Dissertation for the Degree of Doctor of Philosophy

A Chemical Study of Arsenic, Boron and Gases in High-Temperature Geothermal Fluids in Iceland

Niels Giroud

FACULTY OF SCIENCE - UNIVERSITY OF ICELAND

August 2008

Accademic Dissertation
A dissertation Presented to the University of Iceland Faculty of Science in Candidacy for the Degree of Doctor of Philosophy

Supervisor
Prof. Stefn Arnrsson Institute of Earth Sciences, University of Iceland

Doctoral Committee
Prof. Stefn Arnrsson Institute of Earth Sciences, University of Iceland

Dr. Sigurdur R. Gslason Research Professor Institute of Earth Sciences, University of Iceland

Dr. Andri Stefnsson Research Scientist Institute of Earth Sciences, University of Iceland

Opponents
Dr. Bruce Christenson GNS Science Lower Hutt, New Zealand

Dr. Giovanni Chiodini Director of Research at Vesuvius Observatory National Institute of Geophysics and Volcanology Naples, Italy

A Chemical Study of Arsenic, Boron and Gases in High-Temperature Geothermal Fluids in Iceland

c Niels Giroud, 2008 Printed in Iceland by Oddi hf. ISBN 978-9979-70-479-9

Contents
List of Figures List of Tables List of Symbols Abstract tdrttur (in Icelandic) Acknowledgments 1 Introduction
1.1 1.2 1.3 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Selected geothermal elds . . . . . . . . . . . . . . . . . . . . . . .

vii ix xi xiii xv xvii 1

2 3 4

2 Gas chemistry in ve Icelandic high-temperature geothermal systems 7

2.1 2.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Geological background . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1 2.2.2 2.2.3 2.3 2.4 2.5 2.6 2.7 Kraa and Nmafjall . . . . . . . . . . . . . . . . . . . . . . Nesjavellir . . . . . . . . . . . . . . . . . . . . . . . . . . . . Svartsengi and Reykjanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 9 9 11 11 12 12 15 16 18 18 19 19

Alteration mineralogy Well discharge enthalpy Sampling and analysis 2.7.1 2.7.2 Water phase Steam phase

Fluid compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . Aquifer temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

2.8

Thermodynamic data

2.8.1 2.9 2.9.1 2.9.2

Mineral solubility constants and gas solubilities . . . . . . . Note on pH measurement . . . . . . . . . . . . . . . . . . .

19 21 21 21 23 23 27 30 30 32 33 33 35

Data handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Calculation of aquifer water compositions and aqueous speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.10 Mineral-gas equilibria 2.10.1 CO2

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.10.2 H2 S and H2 . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.11 Individual mineral-solution equilibria . . . . . . . . . . . . . . . . . 2.11.1 Calcite and wollastonite . . . . . . . . . . . . . . . . . . . . 2.11.2 Andradite-grossular, epidote-clinozoisite, prehnite . . . . . . 2.11.3 Magnetite, pyrite and pyrrhotite . . . . . . . . . . . . . . . 2.11.4 N2 and Ar . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.12 Discussion and conclusions . . . . . . . . . . . . . . . . . . . . . . .

3 Processes inuencing As, B and Cl concentrations in uids of volcanic geothermal systems in Iceland 39
3.1 3.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Geological features . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1 3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 3.2.7 3.3 3.4 3.5 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kraa and Nmafjall . . . . . . . . . . . . . . . . . . . . . . Landmannalaugar Hveragerdi Geysir area and Hveravellir 40 41 41 42 43 44 44 45 45 45 46 46 46 51 54 55 55 58 59 68 70

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Nesjavellir . . . . . . . . . . . . . . . . . . . . . . . . . . . . Reykjanes and Svartsengi

Fluid compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . Sampling and analytical methods . . . . . . . . . . . . . . . . . . . Data handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.1 3.5.2 3.5.3 Calculation of aquifer uid composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Arsenic, B and Cl concentration in the aquifer uid Sources of As, B and Cl to geothermal uids Boron and Cl distribution in sampled waters As and Cl relationships

3.6

Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.1 3.6.2 3.6.3 . . . . . . . . . . . . . . . . . . . .

Rock derived concentrations . . . . . . . . . . . . . . . . . .

3.7 3.8

Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . .

4 Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld, Iceland 73
4.1 4.2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Geology and hydrology . . . . . . . . . . . . . . . . . . . . . . . . . iv 74 74

4.3 4.4 4.5 4.6

Production history . . . . . . . . . . . . . . . . . . . . . . . . . . . Sampling, analyses and calculations Fluid composition 4.6.1 4.6.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

75 78 78 81 81 83 85 87 87 88 89 90

Evolution of gas concentrations . . . . . . . . . . . . . . . . . . . . Wet-steam wells Dry-steam wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.7 4.8

Changes in dissolved salts and pH Formation of the vapor cap 4.8.1 4.8.2 Results Vapor fraction calculations

. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.9

Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.10 Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . .

A Trace element analyses Bibliography

93 101

List of Figures
1.1 1.2 1.3 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 Hot-spring and fumarole at Hveravellir . . . . . . . . . . . . . . . . Map of Iceland showing the location of the studied high-temperature areas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 6 10 17 25 28 29 31 32 34 34 42 47 53 Well testing at Kraa 3

Location map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Na/K and quartz geothermometers compared for both the phase segregation model and the heat transfer model. . . . . . . . . . . Potential mineral buers controlling CO2 gas concentrations in the initial aquifer uid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mineral buers controlling H2 S in the initial aquifer uid Mineral buers controlling H2 in the initial aquifer uid Saturation indices of selected alteration minerals Ca

. . . . . . . . . . . . . . . . . .

2+

/(H )

+ 2

ratio versus temperature

. . . . . . . . . . . . . . . .

Argon versus N2 in initial aquifer uids for all elds concentration in aquifer uid

Inuence of air addition and boiling on the N2 /Ar ratio versus Ar . . . . . . . . . . . . . . . . . . . . .

3.1 3.2 3.3 3.4

Location map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Phase segregation excess enthalpy model . . . . . . . . . . . . . . . Boron distribution between vapor and liquid phases discharging from wet-steam wells versus sampling temperature . . . . . . . . . Example of the inuence of the selected vapor pressure at which phase segregation occurs on the calculated aquifer B concentration for three high-enthalpy wells. . . . . . . . . . . . . . . . . . . . . .

54 55 59 60

3.5 3.6 3.7

Measured Cl and B concentrations in liquid water samples from all the study areas . . . . . . . . . . . . . . . . . . . . . . . . . . . Measured Cl and As concentrations in liquid water samples from all the study areas. . . . . . . . . . . . . . . . . . . . . . . . . . . . Rock derived As, B and Cl concentrations in aquifer liquid in Geysir and Hveravellir elds . . . . . . . . . . . . . . . . . . . . . . . . vii

3.8 3.9

Rock derived As, B and Cl concentrations in aquifer liquid in Landmannalaugar and Hveragerdi elds . . . . . . . . . . . . . . . . . . Rock derived As, B and Cl in aquifer liquid. . . . . . . . . . . . . . of the Nmafjall area. . . . . . . . . . . . . . . . . . . . . . . . . . 61 64 64 66 75 76 77 77 80 82 84 85 86 86 89

3.10 Time evolution of non-marine B in the aquifer water of three wells 3.11 Cl and B of non-marine origin . . . . . . . . . . . . . . . . . . . . . 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 Location map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Annual discharge and injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cumulated discharge and injection

Annual CO2 emissions from wet-steam and dry-steam wells at Svartsengi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chloride concentration in the aquifer uid of wet-steam wells of wet-steam wells . . . CO2 , H2 S and H2 concentrations versus time in the aquifer uid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CO2 , H2 S and H2 concentrations versus time in the discharging vapor from the dry-steam wells Magnesium concentration in the aquifer uid of wet-steam wells . . Fluoride concentration in the aquifer uid of wet-steam wells

4.10 Mg

+2

versus

2F

activities

. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.11 Fraction of the total liquid that forms the vapor cap

viii

List of Tables
2.1 2.2 2.3 2.4 2.5 Major elements analyses of the sampled waters. Concentrations in mg/kg. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gas analyses of the sampled vapor phase . . . . . . . . . . . . . . . Individual minerals dissolution reactions . . . . . . . . . . . . . . . Aquifer water composition . . . . . . . . . . . . . . . . . . . . . . . Mineral assemblages potentially controlling CO2 , H2 S and H2 concentrations and respective 3.1 3.2 14 16 20 24 26

K -temperature

equations

. . . . . . . .

Arsenic, B and Cl concentrations in liquid and vapor phases of wet-steam wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Arsenic, boron and chloride concentrations in spring waters from high-temperature areas . . . . . . . . . . . . . . . . . . . . . . . . . 57 52

4.1 4.2 4.3

Major and trace elements and major gas concentrations in aquifer liquid of wet-steam wells . . . . . . . . . . . . . . . . . . . . . . . . Gas concentrations in the vapor discharge from dry-steam wells . . Gas concentrations and estimates of the fraction of vapor owing into wells 7 and 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 79 80

A.1 A.1 A.1 A.2 A.2 A.2

Trace element analyses of liquid water samples from wet-steam wells 94 Trace element analyses of liquid water samples from wet-steam wells (cont.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace element analyses of liquid water samples from wet-steam wells (cont.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace element analyses of vapor samples from wet-steam and drysteam wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 98 99 Trace element analyses of vapor samples from wet-steam and drysteam wells (cont.) . . . . . . . . . . . . . . . . . . . . . . . . . . . Trace element analyses of vapor samples from wet-steam and drysteam wells (cont.) . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 95

ix

List of Symbols

Ai Ar As Ad Ae Af Ag Al Am As At Av al Ds fs hl ht hv Ks M d,t M e,l M f,t md,l i md,t i md,v i me,l i me,v i

subscript subscript subscript

i: r: s:

any species any non-volatile species any volatile species

superscript superscript superscript superscript

d: e: f: g:

well discharge conditions conditions where phase segregation occurs between the conditions of the deep aquifer (feed zone) conditions where phase segregation occurs between the

aquifer and discharge of the uid, before it occurs

aquifer and discharge of the uid, after it has occured superscript l: liquid phase superscript superscript superscript superscript

m: marine component s: seawater t: total uid v : vapor phase s

between liquid and vapor

activity in aqueous solution distribution coecient of species fugacity of gaseous species

specic enthalpy of vapor-saturated water (kJ/kg) specic enthalpy of total uid (kJ/kg) specic enthalpy of vapor (kJ/kg) solubility constant of gaseous species Coecient) total mass ow rate from wet-steam well (kg/s) mass ow rate of boiled water retained in aquifer (kg/s) mass ow rate of initial aquifer uid (kg/s) concentration of component concentration of component concentration of component

