CHAPTER 5

FLUID INCLUSIONS
Chapter 5

FLUID INCLUSIONS
5.1 Introduction
Fluid inclusions are small amount of fluids that are trapped within crystals
during initial growth from solution. They are very abundant in common ore and
gangue minerals. The most important applications of fluid inclusion are in
understanding the process of ore deposition (Roedder, 1984). Some times, they
occur in billion or more per cubic centimeter. Inclusions, those are trapped at the
time of growth of host mineral termed primary may be samples of original fluids
and reveal important information regarding the conditions of ore transportation
and deposition. (Roedder, 1980). Secondary inclusions do not reliably give
information on the nature of ore forming fluids or conditions. But, may provide
some insitu into post-depositional conditions. The typical host minerals in which
the fluid inclusions are observed include sphalerite, cassiterite, quartz, calcite,
dolomite, fluorite and barite. Roedder (1979) even notes that some feldspar in
granites contains many fluid inclusions with daughter NaCl crystals. It is very
important to remember that the fluid inclusions in a mineral provide information
only on the fluid present at the time of sealing of the inclusion weather that is
during the growth of the host mineral or during rehealing of the later fracture.

Fluid inclusions range in size from rare megascopically visible, that are greater
than 1 cm in length to submicroscopic size. Fluid inclusions provide a record,
albeit complex fragmentary and miniscule fluid long since gone from the face of
the earth. Hence, they provide a rich source of small, but, valuable clues for
unraveling past geological processes. As such, they are important clues in
understanding geological modules (problems), the temperature, pressure, density
and composition of the fluids that formed or trapped in the rock.

H.C. Sorby (1858) first proposed the use the term "Fluid Inclusion" for
deciphering the temperature of past geological events. Fluid inclusions have
provided much information that has been used in many ways in the mineral
exploration and in problem of understanding the physical and chemical events of
ore deposition. Fluid inclusion studies on Molybdenite mineralization have
revealed the compositional similarities in the ore bearing fluids despite the wide
ranges of host lithologies of ages. (Kamilli, 1978; Konnerup Madsen, 1979;
Bloom, 1981; Olsen and GrifFm, 1984; Roedder, 1984; Norman and Sawkins,
1985; Rice et al, 1985; Larson, 1987; Lang and Eastoe, 1988; Santosh, 1988;
Ahmed et al, 1992; Taner, et al, 1998; Melfos et al, 2002; Somarin and Ashley,
2004; Omkesh Murthy et al, 2004)

In this chapter, an attempt is made to describe in detailed types of fluid

inclusions associated with the Ashapura Molybdenite mineralization along with
the results of microthermometric data. This data will provide the densities of the
inclusions to determine the P-T conditions of mineralization and the origin of the
ore bearing fluids as well.

5.2 Fluid Inclusion Sampling and Methodology

Petrographic study of a rock sample is the first and at the same time essential
step in any fluid inclusion study. Detailed sampling is carried out on mineralized
granites of Ashapura area and surrounding barren granites (Map 3) to understand
the mineralisation process. Although many late fi-actures carrying molybdenite
mineralization with in the mineralized granites, it is assumed that, various
episodes of cross cutting fractures have not altered the properties of the pre-
existing fluid inclusions. Diamond (1990) is of the opinion that the late generation
of fluids within the host rocks may be altered in their composition and density due
to the deformation and become unreliable for study. Therefore, careful selection
of samples for fluid inclusions was made.

A rock may contain millions of fluid inclusions per cubic centimeter and
consequently, an intelligent selection of the fluid inclusions for detailed analysis is
indispensable. The first selection already starts during rock sampling in the field.
The variation in the different lithologies within the mineralized granites of the
Ashapura area was documented and the position of the sample is clearly specified.
Even within the same lithology, fluid inclusions may show considerable variation
54
in composition and density and therefore, 2 to 3 samples from the same outcrop is
taken in order to get an overall impression of the fluid inclusion variation (Van
denKerkhofetal., 1994).

