1

August 27 - 31, 2012

UNIVERSIDAD DE BUENOS AIRES
FACULTAD DE CIENCIAS EXACTAS Y
NATURALES
DEPARTAMENTO DE CIENCIAS GEOLGICAS
Postgraduate course
Fluid inclusions - Petrography
and genetic interpretation of
fluid inclusions. Application of
cathodoluminescence techniques
Dr. Alfons M. van den Kerkhof
Dr. Graciela M. Sosa
Geowissenschaftliches Zentrum
Universitt Gttingen (Germany)
2
Fluid inclusions are small volumes of paleofluid trapped in minerals and the only
direct evidence of the role of the fluid in geological processes. This short course
gives an overview of fluid inclusions in different disciplines of earth sciences and
related analytical techniques.
The textural relationship between fluid inclusions and the host rock is the subject
of fluid petrography, an essential part of any rock study and an important
issue in this course. Cathodoluminescence has shown to be a helpful technique
in the study of paleo-fluids and applications to fluid inclusions are also included
here.
Attention is paid to the physico-chemical properties of the most important
geological fluid systems. This information is essential for interpreting fluid
inclusion data sets. Microthermometry, the study of phase transitions in fluid
inclusions under the microscope at varying temperature is fundamental for any
fluid inclusion study. Therefore the principles of this technique and related
computer software are explained in detail. Special attention is also paid to Laser-
Raman microspectrometry, a technique which has proved to be highly powerful
for fluid inclusion analysis.
Fluid inclusions provide indispensable information about geological processes,
from high temperatures at depth towards low temperatures near the Earths
surface. Discussed are examples of magmatic fluids, hydrothermal ore deposits,
metamorphism, and diagenesis.
The course is meant for any earth scientist, student or professional, who has not
been in touch with fluid inclusions so far and wants to include this interesting
and varied topic in her/his future research.
Preface
3
Monday, August 27
9:00-13:00 Introduction. Definitions, historical notes, literature, classification of fluid
inclusions, daughter phases, mechanisms of fluid inclusion forming, Roedders rules, primary
and secondary inclusions, fracture healing, post-trapping modification of fluid inclusions,
autoclave experiments.
14:00-18:00 Training: microscopy exercises.
Tuesday, August 28
9:00-13:00 Working procedure (sample preparation, equipment), destructive and non-
destructive fluid inclusion analysis, crushing stage, acoustic emission analysis, Laser ablation
ICPMS, principles of microthermometry, isochore definition, computer programs, Raman
analysis.
14:00-18:00 Fluid inclusion petrography, fluid-rock interaction, fluid-induced textures.
Water-salt (ionic) systems with KCl, NaCl, and CaCl
2
in different geological environments.
Training: Microthermometry, crushing stage, software (isochore calculation), videos.
Wednesday, August 29
9:00-13:00 Water-gas systems. Clathrate hydrate stability, fluid-mineral equilibria and
graphite stability, oxygen fugacity in rocks, COHN equilibria calculations, non-aqueous
systems CO
2
-CH
4
and CO
2
-N
2
, working with VX diagrams.
14:00-18:00 Training: Microthermometry, software (COHN), videos.
Thursday, August 30
9:00-13:00 Basic principles of cathodoluminescence microscopy and application to fluid
petrology. Equipment. Cold and hot cathodoluminescence. Crystalline materials.
Activators, sensitizers, quenchers. Wavelength, energy.
14:00-18:00 Microstructures as a result of fluid-rock interaction: fluid pathways, paleo-
porosity, diffusional textures, healed microfractures. Examples.
Friday, August 31
9:00-13:00 Fluid inclusions in the granitic-pegmatitic system, fluid inclusions in ore
deposits, fluid inclusions in metamorphic rocks (examples).
14:00-18:00 Free exercises, presentations of participants and discussion. Examination.
Program
4
Fluid inclusion classification
Labelling of phases in
inclusions (J.L.R. Touret)
Although normally trapped as fluid,
fluid inclusions normally do not contain
(supercritical) fluid at room temperature.
V = vapor
L = liquid
S = solid
Descriptive classification based on the number and composition of phases
present at room temperature. Inclusions in minerals can be classified in solid,
solidified and fluid inclusions. The system can be applied also when the fluid
composition is unknown.
Multiphase (immiscible) liquids solids
L
1
+ L
2
+ V (3-phase) Mixed aqueous-
gaseous
Void (Empty): in terrestrial rocks,
atmospheric air
Supercritical fluids: CO
2
, CH
4
, N
2
, etc. Gas (no visible
liquid)
L + V + S : Multiphase solids
L + V: Aqueous Liquid (in general
liquid + vapor)
FLUID
Aggregate of microcrystals
Devitrified glass Crystallized
M + V + Solids (S)
M + V
Monophase (M) Vitrous (Glass) or
Melt (M)
SOLIDIFIED
Clastic
Crystalline SOLID
5
Estimation of volume fractions
In spherical inclusions the bubble size can be calculated according
r bubble / r inclusion = 3 (1- Vol.frac)
In aqueous inclusions the water volume fraction density (g/cm
3
)
Volume fractions of fluid inclusions in different orientation:
6
Volume fractions and homogenization temperature (C). The critical density of
CO
2
= 0.47, of water ca. 0.322 g/cm
3
.
Th CO
2
9 (V) 25 (V) 30 (V) 31 (C) 30 (L) 25 (L) 14 (L) -3 (L) -26 (L)
Th H
2
O 347 (V) 372 (V) 373
(V/C)
372
(L/C)
366 (L) 345 (L) 308 (L) 250 (L) 178 (L)
Liquid-vapor ratios as
seen through the
microscope in a fluid
inclusion waver in which
all inclusions contain 25
vol % vapor (Huizenga)
7
Optical properties of solid phases in fluid inclusions in order of
increasing refractive index
name composition refract. birefringence crystal habit comments
index system
liquid carbon dioxide CO
2
(liq.) 1.195
carbon dioxide CO
2
(s.) ? M? translucent, microcrystallineT<-56.6
o
C; usually forms a single mass
aggregates euhedral crystals can be formed in liquid CH
4
-CO
2
ICE H
2
O 1.31 negligible H rounded plates or globules anisotropic but appears isotropic
Tm<0
o
C, sometimes yellowish appearance
WATER H
2
O 1.32-1.33
CO
2
-clathrate CO
2
.5
3
/
4
H
2
O ~ negligible rhombic or rounded grains Tm = about 6
o
C; colourless, RI very close to water
(gas hydrate) RI very close to H
2
O and therefore dif ficult to recognize
villiaumite NaF 1.33 isotropic C cubes sometimes yellow/pinkish pleochroism
cryolite Na
3
AlF
6
1.34 negligible M alkaline rocks
elpasolite K
2
NaAlF
6
1.37 isotropic C topase from Volynia USSR
mirabilite /Glaubers s.Na
2
SO
4
.10H
2
O 1.39-1.40 negligible M prismatic, acicular
HYDROHALITE NaCl.2H
2
O ~1.41 negligible M tiny grains giving a speckledhigh relief relative to ice; colourless
appearance Tm (incongruent) = +0.1
o
C
natron (soda) Na
2
CO
3
.10H
2
O 1.40-1.44 low M platy crystals Tm (incongruent) = +32
o
C
FLUORITE CaF
2
1.43 isotropic C cubes rarely octahedral, fluorescence
hexahydrite MgSO
4
.6H
2
O 1.45 low M fibrous, tabular
trona Na
3
H(CO
3
)
2
.2H
2
O 1.41-1.54 moderate M fibrous, acicular
NAHCOLITE NaHCO
3
1.37-1.58 very high M tabular commonly twinned;
marked relief changes on rotation in pol. light
carbonic fluids in granulite facies
alum (Na,K)Al(SO
4
)
2
.12H
2
O 1.44-1.46 isotropic C
sulfohalite Na
6
(SO
4
)
2
ClF 1.45 isotropic C
thermonatrite Na
2
CO
3
.H
2
O 1.42-1.52 moderate O
borax Na
2
(B
4
O
5
(OH)
4
).8H
2
O 1.45-1.47 low M
gaylussite Na
2
Ca(CO
3
)
2
.5H
2
O 1.44-1.52 moderate M elongated or flattened crystals
epsomite MgSO
4
.7H
2
O 1.43-1.46 low O(T) acicular
alunogen Al
2
(SO
4
)
3
.18H
2
O 1.46-1.48 low T(H) fibrous
thenardite Na
2
SO
4
1.46-1.48 low O bipyramidal or tabular c.f. gypsum
CARNALITE KMgCl
3
.6H
2
O 1.47-1.49 low O(H) tabular
pickeringite (Mg)- (Mg,Fe)Al
2
(SO
4
)
4
.22H
2
O mean 1.48 very low M acicular, radiated aggregates
halotrichite (Fe)
SYLVITE KCl 1.49 isotropic C cubes often rounded cube edges, solubility at higher temp.
increases more rapidly compared to halite
burkeite Na
6
CO
3
(SO
4
)
2
mean 1.49 moderate O
arcanite K
2
SO
4
1.49-1.50 low O massive, tabular rarely "octahedral" crystals
pseudo-bischofite MgCl
2
.6H
2
O 1.49-1.53 low to M
moderate
(hydro-)bischofite MgCl
2
.12H
2
O 1.50-1.53 negligible M like hydrohalite identification difficult; colourless
wavellite Al
3
(PO
4
)
2
(F,OH)
3
.5H
2
O 1.52-1.55 low O radiated aggregates,
globules
GYPSUM CaSO
4
.2H
2
O 1.52-1.53 very low M tabular, prismatic, fibrous
hydromagnesite Mg
5
(CO
3
)
4
(OH)
2
.4H
2
O 1.52-1.54 low M(O) acicular crystals or lamellae
hydroboracite CaMg[B
3
O
4
(OH)
3
]
2
.3H
2
O mean 1.52 moderate M associated with gypsum
DAWSONITE NaAl(CO
3
)(OH)
2
1.47-1.60 moderate O fibrous bundles frequent in alpine fissures
aggregates
HALITE NaCl 1.54 isotropic C cubes rarely octahedral, same refractive index as quartz
Fe-chlorides FeCl
n
various moderate to (T) var. tabular, often rhombic commonly light green
high or hexagonal
QUARZ SiO
2
1.54-1.55 low
antarcticite CaCl
2
.6H
2
O 1.49-1.55 low/negligible T like hydrohalite but
occasionally rounded crystals
micas various 1.56-1.60 low to M platy extremely thin plates
moderate
strontianite SrCO
3
1.52-1.67 high O acicular, pseudohexagonal
ANHYDRITE CaSO
4
1.57-1.61 low O prismatic associated with gypsum
aragonite CaCO
3
1.53-1.69 high O prismatic, acicular
whewellite CaC
2
O
4
.H
2
O 1.49-1.65 very high M prisms uranium vein deposits
Ca,Mg CARBONATE (Ca,Mg)CO
3
1.49-1.66 very high T rhombohedral high relief; marked changes in relief on rotation in pol. light
barite BaSO
4
1.64-1.65 low O tabular
APATITE Ca
5
(PO
4
)
3
(F,OH,Cl) 1.63-1.67 low H hexogonal crystals
HEMATITE Fe
2
O
3
(2.9-3.2) T hexagonal plates distinctive red/brown plates
SULFIDES various - var. euhedral grains identification sometimes possible in refelective light
GRAPHITE C - H mostly amorphous euhedral (platy) crystals rare; highly Raman active
(from: Van den Kerkhof & Hein, 2001, Lithos 55, 27-47)
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Diagnostic criteria of primary fluid inclusions
Single crystal Diagnostic criteria for classifying fluid inclusions as primary
(Roedders rules, after Roedder 1979)
Individual
inclusions ( or
3-dimensional
grouping)
Large inclusions
(in relation to
the host
crystal)
Zoned crystal Different occurrences of primary fluid inclusions in relation to
growth zoning (compilation) From: Van den Kerkhof & Hein, 2001, Lithos 55, 27-47
Isolated position
away from other
inclusions
(distance >5x
diamater
Inclusion contains
a solid phase,
which also occurs
as solid inclusion
in the host crystal
