3.

Collecting fluid inclusion data

-  Philosophy of a fluid inclusions study

-  Selec5ng inclusions for microthermometry
-  Fundamentals of Microthermometry

1
Informa(on provided by fluid inclusions

• Composi5on of a fluid present during a geological event

(mineralisa5on, diagenesis, metamorphism, etc.)

• P-T condi5ons of fluid trapping

• In hydrothermal ore deposits:

w Iden5fica5on of fluid circula5on episodes
w Informa5on about the processes involved in ore
precipita5on

2
Philosophy of a fluid inclusion research
There are billions of FI in a sample and data obtained from a few of them will
be extrapolated to the Earth scale. We have to proceed in a ra;onal way!

• Iden5fica5on of the problem we want to solve

Can fluid inclusions offer any answer?

• Selec5on of samples (transparent minerals)

• Specific doubly polished sec5ons

• Fluid inclusions petrography

w Iden5fica5on of fluid inclusion types
w Rela5ve chronology
w FI selec5on for their study
» Which set of FI are related to the problem to be solved?
» Are they suitable for microthermometry?
• Microthermometry (+ other techniques including Raman microspectroscopy)
3
Problem to be solved and FI selection

Bodnar, 19XX)
4
Microthermometry
Hea5ng-cooling experiments on fluid inclusions to record phase
transi5ons temperatures

Measuring of
phase transi5ons
is always
performed during
hea5ng

FI analysis laboratory
Ins5tute of Gesosciences
and Earth Resouces
(Italy)
5
Hea(ng /freezing stage (Linkam THMS 600)

Linkham THSMG 600 (temperature controller -196 to +600°C)

6
Linkam THMS 600

7
Linkam THMS 600

8
Linkam THMS 600

9
Microthermometry: melting T

Tf: L + S → L
+ Raman + ICP

Melting temperatures: COMPOSITIONS

10
Microthermometry: homogenization T

Th: L + V → L, V o F

Homogenization
temperatures: minimum
trapping temperature +
density
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“Roedder´s rules”

In a closed system: no loss of mass + no volume change

Fluid composiJon and inclusion volume (V) are constant

Density (ρ) = m/V = constant

Molar volume Vm = M/ρ = constant

M = molar mass (g/mol)

m = mass

Fluid inclusion represent a system of constant molar

volume or constant density: this is an isochoric system
12
Microthermometry fundamentals

Fluid inclusions evolve as

closed systems aPer
trapping (Roedder’s rules)

PV= nRT
P/T = nR/V
Isochore

Microthermometry gives
composition and density,
allowing the isochore
calculation
13
Post-trapping evolution of fluid inclusions

PV = nRT
P/T = nR/V = density

IF: constant internal

density system. Internal
pressure is fixed by
density and temperature.
PV = nRT i.e. P= dT

Internal pressure is independent from external P

14
Post-trapping evolution of fluid inclusions

IMPORTANT!

FI evolve along
an isocore

15
Post-trapping evolution of fluid inclusions

Pi > Pe
Decrepita5on
(explosion)

The larger FI
become empty, the
smaller ones are
preserved

16
Pi > Pe: decrepitation (explosion)

17
Post-trapping evolution of fluid inclusions

Inclusiones parcialmente decrepitadas (Klemovec, Slovakia)

18
Post-trapping evolution of fluid inclusions

Pi < Pe: Implosion (collapsing cavity). Anular FI.

