Raman spectrometry,a unique tool to analyze and classify ancient ceramics and glasses

Raman micro/macro spectroscopy allows a non-destructive remote analysis: body and glaze, crystalline and amorphous phases can be identified, including the nanosized pigments coloring the glaze. Last-generation instruments are portable, which allows examination in museums, on archaeological sites, etc. This paper gives an overview of the potential of the Raman-spectrometry technique to analyze ancient ceramics and glasses. Selected glasses as well as glazes of various porcelains, celadons, faiences and potteries, representative of the different production technologies used in the Ancient, European, Mediterranean, Islamic and Asian worlds, were studied. Their identification is based on the study of the Raman fingerprint of crystalline and glassy phases. Raman parameters allow for the classification as a function of composition and/or processing temperature. Special attention is given to the spectra of amorphous and coloring phases (pigments). PACS 81.05.Kf; 81.70.Fy; 81.05.Je; 01.65.+g     

Synchrotron powder diffraction on Aztec blue pigments

Some samples of raw blue pigments coming from an archaeological rescue mission in downtown Mexico City have been characterized using different techniques. The samples, some recovered as a part of a ritual offering, could be assigned to the late Aztec period (XVth century). The striking characteristic of these samples is that they seem to be raw pigments prior to any use in artworks, and it was possible to collect a few μg of pigment after manual grain selection under a microscopy monitoring. All pigments are made of indigo, an organic colorant locally known as añil or xiuhquilitl. The colorant is always found in combination with an inorganic matrix, studied by powder diffraction. In one case the mineral base is palygorskite, a rare clay mineral featuring micro-channels in its structure, well known as the main ingredient of the Maya blue pigment. However, other samples present the minerals sepiolite (a clay mineral of the palygorskite family) and calcite. Another sample contains barite, a mineral never reported in prehispanic paints. We present the results of characterization using high resolution powder diffraction recorded at the European Synchrotron Radiation Facility (BM25A, SpLine beamline) complemented with other techniques. All of them gave consistent results on the composition. A chemical test on resistance to acids was done, showing a high resistance for the palygorskite and eventually sepiolite compounds, in good agreement with the excellent resistance of the Maya blue.     

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.     

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.     

拉曼Mapping研究白云鄂博萤石型稀土矿物赋存特征及分布规律

白云鄂博矿以资源丰富、储量巨大而闻名。其中独居石矿物是主要稀土原料之一,在冶金、军事、化工材料等领域都有广泛的应用。前人已经对白云鄂博矿物学特征进行了充分的研究,随着开采深度的增加,原生矿物增多,对现阶段稀土矿物赋存状态有待深入了解。利用拉曼Mapping成像技术结合扫描电子显微镜(scanning electron microscope, SEM)与能谱议（energy dispersive spectrometer, EDS）方法,能够对白云鄂博共伴生矿物赋存特征进行更深的研究。EDS与能谱结果显示：矿物扫描区由萤石、重晶石、独居石、磷灰石和铁矿物构成。拉曼Mapping分析显示：显微共聚焦图下扫描基底为萤石矿物（CaF₂）,拉曼特征峰普遍出现在220～650 cm-1,与已知文献报道的萤石拉曼峰略有不同。较大颗粒为重晶石矿物（BaSO₄）,为典型的硫酸盐矿物。中等颗粒大小为独居石矿物（Ce,La,Nd）PO₄,细小颗粒集中区为磷灰石矿物（Ca₅[PO₄]₃F）。虽然独居石与磷灰石都为典型的磷酸盐矿物且具有相同磷酸根结构,但由于外部金属阳离子的结合种类不同,其拉曼峰位也不相同。拉曼Mapping结合EDS分析矿物的赋存特征及分布规律关系为：独居石呈板状或块状分布在重晶石与磷灰石中间或磷灰石与萤石矿物之间,粒度约为50～120 μm。重晶石矿物颗粒较粗呈块状集合体分布,颗粒大小为50～200 μm,常与独居石共生,矿物颗粒紧密生长。磷灰石呈细粒状或块状,星散分布在独居石与重晶石周围,类似侵染分布在萤石中。少量磷灰石颗粒与独居石相互交代成不规则共生体,大部分磷灰石呈单体分布在矿物之间。萤石矿物中富集最多,占比约55%,与独居石、重晶石、磷灰石、铁矿物伴生。从赋存状态上判断形成时期应早于其他伴生矿物。对矿物成因复杂,共伴生矿物极多白云鄂博矿床。EDS虽能分析矿物学基本关系,但独居石与重晶石矿物中的能谱图部分重合。是由于能谱扫描Ba,S与稀土元素Ce,La,Nd时激发能量线系太相近以及能谱分辨率较低。利用Mapping成像技术对于矿物鉴定上具有简单、可靠的优点,可以弥补EDS分析误判拉曼Mapping为矿物学分析提供一种新的鉴别思路,同时也为白云鄂博矿物的鉴定提供了参考性的拉曼光谱。     

