Journal of Geochemical Exploration 112 (2012) 1–20
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Raman spectroscopy for fluid inclusion analysis Maria Luce Frezzotti a, b,⁎, Francesca Tecce b, Alessio Casagli a a b
Dipartimento Scienze della Terra, Università di Siena, Via Laterina 8, 53100 Siena, Italy Istituto Geologia Ambientale e Geoingegneria - CNR, c/o Dipartimento Scienze della Terra, Università “La Sapienza”, P.le Aldo Moro 5, 00185 Roma, Italy
a r t i c l e
i n f o
Article history: Received 7 June 2011 Accepted 18 September 2011 Available online 25 September 2011 Keywords: Raman spectroscopy Fluid inclusions Geological fluids Raman spectra database
a b s t r a c t 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 CO2 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. © 2011 Elsevier B.V. All rights reserved.
Contents 1. 2. 3. 4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods of analysis . . . . . . . . . . . . . . . . . . . . . . . . Gaseous fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. CO2 fluids . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Gaseous mixtures . . . . . . . . . . . . . . . . . . . . . . 5. Aqueous fluids . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Analyses of solutes: monoatomic ions . . . . . . . . . . . . 5.2. Analyses of solutes: polyatomic ions and molecules . . . . . . 6. Identification of mineral phases: a catalog of reference Raman spectra 6.1. Native elements, halides, oxides and sulfides (Table 2) . . . . . 6.2. Carbonates (Table 3). . . . . . . . . . . . . . . . . . . . . 6.3. Sulfates, phosphates, and borates (Tables 4 and 5) . . . . . . 6.4. Silicates (Tables 6 and 7) . . . . . . . . . . . . . . . . . . 7. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction Fluid inclusions (Fig. 1) represent the only first-hand information on fluids in the Earth's interior (e.g., Roedder, 1984; Wilkinson, 2001). They are acknowledged in an enormous range of lithologies (e.g., hydrothermal ore deposits, metamorphic rocks, igneous rocks, and geothermal systems), and pressure and temperature conditions. ⁎ Corresponding author. Tel.: + 39 0577 233929; fax: + 39 0577 233938. E-mail addresses:
[email protected] (M.L. Frezzotti),
[email protected] (F. Tecce),
[email protected] (A. Casagli). 0375-6742/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.gexplo.2011.09.009
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Fluid inclusions are generally small closed volumes (i.e., b50 μm in diameter; Fig. 1), in which pressure and temperature are interdependent variables. Both are related by the equation of state of the enclosed fluid, resulting in a nearly linear relation in the P–T space (isochore). Therefore, a key requirement for research and applications is the ability to characterize fluid composition and density. These two properties are usually obtained by petrographic and microthermometric methods (Poty et al., 1976). Raman spectroscopy is the non-destructive technique which better characterizes liquid and gaseous compounds, solid phases, and solute species in fluid inclusions. One of the main advantages is that
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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Fig. 1. Photomicrographs of fluid inclusions: a) primary H2O fluid inclusions aligned following chevron halite bands, evaporite from Vitravo diapir, Crotone, Italy. b) Primary H2O fluid inclusions in anhydrite from a geothermal well (2410 m depth), Sabatini Volcanic District, Italy. c) Plane of liquid-rich and vapor-rich H2O fluid inclusions in sanidine from syenite, Sabatini Volcanic District, Italy. d) H2O fluid inclusion containing calcite and anhydrite daughter minerals (same provenance as in c). e) Tri-phase H2O–CO2 (L1 + L2 + G) fluid inclusions from an Alpine quartz vein, Binn, Switzerland. f) CO2 fluid inclusions in orthopyroxene, peridotite from Italy.
it allows the chemical and structural characterization of samples as small as 1 μm in diameter, a resolution not possible by conventional petrography, microthermometry, and other spectroscopic methods (e.g., infrared spectroscopy). Raman spectroscopy has become a conventional method in fluid inclusion research starting from the 70's (Burke and Lustenhouwer, 1987; Dhamelincourt et al., 1979; Dubessy et al., 1982, 1989; Guilhaumou, 1982; Pasteris et al. 1986, 1988; Rosasco et al., 1975; Seitz et al., 1987). The continuing interest and
Fig. 2. Energy level scheme for elastic (Rayleigh) and inelastic (Raman) scattering at the frequency of the light source (νl), and Raman and Rayleigh spectra. The molecular vibration of the analyzed sample is of frequency νm.
Fig. 3. Schematic diagram of a Raman spectrometer.
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
the importance of this technique is demonstrated by the number of publications and of review papers in this research field (e.g., Burke, 1994, 2001; Burruss, 2003; McMillan et al., 1996; Nasdala et al., 2004). Present review gives an introduction to Raman spectroscopy for the analysis of geological fluids trapped as inclusions. Our approach is instructional and we focus on selected examples from the literature and from our laboratory experience, but only as far as concerning the routine analysis. The theoretical and experimental treatment of this spectroscopy is on a basic level, and more advanced approaches, such as high-pressure and/or temperature and cryoscopic Raman measurements of fluid inclusions are not discussed in detail. As a first step toward the use of Raman spectroscopy for the study of geological fluids, we provide a catalog of reference spectra for main phases that can be present in fluid inclusions.
2. Fundamentals Raman spectroscopy is based on inelastic scattering of light by matter in its solid, liquid, or gas state. Monochromatic light scattered by matter contains radiations with frequencies different from the exciting light. This effect, predicted by Smekal (1923), was demonstrated by Raman (1928), and named after him. The discovery of a new optical scattering phenomenon won him the Nobel prize in physics in 1930. In several liquids Raman observed scattered light, which had energy greater than the incoming light (Raman antiStokes, see below). The observation of an increase in energy convinced him that he was in presence of a new light-scattering effect, since energy decreasing light-scattering, such as fluorescence, was already known at that time (Raman and Krishnan, 1928). Landsherg and Mandelstam (1928a,b) also found this effect independently and almost simultaneously in Moscow.
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A straightforward way to explain the Raman scattering of light is by quantum mechanical model, which considers the interaction of photons with molecules in terms of energy-transfer mechanisms (cf., Colthup et al., 1975; Karr, 1975, and references therein). A molecule has different vibrational energy levels, the ground state n = 0, and the excited states n = 1, n = 2, n = 3 etc., which are separated by a quantum of energy ΔE = hνm, where h is the Plank's constant and νm is the frequency of the molecular vibration. The incident visible light (λ = 400–750 nm) with energy νl induces transitions to virtual vibrational energy levels in molecules. A virtual level is not an actual energy level of the molecule and it is generated when light photons interact with the molecule, raising its energy. This virtual level is unstable, and light is instantaneously released as scattered radiation. Returning to the initial state occurs by emitting light of frequency νl, νl − νm, and νl + νm. The concept is illustrated in Fig. 2. The Rayleigh or elastic scattering occurs when the transition starts and finishes at the same vibrational energy level without loss of energy (i.e., no frequency change; νl). Inelastic scattering (Raman effect) induces a change to lower (νl − νm) and higher (νl + νm) frequencies in scattered light, which are known as Stokes and anti-Stokes lines, with νm representing a fundamental rotational, vibrational or lattice frequency of the molecule. Rayleigh scattering can account for the wide majority of light scattered by molecules, being the Raman effect extremely weak – in the order of some 10 − 6–10 − 8 of incident photons – and variable, as the intensity of the Raman scattering is proportional to the fourth power of the frequency of the incident light. Raman spectroscopy is the measurement of the photons arising from inelastic (Raman) scattering of light. A Raman spectrum is the plot of light intensity expressed as arbitrary units, or counts, versus the frequency of scattered light (i.e., Raman vibrational modes) in frequency units (wavenumbers ˜ν = νc = λ1 in cm − 1, where c is the
Cc Dmd
Rt
C
I
C Rt
4000
300
a
c
600
900
1200
1500
-1
cm1800
b
Diamond
d
Rutile
e
Calcite
Fig. 4. Raman spectral images of daughter mineral distribution in an aqueous fluid inclusion. a) Optical microphotograph of analyzed fluid inclusion in garnet from ultra-high pressure metamorphic rocks, western Italian Alps, reporting the grid of single point measurements. b) Single point Raman spectrum showing the selected wavenumber intervals for daughter mineral mapping [diamond (red), rutile (blue), and calcite (green)]. c, d, and e) Spectral images of diamond, rutile, and calcite distribution in the fluid inclusion. The color intensity of the mineral phases (from black to white) reflects the increase in the intensity of the Raman band. The aqueous fluid in the inclusion has no significant Raman signal in the investigated region, and thus does not interfere with the measurement; modified from Frezzotti et al. (2011).
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Table 1 Main Raman vibrations (cm− 1) of major gaseous species and of solutes in aqueous fluids. Gasses
Main vibrations
Ref.
