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ISES course Netherlands Research School of Sedimentary Geology

Fluid inclusions

Alfons van den Kerkhof

Geowissenschaftliches Zentrum der Universität Göttingen (D)

October 1-3, 2008, Vrije Universiteit Amsterdam

Program

Wednesday, October 1, 2008

9.00-12.00

Introduction

Working procedure (sample preparation, equipment)

Classification of fluid inclusions

Mechanisms of fluid inclusion forming

Application of cathodoluminescence

14.00-17.00

Training: Microscopy exercises

Principles of microthermometry, Terminology, Isochore definition

One-component systems

Thursday, October 2, 2008

9.00-12.00

Definition of the fluid inclusion system

Equations of state

Fluid-mineral equilibria and graphite stability

Applications

14.00-17.00

Water-salt systems

Training: Microthermometry, Software-demo

Friday, October 3, 2008

9.00-12.00

Water-gas systems, Clathrate stability

Binary and ternary fluid mixtures

Working with VX diagrams, Examples

Destructive and non-destructive fluid inclusion analysis

14.00-17.00

Training: Microthermometry, Software-demo

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I. Sample preparation

Doubly polished sections

II. Documentation

1. Microscopy and fluid inclusion selection2. Drawings and photos3. Classification of fluid inclusions

a. Description (one-phase, 2-phase, multiphase, daughter crystals etc.)b. Relative phase volumes (fill degree)c. Inclusion size, morphologyd. Relative age (primary, pseudosecondary, secondary)

III. Microthermometry

1. Cooling experi2ment (until ca. -180°C)observation of phase nucleations (Tn V, CO2 S, etc. )

2. Warming experiment (-180 until about 35°C)detection of phase transition temperatures (Te, Tm CO2, Tm ice, Th CO2, Tm ice, Tm hydrate)

3. Heating experiment (aqueous inclusions)Th total, Tm salt

IV. Data treatment

Calculation of compositions and densities, isochore calculation

Fluid inclusion study short working plan

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Working procedure of a fluid inclusion study

(revised after Van den Kerkhof, 1988)

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Estimation of volume fractions 1

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Estimation of volume fractions 2

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Fluid inclusion classification

Classification scheme for fluid and melt inclusions in minerals based upon phases observed at room temperature L=liquid, V= vapour, S=solid, GL=glass (from: Sheperd, 1985)

Examples of phases in fluid inclusions in porphyry copper deposits (from: Nash JT, 1976, US Geol. Survey Prof. Papers 907D)

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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 CO2 (s.) ? M? translucent, microcrystallineT<-56.6 oC; usually forms a single massaggregates euhedral crystals can be formed in liquid CH4-CO2

ICE H2O 1.31 negligible H rounded plates or globules anisotropic but appears isotropic

Tm<0 oC, sometimes yellowish appearanceWATER H

2O 1.32-1.33

CO2-clathrate CO2.5 3/4H2O ~ negligible rhombic or rounded grains Tm = about 6 oC; colourless, RI very close to water (gas hydrate) RI very close to H2O and therefore diff icult to recognize

villiaumite NaF 1.33 isotropic C cubes sometimes yellow/pinkish pleochroismcryolite Na3AlF6 1.34 negligible M alkaline rockselpasolite K2NaAlF6 1.37 isotropic C topase from Volynia USSRmirabilite /Glauber´s s.Na2SO4.10H2O 1.39-1.40 negligible M prismatic, acicularHYDROHALITE NaCl.2H2O ~1.41 negligible M tiny grains giving a speckledhigh relief relative to ice; colourless

appearance Tm (incongruent) = +0.1 oCnatron (soda) Na2CO3.10H2O 1.40-1.44 low M platy crystals Tm (incongruent) = +32 oCFLUORITE CaF2 1.43 isotropic C cubes rarely octahedral, fluorescencehexahydrite MgSO4.6H2O 1.45 low M fibrous, tabulartrona Na3H(CO3)2.2H2O 1.41-1.54 moderate M fibrous, acicularNAHCOLITE NaHCO3 1.37-1.58 very high M tabular commonly twinned;

