JOURNAL OF RAMAN SPECTROSCOPY J. Raman Spectrosc. 2008; 39: 10071011 Published online 9 April 2008 in Wiley InterScience (www.interscience.wiley.

com) DOI: 10.1002/jrs.1939

Micro-Raman spectroscopy applied to the study of inclusions within sapphire

Valentina Palanza,1 Daniela Di Martino,1 Alberto Paleari,1 Giorgio Spinolo1 and Loredana Prosperi2
1 2

` Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Via Cozzi 53, 20125 Milano, Italy Istituto Gemmologico Italiano, Piazza S.Sepolcro1, 20100 Milano,Italy

Received 15 November 2007; Accepted 16 January 2008

The present research concerns the characterization of samples of corundum (Al2 O3 ), varieties of sapphire, by micro-Raman spectroscopy. Ten samples of natural corundum from Australia, Madagascar, Sri Lanka, Thailand, Tanzania, and Vietnam were studied. After standard gemmological analysis, micro-Raman analysis was also performed in order to identify mineral inclusions within the sapphire samples and to obtain information on the geological genres of the minerals. Several inclusions were evidenced within the sapphires and identied by Raman spectroscopy thanks to a confocal spectrometer, which allowed detection also below the external surface of the gem. Finally, the Raman spectra are discussed taking into account the provenance of the samples and their optical absorption. Copyright 2008 John Wiley & Sons, Ltd.

KEYWORDS: micro-Raman spectroscopy; sapphire; provenance; inclusion; confocality

INTRODUCTION
Sapphire is one of the most precious gemstone varieties and is the most precious blue gemstone. Ruby and blue sapphire are the coloured varieties of corundum,1 3 the single-crystal form of aluminum oxide (Al2 O3 ). The corundum structure consists of hexagonal closely packed oxygen atoms, with aluminum lling up two-thirds of the central octahedral sites. When aluminum oxide is pure, the mineral is colourless, but the presence of trace amounts of other elements such as iron, titanium, and chromium in the crystal lattice gives the typical colours of gemstone varieties. The commercial value of sapphires is set by many factors such as colour, clarity, cut, and also by their region of origin. Sapphire deposits are located in several areas of the world. From Asia to Africa, and from America to Australia, corundum is found in several areas with different geological conditions. In fact, corundum may be found both in igneous rocks (e.g. pegmatite) and metamorphic rocks (e.g. dolomitic marble), as well as in alluvial deposits (from alkali basalts, pegmatite, or limestone).3 5 These differences in provenance affect several aspects of the gemstone, such as colour, chemical composition, age, and internal characteristics, or inclusions.6 12 Therefore, microRaman studies of the inclusions and a comparison of their
Correspondence to: Valentina Palanza, Dipartimento di Scienza dei Materiali, Universit` degli Studi di Milano Bicocca, Via Cozzi a 53, 20125 Milano, Italy. E-mail: palanza valentina@yahoo.it

optical absorption spectra are extremely useful to obtain information about the geological environment in which the crystal was formed, and thereby to distinguish gemstones according to their geological and geographical origin. As regards their optical absorption spectra, natural blue sapphire can be discriminated into two main groups: sapphires with an intense Fe2C band at 11 500 cm 1 and sapphires not showing this absorption (see Discussion on Fig. 5). Sapphires from alkali basalts as mother rocks (e.g. from Australia, Thailand, Cambodia, and Nigeria) belong to the rst group.13 Further information is provided by the identication of inclusions in the samples, if any, by micro-Raman analysis. As a matter of fact, the variety of inclusions observed in sapphires is a function of the geological origin and, in some cases, typical of specic deposits. For instance, tourmaline prisms crystals and a needle-like rutile (TiO2 ) inclusions are common in sapphire from Kashmir14 ; diaspore (AlO(OH)) as solid phase in threefold-phase inclusions is typical in unheated Sri Lanka sapphire15 ; uid inclusions, where the uid consists of impure CO2 (probably mixed with H2 S), are related to magmatic origin from marble deposits (e.g. Pakistan and Afghanistan).16 Moreover, the morphology of the inclusions provides information about any treatment on the gems: e.g. heat treatment is a common practice to improve the colour in corundum.17 19 In the present work, 10 samples of natural blue sapphire from Australia, Madagascar, Sri Lanka, Thailand, Tanzania,

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and Vietnam were preliminarily characterized using an optical microscope and standard gemmological laboratory instruments (refractometer, hydrostatic scale, spectroscope, UV lamp), and then investigated by optical absorption spectroscopy and Raman micro-spectroscopy. The results of this study constitute a starting point towards the creation of a database whose purpose is the sorting of gems by geographical origin, as well as demonstration of the effectiveness of Raman spectroscopic technique in characterizing inclusions within gems.

of a microscope, Olympus BH-T equipped with a Sony XC75/75CE CCD. Images of the gemstones were collected by a common digital camera. Absorption spectra were obtained by means of a Perkin-Elmer 950 spectrophotometer in the NIR-vis-UV range at room temperature.

