Raman spectroscopy for fluid inclusion analysis

Abstract Raman spectroscopy is a versatile non-destructive technique for fluid inclusion analysis, with a wide field of applications ranging from qualitative detection of solid, liquid and gaseous components to identification of polyatomic ions in solution. Raman technique is commonly used to calculate the density of CO 2 fluids, the chemistry of aqueous fluids, and the molar proportions of gaseous mixtures present as inclusions. Raman spectroscopy has been applied to measure the pH range and oxidation state of fluids. The main advantages of this technique are the minimal sample preparation and the high versatility. Present review summarizes the recent developments of Raman spectroscopy in fluid inclusions research to provide support for laboratory analyses.

[1]  N. Guilhaumou,et al.  Native-sulphur-bearing fluid inclusions in the CO2H2SH2OS system — Microthermometry and Raman microprobe (MOLE) analysis — Thermochemical interpretations☆ , 1982 .

[2]  P. Davidson,et al.  Extreme alkali bicarbonate- and carbonate-rich fluid inclusions in granite pegmatite from the Precambrian Rønne granite, Bornholm Island, Denmark , 2011 .

[3]  R. Frost,et al.  Comparison of Raman spectra in characterizing gibbsite, bayerite, diaspore and boehmite , 2001 .

[4]  A. I. Komyak,et al.  Vibrational Spectra and Structure of Potassium Alum Kal(SO4)2·12[(H2O)x(D2O)1−x] , 2004 .

[5]  P. Treloar,et al.  Mixed CH4-CO2 fluid inclusions in quartz from the South Wales Coalfield as suitable natural calibration standards for microthermometry and Raman spectroscopy , 2005 .

[6]  G. J. Rosasco,et al.  Application of a new Raman microprobe spectrometer to nondestructive analysis of sulfate and other ions in individual phases in fluid inclusions in minerals , 1979 .

[7]  David A. Banks,et al.  Paleo-fluid composition determined from individual fluid inclusions by Raman and LIBS: Application to mid-proterozoic evaporitic Na–Ca brines (Alligator Rivers Uranium Field, northern territories Australia) , 2007 .

[8]  J. Dubessy,et al.  Analyse d'inclusions fluides à la microsonde MOLE à effet Raman , 1979 .

[9]  G. Dollinger,et al.  Application of Raman spectroscopy to quantify trace water concentrations in glasses and garnets , 2008 .

[10]  T. Mernagh,et al.  The use of the laser Raman microprobe for the determination of salinity in fluid inclusions , 1989 .

[11]  I. Munz.  Petroleum inclusions in sedimentary basins : systematics, analytical methods and applications , 2001 .

[12]  J. Pironon.  Estimation de la longueur de chaîne des hydrocarbures des inclusions fluides par spectrométrie Raman , 1993 .

[13]  J. Pironon,et al.  Semi-quantitative FT-IR microanalysis limits: Evidence from synthetic hydrocarbon fluid inclusions in sylvite , 1990 .

[14]  A. Wesełucha-Birczyńska,et al.  Raman microspectroscopy of organic inclusions in spodumenes from Nilaw (Nuristan, Afghanistan). , 2011, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[15]  E. Neumann,et al.  Carbonatite melt–CO2 fluid inclusions in mantle xenoliths from Tenerife, Canary Islands: a story of trapping, immiscibility and fluid–rock interaction in the upper mantle , 2002 .

[16]  G. Herzberg,et al.  Infrared and Raman spectra of polyatomic molecules , 1946 .

[17]  H. S. Yoder,et al.  Raman study of anorthite, calcium Tschermak's pyroxene, and gehlenite in crystalline and glassy states , 1983 .

[18]  V. Prokof’ev,et al.  Role of boric acids in the formation of pegmatite and hydrothermal minerals: Petrologic consequences of sassolite (H3BO3) discovery in fluid inclusions , 2000 .

[19]  R. Frost,et al.  Synthesis and characterization of K2Ca5(SO4)6·H2O, the equivalent of görgeyite, a rare evaporite mineral , 2004 .

[20]  R. Thomas.  Determination of the H3BO3 concentration in fluid and melt inclusions in granite pegmatites by laser Raman microprobe spectroscopy , 2002 .

