Uvod

Klasifikacija fluidnih inkluzija – morfologija, genetska klasifikacija Prije početka mjerenja

Mehanizmi formiranja fluidnih inkluzija, zahvaćanje fluida
Stupanj punjenja vs. gustoća
Odabir i priprema uzoraka
Oprema
Eutektička svojstva
Osnovni principi mikrotermometrije (zamrzavanje/hlañenje)
Definiranje izohora
Atomska apsorpcija spektroskopija AAS
Jednokomponentni sustav H2O
Dvokomponentni sustav NaCl-H2O
Trokomponentni sustavi NaCl-CaCl2-H2O, NaCl-KCl-H2O
Spektroskopske analitičke metode Atomska emisijska spektroskopija AES
Vježbe
I. Priprema uzoraka (Lab)
Induktivno spregnuta plazma spektroskopija ICP Dvostruko polirane pločice
II. Dokumentacija (Mikroskopska vježba)
1. Petrografija i odabir fluidnih inkluzija
Mikrotermometrija fluidnih inkluzija 2. Crtanje i fotografiranje
3. Klasifikacija FI-s
a. Opis (jednofane, dvofazne, višefazne, minerali kćeri…)
b. Relativni volumen faza (stupanj punjenja)
c. Veličina inkluzija, morfologija
d. Relativna starost (primarne, pseudosekundarne, sekundarne)

Literatura
What is a Fluid Inclusion?
Bakker, R.J., 2003. Package FLUIDS 1. Computer programs for analysis of fluid
inclusion data and for modelling bulk fluid properties. Chemical Geology, 194, 3–
23. Cavity in a mineral that may contain 1 or more phases
vapor (V) - H2O, CO2, CH4, N2, H2S
http://fluids.unileoben.ac.at/Home.html liquid (L)- H2O, CO2, petroleum
Henry Clifton Sorby
(1826-1908) solid (S) - NaCl, KCl, hematite, anhydrite, muscovite,
English microscopist and magnetite, carbonates
Brown P.E., 1989. FLINCOR; a microcomputer program for the reduction and geologist
investigation of fluid-inclusion data. American Mineralogist, 74/11-12, 1390-1393. 1858 On the Microscopical
Structure of Crystals
Roedder, E., 1984. Fluid inclusions. Mineralogical Society America, Review in (Quart. Journ. Geol. Soc.)
Mineralogy 12, Washington, 644 pp.
V
Shepherd, T.J., Rankin, A.H., Alderton, D.H.M., 1985. A practical guide to fluid
inclusion studies. Blackie and Son Ltd, Glasgow, 239 pp. L

The liquid of the inclusion is normally an aqueous solutions with dissolved ions of Na+, Cl-, Ca2+,
Mg2+, SO42-, HCO32-, CO32-
The concentration of the salts ranges from <1 wt. % to >50 wt. %

1
 Top 10 minerals Abundance of FI-s in Average No of FI-s occupying
1. Quartz single crystal if the total FI-s size 0.1% volume
Occurrence and distribution
2. Fluorite population occupy 0.1% 1 mm 1
3. Halite
volume 100 µm 103
4. Calcite
Earth Crust – magmatic, metamorphic and sedimentary rocks, 5. Apatite Size and abundance 10 µm 106
ore deposits, fault zones 6. Dolomite 1 µm 109
7. Sphalerite
8. Barite
9. Topaz
10. Cassiterite
Size of fluid
inclusions in minerals

> mm museum specimens

3-20 µm range for
microthermometry
1.5 µm smallest workable size
for H2O or CO2
inclusions
5 µm smallest workable size
Extraterrestrial - Mars for H2O+CO2 inclusions Volume and diameter of spherical inclusions assuming a fluid of density 1.0 g/cc

What can I study? Which type of material do I use? What can I get from this method?
Ore deposits (hydrothermal, porphyry, Large, well developed crystals in
skarn) vughs and druses, all phases of vein
developing, alterations
1. Composition of fluid form which mineral precipitated
Igneous rocks Quartz (remnant of magmatic fluid or
late stage hydrothermal circulation) 2. Changes of fluid composition during precipitation (mixing, dilution,
boiling, cooling)
Apatite from carbonatite
Phenocrysts from volcanic 3. Minimum temperature and pressure at the time of precipitation
Pegmatites Quartz, beril, tourmaline 4. True temperature and pressure applying pressure correction (i.e.
independent geothermometer or boiling fluid)
5. Depth of formation (i.e. overlying deposits)
Metamorphic rocks Quartz from veins, pods, segregations

