The Origin of Soluble Salts in Rocks of the Thebes Mountains, Egypt: The Damage Potential to Ancient Egyptian Wall Art

Soluble salts are indigenous to the marine sediments of the Esna Formation and Thebes Formation in central Egypt. Natural weathering processes and human impact cause salt efflorescence in tombs and on walls of ancient Egyptian monuments in the Theban Necropolis, resulting in the disintegration of wall paintings and carved hieroglyphs. Determination and quantification of soluble salts and measurements of the porosity were done on tomb marls in order to understand the origin and damage potential of the salts in the royal tombs of the Valley of the Kings. The study shows that sodium chloride (NaCl) is the predominant salt species. Sulphates, anhydrite (CaSO₄) and gypsum (CaSO₄ . 2 H₂O) also occur in the limestone deposits of the Thebes Formation and the underlying shale deposits of the Esna Formation. Member I of the Thebes Formation, into which most of the ancient tombs were hewn, shows the highest amount of soluble salts (up to 6·2 wt-% dry). In addition, the porosity and permeability of the marls in Member I are high, enhancing water molecules and brine migration. Wetting and drying of the tomb surfaces in the past has affected solution, transportation and recrystallization of water soluble minerals, and has led to major destruction of wall paintings and ornamentations. This study shows that large amounts of salt minerals still remain in the wall rocks. Future humidity changes due to flash floods and tourists may favour salt crystallization in the ancient Egyptian monuments. The authors urge the authorities to undertake steps to prevent further destruction to save the magnificent cultural heritage found in the Thebes area.     

岩鸽排泄物对壁画损害特征研究

鸟类排泄物是造成石窟寺壁画、彩塑污染的主要因素之一,科学剖析鸟类排泄物对壁画的损害特征是此类污染物有效清除的前提。本研究利用傅里叶变换红外光谱(FTIR)、气相色谱-质谱联用(GC-MS)、X射线衍射(XRD)等方法分析了炳灵寺石窟壁画表面岩鸽排泄物成分,采用扫描电镜-能谱仪(SEM-EDS)、便携式显微镜、偏光显微镜(PLM)表征了鸟类排泄物对模拟壁画的微观损害特征。结果表明,岩鸽排泄物成分主要由尿酸、纤维素、多肽类有机物,以及以石英为主的无机盐组成。排泄物造成壁画覆盖污染、颜料层和地仗层侵蚀、颜料颗粒间原始粘附结构破坏,导致颜料层起甲、脱落,可溶盐活动及其他生物侵蚀。研究结果对于古代壁画的科学保护与修复具有指导意义。     

BLACK AND RED GRANITES IN THE EGYPTIAN ANTIQUITY MUSEUM OF TURIN: A MINERO‐PETROGRAPHIC AND PROVENANCE STUDY

A recent project to investigate the stone artefacts preserved in the Egyptian Antiquity Museum of Turin has been undertaken, with the aim of supplying their systematic classification and suggesting the provenance site of the original raw materials. This paper focuses on seven sculptures dating back to the New Kingdom (18th–19th Dynasties): the statue of Ramses II, three of the 21 sculptures of the goddess Sekhmet, the statue of the goddess Hathor, the Ram‐headed Sphinx and the sarcophagus lid of Nefertari. Petrographic observations have shown that all the sculptures are made of granitoid rocks, with variable composition from granite to granodiorite and tonalite. The observation of strong macroscopic analogies with the so‐called black and red granites outcropping in the Aswan area has suggested a common origin of all the raw materials used for their manufacture. In order to verify this provenance hypothesis, several samples were collected in the Aswan quarry districts. According to results of a minero‐petrographic and geochemical comparison between the statues and the Aswan quarry samples, it was possible to identify the source area of the stone sculptures and finally to highlight the importance of an archaeometric approach to the solution of archaeological problems.     