[21]  C. Manning,et al.  Activity coefficient and polymerization of aqueous silica at 800 °C, 12 kbar, from solubility measurements on SiO2-buffering mineral assemblages , 2003 .

[22]  J. C. Seitz,et al.  Practical aspects of quantitative laser Raman microprobe spectroscopy for the study of fluid inclusions , 1988 .

[23]  K. Rao,et al.  High resolution infrared spectra of water vapor: ν1 and ν3 bands of H218O , 1969 .

[24]  D. Schüler,et al.  Synthesis and Characterization , 2009 .

[25]  Qiang Sun,et al.  The Raman OH stretching bands of liquid water , 2009 .

[26]  B. Scaillet,et al.  Influence of composition and thermal history of volcanic glasses on water content as determined by micro-Raman spectrometry , 2006 .

[27]  T. Mernagh,et al.  Raman spectra from the Al2SiO5 polymorphs at high pressures and room temperature , 1991 .

[28]  Frank C. Hawthorne,et al.  Spectroscopic methods in mineralogy and geology , 1988 .

[29]  M. Pagel,et al.  Radiolysis evidenced by H2-O2 and H2-bearing fluid inclusions in three uranium deposits , 1988 .

[30]  L. Stixrude,et al.  The 10Å phase: a high-pressure expandable sheet silicate stable during subduction of hydrated lithosphere , 2001 .

[31]  J. Dubessy,et al.  Advances in C-O-H-N-S fluid geochemistry based on micro-Raman spectrometric analysis of fluid inclusions , 1989 .

[32]  Qiang Sun,et al.  Raman OH stretching band of water as an internal standard to determine carbonate concentrations , 2011 .

[33]  R. Bodnar,et al.  Applications of the laser Raman microprobe RAMANOR U-1000 to hydrothermal ore deposits; Carlin as an example , 1986 .

[34]  J. Watson.  Vibrational Spectra and Structure , 1977 .

[35]  B. Tattitch,et al.  Combined microthermometric and Raman spectroscopic technique to determine the salinity of H2O–CO2–NaCl fluid inclusions based on clathrate melting , 2011 .

[36]  Qiang Sun,et al.  Raman spectroscopic measurements of CO2 density: Experimental calibration with high-pressure optical cell (HPOC) and fused silica capillary capsule (FSCC) with application to fluid inclusion observations , 2011 .

[37]  P. Treloar,et al.  Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia , 2004 .

[38]  P. Davidson,et al.  THE FORMATION OF PERALKALINE PEGMATITIC MELT FRACTIONS: EVIDENCE FROM MELT AND FLUID INCLUSION STUDIES , 2007 .

[39]  R. Frost,et al.  Hydrated double carbonates – A Raman and infrared spectroscopic study , 2007 .

[40]  J. Pasteris,et al.  Raman intensities and detection limits of geochemically relevant gas mixtures for a laser Raman microprobe , 1987 .

[41]  R. Bodnar,et al.  In situ quantitative analysis of individual H2O–CO2 fluid inclusions by laser Raman spectroscopy , 2006 .

[42]  L. Curtiss,et al.  Alkali carbonates: Raman spectroscopy, ab initio calculations, and structure , 1996 .

[43]  H. Kagi,et al.  Micro-Raman Densimeter for CO2 Inclusions in Mantle-Derived Minerals , 2003, Applied spectroscopy.

[44]  M. Frezzotti,et al.  Late-Alpine rodingitization in the Bellecombe meta-ophiolites (Aosta Valley, Italian Western Alps): evidence from mineral assemblages and serpentinization-derived H2-bearing brine , 2010 .

[45]  S. Wiberley,et al.  Introduction to infrared and Raman spectroscopy , 1965 .

[46]  C. Karr.  Infrared and Raman spectroscopy of lunar and terrestrial minerals , 1975 .

[47]  J. Rouzaud,et al.  Graphitization in a high-pressure, low-temperature metamorphic gradient: a Raman microspectroscopy and HRTEM study , 2002 .

[48]  J. C. Seitz,et al.  High-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe , 1990 .

[49]  L. Nasdala,et al.  Heterogeneous metamictization of zircon on a microscale , 1996 .