Occurrence after
solid (or melt)
inclusion or
intergrowth
Fluid inclusion
caused by solid
(or melt) inclusion
or intergrowth
Occurrence after
a healed crack of
an older growth
stage
Occurrence in
growth zones
Inclusions related to
skeletal or spiral
growth
Occurrence in the
core of prismatic or
columnar crystals
Occurrence along
intersections of
growth planes
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Homogeneous trapping Heterogeneous trapping
Shrinkage
Saturation
Unmixing
Cogenetic inclusions
Unmixing
& saturation
& shrinkage
Unmixing
& saturation
Unmixing
& shrinkage
Boiling solution
Saturated solution, suspended solids
At room temperature (after cooling)
phase separation may result from
shrinkage, saturation or unmixing of the
original homogeneous fluid.
Fluid inclusions of variable composition and
phase ratio are trapped at the same time
(Van den Kerkhof & Hein, 2001, Lithos 55,
27-47)
PT- conditions of entrapment: Fluid inclusions which are simultaneously trapped in a
single-phase stability field (liquid or vapor) have identical properties (X, d), i.e. the
relative volumetric proportions of the inclusion phases at room temperature are uniform.
These inclusions consitute an assemblage.
If fluid inclusions are trapped in a multi-phase field, the Xd- properties and the relative
volumetric proportions of the inclusion phases at room temperature are variable.
Heterogeneously trapped fluid inclusions. (a) Co-genetic pair of fluid inclusions containig
(left) water with a methane bubble and (right) liquid methane and an invisible rim of water
along the cavity wall. Sample from Armsfeld (Kellerwald, Germany) (Van den Kerkhof &
Hein 2001 Lithos 55, 27-47))
10
Primary and secondary fluid
inclusions
Principle sketch of inclusion classification, based on
Roedders (1981) criteria. The stippled line
denotes growth zoning. P= primary, PS=
pseudosecondary and S= secondary inclusions. The
P and PS inclusions in the inner growth zone are
older than the P and PS ones in the outer zone.
Inclusions along the growth planes are denoted as
primary. The S trail, extending to the surface of
the crystal, postdates all P and PS inclusions
(from: Hansteen, 1988, Cand. Scient. Thesis, Univ.
Oslo)
Definitions
Primary fluid inclusions formed on sealed imperfections on crystal surfaces during
precipitation and contain the fluid present at the moment of sealing.
Pseudosecondary fluid inclusions form when a crystal fractures during its growth and
original fluids are trapped in the rim of the crystal. They commonly occur between
distinct growth zone and end abruptly at growth zone boundaries.
Secondary fluid inclusions form after crystal growth. They often occur along healed
fractures and may cut across growth zones. They also occur in planes or along cleavage
directions or twin planes.
Stages of healing of a microfracture in quartz
Mechanism of crack healing for the formation of a trail of secondaty fluid inclusions
(after Roedder 1984). The final shapes of the inclusions have crystal faces as
surfaces (negative crystal shape). This is the most stable state as it has the lowest
surface-free energy
Brine
Gas
Brine
Gas
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Trail terminology
Trail terminology (Vollbrecht, 1989) composed after Simmons and Richter (1976) and Kranz
(1983). A main distinction is made between transgranular, intergranular, and intragranular
inclusions (b) The intragranular fluid inclusions may decorate different internal grain
textures and are accordingly subdivided.
Intersecting
trails
Examples of intersection
features in trails of
homogeneous secondary
inclusions: 4 commonly
observed cases of
intersection with
chronological implications
(after Pagel 1975).
1: transgranular, -grain
2: intergranular, -grain
3: intragranular, -grain
4: intragranular (grain bd to grain bd.)
5: intragranular (grain bd into interior
6: interphase
7: transphase
Intragranular decoration
1: cleavage plains
2: deformation lamellae
3: deformation bands
4: subgrain boundaries
5: twinning lamellae
(A) An early monophase (higher density) CO
2
trail (I) is intersected by a later lower
density (biphase) trail (II). At intersection, the shape on inclusion I remains, but its
content has adapted to CO
2
density.
(B) Idem, but inclusions I have been totally obliterated at the intersection.
(C) Same as (a), but II = aqueous inclusions. One 3 fluid phase (H
2
O-CO
2
) inclusion at
the intersection (most common occurrence of H
2
O-CO
2
inclusions in granulite.
(D) Same as (a), but the CO
2
content of inclusion I has been refilled by H
2
O.
Note that later trails tend to contain smaller inclusions (samples: granulites from
Bamble, Southern Norway)
(modified after Touret 1981; redrawn by J.-M. Huizenga)
12
Fluid inclusion modification (interaction with host mineral)
In general, many originally trapped fluid inclusions have relative large surface areas.
Processes of recrystallization, generally termed necking-down, immediately start to
reduce the high surface energy in the system resulting in the development of fluid
inclusions with varying proportions of liquid and vapor.
.
Recrystallizazion (tending to negative crystal shape)
Stretching and necking down
Explosion / implosion-decrepitation
Leakage (preferential water)
Negative crystal shapes (from left to right:
quartz, high-temperature quartz, fluorite (or
other cubic mineral), Inclusion in non-
crystalline material like glass
Examples of necking down
Shapes suggesting changes by
overpressure (explosion decrepitation)
Shapes indicative of changes by
underpressure (implosion decrepitation).
J. Touret
Typical fluid inclusion morphologies
Necking-down is a typical dissolution-
precipitation process, which finally leads to
negative crystal shapes. SiO
2
and particularly
CaCO
3
show so-called retrograde solubility in
a limited P-T field. In principle, the total
volume remains constant, except for the
material deposited from the fluid.
Fragmentation occurs for tubular fluid
inclusions, which are positioned oblique to
the crystallographic c-axis; tubular inclusions
parallel to the c-axis are expected to form
negative crystals.
c
-
a
x
i
s
Necking-down of fluid inclusions in uniaxial minerals (quartz)
13
Inclusion A will homogenize
above the trapping temperature
Tt, inclusion B will homogenize
between T1 and T2, whereas
inclusion C will homogenize
between T2 and T3
A
B
C
T
t
T
1
T
2
T
3
T
4
Decreasing temperature
The phenomenon of necking down corresponds to the evolution, at decreasing
temperature, of a large tubular inclusion into a series of smaller inclusions, which
are initially connected by capillaries.
Decrepitation pressure correlates with Mohs
hardness of the host mineral. Different
minerals can hold different pressures.
Smaller inclusions can hold higher
pressures than bigger ones.
Bodnar, Binns & Hall, 1989, J. Metam. Geol. 7,
229-242
14
a
b
c
T C
N
Acoustic emission (AE) analysis
(decrepitometry)
Examples of decrepigrams: (a) Intra-
foliational quartz segregation from
granulite (Bamble, Norway); (b)
Pegmatite quartz vein from the same
area (c) Sulfide-bearing
hydrothermal quartz vein from the
Eersteling gold mine, South Africa
(Transvaal, South Africa). As a
standard procedure 1 cm3 of hand-
picked, crushed, sieved and HCl-
washed quartz (0.25-0.50 mm) was
used for the experiments (20C/min.
for recorded frequencies 0.4-10
KHz). Note that the peak around the
a-b quartz transformation (574C)
can be only recorded in quartz which
formed at low temperatures.
Natural decrepitation of
fluid inclusions during uplift
The three principle regimes of fluid
inclusion modification during retrograde
conditions on isobaric cooling (IBC),
isochoric cooling (ICC), and isothermal
decompression (ITD). Fluid inclusions may
be modified due to the difference between
fluid and confining pressure: fluid
overpressure during uplift may result in
explosion-decrepitation (ED), i.e. volume
expansion, whereas fluid underpressure
may result in implosion-decrepitation (ID),
i.e. volume shrinkage. Fluid inclusions
cooled along the isochore (d2), which
cross-cuts the fluid trapping conditions, are
largely preserved.
Van den Kerkhof & Hein (2001) Lithos 55, 27-47.
15
Application of cathodoluminescence (CL) to fluid petrology
Micro-textures related with fluid inclusions in optical CL
(a) Primary fluid inclusions in quartz (Uranium deposit Groschloppen, Fichtelgebirge,
Oberpfalz, Germany; Reutel, 1992). Complex highly saline Ca-Na-K Li fluid inclusions
are trapped within one growth zone together with U-bearing mineral inclusions
(autunite?).
(b) Hydrothermal quartz (Hakos, Namibia) showing secondary fluid inclusions trapped
in a veinlet cross-cutting the host quartz.
(c) Secondary fluid inclusions in U-bearing quartz from Wldel (Oberpfalz, Germany)
associated with secondary, re-crystallized and non CL-luminescent quartz (collection:
Behr, Gttingen).
(d) Quartz from retrogradely altered quartz from granulite (Bamble, Southern
Norway). The quartz shows 2 generations of healing textures: idiomorphic crystal
nuclei consist of pure quartz (non-detected trace-elements) and represent parts where
fluid inclusions have been healed. Fluid inclusions occur along the fine micro-fractures
and secondary quartz patches formed at a stage of brittle deformation at lower
temperature.
(from Van den Kerkhof & Hein (2001) Lithos 55, 27-47)
a
b
c
d
The integrative fluid-mineral system. The
most important elements in and around a
fluid inclusion in quartz are schematically
drawn. Fluid inclusions are often surrounded
by pure secondary quartz as a result of
partial quartz recovery (here:
recrystallization and diffusion). The overall
host and secondary quartz generations can
be distinguished by CL. Structural defects like
dislocations induced by the fluid inclusion are
frequently found and may function as a
pathway for water leakage.
16
SEM images of fluid inclusions in CL mode
(a) Granite near contact with intrusive enderbite (Natal, South Africa). Micro-pores in
the originally "wet" granite appear as black spots (right) and are largely healed in parts
of the quartz which are affected by the high-temperature event (desiccation). Fluid
inclusions are found along late micro-fractures (Van den Kerkhof and Grantham, 1999)
(b) Quartz from granulite (Bamble, Norway). This detailed photograph clearly shows
the time relations between earlier (high-temperature) idiomorphic nuclei (pure quartz)
and late healed fractures containing fluid inclusions.
(c) Quartz from migmatite (Rogaland, Norway). Fluid inclusions in the sample contain