RESULTS AND DISCUSSION

The various Raman spectra observed from the 10 analysed samples are collected in Figs 1, 3 and 4. Besides the phonon modes of each specic type of inclusion, the spectral features of the corundum matrix are ubiquitous in these spectra. In fact, inclusions are often found deep within the gemstone, and the use of low NA objective is mandatory in order to have a long working distance, with the consequent lowering of confocality efciency in rejecting scattered light collected from the volume outside the focal layer. For reference purpose, Fig. 1 shows the typical Raman spectrum of corundum.20 An example of the spectra of the inclusion observed in the sapphire from Sri Lanka is depicted in Fig. 2, while Fig. 3 shows the Raman spectra of inclusions detected in metamorphic sapphires (samples from Madagascar, Sri Lanka, and Vietnam). The peaks observed in sapphire from Vietnam (modes at 146, 403, 520, and 641 cm 1 in spectrum 1) identify the phases of anatase21 (TiO2 ). Sapphire from Sri Lanka shows modes at 443 and 608 cm 1 (spectrum 2) of rutile (TiO2 ), modes at 153, 223, and 475 cm 1 due to sulfur,22 modes at 157, 335, 450, 667, 795, and 1195 cm 1 (spectrum 5) from diaspore23 (AlO(OH)), and modes at 1285 and 1387 cm 1 (spectrum 5) of CO2 .9 Sapphires from Madagascar

EXPERIMENTAL
The investigated samples were provided by the Istituto Gemmologico Italiano. The results correspond to a set of one rough and nine faceted sapphires, ranging from 0.65 to 3.71 carats (ct). Seven samples are related to known gem-mining regions, whereas three samples are of unknown provenance. The gemstones cover the whole range of colour of sapphire, from light blue to deep dark blue, also showing the typical colour zoning that follows the geometry of growth structures and is related to a lower or higher presence of metal ions responsible for colour within the zones. The Raman spectra were obtained by means of a confocal micro-Raman Labram Dilor spectrometer, with the 488 nm polarized radiation of an argon ion laser beam of about 50 mW as light source, in back-scattering conguration. The 488 nm laser line is preferred to the 633 nm line of a HeNe laser to avoid uorescence excitation of chromium, always occurring in sapphire. The laser beam is focused on the sample through Olympus objectives 20 (numerical aperture NA D 0.40), 50 NA D 0.75 , and 100 NA D 0.90 to study sample volumes of a few to tens of m3 . The scattered light was analysed with a spectrometer equipped with a Peltier-cooled Charge Coupled Device (CCD) detector. The spectra were calibrated using the silicon Raman signal (from a silicon wafer) as reference. Most of the spectra of the mineral inclusions were collected in the spectral range 1501800 cm 1 where the main phonon modes of the solid inclusions are found. The confocality of the system, with a focal layer thickness of a few microns, is crucial to separate the spectral features of the inclusion from those of the host. All samples were investigated at room temperature in air. The spectra acquisition times varied from 60 to 600 s. Assignment of Raman spectra was realized by comparison with literature data, web database, and direct measurements on reference compounds. Minor differences of 2 cm 1 between peak positions and literature data were observed, mainly caused by experimental uncertainty in the spectral calibration. Slightly larger differences are probably evidence of the effects of disorder or stress, likely occurring in microsized inclusions embedded in crystals. Microscopic images of the analysed inclusions and localization of the measured volumes were collected either through a camera on the same optical path as that of the detected Raman signal, or by means

Figure 1. Raman spectrum at room temperature of corundum variety sapphire. Spectral acquisition time, 300 s. This gure is available in colour online at www.interscience.wiley.com/journal/jrs.

Copyright 2008 John Wiley & Sons, Ltd.

