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Bulk analysis of volatiles in fluid inclusions

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CHAPTER 10. BULK ANALYSIS OF VOLATILES IN FLUID INCLUSIONS

Stefano Salvi1 and Anthony E. Williams-Jones2

1
Laboratoire des Mécanismes de Tranfert en Géologie,
UMR 5563, Équipe de Minéralogie
39 Allées Jules Guesde, 31000 Toulouse, France
salvi@cict.fr
2
Department of Earth & Planetary Sciences,
McGill University
3450 University Street, Montreal,
Quebec, Canada H3A 2A7
willyj@eps.mcgill.ca

“...a specimen of the Goldie aplite...was split in vacuo. The liberated gas was
conducted to a ... mass spectrometer, which unfortunately showed nothing.
Rechecking of the specimen by subsequent splitting in air yielded the characteristic
odor, which led us to conclude that the nose is more sensitive than the machine.” 1

INTRODUCTION
Although H2O is the dominant
component of most fluid inclusions, researchers
have long realized that, in some environments,
a significant proportion of the fluid inclusion
population consists of inclusions in which non-
aqueous fluids such as CO2, SO2, N2, H2, H2S,
CH4 and heavier hydrocarbons predominate.
Less well known is the fact that most aqueous
fluids trapped as inclusions contain small
proportions of these gases as solutes. This is
not surprising because, unless the dissolved
gases are in sufficient concentration to exsolve
as a separate phase (or form a clathrate) that can
be distinguished optically, their presence will
be undetected.
Next to H2O, oxidized carbonic species
(CO, CO2) are the most important gases
escaping from active volcanoes (cf. Gerlach
1980, 1989) and are commonly preserved as
primary fluid inclusions in felsic igneous rocks
(e.g., Roedder & Coombs 1967, Holloway
1976, Roedder 1984). Reduced carbonic
species are released in relatively minor
quantities, except during the emplacement of
alkaline and hyperalkaline magmas, when they
are the dominant carbonic species and
commonly comprise methane and a number of
other aliphatic and even aromatic hydrocarbons
(e.g., Petersilie & Sørensen 1970, Ikorski 1981,
Konnerup-Madsen et al. 1981, Salvi &
Williams-Jones 1992 and 1997a, Ikorski et al.
1993, Nivin et al. 1995, Potter et al. 1998,
Potter & Konnerup-Madsen 2003). In addition
to reduced carbonic species, the fluid inclusions
may also contain appreciable proportions of N2,
H2S, and H2. Oxidized and reduced carbonic
species are also commonly observed in fluid
inclusions in sedimentary (e.g., Newman et al.
1996, Giggenbach 1997, Burruss 2003a) and
metamorphic rocks (e.g., Eugster & Skippen
1967, Kreulen & Schuiling 1982, Samson &
Williams-Jones 1991, Moine et al. 1994), in
hydrothermal mineral deposits and in rocks that
have been hydrothermally altered (e.g.,
Giggenbach 1993, Roedder & Bodnar 1997,
Wang et al. 1999, Graupner et al. 2001,
Ishibashi et al. 2002, Simoneit 2002). Higher
hydrocarbon-bearing fluid inclusions (aliphatic
and aromatic species) are particularly common
in sedimentary environments (e.g., Burruss
1981, Jensenius & Burruss 1990, Goldstein
2001, Munz 2001, Burruss 2003a) but have also
been reported to occur in serpentinites (e.g.,
Agafonov & Andreyeva 1972, Berndt et al.
1996, Peretti et al. 1992, Normand 2001). As
in igneous settings, the carbonic species, and
particularly the reduced varieties, may be
accompanied by significant proportions of N2,
H2S and H2. Other volatile species that have
been reported to occur in fluid inclusions
include O2, NH3, SO2, H2S, HCl, HF, He, N2,
and Ar and other noble gases.

1
Heinrich, E. Wm. and Anderson, R.J., 1965. Carbonatites and alkalic rocks of the Arkansas River area,
Fremont County, Colorado. 2. Fetid gas from carbonatite and related rocks. Am. Mineral., vol. 50, pp. 1915-
1916.

