆阿斯塔那古墓群出土了大量的彩塑,为了解其制作工艺与彩绘颜料成分,采用显微激光拉曼光谱,结合剖面观察和能量色散X射线荧光光谱等科技手段,对出土于唐墓的6个样品进行了分析鉴定.结果表明,泥胎表面先用硬石膏做打底层,再施以彩绘,且彩绘颜料厚薄有异.所使用的红、黄、黑、白和绿色颜料有铅丹、密陀僧、朱砂和土红、雌黄、炭黑、硬石膏及氯铜矿等无机颜料,而粉色彩绘是由铅丹(或铅丹和密陀僧的混合物)与硬石膏调和而成,且密陀僧作为彩绘颜料在新疆是较早的发现.其最为重要的发现是蓝色彩绘为植物性染料——靛蓝.这一研究结果,为进一步的彩塑修复与保护方案的制订提供了有价值参考.     

馆藏唐代彩绘人物俑颜料分析与修复保护

为确定深圳博物馆藏唐代彩绘人物俑颜料的矿物成分,利用X射线荧光能谱仪、X-射线衍射仪等对这批俑的颜料成分进行了分析,结果表明:红色颜料为铅丹、朱砂;黑色颜料为无定形碳黑;白色颜料为铅白和高岭土等.同时,将其与陕西省内相关地区的彩绘陶俑或壁画颜料进行了对比,得知其所使用的颜料与后者基本一致.在此基础上,针对这批人物俑的保存现状,遵循最小干预等文物保护的基本原则,对其实施了表面附着物清理、拼对、粘接、修复补全等保护修复技术措施,使其恢复了原有面貌,取得了较为理想的保护效果.     

POTENTIAL MAGNETIC SUSCEPTIBILITY AND FRACTIONAL CONVERSION STUDIES OF ARCHAEOLOGICAL SOILS AND SEDIMENTS*

Potential magnetic susceptibility (χ_MAX) and, hence, fractional conversion (χ_CONV) are shown to be critical in interpreting low‐frequency mass‐specific magnetic susceptibility (χ_LF) data. Results presented from 29 sites in the UK and one in Hungary encompass six types of investigation: Quaternary sedimentary stratigraphies, archaeological contexts, surveys of old ground surfaces, topsoil surveys of lithic scatter sites, topsoil prospection surveys and ‘natural’ topsoils. The findings highlight the wide range of χ_MAX values that may be encountered; identify factors affecting χ_MAX; demonstrate that χ_CONV provides a measure of enhancement resulting from burning; and identify environments in which χ_LF analysis is likely to be problematic.     

A Discussion on the Emergence and Development of Ancient Chinese Artificial Barium Copper Silicate Pigments from Simulation Experiments

The ancient Chinese barium copper silicate minerals mainly comprise Chinese purple (BaCuSi₂O₆) and Chinese blue (BaCuSi₄O₁₀), which were widely used from the late Warring States Period to the late Eastern Han Dynasty. In order to clarify the raw material of the pigment, a series of simulation experiments was conducted to produce Chinese purple pigment under varying mineral conditions. The minerals that we applied in the experiment were quartz as the source of silicon, malachite and copper oxide as the sources of copper, barite and witherite as the sources of barium and lead oxide as the source of lead. Simulation experiments showed that the barium copper silicate minerals and the purple pigment can be produced easily when witherite is used as the barium‐containing raw material. From the perspective of mineral resources, the birth of the ancient Chinese pigment associated with a unique barium mineral resource. The Chinese copper‐based pigments are assumed to have been developed independently and are presumably an outcome of historical developments in glazing techniques.     

Lead pigments and related tools at Akrotiri,Thera, Greece. Provenance and application techniques

This paper refers to an investigation of finds that are associated with the raw materials and tools for the preparation or use of lead pigments at Akrotiri on Thera, Greece, during the Early, Middle and Late Cycladic Bronze Age (c. 3000–1600 BC). For the detection and the preliminary characterisation of remains of pigments that were found on stone tools, the in situ application of X-Ray Fluorescence spectroscopy proved to be invaluable. In order to identify the chemical composition of the pigments and to investigate their provenance from a geological perspective, quantitative X-Ray Diffraction analysis was conducted. A thorough visual macro and microscopic examination of the morphology of the materials permitted the determination of physical features (colour, homogeneity, grain size) as indicators of their nature or degree of processing. Based on the results of these analyses, the traces of lead oxides that were detected on the stone tools are associated with specific collections of litharge items discovered at the settlement of Akrotiri, and probably provide evidence of their earliest use in preparing pigments.     

山东青州龙兴寺部分北齐佛造像石材及朱砂颜料分析研究

山东青州龙兴寺窖藏佛教造像出土于1996年,造像雕刻技艺精湛,数量多,贴金彩绘丰富,展现出一种特殊的佛教造像艺术特征。一些佛像由于长期掩埋和历史上遭到破坏,彩绘发生了褪色、变薄、起翘等现象。为了弄清佛造像彩绘颜料和结构,本研究采用三维视频显微镜、显微拉曼光谱分析、扫描电镜-能谱、偏光显微镜等仪器分析颜料的结构和化学组成。分析结果表明,龙兴寺佛造像红色颜料为辰砂(Hg S)与铅白(2PbCO_3Pb(OH)_2)混用;地子主要为铅白,经过对该批出土佛造像残碎的石块做薄片处理做偏光显微分析,得到造像石材的主要矿相为含菱铁矿、生物碎屑、白云石的泥晶灰岩(灰岩即石灰石)。     

PIGMENT IDENTIFICATION IN GREEK POTTERY BY RAMAN MICROSPECTROSCOPY*

Raman microspectroscopy (RMS) is now established as a key technique for the identification of pigments of archaeological pottery that permits the in situ study of art objects by a non‐destructive procedure. The information obtained represents a great aid to restoration and conservation techniques. In this work, the chemical nature of the red, black and white pigments of five samples of Greek pottery from the end of the fifth century and the first half of the fourth century bc , exhumed from the Iberian necropolis of Cabezo Lucero (Guardamar del Segura, Alicante, Spain), has been identified. The black and the red pigments are found to be magnetite (Fe₃O₄) and hematite (α‐Fe₂O₃), respectively. The white pigment is found, for the first time, to be composed of alumina (α‐Al₂O₃ and γ‐Al₂O₃) probably yielded by the thermal decomposition of Greek bauxite.     

The Provenance of Historical Gunpowder from South‐Western Japan: A Stable Isotopic Approach

Stable isotopic analysis was undertaken for the gunpowder ingredients from crude saltpetre and propellants from several types of gun that prevailed during the late 19th century in south‐western Japan. Stable isotopic signatures for δ¹⁵N_{saltpetre nitrogen}, δ³⁴S_{native sulphur} and δ¹³C_{charcoal carbon} in crude saltpetre, gunpowder magazines bearing the trademark of mills from southern Scotland and cartridges for an improved Sharps rifle (with a US trademark) all imply common assemblages from the same source (saltpetre and native sulphur from British India and Sicily, respectively) in the United Kingdom (UK). One Pritchett patron is common for muzzle‐loading Enfield rifles, while the other suggests a four‐allied lead bullet for an unidentified hand gun. Propellants in the Pritchett patron from the same institution also suggest a common source of these rifles. On the contrary, the ingredients for an unidentified rifle and time fuse for a Paixhans gun with unique stylistic devices showed distinctive isotopic signatures, indicating a local Japanese origin. The Pritchett patron from the Kumamoto Museum involved a mixed provenance from the UK and Japan. The stable isotopic analysis provides direct evidence for the ultimate origin of the propellant.