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Study of Fluid Inclusions: Methods, Techniques and Applications

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 Gond. Geol. Mag., V. 29(1 and 2), June and December, 2014. pp.19-28

Study of Fluid Inclusions: Methods, Techniques and Applications

K. R. Randive1*, K. R. Hari2, M. L. Dora3, D. B. Malpe1 and A. A. Bhondwe1
1
Post Graduate Department of Geology, RTM Nagpur University, Nagpur, India
2
Department of Geology, Pt. Ravishankar University, Raipur, India
3
Geological Survey of India, NER, Shillong, India
*Email: randive101@yahoo.co.in

ABSTRACT fact that they are fluid is just a question of reference

Fluid inclusions are small volumes of paleofluids
trapped in minerals which provide indispensable
information about geological processes, from high
temperatures at depth towards low temperatures near
the Earth’s surface. These inclusions are trapped gases,
liquids or crystals, either trapped singularly (one-phase)
or as a heterogeneous mixture of more than one phase
(multi-phase) in a single cavity. Depending upon the timing
of entrapment of liquid in the crystals, fluid inclusions
are classified as primary, secondary or pseudosecondary.
The inclusions occur either as isolated, clustered, or trail
bound; those occurring in groups form the Group of
Synchronous Inclusions (GSI) having similar composition
and time of entrapment. The composition of trapped fluid
varies greatly; commonly detected constituents include
H2O, CO2, CH2, H2S, Cl, Br, F, I, N2, S, Na, K, Ca, Mg and
Fe. There are several instruments used in the study of fluid
inclusions, but the basic study is carried out using heating-
freezing stages and Laser Raman Microprobe. The study of
fluid inclusions reveal geologically important information
such as temperature, pressure, salinity, density and depth of
trapping; and thereby providing direct information about
the conditions at which given minerals and rocks are
formed.
INTRODUCTION
Fluid inclusions are inclusions in minerals that are
filled with fluid (gas and liquid), and sometimes with
one or more solid phases. They result from defects in
crystals during their growth which lead to the entrapment
of fluid in their surroundings. The trapped fluids may be
liquid, vapor, or supercritical fluid, and the composition
of the trapped fluid may include essentially pure water,
brines of various salinity, gas or gas-bearing liquids,
and silicate, sulfide or carbonate melts, among others
(Roedder, 1984; Shepherd et al., 1985; Bodnar, 1994;
Andersen et al., 2001; Samson et al., 2003). Compared
to rock forming minerals, fluid inclusions are short-lived
objects. Their formation is instantaneous, or at least
very short at geological scale. Fluid inclusions are part
of the rock, they occupy roughly the same volume as
most accessory minerals; therefore, they are as deserving
as that of the study any rock-forming mineral. The
temperature, i.e. if the observation could be done close to
absolute zero, everything would be solid (Tauret, 2001).
Several terminologies are frequently used in the study
of fluid inclusions, important ones are explained in
Table 1.
Fluid inclusions occur in different patterns, e.g.
they are found isolated in a host crystal trapped during
initial crystallization or in trails along former micro-
fractures or grain boundaries. The study of abundance,
orientation and chemistry of fluid inclusions provides
a history of formation and alteration over time,
contributing to both fundamental processes in geology
as well as exploration for mineral deposits. Although,
in practice fluid inclusions are used mainly in studies
related to the metallogeny of mineral deposits due to
its applied character, this type of study is becoming
increasingly frequent in different branches of geology
and in some related sciences. Important areas of the study
includes: (1) ore deposits, (2) hydrothermal environments,
(3) sedimentary environment and diagenetic processes,
(4) metamorphic terranes with different metamorphic
grades, (5) volcanic areas, (6) mantle environments,
(7) petroleum exploration, (8) tectonic history of
deformed areas, (9) gemology, (10) paleoclimatology,
(11) paleohydrogeology, (12) extraterrestrial environ-
ments, (13) weathering of historical monuments, (14)
analysis of air-inclusions in ice cores, (15) ambar, etc
(Hollister and Crawford, 1981; Roedder, 1990; De Vivo
and Frezzotti, 1994; Shmulovich et al., 1995; Bodnar,
2003).