marked relief changes on rotation in pol. lightcarbonic fluids in granulite facies

alum (Na,K)Al(SO4)2.12H2O 1.44-1.46 isotropic Csulfohalite Na6(SO4)2ClF 1.45 isotropic Cthermonatrite Na2CO3.H2O 1.42-1.52 moderate Oborax Na2(B4O5(OH)4).8H2O 1.45-1.47 low M

gaylussite Na2Ca(CO3)2.5H2O 1.44-1.52 moderate M elongated or flattened crystals

epsomite MgSO4.7H2O 1.43-1.46 low O(T) acicular

alunogen Al2(SO4)3.18H2O 1.46-1.48 low T(H) fibrousthenardite Na2SO4 1.46-1.48 low O bipyramidal or tabular c.f. gypsum

CARNALITE KMgCl3.6H2O 1.47-1.49 low O(H) tabular

pickeringite (Mg)- (Mg,Fe´´)Al2(SO4)4.22H2O 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 haliteburkeite Na6CO3(SO4)2 mean 1.49 moderate Oarcanite K2SO4 1.49-1.50 low O massive, tabular rarely "octahedral" crystalspseudo-bischofite MgCl2.6H2O 1.49-1.53 low to M

moderate(hydro-)bischofite MgCl2.12H2O 1.50-1.53 negligible M like hydrohalite identification difficult; colourlesswavellite Al3(PO4)2(F,OH)3.5H2O 1.52-1.55 low O radiated aggregates,

globulesGYPSUM CaSO4.2H2O 1.52-1.53 very low M tabular, prismatic, fibroushydromagnesite Mg5(CO3)4(OH)2.4H2O 1.52-1.54 low M(O) acicular crystals or lamellae

hydroboracite CaMg[B3O4(OH)3]2.3H2O mean 1.52 moderate M associated with gypsumDAWSONITE NaAl(CO3)(OH)2 1.47-1.60 moderate O fibrous bundles frequent in alpine fissures

aggregatesHALITE NaCl 1.54 isotropic C cubes rarely octahedral, same refractive index as quartzFe-chlorides FeCln various moderate to (T) var. tabular, often rhombic commonly light green

high or hexagonalQUARZ SiO

2 1.54-1.55 low

antarcticite CaCl2.6H2O 1.49-1.55 low/negligible T like hydrohalite butoccasionally rounded crystals

micas various 1.56-1.60 low to M platy extremely thin platesmoderate

strontianite SrCO3 1.52-1.67 high O acicular, pseudohexagonalANHYDRITE CaSO4 1.57-1.61 low O prismatic associated with gypsumaragonite CaCO3 1.53-1.69 high O prismatic, acicularwhewellite CaC2O4.H2O 1.49-1.65 very high M prisms uranium vein depositsCa,Mg CARBONATE (Ca,Mg)CO3 1.49-1.66 very high T rhombohedral high relief; marked changes in relief on rotation in pol. light

barite BaSO4 1.64-1.65 low O tabularAPATITE Ca5(PO4)3(F,OH,Cl) 1.63-1.67 low H hexogonal crystals

HEMATITE Fe2O3 (2.9-3.2) T hexagonal plates distinctive red/brown platesSULFIDES various - var. euhedral grains identif ication 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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Eutectic properties of salt solutions

(Hein, Compact course, 1990)

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Microthermometry abbreviations

„ A consensus of fluid inclusion workers on usage of microthermometric terms was

reached and first printed in Vol. 10 of COFFI. It is suggested that if this terminology is

used consistently in the future papers, considerable ambiguity will be avoided (For ease of

typewriting and typesetting, I suggest not using subscripts) „ (Roedder 1981, Fluid

Inclusion Research – Proceedings of COFFI)

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Relative age of fluid inclusions

Primary-secondary“ classification

Principle sketch of inclusion classification, based on Roedder´s (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)

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Prim

ary fluid inclusions (diagnostic criteria)

(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)(from: Van den Kerkhof & Hein, 2001, Lithos 55, 27-47)

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Trail terminology / Homogeneous –heterogeneous trapping

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.