PREHISTORIC WALL PAINTINGS: THE CASE OF THE DOMUS DE JANAS NECROPOLIS (SARDINIA,ITALY)*

The Domus de Janas (Home of the Fairies, or Home of the Witches) are Neolithic hypogea located throughout Sardinia (Italy) and decorated with red and black wall paintings. The objective of this study was to define the painting technique through the analytical characterization of the pigments and binding media. Samples of painting film from different graves have been examined by means of various analytical techniques. XRD, Raman and SEM–EDX analyses identified the red and black pigments respectively as red ochre rich in hematite and carbon black, while GC–MS analyses characterized the organic binder as egg.     

APPLICATION OF LEAD ISOTOPE ANALYSIS TO A WIDE RANGE OF LATE BRONZE AGE EGYPTIAN MATERIALS*

Lead isotope analysis was applied to Egyptian materials from the Late Bronze Age in order to investigate the relationship between these different materials, many of which have lead as a significant component. The galena kohls analysed can be provenanced to Gebel Zeit, a large mining site known to have been active during the period. However, the source of lead metal is different and seems to be outside Egypt, along with the source of copper. Lead‐based pigments such as lead antimonate that were used in glass and glazes seem mostly to come from Egypt, although they may well contain a component of ‘Mesopotamian’ lead. In the Predynastic period, galena from many sources is being exploited for use as kohl. However, by the Middle Kingdom (2055–1650 bc ), extraction has concentrated on one source, Gebel Zeit, perhaps reflecting increasingly centralized control and/or the use of large‐scale exploitation. It therefore appears that a complex pattern of trade in lead‐based materials was evident, with lead metal and galena being separate commodities from separate sources and treated as such.     

THE EFFECT OF SALTS ON THERMAL AND HYDRIC DILATATION OF POROUS BUILDING STONE*

Fifteen desalinated sandstone drill core samples from Umm Ishrin Sandstone Formation in Petra (Cambrian age) were used for this study. The samples were mineralogically analysed using X‐ray diffraction and their physical properties were also determined. Samples with similar physical properties and mineralogical composition were taken for further experimental work. After desalination, thermal and hydric dilatation coefficients were measured, then three types of salts (NaCl, KCl and Na₂SO₄·10H₂O), which have high solubility and consequently are the most dangerous to building stone (and are also detected in the sandstone monuments in Petra), were introduced into the samples and their contents were calculated. The results show that salt crystallization in the pores of building stones can increase their thermal dilatation and decrease their hydric dilatation to varying extents, depending on the nature of the salt. The average increase in the thermal dilatation coefficient per unit mass of salt is the lowest for the Na₂SO₄·10H₂O‐salted samples with a value of 5.3%, while the NaCl‐salted samples have the highest value with 7.8% per salt mass. The average percentage of the decrease of the hydric dilatation coefficient is 1061% for Na₂SO₄·10H₂O‐salted samples per mass of salt content; the NaCl‐salted samples have a value of 1510% per mass of salt content, and the KCl‐salted samples almost the same value. For the salt‐free samples, it was found that in climatic conditions with a high temperature range, the deterioration of sandstone due to temperature fluctuation is more effective than that caused by change in the moisture content, while samples with high salt content suffer more from hydric dilatation.     

Microclimate analysis of deteriorated wall paintings: With restitution of original decoration through imaging

Abstract

The restoration of deteriorated wall paintings in an underground environment requires at the outset a complex analytical approach designed to clarify the deterioration processes. These can be identified and prioritized using continuous microclimatic monitoring with multichannel analytical loggers, providing abundant data on climatology, airflow and hydrogeology in real or semireal time. The investigator can therefore have an almost instantaneous idea of the evolving microclimatic conditions of the monument, identifying among other variables the condensation or evaporation phases of the walls and the rising or sinking of the underground water table when the monument ‘has its feet in the water’, as in the case described here of St Emilion (France). In addition, electronic image capture in situ can be used to decode and restitute very damaged paintings that have become difficult to read, with a view to their being eventually presented to the public.     