10-1
 The challenge for fluid inclusionists is
to develop methods that can be used to
accurately determine the concentrations of the
various volatile species trapped during a single
geological event. Ideally, these methods should
permit analysis of the volatiles in single fluid
inclusions, and, although such methods have
been developed based on laser Raman and
Fourier Transform infrared spectroscopy
(Burruss 2003b), they are not universally
applicable. Owing to the very high detection
limits, important gases present in significant
concentrations can be overlooked (the
minimum detection limit is >1 mole %), and
because of the large minimum size of the
inclusion that must be analyzed (the minimum
diameter is commonly >10 µm) it may be
difficult to find suitable inclusions for analysis.
An additional limitation, in the case of laser
Raman spectroscopy, is that it cannot be used to
analyze inclusions in some minerals or
inclusions that contain cyclic and aromatic
hydrocarbons because of laser-induced
fluorescence. The alternative is to use methods
that involve extraction of the bulk fluid from
large numbers of inclusions. These methods
permit the analysis of a wide variety of
inclusion gases to very low concentration, and
characterization of a fluid entrapment event in a
single analysis. Moreover, they are effectively
independent of the size of the inclusions. On
the other hand, they can only be applied in
cases where petrographic examination and/or
microthermometric analyses have demonstrated
that the sample contains, or is dominated by, a
single population of fluid inclusions.
In this chapter, we start by describing
the crushing technique, a widely used
qualitative method for detecting fluid inclusion
gases, and then proceed to a comprehensive
review of the principal methods used to
quantitatively analyze the composition of the
bulk fluid.
TECHNIQUES AND METHODOLOGY
Crushing tests
A simple, inexpensive, yet very
efficient way of detecting the presence of
volatiles in fluid inclusions, and in some cases
identifying them and roughly estimating their
proportions, is by performing a crushing test.
This technique makes use of the fact that,
except for H2O, these volatiles have vapor
pressures considerably higher than atmospheric
pressure at room temperature (~25°C), and
consequently vapor bubbles in fluid inclusions
10-2
containing them will expand if the inclusions
are breached. By contrast, the vapor bubble of
an aqueous fluid inclusion devoid of other
volatile species will collapse and disappear, as
the vapor pressure of H2O is only 0.03 bars at
25ºC.
A crushing test is initiated by placing a
small grain of the fluid inclusion-bearing
mineral on the lower glass plate of a crushing
stage, covering the grain with a few drops of
immersion oil, lowering the upper glass plate
onto the grain and fastening the two parts of the
assembly (Fig. 10-1). The crushing stage is
then placed on a microscope stage, where the
glass plates are gradually brought closer
together by slowly tightening the knurled
fastening knob while observing the sample. As
the pressure on the sample is increased,
fractures begin propagating in various
directions and, in some cases, will be seen to
intersect fluid inclusions. If a fluid inclusion
breached in this manner contains volatile
species other than or in addition to H2O, the
vapor bubble will expand (unless the proportion
of these volatile species is extremely low) and
be released into the surrounding immersion
liquid. The identity of the dominant volatile
species released in this manner can often be
established by repeating the crushing test with
immersion fluids in which the particular gases
are known to be extremely soluble, e.g., a
barium chloride solution for CO2 or kerosene
for CH4 (the bubble will shrink rapidly and
FIG. 10-1. A crushing stage (A) and a sketch of
the crushing stage designed by Roedder (B;
modified after Roedder 1984).
disappear into the immersion liquid). The
pressure of the gas species, and, in turn, its
mole fraction in the fluid inclusion (assuming
there is one, overwhelmingly dominant species,
and that it can be identified) can be roughly
estimated by measuring the diameter of the
bubble in the immersion liquid (the gas should
be relatively insoluble in this liquid) and
comparing this diameter to that of the vapor
bubble in the fluid inclusion before breaching.
From these data, the corresponding change in
volume can be estimated and used to calculate
the pressure in the fluid inclusion using the
relationship P1V1 = P2V2, where V1 is the
volume of the bubble in the unbreached fluid
inclusion, V2 is its maximum volume in the
immersion liquid, P1 is the pressure in the fluid
inclusion and P2 is the pressure of the bubble in
the immersion fluid (assumed to be 1 bar).
Knowing volume and pressure, the number of
moles of the volatile species can be estimated
using the ideal gas law PV = nRT, where n is
the number of moles and R is the gas constant.
The mole fraction of this species is obtained by
comparing n to the mass of the liquid, which is
calculated from its density by estimating the
inclusion volume and subtracting the volume of
vapor (cf. Roedder 1984, for further inform-
ation on the crushing method).
Quantitative techniques
The techniques routinely employed for
quantitative bulk analysis of fluid inclusion
gases are based on mass spectrometry (MS)
(e.g., Shepherd et al. 1985, Barker & Smith
1986, Kesler et al. 1986, Norman & Sawkins
1987, Guha et al. 1990, Landis & Hofstra 1991,
Sasada et al. 1992, Ruff 1993, Newman et al.
1996), and/or gas chromatography (GC) (e.g.,
Petersilie and Sørensen 1970, Cuney et al.
1976, Andrawes & Gibson 1979, Behar &
Pineau 1979, Burruss 1987, Bray & Spooner
1989, Salvi & Williams-Jones 1997b).
However, the bulk composition of fluid
inclusion gases can also be analyzed
volumetrically. This involves the use of cold
traps to separate the gases into groups based on
their freezing points. For example, by passing
the bulk gas through a trap containing a CO2-
acetone/alcohol mixture (-70°C) followed by
one containing liquid N2 (-196°C), it can be
separated into an H2O group, a CO2 group, and
a group of gases not condensed by liquid N2 (cf.
Piperov & Penchev 1973, Shepherd et al.
1985). The proportions of H2O and CO2 are
determined by placing the corresponding solids
10-3
in containers of known volume, reheating them,
and measuring the corresponding gas pressures
at a fixed temperature (this assumes that H2O
and CO2 dominate their respective groups).
Analyses for gases, such as N2, CH4, H2, CO,
He and Ar, which are not condensed by liquid
N2, require additional steps. In the case of H2
and CO, this involves oxidization to H2O and
CO2 (at a temperature low enough to prevent
oxidation of CH4) and separation of the latter
gases through a second series of CO2-
acetone/alcohol and liquid nitrogen traps (cf.
Piperov & Penchev 1973). Methane is treated
the same way by repeating the oxidation at
higher temperature, N2 is separated by reacting
the gas with hot calcium, and Ar and He are
separated using activated charcoal (cf. Piperov
& Penchev 1973, Moore et al. 2001). Although
the methodology is relatively simple and
inexpensive, the analyses are semi-quantitative
and the detection limits are high.
The main and very important
advantage of using MS is the extremely low
detection limits, on the order of 10-9 µmoles (cf.
Shepherd et al. 1985, Norman & Musgrave
1994), which allows analysis of gases
comprising a very small proportion of the bulk
fluid, and/or very small numbers of fluid
inclusions (cf. Graney et al. 1991, Landis &
Hofstra 1991, Moore et al. 2001). However,
species identification is difficult, partly because
peaks in the mass spectrum may represent more
than one species (e.g., N2, CO, and C2H4 have
the same molecular weight of 28), and partly
because gases fragment on ionization to yield
particles with different masses (cf. Norman &
Sawkins 1987, Landis & Rye 1989). The latter
is particularly problematic because the
fragmentation may produce masses
corresponding to species not present in the gas
or contribute to a peak in the mass spectrum for
a gas that is present, rendering the measured
amount of the latter gas anomalously high; the
apparent amount of the fragmented gas will be
anomalously low. For example, MS analysis of
an inclusion gas consisting only of CO2 will
produce a spectrum with peaks corresponding
to masses of 12, 16, 28 and 44. The peak for
mass 44 would predict an anomalously low
amount of CO2 and the peak for mass 28 could
be misinterpreted to indicate that N2, and/or
CO, and/or C2H4 are also present in the
inclusion. These problems can be greatly
alleviated by separating the gases cryogenically
before analysis into an H2O group, a CO2 group
and a group that is not condensed by liquid
nitrogen (see above), and comparing the spectra
for each group with standard spectra for
appropriate pure gases (see below).
A problem that cannot be addressed
satisfactorily by the above method is the
pyrolysis of hydrocarbons (due to the high
temperature of ionization), which can produce a
large number of lighter hydrocarbons, thereby
yielding an extremely complex mass spectrum
that may be impossible to resolve. Moreover,
even if pyrolysis is not a problem, the number
of hydrocarbons species initially present in the
inclusion fluid may be too large to permit
resolution of the resulting mass spectrum. A
related and potentially serious problem is that
peaks in these spectra may overlap with those
of non-hydrocarbon species and their associated
ion fragments, making reliable analysis of the
latter impossible. For example, Norman et al.
(1991) concluded that their measured content of
CO2 in some hydrocarbon-bearing fluid
inclusions was unreliable because equilibrium
calculations indicated that CO2 should not be
present at the concentrations detected. They
also concluded that the analyzed CO content
was an artifact because it correlated positively
with hydrocarbon content, and therefore
probably reflected pyrolysis of organic
compounds.
Other gases that are difficult to analyze
reliably with MS, include H2O, H2S, SO2, HCl
and H2. The problem with water is that MS
data reduction involves standardization against
N2 (see below), and it is difficult to prepare
standards with known quantities of H2O and N2
(Graney et al. 1991). Hydrogen sulfide is
problematic because it adsorbs onto the metal
of the ion source and inlet line (cf. Shepherd et
al. 1985, Norman & Sawkins 1987), and reacts
with any water introduced into the MS to
produce a variety of other sulfur species
(Newman et al. 1996). Sulfur dioxide and HCl
are commonly overestimated as they may be
produced during extraction of the inclusion
gases into the vacuum (Graney & Kesler 1995),
due to the increased stability of these species
with decreasing pressure (e.g., Shinohara 1992).
Finally, H2 may be produced by the filament
(cf. Bray & Spooner 1992). These problems
can be largely resolved by using glass lines,
keeping the gas frozen until analysis (Norman
& Musgrave 1994) and ensuring that H2O is
removed cryogenically prior to analysis. Water
may be analyzed by weighing the cryogenically
separated ice or determining the pressure of the
corresponding vapor (cf. Norman & Sawkins
10-4
1987, Norman & Musgrave 1994). Continuous
monitoring of real-time analyses (on-line
extraction, see below) can also help unravel
some of these problems, but requires very
careful calibration of the MS (cf. Graney &
Kesler 1995, Williams 1996).
Gas chromatography does not suffer
from the same problem of species identification
as MS, and permits analysis of virtually all
gases likely to be encountered in nature. It is
also non-destructive in the sense that most GC
detectors do not destroy the gases detected, and
consequently other types of analyses can be
conducted on them, e.g., isotopic analyses of
the component elements. However, GC is
considerably less sensitive than MS, with the
lowest reported detection limits being on the
order of 10-6 µmoles (Bray & Spooner 1992),
and thus the sample selected for analysis must
be relatively large.
From the above discussion, it is
apparent that GC and MS are complementary,
the former providing the advantage of
unambiguous species identification and
applicability to all gases, and the latter the
advantage of extremely low detection limits. In
view of this, and in order to capitalize on the
non-destructive nature of gas chromatographic
analysis, a potential approach to the bulk
analysis of fluid inclusion gases is GC followed
by on-line MS of the eluted gases (GC-MS).
As one of the principal objectives of fluid
inclusion analysis is to determine the complete
elemental composition of the fluid, it is also
recommended that bulk gas analysis be
combined with in situ bulk leaching and
analysis of the non-volatile residues of the
crushed sample (see below). In this way the
analyst can be confident that the determined gas
composition and elemental composition of the
non volatile phases apply to the same fluid
inclusion population (cf. Channer & Spooner
1994, Channer et al. 1999, Graupner et al.
2001, Gleeson 2003).
Methods of gas extraction
Historically, gas analysis of fluid
inclusions proceeded in three steps, i.e., the
gases were first released, then collected, and
finally an aliquot of the captured gases was
introduced into the instrument. Extraction
techniques involved stepwise decrepitation by
heating (e.g., Piperov & Penchev 1973),
decrepitation under vacuum (Behar & Pineau
1979, Welhan 1988) or grinding the sample in a
stainless-steel or ceramic ball mill under
vacuum (e.g., Abell et al. 1970, Petersilie & cracking of hydrocarbons or H2O. Bray et al.
Sørensen 1970, Roedder 1972, Ikorski & (1991) subsequently modified the design of
Voloshin 1982) (Fig. 10-2). Among these Andrawes & Gibson (1979), developing an on-
techniques, the decrepitation extraction method line GC system that permits analysis of up to
has proven to be the most problematic because three samples within one session (cf. Thomas et
of thermal decomposition and heat-induced al. 1988 and 1990, Bray & Spooner 1992, Salvi
chemical reactions, which can significantly & Williams-Jones 1997b for further descrip-
alter the original gas compositions. This tions of this system). Similar on-line crushing
produces unreasonably high blank methods have been developed for MS analysis
concentrations of common inclusion (e.g., Graney et al. 1991, Sloan 1992, Ruff
components such as CO2, CH4 and N2 (cf. 1993, Williams & Taylor 1996, Moore et al.
Norman & Sawkins 1987). However, all these 2001). The principal difference is that the
extraction techniques share another major sample chamber and extraction lines are under
weakness, namely that only a small proportion partial vacuum, because the MS operates at
of the released volatiles can be collected for reduced pressure. The released volatiles are
analysis. This significantly decreases the thus "sucked" into the MS. As is the case for
accuracy of the analysis and the ability to detect GC analysis, the extraction lines are heated to
trace components. minimize volatile adsorption (cf. Newman et al.
A substantially more efficient 1996, Parnell et al. 2001). In contrast to the GC
approach to the analysis of bulk inclusion gases
is to release the gases liberated by crushing or
decrepitation directly into the analytical device,
i.e., to extract the gases "on-line". Among the
first to conduct analyses of this type were
Andrawes & Gibson (1979), who designed an
on-line crushing device that they used in
conjunction with a gas chromatograph (see also
Andrawes et al. 1984, Barker & Smith 1986,
Burruss 1987). The device consists of a
piston/cylinder operated by a hydraulic press
and a crushing chamber where the inclusion
gases are released into a carrier gas, which
transports them to the GC (Fig. 10-3). The
sample chamber and all extraction lines are
heated to ~150ºC in order to reduce gas
adsorption and to induce immediate release and
dilution of the volatiles into the carrier gas.
This temperature is also low enough to prevent