(below) (a) Homogeneous trapping of fluids. At room temperature (after cooling) phase separation may result from shrinkage, saturation or unmixingof the original homogeneous fluid. (b) Heterogeneous trappingof fluids. Fluid inclusions of variable composition and phaseratio are trapped at the sametime (Van den Kerkhof & Hein, 2001, Lithos 55, 27-47)

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Fluid inclusion modification

(Hansteen, 1988) (Bodnar, Binns & Hall, 1989, J. Metam. Geol. 7, 229-242

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Overview of methods for analyzing fluid inclusions

NON-DESTRUCTIVE ANALYSIS

1. OPTICAL MICROSCOPY AND

VIZALIZING TECHNIQUES

Petrographical microscope fluid inclusion abundance, chronology

CL-Microscopy /SEM-CL textural relations with host mineral, secondary

quartz

UV-Microscope detection of hydrocarbons

IR-Microscope visualisation of fluid inclusions in semi-opaque

and opaque minerals (e.g. cassiterite, chromite,

sphalerite, pyrite)

TEM dislocations /micro-cracks around FI

2. MICROTHERMOMETRY composition and molar volume

3. VIBRATIONAL SPECTROSCOPY

Laser excited micro-Raman spectroscopy composition of non-aqueous fluids,

identification of daughter crystals

FT-IR detection of CO2, H2O, hydroxyl, ...

Fluorescence spectroscopy detection of hydrocarbons

4. PARTICLE BEAMS TECHNIQUES

Electron microprobe (EPMA) inclusions near the sample surface

Proton probes: PIXE, PIGE, SXRF

Electron synchrotron

DESTRUCTIVE ANALYSIS

B u l k a n a l y s i s

1. MECHANICAL

Crushing stage non-aqueous fluids, qualitative

2. STEPWISE HEATING

Acoustic emission (AE) 'Decrepitometry' finger print of fluid inclusion content

Gas chromatography bulk fluid composition

Mass spectrometry bulk fluid composition, isotopes

3. CRUSH AND LEACH combined with

micro-chemical analysis, AAS, etc.

composition of aqueous fluids, element ratios,

dissolved daughter crystals

S i n g l e i n c l u s i o n s

1. EPMA or SIMS (opened inclusions) identification daughter minerals, composition

of FI (freezing method)

2. LA-ICPMS composition including trace elements

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Analytical equipment

Crushing stage

Heating/freezing stage

Laser Raman Microspectromer (LRM)

(below) Cross-section of the Linkam stage (Sheperd, 1981) Pt= platinum resistance temperature sensor

(right) 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

Scheme of the light path in a Laser Raman Microspectrometer (Microdil-28). INT.R.= interrupter, O.S. = optical scanner, P.M. photomultiplier, G1-3 = holographic gratings, S1-3= opening slits

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Phase transitions during microthermometry runs

Phase transitions in aqueous inclusions

Phase transitions in gaseous inclusions

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1-Component systems

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The system H2O

Schematic, polybaric, V-T-projection of the one-component H2O solid-liquid-vapor equilibria including 3 solid-solid-liquid P, T invariant points for high pressure ice polymorphs. Contructed from data summarized by Eisenberg & Kauzmann (1969)

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H2 O

isochoresH2O isochores modified from Fischer (1976). Enlargement of the low pressure region, in the box, appears to the right.

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Density estimates (CO2 and CH4)

(a) Densities of liquid and gas on the boiling point curve as a function of temperature (b) Molar volume of the liquid on the boiling point curve (from: Van den Kerkhof & Thiéry, 2001, Lithos 55, 49-68)

Saturation curve of methane (after Zagoruchenko & Zhuravlev 1970)

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CO2 isochores

Phase diagram for CO2 showing densities (g/cc) of several isochores. Data from compilation of Angus et al. (1973). CP = critical point at 31°C.