(moles/kg/bar, Henry's Law

i i i

in discharging liquid water (moles/kg) in total well discharge (moles/kg) in discharging vapor (moles/kg)

concentration of component (moles/kg) concentration of component

in liquid water retained in aquifer

in vapor phase at conditions

Pe

xi

mf,l i mf,m i mf,t i ms i Ns ne,l s ne,v s Pe Ps Te Tf V e,l V f,t X d,v X e,v

concentration of component

in initial aquifer liquid (moles/kg)

marine component concentration of component (moles/kg) concentration of component concentration of component

i in initial aquifer uid

i i

in initial aquifer uid (moles/kg) in seawater

number of moles of volatile species mole fraction of volatile species mole fraction of volatile species partial pressure of species

s e e

s s

in the liquid phase at contition in the vapor phase at contition

vapor pressure at which phase segregation occurs (bar)

s (bar) Temperature at which phase segregation occurs ( C) Average aquifer temperature ( C) e,l (M /M d,t ) relative mass (to well discharge) of boiled (and degassed)
water retained in aquifer f,t (M /M d,t ) relative mass (to well discharge) of initial aquifer uid that has boiled vapor fraction at well discharge conditions e vapor fraction at condition P

xii

Abstract
Volatile species provide valuable information on physical and chemical processes occurring in high-temperature (volcanic) geothermal systems. This study focuses on an assessment of the processes that control selected volatile species and arsenic concentrations in the deep aquifers of ve volcanic geothermal elds in Iceland. It is based on analytical data on water and vapor samples collected from wet- and dry-steam well discharges. The elds considered are Kraa, Nmafjall, Nesjavellir, Svartsengi and Reykjanes. The rst three systems are of the dilute uid type; the source uid is considered to be meteoric water. The systems of Svartsengi and Reykjanes, on the other hand, contain saline uid. The source water at Svartsengi is 70% seawater and 30% Some of the wells have excess enmeteoric water but seawater only at Reykjanes.

thalpy, that is the enthalpy of the discharged uid is higher than that of vapor saturated water at the aquifer temperature. Excess well discharge enthalpy is not considered to reect such an enthalpy of the initial aquifer uid. It is considered to be produced in the depressurization zone around wells, where extensive boiling occurs. The results of the quartz and Na-K geothermometers are taken to indicate that phase segregation in producing aquifer is the cause of the excess well discharge enthalpy; a fraction of the liquid is retained in the aquifer due to its adsorption onto mineral grain surfaces by capillary forces, whereas all the vapor ows into the wells. The rst paper presented in this thesis focuses on the reactive gases carbon dioxide (CO2 ), hydrogen sulde (H2 S), and hydrogen (H2 ), and their state of equilibrium with various mineral assemblages, as well as the unreactive argon (Ar) and the relatively unreactive nitrogen (N2 ). The concentrations of CO2 in the aquifer uid of many of the wells corresponds closely to equilibrium with the mineral assemblage epidote-prehnitecalcite-quartz in the case of the dilute waters but to equilibrium with epidote-garnetcalcite-quartz in the case of the saline waters. Some of the wells in Kraa, however, are enriched in CO2 relative to equilibrium, likely because of high ux from the magmatic heat source, whereas most of the wells at Nesjavellir show low CO2 concentrations, probably as a consequence of insucient supply of this gas from the magma. and H2 are likely to be controlled by the same mineral assemblage. H2 S For most wells, The high H2

aquifer uid H2 S concentrations are close to equilibrium with the assemblage epidoteprehnite-pyrite-pyrrhotite, whereas H2 concentrations are often higher. concentrations are considered to reect the presence of a small fraction of equilibrium vapor in the aquifer uid. Such a vapor fraction strongly aects the H2 concentration in the aquifer uid but not so much the much more soluble H2 S, as well as the more soluble CO2 .

xiii

The main sources of N2 and Ar to the aquifer uid is air-saturated groundwater and seawater. The uid is mostly depleted in both gases relative to the source water. N2 /Ar ratios show that N2 has another source, potentially entrapped air bubbles, magmatic gas or decaying organic matter. The second paper aims at describing the sources and behavior of arsenic (As), boron (B) and chloride (Cl) using data from the ve above mentioned geothermal areas, as well as samples from boiling and warm hot springs and hot water wells in four other high-temperature geothermal elds in Iceland, and from four wells in the Southern Lowlands low-temperature area. Arsenic, B, and Cl concentrations in geothermal uids in Iceland are low compared to such uids in many parts of the worlds. The concentrations in the dilute uids are typically in the range 50150 ppb, 0.55 ppm, and 50150 ppm for As, B, and Cl, respectively. Arsenic concentrations in the saline uids are similar, but B and Cl concentrations are much higher. Boron and Cl are highly mobile on the whole range of water temperatures (10320 C) considered in this study. Arsenic is also very mobile in the deep primary geothermal uids but boiling of this uid as well as its mixing with cold groundwater removes As eectively from solution, especially the mixing. Data on Cl/B and Cl/As ratios from boiling hot springs in mature hightemperature geothermal systems show that all these elements are dissolved from the basalt in stoichiometric proportions. In the young geothermal system at Kraa, the At Nesjavellir, most of the Cl in the B and Cl of the deep aquifer uid is largely derived from magmatic volatiles but only to a limited extent from the basalt host rock. deep uid has been dissolved from the host rock, but a large fraction of the dissolved B has a magmatic source. In the saline uids, As is less mobile than B and Cl and is likely to be removed from solution into sulde minerals. If virtually all the Cl in the Svartsengi and Reykjanes saline uids is of seawater origin, which is considered likely, it is evident that a signicant fraction of the B in these uids is magmatic. Arsenic does not partition signicantly into the vapor phase, at least at vapor pressures as high as 40 bar, but B does. Boron distribution between liquid and vapor is closely approached at the wellhead where samples were collected. The third paper deals with the vapor cap in the Svartsengi geothermal system that 240 C liquid-dominated reservoir subsequent to pressure drawdown The mass of uid withdrawn from the reservoir in the

formed over the

by exploitation of the eld.

period 19762006 amounts to 243 megatonnes (Mt), of which 217 came from wet-steam wells (the liquid reservoir) and 25 Mt from dry-steam wells (the vapor cap). In 2006 the cumulated drawdown was 30 bar. Boiling has reduced the gas content of the liquid reservoir and in turn increased and decreased aqueous uoride (F) and magnesium (Mg) concentrations, respectively, due to rapid re-equilibration of the degassed water with Mg and OH-bearing minerals. The gas content of the vapor cap has decreased with time. Initially CO2 concentrations were

80,000

ppm but at present they are

30,000ppm.

It is estimated that to date as much as 3% w/w of the initial aquifer liquid water has boiled to supply vapor to the vapor cap. Wells have been drilled into the vapor cap for electricity production with the consequence of higher CO2 and H2 S emissions into the atmosphere per produced energy units.

xiv

tdrttur (in Icelandic)

mis rokgjrn efnasambnd veita mikilvgar upplsingar um elis- og efnarn ferli hhitasvum. S rannskn sem hr er fjalla um lsir athugun nokkrum rokgjrnum efnum vatni af slenskum hhitasvum me herslu hvaa ferli ra styrk eirra vatninu. Efnagreining uppleystum steinefnum vatnssnum og gsum gufusnum sem safna r renni blaut- og urrgufuhola var notu til a reikna efnainnihald djpvkva mm hhitasvum, Kru, Nmafjalli, Nesjavllum, Svartsengi og Reykjanesi. Djpvkvinn remur fyrst tldu svunum er snauur af uppleystum steinefnum. Upprunavkvinn er talinn vera rkomuvatn. Vkvinn jarhitakerfunum Svartsengi og Reykjanesi er saltur. Svartsengi er upprunavatni 70% sjr og 30% regnvatn en hreinn sjr Reykjanesi. Sumar blautgufuholurnr sem safna var r eru hvermisholur, .e. vermi holurennis er hrra en gufumettas vatns vi ann hita sem rkir . Hvermi renni borhola er ekki tali endurspegla hvermi vkva djpvkva. Tali er a hvermisvkvi myndist vi kafa suu afrslu borhola. Niurstur kvarsog alkal-hitamlanna fyrir hvermisholur benda til ess a vatn og gufa afrslu askiljist, a.m.k. a hluta, og annig myndist hvermisvkvi sem ir inn borholur. Hluti vatnsins situr eftir inni me v a hann loir vi yrbor steinda fyrir hrif hppukraa. Gufan ir hins vegar inn borholurnar.

Fyrsta greinin essari doktorsritger fjallar um hvarfgjarnar lofttegundir, koltvox (CO2 ), brennisteinsvetni (H2 S) og vetni (H2 ) og stand efnajafnvgis eirra vi nokkur fylki ummyndunarsteinda, en einnig um argon (Ar) og kfnunarefni (N2 ) en sarnefnda lofttegundin er tiltlulega hvarfgjrn. djpvkva margra borhola me lgseltu svarar styrkur CO2 vel til efnajafnvgis vi steindafylki epdt-prent-kalst-kvars en til jafnvgis vi epdt-granat-kalst-kvars sltu svunum Svartsengi og Reykjanesi. sumum borholum Kru er styrkur CO2 vkva afrslu hrri en svarar til jafnvgis vi nefnt steindafylki lklega vegna mikils streymis essarar lofttegundar fr kviku undir jarhitakernu. Hins vegar er styrkur CO2 djpvkva Nesjavllum lgri en svarar til jafnvgis, sennilega vegna takmarkas is essa gass fr kviku. Lklegt er tali a styrkur H2 S og H2 djpvatni strist af efnajafnvgi vi sama steindafylki. Fyrir estar holur er svarar styrkur vel til jafnvgis vi fylki epdt-prent-prtpyrrtt. Hins vegar er styrkur H2 stundum of hr. Hinn hi styrkur H2 er ekki talinn rast af frviki fr efnajafnvgi helfur af tilvist efnajafnvgisgufu djpvkva. Tilvist slkrar djpgufu hefur mikinn hrif styrk H2 djpvkva. Hn hefur hins vegar ltil hrif H2 S sem er miklu auleystara vatni en H2 og einnig ltil hrif CO2 sem er

xv

tiltlulega auleyst vatni.

