Hyaline tissue of thermally unaltered conodont elements and the enamel of vertebrates

Comparison of the ultrastructure of the hyaline tissue of conodont elements and the enamel of vertebrates provides little support for a close phylogenetic relationship between conodonts and vertebrates. Transmission and scanning electron microscopy shows that the mineralised component of the hyaline tissue of Panderodus and of Cordylodus elements consists of large, flat, oblong crystals, arranged in layers that run parallel to the long axis of the conodont. Enamel in the dentition of a living vertebrate, the lungfish Neoceratodus forsteri, has crystals of calcium hydroxyapatite, arranged in layers, and extending in groups from the dentine-enamel junction; the crystals are slender, elongate spicules perpendicular to the surface of the tooth plate. Similar crystal arrangements to those of lungfish are found in other vertebrates, but none resembles the organisation of the hyaline tissue of conodont elements. The crystals of hydroxyapatite in conodont hyaline tissue are exceptionally large, perpendicular or parallel to the surface of the element, with no trace of prisms, unlike the protoprismatic radial crystallite enamel of fish teeth and scales, or the highly organised prismatic enamel of mammals.     

The tattoos of the Tyrolean Iceman: a light microscopical, ultrastructural and element analytical study

The Tyrolean iceman, a 5300-year-old mummy, presents tattoos on different parts of his body. Skin samples of several line tattoos and a cross tattoo were investigated by optical microscopy and various electron microscopy techniques (TEM, EFETEM, EELS, EDXS, electron diffraction). The epidermis of the investigated skin areas was mostly lacking. The tattooing particles are distributed in the connective tissue and could be identified as soot. In some areas between the soot particles, different silicate crystals are present such as almandine and quartz, along with some not exactly definable crystals. The crystals possibly derived from stones of the fireplace from which the soot was taken for tattooing. Additionally, in the medial part of the right leg, putative ash particles were seen in the tattooed area. Furthermore, in non-tattooed skin areas, a vivianite crystal and small grains of CaPO₄ and nearby Fe, P and O could be detected, these having formed most probably after the death of the Tyrolean Iceman during his long period in the mountains. On the surface of two leg specimens, a small layer with brown granules was visible by means of optical microscopy, and these were identified as melanin granules in the stratum basale of the epidermis.     

草酸钙晶体形态在中国传统手工纸纤维鉴别中的应用

纤维鉴别是纸质文物、古籍与档案保护中必要的基础工作,对于修复方案的制定、修复材料的选择等具有重要的指导意义。草酸钙晶体是植物中普遍存在的一种后含物,其形态与植物种群具有密切关系。本工作以具有代表性的传统手工纸为研究样品,综合使用衰减全反射傅里叶变换红外光谱法、X射线衍射法、扫描电子显微镜、光学显微镜和偏光显微镜观察等多种仪器分析手段,系统研究各类纸纤维中草酸钙晶体的形态特征,进而探讨草酸钙晶体形态在中国传统手工纸纤维鉴别中的应用价值,以进一步完善现有纤维鉴别方法体系。     

Black Gloss Pottery: Production Sites and Technology in Northern Etruria,Part II: Gloss Technology

The present study aims to understand the reasons for the visual differences of black gloss pottery found in northern Etruria. The results obtained by conventional (scanning electron microscope, electron microprobe) and synchrotron (X‐ray diffraction, X‐ray absorption spectroscopy) techniques indicate that the thickness, porosity or chemical composition of the different types of gloss cannot be used as the principal distinguishing factor. The size of quartz or feldspar crystals may well be a critical factor responsible for the matt effect in some samples, while the range of mixtures of iron compounds indicated by XRD and XAS could be the reason for differences in colour and reflectivity. The Fe L‐edge XAS results in particular show that a correlation does exist between the oxidation state characteristics and the visual appearance. The Si, Fe and Al contents seem to further discriminate the different types of gloss that have differing visual appearances.     