Non-Destructive In-Situ Study of White and Black Coating on Painted Pottery Sherds From Bancun Site (Henan,China) by Raman Microscopy

Abstract

Pottery sherds from the archaeological site of Bancun (Henan, China) were analyzed by Raman microscopy and the pigments used in the coating of this ancient (c. 4000–5000 BC) pottery were determined. It was found that bauxite was used to make the white pigment. The black coating was identified as a magnetite and its particle size was in the nanometer range. This work also showed that the size of pigment had influence on the color of the coating. In principle, Raman spectra could be used not only to identify the mineral source of the pigment but also to estimate the particle size of the pigments.     

基于拉曼光谱的复杂硫化矿快速分类方法研究

热液硫化物型脉状矿作为一类复杂硫化矿,其区域特征、成矿规律及矿物成份已有初步研究。由于成矿时期的不同,矿石中有用矿物的特征存在较大差异,导致不同矿物的性质变化较大。在选矿过程中,矿物性质的差异一定程度增加了选矿难度,减少了有用矿物回收率。因此,迫切需要一种快速、简单的对复杂硫化矿进行分类的方法,进而提高选矿指标。激光拉曼光谱技术作为一种能够分析物质结构信息的手段,已被应用于矿物的成份鉴定和结构分析。通过对大量矿物样本的激光拉曼光谱的研究,结合矿物性质深入揭示其光谱差异的原因,提出了一种基于拉曼光谱的复杂硫化矿矿源分类方法。实验结果表明：由于此类复杂硫化矿成矿时期的差异,从而造成矿物结构和性质存在较大差异。荧光主要由原矿中的脉石矿物产生,猝灭矿物中瞒石的荧光背景后可知201.62, 242.54, 288.38和309.77 cm-1处拉曼峰可以作为此类硫化矿的拉曼指纹谱。为此,基于此类硫化矿的荧光强度和代表谱峰强度与荧光背景比值可以将矿源分为三类,并利用工业试验结果进一步验证分类方法的准确性。本研究深入分析了此类复杂硫化矿的激光拉曼光谱与其矿物性质与类别之间的密切关系,提出了矿源快速分类方法,矿样无需经过复杂的化学前处理过程,对提高选矿作业效率具有重要应用价值。     

Raman classification of glass beads excavated on Mapungubwe hill and K2, two archaeological sites in South Africa

About 200 coloured glass beads (red, yellow, green, blue, white, black, pink, plum) excavated on Mapungubwe hill and at K2, archaeological sites in the Limpopo valley South Africa, were studied with Raman scattering. This is also the most southern site in Africa where evidence for glass reworking has been found. The glass matrix of the beads was classified according to its Raman signature into three main subgroups and corroded glass could also be identified. At least seven different chromophores or pigments (lazurite, lead tin yellow type II, Ca/Pb arsenate, chromate, calcium antimonate, Fe–S ‘amber’ and a spinel) were identified. Many of the pigments were manufactured after the 13th century, confirming the presence of modern beads in the archaeological record. This calls for further research to find a way to reconcile the carbon dating of the hill, which currently gives the last occupation date on the hill as 1290 AD with the physical evidence of the modern beads excavated on the hill. The results are discussed in terms of the glass production origin of the beads (Europe, Mediterranean area, India, China). Copyright © 2011 John Wiley & Sons, Ltd.     

