Keith Nicholson

Geothermal Fluids
Chemistry and Exploration Techniques

Willi 30 Figures

Springer- Verlag
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r-T I ()nl~l.lf,1OFNIJIJ
 School of Applied Sciences Preface
The Robert Gordon University
Aberdeen AB 1 IHG, Scotland
United Kingdom
This book introduces aqueous geochemistry applied to geothermal systems. ]
is specifically designed for readers first entering into the world of geothermal energ:
from a variety of scientific and engineering backgrounds, and consequently is no
intended to be the last word on geothermal chemistry. Instead it is intended t4
provide readers with sufficient background knowledge to permit them to subsequentl~
understand more complex texts and scientific papers on geothermal energy. The bool
is structured into two parts. The first explains how geothermal fluids and thei
associated chemistry evolve, and shows how the chemistry of these fluids can be user
to deduce information about the resource. The second part concentrates on surve]
techniques explaining how these should be performed and the procedures which nee(
to be adopted to ensure reliable sampling and analytical data are obtained.

A geothermal system requires a heat source and a fluid which transfers the tlca:
towards the surface. The fluid could be molten rock (magma) or water. This boo~
concentrates on the chemistry of the water, or hydrothermal, systems. Consequently,
magma-energy systems are not considered. lIot-dry rock (IIDR) systems are
ISBN 3-540-56017-3 Springer-Verlag Berlin Heidelberg New York similarly outside the scope of this text, principally because they contain no indigenous
ISBN 0-387-56017-3 Springer-Verlag New York Heidelberg Berlin fluid for study. Both magma-energy and \lDR systems have potential as energy
sources but await tecllllological developments before they can be exploited
Library of Congress Calatoging-in-!'ublicalion [Jala. Nicholson. Kcilh. 19.1.';- . (;eothcnnal flnids: chemistry
commercially. Geothermal systems based on water, however, arc proven energy
and exploralionlechniques/Keith Nicholson. p. cm. Includes bibliographical references and index
ISBN )-5.10-56017-) (Berlin: acid-free).--ISBN 0-.187-56017-.1 (New York:: acid-free)!. (;eolhennal
resources. 2. Cieochemistry. .1. Waler chemistry. I. Title. resources which have been successfully developed throughout the world. The energy
GBI199.5.N53 1993 551.2'3--dc20 93-29590
within such systems has been directly employed for space heating and other direct-use
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is applications, and for the generation of electricity.
concerned, specifically the rights of translation, reprinting, re-use of illustrations. recitation. broadcasting,
reproduction on microfilms or in other ways, and slorage in data banks. Duplication of this publication or parts
thereof is only pennitted under the provisions of the German Copyright Law of September 9. 1965, in its The chemistry of the terrestrial geothermal systems considered in this work are
current version, and a copyrigbt fee must always be paid. Violations fall under the prosecution act of the
German Copyright Law. (or should be) also of interest to economic geologists, since they represent the modern
@ Springer-Verlag Berlin lIeidelberg 199) equivalents of cerlain epithermal-gold and porphyry-copper deposits. Terrestrial
Printed in Germany
systems, being more accessible, also provide insights into (he processes active in
The use of general descriptive names. registered names, trademarks, etc. in this publication does not imply, submarine geothermal systems which are themselves modern analogues of ancient
even in the absence of a specific statement, that such names are exempt from the relevant protective laws and
regulations and therefore free for general use. stratiform iron, manganese and massive sulphide mineralisation.

Typesetting: Camera-ready by author

32/3145-5432 I 0 - Printedon acid-freepaper
V I Geothennal fluids

Being able to touch waters which have circulated through the Earth's crust,
waters which may have deposited gold just a few hundred metres below and which Acknowledgements
can provide clues to geochemical processes active in the Earth, is one of the most
exciting aspects of geothermal chemistry. All this and energy too.