[50]  Robert G. Eppinger,et al.  Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe , 1992 .

[51]  P. Davidson,et al.  Hambergite-rich melt inclusions in morganite crystals from the Muiane pegmatite, Mozambique and some remarks on the paragenesis of hambergite , 2010 .

[52]  O. Shebanova,et al.  Raman spectroscopic study of magnetite (FeFe2O4): a new assignment for the vibrational spectrum , 2003 .

[53]  H. W. Schrötter,et al.  Raman Scattering Cross Sections in Gases and Liquids , 1979 .

[54]  H. Edwards,et al.  FT-Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals. , 2005, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[55]  J. Pironon,et al.  Calibration of methane analysis by Raman spectroscopy in H2O–NaCl–CH4 fluid inclusions , 2003 .

[56]  J. Pironon,et al.  Aqueous and hydrocarbon inclusions in dolomite fromTouissit-Bou Beker district, Eastern Morocco: a Jurassic carbonate hosted PbZn (Cu) deposit , 2003 .

[57]  C. Schmidt.  Raman spectroscopic study of a H2O + Na2SO4 solution at 21– 600 °C and 0.1 MPa to 1.1 GPa: Relative differential ν1-SO42- Raman scattering cross sections and evidence of the liquid–liquid transition , 2009 .

[58]  C. H. Wang,et al.  Raman studies of the effect of density of the fermi resonance in CO2 , 1973 .

[59]  M. Cathelineau,et al.  Detailed determination of palaeofluid chemistry: an integrated study of sulphate-volatile rich brines and aquo-carbonic fluids in quartz veins from Ouro Fino (Brazil) , 1999 .

[60]  T. Mernagh,et al.  A laser Raman microprobe study of some geologically important sulphide minerals , 1993 .

[61]  W. Lu,et al.  A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts , 2007 .

[62]  D. M. Carey,et al.  Measurement of the Raman Spectrum of Liquid Water , 1996 .

[63]  J. A. Rodríguez-Losada,et al.  Micro‐Raman spectroscopic study of El Gasco pumice, western Spain , 2007 .

[64]  F. Rossetti,et al.  Composition and evolution of fluids during skarn development in the Monte Capanne thermal aureole, Elba Island, central Italy , 2008 .

[65]  S. Ross,et al.  Inorganic infrared and Raman spectra , 1972 .

[66]  R. Frost,et al.  Raman spectroscopy of dawsonite NaAl(CO3)(OH)2 , 2007 .

[67]  E. Belluso,et al.  CHARACTERIZATION OF CHRYSOTILE, ANTIGORITE AND LIZARDITE BY FT-RAMAN SPECTROSCOPY , 2003 .

[68]  J. Wilkinson.  Fluid inclusions in hydrothermal ore deposits , 2001 .

[69]  S. Haussühl,et al.  Raman spectra of orthorhombic sulfate single crystals I: K2SO4, Rb2SO4, Cs2SO4 and Tl2SO4 , 1974 .

[70]  J. Pironon,et al.  Characterization of water in synthetic rhyolitic glasses and natural melt inclusions by Raman spectroscopy , 2004 .

[71]  R. Kaindl,et al.  Raman spectroscopy: Analytical perspectives in mineralogical research , 2004 .

[72]  K. S. Krishnan,et al.  The Optical Analogue of the Compton Effect , 1928, Nature.

[73]  P. Gillet.  Stability Of Magnesite (MgCO3) At Mantle Pressure And Temperature Conditions - A Raman-Spectroscopic Study , 1993 .

[74]  J. Dubessy,et al.  The determination of sulphate in fluid inclusions using the M.O.L.E. Raman microprobe. Application to a keuper halite and geochemical consequences , 1983 .

[75]  G. Walrafen,et al.  Raman Spectral Studies of Water Structure , 1964 .

[76]  C. Manning.  The chemistry of subduction-zone fluids , 2004 .

[77]  C. Sorensen,et al.  Interoscillator coupling effects on the OH stretching band of liquid water , 1992 .

[78]  R. Bakker,et al.  High-temperature Raman spectroscopic study of H 2 O-CO 2 -CH 4 mixtures in synthetic fluid inclusions; first insights on molecular interactions and analytical implications , 1999 .