CH
4
-CO
2
-H
2
O and were trapped <400C/ 2 kbar (Van den Kerkhof et al., 1991). The
median crack is parallel to crystallographic the c-axis. Fluid inclusions outcropping at
the surface are visible in the BSE image.
(d) Combined BSE/CL image of quartz in granite from Flssenburg (Upper Palatine,
Germany). The inclusions (low salinity aqueous in the sample) are surrounded by re-
crystallized pure quartz.
(from: Van den Kerkhof & Hein (2001) Lithos 55, 27-47)
a
b
c
d
17
Overview of methods for analyzing fluid inclusions
Composition including trace elements 2. LA-ICPMS
Identification of daughter minerals, composition of
fluid inclusions (freezing method)
1. EPMA or SIMS (opened
inclusions)
Single inclusions
Composition of aqueous fluids, element ratios,
dissolved daughter crystals
3. CRUSH AND LEACH combined
with micro.chemical analysis, AAS,
etc.
Finger print of fluid inclusion content
Bulk fluid composition
Bulk fluid inclusion and isotope composition
2. STEPWISE HEATING
Acoustic emission (AE)
Decrepitometry
Gas chromatography
Mass spectrometry
Non-aqueous fluids, qualitative
1. MECHANICAL
Crushing stage
Bulk analysis
DESTRUCTIVE ANALYSIS
Detection of hydrocarbons Fluorescence spectroscopy
Detection of H2O, hydroxyl, CO
2
, etc. FT-IR spectroscopy
Composition of non-aqueous fluids, identification of
daughter crystals
Laser-excited micro-Raman
spectrometry
3. VIBRATIONAL SPECTROSCOPY
Composition and molar volume 2. MICROTHERMOMETRY
Microfractures around fluid inclusions /dislocations TEM
Visualisation of fluid inclusions in semi-opaque and
opaque minerals (e.g. cassiterite, chromite,
sphalerite, pyrite)
IR-Microscope
Detection of hydrocarbons UV-Microscope
Textural relations with host mineral, secondary
quartz
CL-Microscopy /SEM-CL
Fluid inclusion abundance, chronology Petrographical microscope
1. OPTICAL MICROSCOPY AND VISUALIZING TECHNIQUES
NON-DESTRUCTIVE ANALYSIS
18
Work flow for fluid inclusion studies
Fluid inclusion study short working plan
I. Sample preparation (doubly polished sections)
II. Documentation
1. Microscopy and fluid inclusion selection
2. Drawings and photos
3. Classification of fluid inclusions
a. Description (1-phase, 2-phase, multiphase, daughter crystals etc.)
b. Relative phase volumes (fill degree)
c. Inclusion size, morphology
d. Relative age (primary, pseudosecondary, secondary)
III. Microthermometry
1. Cooling experiment (until ca. -180C) with observation of phase nucleation (Tn V,
CO
2
S, etc. )
2. Warming experiment (-180 until ca. 35C) with detection of phase transition
temperatures (Te, Tm CO
2
, Tm ice, Th CO
2
, Tm ice, Tm hydrate)
3. Heating experiment (aqueous inclusions) Th total, Tm salt
IV. Data treatment
Calculation of compositions and densities, isochore calculation
19
Glossary of phase transitions in fluid inclusions
Trapping temperature (Tt): The temperature of trapping (formation) of a fluid
inclusion.
Homogenization temperature (Th): The temperature at which a fluid inclusion
transforms from a multi-phase (heterogeneous) to a one-phase (homogeneous)
state. Homogenization may occur in several different modes, i.e., via several different
phase transitions, and therefore the reactants and products must be recorded with
the temperature: (1) homogenization to the liquid state via a bubble-point transition,
Th(LV L); (2) homogenization to the vapor state via a dew-point transition, Th(LV
V); (3) homogenization via a critical transition to a supercritical fluid: Th(LV
SCF) or written as Th(critical); (4) homogenization to the liquid via a liquidus
(melting, dissolution) transition, Th(SL L) and homogenization via a vaporus
(sublimation) transition, Th(SV V). In some gas inclusions, such as N
2
-CO
2
, and in
gas-bearing aqueous fluid inclusions, such as CO
2
-H
2
O salt and CH
4
-H
2
O salt, two
or more homogenization transitions may be observed upon progressive heating: (1)
the partial homogenization of the non-aqueous phases at low temperatures, e.g.,
Th(LCO
2
L
aq
V LV); and(2) the total homogenization of the inclusion at high
temperature, e.g., Th(LV L). Once the reactants and products of the specific
transitions have been described in a given report or article, the following
abbreviations may be used: e.g., Th (provided there is no ambiguity), Th(partial) or
Th(CO
2
), Th(CH
4
) etc., and Th(total).
Melting temperature: Three cases are distinguished in fluid inclusion studies: see
Eutectic temperature (Te), initial melting temperature (Ti), and final melting
temperature (Tm).
Eutectic temperature, Apparent eutectic temperature (Te): The minimum
temperature of liquid stability in a specified system. For any system considered at
specified, fixed pressure, the eutectic is a unique, characteristic temperature and it is
associated with a unique, characteristic mixture of the componenets (the "eutectic
composition"). Upon heating saline aqueous fluid inclusions from low temperature,
melting first occurs at the eutectic temperature. However, if the bulk composition of
the fluid inclusion lies far from the eutectic composition, only a tiny amount of liquid
forms at the eutectic temperature and so it remains invisible. Such inclusions must
be heated well above their eutectic temperature before enough liquid has formed to
be visible. Owing to this overstepping, the temperature at which liquid is first
observed upon heating may be termed the "apparent eutectic temperature". The
reactants and products of the eutectic phase transition must be recorded with the
temperature, e.g. Te(HydrohaliteIceV Ice LV). Sometimes the solid that melts at
the eutectic cannot be identified, and this may be indicated as Te(S1IceV Ice LV).
In gas inclusions and in gas-bearing aqueous inclusions, the first liquid produced
does not necessarily form at the characteristic system eutectic, but at a higher
temperature dependent on the bulk composition and density of the inclusion. In such
inclusions, and whenever it is not clear which system is involved, the temperature at
which liquid is first observed upon progressive heating is best termed the "initial
melting temperature".
Initial melting temperature (Ti): The temperature at which liquid is first observed
to form upon progressive heating of a solid-bearing fluid inclusion. In gas-bearing
inclusions this temperature does not necessarily correspond to the eutectic
temperature or the apparent eutectic temperature. Synonyms: First melting
temperature, Incipient melting temperature.
20
Final melting temperature (Tm): The temperature at which a solid is observed to
melt (or dissolve or dissociate) completely upon progressive heating of a fluid
inclusion. The reactants and products of the phase transition must be recorded with
the temperature, e.g., Tm(IceLV LV). Sometimes the solid that melts cannot be
identified, and this may be indicated as Tm (S
1
LV LV). Once the reactants and
products of the specific transitions have been described in a given report or article,
abbreviations may be used, e.g., Tm(CO
2
), Tm(Ice), Tm(Cla), Tm(Halite). A large
temperature span may separate the initial and final melting temperatures of a given
solid. Occasionally the temperature of final melting of a solid may also coincide with
the temperature of total homogenization of the inclusion, e.g., Tm = Th(HaliteL L).
In non-English literature the symbol Tf is sometimes used instead of Tm, where the
subscript "f" stands for "fusion". The same symbol, Tf, is also sometimes used to
denote "temperature of formation".
Nucleation temperature (Tn): The temperature at which a specified phase first
appears during microthermometry. For example, the temperature at which a vapor
bubble appears upon cooling a homogeneous liquid inclusion is denoted as Tn(L LV)
or simply Tn(Vapor). Similarly, the first crystallization of ice upon cooling is termed the
ice nucleation temperature, e.g. Tn(LV IceLV) or simply Tn(Ice). Phases may also
nucleate upon heating, e.g., Tn(SV SLV).
Decrepitation temperature (Td): The temperature at which a fluid inclusion
irreversibly ruptures, or "decrepitates", upon heating (owing to extreme internal
overpressure caused by fluid expansion) or upon cooling (owing to extreme internal
overpressure caused by crystallization of ice). Use of the term "decrepitation" implies
loss of inclusion contents and changes in inclusion volume.
Metastability: 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. For
example, the persistence of ice above 0C upon heating of fluid inclusions is a case of
metastability. The stable assemblage would involve water, not ice. Some workers
distinguish metastable phase transitions by an asterisk, e.g., Tm*(SLV LV).
Salinity: The amounts of solutes in aqueous solution, including electrolytes (e.g.,
NaCl, CaCl2) and non-electrolytes (e.g., CO
2
, H
2
S). Often the concentrations of the
individual solutes are not known in multi-component fluid inclusions, but phase
transitions can be measured that are sensitive to the overall salinity (e.g., Tm(Ice),
Tm(Hydrohalite), Tm(Halite), Tm(Clathrate)). In these cases, the salinity is
conventionally reported in NaCl (or CaCl
2
) equivalents, e.g., "wNaCl-eq.= 10%" means
that the inclusion shows phase transitions that are consistent with a mass fraction of
10% NaCl in the aqueous phase. Equivalent weight-fraction (symbol: equiv. wt%) is
an alternative (non S.I.) unit. Instead of mass units, salinity may also be expressed as
a mole fraction, e.g., XNaCl equiv. = 3.3%, or in units of molality, e.g., mNaCl equiv.
= 1.9.
(see Diamond: Glossary: Terms and symbols used in fluid inclusion studies. In: Fluid
inclusions, Analysis and interpretation. I. Samson, A. Anderson, D. Marshall (Eds.),
p.365-374.
21
Analytical equipment
Crushing stage
Heating/freezing stages
Linkam stage setup (Univ. Gttingen) and
cross-section (Sheperd, 1981) Pt= platinum
resistance temperature sensor
Cross section (top) and plan view of
the USGS stage from Werre et al.
(1979). Arrows indicate the gas flow
paths. P, portals for gas flow, A-A,
plane of section above
For a CO
2
inclusion of ca. 50
cm
3
/mol the expension would
be ca. 440x (at atmospheric
conditions V 22000 cm
3
/mol).
Results of a crushing test (drawings: J. Van Duin)
22
Laser Raman Microspectromer (LRM)
2.3 2.3 4156 H
2
3657 broad band H
2
O (V)
5.0 5.0 3336 NH
3
3219 broad band H
2
O (L)
2954 C
2
H
6
7.5 7.6 2917 CH
4
18 2890 C
3
H
8
6.4 6.4 2611 H
2
S
2590 H
2
S (aq.)
2580 H
2
S (L)
2574 HS
-
1 1 2331 N
2
0.9 0.9 2143 CO
1.2 1.2 1555 O
2
1.5 1.5 1370 (2
2
)
13
CO
2
1.5 1.5 1388 (2
2
)
1.0 1.0 1285 (
1
)
12
CO
2

