Multi-methodological investigation of kunzite, hiddenite, alexandrite, elbaite and topaz, based on laser-induced breakdown spectroscopy and conventional analytical techniques for supporting mineralogical characterization

Gem-quality alexandrite, hiddenite and kunzite, elbaite and topaz minerals were characterized through a multi-methodological investigation based on EMPA-WDS, LA-ICP-MS, and laser-induced breakdown spectroscopy (LIBS). With respect to the others, the latter technique enables a simultaneous multi-elemental composition without any sample preparation and the detection of light elements, such as Li, Be and B. The criteria for the choice of minerals were: (a) the presence of chromophore elements in minor contents and/or as traces; (b) the presence of light lithophile elements (Li, Be and B); (c) different crystal chemistry complexity. The results show that LIBS can be employed in mineralogical studies for the identification and characterization of minerals, and as a fast screening method to determine the chemical composition, including the chromophore and light lithophile elements.

[1]  D. London.  Holmquistite as a guide to pegmatitic rare metal deposits , 1986 .

[2]  N. Bridges,et al.  The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Body Unit and Combined System Tests , 2012 .

[3]  A. Woodland,et al.  The distribution of lithium in peridotitic and pyroxenitic mantle lithologies — an indicator of magmatic and metasomatic processes , 2000 .

[4]  Israel Schechter,et al.  Laser-induced breakdown spectroscopy (LIBS) : fundamentals and applications , 2006 .

[5]  Savino Longo,et al.  Laser induced breakdown spectroscopy on meteorites , 2007 .

[6]  I. Rauschenbach,et al.  Laser induced breakdown spectroscopy of soils, rocks and ice at subzero temperatures in simulated martian conditions , 2007 .

[7]  Stefano Legnaioli,et al.  A numerical study of expected accuracy and precision in Calibration-Free Laser-Induced Breakdown Spectroscopy in the assumption of ideal analytical plasma ☆ , 2007 .

[8]  Jong-Wan Park,et al.  Diffusion of chromium in chrysoberyl , 2009 .

[9]  M. Li,et al.  Annealing effects on optical properties of natural alexandrite , 2003 .

[10]  C. Fabre,et al.  Advances in lithium analysis in solids by means of laser-induced breakdown spectroscopy: an exploratory study , 2002 .

[11]  R. Howie,et al.  Single-Chain Silicates , 1997 .

[12]  G. Rossman,et al.  Fe2+-Fe3+ interactions in tourmaline , 1987 .

[13]  Roberta Fantoni,et al.  Determination of heavy metals in soils by Laser Induced Breakdown Spectroscopy , 2002 .

[14]  M. Tiepolo,et al.  A laser probe coupled with ICP-double focusing sector-field mass spectrometer for in situ analysis of geological samples and U-Pb dating of zircon , 2003 .

[15]  G. Cristoforetti,et al.  Calibration-Free Laser-Induced Breakdown Spectroscopy: State of the art , 2010 .

[16]  R. Gaudiuso,et al.  A Laser Induced Breakdown Spectroscopy application based on Local Thermodynamic Equilibrium assumption for the elemental analysis of alexandrite gemstone and copper-based alloys , 2012 .

[17]  Leon J. Radziemski,et al.  Handbook of Laser-Induced Breakdown Spectroscopy , 2006 .

[18]  Leon J. Radziemski,et al.  Determining LIBS Analytical Figures‐of‐Merit , 2006 .

[19]  R. Wiens,et al.  Laser-induced breakdown spectroscopy for space exploration applications: Influence of the ambient pressure on the calibration curves prepared from soil and clay samples , 2005 .

[20]  G. Rossman,et al.  Developments in Gemstone Analysis Techniques and Instrumentation During the 2000s , 2010 .

[21]  G. Redhammer,et al.  57Fe Mössbauer spectroscopy, X-ray single-crystal diffractometry, and electronic structure calculations on natural sinhalites , 2007 .

[22]  D. Cremers,et al.  Handbook of Laser-Induced Breakdown Spectroscopy: Cremers/Handbook of Laser-induced Breakdown Spectroscopy , 2006 .

[23]  E. W. Claffy.  Composition, tenebrescence and luminescence of spodumene minerals , 1953 .

[24]  N. Omenetto,et al.  Laser-Induced Breakdown Spectroscopy (LIBS), Part I: Review of Basic Diagnostics and Plasma—Particle Interactions: Still-Challenging Issues within the Analytical Plasma Community , 2010, Applied spectroscopy.

[25]  R. Gaudiuso,et al.  Laser Induced Breakdown Spectroscopy applications to meteorites: Chemical analysis and composition profiles , 2010 .

[26]  Frank C De Lucia,et al.  Use of laser induced breakdown spectroscopy in the determination of gem provenance: beryls. , 2008, Applied optics.