Sedimentary rocks Diagenetic fluids preserved within

veins, pods, vughs, geodes,
diagenetic cement or overgrowth

2
 What type of samples do I need? How to prepare doubly polished wafers?

Type Advantage Disadvantage Stage 1 Sawing to surface 3-4 cm2

Thin sections Available, easy prepared, Can not use for heating-
host rock petrography can freezing, large FI-s Stage 2 Grinding
be determined destroyed
Grit Grit size (F)/µm Lapping time (min)

Cleavage fragments No specific equipment Relationships between SiC 320/29 5-10

needed, fast scanning of the individual FI-s and grains
samples, direct cannot be established SiC 400/17 5-10
measurements
SiC 800/6.5 5-10
Cut, doubly polished wafers Direct use on heating- Mineral identification by
0.2 – 0.5 mm thick freezing stage, large FI-s optical properties difficult -
preserved thick, highly colored or milky Stage 3 Polishing
samples – thin (<100mm),
difficult to prepare Soft polish cloth mounted on rotary lapping machine
ά-Al2O3 /0.3 ~20

Fluid inclusions FI-s Major textural criteria

morphology
Primary (P) FI-s are formed during the mineral growth within the growth zones. These are
overgrowths defined by seudo-secondary (PS) FI-s formed in healed fracture in mineral during
Negative crystal shape (halite cubes) original mineral growth. Secondary (S) FI-s developed after the crystallization of the host.
Irregular
Flattened
Faced along clevage
Spheroidal or oblate PS

Tubular in elongated crystals

P = Primary
PS = PseudoSecondary
S = Secondary
inclusions

Roedder, 1984,
American Mineralogist

3
Primary FI-s classification
Mechanisms of trapping of primary FI-s
(a) Diagnostic criteria for classifying fluid inclusions as primary (after Roedder, 1979)
(b) Different occurrences of primary fluid inclusions in relation to growth zoning (compilation) A dendritic growth
(from: Van den Kerkhof & Hein, 2001, Lithos 55, 27-47) B partial disolution
C between growth spirals
D sub-parallel block growth
E fracture during growth
F foreign object

Secondary inclusions Secondary and

pseudosecondary
Look at essentially any FI-s classification
sandstone/quartzite
Trail terminology (Vollbrecht,
samples in the lab 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

4
Working example 1: FI-s content - classification
(from: Sheperd, 1985)
Determine relative age
(Hansteen, 1988)

Single-phase Two-phase

Liquid or Liquid-rich
growth zoning

Vapor H2O, Vapor-rich

growth zoning

CH4, CO2

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 Classification scheme for fluid and melt inclusions in
primary. The S trail, extending tothe minerals based upon phases observed at room
surface of the crystal, postdates all P Multi-phase Immiscible-liquid temperature
and PS inclusions. L=liquid, V= vapour, S=solid, GL=glass

Working example 2:
Classify the inclusions
Basic Assumptions

1. Trapped fluid was a single homogeneous phase

2. The cavity has not changed in volume
10 µm 3. Nothing is added or lost after sealing
4. Effects of pressure are insignificant or known
5. The origin of the inclusion is known
6. The determinations of Th are both precise and accurate

HOWEVER

15 µm 10 µm 10 µm 1. Bulk leakage
2. Leakage through diffusion
3. Stretching
4. Re-equilibration
5. Necking-down
6. Migration

5
 Recognition
Necking-down
1. Bulk leakage – soft, easy cleaved material – visual estimation on constancy of L to V
ratio, reproducibility of thermometric results
2. Leakage through diffusion – proved as extremely low (H+ found by Raman)
3. Stretching – change of volume without changing of composition
4. Re-equilibration – irregularly shaped FI-s tend to change shape and morphology
during time into negative crystal of spherical – insoluble minerals as quartz -
isochemical at constant volume
5. Necking-down – if original FI is large, flat and irregular will split into many small but
more regular FI-s. If the process occur during homogenous stage – good, preserved
L to V ratio, if not L to V ratio disturbed – erroneous values time
6. Migration – in a thermal gradient – important for water soluble materials

Streaching and leackage

Working example 3:
What happened? Estimation of volume fractions relative to FI-s size – cylindrical FI-s
Why?
How do you know?