CLASSIFICATION OF FLUID INCLUSIONS AND
SILICATE-MELT INCLUSIONS
Classification of Fluid Inclusions
There are many ways to classify fluid inclusions
(Roedder, 1984; Goldstein, 2003), but one of the most
useful classification schemes relates the timing of
formation of the inclusion relative to that of the host
mineral (Bodnar, 2003). Based on their origin, fluid
inclusions are of following types:
20 K. R. Randive and Others

Table 1: Terminology commonly used in the study of fluid inclusions

Sr.
Terminology / phrase used
No.
1. Monophase Inclusions
2. Biphase Inclusions
3. Polyphase Inclusions
4. Homogenous Inclusions
5. Heterogenous Inclusions
6. Common abbreviations
7. Trapping Temperature (Tt)
8. Homogenization Temperature (Th)
9. Melting Temperature (Tm)
10. Eutectic Temperature (Te)
11. Initial Melting Temperature (Ti)
12. Incipient Melting Temperature (Ti)
13. Final Melting Temperature (Tm)
14. Temperature of Fusion (Tf)
15. Nucleation Temperature (Tn)
16. Decripitation Temperature (Td)
17. Metastability
18. Salinity
19. Equivalent weight-fraction (e.g. NaCl
Equivalent)
20. Pressure Correction
Meaning and explanation of the term
The inclusions having a single phase at the room temperatures, e.g. liquid, gas
The inclusions having two phases in the same inclusion at room temperature, e.g. liquid + gas; liquid +
crystals
The inclusions having more than two phases in the same inclusions at the room temperature; e.g. liquid
+ gas + crystals; liquid + vapor + solid(1)+solid(2)
The inclusions composed of a single phase
The inclusions composed of multiple phases (more than one phase)
Although there is no specific rule to abbreviate the commonly used terminologies; following are followed
by notion
V = vapor; L = liquid; S = solid; VL = vapor + liquid (liquid dominated); LV = liquid + vapor (gaseous bubble
with trapped liquid); L2V = two immiscible liquids + vapor; S3LV = three different solids + liquid + vapor;
use same logic with any combination of solid, liquid and gaseous phases.
The temperature of trapping or formation of a fluid inclusion.
The temperature at which a fluid inclusion gets transformed from a heterogenous (multi-phase) to a
homogenous (one-phase) state.
It refers to any temperature at which, when the the inclusions are heated (often measured after attaining
minimum temperature in a system by freezing, by gradually raising temperature). Of the particular interest
however, are following melting temperatures, viz., eutectic temperature, initial melting temperature and
final melting temperature.
The minimum temperature at which liquid is stable in a specified system. In an isobaric (constant
pressure) system, the eutectic temperature is a unique value at which different phases coexist.
Such combination of phases coexisting at a unique temperature are said to represent “eutectic
composition”.
The temperature at which a liquid is first observed due to progressive heating of solid-bearing fluid
inclusion. In gas-bearing inclusion this temperature does not necessarily correspond to the eutectic or
apparent eutectic temperature.
It is synonymous with initial melting temperature mentioned above.
The temperature at which a solid is completely melted (dissolved or dissociated) by progressive heating
of a fluid inclusion.
Known as a temperature of fusion, it is synonymous with final melting temperature discussed above.
Abbreviation ‘Tf’ is also used for denoting ‘temperature of formation’; therefore one needs to be cautious
of the indicated term.
The temperature of first appearance of a particular phase during microthermometry is said to be its ‘nucleation
temperature’. For e.g. if a homogenous liquid cools to form a first crystal, the temperature is denoted by Tn
(L LS) or simply Tn (Solid). Similarly, nucleation can also take place during heating, e.g. Tn(SV 
SLV)
The temperature at which a fluid inclusion irreversibly ruptures, bursts, or ‘decrepitates’. This can happen
either due to heating, which causes extreme internal overpressure due to fluid expansion; or upon cooling
due to extreme internal overpressure caused by crystallization of ice. The decrepitation causes loss of the
contents of inclusion and reduction of inclusion volume.
In the thermodynamic sense, “metastability” refers to a system state characterized by a Gibbs free energy
that is not the lowest attainable under the specific conditions (e.g. T-Vm-X conditions). For fluid inclusions
this means that another phase assemblage should be present instead of the one observed. e.g. the
persistence of ice above 0°C upon heating of fluid inclusions is a cse of metastability.