COS SO2
857 s 1151 w 524 s 1285 vs 1388 w 1370 1555 2143 2331 2611 2890 vs 2917 w 3020 2954 3336 vs 4156 w 4126 w 4143 w 4161 w 1032 w 586 w 354 vs 3657–3756 w 1595
1 2
CO2 Fermi doublet 13
CO2 O2 CO N2 H2S C3H8 CH4 C2H6 NH3 H2
H2O vapor
3
1 1 4 1 1 5 1 1 6
7
Solutes
Main vibrations
Ref.
Si(OH)40 Si2O(OH)60 ClO4−
750–800 590–680 vs 928 w 645 w 460 vs 980 w 620 w 450 vs 1049 w 690 w 1355 vs 1050 w 890 vs 1017 m 1360 vs 1064 w 684 m 1380 vs 1384 m 1276 2570–2590 vs 3040 sh 2870 vs 877 w 495 vs 2750–3900* w 1630
8, 9 8, 9 10
SO42−
NO3−
HSO4− HCO3− CO32−
CO2 in solution −
HS and H2S NH4+ B(OH)30 H2O liquid
10
A spectrum comprises one or more bands which reflect the vibrational energies of the molecules within the analyzed sample; these in turn are related to the nature of the bonding. Main molecular vibrations include stretching and bending modes, stretching frequencies being generally higher than bending frequencies. In order for a normal mode of vibration to be Raman active, it should produce a change in the polarizability of the molecule. The “selection rules” for Raman scattering depend on: 1) the creation of an induced dipole in the molecule (polarization); 2) the modification of the dipole by a molecular vibration; 3) the successive scattering of a photon from the modified dipole (McMillan and Hess, 1988, and references therein). As a thumbnail rule, those molecules which are not easily polarized are poor Raman scatterers. One example is H2O which has a strong dipole moment but electrons are not easily polarized and Raman scattering is weak. 3. Methods of analysis The basic instrumental set up requires a monochromatic light source, generally a laser, focused on a sample (solid, liquid, or gaseous); the light is scattered, collected at a 90° or 180° angle, and analyzed by a detector (Fig. 3). The first dispersive Raman spectrometers had the sun or a mercury lamp as the exciting source, a prism monochromator as the light disperser, and a photographic film as detector (Colthup et al., 1975; Kohlrausch, 1943). In modern commercial instruments, polarized laser light sources in the UV, visible, and IR are used to excite molecular samples, because of the high intensity and narrow bandwidth of wavelengths that are emitted (monochromaticity), and multi-channel charge-coupled devices (CCD) are generally used as detectors. Their combination, together with notch holographic filters to eliminate the Rayleigh line, results in more intense Raman scatter, with considerably reduced measuring time in obtaining high
10
11 12 12
12 11 13 14 15 a,b
vs = very strong; m = medium; w = weak; sh = shoulder; * Broad bands of several hundreds of cm− 1; 1 Burke, 2001; 2 Herzberg, 1945; 3 Rosso and Bodnar, 1995; 4 Herzberg, 1950; 5 Brunsgaard-Hansen et al., 2002; 6 Dubessy et al., 1988; 7 Fraley et al., 1969; 8 Zotov and Keppler, 2000; 9 Hunt et al., 2011; 10 Ross, 1972; 11 Dubessy et al., 1992; 12 Davis and Oliver, 1972; 13 Schmidt and Watenphul, 2010; 14 Schmidt et al., 2005; 15 a,b Walrafen, 1964, 1967. Ref. = References. Underlined vibrations indicate most intense Raman modes.
velocity of light; Fig. 2). Typically, only Stokes Raman scattered frequencies are presented since they have the same energy but are about 10 times more frequent than their anti-Stokes counterparts. The Rayleigh scattered frequency (i.e., light-source wavenumber) lies at 0 cm − 1 and Raman frequencies are expressed as relative wavenumbers, or Raman shifts. On this scale, frequencies correspond to the energy levels of different molecular vibrations and are independent from the wavelength of the light source: a mode at 464 cm − 1 will occur whether the light source wavelength is 514.5 or 632.8 nm.
Fig. 5. Raman spectra and relative wavenumbers of most common gaseous fluid species in fluid inclusions. Note that the hypothetical CO2 Raman band at 1340 cm− 1 is really two bands at 1285 and 1388 cm− 1, see text.
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Fig. 6. Raman spectroscopy applied to CO2 density measurement. a) Main spectral features of CO2 fluids, which consist of the two bands of the Fermi doublet, bounded by the hot bands. The distance between the Fermi doublet (Δ) depends on fluid density. b) Superdense CO2 fluid inclusions (d N1.178 g/cm3) spectral features, including: i) increased Δ (≥106 cm− 1), ii) shifting of bands to lower wavenumbers, iii) increased band intensity ratio, iv) broadened band bases, and v) flattened hot bands (van den Kerkhof and Olsen, 1990); analyzed fluid inclusions are in pyroxenes from peridotite xenoliths, Hawaii; modified from Frezzotti and Peccerillo (2007). c) CO2 density as a function of Δ (cm− 1), as derived from the equations of: 1) Rosso and Bodnar (1995), 2) Kawakami et al. (2003), 3) Yamamoto and Kagi (2006), 4) Song et al. (2009), 5) Fall et al. (2011), and 6) Wang et al. (2011). The inset shows that the maximum difference in CO2 densities derived from the different equations is about 0.1 g/cm3; redrawn and modified from Wang et al. (2011).
signal to noise spectra (i.e., tens of seconds), and low detection limits. A detailed description of the different instrumental set up can be found in scientific Journals (e.g., Vibrational Spectroscopy, Elsevier; and Journal of Raman Spectroscopy, Wiley) and in the web at the pages of single manufacturing companies. Fluid inclusion analysis is based on the same fundamental principle: the laser excites the molecules to generate scattering. Raman
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microspectrometers are the common analytical set up, where the excitation of the sample and collection of the scattered light at a 180° angle (backscattering) are achieved using a ordinary optical microscope focused within single fluid inclusions by means of high-magnification objectives (50× or 100×). Instruments offer perfect visualization of the subsurface of samples and of the laser spot, which makes easy the choice of the appropriate inclusion to be analyzed. The volume of the analyzed sample (spot size) depends mostly on the numerical aperture (N.A.) of the objective, and on the excitation wavelength. As an example, for a 514.5 nm excitation source and a 100× magnification objective with N.A.= 0.9, the spot size is 1 × 1 × 5 μm3. Thick double-polished sections are easily studied and require no special preparation. Fluid inclusions can be studied down to 1 μm diameter in situ, where microstructures are preserved and the different populations of fluid inclusions can be discriminated. This is possible because of the confocal arrangement of the optical pathway which allows a good spatial resolution perpendicular to the optical axis, as well as along the optical axis of the microscope (depth) (see, Nasdala et al., 1996, 2004). However, the depth resolution degrades with increasing optical penetration depth, therefore it is better to analyze fluid inclusions not deeper than 30 μm within a sample. The choice of laser wavelength influences the performance of the spectrometer. The characteristics of each laser are different, so that no laser may be ideal for every fluid inclusion analysis. In general, the optical power of the laser line and the efficiency of Raman CCD detectors tend to increase with decreasing wavelength. However, the cost of the laser, the likelihood of fluorescence (see below), and the risk of sample heating increase as well. The most popular choices are: (1) the green light Ar ion (λ = 514.5 nm) water- or air-cooled; (2) the blue light Ar ion (λ = 488 nm) air-cooled; and (3) the red light He\Ne (λ = 632.8 nm). Raman microspectrometers can be equipped with a programmable x–y microscope stage which allows sample areas to be mapped in the same way as with EDS and WDS microprobes. Single spot spectra are collected by multiple steps within a grid pattern, as illustrated in Fig. 4a. Each analyzed point contains the information of a whole spectrum (Fig. 4b). Generated Raman maps are chemical or structural images where integrated areas of single bands or band ratios, characteristics for the presence of a certain chemical species in a composite sample, are illustrated (Figs. 4c, d, e). The x–y resolution in a map depends on the distance between the single measuring points, while the depth resolution along z is determined by the confocal instrument settings (see above). The best resolution is achieved by setting the distance between two measuring points smaller than the laser spot size (“oversampling”). By increasing the distance between two spots, the spatial resolution decreases, but larger areas can be analyzed in a shorter time. Spatially resolved Raman spectra can be used to identify the distribution of fluid or mineral species within single fluid inclusions (Frezzotti et al., 2011; Korsakov et al., 2011). Fluorescence and the presence of overlapping bands from host mineral are possible competing effects during analysis, since they often overpower and conceal the weak Raman features from the fluid inclusions. Fluorescence generally appears as a very broad background, often much more intense than the Raman scattering. This effect may commonly arise from epoxy used to embed or polish the rock sections and can be easily eliminated using non-fluorescent epoxies and/or cleaning the sample. However, fluorescence can also be emitted by fluids contained in inclusions (e.g., hydrocarbons) or by the surrounding host mineral (e.g., Fe-bearing minerals). These last cases are much more difficult to cope with. Increasing the wavelength of the light source is a way of overcoming fluorescence: red or nearinfrared lower lasers (λ = 630–1060 nm) should not, in principle, give rise to fluorescence (Carey, 1999). Another practical method to mitigate a fluorescent background consists in repeating spectral accumulations for several times in order to bleach out this effect by protracted exposure to laser light (photo-bleaching).
