Multi‐technique study of archaeological cord‐marked wares decorated with red coatings from Taiwan

Archaeological finds of Neolithic to Iron Age pottery show clay potsherds characterized by red cord‐markings. The items date back from 5500 to 1500 B.P. To better understand temporal changes in the provenance of raw‐material sources, and the nature of materials used in the red colorant and ceramic bodies, micro‐Raman spectroscopy, X‐ray diffraction analysis (XRD), and micro X‐ray florescence spectroscopy (μXRF) were applied to 29 red‐coated potsherd samples found at twelve archaeological sites across Taiwan. The techniques identified the chemical and mineralogical composition of the red coatings and ceramic bodies as well as the production methods of ancient potters. Eighteen mineral phases were identified from the Raman spectra, including hematite, α‐quartz, and anatase. Feldspar, rutile, pyroxenes, calcite, gypsum, amorphous carbon, and graphite were also detected. XRD measurements, and μXRF analyses were used as complementary techniques to obtain mineral and chemical compositions. Hematite, anatase, calcite, plagioclase feldspar, and illite were present in potsherds, suggesting pottery produced from illitic clays fired at less than 850 °C under oxidizing conditions. Results further suggest that raw materials were sourced from or near local volcanic rock areas, and more broadly from metamorphic or sedimentary rocks and clays. Chemically, raw materials used for red coatings are different to those of the ceramic bodies. Objects from most sites used the same raw material sources; however, some sites contain objects made from changing sources over time. Pot coatings exhibit polygonal cracks, and loosened cementation strongly suggesting that finely processed moist clays were fired to a biscuit form with no second stage firing process. The non‐destructive Raman experiments identified and characterized mineral phases, which helped understand manufacturing techniques. Overall the multi‐technique approach gave extensive information on the finds, helping to differentiate raw material sources and production technologies. This approach is an important and effective method for investigating archaeological finds. Copyright © 2014 John Wiley & Sons, Ltd.     

利用反射光谱研究砂岩风化与排氮作用——以江西龙虎山为例

近期,《Nature》、《Science》等世界顶级期刊揭示了地表岩石与全球氮循环的相互作用,认为岩石是氮素的重要储库,其风化排氮是生态系统氮素的主要来源之一,对局部乃至全球氮循环具有重大影响。陆地地表岩石分布面积75%是沉积岩,丹霞地貌是受沉积岩风化侵蚀作用形成的重要地貌类型之一,研究丹霞地貌沉积岩的风化与排氮作用对深入了解全球氮循环过程具有重要意义。以江西龙虎山丹霞地貌出露的红色砂岩为研究对象,在系统的野外样品采集工作基础上,利用偏光显微镜、ASD光谱仪和碳氮分析仪对样品的矿物组成、光谱曲线和氮素含量进行鉴定和测量。结果表明：龙虎山砂岩主要为长石砂岩,颗粒矿物为长石和石英,胶结物以铁质、钙质为主,次为泥质;砂岩的化学风化类型主要有胶结物溶蚀和颗粒矿物水化两种,其中胶结物溶蚀以铁质溶蚀为主,溶蚀后岩石的光谱曲线在902 nm处（Fe3+的特征吸收波段）的吸收指数下降,而颗粒矿物水化则主要体现为长石向粘土矿物转变,水化后岩石的光谱曲线在2 210 nm处（粘土Al-OH的特征吸收波段）的吸收指数上升。针对同一件样品,已被化学风化的部分与未被风化的部分相比,其氮元素含量有所下降,且氮元素含量与2 210 nm处的吸收指数存在一定的负相关系（R2=0.802 6）,说明岩石风化有助于氮排放;针对不同样品,氮元素含量与2 210 nm处的吸收指数相关性很差（R2=0.025 6）,说明岩石矿物组成与结构差异对岩石初始氮含量和吸收指数产生影响,从而降低两者间的相关性。以上研究说明,反射光谱为砂岩风化程度检测与氮排放研究提供了一种重要的技术手段,但研究时必须注意岩性的一致性。     

Identification of minerals and organic materials in Middle Eocene ironstones from the Bahariya Depression in the Western Desert of Egypt by means of micro‐Raman spectroscopy

The Middle Eocene ironstones of the Bahariya Depression consist of four iron ore types: manganiferous mud‐ironstone, fossiliferous ironstone, stromatolitic ironstone and nummulitic–ooidal–oncoidal ironstone. The upper surfaces of these sequences were subjected to subaerial weathering and a lateritic iron ore type was formed. The chemical composition of these ironstone types was investigated by means of micro‐Raman spectroscopy. Various closely related iron‐containing and manganese‐containing minerals were detected by means of the above‐mentioned approach. The high spatial resolution and sensitivity of this method allowed us to identify minerals that could not be detected by other techniques. Well‐preserved organic materials were observed in one type of ironstones. Therefore, using Raman spectroscopy, we were able to provide evidence that the formation of some of the investigated rocks was biologically mediated. The application of Raman spectroscopy is considered a powerful technique for the identification of both organic and inorganic substances in the studied iron ore deposits. Copyright © 2011 John Wiley & Sons, Ltd.     