It is the summation of total number of solutes, including electrolytes (e.g. NaCl, CaCl2) and non-
electrolytes (e.g. CO2, H2S), in an aqueous solution. In the multicomponent fluid inclusions compositions
are not known, therefore an indirect method is used wherein phase transitions are measured. The phase
transitions are sensitive to the overall salinity (e.g. Tm(ice), Tm(hydrohalite), Tm(halite), Tm(clathrate)). In such cases,
salinity is conventionally reported as NaCl or CaCl2 equivalents.
Salinity is conventionally expressed as equivalent weight fractions. e.g. weight-NaCl-equivalent of 25%
means that the inclusion shows phase transitions that are consistent with a mass fraction of 25% NaCl
in the aqueous phase.
The difference between homogenization temperature and estimated temperature of entrapment of the
fluid inclusion is called as Pressure Correction.
 Study of Fluid Inclusions
(1) Primary: fluid inclusions which are formed during
the formation of the enclosing crystal are primary in
origin. They are generally trapped along the growth
zones and crystal faces, or tends to occur solitary or
isolated. These are very good indicators of the condition
of crystallization of host minerals.
(2) Secondary: fluid inclusions which are trapped in
the fractures which are developed after the formation
of host mineral and caught due of healing of fractures.
These inclusions occur as trails or clusters which often
cut across the grain boundaries.
(3) Pseudosecondary: fluid inclusions which are trapped
during formation of the host minerals are referred to as
pseudosecondary. These inclusions occur along trails
that end abruptly against grain boundaries or one of the
growth zones.
Classisfication of Silicate Melt Inclusions
Linqui and Clocchiatti (1985) proposed a scheme of
classification for silicate-melt inclusion based on degree
of evolution achieved by the melt, as the above mentioned
scheme of classification based on origin of inclusion,
it may not sufficiently reflect the physico-chemical
condition of formation of silicate-melt inclusions of the
type occurring in volcanic setting.
The silicate-melt inclusions are classified as
(1) Non-evolved: These fluid inclusions have regular
cavity shapes with or without a small shrinkage bubble.
The tapped silicate melt remains almost in eqillibrium
with the host minerals and daughter mineral seldom
nucleate. These are formed when magma crystallizes
near the surface, leading to rapid cooling.
(2) Slightly Evolved: These fluid inclusions too have
regular cavity shapes with or without a shrinkage bubble.
The epitaxial growth of host minerals like mica generally
occur within inclusions, mostly adjacent to the cavity
walls. Such inclusions form towards the periphery of
crystal.
(3) Evolved: In these fluid inclusions, the silicate melt does
not remain in equilibrium with the host crystal, leading to
the growth of several daughter crystals. The silicate glass
occurs as a residue in these inclusions. They are trapped at
a great depth under pressure exceeding to 2 kbars.
Fig.1. a) Crystal showing fluid inclusions developed during formation of crystal: (I) Isolated, (II) inclusions parallel to growth zone,
(III) Inclusions inside the growth zone, and (IV) Inclusions crossing across the growth zone; b) Isolated two-phase inclusions;
c) Inclusions forming cluster within the crystal; d) Inclusions forming trails
21
ROEDDER’S RULES
For obtaining reliable information about the
original trapping conditions of fluid inclusions, either
primary or secondary, following assumptions were laind
down (Roedder, 1981, 1984), which are referred to as
“Roedder’s Rules”.
(1) The inclusions traps a single, homogenous liquid,
(2) Nothing is added to, or removed from, the inclusion
following trapping.
(3) The inclusion volume remains constant following
trapping, i.e. represent an isochoric system.
If the effects of pressure are insignificant or known;
the origin of fluid inclusion is known (by detailed fluid
petrography); the determination of temperature of
homogenization (Th) are both precise and accurate.
CRITERIA FOR RECOGNITION OF
FLUID INCLUSIONS
The fluid or melt inclusions are commonly
identified as primary or secondary on the basis of
detailed petrological study. Primary inclusions are to
be identified accurately, all other inclusions becomes
secondary. Zoned crystals provide important guides for
identifying primary fluid inclusions, important criteria
are listed below (Van Den Kerkhof and Hein, 2001).
Single Crystal
(1) The inclusions or group of inclusions in three
dimensional space are oriented parallel to the crystal
margins (Fig. 1a)
(2) Isolated inclusions usually occurring away from the
cluster of other inclusions. Distance is usually > 5X
diameter (Fig. 1b).