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Fig. 7. Quantitative Raman analysis of H2 and CH4 contained in the gas bubble of an aqueous fluid inclusion in vesuvianite from rodingites, western Italian Alps (Ferrando et al., 2010). Relative mole% of H2 and CH4 in the gas bubble is calculated with Eq. (1) based on band area integration, and considering the relative Raman cross sections (σ) and the instrumental efficiency (ζ) at the wavenumbers of H2 and CH4. (σ of CH4 is 3.5 times higher than of H2; Burke, 2001).
Interpretation of spectra of crystalline phases is often complicated, due to the fact that Raman scattering intensity depends upon lattice orientation. Consequently, variations of band intensity ratios should be taken into account in the analysis of most minerals. Knowledge of the orientation of main crystallographic axes, and/or repetition of analysis after 90° rotation to get random orientations is helpful in mineral identification (Nasdala et al., 2004). In addition, due to lattice geometries, some minerals are very weak Raman scatterers. Unfortunately, among these there are major chloride species (e.g., NaCl, KCl, and CaCl2), which represent relevant constituents of aqueous fluid inclusions. The intensity of the Raman scattering can vary by many order of magnitudes depending on the nature of the molecules. Detection limits for single components within a single fluid inclusion depend on several contributing factors, including fluid inclusions size and geometry (i.e., number of molecules of the analyzed constituent), nature of the other constituents in fluid inclusions, and analytical conditions (e.g., intensity of the laser light, depth of the inclusion in the analyzed sample, etc.). Several approaches can be used, and they will be discussed in the following sections. 4. Gaseous fluids A custom application of Raman spectroscopy to fluid inclusion analysis is the qualitative identification of major gaseous fluid components. The characterizing Raman bands for most important geological fluids are reported in Table 1 and Fig. 5. Most gasses show a single symmetric stretching strong band, whose wavenumber is traditionally reported at ambient P–T conditions, since a progressive slight wavenumber downshift is known to occur with increasing fluid density (Burke, 2001; van den Kerkhof, 1988b). Early work on fluid inclusions allowed to recognize CO2, CH4, and N2 as relevant geological fluids (e.g., Dubessy et al., 1989; Frezzotti et al., 1992; Touret, 2001; van den Kerkhof, 1988a,b, 1990). H2S,
COS, SO2, CO, H2, NH3 and O2 have also been detected in appreciable amounts in some fluids (Bény et al., 1982; Ferrando et al., 2010; Frezzotti et al., 2002; Giuliani et al., 2003; Grishina et al., 1992; Peretti et al., 1992; Siemann and Ellendorff, 2001; Tsunogae and Dubessy, 2009). Identification of hydrocarbons heavier than CH4 is also possible (e.g., Guilhaumou, 1982; Hrstka et al. 2011; Makhoukhi et al., 2003; Munz, 2001; Orange et al., 1996; Pironon, 1993; Pironon and Barrès, 1990; Potter et al., 2004; Rossetti and Tecce, 2008; Schubert et al., 2007; Wesełucha-Birczyńska et al., 2010), although fluorescence often does not allow conventional analysis (see e.g., Pironon et al., 1998).
4.1. CO2 fluids The Raman spectrum of molecular CO2 shows two strong bands at 1285 and 1388 cm − 1, and two symmetrical weak bands below 1285 and above 1388 cm − 1, the so-called hot bands (Colthup et al., 1975; Dhamelincourt et al., 1979; Dubessy et al., 1999; Rosasco et al., 1975; Rosso and Bodnar, 1995; van den Kerkhof and Olsen, 1990). The two sharp bands appear because of a resonance effect, proposed by Fermi (1931) in order to explain the doublet structure in the region of CO2 symmetric stretching vibration. A small peak at 1370 cm − 1 is the 13CO2. Fig. 6a and b shows examples of spectra of CO2 fluid inclusions having different densities. The distance between the Fermi doublet (Δ, in cm − 1) is proportional to fluid density (Garrabos et al., 1980; van den Kerkhof, 1988b; Wang and Wright, 1973). Several equations (e.g., Fall et al., 2011; Kawakami et al., 2003; Rosso and Bodnar, 1995; Song et al., 2009; Wang et al., 2011; Yamamoto and Kagi, 2006) have been proposed to calculate the density (d) of pure CO2 fluid inclusions based on the distance between the Fermi doublet Δ (Fig. 6c). CO2 density can be determined in the range from 0.1 to 1.24 g/cm 3 with an accuracy better than 5% (Wang et al., 2011).
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band intensities on fluid density. Nevertheless, Raman mass-spectroscopy remains a particularly attractive prospective since it could permit to analyze samples several order of magnitude smaller than generally used by mass-spectrometry. 4.2. Gaseous mixtures When fluid inclusions consist of mixtures of two or more gas species, the relative molar fractions of the end-members can be calculated. The prerequisite to quantitative Raman analysis is the knowledge of two essential parameters (cf., Burke, 2001): (1) the Raman scattering cross-section, which indicates the activity of a certain gas component in a mixture (Schrötter and Klöckner, 1979); and (2) the variation of the instrumental efficiency at the different wavenumbers for a specific excitation wavelength. The first parameter is dependent on the laser excitation wavelength. A list of major gas species crosssections for the 632.8 nm red light (e.g., He\Ne laser source), the 514.5 nm green light (Ar-ion laser source), and the 488 nm blue light (Ar-ion laser source) is reported in Burke (2001). The second parameter requires an empirical calibration for each Raman microspectrometer, by measuring synthetic or natural gas-mixture standards of known composition and density (Beeskow et al., 2005; Chou et al., 1990; van den Kerkhof, 1988b). The molar fraction (X) of end-member components in a gas mixture can be obtained using the following equation (Beeskow et al., 2005; Burke, 2001; Dubessy et al., 1989; Morizet et al., 2009; Nasdala et al., 2004; Wopenka and Pasteris, 1986, 1987):
Xa ¼
Fig. 8. Raman spectra of water contained in fluid inclusions, presenting examples for: a) low-salinity (b 1 NaCl wt.%) liquid water, b) high-salinity (20 NaCl wt.%) liquid water, and c) optically-hidden water in a CO2-rich fluid inclusion, peridotite from Ethiopia.
We observe a very good agreement between density data derived from Raman spectroscopy and from microthermometry, also for CO2 fluids containing minor amounts of other gaseous species (i.e., b5 mol% CH4 or N2; Frezzotti and Peccerillo, 2007). These two methods are complementary for the characterization of fluid inclusion composition and densities. Although the precision of microthermometric measurements is higher, the Raman densimeter permits to analyze very small fluid inclusions (b5 μm in diameter), and/or low density fluids. The relative intensities of the 13CO2 and the associated 12CO2 band (Fig. 6a) have been used to calculate the carbon isotope ratios in single fluid inclusions. The development of Raman as a massspectroscopy, however, is still at a very early stage of development; reported δ 13C determinations have uncertainties ≥ 20‰ (Arakawa et al., 2007; Dhamelincourt et al., 1979), and consent only to discriminate between inorganic and organic CO2 at best. This is due to the difficulty in controlling all parameters influencing intensity of scattering, probably including a dependence of 13CO2 and 12CO2
Aa σa ζa ∑ σAiζ i i
ð1Þ
where Xa, Aa, σa and ζa, are the molar fraction, the band area, the Raman cross-section and the instrumental efficiency for gas a, respectively, while ΣAi, σi, and ζi represents the sum of values for all gas species in the fluid inclusion. In order to get reliable quantitative analyses, no change in the analytical conditions should be made during measurements (i.e., laser intensity, focus, number of accumulations, and accumulation time). Accuracy of analyses is reported better than 5% (Pasteris et al., 1988; van den Kerkhof, 1988b). Note that when CO2 fluids are involved, the sum of the two bands forming the Fermi doublet should be used (Dubessy et al., 1989). In Fig. 7 is reported for example an aqueous fluid inclusion contained in vesuvianite from vein in rodingite from Bellecombe, Italian Western Alps (Ferrando et al., 2010). In the gas bubble, bands of CH4 and H2 have been obtained using an Ar-ion laser (λ = 514.5 nm) as the excitation source. The integrated measurements of the single gas Raman band area (A) are reported along with the relative cross-sections (σ) of H2 and CH4 and the instrumental efficiency (ζ) of the Raman spectrometer at 2917 and at 4156 cm − 1. Using Eq. (1), the resulting composition of the gas phase in the Alpine inclusion is equal to 82 mol% H2 and 18 mol% CH4. In more complex gaseous–aqueous fluid mixtures, the quantitative analysis of the different components is much more difficult and often requires measurements at high temperatures. Empirical equations for (semi)quantitative analyses of H2O-CH4 ± NaCl and H2O-CO2 ± NaCl systems have been proposed based on relative band areas in spectra (e.g., Azbej et al., 2007; Guillaume et al., 2003; Lu et al., 2007). In these complex fluid mixtures, analysis should include detection of gasses dissolved in water (e.g., CO2 or CH4), and the characterization of clathrate hydrates (ice-like compounds formed from CO2, CH4, or N2 and water under low-T and high-P conditions; Azbej et al., 2007; Dubessy et al., 2001; Fall et al., 2011; Orange et al., 1996; Pironon et al., 1991) .