[79]  R. Frost,et al.  Raman spectroscopic study of the magnesium-carbonate minerals - artinite and dypingite , 2009 .

[80]  R. J. Clark,et al.  Can the Raman spectrum of anatase in artwork and archaeology be used for dating purposes? Identification by Raman microscopy of anatase in decorative coatings on Neolithic (Yangshao) pottery from Henan, China , 2007 .

[81]  van den Kerkhof,et al.  Phase transitions and molar volumes of CO2-CH4-N2 inclusions , 1988 .

[82]  Li Wenjun,et al.  Hydrothermal preparation and characterization of brookite-type TiO2 nanocrystallites , 2000 .

[83]  J. Pasteris,et al.  Limitations to Quantitative Analysis of Fluid Inclusions in Geological Samples by Laser Raman Microprobe Spectroscopy , 1986 .

[84]  M. Arakawa,et al.  Developing Micro-Raman Mass Spectrometry for Measuring Carbon Isotopic Composition of Carbon Dioxide , 2007, Applied spectroscopy.

[85]  W. Lustenhouwer,et al.  The application of a multichannel laser Raman microprobe (Microdil-28®) to the analysis of fluid inclusions , 1987 .

[86]  Arthur L. Lane,et al.  The Athena Raman Spectrometer , 2000 .

[87]  A. V. D. Kerkhof,et al.  Isochoric phase diagrams in the systems CO2CH4 and CO2N2: Application to fluid inclusions , 1990 .

[88]  W. Heinrich,et al.  The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions , 2006 .

[89]  G. J. Rosasco,et al.  Laser-Excited Raman Spectroscopy for Nondestructive Partial Analysis of Individual Phases in Fluid Inclusions in Minerals , 1975, Science.

[90]  Wenxuan Hu,et al.  CO2 Density‐Raman Shift Relation Derived from Synthetic Inclusions in Fused Silica Capillaries and Its Application , 2009 .

[91]  K. Rao,et al.  High resolution infrared spectra of water vapor , 1969 .

[92]  B. G. Oliver,et al.  A vibrational-spectroscopic study of the species present in the CO2−H2O system , 1972 .

[93]  Ronald J. Bakker,et al.  Raman spectroscopy of pure H2O and NaCl-H2O containing synthetic fluid inclusions in quartz—a study of polarization effects , 2009 .

[94]  A. V. D. Kerkhof,et al.  Retrograde methane-dominated fluid inclusions from high-temperature granulites of Rogaland, southwestern Norway , 1991 .

[95]  W. Lamb,et al.  Methane-bearing aqueous fluid inclusions: Raman analysis, thermodynamic modelling and application to petroleum basins , 2001 .

[96]  R. Schuiling,et al.  Vibrational spectroscopic study of syngenite formed during the treatment of liquid manure with sulphuric acid , 2002 .

[97]  O. Beyssac,et al.  Deposition of highly crystalline graphite from moderate-temperature fluids , 2009 .

[98]  B. Vivo,et al.  Mantle fluids in pyroxenite nodules from Salt Lake Crater (Oahu, Hawaii) , 1992 .

[99]  Alan E. Williams,et al.  Mass spectrometric identification of boric acid in fluid inclusions in pegmatite minerals , 1996 .

[100]  Adolf Smekal,et al.  Zur Quantentheorie der Dispersion , 1923, Naturwissenschaften.

[101]  P. Vandenabeele,et al.  First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[102]  R. L. Moreira,et al.  Vibrational spectra of monazite-type rare-earth orthophosphates , 2006 .

[103]  A. Kleppe,et al.  The effect of pressure upon hydrogen bonding in chlorite: A Raman spectroscopic study of clinochlore to 26.5 GPa , 2003 .

[104]  C. Mandeville,et al.  A composition-independent quantitative determination of the water content in silicate glasses and silicate melt inclusions by confocal Raman spectroscopy , 2005 .

[105]  R. Hemley,et al.  Applications in Earth, Planetary and Environmental Sciences , 1996 .