Crocoite PbCrO4 and mimetite Pb5(AsO4)3Cl: rare minerals in highly degraded mediaeval murals in Northern Bohemia

Mural paintings of exceptional quality, which can be discerned in spite of their extensive mechanical damage and colour fading, have been uncovered in the church of St. Gallus in Kuřívody, Northern Bohemia, dated to the second half of the 13th century. Materials research with particular use of portable X‐ray fluorescence, Raman micro‐spectroscopy and powder X‐ray micro‐diffraction revealed the presence of rare pigments. In Kuřívody, it is only a second identification of intentionally used yellow mineral crocoite (PbCrO₄) in European art. Its identification is facilitated by providing a very good Raman scattering, even when present in small amounts in fragmentarily preserved colour layers. Light yellow mimetite (Pb₅(AsO₄)₃Cl) was never before mentioned as intentionally used pigment in Europe. Its finding in Kuřívody, however, corresponds more likely with undesirable physical–chemical conditions causing its formation by alteration of orpiment (As₂S₃) and minium (Pb₃O₄). Obtained results highlight the importance of Raman spectroscopy for direct identification of mineral pigments in low concentrations, which may be crucial for interpreting cultural heritage objects in historical context. By materials, the almost forgotten paintings in Kuřívody can be seen as outstanding and rare example of ancient artistic tradition that has spread to Europe from Mediterranean in early Middle Ages. After all, mineral crocoite was already used by ancient Egyptians to paint sarcophagi and degraded orpiment decorates the walls of the Nefertari's tomb in Thebes. Copyright © 2014 John Wiley & Sons, Ltd.     

Rapid outdoor non‐destructive detection of organic minerals using a portable Raman spectrometer

Raman spectral signatures have been obtained for a series of organic minerals using a compact portable Raman instrument equipped with 785‐nm laser excitation. Well‐resolved Raman spectra of crystalline salts of carboxylic acids, whewellite and mellite, as well as of the aromatic mineral idrialite were recorded. For comparative purposes, an amorphous fossil resin, baltic amber, was also investigated. The results obtained confirm that portable Raman instruments can be considered as excellent tools for field geological applications, including the detection of organic minerals in the frame of outcrops of sedimentary rocks or coal beds. Organic minerals can be added to the list of established biomarkers, including porphyrins, hydrocarbons and organic acids, which are important for the study with regard to future exobiological missions such as the ESA ExoMars mission to detect the presence of extinct or extant life on Mars. Copyright © 2009 John Wiley & Sons, Ltd.     

Morphological biosignatures from relict fossilised sedimentary geological specimens: a Raman spectroscopic study

Morphological biosignatures (features related to life) and associated terrestrial sedimentary structures that provide possible sampling targets for the remote astrobiological exploration of planets have been analysed using Raman spectroscopic techniques. The spectral data from a suite of samples comprising crypto‐chasmoendoliths, preserved microbial filaments and relict sedimentary structures comprise a preliminary database for the establishment of key Raman biosignatures. This will form the basis for the evaluation of prototype miniaturised instrumentation for the proposed ESA ExoMars mission scheduled for 2013. The Raman spectral biosignatures of carotenoids and scytonemin, organic biomolecules characteristic of the cyanobacterial colonisation of geological matrices and biogeologically modified minerals are also identifiable in the sedimentary specimen materials. The results of this study demonstrate the basis of the molecular recognition of extinct and extant exobiology that will feed into the elemental structural analyses of morphological structures provided by associated SEM, XRD and laser‐induced breakdown spectroscopy (LIBS) techniques on robotic analytical landers. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman identification of lonsdaleite in Popigai impactites

Micro‐Raman spectroscopy and X‐ray diffraction method (XRD) were used to characterize impact carbonaceous rocks excavated from the Popigai crater (Siberia). The deconvolution of the first‐order Raman spectra of the rocks containing different amounts of carbon phases (diamond, lonsdaleite and graphite) allowed the identification of lonsdaleite spectrum. The most intensive band at 1292–1303 cm⁻¹ was ascribed to A_1g vibration mode of lonsdaleite, whereas the less intense band at 1219–1244 cm⁻¹ was attributed, in agreement with previously reported ab initio calculations, to E_2g vibration mode. The established correlation between the intensities of Raman and XRD peaks permits a rough estimation of lonsdaleite/diamond phase ratio in the impact rocks using micro‐Raman measurements. The second‐order Raman spectra of lonsdaleite–diamond rocks were recorded. Copyright © 2014 John Wiley & Sons, Ltd.     