514nm

488nm
(cm
-1
) Species
Raman shifts ( in cm
-1
) and
wavelength dependent (for =488 nm
and 514 nm) relative Raman
scattering cross-sections () of
selected common species in inclusions
(from Burke)
Raman spectrometer (with Notch filter)
Horiba Jobin Yvon LabRam HR800-UV
The measurement of single fluid inclusions
(Semi)-Quantative analysis of the non-aqueous components (Plazcek equation)
High spatial resolution (confocal optics) allow the analysis of single phases
Combined Raman analysis and heating/ freezing stage (bulk fluid composition of multiphase
inclusions)
Analysis of daughter crystals (e.g., salts and graphite); Halite and sylvite are not Raman-
active!
Pressure estimates obtained from Raman peak characteristic (shift, height, width)
Salinity estimates from Raman water-peak shape
23
Roedders rules
Obtaining valid information concerning the original trapping conditions for fluid inclusions
(primary or secondary) is based on three assumptions, referred to as Roedders Rules:
1. The inclusion traps a single, homogeneous phase.
2. Nothing is added to, or removed from, the inclusion
following trapping.
3. The inclusion volume remains constant following
trapping, i.e., represents an isochoric system.
Furthermore: Effects of pressure are insignificant or known; The origin of the inclusion is
known (fluid petrography!); The determinations of Th are both precise and accurate.
Interpretation of phase transition temperatures
Eutectic / first melting (Te) Fluid system
Final melting temperature (Tm) Fluid composition (Salinity)
Homogenization temperature (Th) Fluid density (d) or molar volume (v)
Host mineral
(transparent)
Solid (S
1
)
Daughter
crystal
Solid (S
2
)
Liquid(L)
Vapor or
gas (V)
Host mineral
(transparent)
Solid (S
1
)
Daughter
crystal
Solid (S
2
)
Liquid(L)
Vapor or
gas (V)
The fluid inclusion system
definition
In a closed system:
no loss of mass + no volume change
Composition (X) and volume (V) are constant
Density (d) = m/V = constant (m = mass)
molar volume V = M/d = constant
Where the molecular mass M= MiXi
Equations of state (EOS)
Variations of pressure (P) with temperature (T) are given by an equation of state.
Graphical presentation is the isochore. The EOS can be written in different forms. The
most simple form is the gas law, which is highly inaccuate for high-density fluids, like in
fluid inclusions. The other forms give higher accuracies for a given range of
experimental data. Care should be taken for far extrapolations. Therefore the
applicability should be always checked with the experimental range given in the
literature.
P = RT / V (Gas law)
P = RT/(V-b) - a/(V
2
) (Van der Waals)
P = RT/(V-b) - a/(V+b)T
1/2
(Redlich-Kwong)
P = RT/(V-b) - a/V(V+b)+b(V-b) (Peng-Robinson)
P = RT/(V-e) - a/(V
2
+(V+e)V+be (Heyen)
where P= pressure; T= temperature; V= molar volume (V/n); R= gas constant
a = cohesion correction; b = volume of molecules; e = extra volume correction
24
How to derive trapping PT from the isochore ?
Combination of isochores (simultaneous trapping); Special case (see p. 29):
simultaneous trapping of immiscible fluids (Th = Tt)
Combination of isochore and geothermal gradient (lithostatic or hydrostatic)
Combination of isochores and mineral geothermometers (metamorphic
rocks): mineral-mineral, mineral-fluid equilibria (COHN); Na-K-Ca/Feldspar),
Ti-in-Qtz, etc.
0
100
200
300
400
500
600
100 200 300 400 500 600 700 800
T (C)
P