Fluid inclusions petrography is carried out using ordinary microscopes, where

as microthermometric measurements were done using LINKHAM TH 600 dual
purpose heating and freezing stage that can be heated to +600 °C and cooled to -
190 °C. Calibration is done using synthetic CO2 and CO2-H2O. Doubly polished
wafers of granites are prepared as per the methods given by Holland et al, (1978),
Allman and Lawrance, (1972); Herald Wetlaufer et al (1982); and Roedder,
(1984). Care was taken to avoid excessive heating and mechanical shattering of
the samples and considering the textural relationship between the fluid inclusions
and the host minerals makes the interpretation of the fluid inclusion. Like the
minerals fluid inclusions do not tell us about one particular episode of rock
forming processes (Van den Kerkhof and Hein, 2001), but generally about
different stages of its evolution (Roedder, 1984). When properly interpreted fluid
inclusions provide information that cannot be obtained other wise, they are the
only evidence for the role of the fluid during geological process (Roedder, 1984).
Fluid inclusions formed at more or less the same stage of rock evolution are some
time designated as belonging to the same fluid inclusion generation Touret (2001).

5.3 Descriptive Classification of Fluid Inclusions

Fluid inclusions are described by visual parameters like size, shape, colour,
and refractive index at room temperature. The term fluid inclusion may be
somewhat captious since at the room temperature more than one phase is normally
present. Liquid (L), gas or vapour (V) eventually together with/ without one more
solid phase (S), which may be accidentally trapped as a daughter phase during
cooling.

The number and type of phases present at room temperature is one of the most
useM and widely applied criterions to describe fluid inclusions. Inclusions
trapped during/along the formation of mineral are termed primary or
pseudosecondary and inclusions trapped after some time after the growth of the
55
mineral is termed secondary as proposed by Roedder (1984) and Shephard et al,
(1985).

Although the size of fluid inclusions of Ashapura granites shows extreme

variation from 5 to more than lOOjim. Estimating the size (volume) of fluid
inclusions is normally observed in two dimensions (Anderson and Bodnar, 1993).
Bodnar (1983) described a method to calculate more precisely fluid inclusion
volumes from the bubble diameter and the homogenization temperature, whereas
fluid compositions defined by the freezing temperature.

The fluid inclusion cavity tends to form crystal phases by re-crystallization

and/or dissolution. The 'negative crystal shape', typical for many natural fluid
inclusions (Fig.5.1). Fluid inclusions are colourless in thin section. However, the
difference of refractive index with the host mineral may, depending on the optics
(position of the condenser and the diaphragm), cause dark, greyish or pinkish
colours. By optical observation, we may distinguish the generally higher density
aqueous inclusions (refractive index 1.32-1.33 and showing as bright inclusions)
from the lower density gas inclusions. Liquid CO2 has a refractive index of about
1.195, gaseous CO2 a much lower refi:^ctive index and appears dark.

The number and type of phases present at room temperature is one of the most
usefiil and widely applied criterions to describe fluid inclusions. The content of a
fluid inclusion may be given by the phases and number of phases as a subscript.
For example: an inclusion containing liquid (L), vapor (V), and two salt crystals
(Si and S2) can be typified as LVS1S2. The relative volumes of the phases can be
estimated by using tables proposed by Roedder (1984) and Shepherd et al. (1985).

In many fluid inclusions, solid daughter phases can be found (Fig. 5.3). These
phases nucleate when fluid inclusions become over saturated during cooling. The
daughter phase at any temperature below the dissolution temperature is in
equilibrium with the saturated fluid (normally, but not necessarily water). For
example, the solution in a brine inclusion containing halite at room temperature
(and no other salts present) has a salt concentration of about 27 wt.% (Roedder,
56
1984). The refractive indices of quartz and halite are about the same and as a
consequence, halite crystals nucleated on the inclusion wall may be easily
overlooked.

5.4 Types of Fluid Inclusions

The spatial relationships of fluid inclusions provide information about the time
of formation with regard to the host mineral. The fluid inclusions in Ashapura
Mo-mineralized granites occur both as isolated groups (primary) (Fig 5.1) and
intersecting planar arrays (secondary) along well-healed discontinuous fractures
(Fig 5.2). Based on the phase relations in the inclusions at room temperature, three
principle types are recognized.