绿松石显微拉曼光谱及产地意义初步分析

运用显微拉曼光谱技术（RM）分析了实地采集的我国湖北、安徽两地的4件现代绿松石样品,发现处于同一绿松石成矿带内、成矿背景和成因类型相同的3件湖北绿松石样品,尽管颜色上有差异,但其拉曼图谱保持基本一致,而与成矿背景和含矿岩系明显不同的安徽马鞍山绿松石拉曼图谱在900～100 cm-1区域差别很大,且荧光背景强度和光谱特征也有明显区别;同时选取了2件古代绿松石样品用激光拉曼光谱进行原位无损分析,通过与已知产地绿松石样品（所有样品均为实地采集）拉曼图谱的对比,探讨利用已知产地绿松石样品的拉曼图谱作为“指纹”示踪古代绿松石产地的可行性。     

Investigation of some Chinese jade artifacts (5000 BC to 771 BC) by confocal laser micro‐Raman spectroscopy and other techniques

The study on material properties of ancient stone or jade artifacts is essential to trace the trade routes of raw materials, the tools used to making them, and moreover the social function of the artifacts. In present research, we focused on 23 intact samples that were made of versatile rocks. These samples dated from 5000 bc to 771 bc were unearthed from the Yellow River and Yangtze River basins in China. Based on the analytical results of confocal laser micro‐Raman spectroscopy, 14 minerals consisted of these rocks such as muscovite, antigorite, calcite, quartz, diopside, turquoise, corundum, and sillimanite were identified. The obtained scientific information about their primary material properties helps us to better understand their social functions and technologically related issues. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy and VP‐SEM/EDS applied to the identification of mineral particles and fibres in histological sections

Histological sections of a patient affected by an important respiratory disease were analysed firstly by optical microscope(OM)—crossed polarisers—to identify the presence of incorporated inorganic particles, with particular attention to the fibrous ones. Then, the particles/fibres that were found were studied both with micro‐Raman spectroscopy and variable‐pressure scanning electron microscopy with energy‐dispersive spectroscopy (VP‐SEM/EDS). The two techniques allowed the in situ characterisation of the inorganic phases without disintegration of the organic matter. Micro‐Raman spectroscopy was able to identify the vibrating chemical groups of the mineral phase associated with the inorganic grain while the crystalline structure was preserved by the biological system. The VP‐SEM/EDS characterisation, defining the elemental chemical composition of the analysed particle/fibre, allowed confirmation of the mineral phase deducible from spectroscopic data or its identification with certainty when the spectroscopic data were not exhaustive. Copyright © 2009 John Wiley & Sons, Ltd.     

汝阳地区熊耳群火山岩内夹层硅质岩的微区特征及地质意义

熊耳群是前寒武纪火山-沉积作用的产物,其顶部的马家河组(玄武)安山质火山岩内发育了夹层状热水成因硅质岩。选择熊耳群马家河组硅质岩夹层中的碧玉岩为对象,利用偏光显微镜,XRD,Raman和EBSD等方法剖析了其微区特征。研究结果显示：硅质岩内石英颗粒的显微镜和EBSD照片均表现出颗粒细小、结晶程度低和紧密堆积结构等特点,这完全吻合热水沉积硅质岩的特征;硅质岩内粒径不同的颗粒呈条带(或薄层)状交互出现,不同条带(或薄层)内矿物的组成存在明显的差异,这应该反映了原始物质供给的周期性变化;XRD分析结果指示硅质岩内的主要矿物为低温石英,其晶胞参数为a=b=0.491 3 nm,c=0.540 5 nm和Z=3;EBSD照片和Raman分析结果显示硅质岩内微量的杂质矿物形成于不同阶段,其中粘土矿物和黄铁矿呈零星分布并反映了原始沉积成因,长英质矿物和铁镁硅酸盐矿物均来源于火山凝灰质沉积;火山凝灰质矿物的颗粒偏大并构成了硅质岩内的粗颗粒条带(或薄层),它们与热水沉积为主的细颗粒矿物条带(或薄层)交互产出,这反映了火山作用的周期性反复活动;后期的碳酸盐热液沉淀于硅质岩内裂隙中,它们还导致石英颗粒边缘有序度升高。虽然熊耳群硅质岩内的矿物种类和成因均极为复杂,但火山物质的输入是导致熊耳群硅质岩SiO₂含量偏低的根本原因并得到了硅质岩内大量火山成因矿物的证实。在硅质岩的微组构研究中,Raman光谱分析可以有效的揭示微区上矿物的类型、微区结构及有序度,这些特征是反映硅质岩内部矿物形成与演化过程中微区变化的重要信息。     