(3) The large inclusions in relation to host crystals
(4) Those inclusions that contains a solid phase, which
also occurs as solid inclusion in the host crystal.
Zoned Crystals
(1) Inclusions which occur in the core of prismatic or
columnar crystals
22 K. R. Randive and Others
(2) The inclusions which occur along the inter-section of
growth planes.
(3) The inclusions which are related to skeletal or spiral
growth.
(4) Those inclusions that occur in the growth zones.
(5) The fluid inclusions, which are caused by solid or
melt inclusions or intergrowth.
(6) Those inclusions that occur along the healed crack of
an older growth zone.
(7) Those inclusions that occur after solid or melt
inclusion or intergrowth.
FLUID INCLUSION ASSEMBLAGE (FIA) / GROUP
OF SYNCHRONOUS INCLUSIONS (GSI)
Goldstein and Reynolds (1994) introduced the
concept of Fluid Inclusion Assemblage (FIA) to describe
a group of fluid inclusions that were all trapped at the
same time. An FIA thus defines most finely discriminated
fluid inclusion trapping event that can be identified based
on petrography (Goldstein, 2003).This implies that the
inclusions in the FIA were all trapped at approximately
the same temperature and pressure, and all trapped a
fluid of approximately the same composition. Therefore,
the FIA represents a ‘fluid event’ in the history of the
system, and the fluid in the inclusions making up the FIA
represents the fluid that was present during that event
(Bodnar, 2003). Similar to this, Fonarev et al. (1998)
proposed that, a Group of Synchronous Inclusions (GSI)
corresponds to a limited number of (typically between 10
and 20) of inclusions formed at the same time, which will
serve as the test population to evaluate the homogeneity
of microthermometric data (notably Th).
FLUID TYPES
A fluid type is characteristic of a group of
inclusions, which either occur isolated, form clusters or
trails. They are composed of similar type of fluids and
trapped at the same time. Touret (2001) defined the fluid
type as follows: “a set of inclusions having (roughly) the
same chemical composition (e.g. low salinity, CO2-rich,
etc.), eventually variable density (in nature, a sufficiently
great number of inclusions will never have the same
density), approximately trapped at the same time (the
term ‘approximate’ indicates that the precise timing of
the inclusion formation is rarely known).”
ISOLATED, CLUSTERED AND TRAIL-BOUND
INCLUSIONS
The isolated inclusions are, in principle, primary.
However, additional criteria related to crystal growth
are often necessary to confirm their primary nature (Fig.
1b). The clustered inclusions are typically comprised
of a group of 10-20 neighboring inclusions (Fig. 1c).
Such clusters may have quite different origins such as
neighboring isolated cavities, or by transportation of a
former larger cavity. These clusters may be formed by
decrepitaion of inclusions by explosion or implosion.
The Trail-bound inclusions, occurring in the surface
of a former micro-crack, are certainly secondary (Fig.
1d). These inclusions are far more abundant than early,
isolated or clustered cavities.
Trail Terminology
The trail-bound inclusions either remain confined to a
single mineral or cut across different grains or phases.
Depending upon the observed trails in minerals different
terminologies used are given below (Fig. 2).
(a) Transgranular: a trail of fluid inclusions cutting
across different mineral grains throughout the rock.
(b) Intergranular: a trail of fluid inclusions crossing the
grain boundary and continues into another mineral grain.
(c) Intragranular: A trail of fluid inclusions confined
to a particular mineral grain. In such cases the trail of
fluid inclusions either, (i) remain confined to the crystal
interior, (ii) remain within grain-boundary and crystal
interior, or (iii) continues from grain-boundary to grain-
boundary.
(d) Interphase: a trail of fluid inclusions starts from one
phase and continuous into another phase.
(e) Transphase: a trail of fluid inclusions cutting across
different phases.
Inter-granular Decoration of Fluid Inclusions
The fluid inclusions often remain confined to a certain
textural feature, and are said to ‘decorate’ different inter-
grain textures. Following are commonly noticed (Fig. 3).
(a) Cleavage Plains: fluid inclusions occurring along the
cleavage plains.
(b) Deformation Lamellae: the fluid inclusions that are
confined to and occur along deformation lamellae.
(c) Deformation Bands: the fluid inclusions occurring
along the deformation bands.