8
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Fig. 9. Raman spectroscopy applied to solute analysis in aqueous fluids. a) Band of SO42− ions in a fluid inclusion in feldspar from syenite, Sabatini volcanic district, Italy. b) Bands of native sulfur in a fluid inclusion in orthopyroxene from peridotite, Italy. c) Bands of CO32− and HCO3− ions in a fluid inclusion from ultra-high pressure metamorphic rocks, western Italian Alps. d) Bands of Si(OH)40, and deprotonated H4-nSiO4n− monomers in a fluid inclusion from metamorphic rocks from western Italian Alps. The Raman modes of anhydrite (Anh), quartz (Qtz), and Mg-calcite (MgCc) daughter minerals are also shown. Raman bands of host minerals are marked with asterisks. c and d: modified from Frezzotti et al., 2011.
5. Aqueous fluids The Raman modes of water consist of two main O\H stretching modes at 3657 and 3756 cm − 1 and one very weak H\O\H bending mode at 1595 cm − 1 (Carey and Korenowski, 1998; Fraley et al., 1969). However, the Raman spectrum of liquid H2O consists of several large overlapping bands in the OH stretching region from 2750 to 3900 cm − 1 (Fig. 8a and b), and of a weak bending mode at ~ 1630 cm − 1 (Walrafen, 1964, 1967). Reduced to minimum terms, such spectral complexity results from the strong interactions of a single water molecule with the neighboring molecules, forming intermolecular O\H\O bridging networks (Hare and Sorensen 1992; Sun, 2009). The characteristics of the Raman spectrum of water have been used to prove the presence of H2O in small CO2 fluid inclusions (b5–10 μm in size; Frezzotti and Peccerillo, 2007; Frezzotti et al., 2010; Hidas et al., 2010). Here, a water film of a thickness of 0.2 μm wrapping the CO2 fluid cannot be identified with optical techniques, although it may correspond to as much as 10–20 mol% of H2O. A detailed description of the method can be found in Dubessy et al. (1992) and in McMillan et al. (1996). One example is illustrated in Fig. 8c from CO2 fluid inclusions in peridotites from Ethiopia. The dominant spectral features of optically unnoticed water are the vibrational bands at 3658 and 3750 cm − 1 characteristic of OH − stretching vibrations for isolated molecules of H2O (i.e., lack of significant H intermolecular bonding). Raman spectroscopy allows determination of the appropriate water content of melt inclusion glass in minerals of granites and pegmatites (e.g., Behrens et al., 2006; Chabiron et al., 2004; Di Muro et al.,
2006; Severs et al. 2006; Thomas, 2000; Thomas and Davidson, 2006; Thomas et al., 2008b; Zajacz et al., 2005). Note that, during cooling of a natural water-rich melt inclusions, often SiO2 is deposited on the inclusion wall and makes an apparent aqueous fluid inclusion from what was primary a melt inclusion (Thomas et al. 2011a). 5.1. Analyses of solutes: monoatomic ions Qualitative and (semi)quantitative Raman analysis of water-rich fluid inclusions typically focuses on determination of solutes. Monoatomic charged cations, such as Na +, K +, Ca 2+, and Mg 2+ have too weak Raman spectra to be analyzed in fluid inclusions. A way to obtain spectra is by nucleation of salt-hydrates at low temperatures, but this requires the combination of the Raman microspectrometer with a fluid inclusion cooling stage. Spectra are reported for all major salt-hydrates, such as NaCl·2H2O, FeCl3·6H2O, CaCl2·6H2O, MgCl2·12H2O, KCl·MgCl2·6H2O, FeCl2·6H2O, LiCl·5H2O (Bakker, 2004; Baumgartner and Bakker, 2009, 2010; Derome et al., 2007; Dubessy et al., 1982, 1992; Samson and Walker, 2000; Schiffries, 1990). Chlorine ions have the power of breaking certain hydrogen bonds in aqueous solutions. The variation of OH stretching bands induced by different Cl concentrations in aqueous fluid inclusions (Fig. 8a and b) has been intensively investigated with different approaches. Semiquantitative estimation of the salt content in aqueous fluid inclusions requires development of a specific calibration for each spectrometer and it is complementary to measurements of phase transitions at low temperatures by microthermometry (e.g., eutectic and final melting temperatures).
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
9
Table 2 Main Raman vibrations (cm− 1) of selected native elements, halides, sulfides, oxides and hydroxides. Native elements, halides and sulfides Diamond C Graphite C Sulfur S8 Arsenic As
Main vibrations
Ref. 1332 1355
mw 157 w 187
Halite NaCl Sylvite KCl Fluorite CaF2 Cryolite Na3(AlF6) Elpasolite K2NaAlF6 Pyrite FeS2 Marcasite FeS2 Chalcopyrite CuFeS2
m 220 w 246 mw 220 w 225 vs 253
[1] 1580
s 462 w 437
3 4
358
[1]
vw 291 vw 213
[1] m 322 vw 485
135
vs 293
Covellite CuS Blende ZnS
326 387 w 342 s 377 vs 324 s 387 w 322 w 352 w 378
vw 263 w 218 w 274
Galena PbS Oxides and hydroxides
Main vibrations
Rutile TiO2 Anatase TiO2 Brookite TiO2 Spinel MgAl2O4 Magnetite Fe2+Fe23+O4 Hematite Fe2O3 Ilmenite FeTiO3 Gibbsite Al(OH)3 Diaspore AlO(OH) Corundum Al2O3 Goethite α-FeO(OH)
w 139 vs 143 vw 195 s 127 vs 150
2
m 555
vw 641
[1]
mw 620
5
559
1009
6
vs 428
7 7 7
vs 471 w 300 w 310 vs 349
7
w 419
vs 136
m 270
m 238
vs 444
w 639 w 669
[1]
[1]
Ref.
w 395 s 247
w 193
s 318 w 366 w 313
w 514 w 412
mw 645
vs 408
mw 666
w 306 s 223 vs 290 w 232 mw 242 m 255
w 242 mw 299
s 538 vs 409 w 498
w 920
9 w 768 10 11 vs 1313
vs 685
m 322 vs 380 w 331
vs 538 vs 569 vs 448
mw 378
vs 417
[1] 8
vs 668 m 609
mw 373
vs 389
vs 609 m 696 mw 638
12 13
w 979
14 3
m 644 m 547
mw 681
w 750
15 12
vs = very strong; s = strong; m = medium; mw = medium weak; w = weak; vw = very weak; [1] = Raman Spectra Database, Siena Geofluids Lab (http://www.dst.unisi.it/geofluids/ raman/spectrum_frame.htm); 2 Wopenka and Pasteris, 1993; 3 Giuliani et al., 2003; 4 Thomas and Davidson, 2010; 5 Nazmutdinov et al., 2010; 6 R. Thomas, pers. comm.; 7 Mernagh and Trudu, 1993; 8 Clark et al., 2007; 9 Yanqing et al., 2000; 10 Slotznick and Shim, 2008; 11 Shebanova and Lazor, 2003; 12 Kuebler et al., 2006; 13 Rull et al., 2007; 14 Ruan et al., 2001; 15 Xu et al., 1995; Ref. = References.