When a work such as this is produced over a long period of time, it is difficult
Aberdeen, Scotland.
to limit acknowledgemcnts as many people have contributed in different, often subtlc
August 1993 KEITt I N IClIOt50N
ways. However, I should first like to thank Dick Glover, John Hulston and Mike
Stewart of DSIR, New Zcaland, for finding time in busy schedules to provide helpful,
detailed reviews of earlier chapters. I am also grateful to the many graduate students,
from ovcr 25 countrics, who I taught during my time in New Zealand. Discussions
about gcothermal dcvclopmcnts in their countrics, made me appreciate the difficultics
scientists and engineers from different technical backgrounds have in interpreting
geothermal fluid chemistry. These discussions convinced me of the need for an
introductory text on geothermal chemistry, and formed the basis for the contcnts of
this work. I should also like to thank Pat Browne (Auckland University) who
provided moral support and valuable discussions over the contents of the book,
particularly in the early months of writing. In the later months, John Harper (IHiU)
generously provided me with the time and facilities to complete this work.
Throughout all this time however, my greatest supporter and source of encouragement
has been Angela, my wife, who not only drcw all thc figures in this volume, but also
DEDICATION patiently got on with the more serious business of building a horne, while I got tlccper
into hot water.

For

Jt 1lf]era August 1993

 Contents

Preface " v
Acknowledgements vii

Part I
Geothermal Fluid Chemistry

1 GEOTHERMAL SYSTEMS

1.1 SYSTEM TYPES AND CHARACfERISTICS " 1

Classification 3

1.2 GENESIS OF GEOTHERMAL FLUIDS , 6

Origin of water and solutes '''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''' 6
Evolution of geothermal fluids 7
Evolution of steam: boiling point-depth relations 8
Age of geothermal fluids and geothermal systems 12

1.3 THERMAL, HYDROLOGICAL AND CHEMICAL STRUCfURE 12

Liquid-dominated systems 14
Vapour-dominated systems 16

2 WATER CHEMISTRY

2.1 WATER TYPES 19

Chloride 19
SuIphate 20
Bicarbonate ... 22
Sui phate-chloride 22
Dilute chloride-(hicarhonate) 23
A diagnostic plot of water chemistry 27
,\ (icolhcrmal Huids ContenlS XI

2.2 PROCESSES AFFECfING WATER COMPOSITION 28 3.3 PROCESSES AFFECfING STEAM COMPOSITION "... 89
Mineral-fluid equilibria 28 Geothermal system 90
Boiling (adiabatic) cooling 34 SolubiIity " 90
Conductive cool ing 34 Steam formation , 96
Mixing (dilution) with other waters 35 Condensation " 102
Oxidation. , 102
2.3 INTERPRETATION OF WATER CHEMISTRY 35
Rock-steam reactions 102
pll ".. 3tJ
Mineral equilibria and buffering 102
Common solutes 39
Seism icity 103
Chemical behaviour of common species 39 Con tam inat ion 103
Chemical indicators of physico-chemical processes 49
Statistical analysis of water chemistry 50 3.4 INTERPRETATION OF GAS CHEMISTRY 103

52
Behaviourof commongeothermalgases " 104
2.4 MIXING MODELS
Indicators of physico.chern ical processes 108
Enthalpy - chloride diagrams 52
Enthalpy - silica diagrams tJ2 3.5 GAS GEOTHERMOMETERS 112
Carhonate - silica/ch Imide tJS
C02-1I2S-H2-CH4 geothermometer (D' Amore & Panichi) 112
CO-based geotherrnometer 113
2.5 SOLUTE GEOTlIERMOMETERS tJ7
C02-geothermorneter 114
SiIica , tJ9
H2-Ar geothermometer 114
NalK geothermometer 72
gas/~water - based geotherrnorneters " 114
Na-K-Ca geothermometer 73
NafLi geothermometer 7tJ
KlMg and Li/Mg geothermometers 77 4 ISOTOPE CHEMISTRY
Na-K-Mg geothermometer 78
Ca/Mg & S04/F geothermometers fm carbonate reservoirs 80 4.1 INTRODUCnON 117
2.6 CALCULATING RESERVOIR FLUID CHEMISTRY 80 Notation 118
Standards 120
Heat and mass balance equation 80
Steam fraction calculation 81
4.2 GEOTIIERMAL APPLICATIONS OF ISOTOPES 120
Weirboxcornposition , 82
Stable isotope 120
Reservoir fluid composition 82
Radioactive isotopes 125
Total discharge (TD) composition 83
Reservoir fluid pll 83 4.3 ISOTOPE GEOTIIERMOMETERS 126
Isotope geotherrnometry equations 127
Oxygen isotope geothermometers 128
3 GAS CHEMISTRY Hydrogen isotopegeotherrnometers " 134
Carbon isotopegeotherrnorneters " 135
3.1 INTRODUCfION 87 Sulphur isotope geothermorneter 137
3.2 DISCHARGE FEATURES 88
XII Geothermal Auids Contents X III

