史前漆膜的分析鉴定技术研究

研究了漆膜分析的三种主要方法：裂解质谱,红外光谱,裂解色谱。通过大量实验比较了各种方法的适应性和可靠性,建立了以裂解色谱／富里叶红外光谱联用技术来鉴定漆膜,并对影响裂解反应的因素及色借条件进行了深入的研究,获得了可以重复,具有特征性的漆膜高分辨裂解色谱图,同时对裂解色谱图中主要组分作了定性鉴定,提高了裂解色谱法分析漆膜的可靠性。该方法具有灵敏度高,样品用量小,共存杂质影响小,操作简便等优点。应用核分析技术对河姆渡,良诸庙前遗址出土的二件红色涂料样品进行了鉴定。分析结果证实了河姆渡出土的红色涂料木碗上的涂料是我国至今发现的最早的生漆漆膜。     

红外光谱在传统年画红蓝色料分析中的应用研究

年画是中国特有的民间艺术形式。本研究介绍了传统年画印制所用红蓝色料的发展历史,选取15种中国古代与近现代常用红蓝色料进行红外光谱分析,并归纳总结了标准样品的化学结构与红外谱图特征。在此基础上,利用衰减全反射傅里叶变换红外光谱仪对三幅清末民初时期的传统年画开展无损检测。结果显示三幅年画的红蓝色料均为合成颜料或染料,包括酸性大红G、酸性墨水蓝G、普鲁士蓝等。本研究扩展了红外光谱在书画文物分析检测中的应用范围,为传统年画色料的无损鉴定提供科学依据。     

唐武惠妃墓出土疑似胶结材料的分析研究

为了确定武惠妃墓室内发现的黑色多孔块状物质是否为绘制壁画时使用的胶结材料,联合使用显微镜观察、SEM-EDS、Raman、FTIR和GC-FID多种分析方法对该物质进行了显微结构观察、元素组成及物质组成分析。结果表明,该物质虽已炭化,但内部仍可见一些较新鲜的胶料残留,其成分为动物胶,并在其中发现了少量红色朱砂颜料残留。通过古文献记载和以往研究成果讨论了结果的可靠性。该研究不仅丰富了唐代墓葬壁画绘制技艺的考古学研究,更可为后期文物保护材料和工艺的选择提供借鉴。     

A Pigment Characterization Approach to Selection of Dating Methods and Interpretation of Rock Art: The Case of the Mikinak Site,Lake Wapizagonke,Quebec, Canada

Dating is perhaps the most frequently asked question in rock art studies, but still one of the most difficult to answer. However, chronology is vital in order to understand and interpret rock art sites. Unfortunately, attempts at dating the Mikinak site, at Lake Wapizagonke, Quebec, Canada were unsuccessful. But a multi‐instrumental protocol applied to characterize paintings shows that at least three different paint recipes were employed to create the site. These may reflect three different phases of paintings, and that at least three different artists contributed to the production of this site.     

Phytolith evidence for hearths and beds in the late Mousterian occupations of Esquilleu cave (Cantabria,Spain)

Esquilleu cave site has provided a moderately well preserved archaeological cave deposit from the Late Pleistocene in the Cantabrian area. Phytolith quantification, identification and determination of the refractive index have been carried out, together with FTIR analyses, from sediment samples collected in the profile. The comparison of the data obtained with the previous micromorphological results allows us to make inferences about the site formation processes and the Neanderthals use of the cave. Phytolith results show the presence of grass leaves nearby the hearth suggesting the repetitive existence of a bedding zone on the same area. Neanderthal behavioral patterns should be revised on the light of high resolution analyses, since diagenetic processes can obscure the existence of differentiated activity areas in the site.     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

The painting of the Etruscan “Tomba della Quadriga Infernale” (4th century BC), in Sarteano (Siena, Italy): technical features

