Distinguishing between calcites formed by different mechanisms using infrared spectrometry: archaeological applications

Infrared spectrometry is a well-established method for the identification of minerals. Due to its simplicity and the short time required to obtain a result, it can be practiced on-site during excavation using portable infrared spectrometers. However, the identification of a mineral may not be sufficient. For example, a lime plaster floor and a crushed chalk surface have a similar appearance and are composed of the same mineral – calcite. Here we exploit differences in the infrared spectra of geogenic, biogenic and pyrogenic calcites for the identification of each calcite type. The infrared calcite spectrum has three characteristic peaks in the region of 400–4000 cm⁻¹, designated ν₂, ν₃, and ν₄. When a calcite sample is ground, as part of the measurement preparation procedure, some grinding dependent changes will be revealed in the infrared spectrum. With additional grinding, the ν₃ peak narrows and the heights of the ν₂ and ν₄ peaks decrease, when both are normalized to the ν₃ height. By plotting the normalized heights of the ν₂versus the ν₄ of several grindings of the same sample, a characteristic trend line is formed for each calcite type. The trend lines of geogenic calcites have the shallowest slopes and highest ν₄ values when compared to pyrogenic calcites, which can be further divided to ash and plaster/mortar samples. This method can assist in distinguishing between the various calcites, and provide insights into homogeneity and preservation state of the calcitic materials in question.     

Optical spectroscopy as a rapid and low-cost tool for the first-line analysis of glass artefacts: a step-by-step plan for Roman green glass

Archaeometric research on glass artefacts is continuously evolving and is converging towards a multidisciplinary research domain where different types of techniques are applied depending on the questions asked and the circumstances involved. The technique described in this work is optical spectroscopy. The benefit of this technique being the possibility of building up a knowledge database for a large amount of material in a relatively short period of time and with a relatively limited budget. This is of particular interest for the investigation of extensive and/or unexplored glass collections where a first-line analysis of artefacts could facilitate the selection of material needing further and more detailed examination.     

高分子彩绘类文物保护涂层材料的性能及应用研究

针对彩绘类陶器保护的特殊要求,筛选性能优良的保护材料。在人工气候箱中对所选择的9种有机高分子文物保护涂层材料进行人工老化试验,分别采用傅立叶红外光谱仪测量试验材料的分子结构,分光光度仪测量颜料的主波长、色纯度和高度的变化,粘接强度仪测量颜料的粘接强度变化。结果表明:PrimalAC33、B72、有机硅的耐老化性能好,颜色变化小,粘接强度高,能很好的起到保护彩绘文物的作用,建议在文物保护领域推广使用。     

五种含氯铜合金腐蚀产物的拉曼光谱及扫描电镜的分析研究

为深入研究五种含氯铜合金腐蚀产物(氯铜矿、斜氯铜矿、羟氯铜矿、氯磷钠铜石和铜氯矾)的拉曼光谱图,进一步补充金属锈蚀物的拉曼光谱库,采集不同考古来源的铜合金上腐蚀产物的拉曼光谱,并结合扫描电镜观察了腐蚀产物的形貌特征。研究结果表明,氯铜矿、斜氯铜矿和羟氯铜矿3个同分异构体的拉曼光谱并不相同:氯铜矿和斜氯铜矿较为常见,且经常混合在一起;羟氯铜矿不稳定,非常少见,一般与其他两种混合在一起。扫描电镜观察氯铜矿主要为粒状形貌,同时也发现有葡萄状、皮壳状、钟乳状等形貌;羟氯铜矿因少见,目前只观察到板状形貌。氯磷钠铜石腐蚀产物较厚且疏松柔软,常发现于干旱地区有动物或人遗骸墓葬的出土器物上,扫描电镜观察呈花瓣形状的蓓蕾形貌。铜氯矾更为少见,笔者目前只在2件器物上发现。同时对5种腐蚀产物的形成原因进行了讨论。     

广元千佛崖莲花洞彩绘颜料拉曼光谱分析

为了解广元千佛崖莲花洞造像的制作工艺与彩绘颜料成分,利用体视显微分析、金相显微分析、激光拉曼光谱分析技术对其进行物相和成分分析。分析结果表明,莲花洞造像彩绘直接绘制在岩石雕像表面,无底层。彩绘颜料分为多层,最多有三层,说明历史上至少有两次重绘。红色颜料为赤铁矿、朱砂;蓝色颜料主要为青金石与石青;绿色颜料为石绿、碱式氯化铜;白色颜料为硫酸铅。同时也表明,拉曼光谱分析彩绘颜料成分组成简便、快速、对样品要求量小,对样品无损分析,符合文物材质分析的要求,并可得到准确的信息。造像彩绘制作材料及工艺的分析结果为莲花洞造像彩绘保护研究提供了科学依据。     

Raman spectroscopy and scanning electron microscopy confirm ochre residues on 71 000‐year‐old bifacial tools from Sibudu,South Africa

Micro‐residue analysis of stone tools is generally performed with optical light microscopy and the visual observations are then compared with experimental, replicated pieces. This paper complements such archaeological research by providing physico‐chemical evidence. Raman spectroscopy and scanning electron microscopy have been used to confirm the presence of hematite on red‐stained medial and proximal parts of 71 000‐year‐old Still Bay bifacial tools from Sibudu Cave. Our results confirm the conclusion from optical light microscopy that the tools were hafted with an ochre‐loaded adhesive. However, we point to some instances when hematite residues are incidental or may be inclusions in the rock used to make the stone tools.     