Calcium 172
Part II 0110ride 173
Exploration Techniques & Surveys Fluoride 174
Hydrogen sulphide 175
Iodide, Bromide " 176
5 EXI'LORATION TECHNIQUES Iron 177
Lithium , 178
5.1 INTRODUCnON 141 Magnesium '''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''' 179
Mercury 179
5.2 EXPLORATIONSURVEYS 142 pH 180
Active systems ............. 142 Potassium " 181
Fossil/epithermalsystems 145 Rubidi urn ... 182
SiIica """"""""""""""""" 182
Sodium " 184
6 WATER SURVEYS Su Ipha te 184
Total Dissolved Solids 186
6.1 PRE-FIELD LABORATORY PREPARATION 151
OJllection ..bottles 151 6.5 DATA QUALITY AND PRESENTATION 186
Bottle cleaning 152 Quality control checks 186
Sampling equipment 154 Ionic balance , 187
Mass balance 188
6.2 FIELD SURVEY 154 Units , 188
Mapping springs 155 Tabulation of results 192
Field notes ........ 155
Field measurements 155
Selection and prioritizing springs for sampling 157 7 GAS SURVEYS
6.3 SAMPLING METHODS 158
7.1 PRE-FIELD LABORATORY PREPARATION 195
Springs and pools 158
Sample flasks 195
Wells 160
Flask cleaning and preparation 195
Specialised sampling requirements 162
Sampling equipment 196
Sample storage 163
7.2 FIELD SURVEY 197
6.4 ANALYTICAL METHODS 163
Selection and prioritizing fumaroles for sampling , 197
Introduction " 163
Aluminium 164 7.3 SAMPLING METHODS 197
Ammonia ... 165 Fumaroles , 197
Arsenic 167 Gas dischargesfrom pools , 198
Bicarbonate, Carbonate 168 Wells 198
Boron " 169 General notes on samplinggases , 199
C'1esium 172 Sample storage """""""'"'''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''' 199
X I V Ueothennal Fluids UJlIlU'l:> "~I

7.4 ANALYTICAL METHODS 200

Gas chromatographicdeterminations " 20I REFERENCES 235
Wet chemical .determinations 203
Calculation of gas in the total discharge (fDgas) 205
SUBJECT INDEX " 255
7.5 GAS CONCENTRATIONUNITS 205

8 SOIL AND SOIL-GAS SURVEYS

8.1 INTRODUCTION 209

8.2 SURVEY ORGANISATION 210

Orientation survey 210
Sampling grid 211

8.3 SOIL SURVEYS 211

Soil sampling 212
Sample preparation 213
Ammonia 214
Antimony 214
Arsenic 214
Boron " 214
Mercury 215

8.4 SOIL-GAS SURVEYS 21()

Soil-gas sampling 21()
Carbon dioxide 217
Helium 217
Mercury vapour 218
Radon 219

8.5 DATA QUALITY, PRESENTATION AND INTERPRETATION 220

Presentat ion methods 220
Anomaly identification and interpretation 220

APPENDICES

1. Steam tahles 225

2. Atomic weights 233
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