Re-examining the chemical evaluation of diagenesis in human bone apatite

Isotopic analysis of human bone is becoming an increasingly important tool for the archaeologist in divining past life-ways. The isotopic ratios within bone are often assumed to be preserved as in life, but diagenetic change can alter the ratios, invalidating the results of isotopic analysis. Diagenesis can be evaluated in a number of ways, but most often spectroscopic techniques are utilised as the most efficient and easiest to understand methods for the archaeologist. Many isotopic studies do not report the possibility of diagenetic change, and if it is reported it has often been quantified using a single method of chemical analysis, FTIR spectroscopy. This study set out to test the value of FTIR analysis using human remains from the prehistoric site of Ban Non Wat, Northeast Thailand, and to compare the results with the non-destructive technique of FT-Raman spectroscopy. The study shows that FTIR spectroscopic analysis gives far less detail on the condition of bone than Raman spectroscopy, which does not merely indicate recrystallisation has occurred, but also shows clearly whether or not collagen is present, allows identification of ionic substitions which have occurred and identification of secondary minerals which have formed. Raman spectroscopy, combined with LA-ICP-MS analysis also revealed that soil composition and groundwater flow are the conditions which most affect diagenesis at Ban Non Wat.     

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.     

化隆县纳卡遗址彩陶颜料的拉曼光谱分析

本文利用拉曼光谱(Raman)、X射线衍射(XRD)和X射线荧光光谱(XRF)等方法,分析了青海省化隆县纳卡遗址出土的马家窑文化及齐家文化彩陶。结果显示:马家窑文化黑彩在不同文化阶段其显色机理不同,半山阶段黑彩以磁铁矿及黑锰矿为主,且Fe/Mn比值较低,反射率最低,呈现浓翠的黑色;而马厂阶段黑彩则以赤铁矿及黑锰矿为主,Fe/Mn比值较高,反射率偏高,主波长为400~450nm,呈偏紫色的黑彩。表明马家窑文化陶工已认识到赤铁矿与黑锰矿的混合矿物颜料、含锰磁铁矿二者之间具有不同的呈色性能,并且熟练掌握了浓淡的变换规律,使之满足于彩绘的需求。齐家文化黑彩以磁铁矿为主,含有锐钛矿,主波长为650~700nm,呈偏红黄色的黑彩,表明这个阶段彩陶的烧制温度不高,彩陶文化已趋向衰落。     

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。     

古代文物表面常见天然有机物的显微共聚焦拉曼光谱研究

为了鉴别文物表面常见的天然有机物,采用显微共聚焦拉曼光谱技术采集了古代常用的蛋白类、多糖类、脂肪酸类、树脂类4类6种有代表性的天然有机物的拉曼光谱。通过对皮胶、桃胶、蜂蜡、棕榈蜡、达玛树脂和琥珀标准样品的拉曼光谱分析,发现蛋白类的特征振动峰位于1657cm-1、1305~1252cm-1、1033cm-1及1003cm-1附近;多糖类的特征振动峰位于1463cm-1、1328cm-1、1258cm-1、1088cm-1、977cm-1等;蜡类的特征振动峰位于1470~1350cm-1区间,1659cm-1、1303cm-1、1636 cm-1及1610cm-1;树脂类的特征振动峰位于1660~1650cm-1区间和1460~1440cm-1区间。在对6种天然有机物光谱特征分析的基础上,得出了使用拉曼光谱法可实现古代文物表面常见天然有机物种类鉴别的结论。     

拉曼光谱在纸质文物研究中的应用

纸张的老化程度一直是纸质文物保护中的重要研究方面,以往多采用目测法和经验来推断纸张的老化程度。纸张物理强度、聚合度等能表征老化状态的理化性能测试由于需要大量的样品而无法用于文物检测。近年来随着显微共聚焦拉曼光谱、近红外傅里叶变换拉曼光谱、表面增强拉曼光谱等技术的发展,作为一种原位、无损、微区的分析方法,拉曼光谱被越来越多地应用到了纸质文物的相关分析研究中,为纸质文物的保护修复提供科学依据。结合国内外文献,对拉曼光谱在纸张老化、碳黑颜料以及其他颜料上的应用和研究现状进行了梳理归纳。随着拉曼光谱应用的不断深入,以及与其他分析技术、化学计量学等的结合,未来将在纸质文物研究中发挥更多的作用。     