CHARACTERIZATION OF THE AMPHORAE,STONE BALLAST AND STOWAGE MATERIALS OF THE SHIPS FROM THE ARCHAEOLOGICAL SITE OF PISA–SAN ROSSORE,ITALY: INFERENCES ON THEIR PROVENANCE AND POSSIBLE TRADING ROUTES*

In December 1998, during excavation for the construction of a new building near San Rossore railway station in Pisa, the remains of ancient ships were discovered. These findings have been dated (radiocarbon) to between the end of the 10th century bc and the fifth century ad ( Belluomini et al. 2002 ). Several transport amphorae belonging to the Hellenistic ship, samples of rocks (stone ballast) belonging to ships B, D and the Hellenistic ship, and stowage materials belonging only to ship B have been analysed. The mineralogical and petrographic data of the investigated samples provided information on the possible provenance of the raw materials utilized in the manufacture of the ceramic amphorae, as well as on the provenance of the rock materials found in the ships as ballast and stowage. The compositional data (obtained through XRD, XRF, OM and EPMA) and their statistical analyses suggest that the provenance of the Dressel amphorae belonging to the Hellenistic ship was the Middle Tyrrhenian coast of Italy, and more precisely the area between Tarquinia and Naples, according to the numerous kilns and wine production sites found in this area. The provenance of the volcanic rocks was from southern Tuscany, northern Latium and possibly the Pontine Islands, whereas the intrusive rock possibly comes from the Calabrian–Tyrrhenian coast and/or the Peloritani area. The impure limestones and the dolostone come from southern Tuscany and the Latium coast; the semi‐metamorphic rocks could come from the coast of southern Tuscany, the Tuscan Archipelago or possibly also from the Ligurian coast; only the sample of mylonitized granitoid possibly comes from either the Calabria–Peloritani arc or the Tuscan Archipelago. The stowage materials, consisting of lapilli and scoria of a pyroclastic nature, are sourced from the Neapolitan area. These data might shed some light on the centres of production of the amphorae and of the trading routes followed by the ships, according to the ports of call.     

HISPANO-MORESQUE POTTERY PRODUCTION OF THE FOURTEENTH-CENTURY WORKSHOP OF TESTAR DEL MOLÍ (PATERNA,SPAIN)

Excavation of Testar del Molí, the only workshop found in the Manises-Paterna area, revealed the existence of a fourteenth-century ceramic workshop covering the remains of the thirteenth-century workshop. This study is concerned with the fourteenth-century production, and forthcoming papers will connect both epochs following the findings of current excavations. The chemical and mineralogical characterization of the ceramic production of this workshop shows the presence of three groups of ceramic pastes which could also be distinguished by, and, thus, related to, their daily use. The raw materials found in the excavation have also been mineralogically and chemically characterized, and a model of possible mixtures of raw materials has also been developed in order to determine their possible use in the manufacture of the pottery previously characterized.     

茂陵石刻表面污染物和可溶盐的分析研究

为了厘清造成茂陵石刻文物劣化的原因和机理,对石刻表面的污染物和析出可溶盐进行了分析研究,以找出石刻文物劣化和污染物、可溶盐之间的关系,为制定科学有效的保护措施提供科学依据。采用X射线衍射仪(XRD)、扫描电镜-能谱仪(SEM-EDS)、傅里叶变换显微红外光谱仪(FTIR)等仪器对采集的茂陵石刻文物表面污染物和可溶盐进行了表征,用离子色谱(IC)分析了可溶盐的离子种类和含量。结果表明,“马踏匈奴”石刻雕像表面污染物的主要成分是CaSO4·2H2O,其形成原因是石材与空气污染物经长期化学反应形成的钙质结壳,或者是地下水中可溶盐的毛细运移造成的;“怪兽吃羊”石刻雕像表面析出的可溶盐有Na2SO4、NaNO3和CaSO4·2H2O,主要是由于地下水中可溶盐从砖石基座迁移到石刻文物本体,随温湿度变化反复结晶溶解所造成。可溶盐会引起石质文物表面酥粉、片状剥落、内部结构破坏等侵蚀,是茂陵石刻文物的主要病害之一。     

The Feathered Serpent Pyramid at Teotihuacan: decay,conservation and future perspectives

Abstract

The Feathered Serpent Pyramid at Teotihuacan, Mexico, is one of the most outstanding monuments of Mexican archaeological heritage. However, the volcanic stones that constitute the main façade of this building are subject to complex deterioration phenomena that include decay caused by the presence of water and soluble salts, as well as inappropriate treatments carried out in past decades. Agents of decay are explained in the article, as well as the means of diagnosis employed for their study. Recent conservation activities and other potential conservation treatments are also discussed.     