J. Raman Spectrosc. 2008; 39: 10071011 DOI: 10.1002/jrs

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Figure 2. (a) Sample of Sri Lanka sapphire: the circled area P1 presents the inclusion (enlarged in Fig. 2(b)1), whose Raman spectrum is displayed in Fig. 3 (number 5).

and Sri Lanka show modes at 159, 281, 711, and 1086 cm 1 (spectrum 4), indicating the occurrence of calcite24 (CaCO3 ) together with rutile (modes at 245, 450, 613, and 810 cm 1 in spectrum 3). Figure 4 displays the Raman spectra of inclusions found within sapphires from magmatic environments and from alkali basalts. The identication of Raman peaks at 297, 414, 1084, and 1306 cm 1 (spectrum 1) indicates the presence of hematite24 (Fe2 O3 ) in the sapphire from Australia. The extra band at 690 cm 1 is ascribable to impurity-induced disorder effects similar to those observed in Ti-doped hematite.25 Sapphire from Tanzania shows modes at 245, 445, 613, and 810 cm 1 due to rutile26 (TiO2 ), modes at 1350 and 1591 cm 1 (spectrum 2) from graphite27 phases (C), and zircon28 phase (ZrSiO4 ) within sapphire from alkali basalts (modes at 199, 218, 355, 412, 437, 975, and 1011 cm 1 in spectrum 3). Results reported in Figs 3 and 4 suggest an important correlation between inclusion varieties and geographical origin through a discrimination between magmatic and metamorphic environments. Indeed, one of the main possible targets of a Raman characterization of gemstone inclusions is expected to be the identication of the gemstone origin. In order to achieve a preliminary conrmation of the observed correlation between inclusions and geological origin in the analysed gems, an independent check discriminating between magmatic and metamorphic sapphires may be collected by means of optical absorption spectra, which, as shown in Fig. 5, are largely different around 11 000 cm 1 . The distinguishing spectroscopic feature is the absorption band at 11 500 cm 1 assigned to Fe2C (Refs. 13,29); this is extremely

Figure 3. Raman spectra at room temperature of inclusions in metamorphic sapphires: 1, anatase from Vietnam; 2, rutile and sulfur from Sri Lanka; 3, rutile from Madagascar;4, calcite from Madagascar; 5, diaspore and CO2 from Sri Lanka. Spectral acquisition time, 60600 s. This gure is available in colour online at www.interscience.wiley.com/journal/jrs.

intense in a-type spectrum (sapphire from magmatic environment) and practically undetectable in b-type spectrum (sapphire from metamorphic origin). Sapphires from Australia, Tanzania, and Thailand show a-type spectra, whereas sapphires from Madagascar, Sri Lanka, and Vietnam show b-type spectra (at room temperature).

CONCLUSIONS
Raman spectra and bibliographic information were used to draw conclusions about the range of possible inclusions in corundum gemstones and their correlations with their geological origin. In fact, although rutile is common both to magmatic and metamorphic sapphires,1,2 other inclusions are instead characteristic of the geological environment of gemstones. The obtained results may, indeed, be rationalized in the following way. The presence of zircon in the host crystal with radial cracks and dark brown halos (arising

Copyright 2008 John Wiley & Sons, Ltd.

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Figure 4. Raman spectra at room temperature of inclusions in magmatic sapphires: 1, hematite from Australia; 2, rutile and graphite from Tanzania; 3, zircon from alkali basalts. Spectral acquisition time, 60300 s. This gure is available in colour online at www.interscience.wiley.com/journal/jrs.

deposits23 ; more specically, calcite inclusions suggest the origin from marble-hosted deposit. Finally, other two types of inclusions, anatase and graphite, are found in specic gemstones. In particular, anatase inclusions were identied in corundum from a metamorphic deposit in Vietnam, while graphite was detected in a gemstone from Tanzania. Graphite inclusions are quite common in corundum. Anatase in sapphire is certainly much less frequent, and the identication in samples from Vietnam might be particularly interesting, although no correlation can be drawn at the moment. In summary, the results of this preliminary sampling of origin-controlled corundum gemstones constitute a rst step for the creation of a rational database of gemstones and distinctive inclusions, showing that the identication of inclusions by means of confocal micro-Raman spectroscopy may be a really efcient non-destructive tool for the study of the sapphire origin. From this perspective, this work also demonstrates that parallel analyses by means of optical absorption spectroscopy, possibly to be extended in the future to luminescence investigation and elemental chemical analyses with laser-ablation-ICP-MS, would enable us to draw deeper conclusions about the origin of gemstones.12 In such a manner, a comprehensive database could be compiled that could contribute signicantly to the identication of the nature and origin of gemstones, also against potentially illicit treatments that are nowadays employed to modify the aesthetic quality and declared origin of gemstones in the trade.

Acknowledgements
We thank P. Valentini of the Istituto Gemmologico Italiano for kindly supplying the sapphire samples. This work was supported by Fondo Sociale Europeo and Ministero del Lavoro e della Previdenza Sociale and Regione Lombardia through Sovvenzione Globale INGENIO.

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Figure 5. Absorption spectra at room temperature of magmatic (a) and metamorphic (b) sapphires. This gure is available in colour online at www.interscience.wiley.com/journal/jrs.

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Copyright 2008 John Wiley & Sons, Ltd.

J. Raman Spectrosc. 2008; 39: 10071011 DOI: 10.1002/jrs