(
M
P
a
)
1
10
20
5
15
km
S
o
l
v
u
s

t
o
p

p
u
r
e

H
2
O
S
o
l
v
u
s

2
.
6

w
t
%

N
a
C
l
-
C
O
2
S
o
l
v
u
s

N
a
C
l
-
s
a
t
u
r
a
t
e
d
C
H2O
Hydrostatic
gradient
d = 1.0 cm
3
/g
50C/km
50C/km
40
40
30
30
25
25
20
20 Lithostatic gradient d = 2.7 cm
3
/g
Estimated lithostatic and hydrostatic gradients calculated for Earth's crustal
conditions, based on a mean rock density of 2.7 g/cm
3
and 1.0 g/cm
3
for
water. Also shown are the solvi for aqueous-carbonic fluids for pure water, 2.6
wt% NaCl and NaCl-saturated fluids.
25
Phase transitions during microthermometry runs
Phase transitions in aqueous inclusions
Phase transitions in gaseous inclusions
26
One-component systems
Schematic PT diagram for the system CO
2
showing phase transitions for
inclusions trapped at a, a and a. Dark gray = gas, light gray = liquid phase,
white = solid CO
2
(from Van den Kerkhof & Thiery 2001, Lithos 55, 49-68)
-195.8 13.0 -147.1 -210 N
2
-191.5 35.0 -140.2 -205 CO
-161.5 46.3 -82.5 .182.6 CH
4
-88.6 49.0 32.1 -172 C
2
H
6
-50.2 65.7 104.8 -138.2 COS
-60.8 90.2 100.4 -83.6 H
2
S
-10.0 78.8 157.8 -72.7 SO
2
-78.5
(subl.)
74.0 31.1 -56.6 CO
2
100.00 220.4 374.15 0.015 H
2
O
Boiling
point C
PC bar TC C Triple point
C
Substance
Properties of one-component fluid systems (compiled by Hein, 1990).
27
The system H
2
O
Stretched water
inclusions
One-phase water inclusions
are often metastable,
stretched fluids with negative
pressure
Temperature-density diagram for the system
H
2
O (data of Kennedy, 1950 and Frank,
1966). The homogenization behavior of four
inclusions, all trapped at 540C (but at
different pressures) is indicated. The
inclusions of density 0.7 and 0.9 homogenize
in the liquid phase; that with density 0.4
homogenizes at the critical point; that with
density 0.1 homogenizes in the gas phase
(from Roedder 1962, Scientific Am. 207, 38-
47). The water volume fraction (abcissa) is
equal to the gross density for the system
H2O. L is the 2-phase line (equivalent to line
L), for a 20% NaCl solution of density 1.15 at
20C (data from Lemmlein, 1956).
The basic phase diagram
for H
2
O
The phase stability fields for water, ice
and water vapor, separated by the
melting, boiling and sublimation
curves. Note that contrary most other
systems the slope of the melting curve
is negative for H
2
O.
28
H
2
O isochores
H
2
O isochores modified from Fischer (1976). Enlargement of the low pressure region, in
the box, appears down.
29
CO
2
Isochores
Phase diagram for CO
2
showing densities (g/cc) of several isochores. Data from
compilation of Angus et al. (1973). CP = critical point at 31C.
Combined isochores for CO
2
and H
2
O. At higher PT (>1.5 kbar; >500C) CO
2
has
higher density than for water, which is trapped at the same conditions
30
Density estimates (CO
2
and CH
4
)
(a) Densities of liquid
and gas phases on
the boiling point
curve as a function of
temperature.
(b) The molar
volume of the liquid
phase on the boiling
point curve as a
function of the
temperature
(from: Van den Kerkhof &
Thiry, 2001, Lithos 55,
49-68)
Saturation curve of
methane (after
Zagoruchenko &
Zhuravlev 1970)
31
Eutectic properties of salt solutions
MgCl
2
and FeCl
2(3)
-bearing systems -38 to -33.0C
NaCl dominance -23.5 to -21.2C
Sulfatic and carbonatic systems -5 to +1.2C
Ice + NaHCO
3
5.8% NaHCO
3
-2. H
2
O-Na
2
CO
3
Ice + Na
2
CO
3
.10H
2
O 5.75% Na
2
CO
3
-2.1 H
2
O-Na
2
CO
3
Ice + Na
2
SO
4
.10H
2
O 3.85% NaSO
4
-1.2 H
2
O-Na
2
SO
4
Diagnose Te
Li- and Br-bearing systems -83 to -74.8C
CaCl
2
-bearing systems without Li and Br -55 to -49.8C
Ice + NaHCO
3
+ Na2CO
3
.10H
2
O -3.3 H
2
O-NaHCO
3
-Na
2
CO
3
Ice + KCl 19.7% KCl -10.6 H
2
O-KCl
Ice + NaCl.2H
2
O 23.3% NaCl -21.2
(-20.8)
H
2
O-NaCl
Ice + NaCl.2H
2
O + NaHCO
3
-21.4 H
2
O-NaCl-Na
2
CO
3
Ice + NaCl.2H
2
O + Na
2
SO
4
.5H
2
O -21.7 H
2
O-NaCl-Na
2
SO
4
Ice + NaCl.2H
2
O + NaHCO
3
-21.8 H
2
O-NaCl-NaHCO
3
Ice + NaCl.2H
2
O 20.17% MgCl
2
5.81% KCl
-23.5
(-22.9)
H
2
O-NaCl-KCl
Ice + MgCl
2
.12H
2
O 21.0% MgCl
2
-33.6 H
2
O-MgCl
2
Ice +NaCl.3H
2
O + MgCl
2
.12H
2
O 1.56% NaCl
22.75% MgCl
2
-35.0 H
2
O-NaCl-MgCl
2
Ice + FeCl
2
.6H
2
O -35.0 H
2
O-FeCl
2
Ice + NaCl.2H
2
O + FeCl
2
.6H
2
O -37.0 H
2
O-NaCl-FeCl
2
Ice + (K,Na)
2
CO
3
.6H
2
O +
K
2
CO
3
.6H
2
O
-37.0 H
2
O-Na
2
CO
3
-K
2
CO
3
Ice + KCl.4H
2
O + MgCl
2
.12H
2
O -37.8 H
2
O-KCl-MgCl
2
Ice + CaCl
2
.6H
2
O 30.2% CaCl
2
-49.8 H
2
O-CaCl
2
Ice + CaCl
2
.6H
2
O -50.5 H
2
O-KCl-CaCl
2
Ice + MgCl
2
.12H
2
O + CaCl
2
.6H
2
O -52.2 H
2
O-MgCl
2
-CaCl
2
Ice + NaCl.2H
2
O + CaCl
2
.6H
2
O 1.8% NaCl
29.4% CaCl
2
-55
(-52)
H
2
O-NaCl-CaCl
2
Ice + LiCl.5H
2
O -74.8 H
2
O-LiCl
Ice + LiCl.5H
2
O + NaCl.2H
2
O -77 H
2
O-LiCl-NaCl
Ice + LiCl.5H
2
O + CaCl
2
.6H
2
O -78 H
2
O-LiCl-CaCl
2
Ice + LiCl.5H
2
O + Double salt -78 H
2
O-LiCl-MgCl
Ice + LiCl.5H
2
O + KCl -78 H
2
O-LiCl-KCl
Solid phases Eutectic
composition
Te C Salt system
32
Salinity expressed in NaCl-equivalents
-30
-25
-20
-15
-10
-5
0
0 5 10 15 20 25 30
NaCl mass%eq.
T
m