ANALYSIS OF ROMAN WALL PAINTINGS FROM THE THERMAE OF ‘IULIA CONCORDIA’

Twenty‐six wall painting fragments and some plaster, ‘intonachino’ and stucco samples, discovered at Iulia Concordia, have been studied by different analytical techniques to gain information about the pigment nature and the composition of the materials. The presence of calcite, dolomite and aragonite allow the distinction of four groups of wall samples varying in the nature of pigments and in the application technique. These differences can be attributed to different execution times or, more probably, to the arrangement of the rooms in the building structure. The nature of the pigments found in the Thermae of Iulia Concordia appears similar to that found in other Roman villas of Venetia et Histria, with the use of precious pigments such as Egyptian blue and cinnabar.     

甘肃拉卜楞寺壁画表面涂层材质分析

西藏壁画表面大多刷有保护涂层。据记载,其材质主要是桐油、牛胶或清漆等。但目前,对该涂层材质科学的研究却较少,不利于后期保护修复。为配合拉卜楞寺壁画保护修复项目,本研究以衰减全反射红外光谱法(ATR-FTIR)、核磁共振氢谱法(~1H-NMR)、热裂解-气相色谱-质谱联用(Py-GC-MS)技术等分析手段,对甘肃夏河拉卜楞寺弥勒佛殿、时轮学院主殿壁画的涂层进行了分析。结果表明,两处佛殿壁画涂层可确定是一种干性油,种类与桐油较接近。但由于西藏壁画在材料和工艺上的独特性,材料老化等因素,拉卜楞寺壁画涂层在组成和结构上,与现代桐油有一定差别,表现出一定的丰富性和复杂性。后期修复,可采用性质与西藏传统涂层材料接近的干性油,例如桐油,作为新的壁画表面涂层材料。     

THE APPLICATION OF A PORTABLE X‐RAY FLUORESCENCE SPECTROMETER TO THE ON‐SITE ANALYSIS OF GLASS VESSEL FRAGMENTS FROM SOUTHERN THAILAND*

Ancient glass vessel fragments belonging to the seventh to ninth centuries ad , from the Ko Kho Khao, Laem Pho and Khuan Lukpad sites in southern Thailand, were studied. The glass vessel fragment samples are a collection belonging to the Department of Archaeology, the 15th Regional Office of Fine Arts of Thailand. The chemical compositions of the glasses were analysed using a modified portable energy‐dispersive X‐ray fluorescence spectrometer (OURSTEX 100FA‐II) by the introduction of a MOXTEK^® AP3.3 polymer window (5 mm²?) to the KETEK silicon drift detector for the measurement of light elements. The non‐destructive analysis was performed at the National Museum, Phuket, in Thailand. It is shown that the glass chemical compositions belong to mineral and plant‐ash based soda–lime–silicate glass. The origins of the glass artefacts are discussed in terms of raw materials and glass decoration, and compared with previously reported similar typological glasses from sites in the port city of Rāya and the Monastery of Wadi al‐Tur in Egypt.     

Paper 3: Impact of the Indoor Climate on the Performance of Building Materials Contaminated with Salt Mixtures

Abstract

Archaeological sites are essentially submitted to decay phenomena inherent on their history as well as the environment to which they are exposed after excavation. The history of such archaeological sites is particularly related to their long-term underground conservation conditions during which they were subject to salt migration into the architectural remains.