Kfnunarefni djpvkva er aallega komi t upprunaDjpvkvinn

vatninu og Ar eingngu, loftmettuu grunnvatni og loftmettuum sj.

hefur yrleitt tapa bum essum gsum a hluta mia vi upprunavatni. N2 /Ar hlutfll einstkum snum benda til ess N2 geti tt uppruna var en loftmettuu vatni, hugsanlega loftblum essu vatni, kvikugsum ea jafnvel rotnandi lfrnu efni. nnur greinin lsir uppruna og hegun arsens (As), brs (B) og klrs (Cl) jarhitavkva fyrrnefndra hhitasva en einnig vatni laugum, hverum og heitavatnsholum af fjrum rum hhitasvum slandi og vatni r fjrum borholum lghitasvum Suurlandsundirlendi. Styrkur As, B og Cl jarhitavkva slandi er lgur samanburi vi slkan vkva jarhitasvum erlendis. Einkennandi styrkur As, B og Cl lgseltuvkva hhitasvum er 50150 ppb, 0,55 ppm og 50150 ppm. Styrkur As sltu jarhitavatni er sambrilegur vi lgseltuvkva en miklu hrri fyrir B og Cl. lausn) vi ll hitastig (10320 Br og Cl eru mjg hreyfanleg efni (eftir a au hafa borist vatn haldast au C) slenskum jarhitakerfum. Arsen er einnig mjg

hreyfanlegt upphaegum djpvkva jarhitasva en sua essum vkva og blndun hans vi kalt vatn leiir til tfellinga As og srstaklega blndun. Hlutfllin Cl/B og Cl/As vatni tiltlulega gmlum hhitasvum (liggja tjari gosbeltanna) eru au smu og basalti sem bendir til ess a essi efni skolast r berginu smu hlutfllum og au eru essu bergi. hinu tiltlulega unga hhitasvi (liggur ekamtum) Kru er B og Cl djpvkva aallega tta fr kviku en aeins tiltlulega ltill hluti er komin r berginu sem vatni hefur hvarfast vi. Nesjavllum er mestur hluti Cl djpvkva hins vegar ttaur r bergi en str hluti B er kvikuttaur. sltu djpvatni er hreyfanleiki As lgri en B og Cl og tapast lklega r lausn vi upptku ess slfsteindir. Ef allt Cl djpvatni Svartsengi og Reykjanesi er sjvartta, en lklegt er tali a svo s, er ljst a verulegur hluti B essu vatni hefur borist a fr kviku. Arsen leitar ekki a neinu ri yr jargufu, jafnvel tt gufurstingur s 40 br. Smu sgu er ekki a segja um B. Jafnvgisdreing nst fyrir B milli vatns og gufu holutoppi ar sem snum var safna. rija greininfjallar um gufupann hhitasvinu Svartsengi sem myndaist yr

240 C

heitu vatnsker vegna niurdrttar svinu kjlfar vinnslu. Massataka vatns Af honum

og gufu r svinu tmabilinu 19762006 nam 243 megatonnum (Mt). gufupanum).

komu 217 Mt fr blautgufuholum (r vatnskernu) en 25 Mt r urrgufuholum (r ri 2006 samsvarai uppsfnu rstilkkun svinu 30 brum. Sua vatnskernu hefur leitt til lkkunar gasstyrk djpvatninu sem aftur hefur orsaka hkkun styrk ors (F) en lkkun styrk magnesums (Mg) vegna hrarar nlgunar efnajafnvgi hins afggasaa vatns vi Mg- og OH-steindir. gufupanum hefur fari en er n um 30,000 ppm. lkkandi. Styrkur gass uppha var hann um 80,000 ppm fyrir CO2 Holur hafa veri boraar

tla er a allt a 3% af djpvatni efst vatnskernu

ha soi til essa til a mynda gufu fyrir gufupann. H2 S t andrmslofti hverja framleidda raforkueiningu.

gufupann til raforkuframleislu me eim aeiingum a hkka tstreymi CO2 og

xvi

Acknowledgments
Many, many people deserve my immense gratitude, for helping me in some way bringing this thesis to completion. First of all, I will never be grateful enough to my supervisor Stefn Arnrsson for oering me this PhD position, and for his innite patience in trying to turn a geologist into a geochemist. With him, thermodynamics always seems simple, and the nature His passion is very communicative, and his of geothermal systems self-explanatory. the motivation was running low. I would like to thank Ingvi Gunnarsson and Andri Stefnsson for all the valuable discussions and for their help in the eld and the laboratory, as well as for their excellent company. Special thanks go to Jn rn Bjarnason for his priceless advices and extremely accurate reviews, and for making the great pieces of software WATCH and Steamandwater available. Combining a part-time job and the redaction of a PhD dissertation may be particularly dicult. However, my experience was extremely positive, and for this I would like to express my deep gratitude to my colleagues at Iceland GeoSurvey, and in particular Magns lafsson and Ingibjrg Kaldal for giving me total freedom for managing my work hours. Thrinn Fridriksson and Halldr rmannsson, together with Magns, spent a lot of their precious time helping me through the world of geochemical exploration and monitoring of geothermal systems in Iceland. All my colleagues have been very supportive, and I am very thankful for that. I want to thank warmly all my fellow colleagues in Askja and friends in Iceland for their great company, Jesper, Alex, Jamie, Fredrik, Lillemor and all the others, thank you so much for sharing so many adventures and good times. Special thanks to my friend Caroline; without her friendship and support, I would probably never have come to Iceland to start a new adventure. I would never have achieved such project without permanent support from my family during so many years, no matter how far I could be. Pap, mam et toute la famille, merci. No words can express my gratitude to my better half Tanja, for being the light in my life, for enduring my stress in procrastination, and supporting me all the way to completion of this thesis. I would like to thank the National Power Company Landsvirkjun, Reykjavik Energy, and the Sudurnes Regional Heating Company for their nancial support.

support invaluable, even after months of struggle on rebellious noble gas data or when

xvii

Chapter 1 Introduction
The main focus of this study is the behaviour of various volatile species in hightemperature volcanic geothermal uids in Iceland. This doctoral thesis constitutes of the three following papers, which will be submitted for publication in international journals upon completion of the PhD thesis. They are included here as Chapters: 1. Giroud, N. and Arnrsson, S., 2008. temperature geothermal systems. search. Chapter 2. 2. Giroud, N. and Arnrsson, S., 2008. Processes inuencing As, B and Cl concentrations in uids of volcanic geothermal systems in Iceland. Cosmochimica Acta. Chapter 3. 3. Giroud, N., Arnrsson, S. and Bjarnason, J. ., 2008. Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld, Iceland. Geothermics. Chapter 4. Geochimica et Gas chemistry in ve Icelandic high-

Journal of Volcanology and Geothermal Re-

In addition to these publications, the author participated in related research projects during his studies at the University of Iceland that are not part of this thesis:

Arnrsson, S., Bjarnason, J. ., Giroud, N., Gunnarsson, I., Stefnsson, A., 2006. Sampling and analysis of geothermal uids. Geouids 6 (3), 203216 Stefnsson, A., Gunnarsson, I., Giroud, N., 2007. New methods for the direct determination of dissolved inorganic, organic and total carbon in natural waters by Reagent-Free

TM Ion Chromatography and inductively coupled plasma atomic

emission spectrometry. Analytica Chimica Acta 582 (1), 6974

1.1. OBJECTIVES
Parts of the work were also presented in various meetings, including:

Giroud, N., Arnrsson, S., 2005. Estimation of long-term CO2 and H2 S release

during operation of geothermal power plants. World Geothermal Congress 2005 paper 0233

Giroud, N. and Arnrsson, S., 2004. Formation of a steam-cap in the geothermal

reservoir of Svartsengi, Reykjanes peninsula, Iceland. Poster at the Geoscience Society of Iceland Meeting During the last two years, while writing the present thesis, the author worked as a geochemist at Iceland GeoSurvey, on dierent projects related to geochemistry of high-temperature (> 200 C) and low-temperature geothermal systems.

1.1 Objectives
Study of the geochemical characteristics of geothermal systems is of great importance, both to improve the knowledge of hydrothermal and volcanic systems, and to provide tools for an optimal use of geothermal resources. The unique geological setting of Iceland on a mid-oceanic ridge provides an outstanding opportunity to study geothermal activity in relation with volcanic systems. Electrical power generation from geothermal energy started in Iceland almost 40 years ago, in 1969. Many of the high-temperature elds have been drilled for this purpose and six are being exploited today, whereas several others are being developed. The main objectives and the principal results of this study are the following:

Quantify the processes which aect the concentrations of the most abundant gases, i.e. CO2 , H2 S, H2 , N2 and Ar. The concentrations of reactive gases in the deep aquifer uid in geothermal systems is aected both by geochemical and physical processes, i.e. chemical reactions within the uid, interactions of the uid with the host rock minerals, the presence or absence of equilibrium vapor, uxes from a magmatic source, boiling/condensing and phase separation. The concentrations of three of the reactive gases (CO2 , H2 S, and H2 ) in the uid are compared with predicted concentrations calculated by equilibrium with selected mineral assemblages, using thermodynamic data from the literature. The source of Ar to the uid in the high-temperature geothermal elds is airsaturated groundwater and seawater, and trapped air bubbles. These are also the principal source for N2 although magmatic gases and decaying organic matter may contribute, at least in some elds. As a consequence, their concentrations are largely or solely aected by physical processes and the respective solubilities of the gases. Results on this subject are presented in Chapter 2.

Assess the processes that govern As, B and Cl concentrations in uids of hightemperature geothermal systems. The results indicate that B, as Cl, acts as essentially conservative component in the high-temperature geothermal systems in Iceland, i.e. once in solution it stays there. In volcanically young elds, such as Kraa, NE-Iceland, a large part of the aqueous B and Cl is derived from volatiles escaping from the underlying magma heat source. In mature, high-temperature

CHAPTER 1.