CHEMICAL AND MINERALOGICAL ANALYSES OF GALLO-ROMAN WALL PAINTING FROM DIETIKON,SWITZERLAND

Around 90 samples of Roman wall painting dating from the first to the third century AD were analysed using different analytical techniques: X-ray diffraction, X-ray fluorescence, infrared spectrometry, scanning electron microscopy, energy dispersive spectrometry, optical microscopy and physico-chemical tests. The identified pigments are: ash, calcite, carbon black, celadonite, cinnabar, Egyptian Blue, glauconite, goethite, hematite and red lead. Pigment mixtures were used to get other colours such as brown, pink or purple. Three types of plaster were used: a first, and most dominant, with river sand, a second with crushed tile for damp places and a third, to which cinnabar was exclusively applied, was prepared with crushed calcite crystals.     

石质文物加固中细菌诱导碳酸钙生成的研究

为探讨细菌生物矿化法加固石质文物,利用枯草杆菌-Ⅱ在特殊含钙培养基上进行诱导矿化研究.结果表明,筛选出的菌株枯草杆菌-Ⅱ在M-3+ASP固体和液体培养基上能诱导生成白色物;白色诱导物经X-衍射分析为碳酸钙;电子显微镜下观察发现碳酸钙在细菌周围生成,并包裹细菌菌体,使细菌菌体钙化.     

AN INVESTIGATION INTO THE RELATIONSHIP BETWEEN THE RAW MATERIALS USED IN THE PRODUCTION OF CHINESE PORCELAIN AND STONEWARE BODIES AND THE RESULTING MICROSTRUCTURES*

The microstructures of porcelain and stoneware bodies from north and south China, spanning the period from the Tang to the Ming dynasty (7th–17th centuries ad ), were examined in polished sections in a scanning electron microscope (SEM) after etching the sections with hydrofluoric acid (HF). Mullite, present as fine, mainly elongated crystals, is the dominant crystalline phase observed. The bulk chemical compositions of the bodies are determined by energy‐dispersive spectrometry in the SEM, and the relative amounts of mullite and quartz present in the different ceramics are estimated from X‐ray diffraction measurements. Mullite formed from areas of kaolinitic clay, mica particles and feldspar particles is distinguished through a combination of the arrangement of the mullite crystals, and the associated SiO₂/Al₂O₃ wt% concentration ratios. It is shown that very different microstructures are observed in ceramic bodies produced using kaolinitic clay from north China (Ding porcelain and Jun stoneware), porcelain stone from south China (qingbai and underglaze blue porcelain and Longquan stoneware), and stoneware clays from south China (Yue and Guan stonewares). Therefore, SEM examination of HF‐etched, polished sections of the bodies of high‐refractory ceramics has considerable potential for investigating the raw materials used in their production.     

Electron backscatter diffraction investigation of length‐fast chalcedony in agate: implications for agate genesis and growth mechanisms

Agates of volcanic origin contain a range of silica minerals, with chalcedony and quartz arranged in concentric bands. Although agates are abundant worldwide, little is known about the genesis of their characteristic banding patterns. Current hypotheses suggest the bands result either from precipitation from convecting siliceous hydrothermal influxes or by in situ crystallization of a silica gel. This study combines the use of a variety of analytical techniques, including electron backscatter diffraction (EBSD), cathodoluminescence (CL), and Fourier transform infrared (FT‐IR) spectroscopy, to characterize the silica minerals present and investigate their spatial and crystallographic relationships in the banding arrangement. Microstructural and spectroscopic observations reveal that chalcedony bands are composed of amorphous silica that also contains nanocrystalline and later‐formed microcrystalline quartz. Nano‐ and microcrystalline quartz grew with a‐axes perpendicular to the growth substrate, typical of length‐fast chalcedony. The bands formed as a result of discrete influxes of silica‐rich fluid. Within these individual bands, there is a sequence of minerals: chalcedony‐A (with amorphous silica and nanocrystalline quartz) → chalcedony‐MQ (with microcrystalline quartz) → quartz. This sequence is reflected in the degree of crystallinity, crystal orientations and water content and is analogous to a diagenetic cycle; the initial chalcedony portion of the band commences with amorphous silica with nanocrystalline quartz followed by fibrous microcrystalline quartz crystals; chalcedony then grades into larger equiaxial mesoquartz crystals. This paragenetic sequence suggests a viable model for the growth of chalcedony in agates.     