Raman Microspectroscopic study of Iberian pottery from the La Vispesa archaeological site,Spain

Raman microspectroscopy has been employed for the characterization of 16 samples of ancient Iberian pottery. These sherds of vessels were found in the archaeological site of La Vispesa in Tamarite de Litera (Huesca, Spain) and correspond to the Iberian time. The composition of certain mineral phases such as non‐plastic inclusions has been particularly considered with a view to obtaining information on the source materials and their provenance, as well as the technological conditions of ceramic production. Typical minerals such as calcite and quartz were found in most of the samples. The presence of anatase in a group of the samples suggested the use of different clays in the production of the vessels. Furthermore, the absence of rutile in these samples, together with the identification of calcite, is indicative of a mild firing temperature. Hematite was identified in all samples, both in the ceramic body and in the decoration. Differences in the position of the bands and relative intensities characterized hematite in terms of crystallinity and origin. An attempt to assign the samples to different production centers was made according to their chemical composition and morphology. Copyright © 2011 John Wiley & Sons, Ltd.     

New insights into the colour origin of archaeological Egyptian blue and green by XAFS at the Cu K‐edge

New results on the local chemical environment of Cu²⁺ in archaeological Egyptian blue and green and also modern Egyptian green were obtained by x‐ray absorption fine structure (XAFS) analysis. The information is essential for the understanding of the colouring mechanisms in both pigments. In a previous study, a clear physico‐chemical characterisation of Egyptian blue and green was achieved using a complementary analytical approach with ancient and modern synthesized pigments. Electron microscopy (SEM–EDX and TEM), x‐ray diffraction and micro‐Raman and UV–visible spectroscopy were used to gain information about the conditions of the ancient Egyptian fabrication processes and permitted the clear distinction of both pigments. However, the exact colouring mechanisms could not be elucidated by these methods. Different Cu‐bearing amorphous and crystalline phases were found in both pigments. These phases should be at the origin of the blue and turquoise colours. Using XAFS data at the Cu K‐edge, new insights into the origin of the colouring mechanisms of both pigments could be obtained from the precision of the Cu speciation. In Egyptian blue, Cu²⁺ is mainly allocated in a square‐planar site in a crystalline cuprorivaite phase, whereas in Egyptian green, Cu²⁺ is basically situated in a distorted octahedral site in an amorphous phase. Copyright © 2006 John Wiley & Sons, Ltd.     

Micro‐Raman spectroscopy of decorated pottery from the Iberian archaeological site of Puente Tablas (Jaén,Spain, 7th–4th century B.C.)

In this paper, Raman spectroscopy is used for the first time to identify the pigments on decorated antique Iberian pottery. Ceramic fragments of type Real and others from the archaeological excavation in the oppidum Puente Tablas were examined. Different types of iron oxide pigments (hematite and goethite) were identified, along with amorphous carbon. In some samples, the presence of chalk or gypsum could be demonstrated. Some unattributed Raman bands are believed to be associated either with post‐burial organic deposition or with silicate materials that are present in red ochre. It was possible to relate the findings with geological data from the region and to make assumptions on a local production. Copyright © 2009 John Wiley & Sons, Ltd.     

