Raman Spectroscopy For Fluid Inclusion A

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Journal of Geochemical Exploration 112 (2012) 120
Contents lists available at SciVerse ScienceDirect
Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp
Raman spectroscopy for uid inclusion analysis

Maria Luce Frezzotti a, b,, Francesca Tecce b, Alessio Casagli a
a
b
Dipartimento Scienze della Terra, Universit di Siena, Via Laterina 8, 53100 Siena, Italy
Istituto Geologia Ambientale e Geoingegneria - CNR, c/o Dipartimento Scienze della Terra, Universit 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 uids
Raman spectra database
a b s t r a c t
Raman spectroscopy is a versatile non-destructive technique for uid inclusion analysis, with a wide eld of
applications ranging from qualitative detection of solid, liquid and gaseous components to identication of
polyatomic ions in solution. Raman technique is commonly used to calculate the density of CO2 uids, the
chemistry of aqueous uids, and the molar proportions of gaseous mixtures present as inclusions. Raman
spectroscopy has been applied to measure the pH range and oxidation state of uids. 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 uid 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 uids . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
CO2 uids . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Gaseous mixtures . . . . . . . . . . . . . . . . . . . . . .
5.
Aqueous uids . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Analyses of solutes: monoatomic ions . . . . . . . . . . . .
5.2.
Analyses of solutes: polyatomic ions and molecules . . . . . .
6.
Identication of mineral phases: a catalog of reference Raman spectra
6.1.
Native elements, halides, oxides and suldes (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 rst-hand information
on uids 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: marialuce.frezzotti@unisi.it (M.L. Frezzotti),
francesca.tecce@cnr.it (F. Tecce), casagli@unisi.it (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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1
3
4
6
6
7
8
8
12
15
15
15
16
16
17
17
17
Fluid inclusions are generally small closed volumes (i.e., b50 m in diameter; Fig. 1), in which pressure and temperature are interdependent variables. Both are related by the equation of state of the
enclosed uid, resulting in a nearly linear relation in the PT space
(isochore). Therefore, a key requirement for research and applications is the ability to characterize uid 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 uid inclusions. One of the main advantages is that

2
M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120
Fig. 1. Photomicrographs of uid inclusions: a) primary H2O uid inclusions aligned following chevron halite bands, evaporite from Vitravo diapir, Crotone, Italy. b) Primary H2O
uid inclusions in anhydrite from a geothermal well (2410 m depth), Sabatini Volcanic District, Italy. c) Plane of liquid-rich and vapor-rich H2O uid inclusions in sanidine from
syenite, Sabatini Volcanic District, Italy. d) H2O uid inclusion containing calcite and anhydrite daughter minerals (same provenance as in c). e) Tri-phase H2OCO2 (L1 + L2 + G)
uid inclusions from an Alpine quartz vein, Binn, Switzerland. f) CO2 uid inclusions in orthopyroxene, peridotite from Italy.
it allows the chemical and structural characterization of samples as

small as 1 m 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 uid 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 (l), and Raman and Rayleigh spectra. The molecular
vibration of the analyzed sample is of frequency m.
Fig. 3. Schematic diagram of a Raman spectrometer.

the importance of this technique is demonstrated by the number of

publications and of review papers in this research eld (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 uids 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 uid inclusions are not discussed in detail. As a
rst step toward the use of Raman spectroscopy for the study of geological uids, we provide a catalog of reference spectra for main
phases that can be present in uid 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 uorescence, 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.
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 E = hm, where h is the Plank's constant
and m is the frequency of the molecular vibration. The incident visible light ( = 400750 nm) with energy l 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
l, l m, and l + m. The concept is illustrated in Fig. 2. The
Rayleigh or elastic scattering occurs when the transition starts and
nishes at the same vibrational energy level without loss of energy
(i.e., no frequency change; l). Inelastic scattering (Raman effect) induces a change to lower (l m) and higher (l + m) frequencies
in scattered light, which are known as Stokes and anti-Stokes lines,
with m 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 10 610 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 = c = 1 in cm 1, where c is the
Cc Dmd
Rt
C
Rt
4000
300
600
900
1200
1500
-1
cm1800
Diamond
Rutile
Calcite
Fig. 4. Raman spectral images of daughter mineral distribution in an aqueous uid inclusion. a) Optical microphotograph of analyzed uid 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 uid inclusion. The
color intensity of the mineral phases (from black to white) reects the increase in the intensity of the Raman band. The aqueous uid in the inclusion has no signicant Raman
signal in the investigated region, and thus does not interfere with the measurement; modied from Frezzotti et al. (2011).