i
c
e

C
X =1.78*ABS(T)-(ABS(0.0442*T*T))+(ABS(0.000557*T*T*T))
(after Bodnar, empirical equation)
33
The curves separating the
fields of A + Liquid from
Liquid and B + Liquid from
Liquid are termed liquidus
curves. The horizontal line
seperating the fields of A +
Liquid and B + Liquid from A
+ B all solid, is termed the
solidus. The point E, where
the liquidus curves and
solidus intersect, is termed
the eutectic point. At the
eutectic point in this two-
component system, all three
phases, i.e. Liquid, crystals
of A and crystals of B, all
exist in equilibrium. Note
that the eutectic is the only
point in the diagram where
this is true.
Composition X will be all liquid above temperature T
1
, because it will lie in the field of all
Liquid. If the temperature is lowered, at T
1
crystals of A begin to form.
Further lowering of the temperature causes more crystals of A to form. As a result, the
liquid composition must become more enriched in B as more crystals of A form out of the
liquid. Thus, with lowering of temperature, the liquid composition will change from point 1
to point 2 to point 3 to point E as the temperature is lowered from T
1
to T
2
to T
3
to T
E
,
respectively. At all temperatures between T
1
and T
E
, two phases will be present in the
system: liquid and crystals of A. At the eutectic temperature, TE, crystals of B will begin to
form, and three phases will coexist; crystals of A, crystals of B, and liquid. The temperature
must remain at T
E
until one of the phases disappears. Thus when the liquid crystallizes
completely, only pure solid A and pure solid B will remain and mixture of these two solid
phases will be in the proportions of the original mixture, i.e. 80% A and 20% B.
From: S.A. Nelson, 2011, Tulane University
The binary phase diagram
34
The phase rule applied to aqueous systems
The topology of the aqueous system depends on the number of possible (salt)
hydrate phases.
p = c + 2 f (phase rule)
N N!
n = ( p ) = (N-p)! p!
where
p = number of phases
c = number of components
f = variance (degree of freedom)
n = number of possible phase equilibria (for given p)
N = maximum number of possible phases (f =0)
P = c + 2 - f, Max. number of phases (N) = 4
E = Unique invariant point: f=0 p=4 (quadruple)
Possible phases:
KCl (solid) = Sylvite
H2O (solid) = Ice
Liquid solute
Vapor (supposed always present)
Binary water-salt systems (no hydrates stable) H
2
O-KCl
H
2
O
Sylvite + L
Ice + L
0
19.7%
-10.6
KCl
L
Ice + Sylvite
T C
H
2
O
Sylvite + L
Ice + L
0
19.7%
-10.6
KCl
L
Ice + Sylvite
T C
Not to scale
Rapid cooling below the eutectic temperature (Te) is usually needed before
the inclusion freezes !
E
35
Binary water-salt systems (one possible hydrate stable)
H
2
O-NaCl
NaCl-H
2
O system, temperature-composition diagram at 1 bar. All phases coexist
with vapor (drawing J.M. Huizenga)
E = [H] = Eutectic (HH+I+L) = No halite present
[HH] = Metastable eutectic (I+Lhalite) = No hydrohalite present. Almost always in
halite-bearing inclusions
P = Peritectic, Reaction point Halite Hydrohalite
p = c + 2 - f
Multisystem: one extra phase
Max. number of phases (N) = 4 + 1 = 5
Possible phases: Halite (H), Hydrohalite (HH) = NaCl.2H
2
O (Monoclinic), ice (I), Liquid (L),
vapor (V)
Invariant points (f=0 and p = 4)
5
4 = 5! / (1! 4!) = 5
2 invariant points can be found: [H] and [HH]. Only one stable, one metastable (1st order)
and 3 metastable (higher order)
E=[H]
P
[HH]
36
Distorted schematic PT projection of
the H
2
O-NaCl system modified from
Morey (1957). E= H
2
O-NaCl eutectic
ice + hydrohalite + liquid + vapor (T=-
20.8C, P=0.001 bar, 23.2 wt% NaCl);
T(H
2
O)= H
2
O triple point (T=0.01C,
P= 0.006 bar); C(H
2
O)= H
2
O critical
point (T= 374C, P=220 bar);
T(NaCl)= NaCl triple point (T= 801C,
P= ca. 1 bar); C(NaCl)= critical point
(T= ca. 3600C, P=ca. 258 bar). At the
intersection of the L+V(1) loop with the
L+V(2) loop (1=2), a liquid of
composition (2) is in equilibrium with a
vapor of composition (1). At
temperatures and pressures outside
each isoplethal loop, that particular
composition exists as a single,
homogeneous fluid.
A Trapping of oversaturated fluids Tm (NaCl) < Th L-V V
B Trapping of saturated fluids Th = Tm Tm (NaCl) = Th L-V L
C Trapping of oversaturated solutions Tm (NaCl) > Th L-V L
(Bodnar et al. 1985, GCA 49, 1861-1873).
A
B
C
37
2 liquids in equilibrium:
A low NaCl concentration
and gas-rich (low density)
B high NaCl concentration
and liquid-rich (high
density)
During a boiling episode, fluid
inclusions of different
composition, but the same Th
coexist, e.g. in porphery
copper deposits.
From Samson et al.
Immiscibility in salt-water systems
A
B
Room-temperature phase relations
of fluid inclusions having salinities
of 10 and 25 wt% NaCl and Th
from 100C to the critical
temperature of each composition.
Also shown are the phase relations
of inclusions that trapped the
vapor phase that would have been
in equilibrium with the liquid phase
at each temperature
(from Bodnar 1982)
Room-temperature phase relations of fluid inclusions having salinities of 30, 50, and 70
wt% NaCl and Th of 100 to 700C. Also shown are the room-temperature phase relations
of inclusions that trapped the vapor phase that would have been in equilibrium with the
liquid phase at each temperature. Vapor-rich inclusions are not shown with inclusions
homogenizing by halite disappearance (left side of figure) because these could not have
trapped in equilibrium with the vapor phase (from Bodnar 1982).
38
H
2
O-NaCl isochores
Isochores for water and NaCl solutes for selected homogenization temperatures. Note
that the isochore slopes vary only slightly with salinity for given Th, even when the
densities of these inclusions are very different.
39
Binary water-salt systems (with more than one extra phase)
H
2
O-CaCl
2
(multi-system)
Eutectic
(AA+I+L)
Peritectic-1
(AA TH)
Peritectic-2
(TH DH)
(drawn by J.M.
Huizenga)
CaCl
2
.6H
2
O (hexahydrate) = antarcticite
CaCl
2
.4H
2
O (tetrahydrate)
CaCl
2
.2H
2
O (dihydrate)
40
Ternary water-salt systems
The system H
2
O-NaCl-KCl
The system H
2
O-NaCl-CaCl
2
(Sterner, Hall &
Bodnar, 1988,
GCA 52, 989-
1005)
(Konnerup-Madsen,
1979)
41
The system H
2
O-CO
2
: phase transitions and immiscibility
H
2
O(L)
CO
2
(L)
CO
2
(V)
Clathrate hydrate structure
Structure II clathrate (A), with pentagonal dodecahedron (B) and
hexakaidecahedron (C) cavities
M1 = smaller cavity (e.g. N2, O2) mostly in Structure II
M2 = larger cavity (e.g. CH4, CO2, CO, H2S (mostly structure I)
(from Bakker and Thiery, 1994)
42
PX-plot for the system H
2
O-CO
2
adapted from autoclave experiments of Takenouchi &
Kennedy (1964). Filled circles show composition of samples taken from the upper part of the
autoclave; open circles show samples from the lower parts.
(from Roedder & Bodnar 1980)
Th(V) = 275C
Th(L) = 275C
H
2
O-CO
2
immiscibility
43
Phase changes with clathrate hydrate
H
2
O-CO
2
phase diagram modified from Larsen (1955). Point A is the CO
2
triple point (-
56.6C), invariant point B is where clathrate, ice, aqueous solution, and a vapor phase
coexist (-1.48C, 10.4 bars), and invariant point C is where clathrate, aqueous solution,
liquid CO
2
, and vapor are stable (10.0C, 45 bars). Type II inclusions show only clathrate
dissociation over the entire temperature range as an indicator of the presence of CO
2
.
Type III inclusions show no diagnostic CO
2
phase. Note that the pressure is mainly
determined by the CO
2
subsystem.
I = diagnostic CO
2
(Th and Tm Clathr)
II = only clathrate
dissociation
III = no diagnostic
CO
2
(from Rosso & Bodnar, 1995, GCA)
Clathrates may provide information on
the presence of gases (if not detected
otherwise).
CO
2
L+V
at 25C
limit detectable
CO
2
melting (45 bar)
detection limit
clathr.diss
from: Rosso & Bodnar 1994)
44
VX VX diagram diagram H H
2 2
O O- -CO CO
2 2
( (isotherms isotherms) )
Density and bulk composition can be determined from only 2 temperatures.
The system H
2
O-CO
2
: Total molar volume (V tot) vs. total molar fraction CO
2
(XCO
2
)
after Bakker & Diamond (2000). Inclusions that undergo homogenization to the liquid
phase plot to the left of the upper critical curve (LIQ field); those that homogenize to
the vapor plot to the right (VAP field). Inclusions with carbonic phases that
homogenize to the vapor phase plot above the dotted LCEP curve; those that
homogenize to the liquid plot below. Th car isotherms below 10C correspond to
metastable equilibrium states in which clathrate is absent. Light dashed contours show
volume fractions of the carbonic phase as visible at Thcar. For a given fluid inclusion,
Vtot and XCO
2
can be determined by intersecting the measured Thtot and Thcar
values, taking account of the modes of homogenization. For example, an inclusion with
Thcar(L+V V)=28C and Thtot(L+V L)=310C has Vtot=42 cm
3
/mol, XCO
2
=0.2
and F at 28C=0.64. Alternatively, if an inclusion decrepitates prior to reaching total
homogenization Vtot and XCO2 can be determined by intersecting THcar and an
optical estimate of Fcar. (from: Diamond 2001, Lithos 55, 69-99).
45
Clathrate hydrate melting and salinity
Ice melting: Potter & Clyne (1978)
Hydrate melting: Bozzo et al. (1973)
from: Diamond
(1992) GCA 56, 273
46
Calculation of composition and molar volume
47
Topology of binary gas systems
Topoplogy of the systems CO
2
-CH
4
(a) and CO
2
-N
2
(b), after Thiery et al. (1994). Invariant
points: eutectic point (E, filled square), triple points (T, filled triangles), L=G CPs for pure
fluids (C, filled circles), three-phase critical end-points (filled circles), SL=G intersection
points of a critical curve with the SLG curve (triangles). Univariant lines: two-phase
assemblage for the pure end members (gray lines), three-phase assemblage for the binary
systems (thick solid lines), and critical curves (thin solid lines). The prefix "m" denotes
metastable parts. Regions around the triple points T
CH4
and T
N2
are enlarged. The critical
curves (L=L and L=G) delinit LL and LG immiscibility (shaded areas). Also indicated are the
stability fields of liquid-liquid (LL), solid-gas (SG) and solid-fluid (SF). The calculated
extensions of the critical curve towards high pressures for CO
2
-N
2
are sketched according
to (1) Thiry et al. (1994) and (2) Kreglewski and Hall (1983).The pressure and
temperature scales are arbitrary.
48
Phase transitions in the system CO
2
-CH
4
at varying
temperature and pressure
Schematic PT phase diagram of the binary system CO
2
-CH
4
showing phase
changes along the heating path. Thick gray dashed line (LG
CH4
) = the
saturation curve of CH
4
; thick gray line (LG
CO2
) = the saturation curve of
CO
2
. Univariant curves: dotted line (L=G) = the critical curve, connecting the
two CPs of the pure CO
2
and CH
4
components; thick solid lines = the SLG or
melting curve (from Van den Kerkhof & Thiery 2001, Lithos 55, 49-68)
49
The use of VX diagrams for the determination of molar
volume and composition from microthermometry data
(the systems CO
2
-CH
4
and CO
2
-N
2
)
Thick solid line: L(SG) and G(SL) curves. Inclusions plotting in the shaded areas are
classified as S-type (mostly S2) and may show metastable LG homogenization below
melting (Th<Tm). Inclusions plotting outside the shaded areas are classified as H-type
(Th>Tm). Inclusions plotting below the critical curve (L=G) homogenize to liquid, above
the critical curve to gas. Inclusions between the curve denoted as CCT (cricondentherm
or second-order critical curve) and L=G show homogenization to gas at higher
temperature than critical for a given bulk fluid composition as a consequence of
retrograde condensation. Most common phase sequences are indicated by H2, H3, H4
and S2. The type boundaries are given by line 2 (H2-H3), line 3 (H2-H4) and line 4 (H3-
H4). Line 1 in both diagrams indicates liquid volume fractions of 10%: the liquid phase in
inclusions plotting above these lines can normally not be observed in fluid inclusions due
to optical restrictions. Similarly, line 5 indicates solid volume fractions of 1% for SG
equilibria: the solid phase cannot be observed above this line. Inclusions plotting left of
line 6 show complex S-type behavior (S1, S2 and S3). Line signatures for the phase
transitions are the following: thin solid lines = homogenization (LG L or LG G);
dashed-dotted lines = final melting (SLG LG); dashed-double dotted lines = initial
melting (SG SLG), bubble nucleation (SL SLG) or partial homogenization (SLG
SG or SLG SL).
Following inclusions are given as an example for the system CO2-CH4: (A) Type H2: Tm
= -62.5C, Th(L)=-20C; (A) Type H3: the same Th and Tm as inclusion A, but LG
homogenization to the gas phase and initial melting at 63.5C.
In the system CO2-N2: (B) Type H4: Tm=-58.6C and Th(L)=-3C. As B plots above the
SL=G line, partial homogenization will be to the gas phase (SLG SG) and expected
around 153C (line not shown). Temperature difference between initial and final
melting is very small and lines for Ti are omitted here; (B) Type H4: Inclusion showing
the same Th and Tm as inclusion B, but homogenzation to the gas phase;(B) Type H3:
inclusion showing homogenization to the gas phase at the same temperature as for
inclusion B, but the melting temperature is higher (-57.8C).
(from: Thiry et al., 1994).
S2
H4
H3
H3
H2
H4
S2
50
Sequences of phase transitions in CO
2
-CH
4
-N
2
inclusions
Sequences of phase transitions in CO
2
-CH
4
-N
2
inclusions in the temperature
range between -160C and 31C. Possible metastable transitions (below -
56.6C) of the undercooled phases are shown at the right. The solid phase is
shown in gray; the liquid and the gas phases are not filled. (from: Van den
Kerkhof & Thiry, 2001, Lithos 55, 49-68).
H1
H2
H3
H4
S1
S2
S3
S4
51
VX diagrams for the system CO
2
-CH
4
VX diagram calculated for the system CO
2
-CH
4
for (a) V<100 cm
3
/mole and
(b) for V<60 cm
3
/mole (from Thiry et al. 1994)
(a)
(b)
52
VX diagram for the system CO
2
-N
2
VX diagram calculated for the system CO
2
-N
2
for V<100 cm
3
/mole (from
Thiry et al. 1994).
53
Isochoric projections of the system CO
2
-CH
4
-N
2
showing the behavior on
microthermometry runs in relation to composition and molar volume. Diagrams
are shown for 40, 50, 65 and 100 cm
3
/mole. Note that Th<Tm for the dark gray
areas denoted by S2. (from: Van den Kerkhof & Thiry, 2001, Lithos 55, 49-68)
54
Literature selection