»3ri*»iiiwi»n3
- 236 -C
•\fOlim

< ^ . . ^

\ 2^ ^

-XI
Fig. 5.1 Photomicrograph showing isolated group (negative crystal shape) of primary
inclusion

Type I: Aqueous inclusions type II Carbonic and Aqueous inclusions and type
III Carbonic inclusions. Type I inclusions are present in all samples and their
abundance greatly exceeds the other type. They have high to moderate degree of
fill.

57
 Kt3St13an10/I]6/D3
IK- MS °C
pral-250X
iKieni

Fig 5.2: Photomicrograph showing array of inclusions along healed fractures and some
clusters of biphase inclusions

Fig 5.3: Photomicrograph showing array of aqueous biphase inclusions with some
daughter crystals

Type I: Aqueous inclusions are the most dominant type in all samples of
granitoids. These inclusions occur in different shapes: irregular, tubular, circular
and negative crystal shapes. Their size ranges from 18.1|j.m to 98.19 nm in
dimension. Aqueous inclusions of low to moderate salinity foimd in granites of
the study area. Their generally higher degree fill greater size and shapes help
distinguish them from other type of inclusions in granites. Some inclusions of this
type show variable liquid vapour ratios. Some of the inclusions extend to or cross
the grain boundaries, although small number appears isolated. (Fig. 5.1, 5.2 and
5.3).

58
 Type II: Carbonic and Aqueous inclusions occur in biphase (Lcarb + Laq) as
well as triphase (Vcarb + Lcarb + Laq) states at room temperature. In biphase
inclusions, the carbonic vapor nucleates within a few degrees of cooling from
room temperature (Fig 5.4). These inclusions display variable proportions of
carbonic and aqueous components, but no visual estimation of the volume percent
has been attempted, in view of the uncertainty in the third dimension. Like the
type-I inclusions, there is variation of size and shape in these inclusions:
additionally, different shapes of the Lcarb area (semicircular, oval) are also noticed.
This type of inclusions are subdivided broadly into two groups (1) with CO2 >
50% and (2) with CO2 < 50% by volume. These are moderately saline found in
quartz grains and are the next dominant types of inclusions in the granites of the
study area.

[mc- 23< X
1alc15 -C/m
tdMlm
ixlant

t RATE IS DEG 23.3

COOL RRTE TOO FAST

Fig 5 4 Microphotograph showing nucleation of CO2 carbonic vapour while cooling

Type III: Carbonic inclusions are closely associated with both type I and
type II inclusions. These are rich in CO2 without aqueous phase and nucleate in to
vapour bubble on cooling some times with a thin film of aqueous layer. They are
generally rounded to elliptical in shape. They are present on both isolated and
group of inclusions and along healed fractures and are dark in colour. This is due
to the difference in the refractive index. The inclusion size ranges from 11.21^m
to 216.19pm (Fig 5.1).

59
 287 X
lale-ISIC/mn
120T
4ald-0>n
iaians

Fig. 5.5. Photomicrograph of inclusions showing the evidence of necking

5.5 Fluid Inclusion Analysis

Microthermometric studies were carried out on about 40 doubly polished

sections of mineralized granites and adjacent barren granites. Fluid inclusions
represent the samples of the fluid present at the time during the cooling history of
the crystal and provide a rich source of valuable clues for unravelling the past
geologic process. Most of the samples studied are relatively small, care is taken to
study as many primary inclusions as possible. Inclusions suspected of necking
(Fig.5.5) are omitted from any type of microthermometric studies.

Temperature is obtained by heating of the fluid inclusions generally called

homogenisation temperature, which represents the temperature of trapping. This
temperature was used to obtain isochores.

Pressures of fluid inclusions from the Ashapura molybdenite mineralization

was obtained by computer programs (Bowers and Helgeson, 1985; NichoUs and
Crawford, 1985; Brown and Lamb, 1989)