FIG. 10-3. Schematic design of a piston-cylinder

FIG. 10-2. A sketch of an off-line grinding
system for fluid inclusion volatile extraction
(modified after Petersilie & Sørensen 1970).
crushing system for on-line GC analysis of
fluid inclusion volatiles (modified from
Andrawes & Gibson 1979 and Bray &
Spooner 1989; cf., Salvi & Williams-Jones
1997b).

10-5
method and because ionization involves heating
the sample to high temperature, thermal
decrepitation (typically at a temperature of
~1000°C) is also widely used for gas extraction
in MS analyses (e.g., Barker & Smith 1986,
Kesler et al. 1986, Norman & Sawkins 1987,
Guha et al. 1990, Moore et al. 2001) and offers
the advantage of nearly instantaneous transfer
of the inclusion gases to the ionization
chamber. However, as a result of the
development of better vacuum systems, this
advantage has largely been eliminated, and
crushing is now the preferred method of
extraction for bulk analyses (J.N. Moore 2003,
pers. comm.). On the other hand, the thermal
decrepitation method still offers one important
advantage, namely that the gas spectrum can be
continuously scanned as the sample is heated,
allowing gas compositions of sub-populations
of inclusions (or even single inclusions)
decrepitating at different temperatures to be
determined separately (Landis & Hofstra 1991).
Although on-line extraction techniques
are preferred for releasing volatiles from fluid
inclusions, whether for GC or MS analysis
(e.g., Newman et al. 1996, Volk et al. 2000,
Parnell et al. 2001), off-line extraction
techniques are still used by some researchers
(e.g., Karlsen et al. 1993, Ruble et al. 1998,
George et al. 1997, 2001, Munz 2001),
particularly for GC-MS analysis of petroleum
inclusions. For example, Guilhaumou et al.
(2000) used micro-drilling under a microscope
to extract oil from selected inclusions, thereby
avoiding the averaging effect of bulk methods.
Off-line crushing is recommended for heavy
hydrocarbons, which are in liquid form and not
readily volatilized, but requires the use of
organic solvents and precludes analysis of the
volatile fraction (cf. Ruble et al. 1998) unless
relatively complex analytical protocols are
followed (e.g., leaching in a vacuum chamber,
cf. Munz 2001).
MASS SPECTROMETRY
A mass spectrometer creates charged
particles (ions) from molecules and then uses
the difference in mass-to-ionic charge ratio
(m/e) of the ionized species to separate them
from each other (e.g., Johnstone & Rose 1996,
Breci 2003). Mass spectrometry therefore
provides quantitative data on the amounts of
each molecular species as well as information
about their structures and other aspects of their
chemistry.
10-6
All mass spectrometers consist of three
distinct parts, i.e., an ion source where ions are
created from gas molecules, a mass-selective
analyzer (filter), which separates the ions
according to their m/e, and an ion detector,
which measures the quantity of ions for each
m/e (Fig. 10-4). Some mass spectrometers, i.e.,
those with magnetic-sector, quadrupole, and
time-of-flight designs, also have optical
systems to facilitate extraction and transfer of
ions from the source region to the analyzer.
Quadrupole mass spectrometers (Fig. 10-5) are
by far the most widely used in fluid inclusion
gas analysis because they have very high
scanning speeds, and are therefore ideally
suited to analyze gases introduced in very short
bursts as is the case during crushing or
decrepitation of fluid inclusions. Another
advantage of the quadrupole mass spectrometer
is the low voltage applied to the ion source, i.e.,
the kinetic energy of the ions is on the order of
5x10-10 eV, compared with several keV for a
sector instrument. This eliminates problems
related to high voltage, and makes interfacing
to a GC easier (cf. March et al. 1989).
Additional advantages of the quadrupole mass
spectrometer are its superior transmission
efficiency and wide acceptance angle, which
give it very high sensitivity, its small size, its
relatively low cost and its ease of operation.
Figure 10-6 shows the schematics of an on-line
system for fluid inclusion volatile analysis by
QMS. Time-of-flight mass spectrometers have
also been employed for fluid inclusion gas
analysis (cf. Williams 1996) and make use of
differences in transit time through a drift region
to separate ions of different masses. An electric
field accelerates all the ions into a field-free
drift region with a kinetic energy of qV, where
q is the ion charge and V is the applied voltage.
As the ion kinetic energy is 0.5mv2, lighter ions
FIG. 10-4. Flow chart depicting the principal
steps involved in mass spectrometric analysis.
 FIG. 10-5. Schematic design of a quadrupole MS (modified after Breci 2003).

FIG. 10-6. Design for MS analysis of fluid inclusion volatiles (adapted from Graney & Kesler 1995).

10-7
have a higher velocity than heavier ions and Fragmentation of larger molecules can
reach the detector at the end of the drift region proceed along several paths and lead to a large
sooner. Advantages of time-of-flight mass variety of smaller fragments. For example, the
spectrometers are that they can analyze a wider molecular ion of methanol may decompose
range of m/e than any other type of MS and do according to the reactions:
so more rapidly (e.g., Brunnee 1987).
[CH3OH] +.(molecular ion) →
However, instruments of this type are not well-
[CH2OH] +(fragment ion) + H+.
suited to fluid inclusion analysis because they +.
(or) [CH3OH] (molecular ion) →
operate in a pulsed mode requiring that ions be
[CH3] +(fragment ion) + [OH] + + .
produced or extracted in pulses.
(. is a radical electron)
Analysis of fluid inclusion gases by
MS takes place in the following steps regardless and additional fragments may be created by
of the type of mass spectrometer used: further breakdown of the larger fragments
produced by these two reactions (e.g., De
Extraction → Ionization → Mass Analysis →
Hoffmann et al. 1996, Johnstone & Rose 1996).
Ion Detection → Data Analysis
The fragments are actually charged ions with a
particular mass, and as most fragments have a
Ionization methods
charge of +1, the m/e usually represents the
The two most commonly used
molecular weight of the fragment.
techniques to ionize gases involve electron
bombardment (electron ionization) and
Chemical ionization (CI) is used mainly when
chemical reactions that remove non-bonding
there is a need to enhance the abundance of the
electrons (chemical ionization) (cf.,Breci 2003).
molecular ion, and involves reacting the analyte
The ionization takes place at reduced pressure
molecules with a reagent capable of converting
(<10-7 torr) in order to prevent collisions of ions
them to ions by either proton or hydride
with residual gas molecules in the analyzer
transfer:
during their flight from the ion source to the
detector.
MH + C2H5+ → MH2+ + C2H4
MH + C2H5+ → M+ + C2H6
Electron ionization (EI) is widely used in mass
spectrometry for relatively volatile samples that
where M is the molecule of interest. The
are insensitive to heat and have relatively low
reagent ions are produced by introducing a
molecular weight. It is the preferred ionization
large excess of methane (relative to the analyte)
method for fluid inclusion volatiles. An EI
into an electron impact (EI) ion source.
source uses a high-energy electron beam (70
Electron collisions produce CH4+ and CH3+,
eV), usually generated from a tungsten
which further react with methane to form CH5+
filament, to knock electrons off analyte
and C2H5+.
molecules to create ions (e.g., De Hoffmann et
The two ionization methods described
al. 1996, Johnstone & Rose 1996). EI usually
are limited to the molecular weight range 50 to
produces singly charged ions containing one
800 Dalton, although in rare cases it is possible
unpaired electron. A charged molecule that
to analyze samples of higher molecular weight
remains intact is called the molecular ion.
(Vidavsky 2003). The accuracy of the mass
However, energy imparted by the electron
measurement at low resolving power is ± 0.1
impact and instability in a molecular ion can
Dalton and at high resolution is ± 5 ppm (De
cause that ion to break (crack) into smaller
Hoffmann et al. 1996).
pieces (fragments). Thus, for example, while
Other ionization methods include
the water ionization reaction is:
electrospray (ESI), fast atom bombardment
H2O + 1 (fast) electron → [H2O] + + (FAB), matrix-assisted laser desorption
2 electrons (MALDI), laser ionization (LIMS), plasma-
desorption ionization (PD), resonance
the ionization process will also produce
ionization (RIMS), secondary ionization
fragments of [OH]+, O+, and H+. Consequently,
(SIMS), and spark source thermal ionization
the mass spectrum of water will have four
(TIMS) (cf. Breci 2003). However, EI is the
peaks corresponding to masses of 1 (H+), 16
preferred ionization technique for fluid
(O+), 17 ([OH] +), and 18 ([H2O] +).
inclusion volatile analysis by MS.