MOSAIC GLASS FROM ST PETER'S,ROME: MANUFACTURING TECHNIQUES AND RAW MATERIALS EMPLOYED IN LATE 16TH‐CENTURY ITALIAN OPAQUE GLASS

A recent restoration of late 16th‐century mosaics in one of the vaults beneath the dome of St Peter's Basilica in Rome allowed sampling and analysis of a group of glass tesserae. The aim of this work is the characterization of opaque coloured glasses possibly produced in Rome. The characteristics of the glass from St Peter's were compared with those of Venetian and Tuscan production, in order to assess possible common origins. Chemical analysis of 30 samples was carried out by electron microprobe, while the nature and morphology of opacifiers were determined by X‐ray diffraction and scanning electron microscopy. Almost all the opaque samples were characterized by the presence of SnO₂ crystals. In addition, depending on the colour of the glass, other crystalline phases were identified: lead‐tin oxide (PbSnO₃) in yellow glass, cuprite (Cu₂O) in orange glass and two calcium‐tin silicates with different stoichiometry (CaSnSiO₅ and Ca₃SnSi₂O₉) in the green‐yellow variety. A frame of reference for identifying raw materials and glass‐making techniques is provided by textual sources, here examined in comparison with the compositional characteristics of the tesserae from St Peter's.     

Sulfosalt melts and heavy metal (As‐Sb‐Bi‐Sn‐Pb‐Tl) fractionation during volcanic gas expansion: the El Indio (Chile) paleo‐fumarole

High‐sulfidation vein gold deposits such as El Indio, Chile, formed in fracture arrays <1000 m beneath paleo‐solfatara in volcanic terranes. Stable isotope data have confirmed a predominance of magmatic vapor during the deposition of arsenic‐rich sulfide–sulfosalt assemblages in this deposit. These provide a unique opportunity to analyze the processes and products of high‐temperature volcanic gas expansion in fractures that form the otherwise inaccessible infrastructure deep inside equivalent present‐day fumaroles. We provide field emission scanning electron microscope and LA‐ICP‐MS micro‐analytical data for the wide range of heavy, semi‐metals and metalloids (arsenic, antimony, bismuth, tin, silver, gold, tellurium and selenium) in the complex pyrite‐enargite‐Fe‐tennantite assemblages from Copper Stage mineralization in the El Indio deposit. These data document the progressive fractionation of antimony and other heavy metals, such as bismuth, during crystallization from a sulfosalt melt that condensed from expanding vapor at about 15 MPa (150 bars) and >650°C following higher temperature vapor deposition of crystalline pyrite and enargite. The sulfosalt melt aggressively corroded the earlier enargite and pyrite and hosts clusters of distinctive euhedral quartz crystals. The crystallizing sulfosalt melt also trapped an abundance of vugs within which heavy metal sulfide and sulfosalt crystals grew together with K‐Al silicates and fluorapatite. These data and their geologic context suggest that, in high‐temperature fumaroles on modern active volcanoes, over 90% of the arsenic content of the primary magmatic vapor (perhaps 2000 mg kg^?1) was precipitated subsurface as sulfosalt. Subsurface fractionation may also account for the range of exotic Pb‐Sn‐Bi‐Se sulfosalts observed in fumarole sublimates on active volcanoes such as Vulcano, Italy, as well as on extra‐terrestrial volcanoes such as Maxwell Montes, Venus.     

Chemical composition and colouring agents of Roman mosaic and millefiori glass, studied by electron microprobe analysis and Raman microspectroscopy

About 100 fragments of Roman mosaic and millefiori glass were stylistically attributed to a Hellenistic type, a Ptolemaic and Romano-Egyptian period type and an early imperial period type. Twelve representative fragments were studied by electron microprobe analysis and Raman microspectroscopy. Eleven of them display a Na-pronounced recipe with low K, Mg and P contents, typical for the Roman period. Minor differences in composition are unsystematic, not reflecting the stylistic classification. Ionic colouring agents are Mn³⁺ for violet, Cu²⁺ for light blue, Co²⁺ for deep blue and Fe³⁺ for brown translucent colours. Calcium antimonates, lead antimonate and cuprite are the colourants responsible for white, yellow and red colours, respectively, and additionally serve as opacifiers. Mixing of ionic colouring agents and opacifying colourants led to a more differentiated palette of colours. Pb was used as yellow colouring agent, as a flux material and as a stabiliser for the colourant crystals. The remaining fragment consisting of a K-pronounced but still Na-bearing glass matrix was most likely produced during the Middle Ages or later.     