The salinity expressed in wt % NaCl equivalent is determined from the

equations of Potter and Brown (1977) and Potter et al, (1978). Fluid inclusions
provide direct data on the densities of fluids. The density of inclusions is obtained
by using tables, formulas and fluid inclusions software (Takenouchi and Kennedy,
60
1965; Bodnar, 1983; Nichols and Crawford, 1985; Zhang and Frantz, 1987;
Sterner and Rodnar 199n Kuvemou University Library
Memer and Bodnar, 1991). ^^^^ Sahyadrl. ShankarafthaB*
5.6 Generation of Fluid Inclusions -f ^ 3 ^^ ^
Primary fluid inclusions by definition are trapped during crystal growth,
whereas, secondary fluid inclusions can be trapped at any time after the growth of
the host crystal (Roedder, 1979). Fluid inclusions in microcracks formed during
crystal growth are referred to as 'pseudosecondary'. The 'primary-secondary'
terminology is essentially applied to non-deformed euhedral or subhedral crystals.
Diagnostic criteria for classifying fluid inclusions as primary or secondary is
proposed by Roedder (1979). Examples of primary inclusions are given in (Fig.
5.6) for single crystals, in part, in respect to growth zonation. When applied to
massive rocks, as done in the past by many fluid inclusionists, the terms primary
and secondary may be misleading as primarily grown minerals generally are not
preserved. In this case, the terms early' vs. late' better characterize the relative
chronology of trapping. In spite of the difficulties of applying the 'simple'
primary-secondary terminology to complex natural samples, these terms appeared
to be highly useful as they imply important differences of the fluid regime: the
formation of primary inclusions requires that the rock system was supersaturated
with respect to the host mineral, whereas fractures will heal and trap secondary
inclusion even if the bulk fluid (outside the fracture) was undersaturated with
respect to the host crystal (Diamond, 1991). In massive rocks, fluid inclusions can
be principally subdivided in (a) isolated fluid inclusions,( Fig 5.1) (b) inclusions
in clusters, and (c) fluid inclusions in trails, essentially representing healed
microcracks (Fig.5.2). The trails can be classified according to the terminology
proposed by Simmons and Richter (1976) and Kranz (1983) Transgranular
inclusions form in healed microcracks crosscutting grain boundaries.

a. Intergranular inclusions decorating grain boundaries may be related to two

processes: (1) healing of extensional grain boundary cracks and (2) fluid
collection during grain boundary migration. These textures are particularly
common in rock^ which underwent intensive dynamic re-crystallization (Fig
5.3). ^/^
b. When considering fluid inclusions in textural relationship with different
mineral phases, the terms 'interphase' for fluid inclusions formed along phase
boundaries and transphase' for fluid inclusions in trails crosscutting different
mineral phases can be applied. Intersection of trails of different fluid
inclusions gives rise to a number of features that can be used for establishing
the fluid chronology (Touret, 1981). A common phenomenon is the refilling
of fluid inclusion in the region of intersection.

c. Intragranular inclusions occur within single grains and do not cross-cut grain
boundaries. They may be interpreted as the result of fluid trapping along
surfaces showing preferent crystallographic orientation. These surfaces may
be cleavage planes, deformation lamellae, deformation bands, subgrain
boundaries or twiiming lamellae.

Fig 5 6 Photomicrographs showing different types of primaryfluidinclusions

i Aqueous inclusions (1,2 & 5)
ii Aqueous-Carbonic inclusions inclusions (3 & 4) and
iii Carbonic inclusions at room temperature (6)

5.7 Microthermometry

The selection of fluid inclusions for microthermometric measurements is not

always simple and certain subjectivity caimot be avoided. Any selection is hable
to subjective criteria and finding representative' fluid inclusions an impossible
task. As a general rule, a homogeneous fluid trapped at the same pressure and
temperature conditions must result in fluid inclusions, which are identical in

62
composition and density. Most important is to group the fluid inclusions in a
rational way, depending on the study case, and therewith indicate their geological
relevance. Once distinguished on a textural basis, one must stick to this
classification and better define each of the groups during the subsequent analytical
procedure. The properties of each group should be further constrained and not
differentiated. A general indication about the number of fluid inclusions to be
analyzed cannot be made. Only a few measurements are sufficient to characterize
apparently similar fluid inclusions, which belong to the same generation.

5.7.1 Aqueous Inclusions

Microthermometric runs were taken on primary inclusions in the collected
granite samples associated with the mineralization. Only those inclusions, which
do not show any evidence of leakage or necking down and occur away from the
healed cracks, were chosen. The results of microthermometric runs were
reproducible within ± O.l^C (in case offreezing)and ± 0.5°C (in case of heating).
The results of the microthermometric runs are summarised in the Table 5.1 and
5.2. The temperature of last ice melting (Tm), temperature of homogenization
(Th), and the volume of the vapour bubble were used for calculation salinity
(NaCl Wt% equivalent), density (gm/cc) and volume ratio (VA^+L) of the
inclusion fluids.