10-8
Ion sorting
Molecular and fragment ions are
accelerated through the mass spectrometer by
using electromagnets to manipulate the charged
particles; uncharged molecules and fragments
are pumped away. The quadrupole mass
analyzer employs positive (+) and negative (-)
voltages to control the path of the ions, which
travel along trajectories that are determined by
their m/e ratios. As EI ionization mostly
produces singly charged particles, ions having
the same mass will follow the same path. The
quadrupole (a group of four electromagnets) is
programmed by the computer to only direct
fragments with a particular m/e through the slit
at any given time; the rest bounce away. By
changing voltages continuously, ions of ever-
increasing mass can find paths through the
electromagnets to the detector. The cycle is
then repeated rapidly; 102 – 104 cycles or scans
can be performed per second depending on the
number of masses analyzed. The computer
records a spectrum for each scan, which may be
printed as a graph with an x-axis representing
the m/e ratios and a y-axis representing the
signal intensity (i.e., abundance) for each m/e
(Fig. 10-7) (e.g., Johnstone & Rose 1996).
Detection
There are many types of detectors, but
most operate by producing an electronic signal
when struck by an ion. Timing mechanisms,
which integrate these signals with the scanning
voltages, allow the instrument to identify and
report the m/e of the fragment striking the
detector. The mass analyzer sorts the ions
according to m/e and the detector records the
abundance of each m/e. Regular calibration of
the m/e scale is necessary to maintain accuracy,
FIG. 10-7. Mass spectrum of CO2. M+ designates the molecular ion (adapted from Chiu & Muddiman
2001).
10-9
and is performed by introducing a well
characterized compound into the instrument,
and "tweaking" the circuits until the amounts of
the molecular and fragment ions are reported
correctly.
Because the sensitivity of quadrupole
mass spectrometers has increased so much over
the past few years, the amount of material
needed for analysis is sufficiently small that it
is now possible to determine the composition of
very small populations of fluid inclusions or, in
some cases, even a single fluid inclusion (e.g.,
Barker & Robinson 1984, Barker & Smith
1986, Sommer & Gibson 1986, Moore et al.
2001). Nonetheless, as discussed earlier,
complex procedures and detailed analytical
protocols have to be followed in order to avoid
or minimize problems related to peak overlap,
adsorption etc. (cf. Graney & Kesler 1995).
Data analysis
Owing to the fact that ionization
causes fragmentation of the molecules
introduced into the MS, the mass spectrum for a
fluid inclusion gas containing even a small
number of species can be relatively complex
and include extensive overlap between
molecular and fragment ions. Consequently,
the data are reduced using a matrix algebra
method in which the mass spectrum is
compared to spectra of reference gases that may
be present in the inclusion. The latter are
analyzed to establish their fragmentation
patterns and determine the ionization efficiency
of each gas relative to N2, i.e., the response of
the detector to equal amounts of different gases
(Landis & Hofstra 1991; see also Graney &
Kesler 1995). These data are then used to
prepare a calibration matrix and sensitivity
vector multiplier, which are combined into a
general matrixA. The composition of the
unknown gas is determined by solving the
matrix equation:
Amn Pn = Im (1)
where m is the number of mass peaks, n is the
number of gas species, Amn is the general
calibration matrix, Im is a vector containing
the measured intensities of the different mass
peaks, and Pn is a vector of the partial
pressures of the unknown gases. The vector
Pn is calculated by solving the equation using
standard methods involving an iterative least
squares procedure. The equation is solved
several times for different sets of gases that
might reasonably be predicted to be present in
the inclusion fluid (a gas is assumed to not be
present and excluded from the matrix if the
most abundant ion fragment for this gas is not
detected) and the residuals for each mass
intensity are determined. The latter represent
the difference between the measured intensity
and that calculated by summing the percentage
contribution of each gas to the intensity,
weighted by its calculated partial pressure
(Pn). The reported analysis is provided by
that solution for which the average residual and
individual residuals for each mass are
optimized to minimum values. Results are
normally presented as ratios of partial pressures
of the different gases, mole fractions or mole
percentages, and are considered to have a
precision of 3 to 5% (Landis & Hofstra 1991).
GAS CHROMATOGRAPHY
Any substance that can be introduced
in its gaseous state into a gas chromatographic
column can be potentially analyzed by this
technique. The sample (generally consisting of
a mixture of components) is introduced through
a heated injector, which causes its vaporization
(if not already a gas, e.g., permanent gases and
light hydrocarbons) and is immediately fluxed
in a stream of pressurized gas. Helium, H2, Ar,
N2, CO2 can all be used as carrier gases, but He
is best-suited for most applications. The gas
stream then passes through a stationary phase,
which is contained in a tube of some sort,
referred to as a column (two parallel columns
are also used). The stationary phase is usually a
chemical compound that can selectively attract
components in a sample gas mixture causing
the different species to be retarded to differing
degrees. As the compounds are separated, they
10-10
elute from the column and enter a detector. The
time from when the injection is made (time
zero) to when elution occurs is referred to as the
retention time (RT). The column is contained
in an oven that can be programmed to increase
temperature gradually (or in GC terms, ramp
temperature). As the temperature increases,
compounds with low boiling points elute from
the column sooner than those that have higher
boiling points. One or more detectors
(connected in series or in parallel) analyze the
components as they exit the column and send
the data to a chart recorder or computer-based
data handling software (Fig. 10-8) (e.g.,
Jennings 1987).
While the instrument is in operation,
the computer generates a graph from the signal.
This graph is called a chromatogram (see
below). Each of the peaks in the chromatogram
represents the signal created when a compound
elutes from the GC column into the detector.
The x-axis displays the RT, and the y-axis the
intensity of the signal (proportional to the
abundance of the species analyzed).
Gas chromatography has been
employed for the analysis of volatile
constituents of bulk samples of fluid inclusions
for over thirty years (e.g., Goguel 1963,
Petersilie & Sørensen 1970, Mironova et al.
1972, Ypma 1974, Cuney et al. 1976, Behar &
Pineau 1979). However, until recently, the high
detection limit has restricted analysis to the
major gases. With advances in gas chromato-
graphic technology and the development of on-
line extraction techniques, the sensitivity of the
method has improved greatly, and detection
limits now range from 10-4 to 10-6 µmoles,
depending on the detector used. This makes it
possible to extend the analyses to include
components comprising <0.01 ppm of the fluid.
Choice of column
Gas chromatograph columns are of
two types: packed or capillary (Fig. 10-9).
Packed columns are typically stainless steel
coils filled with a stationary phase, whereas
capillary columns are thin fused-silica tubes
coated with a polar or non-polar stationary
phase on the inner surface. The stationary
phase interacts with the species in the gas
mixture, causing their separation. In columns
coated with a non-polar phase, the extent to
which species are retarded depends on their
volatility, whereas in polar columns it depends
almost entirely on interactions between
functional groups of sample components and
FIG. 10-8. Flow chart depicting the principal steps involved in (A) regular gas chromatography and (B) on-
line gas chromatographic analysis of fluid-inclusion volatiles.
those contained in the stationary phase.
Capillary columns provide higher separation
efficiency than packed columns but are more
easily overloaded by too much sample. Factors
influencing retention times are the length and
internal diameter of the column, the thickness
of the coating, the oven temperature, and the
carrier-gas flow rate (cf. Kaliszan 1987).
The ability of a chromatographic
system to separate complex mixtures depends
almost entirely on the choice of column. A
packed column (Fig. 10-9A) typically consists
of 0.5 m to 3 m of stainless-steel (Ni alloys and
silica glass are also used) tubing, generally has
an internal diameter (ID) between ~2 mm and
~5 mm, and is loaded with stationary phases,
porous polymers, or molecular sieves.
Capillary columns (Fig. 10-9B) usually
comprise between 12 m and 100 m of coiled
fused silica (stainless-steel is also used) tubing
of very small ID (the usual range is from 0.18
mm to 0.53 mm), and are coated with a µm-
scale thickness of stationary phases or porous
polymers (recently developed), molecular
sieves, aluminum oxide or carbon. There are
over a thousand different columns on the
market today, designed to meet the demands of
a wide variety of applications involving a large
number of different gases. Packed columns are
preferred by most fluid inclusion researchers
because they are able to handle a broad range of
sample volumes, satisfactorily separate the light
10-11
gases most commonly present in fluid
inclusions, and are relatively inexpensive (e.g.,
Bray et al. 1991). On the other hand, capillary
columns are better adapted to deal with the high
molecular weight species commonly present in
hydrocarbon-bearing fluid inclusions, but until
recently could not be used for fluid inclusion
analysis because the allowed flow rates were
too low. This problem has been overcome by
the introduction of a megabore class of
capillary columns, which have the added
advantage that they can be used to analyze H2O
(see below).
Choice of detector
Detectors that have been used for fluid
inclusion volatile analysis include the thermal
conductivity detector (TCD) (e.g., Behar and
Pineau 1979, Shephard et al. 1985, Smith et al.
1984, Bray & Spooner 1989), the flame
ionization detector (FID) (e.g., Behar & Pineau
1979, Shephard et al. 1985, Smith et al. 1984),
the helium ionization detector (HID) (e.g.,
Andrawes & Gibson 1979), the photoionization
detector (PID) (Bray & Spooner 1989) and the
flame photometric detector (FPD) (e.g.,
Andrawes & Gibson 1979). Of these, TCDs are
the most widely used for detection of inorganic
gases such as H2, O2, CO, N2, Ar, CO2, and
H2O; FPDs are the detector of choice for sulfur-
and phosphorus-bearing compounds, but their
application is limited to these species; FIDs