Figure 1.1: Hot-spring and fumarole at Hveravellir

elds, on the other hand, the source of these elements to the water is the rock with which the geothermal uid has interacted. Like B, As is highly mobile in the hightemperature geothermal systems. However, it may be removed from solution into sulde minerals, in particular when extensive boiling occurs and in particular when geothermal uid mixes with cold groundwater and ferric hydroxides are precipitated. The details of this study are included in Chapter 3.

Evaluate from geochemical data how extensively the

240 C liquid water reservoir

at Svartsengi, southwest Iceland, has boiled to produce the above lying vapor cap. Data on samples collected on a regular basis by Iceland GeoSurvey, together with samples collected specically for this study indicate progressive boiling within the liquid reservoir. At present as much as 3% w/w of the liquid has boiled to yield vapor to the above lying vapor cap. Results of this study can be found in Chapter 4.

1.2 Methods
A very important part of research on geothermal uids, which is based on data on the composition of well discharges, is calculation of deep uid compositions, individual species activities in this uid, assessment of specic mineral-solution equilibria as well as consideration of the origin of the various component present in the geothermal uid. For the present study, samples were collected from wet-steam and dry-steam wells in ve producing high-temperature geothermal elds in Iceland and from four wet-steam wells in the Southern Lowlands area. Both liquid and vapor phases were sampled from wet-steam wells, i.e. wells producing a mixture of liquid water and vapor. Additionally, vapor was collected from four dry-steam wells at Svartsengi (see Chapter 4). Samples of both phases were subsequently analyzed for major components at the University

1.3. SELECTED GEOTHERMAL FIELDS

of Iceland as described by Arnrsson et al. (2006). Trace elements were analyzed by Analytica (ALS Laboratory Group), Lule, Sweden. A more detailed description of sampling and analytical methods can be found in each chapter, as well as in Arnrsson et al. (2006). Chemical data on samples from boiling and warm hot springs and hotwater wells in four other high-temperature elds collected in 2001 and 2002 by the Institute of Earth Sciences, University of Iceland, were also used. Analyzed liquid and vapor compositions were used to calculate the temperature, composition, and aqueous species distribution of the deep aquifer uid for each well. This calculation is straightforward for liquid enthalpy wells, i.e. wells whose discharge enthalpy can be taken to be the same as that of the aquifer uid. When this is the case, the total well discharge composition equals that of the initial aquifer uid. The majority of the wells included in the present study, however, have excess discharge enthalpy, due either to segregation in the aquifer of the vapor and liquid phases owing into wells, or to enhanced boiling of the liquid by heat-transfer from the aquifer rock. In the latter case, the total discharging uid is representative of the deep aquifer uid, but this is not the case if the cause of the excess enthalpy is phase segregation. A thorough description of the calculation method is given in each chapter. The data interpretation involves calculation of solubility constants for minerals, and activity products from calculated species activities. Stability of various mineral phases in contact with the solution can thus be estimated.

1.3 Selected geothermal elds

This study focuses on ve high-temperature areas that have been drilled for electrical power generation and are being exploited today. These are Kraa and Nmafjall, northeast Iceland, and Nesjavellir, Svartsengi and Reykjanes, southwest Iceland (Fig. 1.2). As mentioned before, four wells in the Southern Lowlands were also sampled. Additionally, data on samples from warm and boiling hot springs, and wells, from four high-temperature areas (Hveravellir, Geysir, Hveragerdi, and Landmannalaugar) were studied with respect of As, B and Cl. All the areas except the Southern Lowlands are located within the active volcanic belts, the axes of which represent the plate boundary between the Eurasian and NorthAmerican lithospheric plates. The Southern Lowlands are located on the Hreppar microplate, between the eastern and the western volcanic belts. The geology of the areas shows an interesting variety of settings; some elds are located within the boundary of central volcanoes, directly above their magma heat source, whereas others are located just outside such volcanoes, astride the ssure swarms that intersect the central volcanoes. Additionally, some elds, like those on the Reykjanes peninsula, southwest Iceland, are not linked to any central volcano but have a sheeted dyke complex as heat source. The elds of Hveravellir and Geysir are located by the margins of the active volcanic belts and have likely drifted away from their heat source. These systems are considered to be mature, and may eventually evolve into low-temperature systems. The rock type hosting the geothermal systems is mostly basaltic volcanics. However, silicic rocks occur in some areas. A more detailed description of the geology is presented in each chapter.

CHAPTER 1.

Figure 1.2: Map of Iceland showing the location of the studied high-temperature areas.

1.3. SELECTED GEOTHERMAL FIELDS

Figure 1.3: Well testing at Kraa

Chapter 2 Gas chemistry in ve Icelandic high-temperature geothermal systems

Giroud, N. and Arnrsson S.

Abstract
Many processes control reactive and unreactive gas concentrations in aquifer uids of high-temperature geothermal systems. This study focuses on CO2 , H2 S, H2 , N2 and Ar concentrations in aquifer uids of ve liquid dominated volcanic geothermal elds. These are Kraa, Nmafjall and Nesjavellir, which are of dilute uid type, and Svartsengi and Reykjanes where uids are saline. Dissolved solids and gas analyses of water and vapor samples were used to calculate aquifer uid compositions. The calculations account for the excess enthalpy of some wells, where the discharge enthalpy is higher than liquid enthalpy at the aquifer temperature due to phase segregation of the owing liquid and vapor. This model yields consistent results for quartz and Na/K geothermometers. In the dilute uids, H2 S concentrations correspond to equilibrium with a mineral assemblage containing epidote, prehnite, pyrite and pyrrhotite. In the saline uids, equilibrium generally seems to be closely approached with a grossular, epidote and wollastonite mineral assemblage. In some of the dilute uids, CO2 concentrations are close to equilibrium with the clinozoisite, prehnite, calcite and quartz assemblage. However, the uids at Nesjavellir are generally depleted in CO2 relative to equilibrium, most likely because of insucient supply from the magma heat source. Some wells at Kraa show excess CO2 due to recent magmatic activity. In the saline uids, CO2 appears to be controlled by equilibrium with the clinozoisite, grossular, calcite and quartz assemblage. The same mineral buer is expected to control aquifer liquid H2 and H2 S concentrations. Indeed many samples of the dilute uids correspond well with equilibrium with the epidote, prehnite, pyrite and pyrrhotite assemblage. Other samples show higher H2

2.1. INTRODUCTION
concentrations. This is considered to be due to the presence of equilibrium steam in the aquifer uid, which raises much the sparingly water soluble H2 concentrations in the aquifer uid but not so much the concentrations of the more soluble CO2 and H2 S. In the saline uids, H2 concentrations are somewhat lower for Reykjanes than predicted by equilibrium with the epidote, wollastonite, grossular and pyrrhotite assemblage. Two of the Svartsengi saline waters are close to equilibrium with this buer, whereas four have lower H2 , most likely due to degassing of the aquifer liquid by boiling and consequent formation of the vapor cap above the liquid reservoir. Fluids are mostly depleted in N2 and Ar relative to air-saturated water. N2 /Ar ratios show that N2 has another source than air-saturated water, potentially entrapped air bubbles, magmatic gas or decaying organic matter.

2.1 Introduction
Many geochemical processes aect the concentrations and ratios of reactive and unreactive gases in uids of volcanic geothermal systems. They include supply of gases from the magma heat source, from the atmosphere and from the rock with which the geothermal uid interacts. Within a particular geothermal system, variations in gas concentrations of the geothermal uid are also aected by gas-gas and mineral-gas reactions and boiling and phase separation. Dissolution experiments involving basalt and pure water at temperatures

> 250 C

do not produce actual geothermal water compositions. The experimental solution pH is too high. The geothermal uid parameters can, however, be duplicated by addition of CO2 (Kacandes and Grandsta, 1989). Data from volcanic geothermal systems in Iceland hosted by basalt, show that sulfur and carbon contents of the altered aquifer rock is much higher in the upow zone where extensive depressurization boiling occurs than those of fresh basalt. These elements are hosted by sulde minerals and calcite (Gunnlaugsson, 1977; Arnrsson, 1995). These minerals precipitated as a consequence of changes in the liquid water composition by its boiling. Modal calcite as high as 20% have been reported (Bjrnsson et al., 1972) which correspond to C concentrations in the rock in excess of 2%. Sulfur concentrations as high as 5% have been reported (Gunnlaugsson, 1977). In fresh undegassed basalt S and C concentrations are around 800 ppm (Moore and Fabbi, 1971) and 1400 ppm as CO2 (Flower et al., 1982), respectively. The value of 1400 ppm is the average of 78 analyses of dyke samples from eastern Iceland. The median value for a total of 250 samples of lavas and dykes is 500 ppm CO2 (see Sveinbjrnsdttir et al., 1995). This lower value probably reects variable degassing of the lavas with respect to CO2 . Several studies have demonstrated that the aquifer water concentrations of the most abundant reactive gases (CO2 , H2 S and H2 ) in volcanic geothermal systems are often controlled by a close approach to equilibrium with hydrothermal mineral buers (Giggenbach, 1981; Arnrsson, 1985; Gudmundsson and Arnrsson, 2002; Stefnsson and Arnrsson, 2002; Fridriksson et al., 2006; Karingithi et al., 2008). However, in other systems, such as at Kraa, Iceland and in the western part of Olkaria, Kenya, the ux of CO2 from the magma heat source is considered to govern its concentration in aquifer uids (rmannsson et al., 1982; rmannsson et al., 1989; Gudmundsson and

CHAPTER 2.
Arnrsson, 2002; Karingithi et al., 2008). Carbon dioxide emissions from active volcanic geothermal systems are largely diffuse and cover large areas. The more visually conned emissions from fumarole or hot springs discharges are only a portion of the total emission (Fridriksson et al., 2006; Chiodini et al., 2005; Aiuppa et al., 2004). This is apparently not the case for the other abundant reactive gases (H2 S and H2 ) indicating that they are removed from the rising dispersed uid, either by reactions with other uid species or by reactions with the host rock minerals. This study focuses on quantifying the geochemical and physical processes which govern the concentrations of the most abundant gases (CO2 , H2 S, H2 , CH4 , N2 and Ar) in the aquifer uid of wet-steam wells drilled into ve volcanic geothermal elds in Iceland. All these systems are hosted by basaltic rocks. In two of the systems the parent uid is essentially seawater but meteoric water in the other three systems. The methodology involves calculation of mineral equilibrium constants with thermodynamic data from the literature, and comparison with the reaction quotient of the minerals, calculated from the chemical analyzes of water and steam samples. Essentially data interpretation involves two steps. One is modelling of initial aquifer uid compositions from data on liquid and vapor samples collected at the wellhead. The other step, which includes the reactive gases, involves calculation of activity products for specic mineral-gas and gas-gas reactions and derivation of the equilibrium constant for these reactions with thermodynamic data from literature.