Mernagh and Wilde (1989) proposed a formula to calculate NaCl wt.%, with a relative error of 15%: 0
1
2ðY−X Þ B X=Y C NaClwt:% ¼ α @2− I 3400 cm−1 A−β ð Þ XþY Ið3200 cm−1 Þ
ð2Þ
where X is equal to the integral of the OH− band from 2800 to 3300 cm− 1, Y is equal to the integral from 3300 to 3800 cm− 1, I is the intensity at the specified wavenumbers, and α and β are regression parameter specific for each spectrometer (cf., McMillan et al., 1996). The idea behind Eq. (2) was to link the shape of the two halves forming the OH stretching band to the amount of Cl− in solution. More recently, calibration curves were expanded also to LiCl, KCl, MgCl2, CaCl2, and to
10
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Table 3 Main Raman vibrations (cm− 1) of selected carbonates. Carbonates
Calcite CaCO3 Aragonite CaCO3 Vaterite CaCO3 Mg-Calcite (Ca,Mg)CO3 Magnesite MgCO3 Dolomite CaMg(CO3)2 Natrite Na2CO3 K-Carbonate K2CO3 Zabuyelite Li2CO3 Siderite (Fe,Mg)CO3 Rhodochrosite MnCO3 Strontianite SrCO3 Witherite BaCO3 Cerussite PbCO3 Smithsonite ZnCO3 Nahcolite NaHCO3 Kalicinite KHCO3 Hydrated carbonates
Malachite Cu2(OH)2(CO3)
Azurite Cu3(OH)2(CO3)2
Artinite Mg2(OH)2(CO3)·3H2O Hydromagnesite Mg5(CO3)4(OH)2·4H2O Dypingite Mg5[(OH)(CO3)2]2·5H2O
Dawsonite NaAl(CO3)(OH)2 Thermonatrite Na2(CO3)·H2O Trona Na3H(CO3)2·2H2O Gaylussite Na2Ca(CO3)2·5H2O
CO32− vibrations
Ref. ν1
ν3
vs 1085
vw 1435
[1]
vs 1085
vw 1463
[1]
w 740 w 750 mw 714
vs 1090 s 1074 vs 1087
vw 1465
2
vw 1438
[1]
w 738
vs 1094
w 1444
3
w 725
vs 1097
vw 1443
[1]
w 698
vs 1078
w 1428
4
m 697
m 1405
5
w 712
vs 1064 sh 1043 vs 1091
w 1459
4
sh 738
vs 1090
vw 1442
[1]
mw 718
vs 1087
vw 1416
[1]
w 700
vs 1073 vw 1057
vw 1450
[1]
w 692
vs 1059
w 1420
[1]
vs 1056
s 1378
[1]
w 731
vs 1093
mw 1408
[1]
mw 688
vs 1048 m 1271 vs 1028 mw 1277
w 1432
[1]
T
ν4
s 284 mw 156 s 154 mw 206 m 301 sh 118 s 281 mw 155 s 329 mw 212 s 299 ms 176
mw 711
s 141 m 192 mw 96 m 301 w 194 s 289 mw 185 mw 149 mw 183 sh 250 s 136 m 152 w 227 s 150 mw 180 sh 215 m 303 mw 196
w 704
m 682
ν2
vw 854
m-w 839
w 635 w 673 CO32− vibrations
4
OH−
Ref.
T
ν4
ν1
ν3
vs 154 vs 178 vs 434 ms 272 ms 537 s 397 m 246 mw 170 mw 279 s 147 s 173 w 472 m 184 m 202 m 232 mw 203 mw 249 w 311 w 434 ms 189 m 260 mw 587 s 156 m 185 w 230 mw 140 mw 185 w 225 s 164 sh 265
w 721
sh 1098
vs 1492
vs 3468 mw 3386
[1]; 6
vs 1095
vw 1457
vs 3453 sh 937
[1]; 6
vs 3593 s 3229 s 3030 n.a.
7 8
w 704
w 727
w 723
vs 1094
vs 1119
sh 1487
vs 1122 mw 1092
mw 1447
vs 3648 m 3421 mw 3515
8
vs 1091 w 1065
mw 1505
vs 3282 m 3250
9
vs 1062
sh 1432
n.a.
[1]
vs 1060
w 1430
n.a.
[1]
vs 2944 s 3334
[1]; 10
vs 1071
7
ν1 = Symmetric stretching vibration; ν2 = Out-of-plane bending vibration; ν3 = Antisymmetric stretching vibration; ν4 = In-plane bending vibration; T = Translational lattice modes; OH− = OH stretching vibrations; vs = very strong; s = strong; ms = medium strong; m = medium; mw = medium weak; w = weak; vw = very weak; sh = shoulder; [1] = Raman Spectra Database, Siena Geofluids Lab (http://www.dst.unisi.it/geofluids/raman/spectrum_frame.htm). 2 Carteret et al., 2009; 3 Gillet, 1993; 4 Thomas et al., 2011a,b; 5 Koura et al., 1996; 6 Frost et al., 2002; 7 Edwards et al., 2005; 8 Frost et al., 2008; 9 Frost and Bouzaid, 2007; 10 Frost and Dickfos, 2007; n.a. = not analyzed; Ref. = References.
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
11
Table 4 Main Raman vibrations (cm− 1) of selected sulfates. SO42− vibrations
Sulfates
Ref.
ν2
ν4
ν1
ν3
Anhydrite CaSO4
mw 430 mw 500
vs 1018
mw 1131
2
Mg-sulfate MgSO4
ms 451 ms 475 ms 499 w 452 w 469 w 485
vs 1023 s 1053
ms 1136 w 1220 vw 1256 w 1103 w 1153 m 1106 m 1140
3
vs 1002
m 1125
[1]
w 1093 w 1109 w 1145 m 1104 mw 1093 ms 1156 mw 1190 w 1143
5
w 1160 vw 1068
[1]
Sulfohalite Na6(F,Cl)(SO4)2 Arcanite K2SO4
m 471
w 611 w 629 w 676 s 608 vw 681 vw 697 w 621 w 632 m 618 m 644 mw 620 mw 633 mw 644 m 634
mw 457
mw 622
vs 983
Aphthitalite (K, Na)3Na(SO4)2 Celestine SrSO4 Barite BaSO4 Anglesite PbSO4
m 457 mw 447 m 452
s 619
vs 984 vs 1000
s 461
ms 656 vw 627 w 617
mw 438 mw 450
w 608 vw 641
vs 978
Thenardite Na2SO4 Glauberite Na2Ca(SO4)2 Burkeite Na6(CO3)(SO4)2
Hydrated sulfates
mw 451 w 474
vs 994 vs 1002 vs 994 m 1065*
SO42− vibrations ν2
ν4
ν1
ν3
Gypsum CaSO4·2H2O Epsomite MgSO4·7H2O
s 494 m 414 mw 447
w 621
vs 1008
w 1142
vw 612
vs 984
Exahydrite MgSO4·6H2O Pentahydrite MgSO4·5H2O
w 445 w 466 m 447 vw 371
vw 610
vs 984
vw 602
vs 1005
vw 1061 vw 1095 vw 1134 w 1146 vw 1085 vw 1106 vw 1159
Starkeyite MgSO4·4H2O
vw 401 vw 462
vw 565 vw 616 vw 664
vs 1000
Sanderite MgSO4·2H2O Kieserite MgSO4·H2O K-Alum KAl(SO4)2·12H2O Alunite KAl3[(OH)3(SO4)]2 Syngenite K2Ca(SO4)2·H2O Görgeyite K2Ca5(SO4)6·H2O
m 447 w 492 m 436 w 481 mw 455 w 442 mw 509 w 485 mw 474 w 494 m 480 w 433 w 440 w 457 m 458
w 597 w 630 m 629
vs 1034
mw 614
vs 989 s 974 vs 1026
w 642 w 662 m 631 w 595 w 602 w 654 mw 627
vs 983 s 1007 vs 1013 vs 1005 w 1085
mw 1117 w 1215 mw 1130 w 1104 mw 1190 w 1079 w 1142 w 1168 w 1108 w 1115 w 1162
vs 989
w 1129
vs 448 mw 474
vs 626 mw 647
vs 1004
sh 1104
Mirabilite Na2SO4·10H20 Cesanite Na3Ca2(OH)(SO4)3
mw 654
[1] 4
vs 988
vs 1046
[1]
w 1156 vw 1086 vw 1116 vw 1186 m 1164
[1] [1] [1]
OH−
Ref.
vs 3405 mw 3491 vs 3303 s 3425
[1]; 6 3
vs 3428 m 3258 vs 3391 vs 3343 m 3553 m 3494 m 3289 vs 3427 s 3481 m 3558 m 3331 vs 3446 m 3539 vs 3297
3
vs 3396 m 3072 vs 3509 vs 3482 vs 3301 s 3378 vs 3525 m 3580
7
vs 3506 m 3340 n.a.
3
3
3 3
[1]; 8 [1]; 9 10
11 [1]
ν1 = Symmetric stretching vibration; ν2 = Out-of-plane bending vibration; ν3 = Anti-symmetric stretching vibration; ν4 = In-plane bending vibration; * = Symmetric stretching vibration of CO3 group. Peak intensities as in Table 3. [1] = Raman Spectra Database, Siena Geofluids Lab (http://www.dst.unisi.it/geofluids/raman/spectrum_frame.htm); 2 Thompson et al., 2005; 3 Wang et al., 2006; 4 Korsakov et al., 2009; 5 Montero and Schmolz, 1974; 6 Kloprogge and Frost, 2000; 7 Barashkov et al., 2004; 8 Frost et al., 2006; 9 Kloprogge et al., 2002; 10 Kloprogge et al., 2004; 11 Hamilton and Menzies, 2010; n.a. = not analyzed; Ref. = References.