唐张臣和墓彩绘陶质文物的拉曼光谱和X衍射分析

利用拉曼光谱和X衍射方法,对张臣和墓彩绘陶质文物颜料及胎体进行分析,结果表明各种颜料保存基本完好,为以后科学保护修复这批彩绘陶质文物提供了科学依据。同时也证明,在样品量极少的情况下,利用拉曼光谱和X衍射等方法可有效鉴别古代颜料的种类及文物胎体的成分。     

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.     

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。     

几种罕见的黄铜钱币锈蚀产物的识别与形成原因探析

我国从明中期开始使用黄铜钱币,一直到清末。过去,对古代铸币的科学研究主要集中于合金成分分析和铸造工艺两方面,对锈蚀产物和锈蚀机理的研究主要针对青铜铸币。黄铜的合金元素中较青铜多锌元素,其腐蚀产物与腐蚀行为较青铜有一定的差别,也较青铜更为复杂,然而现有的文献关于此方面的研究匮乏,特别是对于大气保存环境下黄铜钱币的锈蚀产物及锈蚀成因的研究基本空白。本研究通过多种分析手段包括X射线荧光分析仪(XRF)、扫描电镜能谱仪(SEM-EDS)和显微激光拉曼光谱仪(Raman)对国家博物馆馆藏一批传世明清各时期的黄铜钱币合金组成,不同颜色的锈蚀产物等开展科学分析。研究结果表明,嘉靖、隆庆和万历年的黄铜铸币,为Cu+Sn+Pb+Zn四元合金,平均含量Cu 66.4%,Sn 6.8%,Pb 10.4%,Zn 15.6%,并含有微量Fe,不含As。泰昌、天启和崇祯年间及清代各时期的黄铜铸币,主要为Cu+Pb+Zn三元合金,并含有微量Fe、As和Sn。这批黄铜锈蚀产物与常见的青铜锈蚀产物不同,最典型的是钱币表面蓝绿色和白色锈蚀物,经Raman和SEM-EDS分析并结合相关文献初步确认蓝绿色锈蚀物为一种含铜、钠...     

便携式X射线荧光现场分析壁画颜料适用性研究——以西藏拉萨大昭寺壁画为例

便携式X射线荧光光谱仪作为快捷的无损分析技术,广泛应用于壁画文物的现场分析中.本文利用便携式X射线荧光光谱仪分析了西藏拉萨大昭寺转经廊壁画,选取部分样品,利用实验室X射线荧光分析,发现所分析颜料的主要显色元素具有一致性,并利用拉曼光谱确定了壁画颜料的成分.通过比较研究,发现便携式X射线荧光光谱仪可确定大部分色彩较为纯正的颜料的成分,同时,由于西藏拉萨大昭寺壁画颜料的杂多性,对于含砷的橙色颜料、含砷或含铅与含铁的黄色颜料、含铜砷的绿色颜料、含钙硫的白色颜料、群青与孔雀石的混合颜料则需结合拉曼光谱确定之.本研究工作显示,利用便携式X射线荧光光谱仪开展现场检测,可极大地减少实验室分析样品的取样数量,有利于壁画颜料的无损分析与微损分析.     