谱学分析在造山带硅质岩中的应用及其地质意义

南秦岭造山带旬阳盆地吕河地区发育有泥盆系硅质岩剖面,该剖面中的硅质岩以谱学特征为基础的微区特征清晰的记录了硅质岩的形成及后期演变信息。以南秦岭造山带旬阳盆地吕河硅质岩样品为对象,借助XRF、拉曼光谱、红外光谱和X射线粉晶衍射分析结果表明：该硅质岩内矿物主要为低温石英并包含极少量的碳酸盐矿物。XRD分析结果进一步证实该碳酸盐矿物为白云石。在吕河硅质岩内,SiO₂结构463 cm-1附近拉曼特征峰经高斯拟合后的峰面积和FWHM值证实发生了低温石英的重结晶作用,该过程中伴随了流体作用引发的有序度变化和石英颗粒的自身有序度变化。在重结晶过程中,石英颗粒的自身重结晶伴随了有序度随时间推移而逐渐增高。流体作用对硅质岩的改造表现为硅质岩内碳酸盐脉体的穿插,该过程还导致低温石英有序度提升,其中越靠近矿物边缘处的SiO₂结构有序度越高。造山带演化过程对硅质岩进行的改造主要体现在两个方面：一方面,构造应力破坏了岩石的连续性并为后期热液流体的运移穿插提供了空间;另一方面,后期流体作用的参与促进了石英颗粒重结晶的进程。红外光谱可以系统的识别硅质岩内矿物的结构类型,拉曼光谱分析可以揭示原位（in situ）微组构特征,XRD在硅质岩内微量杂质矿物的识别优势明显,这些谱学手段为研究硅质岩的成岩演化提供了重要示范。     

Synthesis and Raman spectroscopic characterisation of the oxalate mineral wheatleyite Na2Cu2+(C2O4)2·2H2O

The mineral wheatleyite has been synthesised and characterised by Raman spectroscopy complimented with infrared spectroscopy. Two Raman bands at 1434 and 1470 cm⁻¹ are assigned to the ν_{(C O)} stretching mode and implies two independent oxalate anions. Two intense Raman bands observed at 904 and 860 cm⁻¹ are assigned to the ν(C C) stretching mode and support the concept of two non‐equivalent oxalate units in the wheatleyite structure. Two strong bands observed at 565 and 585 cm⁻¹ are assigned to the symmetric CCO in plane bending modes. The Raman band at 387 cm⁻¹ is attributed to the CuO stretching vibration and the bands at 127 and 173 cm⁻¹ to OCuO bending vibrations. A comparison is made with Raman spectra of selected natural oxalate bearing minerals. Oxalates are markers or indicators of environmental events. Oxalates are readily determined by Raman spectroscopy. Thus, deterioration of works of art, biogeochemical cycles, plant metal complexation, the presence of pigments and minerals formed in caves can be analysed. Copyright © 2008 John Wiley & Sons, Ltd.     

中国古代艺术品常用矿物颜料的拉曼光谱(二)

在本刊前一篇文章中,我们讨论了拉曼光谱在艺术品分析和考古学应用方面的实验技术并报道了一些中国古代艺术品中经常使用的红色、黄色和白色矿物颜料的拉曼光谱。本文延续前文工作,测量了一些中国古代艺术品中常用的蓝色、绿色和黑色矿物颜料的拉曼光谱,介绍了相关的背景知识,并对这些光谱进行了解析,我们相信,一套比较全面的颜料拉曼光谱数据,对于拉曼光谱技术在考古学和艺术品分析方面的应用将会起到重要的参考价值。     