A multi‐technique approach for the characterization of decorative stones and non‐destructive method for the discrimination of similar rocks

In this paper, a multi‐technique approach, at different scale of observation, is used to characterize a group of decorative stones and to permit to distinguish rocks with similar aspect but coming from different areas. In particular, the samples under study are sedimentary and metamorphic rocks, widely used as building blocks of modern and historical constructions and sculptures. The petrographic and mineralogical features of such rocks were performed by optical microscopy and Raman and Fourier transform infrared absorbance spectroscopies. These techniques permitted to obtain a complete structural, textural, and mineralogical characterization. At elemental level, the investigation was carried out by X‐ray fluorescence (XRF). In particular, XRF and Raman measurements were collected using portable instrumentations, whose advantages for the in situ analysis have been pointed out. The obtained results evidenced the high discriminant capability of the portable XRF for the decorative stones especially when this method is coupled with mineralogical and petrographic information. In this context, we propose to create a database for precious ornamental stones, which could be a starting point for a non‐destructive characterization, even useful for provenance study and/or certification of origin. Copyright © 2013 John Wiley & Sons, Ltd.     

Combined X‐ray microanalytical study of the Nd uptake capability of argillaceous rocks

Argillaceous rocks are considered as suitable host rock formation to isolate the high‐level radioactive waste from the biosphere for thousands of years. Boda Claystone Formation, the possible host rock formation for the Hungarian high‐level radioactive waste repository, has geologically and mineralogically been studied in detail, but its physico‐chemical parameters describing the retention capability of the rock needed further examinations. Studies were performed on thin sections subjected to 72 h sorption experiments using inactive Nd(III). Nd(III) has been used as a chemical analogue for transuranium elements of the radioactive waste to examine the ion uptake capability of the micrometre size mineral phases occurring in the rock. The elemental mapping of synchrotron radiation‐based microscopic X‐ray fluorescence (micro‐XRF) combined with scanning electron microscopy energy dispersive X‐ray analysis (SEM/EDX) has sufficient sensitivity to study the uptake capability of the different mineral phases on the microscale without the necessity of applying radioactive substances. Elemental maps were recorded on several thousand pixels using micrometre magnitude spatial resolution. By interleaving micro‐XRF and SEM/EDX data sets from the same sample area and applying multivariate methods, calcite and clay minerals could be identified as the main mineral phases responsible for Nd(III) uptake without using additional microscopic X‐ray diffraction mapping. It should be highlighted that the ion uptake capability of dolomite containing calcium and magnesium could be distinguished from the characteristics of calcite only by the interleaving of micro‐XRF and SEM/EDX data sets. The presence of minerals was verified by applying microscopic X‐ray diffraction point measurements. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic study of medieval Indian art of 17th century

We report the first Raman spectroscopic investigations of medieval Indian art of 17th century. Three miniature paintings, belonging to Mogul and Rajput schools from the collections of the Madras Museum, were investigated by micro‐Raman spectroscopy using different excitation wavelengths. Many areas in the paintings exhibited rich spectra containing several intense Raman bands. The Raman bands were assigned on the basis of the reported reference spectra of the pigments. Evidences for the presence of massicot, red‐lead, lead‐white, vermilion, litharge, Indian yellow and anatase are found. In addition, tentative assignments of some of the Raman bands to atacamite and orpiment are also made. The present studies suggest that several mineral‐based unique pigments were popular among the Indian artists of this period. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman micro‐spectroscopy of DNA/RNA bases adsorbed on pyroxene rocks as a test of in situ search for life traces on Mars

SERS spectroscopy with 785‐nm laser excitation minimizing fluorescence emission is exploited for remote analysis of life traces in an extraterrestrial environment. Adenine and guanine, nucleobases present in both DNA and RNA strands, and microRNA containing adenine and guanine have been used as testing ligands for identifying traces of nucleic acids in Martian rocks and sediments. SERS spectra of these nucleobase samples adsorbed on pyroxene substrates have been investigated with micro‐Raman apparatus in the absence of sample manipulation and inducing the signal enhancement by deposition of silver colloidal nanoparticles over the pyroxene/nucleobase substrates. An order‐of‐magnitude estimate of the sample amount responsible for the SERS spectra is given. Copyright © 2009 John Wiley & Sons, Ltd.     