Fig.2. Terminologies used for fluid inclusions (I) Transgranular,
(II) Intragranular (grain boundary to grain boundary), (III)
Intragranular (grain boundary to crystal interior, (IV) Intragranular
(crystal interior), (V) Interphase, (VI) Transphase, and (VII)
Intergranular
 Study of Fluid Inclusions
Fig.3. Fluid inclusions within different textural locations also
known as decorations, (I) along cleavage planes, (II) along
twinning lamelle, (III) along subgrain boundaries, (IV) along
deformation lamelle, and (V) along deformation bands
(d) Sub-grain Boundaries: the fluid inclusions that are
confined to sub-grain boundaries.
(e) Twin Lamellae: the fluid inclusions which occur
along the twin lamellae.
MODIFICATION OF FLUID INCLUSIONS
Originally trapped fluid inclusions are sometimes
modified because of several processes subsequent to
their trapping. These modifications cause reduction in
their volume, change in morphology and often loss of
originally trapped fluid. It is very important to identify
such modifications and study them (Sterner and Bodnar,
1987; Bekker and Jensen, 1990; Cordier et al., 1994;
Parnell, 1994). Commonly known mechanisms are
discussed below.
(1) Recrystallization: crystallization of fluids and re-
crystallization of solids trapped within fluid inclusions can
lead to substantial change in the fluid inclusion morphology
and lead to the development of negative crystal shapes.
(2) Stretching and Necking-down: necking-down is a
typical dissolution-precipitation process, which finally
leads to negative crystal shapes. The phenomenon of
necking-down corresponds to the evolution of decreasing
temperature, of a large tubular inclusion into a series
of small inclusions, which are initially connected by
capillaries.
(3) Explosion/Implosion Decrepitation: due to changes
in pressure-temperature conditions, large fluid inclusions
get busted or ‘decrepitated’ into smaller inclusions. When
pressure increases (overpressure), the decrepitation is
said to be ‘explosion decrepitation’. Similarly, when the
pressure is considerably reduced (underpressure), the
inclusion gets collapsed. Such decrepitation is known as
‘implosion decrepitation’.
(4) Leakage: sometimes, originally trapped fluid in the
inclusion gets leaked-out due to external processes such
as deformation.
23
METHODS OF STUDY OF FLUID INCLUSIONS
Sample Preparation
A Fluid Inclusion Section (FIS) is a doubly polished loose
plate, of the size of normal thin section (approximately
3 x 5 cm), but significantly thicker than those used for
petrological studies. The quality of polishing, the ideal
thickness (typically between 90 and 120 µm), depending
on transparency of the host crystal and the inclusion size
and abundance, are very important factors (Touret, 2001).
Fluid Inclusion Petrography
The textural relationship between fluid inclusions and
the host rock is studied in detail in fluid petrography. It
begins with careful study of the different populations
of fluid inclusions in such way that the fluid inclusions
analyzed is a true representative of the characteristic fluid
of the process. The fluid inclusions that are observed in a
crystal can be the result of different fluids with which the
crystal has interacted throughout its history. Therefore,
in order to ensure the representativeness of the inclusion,
it is necessary to conduct a proper petrographic study
that selects the representative inclusions and avoids the
temptation of focusing solely on the more aesthetically
beautiful, best-formed or larger fluid inclusions. A
petrographic study must provide information about
populations of fluid inclusions, such as number of
inclusions, their type, and chronology with respect
to geological events, etc. A thorough and systematic
petrographic study is a key for proper decision-making
about the type of fluid inclusions to be examined further
(Roedder, 1981; 1984; Tauret, 2001).
Microthermometry
The microthermometric study of fluid inclusions is
done using a heating and cooling stage, a device that
allows increasing or decreasing temperature over a wide
range, between –200°C and +1500°C approximately.
This stage is placed on a microscope, so that the phase
changes occurring as well as the temperature at which
these changes taking place can be observed. As a normal
working protocol, the fluid inclusions are cooled to
the lowest temperature that the stage can achieve and
subsequently, the phase changes taking place are observed
while the temperature rises towards room temperature
again. The first change of phase that should be observed
in the liquid phase is the appearance of the first liquid
in the cavity (eutectic temperature). This temperature
is characteristic of each system and, therefore, helps
to associate the composition of the fluid inclusion with
a chemical system (Macdonald and Spooner, 1981;
Shepherd, 1981; Rosso and Bodnar, 1994; Bakker, 2001;
Fall et al., 2011).