4
Table 1
Main Raman vibrations (cm 1) of major gaseous species and of solutes in aqueous
uids.
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 36573756
w 1595
1
2
CO2 Fermi doublet

13
CO2
O2
CO
N2
H2S
C3H8
CH4
C2H6
NH3
H2
H2O vapor
1
1
4
1
1
5
1
1
6
Solutes
Main vibrations
Ref.
Si(OH)40
Si2O(OH)60
ClO4
750800
590680
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
25702590
vs 3040
sh 2870
vs 877
w 495
vs 27503900*
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 reect 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 modication of the dipole by a molecular vibration; 3) the successive scattering of a photon from the modied 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 rst dispersive Raman spectrometers
had the sun or a mercury lamp as the exciting source, a prism monochromator as the light disperser, and a photographic lm 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
lters 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 uid species
in uid inclusions. Note that the hypothetical CO2 Raman band at 1340 cm 1 is really
two bands at 1285 and 1388 cm 1, see text.

Fig. 6. Raman spectroscopy applied to CO2 density measurement. a) Main spectral features of CO2 uids, which consist of the two bands of the Fermi doublet, bounded by
the hot bands. The distance between the Fermi doublet () depends on uid density.
b) Superdense CO2 uid inclusions (d N1.178 g/cm3) spectral features, including: i) increased (106 cm 1), ii) shifting of bands to lower wavenumbers, iii) increased
band intensity ratio, iv) broadened band bases, and v) attened hot bands (van den
Kerkhof and Olsen, 1990); analyzed uid inclusions are in pyroxenes from peridotite
xenoliths, Hawaii; modied from Frezzotti and Peccerillo (2007). c) CO2 density as a
function of (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 modied 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 scientic 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
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 uid inclusions by means of high-magnication 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 magnication objective
with N.A.= 0.9, the spot size is 1 1 5 m3.
Thick double-polished sections are easily studied and require no
special preparation. Fluid inclusions can be studied down to 1 m diameter in situ, where microstructures are preserved and the different
populations of uid 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
uid inclusions not deeper than 30 m within a sample.
The choice of laser wavelength inuences the performance of the
spectrometer. The characteristics of each laser are different, so that
no laser may be ideal for every uid inclusion analysis. In general,
the optical power of the laser line and the efciency of Raman CCD
detectors tend to increase with decreasing wavelength. However,
the cost of the laser, the likelihood of uorescence (see below), and
the risk of sample heating increase as well. The most popular choices
are: (1) the green light Ar ion ( = 514.5 nm) water- or air-cooled;
(2) the blue light Ar ion ( = 488 nm) air-cooled; and (3) the red
light He\Ne ( = 632.8 nm).
Raman microspectrometers can be equipped with a programmable xy 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 xy 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 uid or mineral species within single uid 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
uid 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-uorescent epoxies and/or cleaning the sample. However, uorescence can also be
emitted by uids contained in inclusions (e.g., hydrocarbons) or by
the surrounding host mineral (e.g., Fe-bearing minerals). These last
cases are much more difcult to cope with. Increasing the wavelength
of the light source is a way of overcoming uorescence: red or nearinfrared lower lasers ( = 6301060 nm) should not, in principle,
give rise to uorescence (Carey, 1999). Another practical method to
mitigate a uorescent background consists in repeating spectral accumulations for several times in order to bleach out this effect by protracted exposure to laser light (photo-bleaching).