12
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Table 5 Main Raman vibrations (cm− 1) of selected phosphates and borates. PO43− vibrations
Phosphates
Ref.
ν2
ν4
ν1
ν3
Apatite Ca5(PO4)3(OH,F,Cl) Fluorapatite Ca5(PO4)3F
w 428 w 446 mw 432 w 449
vs 960
w 430
983
425
584 595 610
w 1026 w 1040 m 1053 mw 1081 w 1042 mw 1039 w 1127 1005
[1]
Chlorapatite Ca5(PO4)3Cl Herderite CaBePO4 (F,OH) Triplite (Mn,Fe,Mg,Ca)2(PO4)(F,OH) Berlinite AlPO4 Amblygonite LiAl(PO4)F Lacroixite NaAl(PO4)F Na-phosphate Na3PO4
w 578 w 588 m 592 w 608 mw 581 w 581
980
1034
1111
1229
1011
4; 5 4; 5 4
1001
4
910 942 993 1059
5
601 644 609 623 524 544
391 482 344
Xenotime (Y,Yb)PO4 Monazite (La,Ce,Nd,Th)PO4
485
611 630 741 642
m 466
m 620
998 1056 vs 987
2
3 4
1100 1136
5
1394
5
mw 1054
6
Main vibrations
Ref. 428 475 401 415 475
Metaboric acid HBO2 (monoclinic) Metaboric acid HBO2 (orthorhombic) Li-metaborate LiBO2 Sassolite H3BO3 Hambergite Be2BO3(OH,F) Na-tetraborate Na2B4O7·10H2O Li-tetraborate Li2B4O7·5H2O
vs 963
437 461
Lazulite (Mg,Fe)Al2(PO4)2(OH)2
Borates
vs 965
782
518 533 595
5 809
5
713 w 500
1419 vs 880
vs 153
Borax Na2B4O5(OH)4·8H2O Ca–Mg-hexaborates CaB6O10, MgB6O10 with 4 to 7.5 H2O Hydroboracite CaMgB6O11·6H2O
181 257
Cs-Ramanite CsB5O8·4H2O Rb-Ramanite RbB5O8·4H2O
m 98 mw 293 mw 101
7 w 992
385
461
576
756
852
391
446 493
543
772
845 896
344
405 463
571
776
322 383 398
524 548 564 vs 548 w 508 vs 554
634 638 641 606
753
852 855 861 837 876
4
948
943 997 953 964
7 1036
5
1028 1097 1352
5
5 4
5
m 768
m 907
8
w 765
w 914
8
ν1 = Symmetric stretching vibration; ν2 = In-plane bending vibration; ν3 = Antisymmetric stretching vibration; ν4 = Out-of-plane bending vibration. Peak intensities as in Table 3. [1] = Raman Spectra Database, Siena Geofluids Lab (http://www.dst.unisi.it/geofluids/raman/spectrum_frame.htm); 2 Penel et al., 1997; 3 Kuebler et al., 2006; 4 Rickers et al., 2006; 5 R.Thomas, pers. comm.; 6 Silva et al., 2006; 7 Thomas and Davidson, 2010; 8 Thomas et al., 2008a,b; Ref. = References.
other more complex salt systems (Dubessy et al., 2002; Sun et al., 2010). The methods described above are all similar, they only differ in the selected bands of water in the OH-stretching region taken as standards. 5.2. Analyses of solutes: polyatomic ions and molecules Polyatomic charged anions have Raman spectra characterized by the presence of one or more bands (Table 1). Band area and
intensity, although proportional to the solute concentration, cannot be linearly transformed into absolute concentrations, since these are considerably influenced also by measurement conditions (e.g., laser power, optical arrangement, etc.; McMillan et al., 1996; Nasdala et al., 2004). Semi-quantitative analysis of polyatomic solutes in fluid inclusions has been in some cases possible based on relative band-intensity ratios, using selected bands of water as standard. The application of intensity ratios eliminates the influence of measurement conditions. Note that during analyses high laser power
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
13
Table 6 Main Raman vibrations (cm− 1) of selected orthosilicates and tectosilicates. Orthosilicates
Main vibrations
Ref.
Forsterite (Mg0.9,Fe0.1)2SiO4
227
303
Pyrope Mg3Al2Si3O12 Almandine Fe32+Al2Si3O12
211 170
216
Spessartine Mn3Al2Si3O12 Grossular Ca3Al2Si3O12
175
221
181
247 280
Uvarovite Ca3Cr2Si3O12
176
242 272
370
Andradite Ca3(Fe3+, Ti)2Si3O12
174
236
Kyanite Al2SiO5
142
Sillimanite Al2SiO5 Andalusite Al2SiO5 Zircon ZrSiO4
235 293 202 225
Tectosilicates
Main vibrations
Orthoclase KAlSi3O8
157 177 197 159 178 199 163
Microcline KAlSi3O8 Sanidine KAlSi3O8 Albite NaAlSi3O8 Quartz SiO2 Coesite SiO2 Cristobalite SiO2
183 128
116 151 176 114
423
548
608
364
563
650
323 342 370 321 350 373
500 556
1038
3
849 879 827 848 880 828 894
905
1029
3
1007
3
816 842 874
995
3
952
4
325 370
452 494
509 526 590 516 574
302 325 360 386 310
405 419 437 486 456
562
597
708
874
323 361 356
453
553
719
834
669
438
3
907 964 920 992 974
1127
[2]
1065 1111 1008
[2] [2]
Ref. 514 583
263 267 286 284
455 475
514
462 475 457 480 402 464 485 427 466
230 273 286
3
420
458 477
204 269
[1]
1066
863 897 630
921 964 902 928 916
500 552 550
284
210 292 206 265
824 856 882 871
356
326 355
751
814
749
813
514
767
813
508
764
816
520
521
420
651
608 698 785
792
967
1035 1062
1137
[1]
1007
1128 1142
[1]
1123
[1]
807
1032 1098 1066
1161
[2]; 5 6
815 837
1036 1065
1144 1164
977
1075
6
[2]
[1] = Raman Spectra Database, Siena Geofluids Lab (http://www.dst.unisi.it/geofluids/raman/spectrum_frame.htm); [2] = Raman Spectra Database Lyon (http://www.ens-lyon.fr/ LST/Raman). 3 Kolesov and Geiger, 1998; 4 Mernagh and Liu, 1991; 5 Sendova et al., 2005; 6 Palmeri et al., 2009. Ref. = References.
could result in heating the inclusion fluid with consequent possible changes in the speciation of ions. The study of the speciation of sulfur in aqueous solution to determine the redox potential (H2S/SO42−) and pH range (SO42−/HSO4−; HS−/H2S) of geological fluids represents one of the first applications of Raman microspectroscopy to fluid inclusion research (Boiron et al. 1999; Dubessy et al., 1983, 1992, 2002; Rosasco and Roedder, 1979). Sulfate ions give rise to a main S\O stretching band at ~980 cm− 1 (Fig. 9a) and to two additional weak bands around 620, and 450 cm− 1 (Table 1; Ross, 1972; Schmidt, 2009). Only the 980 cm− 1 band is generally strong enough to be observed in fluid inclusions, and has very low detection limits (0.01–0.05 mol/kg; Dubessy et al. 1982, 1983; Rosasco and Roedder, 1979). Bisulfate ions (HSO4−) can be identified by their main S\O and S\OH stretching modes at ~1050 and 890 cm− 1, respectively (Table 1). Hydrogen sulfide (H2S0 and HS−) is characterized by S\H stretching modes in the 2570– 2590 cm− 1 range.
The carbonate ion CO32− fundamental stretching mode is expected at 1064 cm − 1. Other less intense bands at ~1380, and 684 cm − 1 may be observed in concentrated solutions. HCO3− has a very strong C\OH stretching mode at ~1017 cm − 1, and a less intense C\O stretching mode at ~ 1360 cm − 1 (Table 1). Raman studies of carbonates and bicarbonates in solution were initiated by Davis and Oliver (1972) and Dubessy et al. (1982), although these ions were not detected in fluid inclusions at that time. Absence was attributed mainly to their low Raman scattering compared, for example, to that of sulfate ions, and to their relatively low solubility in geological fluids (cf., Burke, 2001; Dubessy et al., 1982; McMillan et al., 1996). More recently, there has been increasing Raman evidence for significant HCO3−(aq) and CO32−(aq) in fluid inclusions (Fig. 9c) mainly from pegmatites, ore deposits, and high pressure metamorphic rocks (Frezzotti et al., 2011; Hrstka et al., 2011; Thomas et al., 2006, 2009a,b, 2011a; Xie et al., 2009). CO32−(aq) concentrations as low as 0.36 wt.% can be measured using a modified technique by Sun and Qin (2011) (R. Thomas,
14
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
Table 7 Main Raman vibrations (cm− 1) of selected phyllosilicates and inosilicates, both single and double chains. Phyllosilicates
Main vibrations
Biotite K2(Mg,Fe2+)6-4(Fe3+,Al,Ti)0-2(Si6-5Al2-3O20)(OH,F)4 Muscovite KAl4(Si6Al2O20)(OH,F)4 Phlogopite K2(Mg,Fe2+)6(Si6Al2O20)(OH,F)4 Paragonite Na2Al4(Si6Al2O20)(OH)4
178
Talc Mg6(Si8O20)(OH)4 Clinochlore (Mg, Fe2+)5Al(OH)8(AlSi3O10)
113 196 104 198
178 197 192
549 216 261 279 203 218 272 295
385
407
639
331 372
335 366 358
Chrysotile Mg3Si2O5(OH)4
231
345 389
Antigorite (Mg,Fe2+)3(OH)4Si2O5
230
375
Lizardite Mg3(OH)4Si2O5
233
679
680
717 767 702 754 792
413 465
647
708 756
434
678
786 793
548
914 957
1117 1038 1096 1062
Ref.