2.2 Geological background

Volcanic geothermal systems in Iceland are located within the active volcanic belts, most of them in the center of these belts but some close the their margins (Fig. 2.1). The volcanic belts represent the diverging boundary between the North-American and Eurasian plates. The marginal volcanic geothermal systems are considered to be mature and have drifted away from their magma heat source within the active volcanic belts. Relatively young geothermal systems are characteristically located on the plate boundary where it is intersected by a ssure swarm that runs perpendicular to the plate movements. Except for geothermal systems on the Reykjanes Peninsula, these systems typically coincide with central volcanic complexes, which represent points of maximum volcanic activity within the volcanic belts. Silicic volcanics are typically associated with these complexes considered to have formed by partial melting of basalt at the base of the crust. The ve volcanic geothermal systems in Iceland (Kraa, Nmafjall, Hengill, Svartsengi and Reykjanes), which are the subject of the present study, have been extensively drilled. Hengill system. Nesjavellir represents one of the wellelds within the In these systems, the drilled reservoir rocks either contain no silicic

rocks or they are very minor (Franzson, 1998).

2.2.1 Kraa and Nmafjall

The Kraa eld lies within the caldera of the Kraa central volcano which has erupted both basaltic and silicic magma (Jnasson, 1994). The aquifer rock is, however, largely

2.2. GEOLOGICAL BACKGROUND

Figure 2.1: Map showing the active volcanic belts and high-temperature geothermal areas.

basaltic, sub-aerially erupted lavas, sub-glacially erupted hyaloclastites as well as small intrusive bodies of basalt, dolerite and gabbro. Intrusions of granophyre also occur. The volcanics dominate the succession above about 1200 m depth but at deeper levels intrusions become more abundant and they dominate below about 2000 m. A volcanic episode occurred in the area between 1975 and 1984 and fresh magma was intruded into the roots of the Kraa geothermal system at 47 km depth (Einarsson, 1978). On nine occasions partial emptying of the magma chamber did not reach the surface but owed laterally north or south along the tensional fractures that intersect the Kraa central volcano. This subsurface discharge was witnessed by earthquake activity of deation of the Kraa caldera (Bjrnsson et al., 1979). Degassing of the fresh magma was accompanied by an increase in gas uxes from the geothermal system, particularly with respect to CO2 (rmannsson et al., 1982; rmannsson et al., 1989). About twenty years after cessation of the 197584 volcanic episode, many well discharges were still aected by this gas pulse (Gudmundsson and Arnrsson, 2002). The drilled geothermal reservoir at Kraa has been divided into two main depth zones, an upper sub-boiling zone at 190200 C and a lower two-phase zone with tem peratures of up to 350 C (rmannsson et al., 1989; Arnrsson, 1995). Geothermometer (quartz and Na-K) temperatures indicate that most aquifers producing into wells are below 300 C (Gudmundsson and Arnrsson, 2002). The Nmafjall eld, which lies 8 km south of Kraa, may be regarded as a parasite system to the Kraa volcano. This eld was also aected by the 1975-84 volcanic episode. During periods of fracturing, magma sometimes owed to the south along the fractures from the magma chambers under Kraa. This magma, however, did not reach 3 the surface except on one occasion when a geothermal well erupted 3 m of magma (Larsen et al., 1978). The 197584 volcanic episode suggests that the heat source to the Nmafjall geothermal system is represented by the dykes formed by magma intrusion

10

CHAPTER 2.
into tensional ssures from the magma body in the roots of the Kraa system. Intrusive formations dominate below about 1500 m depth. In wells drilled at Nmafjall prior to the 197584 volcanic episode (well nos. 19) temperatures follow the boiling point curve with depth. In wells drilled in another part of the eld and after the 197584 volcanic episode, the temperature at the top of the reservoir is sub-boiling. These low temperatures are considered to be the consequence of cold shallow groundwater incursion along fractures that were activated during the 197584 volcanic episode. Maximum recorded temperatures in drillholes at Nmafjall is 320 C (Gudmundsson and Arnrsson, 2002). As at Kraa, geothermometry indicates that aquifers producing into wells at Nmafjall have considerably lower temperatures than this maximum (Gudmundsson and Arnrsson, 2002). Fumarolic activity at both Kraa and Nmafjall increased during the early part of the 1975-84 volcanic episode. However, at Nmafjall no changes in the gas content of well discharge and fumarole steam was observed (Arnrsson and Gunnlaugsson, 1985). The increase in the fumarolic activity is likely caused by increased boiling by heat ux to already two-phase aquifer uid. At Kraa, the gas ux from the fresh magma may also have contributed to increased boiling. The apparent lack of increase in the gas content of the uid in the Nmafjall system during the 1975-84 volcanic episode indicates that the magma intruded from the chambers below Kraa had already been largely degassed. The aquifer rock at Nmafjall is the same as at Kraa except that silicic rocks are absent.

2.2.2 Nesjavellir
The Nesjavellir eld lies in a tectonically active graben to the northeast of the Hengill central volcano. The drilled formations at depth are largely basalt lavas and basaltic hyaloclastites as wells as small intrusions of basalt and dolerite. Granophyre is sporadic (Franzson, 1998). Intrusions are dominant below some 1500 m depth. A volcanic ssure, which lies immediately to the north of the welleld erupted about 2000 years ago (Saemundsson, 1963, 1992; Bull et al., 2005). The permeability is mostly fracture controlled (Bdvarsson et al., 1990). The drilled geothermal system at Nesjavellir is two-phase, at least to the depth penetrated by the deepest wells (2200 m). The maximum recorded temperature is > 380 C. The well in which this temperature was recorded (the maximum for the instrument used) was drilled close to the ssure which erupted

2000

years ago.

2.2.3 Svartsengi and Reykjanes

The Svartsengi and the Reykjanes geothermal systems are both located on the Reykjanes peninsula in southwestern Iceland which represents the landward continuation of the Reykjanes Ridge. The peninsula consists mostly of Holocene lavas protruded by hyaloclastite hills formed by sub-glacial eruptions during the last glaciation (Jakobsson et al., 1978; Clifton and Kattenhorn, 2006). They lie astride two of the ve active ssure swarms on the Reykjanes peninsula. In view of their geological setting, the heat source to these systems are considered to be sheeted dyke complexes and the permeability is fracture controlled. The two exploited geothermal systems are hosted by basaltic

11

2.3. ALTERATION MINERALOGY

rocks, subglacial hyaloclastites, breccias, and pillow lavas as well as tuaceous sediments. Abundance of intrusions increases with depth. They dominate the succession at the greatest depth reached by the wells. The temperature in Svartsengi is very homogeneous. Between 500 and 2000 m depth 240 C, reecting good vertical permeability in the system. At Reykjanes, the highest temperature recorded is 320 C at 2000 m depth. The aquifer is two-phase it is above

1000

m but subboiling at greater depths.

2.3 Alteration mineralogy

All systems considered in this study are located in basaltic environments and have similar mineralogy. The dierent salinity of the uid is not sucient to change drastically the alteration mineralogy from one system to another. Alteration mineralogy in the high temperature geothermal systems in Iceland has been summarized by Arnrsson (1995). All elds show a zonation with depth reecting the temperature stability range of the minerals within the system. Calcite and pyrite are stable over the whole range of temperature. Chalcedony is stable up to 180 C and above that temperature quartz is formed. Prehnite appears above 200 C and epidote at slightly higher temperature (Hreggvidsdttir, 1987; Lonker et al., 1993). Albite is common, especially at temperatures above 150 C, whereas Kfeldspar (adularia) is scarce, due to the low K content of the host rocks. Hydrothermal sheet silicates are represented by smectite, that is interstratied with chlorite above 200 C and above 230240 C, discrete chlorite is formed. Garnet, represented by the grossular-andradite solid solution is widely present in Reykjanes and Svartsengi (Lonker et al., 1993). Magnetite is mostly present as primary mineral but is generally unstable in high-temperature geothermal systems. The present study focuses on ten alteration minerals that were considered as potential gas buers. In alphabetical order these are, calcite, pyrite, pyrrhotite, magnetite and wollastonite, and the solid-solutions epidoteclinozoisite and grossular-andradite. Quartz is assumed to be at equilibrium in all the geothermal systems considered in this study.

2.4 Fluid compositions

The geothermal uid at Reykjanes represents seawater which has reacted with basalt (Bjrnsson et al., 1972; Mottl and Holland, 1978; Arnrsson, 1995). The Cl concentrations of the unboiled aquifer water is thus close to that of seawater. of seawater (Sveinbjrnsdttir, 1983; Sveinbjrnsdttir et al., 1986). The deuterium This has been content of the aquifer water is, however, signicantly negative and thus lower than that explained by mixing of seawater with fresh groundwater and dissolution of Cl from the basalt to account for the observed Cl concentration in the geothermal water of the aquifer (rnason, 1976; lafsson and Riley, 1978). In view of the low Cl content of basalt (Sigvaldason and skarsson, 1976; Floyd and Fuge, 1982) this explanation appears unlikely. However, recent studies by Pope et al. (2008) conclude that the low 2H values of the geothermal seawater at Reykjanes is a consequence of equilibration of

12

CHAPTER 2.
the geothermal uids with hydrous alteration minerals. Alteration mineralogy seems to 2 have formed from a glacial dominated uid source with a signicantly lower H signature than that of seawater. As a result, the present geothermal uid source at Reykjanes is seawater that has reacted and experienced isotope exchange with alteration minerals. The Svartsengi geothermal system has a mixed meteoric-seawater uid origin with Cl content corresponding to about 2/3 that of seawater (Arnrsson, 1978; Ragnarsdttir et al., 1984; Lonker et al., 1993) and the deuterium content of this water is consistent with such an origin. Reaction of the seawater at Reykjanes and the seawater/meteoric water mixture at Svartsengi has lead to almost quantitative removal of Mg and SO4 from solution, a slight decrease in Na but substantial increases in the concentrations of Ca and K. Silica is increased strongly but F decreased much (Table 2.1). Experiments involving reaction of seawater with basalt have reproduced the uids at Reykjanes (Mottl and Holland, 1978).