6
Fig. 7. Quantitative Raman analysis of H2 and CH4 contained in the gas bubble of an aqueous uid 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 () and the instrumental efciency () at the wavenumbers of H2 and CH4. ( 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 identication (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 uid
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 uid inclusion depend
on several contributing factors, including uid inclusions size and
geometry (i.e., number of molecules of the analyzed constituent),
nature of the other constituents in uid 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 uids
A custom application of Raman spectroscopy to uid inclusion
analysis is the qualitative identication of major gaseous uid components. The characterizing Raman bands for most important geological
uids are reported in Table 1 and Fig. 5. Most gasses show a single
symmetric stretching strong band, whose wavenumber is traditionally reported at ambient PT conditions, since a progressive slight
wavenumber downshift is known to occur with increasing uid density (Burke, 2001; van den Kerkhof, 1988b).
Early work on uid inclusions allowed to recognize CO2, CH4, and
N2 as relevant geological uids (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 uids (Bny 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). Identication 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 Barrs, 1990; Potter et al., 2004; Rossetti and
Tecce, 2008; Schubert et al., 2007; Weseucha-Birczyska et al.,
2010), although uorescence often does not allow conventional analysis (see e.g., Pironon et al., 1998).
4.1. CO2 uids

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 uid inclusions
having different densities. The distance between the Fermi doublet
(, in cm 1) is proportional to uid 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 uid inclusions
based on the distance between the Fermi doublet (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).

band intensities on uid 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 uid 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 (Schrtter and Klckner, 1979); and (2) the
variation of the instrumental efciency at the different wavenumbers
for a specic excitation wavelength. The rst 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
Fig. 8. Raman spectra of water contained in uid 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 uid inclusion, peridotite from
Ethiopia.
We observe a very good agreement between density data derived

from Raman spectroscopy and from microthermometry, also for CO2
uids 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 uid inclusion composition and densities. Although the precision of microthermometric measurements is higher, the Raman densimeter permits to
analyze very small uid inclusions (b5 m in diameter), and/or low
density uids.
The relative intensities of the 13CO2 and the associated 12CO2
band (Fig. 6a) have been used to calculate the carbon isotope ratios
in single uid inclusions. The development of Raman as a massspectroscopy, however, is still at a very early stage of development;
reported 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
difculty in controlling all parameters inuencing intensity of
scattering, probably including a dependence of 13CO2 and 12CO2
Aa
a a
Ai
i i
where Xa, Aa, a and a, are the molar fraction, the band area, the
Raman cross-section and the instrumental efciency for gas a, respectively, while Ai, i, and i represents the sum of values for all gas species in the uid 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 uids 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 uid 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 ( = 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 () of H2 and CH4 and the instrumental efciency
() 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 gaseousaqueous uid mixtures, the quantitative analysis of the different components is much more difcult
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 uid 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
Fig. 9. Raman spectroscopy applied to solute analysis in aqueous uids. a) Band of SO42 ions in a uid inclusion in feldspar from syenite, Sabatini volcanic district, Italy. b) Bands of
native sulfur in a uid inclusion in orthopyroxene from peridotite, Italy. c) Bands of CO32 and HCO3 ions in a uid inclusion from ultra-high pressure metamorphic rocks, western
Italian Alps. d) Bands of Si(OH)40, and deprotonated H4-nSiO4n monomers in a uid 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: modied from Frezzotti et al., 2011.
5. Aqueous uids
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 uid inclusions
(b510 m in size; Frezzotti and Peccerillo, 2007; Frezzotti et al.,
2010; Hidas et al., 2010). Here, a water lm of a thickness of 0.2 m
wrapping the CO2 uid cannot be identied with optical techniques,
although it may correspond to as much as 1020 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 uid 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 signicant 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 uid 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
uid 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 uid 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 uid inclusion cooling stage. Spectra are
reported for all major salt-hydrates, such as NaCl2H2O, FeCl36H2O,
CaCl26H2O, MgCl212H2O, KClMgCl26H2O, FeCl26H2O, LiCl5H2O
(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 uid inclusions (Fig. 8a and b)
has been intensively investigated with different approaches. Semiquantitative estimation of the salt content in aqueous uid inclusions
requires development of a specic calibration for each spectrometer
and it is complementary to measurements of phase transitions at
low temperatures by microthermometry (e.g., eutectic and nal melting temperatures).