Biofilm growth in human skeletal material from ancient Mesopotamia

Investigators have long recognised the effects of microbial activity on archaeological bone. These investigators, however, have focused on single or groups of microbes rather than on complex microbial aggregates such as biofilms, a focus that has affected our understanding of archaeological bone biodeterioration. In this paper, we report on the investigation of a biofilm in archaeological human bone from the site of Tell Leilan, Syria (2900–1900 BCE). Scanning electron microscopy indicated that the biofilm is characterised by single cells and microcolonies of bacteria and fungi, as well as calcite crystals that were all embedded within extracellular polymeric substances. Using culture techniques and DNA sequencing, we isolated and identified several microbes from the biofilm including Amycolatopsis sp., Penicillium chrysogenum, Aspergillus sp., Chaetomium sp., and Cladosporium sp. Having characterised the Leilan biofilm, we are now closer to understanding the complex process of bone biodeterioration in archaeological bone collections.     

五代耀州窑天青瓷的研究

为揭示五代天青瓷釉的呈色机理以及胎体的透光机理,本研究以五代耀州窑天青瓷为主要对象,分别采用EDXRF、XRD、XPS和SEM/EDS等测试方法,分析了化学组成、物相、着色元素的化学状态及微观结构对瓷釉的呈色及瓷胎透光性的影响。结果表明,天青瓷釉为复合呈色方式,釉中Fe_2O_3产生的化学着色作用和釉层中物理结构(残余晶体和分相液滴)对入射光的散射作用产生的结构色,或加深或淡化了呈色,且对釉面的色饱和度和乳浊度也有一定的影响。天青瓷胎的透光性主要与着色氧化物对入射光的吸收以及晶界、气泡对入射光的散射有关。低含量的Fe_2O_3和铁钛固溶体,大大减少了其对入射光的吸收。同时,较少的晶界也减弱了对入射光的散射。因此,天青瓷的透光性良好。     

Dental root dentine translucency used in age determination of medieval Norwegians from Trondheim

A pilot study on eight skulls from the churchyard of St Olav's church in Trondheim, excavated in 1988–1989, was carried out to compare age determined by root dentine translucency with the age assessed by a physical anthropologist. The difference in mean age between the two methods was not significant (p = 0.06). Age determinations based on root dentine translucency were then performed on removable teeth from the adults among the 248 skeletons found in the same churchyard, excavated in 1984–1985. A comparison between the ages determined using root dentine translucency and the ages previously determined by the direct inspection method was performed. A significant systematic difference was seen between the two methods (p = 0.000). The root dentine translucency method gave an age range for the cohort excavated in 1984–1985 between 30 and 72 years, whereas the direct inspection method gave a range between 15 and 63 years. Because evaluation of many criteria are required to achieve reasonably accurate estimates of age in connection with the direct inspection method, expertise in skeletal biology is necessary. The method of measuring root dentine translucency as a tool in archaeological and anthropological work and fieldwork and in forensic science seems to have advantages because the method can be used without previous extensive training.     

Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments

Oscillatory zoning and fine‐scale variations in trace element chemistry are commonly observed in hydrothermal minerals. It has been suggested that fine‐scale chemical variations are caused by extrinsic changes in the parent hydrothermal system, such as varying fluid composition, pressure or temperature, as well as changes in mineral growth rate. In this study, LA–ICP–MS (laser ablation, inductively coupled plasma mass spectrometer) analyses were carried out on calcite crystals grown in Ca–NH₃–Cl solutions doped with rare earth elements (REE). The variety of crystal morphologies observed (euhedral to acicular), likely relate to variations in trace element abundance and calcite supersaturation state. Crystals display oscillatory and sector zoning, with significant variations in REE concentrations among zones. Cyclic variations in REE concentrations (exceeding 10‐fold) occur over distances of <1 mm along the growth direction of acicular calcite crystals. In general, trace element concentrations decrease during progressive crystal growth, implying that the concentration of trace and REEs within crystals reflects the overall composition of the growth solution. However, bulk changes in crystal composition are modulated by fine‐scale (<1 mm) variations, which are inferred to be caused by growth‐rate‐controlled incorporation of trace elements. These results have important implications for using hydrothermal minerals to infer fluctuations in fluid compositions in ancient, exhumed hydrothermal systems.     