Textbooks
ANDERSEN T, FREZZOTTI ML, BURKE EAJ eds. (2001) Fluid inclusions: phase relationships
- methods- applications (special issue). Lithos 55 (1-4), 320 pp.
SHMULOVICH KI, YARDLEY B, GONCHAR GG (1995) Fluids in the crust. Equilibrium and
transport properties. Chapman & Hall, 323 pp.
De VIVO B, FREZZOTTI ML (1994) Fluid inclusions in minerals: methods and applications.
Short course of the working group (IMA) "Inclusions in Minerals" (Siena) Fluids Research
Laboratory, Department of Geological Sciences, YPI, Blacksburg
GOLDSTEIN RH, REYNOLDS TJ (1994) Systematics of tluid inclusions in diagenetic
minerals. SEPM Short Course 31. Society for Sedimentary Geology. SEPM, Tulsa,
Oklahoma
PARNELL J ed. (1994) Geofluids: Origin, Migration and Evolution of Fluids in Sedimentary
Basins. Geol. Soc. Spec. Publ. 78, 372 pp.
WALTHER JV, WOOD BJ eds. (1986) Fluid-rock interactions during metamorphism.
Advances in physical chemistry 5, Springer-New York
LEEDER O, THOMAS R, KLEMM W (1987) Einschlsse in Mineralien. VEB Deutscher Verlag
fr Grundstoffenindustrie, Leipzig., 180 pp.
SHEPHERD TJ, RANKIN AH, ALDERTON DHM (1985) A practical guide to fluid inclusion
studies 239 pp. Blackie-Glasgow.
ROEDDER E (1984) Fluid inclusions. Reviews in Mineralogy, Vol. 12, 644 pp. Mineralogical
Society of America, Washington.
HOLLISTER LS, CRAWFORD ML eds. (1981) Short course in fluid inclusions: application to
petrology. 304 p. (Calgary, Mineralogical Association of Canada)
SAMSON I, ANDERSON A, MARSHALL D eds. (2003) Fluid inclusions - Analysis and
Interpretation. Short Course Series Vol. 32, Mineralogical Association of Canada. 374 pp.
SORBY HC (1858) On the microscopic structure of crystals, indicating the origin of
minerals and rocks. Geol. Soc. London Quart. J., 14, pt. I, 453-500.
Regular issues
FLUID INCLUSION RESEARCH - Proceedings of COFFI (1968-1998) Roedder E & Kozlowski
A (eds.) Ann Arbor. The University of Michigan Press.
ECROFI Abstracts (biannual from 1970). Abstract volumes. Selections of contributions
published in special issues of Eur. J. Mineral.
PACROFI Abstracts (biannual from 1984). Abstract volumes (some published in special
issues of Geochim. Cosmochim. Acta).
Literature selection "geofluids"
BODNAR RJ (1983) A method of calculating fluid-inclusion volumes based on vapor bubble
diameters and P-V-T-X properties of inclusion fluids. Econ. Geol. 76, 535-542.
DUBESSY J, POTY B., RAMBOZ C (1989) Advances in C-O-H-N-S fluid geochemistry based
on micro-Raman spectrometric analysis of fluid inclusions. Eur. J. Mineral. 1, 51 7-534.
HALL DL, BODNAR RJ (1990) Methane in fluid inclusions from granulites: A product of
hydrogen diffusion? Geochim. Cosmochim. Acta 54, 641-651.
HUIZENGA JM (1995) Fluid evolution in shear zones from the late Archean Harare-
Shamva-Bindura Greenstone Belt (NE Zimbabwe). Thermodynamic calculations of the C-
O-H system applied to fluid inclusions. Ph.D. Dissertation. Free University -Amsterdam.
55