Homogenization temperatures of type 1 inclusions in granites of Ashapura

range from 175 ^C to 340 °C, most primary inclusions homogenized at >300 ^C
(Fig. 5.7). After being frozen, the first liquid was observed at -55 °C to -25 '^C for
primary type 1 inclusions which, corresponds to the eutectic temperature of NaCl-
CaCla-HjO or MgCla-HjO (Shephard et al, 1985) and from about -77 °C to -24 ^C
for secondary type 1 inclusions. The temperature of final ice melting ranges from
about -27 °C to 0 °C. Hydrate phase was not recognized in these inclusions.
Salinities were calculated from the final melting temperature of ice using the
equation of Potter et al, 1976 and Hall et al, (1988) the salinities are range from
1.6 to 22.35 equivalent wt.% inclusions. A few eutectic temperatures of-21.6^ C
were determined represent a single NaCl-H20±KCl system. The salinities of the
inclusions containing a halite daughter mineral were obtained from the melting
63
temperature of halite (Tm Halite) returning to the solubility data of Potter et al,
(1977). For fluid inclusions containing halite and sylvite daughter minerals
salinity was determined by applying temperature of solutions of each such salt to
the ternary diagram of NaCl-KCl-HzO (Roedder 1984) and from the Solubility
curves for NaCl and KCl in aqueous solutions (Fig. 5.10). The halite dissolution
temperature was around 220 °C-365 "C with the homogenization temperature of
250 ^C-385 °C giving 15 - 22 Wt % NaCl. Densities of all type I fluid inclusions
at Th (p Th in gm/cc) were calculated with the regression equation of Bodnar
(1983). Salinity obtained from fluid inclusion thermometry was plotted versus the
homogenization temperatures (Fig. 5.9). A clear scattering of the data can be seen
which is inferred to the change in the composition of the fluid inclusions. A very
clear pattern has emerged, possibly the salinity path for the Mo mineralization. It
can be seen from the plots of Density Vs. Salinity (Fig.5.10) that the Molybdenite
might have precipitated during the cooling of the saline inclusions at a density of
> 0.8 gm/cc.

Th Diagram

Fig.5.7 Histogram Aqueous inclusions

^
^
^ 40

100 200 300 400 500 600

Temperature in °C

Fig 5.8: Solubility curves for NaCl and KCI in aqueous inclusions. 64
 1 i Ptmmy
1 jfx^ Pc nt Curve 1

• — :

Salijnit) pa F^ 1
i

Srtuijb „c^

•
i
1
•
2 4 6 B 10 '2 14 II6 18 2 0 2 Z 2 4
/ 2
t—,—H
E 2 S 3 0 3 e M
— •
3
— 1
1 e
. •
3
. 1
S
EdBt-fHACl

Fig 5 9: Th-Salinity plot of mineralized granites of Ashapura

04

02

5 10 15 20 25
Salinity in Wt % NaCI

Fig 5.10. Density and salinity variation diagram of Ashapura granites.

The Density ranges obtained are given in the table, 5.1 which clearly show that
the density values vary between 0.95 to 1 gm/cc. This is in the conformity with
the Th data.

65
Table 5.1: Fluid Inclusion Data For the Ashapura Granites

Stenqirilells XilASl mtA9t M«A15 m»kn Mi4l4 Mini tS

Type P p P p P p P
Cfatti L+V L+V L+V L+V L+V L+V L+V
Size range 44.65 92.17 30.89 96.1 88.7 213.33 15.35