Table 2
Main Raman vibrations (cm 1) of selected native elements, halides, suldes, oxides and hydroxides.
Native elements, halides and suldes
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
-FeO(OH)
w 139
vs 143
vw 195
s 127
vs 150
m 555
vw 641
[1]
mw 620
559
1009
vs 428
7
7
7
vs 471
w 300
w 310
vs 349
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 Geouids Lab (http://www.dst.unisi.it/geouids/
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
2YX B
X=Y
C
NaClwt:%
@2 I 3400 cm1 A
XY
I3200 cm1
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 specied wavenumbers, and and are regression
parameter specic 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
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)24H2O
Dypingite
Mg5[(OH)(CO3)2]25H2O
Dawsonite
NaAl(CO3)(OH)2
Thermonatrite
Na2(CO3)H2O
Trona
Na3H(CO3)22H2O
Gaylussite
Na2Ca(CO3)25H2O
CO32 vibrations
Ref.
1
vs 1085
vw 1435
[1]
vs 1085
vw 1463
[1]
w 740
w 750
mw 714
vs 1090
s 1074
vs 1087
vw 1465
vw 1438
[1]
w 738
vs 1094
w 1444
w 725
vs 1097
vw 1443
[1]
w 698
vs 1078
w 1428
m 697
m 1405
w 712
vs 1064
sh 1043
vs 1091
w 1459
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]
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
vw 854
m-w 839
w 635
w 673
CO32 vibrations
OH
Ref.
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
vs 1091
w 1065
mw 1505
vs 3282
m 3250
vs 1062
sh 1432
n.a.
[1]
vs 1060
w 1430
n.a.
[1]
vs 2944
s 3334
[1];
10
vs 1071
1 = Symmetric stretching vibration; 2 = Out-of-plane bending vibration; 3 = Antisymmetric stretching vibration; 4 = 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 Geouids Lab (http://www.dst.unisi.it/geouids/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.

11
Table 4
Main Raman vibrations (cm 1) of selected sulfates.
SO42 vibrations
Sulfates
Ref.
Anhydrite
CaSO4
mw 430
mw 500
vs 1018
mw 1131
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
vs 1002
m 1125
[1]
w 1093
w 1109
w 1145
m 1104
mw 1093
ms 1156
mw 1190
w 1143
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
2
Gypsum
CaSO42H2O
Epsomite
MgSO47H2O
s 494
m 414
mw 447
w 621
vs 1008
w 1142
vw 612
vs 984
Exahydrite
MgSO46H2O
Pentahydrite
MgSO45H2O
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
MgSO44H2O
vw 401
vw 462
vw 565
vw 616
vw 664
vs 1000
Sanderite
MgSO42H2O
Kieserite
MgSO4H2O
K-Alum
KAl(SO4)212H2O
Alunite
KAl3[(OH)3(SO4)]2
Syngenite
K2Ca(SO4)2H2O
Grgeyite
K2Ca5(SO4)6H2O
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
Na2SO410H20
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
vs 3396
m 3072
vs 3509
vs 3482
vs 3301
s 3378
vs 3525
m 3580
vs 3506
m 3340
n.a.
3
3
[1];
8
[1];
9
10
11
[1]
1 = Symmetric stretching vibration; 2 = Out-of-plane bending vibration; 3 = Anti-symmetric stretching vibration; 4 = In-plane bending vibration; * = Symmetric stretching
vibration of CO3 group. Peak intensities as in Table 3. [1] = Raman Spectra Database, Siena Geouids Lab (http://www.dst.unisi.it/geouids/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
Table 5
Main Raman vibrations (cm 1) of selected phosphates and borates.
PO43 vibrations
Phosphates
Ref.
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
910
942
993
1059
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
3
4
1100
1136
1394
mw 1054
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
Na2B4O710H2O
Li-tetraborate
Li2B4O75H2O
vs 963
437
461
Lazulite
(Mg,Fe)Al2(PO4)2(OH)2
Borates
vs 965
782
518
533
595
5
809
713
w 500
1419
vs 880
vs 153
Borax
Na2B4O5(OH)48H2O
CaMg-hexaborates
CaB6O10, MgB6O10 with 4 to 7.5 H2O
Hydroboracite
CaMgB6O116H2O
181
257
Cs-Ramanite
CsB5O84H2O
Rb-Ramanite
RbB5O84H2O
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
948
943
997
953
964
7
1036
1028
1097
1352
5
4
m 768
m 907
w 765
w 914
1 = Symmetric stretching vibration; 2 = In-plane bending vibration; 3 = Antisymmetric stretching vibration; 4 = Out-of-plane bending vibration. Peak intensities as in
Table 3. [1] = Raman Spectra Database, Siena Geouids Lab (http://www.dst.unisi.it/geouids/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 inuenced 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
uid 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 inuence of measurement conditions. Note that during analyses high laser power