FIG. 10-9. Examples of A) a packed column and
B) a capillary column.
owe their popularity to their wide dynamic
range (ability to deal with a wide range of
concentrations), universal response to organics,
and simple design, but have relatively high
detection levels; HIDs have greater sensitivity
than other detectors (1 x 10-6 µmoles for most
compounds), but are difficult to use (for
example, Andrawes & Gibson (1979) had to
add H2 to the carrier gas to provide positive
responses from their HID), cannot analyze H2O,
and are very costly; PIDs have a dynamic range
similar to FIDs (Driscoll & Duffy 1987), lower
detection limits (cf. Table 2 in Bray et al.
1991), and respond to all compounds with an
ionization potential ≤12 eV.
An analytical approach that is suitable
for many applications is to direct the gas flow
sequentially through a PID and TCD (which is
possible because the PID analysis is non-
destructive). PIDs can be equipped with
ultraviolet lamps having energies ranging from
8.3 eV to 11.7 eV. The 10.2 eV lamp has the
greatest sensitivity of the available light sources
(cf. Driscoll & Duffy 1987), but cannot detect
low-molecular-weight compounds such as CH4,
10-12
C2H2, C2H4 and C2H6, which are more tightly
bonded and hence have higher ionization
potentials than heavier molecular weight
compounds. A substantially wider range of
molecular weights can be detected with the
higher energy, 11.7 eV lamp, but this lamp has
an expected lifetime of only ~500 hrs and is not
designed to be operated at temperatures greater
than 125°C. The window is constructed from
lithium fluoride in order to be transparent to the
low-wavelength emission lines of argon in the
11.7 eV lamp, and consequently undergoes
solarization (color center formation) with time,
particularly at higher temperatures (cf. Driscoll
& Duffy 1987). Methane ionizes at ≥12.98 eV
and therefore does not produce a linear
response even with this lamp. However, it can
be analyzed with the TCD down to masses
below 10-4 µmoles. Many inorganic gases
ionize at >12 eV (N2, CO, CO2, CH4, SO2 and
H2O) and cannot be detected with the PID. As
noted above, the TCD is the detector of choice
for the analysis of these gases.
Principles of detection
Micro-thermal conductivity detector (TCD)
A TCD measures the difference in
thermal conductivity between the effluent flow
from the column (carrier gas + sample
components) and a reference flow of carrier gas
alone. A voltage is produced that is proport-
ional to this difference, i.e., to concentration,
and generates the output signal. In the original
design, one TCD analyzed the column effluent
while a second received a reference flow from a
separate column. The resistances of the two
sets were compared in a bridge circuit. The
TCD employed in the system described below
uses a single filament, and examines the
reference and column effluent gas streams
alternately (switching every 200 msec) (Fig. 10-
10). This is a convenient design but causes
sample dilution of ~50 % at the detector vent.
Therefore, it is preferable to connect this TCD
model to the exhaust port of the PID.
Photoionization detector (PID)
Figure 10-11 shows the schematics of
a PID, which consists of a lamp (Fig. 10-11B)
and an ionization chamber (Fig. 10-11C). The
lamp is filled with a low pressure noble gas (Ar
in the 11.7 eV lamp), which produces an
emission line of specific wavelength in the far
UV region of the spectrum when excited by
electrical discharge. The flowing gas is
exposed to the UV light in the ionization
FIG. 10-10. Schematic cross-section of the micro-thermal conductivity detector used on the GC at McGill
University (designed by Hewlett Packard®, now Agilent®) and its external components. A solenoid
switching valve allows the detector to analyze alternately (every 200 msec) (A) the column effluent gas
and (B) a flow of carrier gas alone (from Salvi 1995).
chamber and is ionized by absorption of the UV
radiation according to the expression: Data collection and processing
+ - If the GC conditions (oven temperature
R + hv = R + e (2)
ramp, column type, etc.) are the same, a given
where R is the species to be ionized, and hv gas species will always elute from the column
(Planck’s constant times frequency) describes a at nearly the same RT and be accompanied by a
photon with energy greater than the ionization signal created by the detector, which is
potential of R. The ions become part of an recorded on a graph in form of a peak. The
electric field, and the resulting current, which is graph is a chromatogram displaying the RT on
proportional to concentration, is measured by the x-axis and the intensity of the signal
an electrometer and sent to the data collection (corresponding to the amount of the gas) on the
interface. y-axis.

10-13
FIG. 10-11 (A) Schematic cross-section of the photoionization detector used on the McGill system (PI-52-
02A model of HNU® Systems), and exploded views of (B) the lamp assembly and (C) the ionization
chamber (from Salvi 1995).
Historically, chromatograms were
printed on chart recorders, and peak integration
had to be done by hand. Nowadays, most
machines are connected to a computer and the
data is processed digitally by software
specifically designed for the purpose.
Computer-based manipulation of spectra
represents a major advance over hand treatment
of chart records. For example, there is no
limitation on the scale to which specific
segments of a signal trace can be enlarged.
This allows recognition of small peaks that
previously would have gone undetected.
Computer-manipulation also eliminates the
danger of off-scaling, as discussed by Bray et
al. (1991), who reported that they had to switch
the TCD to low sensitivity before elution of
CO2 and H2O to prevent loss of data by peak
truncation. As long as the signal is not stronger
than 1 V, which is highly unlikely for the
amounts of gas typically extracted from fluid
inclusions, the entire spectrum is stored by the
software.
Example of a system for on-line GC analysis
In the paragraphs below, we describe
in some detail the GC system installed at
McGill University (Salvi & Williams-Jones
1997b). A similar system can be found in the
F. Gordon Smith Fluid Inclusion Laboratory,
Department of Geology, University of Toronto
10-14
(cf. Bray & Spooner 1989). The gas extraction
part of the McGill system is based on the design
of Andrawes & Gibson (1979) and employs
crushing stages supplied by the University of
Toronto. The GC is an HP® 5890 equipped
with a PID and TCD, and a mega-bore capillary
column for gas separation.
In the above system (Fig. 10-12), the
carrier gas (ultra-high purity He) is routed to a
three-way valve that directs it either to the
internal flow controller of the gas
chromatograph, used with most capillary
columns (these require a split flow, thus the
injector is configured as in Fig. 10-13A), or to
an external regulator (0 to 400 kPa), which
mimics the controller generally employed with
packed columns (i.e., unsplit flow, injector
configured as in Fig. 10-13B). Both flow
controllers are connected to a second three-way
valve that directs the selected flow to a
switching panel comprising four three-way
valves (control valves) (Fig. 10-14). From
there the carrier gas can be directed to any of
the three crushers or to the injector by opening
the appropriate control valve to carrier gas
flow. All four injection ports are routed to a 6-
port valve, which selects one of the entry ports
while venting all others at a common exit (Fig.
10-14). The carrier gas passes through the
selected entry port where it is directed to the
10-15
FIG. 10-12. A schematic diagram showing the gas chromatographic system for analysis of fluid-inclusion volatiles at McGill University (after Salvi & Williams-Jones
1997b). The design is similar to that of the gas chromatographic system installed in the F. Gordon Smith Fluid Inclusion Laboratory at the University of Toronto.
FIG. 10-13. Schematic cross-section of the split/splitless gas chromatograph inlet depicting the gas flows in
(A) the split configuration typically used with capillary columns and (B) in the splitless mode, compatible
with packed columns (after Salvi & Williams-Jones 1997b).
oven of the GC and into the chromatographic second cylinder flows to two metering valves
column. mounted on the switching panel. From here the
A second tank of ultra-high purity He gas is directed to the other end of the four
(labeled ‘auxiliary gas’ in Fig. 10-12) is used to control valves allowing the crushers and/or
provide the confining pressure in the upper injector that are not on-line with the column to
portion of the crushers, and to supply He for be flushed with a stream of He at a flow rate
flushing the crushing chamber in preparation regulated by the metering valve. The He
for analysis (Fig. 10-12). The gas from the employed for flushing and that as the carrier