THE TECHNOLOGY OF PRODUCTION OF SASANIAN GLAZED POTTERY FROM VEH ARDAŠ?R (CENTRAL IRAQ)

Scanning electron microscopy coupled with an energy dispersive X‐ray detector (SEM‐EDS) has been used to study samples of Sasanian glazed pottery. Analysis of ceramic bodies revealed a general homogeneity in composition among the studied samples and the use of calcareous clay for their manufacture. Glazes are typically alkaline in composition, with sodium and potassium oxide contents between 8 and 13%, and between 3 and 5%, respectively; calcium and magnesium oxide contents are between 7 and 10%, and between 3 and 5%, respectively. These data suggest the use of plant ash together with a silica source for glaze production. Coating thickness is highly variable among different samples, from some 400 up to 1200 µm, but it is generally uniform when a single sample is concerned. Glazes are mostly coloured blue or blue‐green; copper and iron are the colouring agents detected; abundance of bubbles, silicate crystals and relics of unmelted material are responsible for their generally opaque appearance, together with the presence of weathering products. The characteristics of the body to glaze contact zone, together with the widespread presence of bubbles, would not rule out production by a single firing process. A few samples feature a peculiar gritty coating on one side of their surface; SEM images show that they are actually partially vitrified, and EDS data denote a rather heterogeneous composition. It seems possible that they result from mixing clay together with the frit used for glaze development.     

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.     

实验室模拟硅酸盐质文物除盐控盐的可视化研究

针对目前广泛使用的材料吸附除盐和加湿喷雾控盐等方法对含盐硅酸盐质文物可能造成的损伤,采用扫描电子显微镜、电阻仪和高分辨摄影仪等实时在线记录具有显色性质硫酸铜溶液在吸附除盐和水雾控盐加湿干燥过程中文物内部盐带分布的变化。研究结果表明：吸附材料除盐法和表面喷雾控盐法均会加速样品内部盐离子的扩散迁移,在样品中形成双层或多层盐结晶带;所形成的盐结晶带与样品结构特性、盐溶液在样品中的运移和蒸发速率、加湿-干燥频率等因素有关,其中溶液毛细上升高度和样品透气性越好,以及环境温度和盐溶液浓度越高,加湿-干燥频率越快,样品内部的盐带分布变化越明显。材料吸附除盐和水雾控盐等方法加速了盐溶液在样品内部的扩散,促进多层盐带的形成。这些结果对于目前文物保护所采取的除盐控盐技术手段提出了新的挑战。     

Identification of urate crystals in gouty individuals

In paleopathology cases of gout have traditionally been identified using the character of erosive bony lesions, but in clinical medicine identification of monosodium urate crystals in joint fluid plays a central role in diagnosis. Work undertaken on three skeletal individuals who had been buried, demonstrates that crystals can be identified using polarising microscopy. The crystals were identified as monosodium urate. Results from this study appear to demonstrate that identification of monosodium urate crystals could be used to assist in the diagnosis of gout in paleopathology. Further work is required to establish the full range of spatial and temporal contexts from which such crystals might be found.     

冻融作用对古青砖宏观性能及微观结构劣化的影响

砖质文物建筑多数处于室外工作环境,其损伤呈现出冻融循环条件下的物理风化和材料水解条件下的化学风化联合作用破坏形态,致使古青砖文物面临着严重的环境侵蚀风化问题。为此,以古建筑青砖为研究对象,通过对6组试样分别进行0,15,30,45,60和75次冻融循环试验,分析冻融循环次数对古青砖的孔洞率、质量、抗压强度的影响规律。在此基础上,通过TEM(透射电子显微镜)扫描探讨了冻融作用对古青砖微观结构的损伤过程及劣化机理。结果表明:随着冻融循环次数的增加,古青砖的孔洞率、质量损失率以及强度损失率均增大;TEM扫描发现冻融对古青砖造成了明显的微观孔隙结构损伤,特别是75次冻融循环后该损伤明显激增。同时,利用XPS(X射线光电子能谱仪)测试古青砖化学成分的组成,说明青砖体内碳酸盐等可溶性盐类的晶体水解造成青砖的微观孔隙结构损伤,是其遭受化学风化作用的主要原因。