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
849
879
827
848
880
828
894
905
1029
1007
816
842
874
995
952
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
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
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
[2]
[1] = Raman Spectra Database, Siena Geouids Lab (http://www.dst.unisi.it/geouids/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 uid 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 uids represents one of the rst applications
of Raman microspectroscopy to uid 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 uid inclusions,
and has very low detection limits (0.010.05 mol/kg; Dubessy et al.
1982, 1983; Rosasco and Roedder, 1979). Bisulfate ions (HSO4) can
be identied by their main S\O and S\OH stretching modes at
~1050 and 890 cm 1, respectively (Table 1). Hydrogen sulde (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
uid 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 uids (cf., Burke,
2001; Dubessy et al., 1982; McMillan et al., 1996). More recently,
there has been increasing Raman evidence for signicant HCO3(aq)
and CO32(aq) in uid 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 modied technique by Sun and Qin (2011) (R. Thomas,

14
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
3673
1018
1055
679
OH
3477
[1]
3715
[1]
3631
[1]
3677
3605
3647
3679
3657
620
692
1105
520
683
1044
350
388
510
630
690
1096
343
382
320
389
414
664
684
662
1011
[1]
1009
224
667
1040
[1]
229
665
1017
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/geouids/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 uids.
Raman spectroscopy is a powerful technique to study the speciation
of silica in aqueous uids at different PT 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 PT conditions. Si(OH)40(aq) can be identied by a
Raman band in the 750800 cm 1 region (Table 1). In alkaline uids,

increasing dissociation of monomers and dimers in deprotonated species (e.g., SiO(OH)3, Si2O2(OH)5) yields additional Raman bands in
the 9501100 cm 1 region, as shown in Fig. 9d.
B(OH)30 is the predominant boron species in aqueous uids over a
wide range of PTpH 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 uid
Fig. 10. Raman spectra of carbon phases in uid inclusions; a) Diamond in a CO2 uid inclusion from peridotites, Hawaii; modied from Frezzotti and Peccerillo (2007). b) Graphite
in a CO2 uid inclusion from peridotites, Italy. Excitation light source: Ar ion laser ( = 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 HeNe laser light ( = 632.8 nm), the graphite D-band is
expected at about 1330 cm 1.

15
A catalog of about 140 spectra of minerals which are of interest in

uid inclusion research is presented in Tables 27, as a supplement to
the web Raman mineral library available at: http://www.dst.unisi.it/
geouids/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 notation in scattering
geometries, where the symmetric stretching vibration (1) 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
uid inclusions were measured on a Horiba (Jobin Yvon) Labram spectrometer at the University of Siena, using a water-cooled Ar ion laser
( = 514.5 nm) as the excitation source. Present catalog intends to provide a rst library dedicated to uid inclusion research.
6.1. Native elements, halides, oxides and suldes (Table 2)
Fig. 11. Comparison of the Raman spectra of calcite, dolomite, and magnesite in the interval 01600 cm 1. Main CO32 group vibrations are illustrated. 1 = Symmetric
stretching vibration; 3 = Antisymmetric stretching vibration; 4 = 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 uid inclusions, while NaOH(aq) and LiOH(aq)
can be present in some ore-forming uids (Thomas et al., 2011b)
6. Identication 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 uid mixtures, precipitation of C (graphite, or diamond at higher pressures) reects a
decrease in fO2 buffer conditions in the uidrock 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 uid 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 uid 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 orderdisorder 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 orderdisorder geothermometer to graphite contained within
uid inclusions. The crystallinity of graphite precipitated from uids
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 uid 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 uid inclusions. The problem with halides is that they are extremely weak Raman scatterers:
one exception is represented by uorides (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
uid inclusions (Frezzotti et al., 2007).
6.2. Carbonates (Table 3)
Fluid inclusions may contain mineral phases, which form by different processes, including direct uid precipitation (daughter minerals) and reaction of uid contained within inclusions with the
host mineral (step-daughter minerals) (Fig. 1; Roedder, 1984). Minerals including or included within uid inclusions can be readily identied by comparison of their spectral ngerprints with reference
spectra.
Carbonates are common phases in uid inclusions, and a recent

example of Raman identication of multiple carbonates in uid inclusions in pegmatites is reported in Thomas et al. (2011a). Raman
vibrational modes are dependent on the main carbonate groups,
modied by the interactions with the bonded mineral lattice. CO32
exhibits three main distinct internal vibrational modes over the