10-16
FIG. 10-14. A schematic diagram illustrating the operation of the 6-port valve used to direct one of the
sample inlets to the gas chromatographic column. As one port is selected to allow gas flow to the
column, all others continue purging to a common exit (after Salvi & Williams-Jones 1997b).
gas are isolated from each other but vent at a m x 0.53 mm ID particle trap, connected at the
common exit controlled by the 6-port selector start of the column.
valve. A shut-off valve fitted on this exit The mega-bore capillary column (0.53
allows the plumbing system to be closed and mm ID) provides the high capacity needed to
the pressure to build up as needed. The second separate volatile compounds as well as handle
metering valve adjusts the flow to the top the wide range of sample volumes that are
chambers of the crushers where shut-off valves intrinsic to fluid inclusion gas analysis. The
on the chamber outlets allow the system to be wide bore also allows for the fast flow rates
pressurized. required to deal with the large dead volumes in
In order to minimize absorption/ the extraction system, thereby obviating the
condensation of sample components between need to split the flow (cf. Fig. 10-13A),
the crushers and the column, gas lines and something which creates problems when there
connectors were constructed from Ni alloy is a crusher on line. The principal drawback of
stainless-steel and the valves with Hastelloy®. most mega-bore capillary columns is that they
In addition, all these parts are heated to ~120°C cannot be used in the presence of H2O.
during runs. To prevent rock particles and dust However, this problem is overcome by the
from damaging the selector valve and the recently developed PLOT (porous layer open
column, a silk-screen particle filter (~200 µm tubular)-type columns. The McGill University
pores) and a 1-µm frit filter are connected in system uses a fused-silica PoraPLOT® Q
series to the sample chamber outlets of the column manufactured by Chrompack Inter-
crushers. A similar pair of filters is fitted on the national, featuring a 20-µm-thick uniform layer
injector-line to keep flows equal. Additional of particles immobilized on the inner wall,
protection for the column is provided by a 2.5 which separates both polar and non-polar
volatile compounds, including H2O.

10-17
FIG. 10-15. Chromatograms showing the signals from (A) the micro-thermal conductivity (TCD) and (B)
photoionization (PID) detectors of fluid-inclusion volatiles released by crushing 1.5 g of pegmatite quartz
from the Strange Lake peralkaline complex (sample 55-A-1; cf., Salvi & Williams-Jones 1997a and
1997b). The analysis was carried out using the PoraPLOT®-Q capillary column. The label N2+ refers to
the fact that this peak is an unresolved composite N2 ± H2 ± CO ± Ar ± O2 peak.
Output from the detectors takes the these spectra and analysis of the gas
form of analog signals in the range -18mV to composition.
+1V, which, in the system described here, are
converted to digital data by an HP® 35900C Sample analysis
dual-channel interface and transmitted to an Before analysis, the sample is frag-
HP® 3365 Chromatographic ChemStation® (a mented to pieces between 0.75 mm and 2 mm
PC Microsoft® Windows™ operated computer in diameter, hand-picked, and cleaned with
code). This code displays the chromatographic doubly distilled H2O (~8 MΩ-cm; ethanol is
spectra on a computer monitor and provides the used in the case of sulfide samples). Between
algorithms necessary for the manipulation of ~0.5 g and 2 g of material are loaded into the
crusher, and the piston is lowered to just touch