19
Pi < Pe: Implosion (collapsing cavity)

20
Negative crystals: equilibrium shape

21
4. Phase changes in fluid inclusions

-  Understanding real fluids

-  Chemical systems of geological interest

22
Understanding real fluids

•  Four phases: solid, liquid, vapour, and supercri5cal phase

•  Triple and cri5cal point
23
Understanding real fluids

24
Understanding real fluids

Every single component system has its own triple point and critical point

25
Understanding real fluids H2O

H2O density along the liquid-vapour (boiling) curve

26
Understanding real fluids

H2O

Isocores cannot have a negative slope

27
Understanding real fluids CO2

CO2 density along the liquid-vapour curve

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Understanding real fluids

CO2

29
Understanding real fluids

Grey area:
H2O is heavier than CO2

At higher PT geological
conditions CO2 is
heavier than H2O.
That is why CO2 is
concentrated in the
lower crust

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H2O system

TP = 0 ºC
CP = +374ºC

+374º C
0º C
31
CO2 system

TP = -95ºC
CP = +31.1ºC

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 CH4 system

TP = -182.5ºC
CP = -82.62ºC
Low density CH4
Th = -87ºC (V)

High density CH4

Th = -83.2ºC (L)
Never
ignore dark
inclusions!

R&G, 1994 R&G, 1994

Fig. 7.20 Fig. 7.21
33
H2O-NaCl

G&R, 1994

Halite: NaCl
Hydrohalite:
NaCl ⋅2H2O

•  Ini5al/eutec5c mel5ng point is component specific: -21.1°C for H2O-NaCl

•  Final mel5ng point indicates salinity
•  High-salinity fluid inclusions (> 26 wt.% NaCl) show halite 34
 H2O-NaCl
I One crystal is left and it melts at -6.6ºC

H. Only two ice crystals are left 10 wt.% NaCl

G. Four ice crystals are left

F. 0.3 above eutectic. Only ice is

present. Crystals are larger.
E. 0.1ºC below eutectic. Hydrohalite will
melt.
D. Crystals outlines are obvious and some
are brighter (hydrohalite) than others

C. First indication of any crystals

(recrystallization?)

G&R, 1994
35
H2O-NaCl: undersaturated region
10 wt.% NaCl

36
H2O-NaCl: eutectic point (-21.1ºC)

23.3 wt.% NaCl - Eutectic composition

F. “Orange peel texture” at the eutectic

temperature, followed by a immediate “clearing”

E. Crystal outlines are easily noted. Some

crystals (hydrohalite) are brighter

D. Very diffuse crystal boundaries begin to show

C. Nothing has changed. Bubble is a little

more deformed

B. Freezing at about -70ºC

37
H2O-NaCl: eutectic point

23.3 wt.% NaCl - Eutectic composition

38
 Ice and hydrohalite distinctive features

Goldstein y
Reynolds, 1994
ice

ice
Synthetic H2O-NaCl
inclusion of eutectic
HH composition in quartz

HH ice

A.  T just below Te after short cooling and warming cycles on the stage. Ice
crystals are rounded, large and dull; hydrohalite crystals are small and bright

B.  Same as in A, but after more cycling, the hydrohalite crystals are large enough
to see crystal faces and differences in relief compared to ice and quartz

C.  Same inclusion as B, showing one ice crystal and three hydrohalite crystals 39
H2O-NaCl

40
H2O-NaCl: saturated region

Melting of halite indicates the salinity of the fluid

Total homogenization by bubble dissapearance, by halite melting or both

41
 Salts in aqueous inclusions

Ini5al/eutec5c mel5ng temperature H2O-salt systems

Initial/eutectic melting
Components
temperature (°C)
H2O-NaCl -21.2

H2O-KCl -10.5

H2O-CaCl2 -50

H2O-NaCl-KCl -23

H2O-NaCl-CaCl2 -52

42
H2O-NaCl-KCl

43
H2O-NaCl-KCl

44
H2O-CO2 systems

Typical features:
• Liquid-liquid immiscibility
•  Clathrate are present at low temperature. It is stable at T <
∼10°C

Clathrate: 3D network of H2O molecules

45
H2O-CO2: behaviour at low temperature

Bakker y
Brown, 2003
Fig. 7.4

46
H2O-CO2: behaviour at high temperature

47
H2O-CO2: behaviour at high temperature

88 mol.% H2O

31 mol.% H2O

48
Raman microspectroscopy

49
Raman microspectroscopy

50