FBI
9lMto 93.05 88.41 to 70J2^
9543
t^.3StO
1^.42
96.87 97.18 98.59
-l-fCto- -25°Cto -20°Cto -28.5° C
Te -22"C -30° C -33° C
27" C -44° C -32° C to -32°C
1563 to 138.9 to 142 tt»
Tk total i'3^te349 173 2^ 193
176.1 140.4 170
Phase V
1.65,
Wt% 146,
1175,
20.2
6.37 2.3»3.45 3.91 9.18 n:^
22J5
0.92 to 0.931 to 0.92 to 0.84 to
Density 0.67 - 0.9 0.922 0.943
1.062 0.97 0.971 0.909
%*teM nao^m
5.7.2 COrHzOsystem
This system involves two different critical points Water (Critial Point 371 °C)
and CO2 (31.1 ^C). The Ashapura molybdenite mineralization shows very
reasonable CO2-H2O inclusions. At room temperature, these inclusions are
immiscible, at high temperature the solubility increases dramatically. Kerrick and
Jacobs (1981) developed Redlich-Kwong equation for homogeneous mixtures of
CO2-H2O.

The CO2-H2O Fluid inclusions freeze to a solid phase below -95 ^C. During
heating runs, melting of the carbonic phase (Tm CO2) occurs either at the CO2
triple point of -56.6 ''C or over a small interval with depressed melting
temperatures between -57.8 to -55.6 °C (Table 5.2). These measurements indicate
that the carbonic phase in these inclusions is nearly pure CO2, in contrast the
inclusions with depressed melting temperatures that probably contain minor
amounts of additional gas species, most likely CH4 and/or N2 (Roedder, 1984,
Konnerup Madsen, 1979, 1981, Bumiss 1981, Diamond, 1990). Melting of the
CO2 clathrate (Tniciath) in the presence of CO2 liquid occurs between 8.1°C to 9.8

66
°C (Table.5.2), below and just above the invariant point of a pure CO2 clathrate 10
°C (Hollister and Burruss 1976). Partial homogenization (TI1CO2) of CO2 liquid +
CO2 vapor to liquid CO2, less commonly to vapor, occurs between 7.4 and 22.4 °C
The CO2 densities of the carbonic phase are 0.86-1.13 gm/cm3, and densities of
the bulk inclusions range from 0.67 to 1.06 g/cm3. Calculated salinities of the
aqueous phase in these inclusions range between about 5-15 wt% NaCl equiv,
with few inclusions showing salinities from up to 20 wt% NaCl equiv Fig.5.11).
Upon heating runs, more than one-half of the studied inclusions decrepitated prior
to final homogenization, at temperatures from 215-380 ^C. Total homogenization
temperatures to liquid, obtained mainly from inclusions witii lower CO2 contents
and smaller diameters, rangefrom245-385 °C (Table 5.2).

Table 5.2: Fluid Inclusion Data Aqueous Carbonic Inclusions With Some Salt Crystals

SttH^Wt Bvif M«A$I Mfl^lS Mmu

11.21jmito 96.1pinto
Size range 18.1jmi
44.65 pm 216.19tun
L+V

Fill 73.22 to 91.68 96.38 to 96.87 82.35

ThCC^ 8.fCto8.6°C -48.f*Cto-58*C -43®C
Clathrate -17°Cto-34°C 8.l"Cto9.l"C 8.9"C -9.8°C
D&mfCOi 0.857 toO.9 0.9S to 0.932 1.113
System H2O-CO2
HaBi^^eraiiipiB 215-3®)''C

5.7.3 C0rH20-NaCl system

A.

These inclusions are present in three phases and have sharp contacts. They are
characterised by the visible amount of H2O and CO2. They contain H2O + CO2
(liquid) at room temperature and nucleate in to the third phase the CO2 (Vapour).
Formation of clathrates are frequently noticed in these inclusions. The
temperature of decomposion of the clathrates occurred with in the range of +6.7
to 8.8° C. Collins (1979) observed the freezing of clathrates range from +8.0 to

67
+8.9° C. The complete set of data for these inclusions is given in the Table 5.3.
The CO2 rich liquid phase diminish slowly in volume and disappear completely.

These inclusions containing halite daughter mineral homogenize by

dissolution of halite at temperatures between 170 °C and 340 °C (Table 5.3). In
few cases, the liquid-vapor homogenization and halite dissolution occurred
simultaneously. The ice in frozen inclusions begins to melt at -60 °C to -40 °C.
Final melting occurs between -27 °C and -19 °C. Hydrate melts at temperature
from -16 °C to +18 °C. Type 2 fluid inclusion compositions were estimated using
the model system NaCl-CaCla-HiO. This was done using Tm ice, Tm hydrohalite
and Tm halite following the method of Williams-Jones and Samson (1990). The
homogenization temperature of this type of inclusions range from 150-380°C with
the peak of around 200-250 *^C (Fig. 5.12). The compositions of the halite-bearing
aqueous inclusions determined by this method vary from 18 to 26 wt.% NaCl.