Spectrochemical Characterization of Red Pigments Used in Classic Period Maya Funerary Practices

We studied the composition, colour chromaticity and form of application of red pigments in human bone samples from seven Classic period Lowland Maya sites. The samples were analysed by X‐ray diffraction, scanning electron microscopy (SEM) and X‐ray energy‐dispersive spectroscopy (EDS). Colour was measured using conventional colour identification standards (Munsell) and reflectance spectroscopy. Cinnabar and hematite were identified as the pigments used. We conclude that the reflectance method has advantages over conventional visual results, as it provides precise, objective and quantifiable optical data to distinguish the chromaticity, colour saturation and brightness of the pigments.     

A Multi‐Method Database of the Black and White Marbles of Göktepe (Aphrodisias), Including Isotopic,EPR, Trace and Petrographic Data

A database of the ancient marbles of Göktepe near Aphrodisias is reported, and includes 160 white, black and bichrome samples from 13 quarries and two waste deposits. The quarries are grouped into four districts. Districts 1 and 2, to the north, produced exclusively black or dark grey marbles (nero antico). Districts 3 and 4 produced white statuary marble. Nero antico and a black and white stone were also quarried in district 4, where the black marble surfaces again. The samples were characterized using petrography, isotopic analysis, EPR spectroscopy and trace analysis. The Göktepe white exhibits an unparalleled combination of fine grain, low EPR intensity and high strontium concentration that often allows easy identification. The isotopic values are less distinctive and similar to those for Carrara. In most cases, however, they are tightly grouped and also quite indicative. The black marbles exhibit a much weaker metamorphic overprint. With respect to the white marbles, they show analytical similarities but also notable differences. Therefore, establishing their provenance can be more difficult and may require the support of petrographic analysis. The results suggest that the Göktepe marbles were among the most prized and widespread statuary marbles used in Roman times, particularly from the early second century ad onwards.     

Different staining substances were used in decorative and therapeutic tattoos in a 1000-year-old Peruvian mummy

From a 1000-year-old mummy, found unwrapped in the sand of the desert at Chiribaya Alta in Southern Peru, two different kinds of tattoos were investigated: decorative tattoos displaying different animals and symbolic ciphers were present on the extremities and tattooed circles on the neck region.     

Retrograde P–T evolution and high temperature–low pressure fluid circulation in relation to late Hercynian intrusions: a mineralogical and fluid inclusion study of the Charroux-Civray plutonic complex (north-western Massif Central, France)

The calc‐alkaline plutonic complex from Charroux‐Civray (north‐western part of the French Massif Central) displays multiphase hydrothermal alteration. Plutonic rocks, as well as early retrograde Ca–Al silicate assemblages, which have crystallized during cooling and uplifting of the plutonic series, are affected by multiphase chlorite–phengite–illite–carbonate alteration linked to intense pervasive fluid circulation through microfractures. The petrographic study of alteration sequences and their associated fluid inclusions in microfissures of the plutonic rocks, as well as in mineral fillings of the veins, yields a reconstruction of the P–T–X evolution of the Hercynian basement after the crystallization of the main calc‐alkaline plutonic bodies. This reconstruction covers the uplift of the basement to its exposure and the subsequent burial by Mesozoic sediments. Cooling of the calc‐alkaline plutonic series started at solidus temperatures (～650°C), at a pressure of about 4 kbar (1 bar = 10⁵ N m^?2), as indicated by magmatic epidote stability, hornblende barometry and fluid inclusion data. Cooling continued under slightly decreasing pressure during uplift down to 2–3 kbar at 200–280°C (prehnite–pumpellyite paragenesis). Then, a hot geothermal circulation of CO₂‐bearing fluids was induced within the calc‐alkaline rocks leading to the formation of greisen‐like mineralizations. During this stage, temperatures around 400–450°C were still high for the inferred depths (～2 kbar). They imply abnormal heat flows and thermal gradients of 60–80°C km^?1. The hypothesis of the existence of one large or a succession of smaller peraluminous plutons at depth, supported by geophysical data, suggests that localized heat flows were linked to concealed leucogranite intrusions. As uplift continued, greisen mineralization was subsequently affected by the chlorite–phengite–dolomite assemblage, correlated with aqueous and nitrogen‐bearing fluid circulations in the temperature range of 400–450°C. In a later stage, a continuous temperature decrease at constant pressure (～0.5 kbar) led to the alteration of the dolomite–illite–chlorite type in the 130–250°C temperature range.