16
Fig. 12. Raman vibrational mode regions for major silicate classes. Main vibrational regions of borates, phosphates, sulfates, and carbonates are reported for comparison.
range 4001400 cm 1. Generally, strong Raman modes appear

around 10501100 cm 1 due to the symmetric stretching vibration
(1) 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 (4) and the antisymmetric stretch (3) 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, signicant differences are evident in the positions of their respective
lattice modes over the range 100350 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 identiable without difculty.
Raman spectroscopy is well suited to distinguish among the polymorphs calcite, aragonite and vaterite (Table 3). Calcite has main
Raman modes at 1085 (1), 1450 (3), and 712 cm 1 (4). Aragonite
has the main vibrational mode at 1085 cm (1), and weak vibrations
at 1463 (3) and 704 cm 1 (4), and an additional very weak band
at 854 cm 1 (2). In vaterite, the main vibration mode (1) forms a
doublet at 1074 and 1090 cm 1. A doublet is also present at 740 and
750 cm 1 (4). 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 (1), 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 400500 cm 1,
600700 cm 1, and 11001200 cm 1 are due to the in-plane (2)

and the out-of-plane (4) 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.,
boronoxygen ratio, charge, and hydroxyl groups present); vibrational modes are observed in the regions: 490670, 690800, 820910,
and 9501040 cm 1 (Table 5). Borates in uid 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 uid inclusion research: quartz, olivine, pyroxenes and garnet represent very common
host phases for uid inclusions, and their Raman bands should be
fully characterized before analyzing uid inclusions. In addition,
they can be found as daughter mineral phases in uid inclusions, because of high silica solubility in aqueous uids at most crustal and
upper mantle PT 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 8001050 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 600700 and the 9001050 cm 1 regions, respectively (Fig. 12; Wang et al., 2000). Clinopyroxene (diopside-

hedembergite series) and orthopyroxene (enstatiteferrosilite series) can be easily distinguished by the number of bands in the
600700 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 uid inclusion is often difcult. 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
380530 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 380480 cm 1 region (Table 6).
7. Concluding remarks
Raman analysis of uid 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
uids). Major advantages of Raman spectroscopy are the minimal
sample preparation, and the excellent volume resolution: uid inclusions as small as the laser spot size (12 m) 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 uid inclusions.
Fluorescence, that can cover the Raman spectrum, represents the
most signicant disadvantage during analysis, and the risk of uorescence must be always considered when selecting uid samples to analyze (e.g., hydrocarbons). Another signicant 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 uid inclusion research, presented in our review
paper.
Raman spectroscopy has been used to successfully analyze uid
inclusions with an increasing number of publications through the
years. No other technique can analyze liquid, gas and solid constituents in uid 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 uids.
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.
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Journal of Geochemical Exploration

Raman spectroscopy for uid inclusion analysis

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

it allows the chemical and structural characterization of samples as

Fig. 3. Schematic diagram of a Raman spectrometer.

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the importance of this technique is demonstrated by the number of

A straightforward way to explain the Raman scattering of light is

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

CO2 Fermi doublet

vs = very strong; m = medium; w = weak; sh = shoulder; * Broad bands of several

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

Interpretation of spectra of crystalline phases is often complicated,

4.1. CO2 uids

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We observe a very good agreement between density data derived

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

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Mernagh and Wilde (1989) proposed a formula to calculate NaCl

where X is equal to the integral of the OH band from 2800 to

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

intensity, although proportional to the solute concentration, cannot

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could result in heating the inclusion uid with consequent possible

The carbonate ion CO32 fundamental stretching mode is expected

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

pers. comm.). Higher carbonate concentrations can be determined

Raman band in the 750800 cm 1 region (Table 1). In alkaline uids,

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A catalog of about 140 spectra of minerals which are of interest in

inclusions has been presented by Thomas (2002), with a minimum

Carbonates are common phases in uid inclusions, and a recent

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

range 4001400 cm 1. Generally, strong Raman modes appear

600700 cm 1, and 11001200 cm 1 are due to the in-plane (2)

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

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M.L. Frezzotti et al. / Journal of Geochemical Exploration 112 (2012) 120

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