KONNERUP-MADSEN J (1979) Fluid inclusions in quartz from deep-seated granitic
intrusions. Lithos 12, 13-23.
KREULEN R (1987) Thermodynamic calculations of the C-O-H system applied to fluid
inclusions: are fluid inclusions unbiased samples of ancient fluids ? Chem. Geol. 61,
59-64.
LAMB WM, VALLEY JW, BROWN PE (1987) Post-metamorphic CO
2
-rich fluid inclusions
in granulites. Contr. Mineral. Petrol. 96, 485-495.
NEWTON RC (1989) Metamorphic fluids in the deep crust, Ann. Rev. Earth Planet. Sci.
17, 385-412.
ROEDDER E (1979) Fluid inclusions as samples of ore fluids. In: HL Barnes (ed.)
Geochemistry of hydrothermal ore deposits. 2nd ed. 684-737. Wiley- New York
ROEDDER E (1990) Fluid inclusion analysis Prologue and epilogue. Geochim.
Cosmochim. Acta 54, 495-507.
SWANENBERG HEC (1980) Phase equilibria in carbonic systems and their application to
freezing studies of fluid inclusions. Contr. Mineral. Petrol. 88, 3303-3306.
TOURET JLR (1977) The significance of fluid inclusions in metamorphic rocks. In:
Fraser (ed.), Thermodynamics in Geology, 203-22T, D. Reidel - Dordrecht.
TOURET JLR (1987) Fluid inclusions and pressure-temperature estimates in deep-
seated rocks. In: Helgeson (ed.) Chemical transport in metasomatic processes. NATO
ASI Series C: Mathematical and Physical Sciences. Vol. 218, 91-121.
TOURET JLR (1992) CO
2
transfer between the upper mantle and the atmosphere:
temporary storage in the lower continental crust Terra Nova 4, 87-98.
VAN DEN KERKHOF AM, HEIN UF (2001) Fluid inclusion petrography. In: ANDERSEN T,
FREZZOTTI ML, BURKE EAJ ed. Fluid inclusions: phase relationships - methods-
applications (special issue). Lithos 55 (1-4), 320 pp.
VITYK MO, BODNAR RJ (1995) Do fluid inclusions in high grade metamorphic terranes
preserve peak metamorphic density during retrograde decompression? American
Mineralogist.
Fluid systems
BISCHOFF JL, PITZER KS (1989) Liquid vapor relations for the system NaCI-H
2
O;
summary of the P-T- X surface from 300 to 500'C. Am. J. Sci. 289, 217-248.
BODNAR RJ, BURNHAM CW, STERNER SM (1985) Synthetic fluid inclusions in natural
quarlz. - III. Determination of phase equilibrium properties in the system H
2
O-NaCl to
1000C and 1500 bars. Geochim. Cosmochim. Acta 49, 1861-1873.
BURRUSS RC (1981) Analysis of fluid inclusions: Phase equilibria at constant volume.
Amer. J. Sci. 281, 1104-1126.
CHOU I.-M., STERNER SM, PITZER KS (1992) Phase relations in the system NaCI-KCI-
H2O. IV. Differential thermal analysis of the sylvite liquidus in the KCI-H
2
O binary, the
liquidus in the NaCI-KCI-H
2
O ternary, and the solidus in the NaCI-KCI binary to 2 kb
pressure, and a summary of experimental data for the thermodynamic PTX analysis of
solid-liquid equilibria at elevated PT conditions. Geochim. Cosmochim. Acta 56, 2281-
2293.
DIAMOND LW (1994) Salinity of multivolatile fluid inclusions determined from clathrate
hydrate stability. Geochim. Cosmochim. Acta 58, 19-41.
FALL A, TATTITCH B, BODNAR R (2011) Combined microthermometric and Raman
spectroscopic technique to determine the salinity of H
2
O-CO
2
-NaCl fluid inclusions
based on clathrate melting Geochim. Cosmochim. Acta 75, 951-964.
FISHER JR (1976) The volumetric properties of H
2
O - a graphical portrayal. Joum.
Research U.S. Geol. Survey 4 (2), 189-193.
HALL DL, STERNER SM, BODNAR RJ (1988) Freezing point depression of NaCI-KCI-H
2
O
solutions. Econ. Geol. 83, 197-202.
HANOR JS (1980) Dissolved methane in sedimentary brines: potential effect on the
PVT properties of fluid inclusions. Econ. Geol. 75, 603-617.
56

JOYCE DB, HOLLOWAV JR (1993) An experimental determination of the
thermodynamic properties of H
2
O-CO
2
-NaCl fluids at high pressures and
temperatures. Geochim. Cosmochim. Acta 57, 733-746.
ROSSO KM, BODNAR RJ (1994) Detection limits of CO
2
in fluid inclusions using
mcrothermometry and Laser Raman Spectroscopy and the spectroscopic
characterization of CO
2
. Geochim. Cosmochim. Acta.
SEITZ JC, PASTERIS JD (1990) Theoretical and practical aspects of differential
partitioning of gases by clathrate hydrates in fluid inclusions. Geochim. Cosmochim.
Acta 54, 631-639.
STERNER SM, HALL DL, BODNAR RJ (1988) Synthetic fluid inclusions. V. Solubility
relations in the systern NaCI-KCI-H
2
O under vapor-saturated conditions. Geochim.
Cosmochim. Acta 52, 989-1 005.
STERNER SM, CHOU I-M, DOWNS RT, PITZZER KS (1992) Phase relations in the
system NaCI-KCI-H
2
O. V. Thermodynamic -PTX analysis of solid-liquid equilibria at
high temperatures and pressures. Geochim. Cosmochim. Acta 56, 2295-2309.
TAKENQUCHI S, KENNEDY GC (1965) The solubility of carbon dioxide in NaCI
solutions at high temperatures and pressures. Amer. J. Sci. 263, 445-454.
THIRY R, VAN DEN KERKHOF AM, DUSESSV J (1994) vX properties of CH
4
-CO
2
and
CO2-N2 fluid inclusions: modelling for T<31C and P<400 bars. Eur. J. Mineral. 6,
753-771.
VAN DEN KERKHOF AM (1988) CO
2
-CH
4
-N
2
in fluid inclusions: theoretical modelling
and geoiogical applications. Ph.D. Diss. Free Univ., Amsterdam, 206 pp.
VAN DEN KERKHOF AM (1990) Isochoric phase diagrams in the systems CO
2
-CH
4
and CO
2
-N
2
: application to fluid inclusions. Geochim. Casmochim. Acta 54, 621-629.
VAN DEN KERKHOF AM, OLSEN SN (1990) A natural example of superdense CO
2
inclusions: Microthermometry and Raman analysis. Geochim. Cosmochirn. Acta 54,
885-901.
KISCH HJ, VAN DEN KERKHOF AM (1991) CH
4
-rich inclusions from quartz veins in
the Valley-and Ridge province and anthracite fields of the Pennsylvania
Appalachians. American Mineral. 76, 230-240.
WALTHER J. (1981) Fluide Einschlsse im Apatit des Carbonatits vom Kaiserstuhl
(Oberrheingraben) Ein Beitrag zur Interpretation der Carbonatitgenese. Doctoral
Thesis University of Karlsruhe, 195 pp.
ZHANG YG, SCHWARTZ JD (1989) Experimental determination of the compositional
limits of immiscibility in the system CaCI
2
-H
2
O-CO
2
at high temperatures and
pressures using synthetic fluid inclusions. Chem. Geol. 74, 269-308.
ZWART EW, TOURER JLR (1994) Melting behaviour and composition of aqueous fluid
inclusions in fluorite and calcite: applications within the system H
2
O-CaCI
2
-NaCI.
Eur. J. Mineral. 6, 773-786.
Equations of state /technical
BAKKER RJ (2001) FLUIDS: new software package to handle microthermometric
data to calculate isochores (available from the author)
BAKKER RJ (1997) Clathrates: computer programs to calculate fluid inclusion V-X
properties using clathrate melting temperatures. Computer & Geosciences 23,1-18.
BAKKER RJ, DIAMOND LW (2006) Estimation of volume fractions of liquid and vapor
phases in fluid inclusions, and definition of inclusion shapes. American Mineralogist
91, 635-657.
BOWERS TS, HELGESON HC (1985) Fortran programs for generating fluid inclusion
isochores and fugacity coefficients for the system H
2
O-CO
2
-NaCI at high pressures
and temperatures. Computers R Geosciences 11(2), 203-213.
BROWN PE (1989) FLINCOR: A fluid inclusion data reduction and exploration
program (abstr.). 2nd Biennal Pan-American Conf. on Research on Fluid Inclusions
Abstr., 14.
BROWN PE, LAMB WM (1989) P-V-T properties of fluids in the system
H
2
O+CO
2
+NaCI: New graphical presentations and implications for fluid inclusion
studies. Geochim. Cosmochim. Acta. 53, 1209-1221.
57

HOLLOWAY JR (1977) Fugacity and activity of molecular species in supercritical fluids.
In: DG Frazer (ed.) Thermodynamics in Geology, D. Reidel - Dordrecht, 161-181.
MACDONALD AJ, SPOONER ETC (1981) Calibrations of a LINKAM TH600 programmable
heating-cooling stage for microthermometric examination of fluid inclusions. Econ. Geol.
76, 1248-1258.
SHEPHERD TJ (1981) Temperature-programmable heating-freezing stage for micro-
thermometric analysis of fluid inclusions. Econ. Geol. 76, 1244-1 247.
ZHANG YG, FRANTZ JD (1987) Determination of homogenization temperatures and
densities of supercritical fluids in the system NaCI-KCI-CaCI
2
-H
2
O using synthetic fluid
inclusions. Chem. Geol. 64, 335-350.
Fluid inclusion experiments
BAKKER RJ, JANSEN JB (1990) Preferential water leakage from fluid inclusions by means
of mobile dislocations. Nature 345, No.6270, 58-60.
BODNAR RJ, STERNER SM (1985) Synthetic fluid inclusions in natural quartz. II.
Application to PVT studies. Geochim. Cosmochim. Acta 49, 1855-1859.
BODNAR RJ, BINNS PR, HALL DL (1989) Synthetic fluid inclusions. -VI. Quantitative
evaluatian of the decrepitation behavior of fluid inclusions in quartz at one atmosphere
confining pressure. J. metamorphic Geol. 7 (2), 229-242.
CORDIER P, DOUKHAN JC, RAMBOZ C (1994) Influence of dislocations on water leakage
from fluid inclusions in quartz: a quantitative reappraisal. Eur. J. Mineral. 6, 746-752.
STERNER SM, BODNAR RJ (1989) Synthetic fluid inclusions - Vll. Re-equilibration of fluid
inclusions in quartz during laboratory-simulated metamorphic burial and uplift. J. metam.
Geol. 7 (2), 243-260.
WATSON EB, BRENAN JM (1987) Fluids in the lithosphere, 1. Experimentally-determined
wetting characteristics of CO
2
-H
2
O fluids and their implications for fluid transport, host-
rock physical properties, and fluid inclusion formation. Earth Planet. Sci Letters 85, 497-
515.