Raman Microprobe
Raman Spectroscopy is routinely associated with the
study of fluid inclusions to determine the composition
of fluids. A confocal Raman microscope, uses an optical
24 K. R. Randive and Others

arrangement that inserts a limiting aperture at an image
plane. This approach serves to limit the Raman signal
entering the spectrograph to a very specific, sharply
in focus, volume in the sample. The resulting Raman
spectrum is characteristic of that isolated region alone,
eliminating or strongly reducing Raman signals from
out-of-focus regions in the field of view. By definition
a fluid inclusion is surrounded by a host mineral, yet a
Raman spectrum of the contents of the inclusion alone
can be obtained by focusing at a plane inside the specimen
and bringing the inclusion into focus. The analysis is
completely non-destructive, and spectra of volumes as
small as a few microns in size can be obtained (Dubessy
et al., 1989; Roedder, 1990; Van Den Kerkhof and Olsen,
1990; Tauret, 2001).
Apart from the above routine techniques, several
special techniques are also used for the study of fluid
inclusions. Table 2 lists all, but their detailed description
is beyond the scope of present paper.
INFORMATION PROVIDED BY FLUID INCLUSIONS
Fluid inclusions provide a wealth of information
on the geofluids that influenced the petrogenesis of
rocks. Such inclusions provide important information of
temperature, pressure, density, salinity and composition of
fluids (Roedder, 1979; Kreulen, 1987; Touret, 1987; 1992;
Santosh et al., 1991; Zhang and Frantz, 1987; Newton,
1989; Diamond, 1994; Vityk and Bodnar, 1995; Mukherjee
and Sachan, 2001; Bakker and Diamond, 2006).
Temperature of Entrapment of Fluid
One of the most important aspects of fluid inclusions
study is its ability to measure the temperature of
entrapment of fluids in the system by direct measurement
using microthermometry. In this technique two-
phase inclusions are heated till they homogenize. The
temperature at which homogenization takes place, is the
minimum temperature of entrapment of that fluid. If the
pressure of the system is known (by separate barometric
estimates) then the temperature of entrapment can be
estimated from intersection of isochore passing through
the temperature of homogenization.
Pressure of the Fluid System
It is very difficult to measure the pressure of fluid
system directly; however, it can be estimated using
separate barometric techniques such as phase relations
or geobarometry.
Density of Fluids
The density of the fluid can be calculated by knowing the

Table 2: Summary of methods employed in the study of fluid inclusions

Sr.
Name of the Technique Purpose Technique Type
No.
1. Petrological Microscope Primary study of inclusions, their abundance and Non-Destructive Optical
chronology
2. Cathodoluminiscence Mincroscopy / SEM Textural relations with host mineral, secondary Non-Destructive Optical
Cathodoluminiscence (CL-SEM) quartz
3. Ultraviolate Microscopy (UV) Detection and study of hydrocarbons Non-Destructive Optical
4. Infrared Microscopy Visualization of fluid inclusions in semi-opaque Non-Destructive Optical
and opaque minerals (e.g. cassiterite, chromite,
sphalerite, pyrite)
5. Scanning Electron Microscopy (SEM) Morphology of inclusions Non-Destructive Optical
6. Transmission Electron Microscopy (TEM) Microfractures around fluid inclusions /dislocations Non-Destructive Optical
7. Atomic Force Microscopy (AFM) Topology and irregularities at the atomic scale Non-Destructive Optical
8. Microthermometry Composition and molar volume Non-Destructive thermometric
9. Laser-excited micro-Raman Composition of non-aqueous fluids, identification of Non-Destructive Vibrational
spectrometry daughter crystals Spectroscopic
10. Fourier Transform Infrared Spectroscopy Detection of H2O, hydroxyl, CO2, etc Non-Destructive Vibrational
(FTIR) Spectroscopic
11. Fluorescence Spectroscopy Detection of hydrocarbons Non-Destructive Vibrational
Spectroscopic
12. Mechanical crushing of samples Non-aqueous fluids, qualitative Destructive Mechanical
13. Acoustic emission (AE) Decrepitometer Finger print of fluid inclusion content Destructive thermionic
14. Gas chromatography Bulk composition of fluid Destructive
15. Mass spectrometry (MS) Bulk fluid inclusion and isotope composition Destructive
16. Crush and leach combined Composition of aqueous fluids, element ratios, Destructive
with micro.chemical analysis, AAS, etc. dissolved daughter crystals
17. EPMA or SIMS (opened Identification of daughter minerals, composition of Destructive Single inclusion
inclusions) fluid inclusions (freezing method)
18 LA-ICPMS Composition including trace elements Destructive Single inclusion
 Study of Fluid Inclusions
temperature of final melting of (Tmf) and homogenization
temperature (Th) of the fluid. Placing these values into
equations of state for fluids of known composition (i.e.