6
 Estimation of volume fractions of vapor-rich
inclusions – here comes the problem
Estimation of volume fractions of spherical inclusions

Cylindrical
Trapping mode

Spherical

7
 Naziv faze Sastav Stupanj Kristalni Habitus
Accidental trapping of solids refleksije sustav
Tekući ugljik- CO2 (l) 1,195
dioksid
Led H2O 1,31 Heksagonski Zaobljen,anizotropan,
izgleda izotropno
Hidrohalit NaCl×2H2O 1,41 Monoklinski Sitna zrnca
svjetlucavog izgleda
Silvin KCl 1,49 Kubični Kockice

Gips CaSO4×2H2O 1,52 Monoklinski Tabularni, prizmatski

Halit NaCl 1,54 Kubični Kockice

Ahidrit CaSO4 1,57 Rompski Prizmatski

Ca,Mg (Ca,Mg)CO3 1,49 – 1,66 Trigonski Romboedrijski

karbonati

Phase proportion of individual inclusion

Analytical equipment – Linkam stage
Degree of fill (F) of two phase L+V FI-s
Cross-section of the Linkam stage (Sheperd, 1981) Pt= platinum resistance temperature sensor
F = VL/VL + VV where VL + VV = VTOT

F is related to total density (ρTOT) of the fluid by following expression

ρTOT = ρLF + ρV(1-F) where ρL = density of the liquid phase

ρV = density of the vapor phase

In most cases we can assue that density of the vapor phase is zero, thus:
1 0 15 25 wt % NaCl equ.
ρTOT = ρLF

Technical specifications
Degree of fill (F)

-180º to +600ºC (gaseous N2)

0.5 Fully automatic
0.1º - 0.9ºC/min; 1º - 9ºC/min; 10º -
90ºC/min
Max. sample size 20 mm, 1.5 mm thick
Total density (ρTOT) of the fluid in g/cm3
Viewing area – 2.2 mm
0
0 0.5 1 1.1 1.2 x-y micromanipulators

8
Eutectic properties of
SALT SOLUTIONS Diagnostic features

What types of FI-s

can we found?

(Hein, 1990)

Phase transitions during microthermometry runs

2D phase diagram A B C D
Phase transitions in aqueous inclusions Trapping temperature
pt diagram for water Supercritical fluid

H2O system

vapor
liquid

cooling
Two phase L+ V

Lines of equilibrium or Density (g/cm3) or degree of fill

phase boundaries
Tripple point
Critical point

9
H2O system H2O system
Principle of fluid inclusion geothermometry PT diagram Consider an inclusion trapped at a given
for pure water temperature and pressure (Tt, Pt)
1.0 1.0

Liquid Liquid
water Isochore Isochore
(g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point
0.5 0.5

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e
ling
Dry steam curv
Boi curve -Vapour L= V Vapour
0 L= V 0
50 150 350 Temp oC 50 150 Tt 350 Temp oC

H2O system H2O system

On cooling, the inclusion follows an isochoric PT path Beyond this point the inclusion cools along the L=V
until it meets the L=V curve curve and a vapour bubble nucleates

1.0 1.0

Liquid Liquid
Isochore Isochore
Pt (g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point
0.5 0.5
0

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e e
curv curv
L= V Vapour L= V Vapour
0 0
50 150 Tt 350 Temp oC 50 150 Tt 350 Temp oC

10
H2O system H2O system

Continued cooling results in further shrinkage of liquid On heating along the V/L curve, the liquid expands and
and growth of the vapour bubble the bubble shrinks

1.0 1.0

Liquid Liquid
Isochore Isochore
Pt (g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point
0.5 0.5

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e e
curv curv
L= V Vapour L= V Vapour
0 0
50 150 Tt 350 Temp oC 50 150 Tt 350 Temp oC

H2O system H2O system

Until the bubble disappears at the homogenisation The point Th uniquely defines the isochore along which
temperature (Th) the inclusions originally cooled

1.0 1.0

Liquid Liquid
Isochore Isochore
Pt (g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point

ore
0.5 0.5

Isoch
0

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e e
curv curv
L= V Vapour L= V Vapour
0 0
50 150 Th Tt 350 Temp oC 50 150 Th Tt 350 Temp oC

11
H2O system H2O system

With continued heating the inclusion follows the original If Pt is known, or estimated, the trapping temperature
isochore (Tt) can be determined

1.0 1.0

Liquid Liquid
Isochore Isochore
Pt (g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point
0.5 0.5

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e e
curv curv
L= V Vapour L= V Vapour
0 0
50 150 Th Tt 350 Temp oC 50 150 Th Tt 350 Temp oC

H2O system H2O system

The difference between Th and Tt is known as the Principle of fluid inclusion geothermometry based on
Pressure Correction PVT diagram for pure water
1.0 1.0