新疆软玉仔料中黑色树枝状物质的拉曼光谱和显微结构特征

软玉仔料表层微裂隙处常见一种黑色树枝状物质,该物质极大程度地揭示了仔料历经的次生风化过程,然而目前对其岩石矿物学特征研究甚少。选取新疆软玉仔料为研究对象,采用电子探针、激光拉曼光谱仪和扫描电子显微镜就其表层微裂隙处黑色树枝状物质的化学成分、拉曼光谱和显微结构进行测试分析。结果表明：黑色树枝状物质的主要化学成分为MnO和BaO,MnO含量为49.045%~54.012%,BaO含量为9.012%~10.961%。拉曼光谱分析显示软玉仔料主体部分主要由透闪石矿物组成,而黑色树枝状物质则主要由表生锰矿物和有机质组成。表生锰矿物中由MnO₆八面体Mn—O伸缩振动所致拉曼特征谱峰位于475,498,510,575和617 cm-1附近;且树枝各处锰矿物结晶程度不一,表现为拉曼谱峰强度和峰形尖锐程度存在区别。有机质由分子结构中C—C伸缩振动和分子结构单元间缺陷、无序排列所致拉曼特征谱峰分别位于1 590和1 370 cm-1附近。扫描电子显微镜观察显示黑色树枝状物质呈薄膜状覆盖于交织排列的透闪石纤维表面,并与其突变接触。综合化学成分、拉曼光谱和显微结构测试分析,软玉仔料中黑色树枝状物质的形成与河流中锰化合物和有机质的多期次沉降有关。     

Raman microscopy of prehistoric paintings in French megalithic monuments

Remains of pictorial decorations in a series of six representative megalithic monuments of Brittany (France) and two French stelae have been studied by micro‐Raman spectroscopy for the first time. Fungal colonies on the painted orthostats made it difficult to obtain in situ Raman spectra of the paint components. Nevertheless, paint micro‐specimens studied in the laboratory by micro‐Raman spectroscopy, X‐ray photoelectron spectroscopy and scanning electronic microscopy combined with energy dispersive X‐ray spectroscopy have made possible to characterise the materials present. The minerals α‐quartz, albite, microcline, muscovite, phlogopite, celadonite, beryl and anatase have been identified in the granitic rocks supporting the paintings, while dolomite and calcite are dominant in the calcareous rocky substrata. Haematite is the main component of the red pictographs, whereas amorphous carbon and manganese oxides/oxihydroxides have been used in the black ones. Calcite, gypsum and amorphous carbon have been detected as additional components of the paint in some cases. Contamination with modern tracing materials (polystyrene and ε‐copper‐phthalocyanine blue) has been detected in several cases. The presence of pigments as decorative elements in megalithic monuments of Western France and its possible relation with those of the Iberian Peninsula create interesting expectations for the knowledge of the European megalithic culture. Copyright © 2015 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopic study of El Gasco pumice,western Spain

A micro‐Raman spectroscopic study of pumice materials from El Gasco (Sierra de Gata, Spain) has been performed for the first time. The obtained spectra allow the precise identification of the minerals, quartz, haematite, magnetite, ilmenite, rutile and anatase, in general agreement with results obtained by complementary techniques of X‐Ray Diffraction (XRD) and Electron Microprobe. Also, fayalite and ferroan ringwoodite have been identified. The presence of high‐pressure polymorphs indicates that the pumice rocks were subjected to high‐pressure conditions quite similar to those observed in shock‐induced molten and recrystallised materials, such as some meteorites and impact‐related rocks. Copyright © 2006 John Wiley & Sons, Ltd.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

On‐and off‐site Raman study of rock‐shelter paintings at world‐heritage site of Bhimbetka

Rock‐shelter paintings of Bhimbetka world‐heritage site near Bhopal, India have been investigated using a portable Raman spectrometer. These paintings in the rock shelters belong to periods starting from pre‐historic to the 19th century AD (Gond period). In addition, tiny fragments of pigments (100–200 µm in size) extracted from some of the artworks were also studied in laboratory using a micro‐Raman spectrometer and analyzed using energy‐dispersive X‐ray analysis for elemental composition. Based on the Raman spectra and the elemental analysis mineral‐based pigments such as calcite, gypsum, hematite, whewellite, and goethite could be identified. A comparison of the spectra recorded on‐site using a light‐weight portable spectrometer with those using laboratory equipment is also made and discussed. Copyright © 2012 John Wiley & Sons, Ltd.