13

Table 2.1: Major elements analyses of the sampled waters. Concentrations in mg/kg.
Sampling meas. pH pH corr. pressure /at C for silicac bar-g CO2 H2 S F Cl SO4 SiO2 Na K Ca Mg Fe Al Sr B

Sample # Sampling date

Well

Discharge enthalpy kJ/kg

8.67 8.34 8.68

8.58 9.29 9.03 8.40 8.41 8.27 8.66 8.18 8.80 8.59 8.42 8.67 8.52 8.54 8.11 8.28 8.28

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 6.24/20.2 6.77/21.7 7.19/23.3 5.72/23.5 7.24/20.1 7.58/20.3 4.88/21.9 5.16/21.7

19.10.2004 19.10.2004 20.10.2004 20.10.2004 21.10.2004 21.10.2004 21.10.2004 20.10.2004 21.10.2004 20.10.2004 20.10.2004 20.10.2004 10.12.2004 10.12.2004 10.12.2004 10.12.2004 10.12.2004 15.12.2004 09.09.2004 15.12.2004 10.12.2004 09.09.2004 15.12.2004 15.12.2004 15.12.2004 10.12.2004

N-12 N-9 K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23

7.86/21.7 8.90/18.6 8.43/18.1 9.26/18.0 7.36/19.0 7.88/18.9 7.80/18.1 8.80/17.8 9.59/16.9 9.51/19.7 8.89/19.1 7.24/19.4 8.70/22.6 8.45/22.8 9.11/22.6 8.25/22.6 9.46/22.7 9.19/21.8 8.95/21.7 9.22/21.9 8.92/22.3 7.13/21.7 8.93/22.0 8.10/21.8 8.55/21.7 8.54/22.6

04-3005

10.09.2004 SV-7

04-3003

10.09.2004 SV-8

04-3032

01.12.2004 SV-9

04-3029

01.12.2004 SV-11

04-3004

10.09.2004 SV-18

04-3006 05-3004 05-3003

10.09.2004 SV-19 14.01.2005 R-12 14.01.2005 R-15

1759 1060a 1941 1499 2451 2547 2543 1167a 887a 1199a 1910 2636 1800 2136 1182a 1700 1133a 1948 1937 1195a 1252a 1711 1400 2400 1612 2662 1028a,b 1028a,b 1028a,b 1028a,b 1028a,b 1028a,b 1316a 1256a

20.0 14.0 15.5 14.5 11.0 28.5 11.0 15.0 2.9 12.0 14.5 17.5 15.5 15.8 15.5 15.3 15.0 7.8 10.5 16.1 15.5 6.0 16.2 16.0 15.6 15.5 15.5 14.0 14.8 19.0 14.0 14.5 42.0 25.0

21.7 38.6 67.9 16.0 159.3 69.4 158.0 49.7 20.3 38.3 17.9 90.6 58.5 12.9 56.0 36.5 25.7 15.1 2.8 18.1 37.5 25.7 32.9 51.2 14.3 9.2 24.8 16.9 6.9 46.6 12.3 8.6 103.9 47.4

90.9 62.1 72.6 93.2 61.9 108.5 75.2 62.1 31.7 46.1 89.5 88.9 59.6 46.3 69.6 47.1 50.2 111.7 72.1 28.8 86.1 85.3 49.9 83.8 56.8 59.6 2.2 1.2 1.2 3.8 1.3 0.8 11.5 3.4

0.522 0.585 0.933 1.271 2.114 1.847 1.272 1.017 0.825 1.047 1.380 1.341 0.936 0.723 1.232 0.928 1.582 1.160 0.954 1.136 1.343 1.105 0.944 1.157 1.047 1.361 0.140 0.162 0.161 0.147 0.158 0.147 0.129 0.138

107.8 35.6 31.8 36.4 133.2 14.9 227.0 72.2 45.6 49.5 147.8 99.6 117.0 164.8 95.4 172.3 122.3 78.1 151.4 182.7 65.0 147.9 169.1 110.5 164.1 124.8 13831 13493 13230 12916 14255 14235 19288 19251

3.7 43.9 303.9 247.9 12.4 4.7 5.8 67.0 241.3 262.4 167.5 44.5 8.1 6.0 14.1 8.8 12.7 20.8 3.2 10.7 25.8 1.9 12.8 1.9 4.3 5.5 26.0 28.2 28.2 29.1 27.6 28.5 15.8 24.3

621 457 432 730 662 653 859 502 381 558 867 554 713 758 671 753 739 796 881 721 713 861 693 786 859 829 468 488 492 460 471 463 679 672

133 151 244 222 194 118 259 150 221 237 235 162 164 156 171 167 171 150 150 171 157 147 172 142 153 144 7263 7043 6995 6825 7522 7490 10166 10089

24.4 0.398 19.4 2.581 26.6 4.473 39.1 2.059 32.8 0.883 19.8 0.202 52.4 1.966 19.8 1.188 17.5 3.585 34.5 2.654 53.9 1.558 30.7 1.181 31.4 0.334 32.2 0.246 30.0 0.397 33.5 0.367 32.3 0.322 28.6 0.308 33.7 0.136 31.2 0.290 28.4 0.424 32.9 0.087 32.4 0.445 31.4 0.298 33.4 0.210 30.5 0.416 1050 1167 1011 1141 1004 1125 982 1102 1114 1129 1093 1170 1434 1680 1447 1637

0.0042 0.0016 0.0017 0.0005 0.0020 0.0003 0.0016 0.0008 0.0007 0.0041 0.0009 0.0037 0.0011 0.0004 0.0018 0.0005 0.0009 0.0023 0.0017 0.0009 0.0071 0.0007 0.0007 0.0053 0.0080 0.0019 0.4279 0.6780 0.3068 0.5668 0.4712 0.4063 0.7960 1.0748

0.0044 0.0012 0.0040 0.0012 0.0038 0.0017 0.0022 0.0035 0.0027 0.0137 0.0022 0.0137 0.0014 0.0010 0.0007 0.0018 0.0020 0.0010 0.0164 0.0009 0.0049 0.0093 0.0015 0.0011 0.0031 0.0026 0.0397 0.0110 0.1568 0.1331 0.0090 0.0037 0.4315 0.2930

0.966 0.923 1.166 1.878 1.026 1.929 1.072 1.511 0.855 1.550 1.674 1.236 1.749 1.605 1.745 1.425 2.052 2.323 1.906 1.818 2.067 2.093 1.790 1.642 1.991 1.886 0.066 0.070 0.119 0.163 0.063 0.065 0.023 0.045

0.003 0.025 0.021 0.009 0.005 0.001 0.008 0.009 0.027 0.013 0.008 0.006 0.002 0.002 0.003 0.004 0.002 0.002 0.001 0.002 0.002 0.001 0.004 0.002 0.001 0.003 8.003 7.843 7.632 7.530 7.735 7.999 9.104 9.189

3.541 0.724 0.900 1.128 1.735 1.359 2.175 0.603 0.550 0.673 1.619 0.693 1.588 2.431 1.400 2.209 1.523 2.042 2.241 1.819 1.890 3.324 1.828 1.891 2.008 7.678 7.072 7.134 6.633 6.767 8.128 7.650 6.786 6.718

a Liquid enthalpy wells b Selected, corresponds to enthalpy of steam-saturated liquid at 238 C c pH values above 8.0 were corrected for silica polymerization. If present, the corrected value was used for the calculations.

CHAPTER 2.
local or near local meteoric water according to At Kraa, Nmafjall and Nesjavellir the source water to the geothermal uid is 2H data (Darling and rmannsson,

1989; Arnrsson, 1995). The total dissolved solids content of the aquifer water in these elds is very low (10002000 ppm) compared to most other geothermal systems in the world (e.g. Ellis and Mahon, 1977). The low salt content is considered to be the consequence of the low Cl content of the host basalt with which the water has reacted 2 (Arnrsson, 1995). The most important anions are Cl and SO4 , the most abundant + cation is Na and silica as SiO2 is typically the most abundant dissolved solid (Table 2.1). The gas content of vapor samples is quite variable. N2 /Ar ratios are most often

between that of air-saturated water and that of air. Carbon dioxide is generally the most abundant gas (18600 mmol/kg of condensate), followed by H2 (<0.5110 mmol/kg) or H2 S (<251 mmol/kg) (Table 2.2). Methane concentrations are quite low. Systematic dierences are observed in the aquifer uid composition of the study areas. Thus, the saline waters are low in both H2 S and H2 compared to the dilute waters. The magmatic activity at Kraa in the late 1970's and the early 1980's had an important impact on the CO2 content of well discharges at Kraa (rmannsson et al., 1989). This CO2 anomaly is still quite strong in some of the Kraa wells (Gudmundsson and Arnrsson, 2002, 2005). In the parasitic systems of Nesjavellir and Nmafjall, aquifer uid CO2 concentrations are relatively low, whereas those of H2 S and H2 are relatively high. On a molar basis, the gas content of dilute aquifer uids is typically much higher than those of the dissolved solids. The pH of water samples, as measured at room temperature is typically below 7 for the saline water but above 8 for samples of dilute water. The pH of the unboiled and undegassed water in the aquifer is lower.

2.5 Well discharge enthalpy

The enthalpy of the well uids sampled for the present study ranges between that of saturated vapor and liquid enthalpy, i.e. the enthalpy of the discharged uid equals the enthalpy of vapor saturated liquid at the aquifer temperature. Many of the studied wells have excess enthalpy, i.e. the enthalpy of the discharged uid is higher than that of liquid enthalpy (Table 2.1). All the geothermal elds considered for the present study are liquid-dominated, as dened by White et al. (1971), meaning that the aquifer uid is liquid only or liquid with a small vapor fraction, even in terms of volume. The enthalpy of the uid owing into wells has increased from the initial liquid enthalpy in the depressurization zone around the wells by one or two processes. Cooling of the uid due to depressurization boiling creates a temperature gradient between aquifer rock and the owing uid which favour conductive transfer of heat from rock to uid thus enhancing vapor formation. Capillary forces between mineral grain surfaces and liquid reduce partly or even completely the mobility of the liquid. At Svartsengi, exploitation of the reservoir has led to the formation of a vapor cap on top of the hot water reservoir. Reservoir pressure drawdown has enhanced boiling in the uppermost part of the liquid reservoir and gravity segregation of the two uids led to the formation of the vapor cap.