Liquid Liquid
Isochore Isochore
Pt (g/cc) Pt (g/cc)
Pressure KBar

Pressure KBar
Critical Critical
point point
0.5 0.5
0

0
0. 6

0. 6
0.80

0.80
0.95

0.95
e e
curv curv
L= V Vapour L= V Vapour
0 0
50 150 Th Tt 350 Temp oC 50 150 Th Tt 350 Temp oC

12
H2O system
SC
F
H2O isochores modified from Fischer (1976).
Enlargement of the low pressure region, in the box, appears to the right. 3D phase diagram –
two component system Liquid
So
l A
+L

Sol B + L

Sol A + sol B

So
lA
+
V
r
Va po
po
r va
A +V
com So
lB lB
pos + So
itio V
n

Phase transitions during microthermometry runs

Phase transitions in two-phase NaCl-H2O aqueous inclusions

The next slides show the freezing and

subsequent melting of a two phase aqueous
inclusion. Note the first and last melting
temperatures which tell us about composition

Heating

Cooling

13
350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

14
 350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

350oC 350oC
Temperature of Homogenisation Th

25oC 25oC
0oC 0oC

-100oC -100oC

15
350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

350oC The next slides show the freezing and

subsequent melting of a two phase aqueous
inclusion. Note the first and last melting
temperatures which tell us about composition

25oC
0oC Heating

Cooling
-100oC

16
 350oC 350oC

25oC 25oC
0oC 0oC

-100oC Freezing after Supercooling -100oC

Eutectic properties of
SALT SOLUTIONS

350oC

25oC
0oC

First melting temperature - Tfm

-100oC
Eutectic - telling us about composition

17
350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

350oC 350oC

25oC 25oC
0oC 0oC

-100oC -100oC

18
 350oC 350oC

25oC 25oC
0oC 0oC

-100oC Last ice melting temperature Tm(ice) -100oC

Telling us about salinity

NaCl-H2O system NaCl-H2O system

Phase diagram for NaCl-H2O showing stability fields
An inclusion with 10 wt.% solution cooled below
for halite, hydrohalite, liquid and vapour 0oC does not form ice because of metastability

25 25

L+V NaCl L+V NaCl

+L+V +L+V
Temperature oC

Temperature oC
0 0.1oC 0 0.1oC

NaCl.2H2O NaCl.2H2O
Ice + L+ V +L+ V Ice + L+ V +L+ V
-20.8oC -20.8oC
-25 -25

Ice + NaCl.2H2O + V Ice + NaCl.2H2O + V

-50 -50
0 10 20 30 0 10 20 30
Weight % NaCl Weight % NaCl

19
NaCl-H2O system NaCl-H2O system
Rapid cooling below the eutectic temperature (Te) On heating first melting (Tfm) occurs at -20.8
is usually needed before the inclusion freezes (Te), evident by “unlocking” of the vapour bubble

25 25

L+V NaCl L+V NaCl

+L+V +L+V
Temperature oC

Temperature oC
0 0.1oC 0 0.1oC

NaCl.2H2O NaCl.2H2O
Ice + L+ V +L+ V Tfm Ice + L+ V +L+ V
-20.8oC -20.8oC
-25 -25

Ice + NaCl.2H2O + V Ice + NaCl.2H2O + V

-50 -50
0 10 20 30 0 10 20 30
Weight % NaCl Weight % NaCl

NaCl-H2O system NaCl-H2O system

Continued heating results in the melting of the last Continued heating results in the melting of the last
ice crystal (Tm_ice) at -6oC ice crystal (Tm_ice) at -6oC

25 25

L+V NaCl L+V NaCl

+L+V +L+V
Temperature oC

Temperature oC
0 0.1oC 0 0.1oC
Tm(ice) Tm(ice)
NaCl.2H2O NaCl.2H2O
Tfm Ice + L+ V +L+ V Tfm Ice + L+ V +L+ V
-20.8oC -20.8oC
-25 -25

Ice + NaCl.2H2O + V Ice + NaCl.2H2O + V

-50 -50
0 10 20 30 0 10 20 30
Weight % NaCl Weight % NaCl

20
 Sample calculations from fluid inclusion observations
Temperature of ice melting directly determine the salinity
For diferent composition of inclusions (Te) we apply different 300 bars fluid pressure (hydrostatic)
phase diagrame to calculate salinities Fluid T = Rock T
Average fluid density = 1.0 g/cc
=> Depth = 3 km

Temperature = 300°C
=> Thermal gradient = 100°C /km

Age: rock passed through 300°C

1 million years ago
=> Uplift rate = 3 mm/year

CaCl2-H2O system Ternary water salt systems

21
Ternary water salt systems

22