[106]  A. Kavner,et al.  Polymerization of aqueous silica in H2O-K2O solutions at 25-200°C and 1bar to 20kbar , 2011 .

[107]  M. Probst,et al.  A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios. , 2010, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[108]  M. Frezzotti,et al.  Intermediate Alkali–Alumino-silicate Aqueous Solutions Released by Deeply Subducted Continental Crust: Fluid Evolution in UHP OH-rich Topaz–Kyanite Quartzites from Donghai (Sulu, China) , 2007 .

[109]  J. Pironon,et al.  Volumetric reconstruction of individual oil inclusions by confocal scanning laser microscopy , 1998 .

[110]  C. Rey,et al.  Infrared and Raman microspectrometry study of fluor-fluor-hydroxy and hydroxy-apatite powders , 1997, Journal of materials science. Materials in medicine.

[111]  Jan Marten Huizenga,et al.  Thermodynamic modelling of C O H fluids , 2001 .

[112]  J. Dubessy,et al.  Highly reducing conditions during Alpine metamorphism of the Malenco peridotite (Sondrio, northern Italy) indicated by mineral paragenesis and H2 in fluid inclusions , 1992 .

[113]  D. Beysens,et al.  Rayleigh and Raman scattering near the critical point of carbon dioxide , 1980 .

[114]  H. Keppler,et al.  Silica speciation in aqueous fluids at high pressures and high temperatures , 2002 .

[115]  B. Jolliff,et al.  Database of Raman Mineral Spectra for Planetary Surface Exploration , 2006 .

[116]  P. Davidson,et al.  Tantalite-(Mn) from the Borborema Pegmatite Province, northeastern Brazil: conditions of formation and melt- and fluid-inclusion constraints on experimental studies , 2011 .

[117]  E. Burke.  Raman microspectrometry of fluid inclusions , 2001 .

[118]  H. Barnes.  Inclusions in Minerals , 1966 .

[119]  A. Hamilton,et al.  Raman spectra of mirabilite, Na2SO4·10H2O and the rediscovered metastable heptahydrate, Na2SO4·7H2O , 2010 .

[120]  J. Pironon,et al.  Letter : NIR FT-Raman microspectroscopy of fluid inclusions: Comparisons with VIS Raman and FT-IR microspectroscopies , 1991 .

[121]  P. Davidson,et al.  Ramanite-(Cs) and ramanite-(Rb): New cesium and rubidium pentaborate tetrahydrate minerals identified with Raman spectroscopy , 2008 .

[122]  R. Davies,et al.  Pressure‐induced incipient amorphization of α‐quartz and transition to coesite in an eclogite from Antarctica: a first record and some consequences , 2009 .

[123]  M. Sendova,et al.  Micro‐Raman spectroscopic study of pottery fragments from the Lapatsa tomb, Cyprus, ca 2500 BC , 2005 .

[124]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[125]  P. Davidson,et al.  Progress in the determination of water in glasses and melt inclusions with Raman spectroscopy: A short review , 2006 .

[126]  B. Reynard,et al.  High-pressure behaviour of serpentine minerals: a Raman spectroscopic study , 2004 .

[127]  S. Slotznick,et al.  In situ Raman spectroscopy measurements of MgAl2O4 spinel up to 1400 °C , 2008 .

[128]  J. Toporski,et al.  Raman imaging of fluid inclusions in garnet from UHPM rocks (Kokchetav massif, Northern Kazakhstan). , 2011, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[129]  C. Raman.  A new radiation , 1953 .

[130]  J. Pironon,et al.  Inclusions in salt beds resulting from thermal metamorphism by dolerite sills (eastern Siberia, Russia) , 1992 .

[131]  B. Cesare,et al.  Fluid-present anatexis of metapelites at El Joyazo (SE Spain): constraints from Raman spectroscopy of graphite , 1999 .

[132]  C. M. Schiffries.  Liquid-absent aqueous fluid inclusions and phase equilibria in the system CaCl2NaClH2O☆ , 1990 .

[133]  J. Dubessy,et al.  Ethane- and hydrogen-bearing carbonic fluid inclusions in a high-grade metamorphic rock , 2009 .

[134]  R. Bodnar,et al.  Synthetic fluid inclusions in natural quartz I. Compositional types synthesized and applications to experimental geochemistry , 1984 .