Sample No Moa31 Moa 01 Moa 22 Moa 15 Moa 26

Size range 40.78 91.8 48.5 62.1 15.35
Degree of fill 91.68 93.05 97.19 88.41 83.42

ThC02 +25.2 and +29.5 °C +25-31 **€ 30/31 "C 21-28°C 20 -29°C

Clathrate 6.8 7.1 8.2 7.8 8.7

TmC02 -55.6 to -58.2 °C -55.6 -55.6 -55.6 -52

Salinity 19 22 18.6 21.5 16.8

System CO2- H2O -NaCl

Bulk density 0.89 0.75 0.88 0.82 0.87

Homogenization Temp. 175 278 179 228 193

Table 53: Fluid Inclusion Data for Aqueous Carbonic Inclusions

6 -]

5
(A
0) 4 -
Q.
£
CO o
<0 •i
<*-
0 1
0 2-
1 -

1 5 10 15 20
Salinity Wt°/.

Fig.5.11: Histogram of salinity Aqueous carbonic inclusions with NaCl crystal

68
 14

12

10

8 -

I
•^

150 200 250 300 350

Th in Degrees

Fig. 5 12. Histogram showing Th vs. frequency

5.8 Determination of Salinities using Clathrate

The melting of CO2 - clathrate depends upon the concentration of the salt in
the system and on whether clathrate melting is univarient or divarient (Olsen and
Griffin, 1984) and also on the CO2- H2O ratio. The dissociation temperature of
CO2 - clathrate (Tmdathrate forms a well defined peak around 9.1 to 9.8 ^C.
Clathrate dissolution occurs in equilibrium with vapour, carbonic liquid and
aqueous liquid. The homogenisation of these inclusions range between 27.2 to
29.2 °C. The associated Tm car, Te„ Tm ice and Tm clathrate data indicate only a
slight compositional variation.

The temperature of decomposition of the CO2 hydrate in the presence of Th

CO2 (liquid) and CO2 (gas) is depressed by NaCl in solution in a manner similar to
the effect of NaCl on the fusion temperature of ice. The measurement of salinity
becomes more erroneous due to the formation of the clathrate because the solution
becomes more saline. Therefore, the melting temperature of ice will not give the
real salinity (Collins, 1979, Parry, 1989), the salinities were determined from the
clathrate melting by using equations of Buzzo et al. 1973 and Parry, 1988).

Some of the inclusions containing both an aqueous phase and CO2 -rich liquid
phase, it was observed that the aqueous phase undergoes two distinct fi"eezing.
The first freezing is attributed to the formation of the clathrate compound CO2
hydrate (CO2 5.7 H2O) and the second freezing to the formation of ice (Collin,
1979). The presence of the CO2- clathrate obscures the initial melting of the salt-
69
hydrates and ice, consequently, the temperature recorded as the apparent eutectic
of salt - H2O subsystem refers to the lowest temperature at which the liquid
assemblages such as ice + CO2. clathrate + vapour + CO2 - liquid + aqueous liquid
could recognised (Diamond 1990). The result given in the figure therefore
provides only maximum values for the true eutectic temperatures.

The presence of volatile components such as methane and the addition of salts
decrease the melting temperature by about 2°C. per mole of NaCl in solution
(Holister and Burrus, 1976).

5.9 CO2 Inclusions

The C02 inclusions are dark in colour, due to this Refractive index the C02
inclusions can be identified easily. The temperature of melting of C02 (Tmco2)
was recorded around -56.8 ± 0.2 °C indicating very pure CO2. The
homogenization temperatures are given in Fig.5.13, which range from -20 to 30
°C giving the density of 0.595 to 1.032.