knowing which system to deal with) can help to determine
the density of the fluid and to calculate isochores.
Salinity of Fluids
Salinity can be measured by observing the depression of
the freezing point of the aqueous fluids in the inclusion.
The salinity is expressed as NaCl equivalent since, the
presence of other ions such as Ca+2, cannot be determined
and will greatly influence the salinity estimates. For
determination of salinity, the stage is cooled with the
help of liquid N2 during cooling; the phase changes in the
inclusion are carefully monitored. After the liquid in the
inclusion completely solidifies, the stage is heated slowly
while the inclusion is observed. The temperature at
which the last piece of solid melts (Tmf) is then recorded.
This will correspond to the freezing temperature of the
inclusion. Knowing the freezing points of pure H2O
and CO2, the recorded freezing point (Tmf) is inserted
into an equation of state (one of the form: PV= nRT).
This freezing point depression for the system under
observation is directly related to the amount of impurities
present in this system, which provides information on
the concentration of salts in this fluid (i.e. salinity of the
fluid).
Composition of Fluids
Information about the composition of the fluids can
be obtained indirectly by measuring the first melting
temperature (also known as the eutectic melting
temperature Te or Tme). After freezing the inclusion, it
is heated slowly while being carefully observed under
the microscope. The temperature of first melting of solid
(ice) is recorded. Comparing this temperature to eutectic
melting points on published phase diagrams for binary
and ternary systems are used to estimate the composition
of the fluid. Fluid composition can also be determined by
Laser Raman Spectroscopy.
P-T History of the Sample
Careful study of the textural relations of fluid inclusion
assemblage may provide important clues to the P-T
history of the sample. For example, significant isothermal
decompression would cause some of the larger inclusions
to “explode” resulting in a decrepitated inclusion
surrounded by a number of satellite inclusions around it.
Isobaric cooling can also produce distinct textures.
Gas Composition of the Inclusions
Gases are common and are very important constituents
of fluid inclusions. CO2, CH4, N2, H2S, and inert gases
are the most commonly present gases in the inclusions.
Microthermometry is useful in determining the presence
and quantity of CO2 using freezing measurement
temperatures on the CO2-Clathrate. Methane can be
determined by its low liquefaction temperature below
25
-56°C. But most measurements of the gases species
require Laser Raman microprobe.
APPLICATION IN MINERAL EXPLORATION
The use of fluid inclusions in mineral exploration has
received varying degrees of attention over the years. The
more direct uses of fluid inclusions in exploration mainly
rely on defining an empirical relationship between some
inclusion characteristic and mineralization. Methods
for using fluid inclusions to assist target selection on
a regional scale or for more localised definition of
likely zones of focussed fluid flow or ore shoots can be
subdivided into three categories (Wilkinson, 2001):
1.  The occurrence or relative abundance of a specific
inclusion type
2.  Systematic variations in microthermometric
properties
3. Systematic variations in other properties (e.g.
descrepitation behavior, inclusion chemistry).
Occurrence or Relative Abundance of a Specific
Inclusion Type
The occurrence of CO-bearing inclusions has been
suggested as a favourable characteristic for exploration of
vein–gold deposits (e.g. Ho, 1987). Rankin and Alderton
(1983) used this type of approach to correlate the relative
abundance of specific inclusion types in granite samples
with the distribution of Sn–W–Cu mineralization in
the Cornish ore field. It was found that there was an
empirical relationship between inclusion abundance in
granite samples and mineralized areas.
A similar approach has been used in porphyry–
copper systems, where the occurrence of hypersaline
fluid inclusions containing several daughter minerals
and/or vapour-rich inclusions has been linked to ore
formation (Roedder, 1971; Nash, 1976; Bodnar, 1981).