15

2.6. AQUIFER TEMPERATURES

Table 2.2: Gas analyses of the sampled vapor phase in mmol/kg of condensate.
Sample # 04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 04-3032 04-3029 04-3004 04-3006 05-3004 05-3003 Well N-12 N-9 K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-9 SV-11 SV-18 SV-19 R-12 R-15 N2 Ar O2 CH4 H2 CO2 H2 S N2 /Ar

4.35 8.07 13.12 3.22 3.59 3.62 1.97 1.08 3.73 9.47 1.95 7.99 9.73 2.90 9.40 5.00 8.63 5.82 5.41 1.26 5.46 1.98 1.15 4.52 9.85 2.10 2.21 13.12 3.33 30.95 1.70 2.17 7.02 7.88

0.236 0.201 0.222 0.072 0.097 0.081 0.052 0.024 0.091 0.174 0.042 0.175 0.153 0.040 0.144 0.079 0.150 0.110 0.075 0.026 0.081 0.040 0.012 0.083 0.147 0.039 0.044 0.160 0.053 0.410 0.035 0.036 0.109 0.122

0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000

0.757 3.788 0.117 0.055 1.025 0.628 0.333 0.240 0.353 0.511 0.045 0.344 1.357 0.060 2.006 0.741 1.611 0.684 0.110 0.154 0.992 0.089 0.325 0.414 0.043 0.145 0.050 0.038 0.010 0.088 0.011 0.012 0.062 0.067

103.95 105.82 46.99 11.69 78.27 32.18 41.47 5.26 0.35 6.86 24.35 110.42 34.00 30.14 61.49 31.51 1.60 51.05 32.50 1.54 51.60 30.06 12.30 41.45 19.89 40.38 2.22 0.19 0.22 3.64 0.09 0.12 0.87 0.87

92.6 64.8 157.7 58.0 600.0 165.9 437.0 96.6 23.8 50.0 79.8 413.0 142.8 37.0 95.9 122.4 41.7 32.7 25.2 39.8 49.4 30.4 72.4 139.5 43.0 18.3 167.8 93.5 56.4 314.8 74.0 53.4 446.9 389.7

25.7 24.1 11.9 12.6 32.2 18.9 25.8 7.2 3.4 3.6 24.2 27.6 40.8 44.8 31.6 40.8 18.5 49.8 37.3 8.9 44.5 37.9 21.2 51.1 33.6 43.5 4.8 0.0 1.4 3.4 1.9 1.2 14.7 10.3

18.4 40.2 59.1 44.8 37.0 44.9 37.8 44.2 41.1 54.4 46.0 45.6 63.5 72.4 65.1 63.2 57.6 52.9 72.3 48.5 67.1 48.9 92.1 54.7 67.1 54.2 49.8 82.2 62.6 75.5 48.2 60.2 64.5 64.4

2.6 Aquifer temperatures

Aquifer temperatures have been estimated by the quartz and Na/K geothermometers for all wells. The Na/K geothermometer results are independent of the process producing excess well discharge enthalpy because it is based on a component ratio. This is, however, not the case for the quartz geothermometer. If excess well discharge enthalpy is produced by conductive heat transfer from the aquifer rock to the uid owing into wells, component concentrations, including silica, in the total well discharge are the same as in the aquifer uid. If, on the other hand, phase segregation is responsible for the excess enthalpy, silica concentrations are lower in the total well discharge than in the aquifer uid because some of the liquid with its dissolved silica is retained in the formation. Quartz equilibrium temperatures have been calculated according to both models for excess enthalpy wells together with the Na/K temperature (Fig. 2.2). It is seen that the two geothermometers yield similar results by the phase segregation model, although quartz equilibrium temperatures are systematically higher (13 C on average). The conductive heat transfer model yields quartz equilibrium temperatures that are lower than the Na/K temperatures for excess enthalpy wells and the dierence increases with increasing discharge enthalpy. These results indicate that phase segregation is largely the cause of excess enthalpy. It is therefore reasonable to calculate component concentrations in the initial aquifer uid according to this model. For the Svartsengi wells, which receive uids from sub-boiling aquifers, quartz equi-

16

CHAPTER 2.

Figure 2.2: Na/K and quartz geothermometers compared for both the phase segregation model and the heat transfer model.

17

2.7. SAMPLING AND ANALYSIS

librium and Na/K temperatures compare well (Fig. 2.2), the average dierence for Svartsengi being 3.3 C suggesting that the calibration of the two geothermometers is internally consistent likely, at least, in the temperature range of 200300 C. For liquid enthalpy wells discharging dilute waters (see Table 2.1), average Na/K temperatures are 18 C lower than average quartz equilibrium temperatures. This dierence is considered to be due to cooler water recharge into producing aquifers and insucient time for equilibration with alkali-feldspars (the Na/K geothermometer) as the recharging water gains heat by ow through the aquifer rock (Arnrsson et al., 2000; Gudmundsson and Arnrsson, 2002). temperatures. At Reykjanes, Na/K temperatures are signicantly lower than quartz equilibrium temperatures (Fig. 2.2). The cause is believed to be insucient supply of K from the basalt to the uid to saturate it with K-feldspar. The seawater source uid contains enthalpy wells, Na/K temperatures are on average Such recharge has not been observed in Svartsengi. For excess 13 C lower than quartz equilibrium

400

ppm K but the geothermal seawater 14001500 ppm.

The dierence, which is

due to leaching from the basalt host rock, is comparable, or even higher, than the K content of fresh basalt in the Reykjanes area. The calibration (quartz solubility constant) used here for the quartz geothermometer is that proposed by Gunnarsson and Arnrsson (2000). The calibration of Fournier and Potter (1982) is more widely used. The two calibrations, however, yield similar results in the temperature range of the wells under study, the dierence being only 6 , 1 and 17 C at 200 , 250 and 300 C, respectively. The Na/K geothermometer equation used is based on thermodynamic data on low-albite and microcline solubility (Arnrsson and Stefnsson, 1999; Arnrsson et al., 2000).

2.7 Sampling and analysis

Only a short description of the sampling and analytical techniques used in this study is given here. For further details, see Arnrsson et al. (2006). Water and steam samples were collected from the two-phase pipeline (or steam pipeline in case of dry steam wells) close to the wellhead by mean of a stainless (N316) steel Webre separator.

2.7.1 Water phase

Sample treatment
Water samples were ltered through 0.2 sample was analyzed on a Reagent-Free

cellulose acetate membrane using a Teon

lter holder and collected into low-density polyethylene bottles. An untreated 200 ml

TM ion-chromatograph (RFICTM , Dionex 2000) for F, Cl and SO4 . A 200 ml sample was acidied with 2 ml Suprapur R HNO3 (E. Merck
Another 100 ml

1.00441) for major element analyses on an Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES) (Al, B, Ca, Cl, Fe, Mg, Na, Si, Sr). acidied sample was used for trace elements determination on an ICP-MS. Glass bottles with air-tight cap were used for pH and total carbonate carbon determination in the laboratory shortly after sampling. Hydrogen sulde was measured on

18

CHAPTER 2.
site by titration with standard mercuric acetate solution, using dithizone as endpoint indicator (Arnrsson et al., 2006).

Note on sulfate analysis

Special samples were collected for sulfate determination. One 1 ml of 1% Zn-acetate solution was added to 100 ml sample to remove H2 S. Subsequently, sulfate concentrations were determined by RFIC

TM .

Sulfur was also analyzed by ICP-AES. In the absence of Subsequent oxidation of

sulfur bearing species other than sulfate, this measurement yields a value for sulfate. Upon sample storage the ZnS precipitate tends to dissolve. reported SO4 numbers in Table 2.1 are maximum values. H2 S will cause an increase in the SO4 concentrations in the sample. Accordingly, the

2.7.2 Steam phase

Steam samples for analysis of major gases were collected into evacuated 300 ml glass bulbs containing 10 or 20 ml of KOH 50% w/v solution. gases in the gas phase. analysis. Carbon dioxide and H2 S dissolve quantitatively in the hydroxide solution, concentrating the non-condensable This allows a better precision of the non-condensable gas Hydrogen, N2 , O2 , Ar and CH4 were analyzed on a PerkinElmer-ARNEL

4019 gas-chromatograph. Condensate was analyzed for CO2 and H2 S by titration.