16
14 H
12
%
I 10
I 8
O"
u. 6
4
2
m//if/////////////^y^^^^^^^
0-f
-20 -15 -10 -5 1 10 20 30
ThC02

Fig.5.13: Histogram of Th vs. Frequency of carbonic inclusions

5.10 Estimation of Pressure

Pressures for the Ashapura Molybdenite mineralization was calculated using
CO2, pure aqueous-carbonic inclusions. Fluid isochores and densities were
calculated using MacFlinCor computer program of Brown and Hageman (1994),
NichoUs and Crawford. The equations of state used for the isochore calculation

70
are adopted from Bowers and Helgeson (1983) and Kerrick and Jacobs (1981) for
the H20-NaCl (KCl) and CO2 systems, respectively.

The significance of Th measurements of homogeneously trapped inclusions is

simple in the ideal isochoric measurements. The mineral hosts expand during
microthermometric heating at atmospheric confining pressure, causing fluid
inclusions to deviate very slightly from perfect isochoric behaviour (Diamond,
2001). Schmidt et al. (1998) and Schmidt and Bodnar (2000) homogenised
synthetic C02-H20-NaCl fluid inclusions in quartz under confining pressures
demonstrating that reversible expansion of inclusions upon heating may
significantly exceed that expected from the equation of state of bulk quartz. Zhang
(1998) attributed this additional stretching at low confining pressure to local stress
gradients around the inclusions, and formulated corrections for simple inclusion
geometries.

Representative inclusions were selected and their isochores are drawn for each
type of inclusions a wide range of salinity and homogenisation temperatures were
selected from the histograms. The isochores thus obtained are appropriate to their
Th values. The calculation of densities and isochores for the C02 inclusions
along with its purity was followed that of Burrus (1981) and Crawford (1981).

The isochores obtained are plotted in the Fig. 5.14. P-T diagrams display
isochores for CO2 and H2O inclusions were calculated using computer programs
(Bowers and Helgeson, 1985; Nicholls and Crawford, 1985; Brown and Lamb,
1989). It can be seen that the isochores obtained from the H2O and CO2 phases
show a pressure of frapping of around 2.8 - 3.7 kb and a temperatures up to 370
°C. To calculate the P-T estimates fluid inclusions were carefiiUy selected.
Aqueous and carbonic phases of inclusions showing maximum peaks from the
systems of H20-NaCl, C02-H20-NaCl and also the carbonic inclusions were
selected. The intersection of the isochors of these inclusions is taken as the P-T
estimates of the Ashapura molybdenite mineralization.

71
 P-T Diagram of Ashapura Molybdenite Mineralization

6000 ^
0 93 / ^ 8 6
0 88
5000 -

0 83
2" 4000 -
eg

'^ 3000 -
3
10
(fl
£ 2000 -
Q.

1000 -

0-
200 250 300 350 400 450 500 550
Th (in Degrees)

Fig. 5.14: P-T estimates of fluid inclusions of Ashapura area calculated from the
Aqueous and CO2 inclusions

Given that the state of the parent fluid can be identified, the P-T conditions of
the parent fluid can be estimated. If the inclusions represent the assemblages of
homogeneously trapped inclusions, then it is clear that the original P-T conditions
of entrapment cannot be reconstructed from fluid inclusion evidence alone. The
total homogenisation temperature (measured by microthermometry) and the
homogenisation pressure (derived from a quantitative phase diagram) serve only
as minimum constraints on the entrapment conditions. The isochores thus
produced also yields the ratio of the entrapment P-T conditions, but an
independent fluid barometer (the so-called pressure correction') or thermometer
is required to determine the exact conditions by intersection with the isochores
(Diamond 2001).

In view of the complications in interpreting entrapment P-T conditions from

inclusion assemblages with variable phase proportions, it is often more reliable to
use cogenetic assemblages of inclusions that trapped only one of the two
coexisting phases; carbonic liquid, or aqueous liquid. Such assemblages have
72
uniform phase proportions, and in favourable samples, distinct assemblages of
both end-member types may be present in addition to assemblages with non-
uniform phase proportions. The main prerequisite in applying this method is to
prove convincingly by petrographic arguments that the various inclusion
assemblages are truly cogenetic (Van den Kerkhof and Hein, 2001). If this
prerequisite is fulfilled and if internal pressures are not high enough to cause
reversible stretching during microthermometry, then the measured values yield the
P - r conditions of inclusion entrapment.

73