Combined isochores for CO2 and H2O. At higher PT (>1.5 kbar; >500°C) CO2has higher density than for water, which is trapped at the same conditions

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Binary water-salt systems

NaCl-H2O system, temperature-composition diagram at 1 bar. All phases coexist with vapor. data from Potter et al. (1978) and Linke (1965).

The system H2O-NaCl

The system H2O-CaCl2

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The system H2O-NaCl (PT)

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The system H2O-NaCl (XT)

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H2O-NaCl isochores (1)

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H2O-NaCl isochores (2)

Iso-Th lines for NaCl-H2O inclusions having salinities of 0, 5, 10, 15, 20 and 25 wt%% NaCl calculated using data from Bodnar and Vityk

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The system H2O-CO2 : phase transitions and immiscibility

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The system H2O-CO2 (PT)

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The system H2O-CO2 (VX)

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Calculation of composition and molar volume

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Ternary water salt systems

H2O-NaCl-KCl

H2O-NaCl-CaCl2

(Sterner, Hall & Bodnar, 1988, GCA 52, 989-1005)

(Konnerup-Madsen, 1979)

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Binary gas systems (topology)

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Binary gas systems: CO2-CH4 (PT)

Phase transitions in the system CO2-CH4 at varying temperature and pressure

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The system CO2-CH4 (VX) (1)

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The system CO2-CH4 (VX) (2)

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The system CO2-N2 (VX)

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Gas systems (phase transitions at constant volume)

(Van den Kerkhof & Thiéry, 2001, Lithos 55, 49-68)

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The application of VX-diagrams

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The ternary system CO2-CH4-N2

(Van den Kerkhof & Thiéry, 2001, Lithos 55, 49-68)

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Literature selection (1)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) Einschlüsse in Mineralien. VEB Deutscher Verlag für 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.

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Literature selection (2)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 CO2-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) CO2 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-H2O; 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 H2O-NaCl to 1000°C 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-H2O binary, the liquidus in the NaCI-KCI-H2O 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.

FISHER JR (1976) The volumetric properties of H2O - 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-H2O 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.

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Literature selection (3)JOYCE DB, HOLLOWAV JR (1993) An experimental determination of the thermodynamic

properties of H2O-CO2-NaCl fluids at high pressures and temperatures. Geochim. Cosmochim. Acta 57, 733-746.

ROSSO KM, BODNAR RJ (1994) Detection limits of CO2 in fluid inclusions using mcrothermometry and Laser Raman Spectroscopy and the spectroscopic characterization of CO2. 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-H2O 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-H2O. 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.

THIÉRY R, VAN DEN KERKHOF AM, DUSESSV J (1994) vX properties of CH4-CO2 and CO2-N2 fluid inclusions: modelling for T<31°C and P<400 bars. Eur. J. Mineral. 6, 753-771.

VAN DEN KERKHOF AM (1988) CO2-CH4-N2 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 CO2-CH4 and CO2-N2: application to fluid inclusions. Geochim. Casmochim. Acta 54, 621-629.

VAN DEN KERKHOF AM, OLSEN SN (1990) A natural example of superdense CO2

inclusions: Microthermometry and Raman analysis. Geochim. Cosmochirn. Acta 54, 885-901.

KISCH HJ, VAN DEN KERKHOF AM (1991) CH4-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 Einschlüsse 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 CaCI2-H2O-CO2 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 H2O-CaCI2-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. BOWERS TS, HELGESON HC (1985) Fortran programs for generating fluid inclusion

isochores and fugacity coefficients for the system H2O-CO2-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 H2O+CO2+NaCI: New graphical presentations and implications for fluid inclusion studies. Geochim. Cosmochim. Acta. 53, 1209-1221.

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Literature selection (4)

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-CaCI2-H2O 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 fluidinclusions 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 CO2-H2O fluids and their implications for fluid transport, host-rock physical properties, and fluid inclusion formation. Earth Planet. Sci Letters 85, 497-515.