论晚清"裁厘统捐"与"裁厘认捐"的尝试及夭折

厘金在晚清财政中占有重要地位,但因多次征收而导致的税率过高使多方极为不满,也造成了中央与地方的财政矛盾。《辛丑条约》签订后,为了预备“裁厘加税”,清政府决定对厘金进行改革,实施“裁厘统捐”。随着立宪运动的展开,商民势力较大的江浙等省发起“裁厘认捐”,以抵制清廷的“裁厘统捐”。由于厘金问题事涉中央、地方、商民等多方利益与矛盾,加之清廷措置失当,短时期内难以顺利调适,博弈的结果是官方的“裁厘统捐”和商民的“裁厘认捐”均以失败告终。     

A non-invasive study of Roman Age mosaic glass tesserae by means of Raman spectroscopy

Ancient mosaic tesserae are a range of materials of very varied and complex nature, including pottery, stone and glass. Raman spectroscopy is a powerful tool for the analysis of all these kinds of materials. In the particular case of glasses, this technique can be used both for a study of surface weathering and for the characterization of bulk structure, but it has not yet been extensively used for the characterization of mosaic glass tesserae. We carried out Raman analyses on a set of Roman and Late Antiquity period mosaic glass samples, which allowed a good characterization of both the glass matrix and the crystalline inclusions. All the samples show the typical Raman signatures of soda-lime-silicate glasses. Several crystalline phases were also identified, being relics of raw materials used during the glass manufacturing process, such as quartz and feldspars, or linked to the glass color/opacification, such as bindheimite and cuprite. The analyses also led to the identification in some blue, turquoise and green tesserae of calcium antimonate, whose Raman signature has only recently been recognized in the scientific literature on mosaic glasses. Some emphasis is given to the analysis of red lead-containing tesserae, colored with Cu⁺ ions or even Cu⁰ (or Au⁰) metal nanoparticles. Samples with peculiar compositions, as well as “modern” (and restoration) samples, could quite easily be distinguished from the ancient ones by their Raman spectra.     

Archaeometrical characterization of pigments and paintings on Pre-Hispanic pottery from the regions of Fiambalá and Chaschuil (Catamarca,Argentina)*

The results of an analysis of pigments used in slips and designs deployed in ceramic assemblages recovered from archaeological sites located in different environments, expressing the socio-historical process developed in the regions of Fiambalá and Chaschuil (Catamarca, Argentina) during the last 1500 years are presented. The sample, formed by fragments of different ceramic styles and natural pigments, was analysed via Raman spectroscopy and X-ray diffraction. Results indicate the continuity in use of certain pigments (mainly hematite for red hues and Mn oxides in combination with magnetite for black paints) within the different socio-political organizations that inhabited the region from the first to the 14th centuries ce , in spite of the diverse shades of colour, which suggests an intentional search linked with their cultural conventions. For the Inca Period, this scenery of continuities in minerals employed for reds and blacks is complemented by the use of new compounds (Ti oxide, apatite and gypsum) in order to generate the ‘cream’ tones applied as slips, all of which have not been identified for previous moments.     

Identification of colourants in icons of the Cretan School of iconography using Raman spectroscopy and liquid chromatography

The stratigraphies of twenty five (25) samples removed from twenty (20) icons of the Cretan School of iconography are studied using Optical Microscopy and micro-Raman spectroscopy. The objects are dated in 15th–17th c. and belong to the collection of the Benaki Museum, Athens, Greece. Cinnabar, red ochre, minium, yellow ochre, azurite, malachite, lapis lazuli, lead white, carbon black, and indigo are identified in the cross-sections of the icon samples using Raman spectroscopy.     

中华民国三十四年中央银行纸币印刷颜料无损研究

法币在中国货币史特别是近代货币史上有着重要地位。1935年11月至1948年8月间,先后发行了15种从\"壹分\"到\"壹萬圆\"不同面额的法币,由中外十六家不同印刷公司承印,版别多达百余种。本研究利用超景深三维视频显微镜、激光显微共聚焦拉曼光谱仪和便携式X射线荧光光谱仪,对11枚1945年(中华民国三十四年)中央银行发行的壹仟圆法币的印刷颜料进行了无损研究。结果表明,红色部分(印章、冠字号、纹饰等)普遍使用了有机合成染料系列颜料红PR,而蓝色、绿色、棕色部分普遍使用了普鲁士蓝、铅铬黄和炭黑等颜料进行调配呈色。这些信息能够为纸币类文物的鉴别、保护修复以及相关研究提供依据。