[135]  J. Dubessy,et al.  The use of the Raman microprobe MOLE in the determination of the electrolytes dissolved in the aqueous phase of fluid inclusions , 1982 .

[136]  H. Kagi,et al.  Extended Micro-Raman Densimeter for CO2 Applicable to Mantle-originated Fluid Inclusions , 2006 .

[137]  L. Diamond,et al.  Fluid-inclusion evidence of petroleum migration through a buried metamorphic dome in the Pannonian Basin, Hungary , 2007 .

[138]  F. J. Luque.  Natural fluid-deposited graphite: Mineralogical characteristics and mechanisms of formation , 1998 .

[139]  Ray L. Frost,et al.  Raman spectroscopic study of azurite and malachite at 298 and 77 K , 2002 .

[140]  F. Gaillard,et al.  Raman quantification factor calibration for CO-CO2 gas mixture in synthetic fluid inclusions: Application to oxygen fugacity calculation in magmatic systems. , 2009 .

[141]  D. Schwarz,et al.  CO2–H2S–COS–S8–AlO(OH)-bearing fluid inclusions in ruby from marble-hosted deposits in Luc Yen area, North Vietnam , 2003 .

[142]  C. Szabó,et al.  Coexisting silicate melt inclusions and H2O-bearing, CO2-rich fluid inclusions in mantle peridotite xenoliths from the Carpathian–Pannonian region (central Hungary) , 2010 .

[143]  P. Davidson,et al.  The miarolitic pegmatites from the Königshain: a contribution to understanding the genesis of pegmatites , 2009 .

[144]  R. Bakker,et al.  Raman spectra of ice and salt hydrates in synthetic fluid inclusions , 2010 .

[145]  A. Peccerillo,et al.  Diamond-bearing COHS fluids in the mantle beneath Hawaii , 2007 .

[146]  F. Rull,et al.  Determination of Chlorinity in Aqueous Fluids Using Raman Spectroscopy of the Stretching Band of Water at Room Temperature: Application to Fluid Inclusions , 2002 .

[147]  E. Fermi.  Über den Ramaneffekt des Kohlendioxyds , 1931 .

[148]  S. Palmer,et al.  A Raman spectroscopic study of humite minerals , 2007 .

[149]  M. Frezzotti,et al.  Evidence of magmatic CO2-rich fluids in peraluminous graphite-bearing leucogranites from Deep Freeze Range (northern Victoria Land, Antarctica) , 1994 .

[150]  J. Touret.  Fluids in metamorphic rocks , 2001 .

[151]  Cédric Carteret,et al.  Polymorphism Studied by Lattice Phonon Raman Spectroscopy and Statistical Mixture Analysis Method. Application to Calcium Carbonate Polymorphs during Batch Crystallization , 2009 .

[152]  P R Carey,et al.  Raman Spectroscopy, the Sleeping Giant in Structural Biology, Awakes* , 1999, The Journal of Biological Chemistry.

[153]  The Quantum Theory of Dispersion , 1927 .

[154]  J. Theo Kloprogge,et al.  A Raman spectroscopic study of alunites , 2006 .

[155]  Lilian Xu,et al.  Raman study at high pressure and the thermodynamic properties of corundum: Application of Kieffer's model , 1995 .

[156]  Z. Sharp,et al.  Carbonate dissolution during subduction revealed by diamond-bearing rocks from the Alps , 2011 .

[157]  I-Ming Chou,et al.  Sulfates on Mars: A systematic Raman spectroscopic study of hydration states of magnesium sulfates , 2006 .

[158]  B. Velde,et al.  Comparison of the raman microprobe spectra of (Mg, Fe)2SiO4 and Mg2GeO4 with olivine and spinel structures , 1986 .

[159]  P. McMillan,et al.  Ab initio valence force field calculations for quartz , 1990 .

[160]  B. A. Kolesov,et al.  Raman spectra of silicate garnets , 1998 .

[161]  J. Dubessy,et al.  Bicarbonate-rich fluid inclusions and hydrogen diffusion in quartz from the Libčice orogenic gold deposit, Bohemian Massif , 2011 .

