A Thermodynamic Approach to Water Geothermometry

426 Pages·2020·20.779 MB·English

by  Roberto Cioni, Luigi Marini

Springer Geochemistry
Roberto Cioni
Luigi Marini
A Thermodynamic
Approach to Water
Geothermometry
Springer Geochemistry
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Roberto Cioni Luigi Marini
(cid:129)
A Thermodynamic Approach
to Water Geothermometry
123
RobertoCioni Luigi Marini
Istituto di Geoscienze eGeorisorse Viareggio, Italy
Consiglio Nazionale delleRicerche
Pisa,Italy
ISSN 2366-6285 ISSN 2366-6293 (electronic)
SpringerGeochemistry
ISBN978-3-030-54317-4 ISBN978-3-030-54318-1 (eBook)
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Preface
Dear reader, I am sure you have seen the beautiful images of Earth taken from
space.Amongtheseimages,thoseportrayingbothanareastilllitbytheSuntothe
west and an already dark area to the east are particularly fascinating to me. As a
geologist, I can appreciate the prevalence of natural elements in the lit side of our
planet, such as the different continental landscapes and the blue ethereal vastness
oftheoceans,whilethedarkareaappearstobedominatedbythepresenceofman,
especiallythosecontinentalareassprinkledwithcountlessman-madelightsources.
Bynow,theanthropogenicimpactonclimateisplainforeveryonetosee—apart
from a minority of people, who deny this evidence for trivial and despicable eco-
nomicreasonsonly. Afterall,economyisnotascience,butasetofprocesses that
caneasilybemanipulatedaccordingtotheinterestsoffewpeople,whoseattemptis
to make economy look like a scientific discipline. Not surprisingly, economy had
notbeenincludedamongtheoriginaldisciplinesworthyoftheNobelPrize.Allow
meabriefdigressiononthispoint.AlfredBernhardNobel,aSwedishchemistwho
inventeddynamiteandballistite,madeafortunethankstohispatentsandindustrial
activities.Inhis will, hearrangedthathis economicresourcesweretobemanaged
by a foundation, which was to award five annual prizes to exceptional benefactors
of humanity in the fields of chemistry, physics, medicine or physiology, literature,
and the defence offriendly relations between peoples. The prize was awarded for
the first time in 1901. Only many years later, in 1968 (ironically, the year of the
idealistic revolution that moved the young people of the time, including Roberto
and myself) another prize was established by the Bank of Sweden, but this time it
wascalled“InmemoryofNobel,”anditwastobeawardedtotheimproperlycalled
“economic sciences”1.
Today,theexploitationofrenewableresourcesasanalternativetofossilfuels—
oratemporaryadditionalsupport,atleastforacertainperiodoftime—isoneofthe
possible ways to satisfy our growing energy demand, while limiting our obvious
impact on our planet. One of these renewable resources is geothermal energy,
whose exploitation for electricity production started in 1904 in Italy—more
1Translatedandmodifiedfromhttps://www.focus.it/cultura/storia/come-e-nato-il-premio-nobel.
v
vi Preface
precisely in Larderello (Tuscany), not far from where Roberto and I worked
togetherfor many years—when Prince Piero Ginori Conti managed toturnonfive
electric bulbs using a dynamo coupled to a piston engine, which was powered by
the geothermal steam coming from a fumarole or a shallow well (Marinelli 1990).
Forthefirsttimeever,theheatproducedwithinourplanetbytheradioactivedecay
of the isotopes of uranium, thorium, and potassium was used not directly as heat,
but transformed into mechanical energy by a motor and subsequently into elec-
tricity by a dynamo. The same energy that moves continental and oceanic plates,
controlsorogeniccycles,andcausesearthquakesandvolcaniceruptionswasfinally
used to improve the quality of human life (Marinelli 1990).
Withthisbook,RobertoandIwishtoprovideoursmallcontributiontothestate
of the art and possible developments in the use of geothermometers: the most
acknowledged and widespread geochemical tools for identifying and exploiting
geothermal resources. In this way, we hope to contribute—even though to a small
extent—to the oceans of things to be done in order to reduce the enormous
anthropogenicimpactonourplanet,whichistheonlyonewehave.Aboveall,we
hope that this book will be useful food for thought for the new generations of
geochemists, and that it might encourage a different methodological approach in
their future scientific research.
I have now reached a certain age, while Roberto has left us forever on January
31, 2020. However, I believe Roberto will always be part of the scientific com-
munity, thanks to his important discoveries in the geochemistry of volcanic and
geothermal gases, as well as of thermal waters and crater lakes. In particular, we
havetothankhimforconceivingthemeasurementofCO fluxesfromsoilthrough
2
accumulation chambers, a method used to date for the surveillance of active vol-
canoes,geothermalexploration,andenvironmentalcontrolallovertheworld:Itisa
creature of Roberto, the most splendid jewel he left us.
Viareggio, Italy Luigi Marini
February, 2020
Acknowledgements WeareindebtedtoProf.NiniekRinaHerdianitaoftheBandungInstituteof
Technology, Indonesia, for permissionto use thecompositional dataof prehnite, wairakite, lau-
montite,garnet,andcalcitefromtheDarajatgeothermalfieldthatshestudiedaspartofherPh.D.
thesis,whichisamineofinformationonhydrothermalmineralogy.
ThisbookhasgreatlybenefittedfromtheeditorialassistanceofAnnettBuettnerandfromthe
criticalreviewofananonymousreviewer,whoarebothgratefullyacknowledged.
Reference
MarinelliG(1990)Larderelloattheoriginsofgeothermicenergy.FratelliAlinari,Florence,p102
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Thermodynamics, Geochemical Modeling and Related
Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 A Synthesis of Thermodynamics for Geothermal Geochemistry. . . 6
2.1.1 Gibbs Free Energy, Enthalpy, and Entropy . . . . . . . . . . 6
2.1.2 Standard State, Activity and Fugacity . . . . . . . . . . . . . . 6
2.1.3 The Equilibrium Constant. . . . . . . . . . . . . . . . . . . . . . . 8
2.1.4 Thermodynamic Properties of Solids and Gases
as a Function of T and P . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.5 Thermodynamic Properties of Aqueous Species
as a Function of T and P . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 Supcrt92 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 The Equilibrium Constant of the Dissolution Reaction
of a Solid Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 Geochemical Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3.1 Equilibrium State Models . . . . . . . . . . . . . . . . . . . . . . . 19