10-18
the grains. The crusher and all lines are heated,
and both sample and confining chambers are
pressurized with a low flux of He (≤1 ml/min)
for a duration of at least 12 hours (overnight).
Flushing removes all air and H2O that may be
absorbed onto the sample. An oil pump is
connected to the ram by an on/off valve. Just
prior to analysis, this valve is in the “off”
position and the pump is loaded to about 30 to
35 MPa. Releasing this pressure by switching
the valve “on” causes a sharp and sudden stroke
of the ram on the piston, which crushes the
sample. The gas chromatograph run is started
synchronously.
During analysis with the capillary
column described above, carrier gas flow is set
to 20 ml/min at 35°C (because of its high
capacity, the 25 m x 0.53 mm ID PoraPLOT® Q
column operates best at high flow rates, which
are compatible with the injector set-up in
unsplit mode), and reference gas flow to the
TCD at 30 ml/min. A convenient temperature
program, i.e., one that enables separation of the
light gases with relatively short total run times
(longer retention times result in inferior peak
definition) is set up as follows: The oven is
cooled to -20°C before the analysis is started,
and 6.5 min into the run, after elution of CO2 on
the TCD, the oven temperature is ramped at
10°C/min to 35°C where it is held for 10 min to
allow H2O elution on a flat background (the
TCD is much more sensitive to temperature
fluctuations than the PID, as illustrated by the
rise in background coinciding with the onset of
the heating program on the TCD plot on Fig.
10-15A). The temperature is then increased at
5°C/min to 115°C and left unchanged for ~40
min, when the run is stopped. The total running
time is about 80 min.
Identification of peaks and standard-
ization is achieved by injecting different
amounts of known gas mixtures (available
commercially) into the GC, except for water,
which can be injected as saturated vapor at
known temperatures and pressures. Identific-
ation of species is accomplished by comparing
retention times. Calibration curves (Fig. 10-
16), constructed by plotting the integrated peak
areas against the injected amounts of a species
(known), are used to determine the amounts of
the eluted gases. Blanks are run by simulating
crush action with an empty sample chamber,
i.e., by just moving the piston, and by crushing
inclusion-free Brazilian quartz.
The first species to exit the column are
N2 ± H2 ± CO ± Ar ± O2, which form a
10-19
FIG. 10-16. Examples of calibration curves for
volatile species created by analyzing several
gas mixtures of known composition (after
Salvi & Williams-Jones 1997b).
composite peak with the TCD detector at 2.7
min. This peak is commonly assumed to
represent only N2. However, it is possible to
resolve this peak by changing the carrier gas, as
discussed below. Methane is detected at 2.9
min and CO2 at 5.6 min. The PID detects C2H4,
C2H2 and C2H6 at 9.9 min, 10.3 min, and 11.6
min, respectively. Water is separated at 14.5
min, on the 35°C plateau of the oven
temperature program and its elution typically
lasts about 2 to 4 minutes, depending on the
amount. After elution of H2O, data collection is
stopped on the TCD, as species not yet eluted
are detected on the PID. It is worth noting that
if a species were to elute at the same time as
water, the retention time of H2O could be easily
changed, and the two peaks resolved by simply
holding the oven temperature below zero for a
slightly longer/shorter time.
At the beginning of the second
temperature program, the C3 hydrocarbon
species, i.e., propane (C3H8), propylene (C3H6),
propadiene (C3H4) and propyne (C3H4), elute on
a flat background starting at 24.5 min.
Isobutane (C4H10) elutes at 34.5 min, and at
36.3 min n-butane exits the column followed
immediately by the ethanol peak. Isopentane
and n-pentane (C5H12) elute after the oven has
reached 115°C, at 44.5 min and 46.8 min,
respectively (Fig. 10-15). In samples of
hydrocarbon-bearing fluid inclusions from the
hyperalkaline Strange Lake granite (Salvi &
Williams-Jones 1997b) peaks were also
observed at 66.8 min, 69.2 min and 75.0 min.
The last peak corresponds to n-hexane (C6H14),
and, although the other two are uncalibrated,
based on their boiling points, they are
tentatively assigned to isohexane and
neohexane, respectively. The poorer shape
(width/height ratios ≥10-3) of the hexane signals
is due to the late elution of these isomers and
can be improved by running the samples
isothermally at 115°C, which shortens retention
times of these species to ~30 min. After elution
of the hexanes, the run is stopped, at about 80
min, and the oven is returned to -20°C.
Because of the nature of its construction, this
column reaches thermal equilibrium with the
oven almost immediately, which is convenient,
especially when making sub-ambient
temperature runs.
Heavier aliphatic and some aromatic
hydrocarbons (e.g., benzene, chlorobenzenes,
toluene) can be separated on this column at
115°C, but their retention times are extremely
long, producing very wide peaks (»5 min)
which drastically limits detection. This could
be improved by fitting the PID with a 10.2 eV
lamp, which would allow an oven temperature
of up to 300°C, and would dramatically reduce
the elution times of species with boiling points
higher than ~100°C (e.g., octane b.p. = 125°C).
It would also improve detector sensitivity for
aromatics by a factor of ten (cf. Driscoll &
Duffy 1987). However, as mentioned earlier,
the 10.2 eV lamp cannot detect the C2 alkanes.
H2S and SO2 have similar retention times to
C2H4 and H2O, respectively, but have not been
analyzed on the McGill system. This system
may, however, not be well-suited for analysis of
these gases as they are reported to absorb on the
metal surfaces of the crusher and transfer lines
(C. Bray, pers. comm., 2003).
Analysis for H2 and Ar
Hydrogen and argon can be analyzed
successfully using the PoraPLOT® capillary
column described earlier if separate aliquots of
the same sample are analyzed and the carrier
gas is changed from He to N2 (Salvi &
Williams-Jones 1997b). As noted above, the
first analysis will yield a composite peak for N2
± H2 ± CO ± Ar ± O2, using a TCD. By
contrast, the peak for N2 will be eliminated in
the second analysis and there will be no peak
for CO because of the very high detection limit
for this gas (~5 x 10-2 µmoles) with N2 as the
carrier. Furthermore, peaks for H2 and Ar will
be distinguishable because the latter peak has
inverted polarity (Fig. 10-17). Oxygen can be
ignored because of its extremely low partial
pressure, even under the most oxidizing
conditions. The second analysis is related to
10-20
the first by normalizing it against a gas detected
in both analyses with the TCD, for example,
CH4. Carbon dioxide should not be used in the
normalization as it does not respond linearly
with amount when N2 is the carrier gas. The
composite peak of the first analysis is used to
determine the content of N2 after correction to
remove the contributions of H2 and Ar; except
for fluids trapped at near magmatic
temperatures, the contribution from CO can be
assumed to be negligible.
The composite peak discussed above
can also be separated into its constituent gases
by cooling the column down to –70°C and
subsequently heating it in a series of
programmed steps to ambient temperatures
(Thomas et al. 1988 and 1990, Bray & Spooner
1992).
Some researchers have tried analyzing
H2 using molecular sieve packed columns in
order to solve the problem of peak overlap with
N2, Ar, CO, O2 (e.g., Andrawes & Gibson
1979). However, although H2 is detected at low
concentrations with such columns, most other
gases cannot be detected at the required levels.
Consequently, the amount of H2 cannot be
related to those of the remaining fluid inclusion
gases, which must be analyzed on another
column from a separate extraction.
GC-MS
As mentioned earlier and as has been
discussed above, GC and MS are
complementary, the former providing the
advantage of unambiguous species
identification and applicability to all gases, and
the latter the advantage of extremely low
detection limits. In principle, an approach to
fluid inclusion gas analysis, which would
combine the different strengths of the two
techniques (and is used routinely in other
analyses) is sequential on-line analysis with GC
and then MS. This approach would employ the
GC to identify the various gas species (where
concentrations are sufficient for detection) and
separate them physically (by their different
retention times) for subsequent MS analysis.
The MS would thus receive a continuous stream
of gas directly from the GC comprising the
carrier and a sequence of fluid inclusion gases
separated in time. By thus allowing the MS to
analyze individual gas species rather than
mixtures, on-line GC-MS would greatly reduce
the complexity of the spectra that must be
resolved (ionization of even simple mixtures
can create large numbers of ion fragments with
FIG. 10-17. Chromatograms showing the response of the TCD to gases released by crushing two aliquots of
quartz from the same sample of the Strange Lake peralkaline complex using (A) helium and (B) nitrogen
as carrier gases (sample TTR-22; cf., Salvi & Williams-Jones 1997b).
overlapping peaks), and thus significantly analytical sensitivity that might be afforded by
improve the accuracy of the analysis. Where the MS. In order to minimize sample loss
concentrations are too low for GC detection, the during flow splitting, a number of GC/MS
approach would also ease the difficulty of MS interfaces have been designed that make use of
species identification. devices such as molecular sieves or semi-
The main obstacle to the application of permeable membranes. However, the majority
GC-MS analysis to fluid inclusion gases is that of these designs have intrinsic drawbacks that
the MS can only handle very low rates of gas limit the quality of the analyses.
flow. Consequently, the flow rate from the GC In principle, the problem of interfacing the GC
needs to be reduced before introduction of the with the MS could be solved by the use of
fluid inclusion gases into the MS. In the case of narrow bore capillary columns in the former, as
packed columns, approximately 99 % of the these provide for flow-rates low enough to
flow has to be diverted to waste leaving only permit direct entry of the gas into the MS.
1% to enter the MS. This results in a two However, on-line extraction of fluid inclusion
orders of magnitude increase in the detection gases produces a wide range of sample volumes
limit, which largely negates any advantages in and large dead volumes, necessitating the use of