[162]  R. Frost,et al.  Raman microscopy at 77 K of natural gypsum CaSO4·2H2O , 2000 .

[163]  D. Neuville,et al.  Quantification of dissolved H2O in silicate glasses using confocal microRaman spectroscopy , 2006 .

[164]  C. Mandeville,et al.  Experimental determination of H2O loss from melt inclusions during laboratory heating: Evidence from Raman spectroscopy , 2007 .

[165]  A. Peccerillo,et al.  Chlorine-rich metasomatic H2O-CO2 fluids in amphibole-bearing peridotites from Injibara (Lake Tana region, Ethiopian plateau): nature and evolution of volatiles in the mantle of a region of continental flood basalts. , 2010 .

[166]  R. Thomas.  Determination of water contents of granite melt inclusions by confocal laser Raman microprobe spectroscopy , 2000 .

[167]  C. Manning,et al.  Thermodynamics of SiO2–H2O fluid near the upper critical end point from quartz solubility measurements at 10 kbar , 2008 .

[168]  A. V. D. Kerkhof,et al.  A natural example of superdense CO2 inclusions: Microthermometry and Raman analysis , 1990 .

[169]  M. Siemann,et al.  The composition of gases in fluid inclusions of late Permian (Zechstein) marine evaporites in Northern Germany , 2001 .

[170]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure: I. Spectra of Diatomic Molecules , 1944 .

[171]  A. Watenphul,et al.  Ammonium in aqueous fluids to 600 °C, 1.3 GPa: A spectroscopic study on the effects on fluid properties, silica solubility, and K-feldspar to muscovite reactions , 2010 .

[172]  J. C. Seitz,et al.  Characterization of CO2CH4H2O fluid inclusions by microthermometry and laser Raman microprobe spectroscopy: Inferences for clathrate and fluid equilibria , 1987 .

[173]  I. Samson,et al.  CRYOGENIC RAMAN SPECTROSCOPIC STUDIES IN THE SYSTEM NaCl–CaCl2–H2O AND IMPLICATIONS FOR LOW TEMPERATURE PHASE BEHAVIOR IN AQUEOUS FLUID INCLUSIONS , 2000 .

[174]  P. Davidson,et al.  A melt and fluid inclusion assemblage in beryl from pegmatite in the Orlovka amazonite granite, East Transbaikalia, Russia: implications for pegmatite-forming melt systems , 2009 .

[175]  J. Pasteris,et al.  Structural characterization of kerogens to granulite-facies graphite; applicability of Raman microprobe spectroscopy , 1993 .

[176]  J. Dubessy,et al.  Determinations of water, hydrates and pH in fluid inclusions by micro-Raman spectrometry , 1992 .

[177]  Jianguo Du,et al.  Geochronological and geochemical constraints on formation of the Tongling metal deposits, middle Yangtze metallogenic belt, east‐central China , 2009 .

[178]  H. Keppler,et al.  Letters. In-situ Raman spectra of dissolved silica species in aqueous fluids to 900 °C and 14 kbar , 2000 .

[179]  Kevin M. Rosso,et al.  Microthermometric and Raman spectroscopic detection limits of C02 in fluid inclusions and the Raman spectroscopic characterization of C02 , 1995 .

[180]  G. Walrafen,et al.  Raman Spectral Studies of the Effects of Temperature on Water Structure , 1967 .

[181]  R. Thomas,et al.  Boron speciation in aqueous fluids at 22 to 600°C and 0.1 MPa to 2 GPa , 2005 .

[182]  R. Bakker.  RAMAN SPECTRA OF FLUID AND CRYSTAL MIXTURES IN THE SYSTEMS H2O, H2O–NaCl AND H2O–MgCl2 AT LOW TEMPERATURES: APPLICATIONS TO FLUID-INCLUSION RESEARCH , 2004 .

[183]  Qiang Sun,et al.  Raman spectroscopic study for the determination of Cl − concentration (molarity scale) in aqueous solutions: Application to fluid inclusions , 2010 .

[184]  E. Stenby,et al.  How to determine the pressure of a methane-containing gas mixture by means of two weak Raman bands, v(3) and 2v(2) , 2002 .