Another example is in epithermal precious metal systems,
where the occurrence of cogenetic vapour and liquid rich
inclusions may be used to identify zones of boiling and
ore mineral precipitation (Kamilli and Ohmoto, 1977).
Systematic Variations in Microthermometric
Properties
One of the most important use of inclusion data is the
use of inclusion homogenization measurements to map
out thermal zonations, an approach of direct relevance
to exploration in epithermal and intrusion-centred
hydrothermal mineralization. Utilising coupled salinity
and homogenization measurements can also provide
important information concerning the anatomy of a
hydrothermal system, with exploration implications
(Fig. 4). Everett et al. (1999) showed how inclusion
homogenization temperatures declined and fluid
salinity decreased within the Silvermines fault zone
with increasing distance from the Zn–Pb–Ba deposits
in Ireland. Interestingly, homogenization temperatures
26 K. R. Randive and Others
Fig.4. Homogenization temperature–salinity diagram illustrating typical ranges for inclusions
from different deposit types after Willkinson (2001)
also decreased but fluid salinities generally increased on
moving into the footwall of the same fault zone.
Systematic Variations in Other Properties
The chemistry of fluids related to mineralization
show a distinct chemical signature, with systematic
variations in relative abundances of Na, Ca, S, Ba,
Sr and Rb being correlatable with mineralized and
unmineralized areas. Another empirical relationship
between inclusion chemistry and mineralization was
demonstrated by Haynes and Kesler (1987) in a study of
MVT mineralization in east Tennessee. They showed that
the Ca/Na ratios of inclusion decrepitates as measured by
SEM-EDS analysis were higher in ore-related dolomites
than in barren dolomites.
FLUID INCLUSIONS STUDY OF PALAEOGENE –
NEOGENE – HOLOCENE ROCKS
Fluid inclusions have been effectively applied in
the study of geothermal fields, where hydrothermally
precipitated minerals were found to be suitable phases
for such study. The entrapped fluids provide reasonable
estimates of the Pressure-Temperature-Salinity
conditions of the geothermal water and be reasonably
good geothermometers (Browne et al., 1976; Sasada et
al., 1986; Magro et al., 1998; Lutz et al., 2002; Ruggieri
et al., 2004). Fluid inclusions are among the potential
tools for the exploration of geothermal fields (Leach,
1981) and also for the study of genesis of minerals such
as anhydrite (Maramatsu et al., 2000).
Other areas where fluid inclusions find exclusive
importance are hydrocarbons in the petroliferous basins
and the areas of recent and sub-recent active volcanoes
(Frezzhotti, 2001). The fluid inclusions in petroliferous
rocks have been used to determine the physical limit of
petroleum migration and to reconstruct the geothermal
history of the sedimentary basin (Burruss, 1981; Pagel
et al., 1986; McLimans, 1987); such study has recently
been undertaken in sandstones of Jaisalmer basin,
Rajasthan (Verma et al., 2012).
The studies of fluid and melt inclusions had been
effectively used to explain important petrogenetic
processes; such as, liquid immiscibility (e.g. La Gomera,
Canary Islands; Frezzhotti et al., 2002), crustal anatexis
and crust-magma interaction (e.g. Aeolian Arc, Southern
Italy; Frezzhotti et al., 2004). The technique of fluid
inclusions study is very much there and finds applications
across the geological sciences. It is however, difficult to
specify their application in geologically recent rocks.
Nevertheless, the examples cited above provide vital
clues for using fluid inclusions in the study of Palaogene –
Neogene – Holocene rocks. The recently active volcanoes
and geothermal fields are particularly very promising.
SUMMARY
The study of fluid inclusions has come a long way
since their initial description by Sorby (1857). New
instrumentation has facilitated deeper focus in the study
by way of understanding their composition, morphology,
phase relations and thermodynamic properties.
Moreover, laboratory simulations of the synthetic
fluid inclusions allowed predicting exact conditions of
entrapment. Nevertheless, it is of paramount importance
to identify and classify the fluid inclusions by careful
petrographic study. Microthermometry aided by Raman
Spectroscopic study helps to estimate composition and
T-P-X composition of the fluid system, which is used
further for construction of isochors and evolution of the
fluid system.
 Study of Fluid Inclusions
ACKNOWLEDGEMENTS
We thank Prof. S. J. Sangode for inviting us to write
a paper in the special issue on “Advances in Geoscientific
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