3658 3680 3627
2
3673
1018 1055
679
OH−
3477
[1] 3715
[1]
3631
[1]
3677
3
3605 3647 3679 3657
4
620 692
1105
520
683
1044
350 388
510
630 690
1096
343 382 320 389
414
664 684 662
1011
[1]
1009
7
224
667
1040
[1]
229
665
1017
8
Inosilicates
Main vibrations
Enstatite MgSiO3 Diopside CaMgSi2O6 Hornblende (Na,K)0-1Ca2(Mg, Fe2+,Fe3+,Al)5(Si6-7Al2-1O22)(OH,F)2 Pargasite NaCa2Mg4Al3Si6O22(OH)2
237
3658 3687
3703 3718 3745 3709 3729 3774 3708 3723
5; 6 5; 6 5; 6 Ref.
OH− = OH stretching vibrations; [1] Raman Spectra Database, Siena (http://www.dst.unisi.it/geofluids/raman/ spectrum_frame.htm); 2 Kuebler et al., 2006; 3 Fumagalli et al., 2001; 4 Kleppe et al., 2003; 5 Rinaudo et al., 2003; 6 Auzende et al., 2004; 7 Thompson et al., 2005; 8 Downs, 2006. Ref. = References.
pers. comm.). Higher carbonate concentrations can be determined easily. These results are of particular interest since they suggest that alkaline aqueous solutions may represent relevant geological fluids. Raman spectroscopy is a powerful technique to study the speciation of silica in aqueous fluids at different P–T and pH conditions (e.g., Hunt et al., 2011; Newton and Manning, 2003, 2008; Zotov and Keppler, 2000, 2002). In neutral solutions, SiO2 dissolves predominantly as neutral monomers (Si(OH)40) and dimers (Si2O(OH)60) under most crustal and upper mantle P–T conditions. Si(OH)40(aq) can be identified by a
Raman band in the 750–800 cm− 1 region (Table 1). In alkaline fluids, increasing dissociation of monomers and dimers in deprotonated species (e.g., SiO(OH)3−, Si2O2(OH)5−) yields additional Raman bands in the 950–1100 cm− 1 region, as shown in Fig. 9d. B(OH)30 is the predominant boron species in aqueous fluids over a wide range of P–T–pH conditions. The Raman spectrum of B(OH)30(aq) shows a strong band at 877 cm − 1 and an additional weaker band at 495 cm − 1 (Table 1; Janda and Heller, 1979; Schmidt et al., 2005). A method of determining the B(OH)30(aq) concentration in fluid
Fig. 10. Raman spectra of carbon phases in fluid inclusions; a) Diamond in a CO2 fluid inclusion from peridotites, Hawaii; modified from Frezzotti and Peccerillo (2007). b) Graphite in a CO2 fluid inclusion from peridotites, Italy. Excitation light source: Ar ion laser (λ = 514.5 nm). G_G-band, or order band; D_D-band, or disorder band. Note that the Raman wavenumber of the D-band decreases with increasing wavelength of the excitation light source: for example using a He–Ne laser light (λ = 632.8 nm), the graphite D-band is expected at about 1330 cm− 1.
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A catalog of about 140 spectra of minerals which are of interest in fluid inclusion research is presented in Tables 2–7, as a supplement to the web Raman mineral library available at: http://www.dst.unisi.it/ geofluids/raman/spectrum_frame.htm. Each table reports mineral name and formula, a list of the main Raman modes observed, and references. Main vibrations are reported using the ν notation in scattering geometries, where the symmetric stretching vibration (ν1) represents the strongest Raman mode. Reference spectra catalog also includes selected gas and solute species that were discussed above and listed in Table 1. All measured spectra correspond well to spectra reported in literature. Relatively pure phases and/or phases contained within fluid inclusions were measured on a Horiba (Jobin Yvon) Labram spectrometer at the University of Siena, using a water-cooled Ar ion laser (λ = 514.5 nm) as the excitation source. Present catalog intends to provide a first library dedicated to fluid inclusion research. 6.1. Native elements, halides, oxides and sulfides (Table 2)
Fig. 11. Comparison of the Raman spectra of calcite, dolomite, and magnesite in the interval 0–1600 cm− 1. Main CO32− group vibrations are illustrated. ν1 = Symmetric stretching vibration; ν3 = Antisymmetric stretching vibration; ν4 = In-plane bending vibration; T = Translational lattice modes. Calcite, skarn from Vulsini volcanic district, Italy. Dolomite, eclogite from Sulu, China. Magnesite, peridotite from Baldissero, southern Italian Alps.
inclusions has been presented by Thomas (2002), with a minimum detection limit of 0.050 wt.%. Nitrate and phosphate ions have not yet been reported in fluid inclusions, while NaOH(aq) and LiOH(aq) can be present in some ore-forming fluids (Thomas et al., 2011b) 6. Identification of mineral phases: a catalog of reference Raman spectra
Carbon is by far the strongest Raman scatterer and the most studied phase by Raman spectroscopy. In C\O ± H fluid mixtures, precipitation of C (graphite, or diamond at higher pressures) reflects a decrease in fO2 buffer conditions in the fluid–rock system (e.g., redox reactions), often induced by a change in P and/or T. The process has been studied and modeled in natural and synthetic fluid inclusions by various authors (e.g., Frezzotti et al., 1994; Huizenga, 2001; Luque et al., 1998, 2009; Sterner and Bodnar 1984; van den Kerkhof et al., 1991). Fig. 10 reports the spectra of diamond and graphite detected within fluid inclusions. Diamond is characterized by a very strong mode at 1332 cm − 1 (sp 3 bonds; Table 2). Well-crystallized graphite shows one intense bands at 1580 cm − 1 (sp 2 bonds; socalled G-band or order band). In microcrystalline graphite and disordered carbon, presence of defects gives rise to an additional band at 1350 cm − 1 (D-band or disorder band; excitation light source at 514 nm), which increases in intensity with increasing disorder, and to an upshift to 1600 cm − 1 of the G-band (e.g., Wopenka and Pasteris, 1993 and references therein). The area ratio of the order–disorder bands has been proved to represent a reliable geothermometer in natural graphite (i.e., increasing disorder at decreasing temperature; Beyssac et al., 2002; Wopenka and Pasteris, 1993). However, caution should be used in applying the order–disorder geothermometer to graphite contained within fluid inclusions. The crystallinity of graphite precipitated from fluids does not show large variations and it is generally rather high – even at moderate temperatures – unlike what observed in natural graphite (Cesare and Maineri, 1999; Luque et al. 1998, 2009). The solubility of uncharged molecules of S in water is appreciable, and S80 in fluid inclusions (Fig. 9b) has been recognized by the dominant broad bands at 462 (S\S stretching) and 220 cm − 1 (S\S\S bending). Additional minor bands may occur at 153, 187, 246, and 437 cm − 1 (Giuliani et al., 2003). Spectra of chlorides (e.g., halite and sylvite) have not been reported from fluid inclusions. The problem with halides is that they are extremely weak Raman scatterers: one exception is represented by fluorides (Table 2; Burruss et al., 1992; Rickers et al., 2006). Raman bands of most common oxide and hydroxide minerals are listed in Table 2. The three polymorphs of TiO2 are also reported, although only rutile has been observed in fluid inclusions (Frezzotti et al., 2007). 6.2. Carbonates (Table 3)
Fluid inclusions may contain mineral phases, which form by different processes, including direct fluid precipitation (daughter minerals) and reaction of fluid contained within inclusions with the host mineral (step-daughter minerals) (Fig. 1; Roedder, 1984). Minerals including or included within fluid inclusions can be readily identified by comparison of their spectral fingerprints with reference spectra.