常见翡翠产地的激光拉曼光谱特征研究

缅甸是商业性翡翠主要产地,危地马拉、俄罗斯也有翡翠产出。不同产地的翡翠价值差异较大,其他产地的翡翠冒充缅甸翡翠以获取价格上涨。迫切需要一种可靠方法来确定地理起源,翡翠的产地研究具有重要的宝石学意义,目前主要在翡翠生成时代、矿物组合、硬玉组分含量等方面探讨不同产地翡翠,缺乏快速有效鉴别产地的方法,以缅甸、俄罗斯、危地马拉翡翠为研究对象,对不同产地翡翠样品的激光拉曼光谱特征研究发现：缅甸翡翠矿物为硬玉、绿辉石、透闪石;危地马拉翡翠矿物相对复杂,为硬玉、绿辉石、绿泥石、榍石;俄罗斯翡翠矿物为硬玉、钠长石、绿辉石。对比不同产地硬玉矿物拉曼特征发现,缅甸翡翠硬玉矿物分别在1 037,988,697,372和201 cm-1等处显示硬玉的典型光谱特征。在1 020,679,369和216 cm-1处附近显示为绿辉石特征拉曼峰,在215,332,394,680和1 073 cm-1 处有明显透闪石吸收峰,为翡翠中的次生矿物。危地马拉翡翠硬玉矿物多叠加680和218 cm-1拉曼峰值,为绿辉石特征的峰值,还含有603,537和306 cm-1附近绿泥石特征拉曼光谱峰值,表明危地马拉翡翠硬玉矿物多被Fe,Mg和Ca元素的类质同像替换,形成硬玉-绿辉石固溶体矿物,硬玉矿物表面检测出603,537和306 cm-1绿泥石特征拉曼光谱峰值,硬玉矿物表面发生绿泥石蚀变。俄罗斯翡翠硬玉拉曼峰值,多叠加1 100,507,473和164 cm-1附近钠长石特征拉曼峰值,俄罗斯翡翠硬玉颗粒普遍被钠长石交代,表面多分布灰绿色网脉,显示1 025,669,366和219 cm-1绿辉石矿物拉曼峰值。     

An integrated Raman and petrographic characterization of Italian mediaeval artifacts in pietra ollare (soapstone)

Ten fragments of pots made by pietra ollare (basic and ultrabasic metamorphic rocks belonging to greenschist facies) found in the archaeological site of Crocetta di Sant'Agata Bolognese (Bologna, Italy) have been studied to characterize them and to define their provenance. The fragments, dated between the 9^th and 10^th century AD, show traces of blackening from fire, indicating the use of these findings as pots by fire. The extensive use of a non‐destructive technique, Raman spectroscopy, in both laboratory and portable forms, for the provenance analysis of pietra ollare artifacts has been evaluated. Micro‐Raman spectroscopy was used for a detailed study of the main components, to identify the secondary minerals and to study the distribution of the mineral phases in the samples. The samples show schistose texture, are fine grained and consist mainly of talc and chlorite, and subordinate carbonates, oxides and serpentine. Olivine is rare. Based on the mineralogical composition, the material can be defined as chlorite and carbonate talc‐schist. Our samples of pietra ollare may be assigned to chlorite and magnesite‐bearing talc‐schists. The alpine areas of origin of this lithotype are Valtellina, Valchiavenna and Val Bregaglia. In particular, we can hypothesize that the origin of these findings is Valchiavenna, which had great commercial importance in the Middle Ages. Further measurements, obtained with a portable Raman spectrometer, directly on a quarry near Chiavenna, support our hypothesis. Copyright © 2013 John Wiley & Sons, Ltd.     

New advancements in SERS dye detection using interfaced SEM and Raman spectromicroscopy (μRS)

In the past decade Surface Enhanced Raman Scattering (SERS) has emerged as a powerful technique for the analysis of artistic, historical and archaeological material culture. However, the identification of organic compounds in complex samples using SERS can be challenging owing to the complexity in optimizing the adsorption of target analytes onto the plasmonic substrate and the difficulty to identify proper areas on the sample for robust SERS analysis using optical systems. Scanning electron microscopy (SEM) interfaced with Raman spectromicroscopy (μRS) provides an ideal hyphenated system to overcome the last challenge by: (1) evaluating the nanoparticles coverage/distribution on the sample and (2) locating suitable areas for successful and reproducible SERS analysis. In this paper we demonstrate the potential of a system interfacing SEM and μRS for single fiber, extractionless analysis in the characterization of dyes from reference collections and archaeological textiles. Copyright © 2015 John Wiley & Sons, Ltd.     