2.3.2 Multicomponent Chemical Geothermometry:
A Reaction Path Model of Special Interest. . . . . . . . . . . 21
2.3.3 Activity Coefficients in Relatively Dilute Solutions . . . . 23
2.3.4 Activity Coefficients in Concentrated Solutions . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3 The Reservoir Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.1 Calculation of the Chemical Composition of Reservoir
Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.1 Calculation of Reservoir Liquid Chemistry for Liquid
Enthalpy Wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.2 Calculation of Reservoir Liquid Chemistry for Excess
Enthalpy Wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
vii
viii Contents
3.1.3 Further Details on the Reconstruction of Reservoir
Liquid Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.1.4 Presentation of the Main Results of Speciation-
Saturation Calculations and Approach Adopted for the
Chemical Classification of Reservoir Liquids. . . . . . . . . 43
3.2 The Reservoir Liquids from the Geothermal Systems
in Iceland. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.2.1 Chemistry of the Reservoir Liquids from the
High-Temperature Geothermal Systems in Iceland . . . . . 46
3.2.2 Chemistry of the Reservoir Liquids from the Medium-
Temperature Geothermal Systems in Iceland . . . . . . . . . 49
3.3 The Reservoir Liquids from the Geothermal Systems in
Northern and Central America. . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3.1 Dixie Valley . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3.2 Long Valley. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.3.3 Coso . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.3.4 Valles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3.5 Salton Sea, Heber, and Cerro Prieto . . . . . . . . . . . . . . . 55
3.3.6 Los Azufres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.7 Berlin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.3.8 Miravalles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.3.9 Chemistry of the Reservoir Liquids from the
Geothermal Systems in Northern and Central
America. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.4 The Reservoir Liquids from the Geothermal Systems
in Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4.1 Mori-Nigorikawa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4.2 Sumikawa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.4.3 Uenotai-Wasabizawa . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.4.4 Onikobe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.4.5 Oku-Aizu. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.4.6 Takigami. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.4.7 Oguni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4.8 Fushime. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.9 Chemistry of the Reservoir Liquids from
the Geothermal Systems in Japan . . . . . . . . . . . . . . . . . 71
3.5 The Reservoir Liquids from the Geothermal Systems
in the Philippines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.5.1 Bacon-Manito . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.5.2 Tongonan-Mahanagdong. . . . . . . . . . . . . . . . . . . . . . . . 74
3.5.3 Alto Peak . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.5.4 Palinpinon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.5.5 Chemistry of the Reservoir Liquids from the
Geothermal Systems in the Philippines . . . . . . . . . . . . . 77
Contents ix
3.6 The Reservoir Liquids from the Geothermal Systems
in New Zealand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.6.1 Broadlands-Ohaaki. . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.6.2 Kawerau . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.6.3 Mokai . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.6.4 Ngatamariki. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.6.5 Ngawha. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.6.6 Orakeikorako. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.6.7 Rotokawa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.6.8 Waiotapu. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.6.9 Wairakei . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.6.10 Chemistry of the Reservoir Liquids from
the New Zealand Geothermal Systems. . . . . . . . . . . . . . 87
3.7 The Reservoir Liquids from Miscellaneous Geothermal
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.7.1 Yangbajing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.7.2 Kizildere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.7.3 Bagnore. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.7.4 Latera . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.7.5 Mofete. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.7.6 Ribeira Grande. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.7.7 Asal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.7.8 Tendaho . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.7.9 Aluto-Langano. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.7.10 Olkaria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.7.11 Chemistry of the Reservoir Liquids from
Miscellaneous Geothermal Systems. . . . . . . . . . . . . . . . 100
3.8 Main Results of Speciation Calculations for the Reservoir
Liquids and Implications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.8.1 The pH Value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.8.2 The Fraction of Undissociated SiO . . . . . . . . . . . . . 107
2(aq)
3.8.3 The Fractions of Free Na+, K+, Ca2+, and Mg2+ Ions . . . 107
3.8.4 The Activity Coefficient of Undissociated SiO . . . . . 119
2(aq)
3.8.5 The Activity Coefficients of Free Na+, K+, Ca2+,
and Mg2+ Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.9 Final Considerations on the Reservoir Liquids . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4 The Hydrothermal Minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
4.1 The Hydrothermal Alteration Suites and Their Zones . . . . . . . . . 139
4.2 Feldspars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
4.2.1 Main Characteristics of Feldspars . . . . . . . . . . . . . . . . . 141
4.2.2 The Chemistry of Hydrothermal Feldspars. . . . . . . . . . . 142
4.2.3 The Structural State and Degree of Ordering
of Hydrothermal Alkali Feldspars . . . . . . . . . . . . . . . . . 147