10-21
packed columns or megabore capillary columns
for GC analysis (see discussion of McGill GC
system). Consequently, most researchers who
use GC-MS systems to analyze fluid inclusion
gases do their extraction off-line and inject the
collected gas (typically after cryogenic
separation) directly into the GC-MS (e.g.,
Norman et al. 1991, George et al. 1997, 2001).
This re-introduces the problem (solved by on-
line crushing) that only a very small proportion
of the released fluid inclusion gases can be
collected. An alternative approach, which has
been developed recently and retains on-line
extraction, is to run a loop off the extraction
line into a N2 trap (inside the GC or just before
it, e.g., Volk et al. 2000, Ruble et al. 1998)
designed to collect all the extracted volatiles
(Fig. 10-18). By subsequently warming the trap
along a programmed temperature gradient in
the GC oven, the gases are released sequentially
and analyzed (after splitting the flow; see
above) with a small bore capillary column
(Ruble et al. 1998, report the use of a 25 m x
0.32 mm fused silica column). However, this
method does not permit real-time analysis of
the released inclusion gases.
The above notwithstanding, GC-MS
remains a valuable tool, particularly for the
analysis of complex molecules, e.g., those in
petroleum inclusions (cf. Ruble et al. 1998,
Volk et al. 2000, Guilhaumon et al. 2000,
George et al. 2001), and can also be very useful
in analyzing complex mixtures involving
common inclusion volatiles such as CO2, H2S
N2, H2, CO, SO2, He, Ar, CH4 and light
hydrocarbons (e.g., Norman et al. 1991),
especially when these species are in low
concentrations.
The data obtained in GC-MS analyses
consist of a series of mass spectra that are
acquired sequentially in time. To generate this
information, the mass spectrometer scans the
selected mass range repeatedly during the
chromatographic run. If a scan is taken every
second and the run is 30 minutes long, 1800
spectra are recorded. This information may be
displayed in several ways, as shown in Figure
10-19. Firstly, the intensities of all the ions in
each spectrum are summed, and this sum is
plotted as a function of chromatographic
retention time to give a total ion chromatogram
(TIC), the appearance of which is similar to the
output of a conventional chromatographic
detector. Secondly, as shown in the diagonal
display in Figure 10-19, any of the spectra can
be displayed. Each peak in the TIC represents
10-22
FIG. 10-18. Sketch of a closed system for
analysis of inclusion volatiles by GC-MS
(adapted from Volk et al. 2000).
an eluting compound that can be identified by
interpretation of the mass spectra recorded for
the peak. Finally, as shown in the lower part of
Figure 10-19, the intensity at a single m/e ratio
over the course of a chromatographic run can
be displayed to yield a selected ion current
profile or mass chromatogram. This allows
components of interest to be found in a
complex mixture without having to examine
each mass spectrum individually.
GEOLOGICAL APPLICATIONS
Analyses of bulk fluid inclusion gases
represent a valuable source of data for
interpreting a variety of geological phenomena
and processes, and are playing an increasingly
important role in both mineral and petroleum
exploration. In this section we briefly review
examples of some of these applications.
Two of the questions which commonly
challenge researchers investigating hydro-
thermal systems are the nature of the fluid
source(s) and how the fluid evolved temporally
and spatially. Moore et al. (2001) have recently
used MS analyses of fluid inclusion gases to
address these questions for The Geysers, one of
the largest producing geothermal systems in the
world. On the basis of N2/Ar, 3He/4He and
CO2/CH4 ratios, they showed that the fluids
come dominantly from magmatic and meteoric
sources, that the latter fluid is important mainly
in the central and southeastern parts of the field,
and that its influx coincided with the change
from liquid- to vapor-dominated conditions.
They also showed that episodes of boiling could
FIG. 10-19. Example of a spectrum produced by a GC-MS analysis (adapted from Chiu & Muddiman
2001).
be readily identified by changes in the N2/Ar
ratio, variable incondensable gas to H2O ratios
and systematic variations in the proportions of
CH4, CO2 and H2. In the case of ore-forming
hydrothermal systems, analyses of the bulk
gases have also provided valuable information
with which to interpret depositional mechan-
isms. For example, Graney et al. (1991), in a
study of inclusion gases from Carlin-type gold
deposits in Nevada, showed that samples from
mineralized areas had higher H2S/CO2 ratios
and more consistent H2O/CO2 and H2O/N2
ratios than samples from unmineralized areas,
and used these relationships to argue
convincingly that the gold was transported as a
bisulphide complex and deposited as a result of
boiling. Contrasting H2S/CO2 ratios are also
characteristic of mineralized and unmineralized
samples from Mississippi-Valley-Type lead-
zinc deposits, and have been used by Landis &
Hofstra (1991) to support a fluid mixing model
for ore deposition. More generally, by helping
to identify fluid sources, evaluate metal
transport potential (estimate ligand concent-
ration, e.g., H2S), establish the redox state (e.g.,
using CH4/CO2 and H2S/SO2), estimate
temperature and pH, and record gradients in
fluid chemistry, bulk inclusion gas
geochemistry represents a valuable data source
for genetic modeling of ore deposition and a
potentially powerful tool for metallic mineral
exploration (cf. Kesler et al. 1986, Graney et al.
1991, Landis & Hofstra 1991, Norman et al.
1991, and Wang et al. 1999).
In petroleum geology, fluid inclusion
gas geochemistry has found extensive
10-23
application in assessing the maturity of crude
oils (e.g., George et al. 2001), determining their
evolution during migration (e.g., Jensenius &
Burruss 1990) and reconstructing the history of
reservoir filling (e.g., Karlsen et al. 1993).
Recently, several authors, notably Barclay et al.
(2000) and Parnell et al. (2001), have suggested
that fluid inclusion gas geochemistry could be
used as a tool for estimating petroleum
reserves. One of the key pieces of information
required for the latter is the location of the oil-
water contact, which normally is interpreted
from geophysical well logs (e.g., electrical
resistivity, gamma ray spectrometry). Barclay
et al. (2000) have proposed that this
information can also be provided by fluid
inclusion stratigraphy (FIS) and in some cases
more reliably so than by geophysical well-logs.
This new approach involves MS analysis of the
bulk fluid inclusion gases in large numbers of
drill cuttings or core samples and developing a
stratigraphy for specific compositional
indicators. As the oil-water contact represents a
zone where the composition of petroleum is
modified by large differences in the solubility
of various hydrocarbon components in water,
changes in the ratios of key species, e.g., a
sharp increase in the benzene/toluene ratio
(toluene is 10 times more soluble in water than
benzene), might signal close proximity to the
oil/water contact. Similarly, FIS could play an
important role in optimizing oil recovery by
locating stratigraphic barriers to fluid flow, e.g.,
shale horizons from up-well reversals in
petroleum density (e.g., sharp increases in the
proportion of longer chain alkanes).
 As a final example of the application
of bulk fluid inclusion gas geochemistry, we
turn to an interesting feature of hyperalkaline
intrusions, namely that they commonly contain
abundant carbonic fluid inclusions dominated
by methane and other more complex
hydrocarbons (Petersilie 1962, Sobolev et al.
1970, Konnerup-Madsen et al. 1981). In the
absence of detailed information on the nature
and concentration of the different
hydrocarbons, the preferred explanation for
their presence had been that they were
components of a C-O-H fluid, which exsolved
from the magma and evolved by cooling along
a relatively reduced (QFM) rock-buffered redox
path (e.g., Gerlach 1980, Konnerup-Madsen et
al. 1985, Kogarko et al. 1986, Nivin et al.
1995). However, using the GC system
described above, Salvi & Williams-Jones
(1997a) were able to determine the
concentrations of alkanes up to C6 for
inclusions in the hyperalkaline Strange Lake
granite, and show that those for C2 to C6 alkanes
are far too high to support this simple magmatic
model. On the other hand, the proportions of
the alkanes relative to methane are remarkably
similar to those resulting from Fischer-Tropsch
synthesis, an industrial process used to produce
synthetic fuels by reacting CO or CO2 with
hydrogen in the presence of a Group VIII metal
(e.g., Fe or Ni) or its oxide (cf. Anderson 1984).
This suggested a natural Fischer-Tropsch
synthesis, which Salvi & Williams-Jones
(1997a) proposed occurred as a result of the
reaction of orthomagmatic CO and CO2 with H2
generated during alteration of arvedsonite to
aegirine. Magnetite, which was a product of
the alteration, was inferred to be the catalyst. A
similar hypothesis has been proposed to explain
the presence of hydrocarbons in serpentinites
(e.g., Berndt et al. 1996) and extraterrestrial
bodies (e.g., Zolotov & Shock 2000), and has
even been proposed as the mechanism by which
life originated (e.g., McCollom et al. 1999).
SUMMARY AND CONCLUSIONS
In this chapter, we have shown that
bulk analysis of fluid inclusion volatiles
provides an attractive alternative to individual
inclusion analysis for cases where the
inclusions are too small and/or the gases of
interest are in concentrations too low for the
latter analytical approach. In other cases, bulk
analysis can provide a valuable complementary
data set to that provided by the analysis of
single inclusions. The major limitation of the
10-24
bulk analytical approach is that for the results to
be meaningful a single population must be
sampled, something that is commonly difficult
to achieve because of multiple episodes of fluid
entrapment. Modern methods that have been
developed for bulk inclusion analysis are based
on gas chromatography and quadrupole mass
spectrometry, and generally involve on-line
extraction of the gases by crushing or thermal
decrepitation directly into the analytical device.
The advantage of gas chromatography is that
the species analyzed can be easily identified,
however, the detection limits are relatively
high. By contrast, mass spectrometry is
extremely sensitive but species identification is
more difficult. The two methods are thus
complementary. In principle, on-line extraction
of fluid inclusions into a gas chromatograph,
followed by on-line analysis of the eluted gases
by mass spectrometry, could provide an
approach to bulk fluid inclusion gas analysis
applicable to samples approaching the size of
single inclusions. If this goal were realized, the
method would combine most of the advantages
of single inclusion analysis with the superior
detection capability of bulk inclusion analysis.
In practice, however, this combination of gas
chromatography and mass spectrometry
introduces technical problems related to the rate
of injection of the gases into the mass
spectrometer, which are still not fully resolved.
Thus, while bulk fluid inclusion gas analysis is
an important complement to single inclusion
gas analysis, it cannot replace the latter.
Analyses of the gas chemistry of bulk inclusion
fluids have played an important role in
resolving a variety of geological questions
ranging from the controls of metal
concentration in the Earth’s crust to the origin
of hydrocarbons in extraterrestrial bodies, and
there is every reason to expect that such
analyses will find even greater application in
the future.
ACKNOWLEDGMENTS
We are grateful to J. Moore, M.
Malcomson, L. Beci, D. Hall and M. Paddison
for their help in answering some of the
technical questions raised during the
preparation of this chapter. Constructive
reviews by C. Bray, S. Kesler and I. Samson
helped improve the quality of the manuscript.
Finally, we would like to again thank C. Bray
for his advice and assistance during the
installation of the gas chromatographic system
in the fluid inclusion laboratory at McGill
University.
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