It is well known that soluble salts present in building materials can cause damage, mainly by producing stresses in the substrate. A lot of research has been done in the past concerning the behaviour of salts in built constructions. However, most studies include single salts, of which the deliquescence points are well documented, while in situ one mostly finds complex salt mixtures, which makes the conservation strategy much more intricate.

The environmental conditions to minimize damage of salt-laden porous building materials can be modelled using a computer program ECOS capable of predicting the crystallization behaviour of salt mixtures. To use the model data of quantitative salt analyses are required as input. The program is then able to predict from a thermodynamic point of view which minerals will exist in the solid state under specified climatic conditions.

This paper deals with the results of a systematic investigation of the salt contamination of the building materials of the Coudenberg site and a prediction of the behaviour of the salt mixture related to the actual climate, as part of the environmental assessment.     

THE ORIGIN AND GEOCHEMICAL CHARACTERIZATION OF RED OCHRES FROM THE TITO BUSTILLO AND MONTE CASTILLO CAVES (NORTHERN SPAIN)*

Ochres were the most common source materials for pigments used in Palaeolithic rock art paintings. This work analyses the petrographic and geochemical signatures of different ochre samples from outcrops inside Tito Bustillo Cave and the Monte Castillo Caves using the most common techniques (petrography, XRD, SEM–EDS and ICP–MS) in archaeological pigment characterization studies. The results obtained permit the identification and characterization of the different source ochre types and, furthermore, allow the establishment of mineralogical and geochemical proxies for the study of questions related to ochre characterization, formation processes and provenance.     

DOMUS AUREA,THE ‘SALA DELLE MASCHERE’: CHEMICAL AND SPECTROSCOPIC INVESTIGATIONS ON THE FRESCO PAINTINGS

In this paper, data collected from the wall fresco paintings of room 114, called the ‘Sala delle maschere’, of the Domus Aurea in Rome is analysed. The chemical composition of the efflorescence is investigated by infrared spectroscopy. The colour palette is determined by means of EDXRF, Raman spectroscopy and visible reflectance spectroscopy. EDXRF has allowed an extensive mapping of the elements present in the pigments and plaster; whilst in‐situ Raman spectroscopy has been determinant for attributing the molecular composition of the pigments in a number of doubtful cases. Most pigments identified are typical of Imperial Roman fresco paintings (first to fourth centuries AD) ( Ward‐Perkins 1981 ); more interestingly, we found evidence of fragments painted with Egyptian blue, which was normally used mostly in official rooms.     

ANCIENT EXPLOITATION AND USE OF COBALT ALUMS FROM THE WESTERN OASES OF EGYPT*

Cobalt alums from the Western Oases of Egypt were used in the second millennium bc as a colorant to produce dark blue glasses and glazes. A collection of these alums was gathered together and analysed by a series of techniques to accurately characterize them. They were then used alongside artificial analogues in experimental work aiming to determine the process that was used to convert the raw alum into a suitable pigment that might be used in a glass. Finally, the broader picture of the use of these alums is considered together with the implications for the trade in these materials across the Near East and into Europe.     

结合热力学对古建筑墙体砖(雕)风化侵蚀机理探究

为了揭示古砖的风化侵蚀机理,采用X射线衍射法(XRD)、X射线荧光光谱法(XRF)、扫描电子显微镜观察(SEM)进行微观结构分析,结合压汞仪测试孔的性质,并使用热力学软件(HSC)对砖内的化学反应进行验证。研究结果表明:对于靠近地面一定高度内的古建筑墙体砖,地下水及离子通过砖内的毛细管网络不断向上部和表面进行迁移,在砖内可溶性盐类的结晶以及水结冰时产生的压力是造成墙体砖风化破坏的主要因素;对于NO X、SO 2浓度较高、酸雨较多的地区,酸性物质进入砖体并与钾长石,钠长石等发生反应形成新的盐类,盐的结晶、溶解、流失也是导致古砖破坏的一个不可忽略的因素,尤其是对于地下水无法渗透到的墙体砖,这些可能成为主要的物理化学损毁因素。本研究为古砖以后的保护提供了一种新的研究思路以及科学的理论基础。