Carbonates are common phases in fluid inclusions, and a recent example of Raman identification of multiple carbonates in fluid inclusions in pegmatites is reported in Thomas et al. (2011a). Raman vibrational modes are dependent on the main carbonate groups, modified by the interactions with the bonded mineral lattice. CO32− exhibits three main distinct internal vibrational modes over the
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Fig. 12. Raman vibrational mode regions for major silicate classes. Main vibrational regions of borates, phosphates, sulfates, and carbonates are reported for comparison.
range 400–1400 cm − 1. Generally, strong Raman modes appear around 1050–1100 cm − 1 due to the symmetric stretching vibration (ν1) of the carbonate group, while weaker (around 20 time less intense) Raman bands near 700 cm − 1 and 1400 cm − 1 are due to the in-plane bending mode (ν4) and the antisymmetric stretch (ν3) of CO3, respectively. Lattice modes show Raman shifts below 400 cm − 1. As shown in Fig. 11, close similarities exist in the Raman modes of the CO3 group between different carbonate minerals. However, significant differences are evident in the positions of their respective lattice modes over the range 100–350 cm− 1 (T in Fig. 11 and Table 3): for example bands of CaCO3 (156 and 284 cm− 1), CaMg(CO3)2 (176, 299 cm− 1), and MgCO3 (212 and 329 cm− 1) are distinct and identifiable without difficulty. Raman spectroscopy is well suited to distinguish among the polymorphs calcite, aragonite and vaterite (Table 3). Calcite has main Raman modes at 1085 (ν1), 1450 (ν3), and 712 cm − 1 (ν4). Aragonite has the main vibrational mode at 1085 cm (ν1), and weak vibrations at 1463 (ν3) and 704 cm− 1 (ν4), and an additional very weak band at 854 cm− 1 (ν2). In vaterite, the main vibration mode (ν1) forms a doublet at 1074 and 1090 cm− 1. A doublet is also present at 740 and 750 cm− 1 (ν4). The most intense lattice Raman modes are at 284, 206, and 301 cm− 1 for calcite, aragonite and vaterite, respectively. Mg-calcite shows a slight upshift of the main stretching band to 1087 cm− 1 and has a broader band base than pure calcite (Burke, 2001). In hydrated (i.e., hydrous and OH-bearing) carbonates, the OH stretching vibrations give rise to additional broad Raman bands located between 3000 and 3700 cm− 1 (Table 3). 6.3. Sulfates, phosphates, and borates (Tables 4 and 5) Sulfates and phosphates are strong Raman scatterers. The Raman bands of these minerals are due to the vibrations within SO4 and PO4 tetrahedra. Differences among spectra listed in Tables 4 and 5 result from the nature of metals within the main molecular unit, from the bond strength between the main molecular units and neighboring atoms, and from the different degrees of distortion of the main molecular unit in the mineral lattice (cf., Nasdala et al., 2004, and references therein). In sulfates, the strongest Raman band due to the symmetric stretching vibration (ν1), of SO4 tetrahedra is at about 1000 cm − 1, at lower wavenumbers than that of CO3 groups: 1018 cm − 1 for anhydrite, 994 cm − 1 for thenardite, and 1008 cm − 1 for gypsum (Table 4). Additional weaker bands over the ranges 400–500 cm − 1,
600–700 cm − 1, and 1100–1200 cm − 1 are due to the in-plane (ν2) and the out-of-plane (ν4) bending modes, and to the asymmetric stretching of SO4 tetrahedra. The Raman bands of hydrated sulfates are closely related to those of the sulfate ion in aqueous solution (i.e., 980, 620, and 450 cm − 1; Table 1), and show a progressive shift toward higher wavenumbers with decreasing of the hydration state (cf., hydrous magnesium sulfate list in Table 4; Wang et al., 2006). In borates, the distribution of the main Raman bands is mainly dependent on the mineral structure and on the type of borate ion (i.e., boron–oxygen ratio, charge, and hydroxyl groups present); vibrational modes are observed in the regions: 490–670, 690–800, 820–910, and 950–1040 cm − 1 (Table 5). Borates in fluid inclusions have been investigated by Williams and Taylor (1996), Peretyazhko et al. (2000), Thomas (2002), and Rickers et al. (2006). 6.4. Silicates (Tables 6 and 7) Silicate minerals are critically important to fluid inclusion research: quartz, olivine, pyroxenes and garnet represent very common host phases for fluid inclusions, and their Raman bands should be fully characterized before analyzing fluid inclusions. In addition, they can be found as daughter mineral phases in fluid inclusions, because of high silica solubility in aqueous fluids at most crustal and upper mantle P–T conditions (e.g., Manning, 2004). Compared to carbonates and sulfates, silicate minerals are weaker Raman scatterers, due to the low polarizability of the Si\O bonds. Silicates having different chemical composition or/and structure are discriminated from their spectral features. Fig. 12 compares main vibration regions for the different classes of silicates. In orthosilicates, Raman bands are determined by the vibration modes of the isolated SiO4 tetrahedra, similarly to what observed in sulfates and phosphates. Olivine and garnet show the main stretching modes of SiO4 group in the 800–1050 cm − 1 region (Table 6). A very good correlation has been shown between the wavenumbers of the SiO4 main bands and cation substitution (e.g., Mg/Fe + Mg in olivine) which permits the determination of the chemical composition of these minerals (e.g., Guyot et al. 1986). In inosilicates and phyllosilicates, where tetrahedra are to some extent connected, bands generated by the vibration modes of the Si\Ob\Si bonds (Ob = bridging oxygen) dominate the spectra. Spectra of pyroxenes show main Si\O bending and stretching modes over the 600–700 and the 900–1050 cm − 1 regions, respectively (Fig. 12; Wang et al., 2000). Clinopyroxene (diopside-
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 1–20
hedembergite series) and orthopyroxene (enstatite–ferrosilite series) can be easily distinguished by the number of bands in the 600–700 cm − 1 region: orthopyroxene has two bands, while clinopyroxene has only a single band (cf., Table 7). Most amphiboles and phyllosilicates are very weak Raman scatterers and reconnaissance within fluid inclusion is often difficult. As shown in Fig. 13, however, the position and the shape of the more intense OH stretching band(s) can be used to distinguish among minerals containing hydroxyl groups. Tectosilicate spectra are dominated by vibrations of Si and O atoms within the framework structures of fully linked tetrahedra (McMillan and Hess, 1990). Main bands, which occur over the range 380–530 cm − 1 (Fig. 12), are due Si\O\Si symmetric stretching and bending modes. The Raman frequencies of main modes show a relationship with the size of rings made by tetrahedra (Sharma et al., 1983): four-membered ring structures, such as feldspars and coesite, have main modes above 500 cm − 1, whereas structures with
17
six-membered rings, such as quartz, tridymite, cristobalite, and nepheline have main modes in the 380–480 cm − 1 region (Table 6). 7. Concluding remarks Raman analysis of fluid inclusions permits to qualitatively detect or identify gaseous and liquid phases, as well as enclosed (or enclosing) minerals. In some cases, quantitative analyses are possible (e.g., relative mole% in gas mixtures, and solute concentration in aqueous fluids). Major advantages of Raman spectroscopy are the minimal sample preparation, and the excellent volume resolution: fluid inclusions as small as the laser spot size (1–2 μm) can be precisely located and analyzed within double polished thick sections. In addition, Raman is a non-destructive technique, meaning that there is no need to decrepitate fluid inclusions. Fluorescence, that can cover the Raman spectrum, represents the most significant disadvantage during analysis, and the risk of fluorescence must be always considered when selecting fluid samples to analyze (e.g., hydrocarbons). Another significant disadvantage is the absence of adequate libraries of reference spectra. This last inconvenience is in part remedied by the compilation of a small spectral library dedicated to fluid inclusion research, presented in our review paper. Raman spectroscopy has been used to successfully analyze fluid inclusions with an increasing number of publications through the years. No other technique can analyze liquid, gas and solid constituents in fluid inclusions. Incorporating this exclusive method with evolving new technologies (e.g., spectral imaging) provides a bright future for this “old” technique in the analysis of geological fluids. Acknowledgments Present research was in part supported by the PRIN 2008-BYTF98. We acknowledge helpful reviews by R. Thomas and an anonymous reviewer of an earlier version of the manuscript. We are grateful to the Museo di Mineralogia of the University of Rome “La Sapienza” and to the Museo di Mineralogia of the University of Siena for providing several mineral samples for Raman analysis. Raman facilities in Siena were provided by PNRA, the Italian research program for Antarctica. References
Fig. 13. Comparison of O\H stretching modes for selected phyllosilicates analyzed in fluid inclusions. Phlogopite, peridotite from Italy. Muscovite, quartzite from Sulu, China. Paragonite, quartzite from Sulu, China. Talc, peridotite from Italy. Clinochlore, peridotite from Ethiopia. In clinochlore OH spectrum, the additional vibration at 3565 cm− 1 indicates excess of Al, or presence of a humite phase (Frost et al., 2007).
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