This work presents the results of an investigation of the painting technique used in the Etruscan tomb “Tomba della Quadriga Infernale”. This tomb was discovered in Sarteano (Siena, Italy) in October 2003 and dated back to the second half of the 4th century BC. Red, dark red, pink, yellow, white, black, and grey colours were used in the tomb in order to create paintings, which now represent a very precious record of the Etruscan art of wall painting in a hypogeal environment. The technical features of the painting were revealed by stratigraphy using optical and electronic microscopy. The components and preparatory layers of the painted areas were characterized using Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray microanalysis (SEM-EDS), X-ray diffraction (XRD), and gas chromatography/mass spectrometry (GC/MS). XRD, SEM-EDS, and optical microscopic techniques were also used for mineralogical analysis of the rock substrate. The SEM-EDS and FTIR analyses showed that red and yellow ochre, calcite, and vegetable charcoal were used to paint the walls of the tomb: the pigments, either alone or mixed together, were utilized to produce pure colours (red, yellow, white, and black) and intermediate tonalities (pink, dark red, and grey). SEM-EDS, FTIR, and XRD highlighted that the painting was made on a preparatory layer of calcite, applied onto a levelling material made up of calcite, clay minerals, quartz, and iron oxides. GC/MS analyses revealed that egg was used as an organic binder to disperse the pigments.     

TESTING AN ALTERNATIVE HIGH‐THROUGHPUT TOOL FOR INVESTIGATING BONE DIAGENESIS: FTIR IN ATTENUATED TOTAL REFLECTION (ATR) MODE*

Archaeological bone undergoes alterations after burial (diagenesis) that constitute a problem for the survival of archaeological information. A common method to assess this alteration is Fourier transform infrared spectrometry (FTIR). However, the commonly applied method (FTIR–KBr) is destructive and sample preparation may influence the results. This paper tests the suitability of FTIR attenuated total reflection (FTIR–ATR), a method not commonly used to investigate bone diagenesis. FTIR–ATR requires less sample preparation and can be non‐destructive, allowing analysis of bone cross‐sections. Modern and archaeological bones were analysed using both methods and different sample preparation methods were tested. The results show that FTIR–ATR has advantages for the rapid assessment of bone diagenesis.     

The effect of charring and burial on the biochemical composition of cereal grains: investigating the integrity of archaeological plant material

Stable isotope analysis of charred archaeobotanical cereal grains has the potential to provide direct evidence of crop growing conditions in the past and to refine palaeodietary predictions. If isotope values of archaeobotanical material are to be considered robust, it is necessary to characterise the compositional changes associated with their charring and burial. This study used a suite of analytical techniques, including FT-IR and solid state ¹³C NMR, to characterise changes in the biochemical composition of modern einkorn grains with heating at 230 °C for 2 h, 4 h, 8 h and 24 h, encompassing conditions that replicate their undistorted ancient counterparts. The biochemical composition of archaeobotanical charred einkorn grains was also investigated by FT-IR and solid state ¹³C NMR in order to assess the changes in composition which occur during burial. Results of FT-IR and solid-state ¹³C NMR show that heating of modern einkorn grains resulted in Maillard reactions between cereal proteins and starch, forming high molecular weight melanoidins, which contain both alkyl and aromatic carbon. Loss of low molecular weight carbon and nitrogen-containing volatiles resulted in a slight but non-systematic increase in the δ¹³C values and a systematic increase of 0.8‰ in the δ¹⁵N values of the charred einkorn grains. Solid-state ¹³C NMR shows that the ancient charred einkorn grains consisted entirely of aromatic carbon and retained a similar proportion of nitrogen to their modern 24 h charred counterparts, despite a significantly lower concentration of amino acids. This indicates that the amino acid nitrogen in the ancient charred grains was retained in the stable melanoidins whose polymeric structure makes them resistant to subsequent degradation.     

湖北省鄂州五里墩出土孙吴时期“红色粉状物”的测试分析

利用X射线荧光（XRF）,红外光谱（FTIR）和X射线衍射（XRD）等方法对湖北省鄂州市五里墩M2墓葬出土孙吴时期的红色物质进行了分析,结果表面这种红色物质主要是超细的朱砂粉料与油脂等的混合物,结合考古资料推测可能是调制的古代化妆品;其制作工艺是：从矿石中选出朱砂,研磨成很细的粉状,加入油脂（或许还加入了白色的高岭土）调和成膏状。本研究结果不但为该墓葬分析提供重要考古信息,对古代朱砂质化妆品的相关研究也有借鉴和参考作用。