[27]  E. Tognoni,et al.  New Procedure for Quantitative Elemental Analysis by Laser-Induced Plasma Spectroscopy , 1999 .

[28]  D. L. Death,et al.  Multi-element and mineralogical analysis of mineral ores using laser induced breakdown spectroscopy and chemometric analysis , 2009 .

[29]  L. Groat,et al.  Gem Formation, Production, and Exploration: Why Gem Deposits Are Rare and What is Being Done to Find Them , 2009 .

[30]  Roberto Teghil,et al.  Laser Induced Breakdown Spectroscopy methodology for the analysis of copper-based-alloys used in ancient artworks , 2008 .

[31]  David London,et al.  The application of experimental petrology to the genesis and crystallization of granitic pegmatites , 1992 .

[32]  Reinhard Noll,et al.  Laser-Induced Breakdown Spectroscopy: Fundamentals and Applications , 2012 .

[33]  T. Miano,et al.  Heavy metal concentrations in soils as determined by laser-induced breakdown spectroscopy (LIBS), with special emphasis on chromium. , 2009, Environmental research.

[34]  F. Pezzotta,et al.  Tourmaline: The Kaleidoscopic Gemstone , 2011 .

[35]  I. M. Botheroyd,et al.  Remote material analysis of nuclear power station steam generator tubes by laser-induced breakdown spectroscopy , 2001 .

[36]  L. Marinangeli,et al.  Investigation of LIBS feasibility for in situ planetary exploration: An analysis on Martian rock analogues , 2004 .

[37]  V. V. Hinsberg,et al.  Tourmaline: an ideal indicator of its host environment , 2011 .

[38]  James E. Shigley,et al.  Laboratory-Treated Gemstones , 2009 .

[39]  Nancy J. McMillan,et al.  Laser-induced breakdown spectroscopy analysis of complex silicate minerals—beryl , 2006, Analytical and bioanalytical chemistry.

[40]  S. Clegg,et al.  Multivariate analysis of remote laser-induced breakdown spectroscopy spectra using partial least squares, principal component analysis, and related techniques , 2009 .

[41]  B. Dutrow,et al.  Nomenclature of the tourmaline-supergroup minerals , 2011 .

[42]  P. B. Barton,et al.  Fluid-Mineral Equilibria in Hydrothermal Systems , 1984 .

[43]  J.-L. Pouchou,et al.  Quantitative Analysis of Homogeneous or Stratified Microvolumes Applying the Model “PAP” , 1991 .

[44]  G. Rossman,et al.  An Update on Color in Gems. Part 3: Colors Caused by Band Gaps and Physical Phenomena , 1988 .

[45]  Roger C. Wiens,et al.  Evaluation of a compact spectrograph for in-situ and stand-off Laser-Induced Breakdown Spectroscopy analyses of geological samples on Mars missions , 2005 .

[46]  George R. Rossman,et al.  The Geochemistry of Gems and Its Relevance to Gemology: Different Traces, Different Prices , 2009 .

[47]  D. London,et al.  Experimental silicate mineral/melt partition coefficients for beryllium and the crustal Be cycle from migmatite to pegmatite , 2002 .

[48]  M. Tiepolo,et al.  Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation‐Inductively Coupled Plasma‐Sector Field Mass Spectrometry , 2005 .

[49]  G. Rossman,et al.  Identifying characteristics of charge transfer transitions in minerals , 1987 .

[50]  K. Heinrich,et al.  Electron Probe Quantitation , 1991, Springer US.

[51]  Cristian A. D'Angelo,et al.  Analysis of Minerals and Rocks by Laser-Induced Breakdown Spectroscopy , 2011 .

[52]  Stewart Clegg,et al.  Optimization of laser-induced breakdown spectroscopy for rapid geochemical analysis , 2010 .

[53]  M. Saccoccio,et al.  The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Science Objectives and Mast Unit Description , 2012 .

[54]  Demetrios Anglos,et al.  Laser-induced breakdown spectroscopy (LIBS) in archaeological science—applications and prospects , 2007, Analytical and bioanalytical chemistry.

[55]  David A. Cremers,et al.  Characterization of Laser-Induced Breakdown Spectroscopy (LIBS) for Application to Space Exploration , 2000 .

[56]  Rosalba Gaudiuso,et al.  Monitoring of Cr, Cu, Pb, V and Zn in polluted soils by laser induced breakdown spectroscopy (LIBS). , 2011, Journal of environmental monitoring : JEM.

[57]  S. Maurice,et al.  Comparative study of different methodologies for quantitative rock analysis by Laser-Induced Breakdown Spectroscopy in a simulated Martian atmosphere , 2006 .

[58]  G. Rossman,et al.  An Update on Color in Gems. Part 2: Colors Involving Multiple Atoms and Color Centers , 1988 .