红外和拉曼光谱的煤灰矿物组成研究

研究煤灰中矿物质的性质通常从矿物组成的表征入手。为了分析两种高硅铝煤灰的矿物成分,采用傅里叶变换红外光谱(FTIR)、拉曼光谱和X射线衍射(XRD)技术对煤灰样进行了测试和综合表征,将FTIR和拉曼光谱的分析结果与XRD进行了比较。FTIR结果表明,在1 100~1 000 cm-1范围内高硅铝煤灰出现最强的特征峰,例如石英峰(1 089 cm-1)和偏高岭石峰(1 042 cm-1),它们都归属于Si-O伸缩振动。对原始红外谱图进行二阶导数处理后,可获得重叠峰的峰位,有助于更完整的解析矿物吸收峰,从而获得更丰富的矿物组成信息。煤灰中硬石膏的红外和拉曼光谱发现,在1 157,1 126和674 cm-1的拉曼光谱峰与在1 151,1 120和678 cm-1的红外光谱峰振动模式分别相同且峰位接近,还存在一些完全不同的拉曼光谱与红外光谱峰,表明这两种光谱存在互补性。尽管煤灰中锐钛矿含量很低,但由于Ti-O的极化率很高,因此拉曼光谱显示锐钛矿的144 cm-1峰远远强于石英的461 cm-1峰。XRD结果表明,煤灰中主要存在石英、云母、赤铁矿、硬石膏和未知的无定形相矿物,FTIR和拉曼光谱综合分析的结果表明除了这些矿物,还存在偏高岭石、无定形氧化硅、长石、方解石和锐钛矿等。在定性分析方面,将FTIR和拉曼光谱结合起来比XRD单独获得的矿物组成信息更为详细。     

In situ Raman study of mineral phases formed as by‐products in a rotary kiln for clinker production

Portland clinker production consists essentially in the burning of material with defined composition in a rotary kiln at temperatures around 1450 °C. The main fuel used in this process is coal, even though in the last few years the use of alternative fuels has been increasing. Four main minerals are formed, namely, tricalcium and dicalcium silicate, tricalcium aluminate and tetracalcium aluminoferrite. Along with these main phases, variations in burning conditions of fuels or in the local composition of raw materials can lead to the formation of relatively high amounts of secondary by‐products, which can negatively affect the quality of the final material. Characterization of these by‐products allows not only optimization of the process of clinker production but also the design of special refractory materials for the wall of kilns and preheaters. Being found as particles included in (or alternating to) a hard solid clinker matrix, a detailed characterization of these extra phases could be achieved only via microscopic techniques. In this work, micro‐Raman spectroscopy has been successfully tested as a highly selective method for characterization and localization of included minerals that formed as overlapped crusts deposited on the internal wall of a conventional rotary kiln for cement production, without any manipulation of the sample. Understanding the chronological order of deposition of these overlapped layers is extremely important, as it is the only way to go back up to the production process and to individuate the problem. Copyright © 2008 John Wiley & Sons, Ltd.     

大气可吸入颗粒物中锐钛矿的发现及意义

激光拉曼微探针(laser Raman microprobe,简称LRM)能将激光聚焦在1 μm2的极小区域进行分子成分和结构的微区分析,是一种可靠的物相鉴定手段,非常适用于单个微小颗粒物的物相鉴定。文章利用LRM对北京市大气可吸入颗粒物(PM₁₀)进行单颗粒物相分析 将实验图谱与Renishaw矿物与无机材料拉曼光谱数据库中标准图谱进行对比,通过简正坐标分析对谱带进行指认和对各谱峰分子类型及振动模进行归属,首次在PM₁₀中发现了锐钛矿型TiO₂,其实验图谱具有638 cm-1处的较强峰以及398和517 cm-1处中等强度峰,为O—Ti—O特征振动,确认了大气中富Ti颗粒的矿物物相为锐钛矿型TiO₂。锐钛矿型TiO₂是一种重要的光催化剂,锐钛矿与其他矿物颗粒(尤其是含Ca碳酸盐)的聚集能够加剧非均相反应的发生。锐钛矿的晶体结构及所处大气环境的相对湿度和pH值对其光催化反应有重要影响。