2.8 Thermodynamic data

2.8.1 Mineral solubility constants and gas solubilities
Equilibrium constants for the reactions given in Tables 2.3 and 2.5 were taken from Karingithi et al. (2008). They are based on thermodynamic data (Gf , S , V , Cp ) on the minerals from Holland and Powell (1998) except for pyrite, pyrrhotite and calcite. Data on the sulde minerals were taken from Robie and Hemingway (1995). The calcite solubility constants is from Arnrsson et al. (1982). The standard Gibbs energy of the dissolved gases are based on the gas solubility constants given by Fernndez-Prini et al. (2003) assuming ideal behavior of the gases. The thermodynamic properties of the aqueous species and liquid water entering the reactions in Table 2.3 were taken from 0 various sources; data on H4 SiO4 are from Gunnarsson and Arnrsson (2000), those on +2 +2 H2 Ol , Ca , Fe , and OH are from SUPCRT92 (Johnson et al., 1992) using the slop98.dat data set and those on Fe(OH)4 and Al(OH)4 from Diakonov et al. (1999) and Pokrovskii and Helgeson (1995), respectively. Three of the hydrothermal minerals considered for the present study form extensive solid solutions (epidote, garnet and prehnite). The other minerals considered (calcite, magnetite, pyrite, pyrrhotite, quartz and prehnite) are taken to be pure. assuming ideal behavior. At Kraa and Nesjavellir, the composition of epidote, expressed as Xps , the mole fraction of pistacite (Ca2 Fe3 Si3 O12 OH), is in the range 0.180.32 (Bird and Spieler, Activities of endmembers in solid solution have been retrieved from their analyzed composition

19

2.8. THERMODYNAMIC DATA

Table 2.3: Individual minerals dissolution reactions
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.

and + 4H+ + 8H2 O = 3Ca2+ + 2Fe(OH) + 3H4 SiO0 4 4 cal + 2H+ = Ca2+ + H2 Ol + CO2,aq czo + 12H2 Ol = 2Ca2+ + 3Al(OH) + 3H4 SiO0 + OH 4 4 epi + 12H2 Ol = 2Ca2+ + Fe(OH) + 2Al(OH) + 3H4 SiO0 + OH 4 4 4 gro + 4H+ + 8H2 Ol = 3Ca2+ + 2Al(OH) + 3H4 SiO0 4 4 mag + 4H2 Ol = 2Fe(OH) + Fe2+ 4 pre + 10H2 Ol = 2Ca2+ + 2Al(OH) + 3H4 SiO0 + 2OH 4 4 pyr + 2H+ + H2,aq = 2H2 Saq + Fe2+ pyrr + 2H+ = H2 Saq + Fe2+ qtz + 2H2 Ol = H4 SiO0 4 wol + 2H+ + H2 Ol = Ca2+ + H4 SiO0 4

2004) and 0.140.38 (rnason and Bird, 1992), respectively. This gives an average epidote endmember (Ca2 FeAl2 Si3 O12 OH) activity of 0.75. The corresponding clinozoisite activity is therefore 0.25. In Svartsengi and Reykjanes, Xps ranges between 0.19 and 0.44, which corresponds to an endmember epidote activity of 0.9 (Bird and Spieler, 2004). The substitution of Al by Fe in epidote occurs mostly in the M3 site, and to calculate the epidote and clinozoisite activities, we considered a full substitution of Al by Fe on this site. Nevertheless, the M1 site can also accommodate some Fe, and this can lead to a modest overestimation of the calculated activities (Deer et al., 1992). In prehnite (Ca2 Al(Al,Fe)Si3 O10 (OH)2 ), Al-Fe substitution occurs on one site and the activity, assuming ideal behavior, is proportional to the ratio of Fe to one Al. The selected activities for the dilute aquifers is equal equal to 0.9, corresponding to an XF e of 0.1 (Hreggvidsdttir, 1987) and 0.8 (XF e elds. Garnet (grossular-andradite, Ca3 (Fe,Al)Si3 O12 ) has only been reported from the saline uid elds in Svartsengi and Reykjanes. Substitution occurs on two sites, so ai,ideal = X2 where ai,ideal is the activity of the endmember i, and X its mole fraction. i The average Al mole fraction in the garnet at Svartsengi and Reykjanes is very variable (Lonker et al., 1993). From the average XAl in grossular and XF e in andradite, activities of 0.2 and 0.3 is obtained for the grossular and andradite endmembers, respectively, assuming ideal solid-solution. Mineral compositions used in this study are averages of chemical analyses from the cited authors. The question raises whether the numbers selected are representative of the mineral composition with which the present uid is reacting. Some minerals show a zonation and the core of those grains is not expected to be reacting with the present uid, neither will be the rim if the grain has ceased to grow. In addition, analyses are more likely to be performed on coarse-grained rather than ne-grained crystals that recently formed from solution. The average mineral compositions were selected because it is the simplest one. Also, the uids sampled must be a mixture of many components and individual components likely have reacted with garnets of dierent compositions.

= 0.2)

(Lonker et al., 1993) for the saline

20

CHAPTER 2.

2.9 Data handling

2.9.1 Note on pH measurement
The waters sampled for the present study contain 380880 ppm of dissolved silica (as SiO2 ). Some of these waters are slightly amorphous silica supersaturated at sampling conditions, whereas other waters become supersaturated upon cooling to room temperature subsequent to sampling. Silica polymerization aects the solution pH as it involves removal of silica monomers, which act as weak acid, from solution and the formation of silica oligomers, which are stronger acids than silica monomers (Tossell and Sahai, 2000). Therefore, removal of monomers from solution tends to raise its pH, whereas the formation of oligomers has the opposite eect. At high pH (above

9),

when the dissolved silica is signicantly ionized, decrease in silica monomer concentration by its polymerization dominates the pH change over oligomer formation and causes it to increase. In contrast, when ionized silica concentrations are insignicant (pH below

8),

oligomer formation dominates the pH change over decrease in silica As the acid dissociation constants for silica oligomers are

monomer concentrations.

only poorly known from ab initio calculations their eects on pH cannot be quantied. Besides their concentration cannot be measured and their concentrations change with time, sometimes rapidly. The pH of the samples collected for the present study was measured when practically all silica in excess of amorphous silica polymerization had polymerized. When the measured pH was above 8, the pH was corrected for the eect of silica polymerization on the assumption that the solution pH was essentially governed by the silicic acid buer and following the results of Gunnarsson and Arnrsson (2005). The results are shown in Table 2.1. The only way to obtain reliable values for pH of amorphous silica supersaturated solutions is to measure it on site before onset of silica polymerization.

2.9.2 Calculation of aquifer water compositions and aqueous speciation

As demonstrated in section 2.6 above, the quartz and Na/K geothermometer results indicate that excess enthalpy of well discharges is essentially produced by phase segregation. Therefore, the phase segregation model was used to calculate initial aquifer uid compositions for excess enthalpy wells, i.e. model 3 in Arnrsson et al. (2007). For liquid enthalpy wells, it is reasonable to take total well discharge compositions to represent the initial aquifer uid. The pressure at which phase segregation occurs aects the composition of the initial aquifer uid in relation to the total well discharge. the wellhead vapor pressure. It is considered likely that segregation occurs over a range of pressures between the aquifer vapor pressure and Since the segregation pressure range is not known, we selected this pressure to be halfway between aquifer and wellhead vapor pressures. The initial temperature selected for calculating aquifer uid component compositions was the average of the quartz and Na/K geothermometers (Table 2.1). Aquifer uid compositions and speciation distribution in this uid were calculated with the aid of the WATCH speciation calculation software, version 2.1 (Arnrsson et al.,

21

2.9. DATA HANDLING

1982; Bjarnason, 1994). For liquid enthalpy wells, the initial aquifer uid composition for component

is obtained from

mf,t = md,t = md,l (1 X d,v ) + md,v X d,v i i i i mi

designates concentration on component i. The superscript i.e. sampling pressures,

(2.1)

d stands for discharge,

for total uid and

f, v

and

for initial aquifer uid, vapor

and liquid, respectively. For components that partition almost exclusively in the liquid d,v phase, at sampling conditions, mi is taken to be zero by the WATCH program and for gaseous components that are present in insignicant concentrations in liquid samples, d,l and therefore not analyzed, mi is taken to be zero. In fact the only components analyzed in both phases are carbonate carbon, sulde sulfur and boron. For excess enthalpy wells, the WATCH calculations involve two steps. The rst step consists of calculating the vapor fraction and the liquid and vapor compositions at the g pressure (P ) at which phase segregation is assumed to occur. The second step involves calculating aquifer uid composition from the liquid and vapor phase compositions at P g , assuming that the owing uid enthalpy before phase segregation occurred is the same as that of vapor saturated liquid at the aquifer temperature. For the rst step we have

md,t = mg,l (1 X g,v ) + mg,v X g,v i i i

where (2.1).

(2.2)

g,v

occurs, at vapor pressure

denotes the steam fraction in the uid immediately after phase segregation P g . Other symbols have the same notation as in equation

The owing uid enthalpy after phase segregation is taken to be the same as that of the well discharge. Therefore

hd,t = hg,l (1 X g,v ) + hg,v X g,v

so

(2.3)

X g,v = h
stands for specic enthalpy. As before, (2.1) through (3.5).

hd,t hg,l hg,v hg,l

(2.4)

Superscripts have the same notation as in equation

is taken to be zero for dissolved solids that do g not partition signicantly into the vapor phase at conditions P . Gaseous species g are assumed to be present in both phases at P . The distribution coecient (Ds for species

mg,v i

s)

vapor pressure

describes its relative concentrations in the two phases at equilibrium. P g we have

g Ds =

At

ng,v s ng,l s

and for dilute uids:

(2.5)

g Ds =

mg,v s mg,l s s

(2.6) (see Arnrsson et al., 2007).

From

denotes mole fraction and subscript s gaseous species Ps = xv Ptot and ml = Ks Ps , it follows that s s

Ds =

55.508 Ks Ptot
22

(2.7)

CHAPTER 2.
Ks
total pressure, respectively, and rewritten as
g md,t = mg,l (1 X g,v ) + Ds mg,l X g,v i i i

is the Henry's Law constant for gas s, Ps and Ptot are partial pressure of gas s and xv the mole fraction of gas s in the vapor phase. The s

number 55.508 is the number of moles of water in one kg. Now equation (2.2) can be (2.8)

allowing calculations of the concentrations of all components in both liquid and vapor g phases at pressure P . The second calculation step by the WATCH program for excess g enthalpy wells involves calculating the steam fraction at pressure P on the basis that the owing uid enthalpy before phase segregation occurs is that of the initial aquifer e,v uid. This steam fraction is symbolized as X

X e,v =

hf,t hg,l hg,v hg,l

and,

(2.9)

mf,t = mg,l (1 X e,v ) + mg,v X e,v i i i

As before for non-volatile species,

(2.10)

mg,v i

is taken to be zero. The results for component

concentrations in the initial aquifer uid of excess enthalpy wells, as calculated by the method just described, is given in Table 2.4, together with the aquifer composition of uids feeding liquid enthalpy wells.

2.10 Mineral-gas equilibria

In the discussion below (section 2.12) it is assumed that the initial aquifer uid is represented by liquid only, i.e. the calculated gas concentrations in the initial aquifer uid represent aqueous gas concentrations. If some vapor is present in the aquifer uid, the true gas concentration in the aquifer liquid would be lower than assumed here, particularly for the less water soluble gases, such as H2 .

2.10.1 CO2
Figure 2.3 shows that the calculated aquifer liquid concentrations of carbon dioxide (CO2,aq ) as a function of temperature. Also shown are equilibrium constants for two potential mineral assemblages that would x CO2,aq if equilibrium was attained. The respective reactions for dilute and saline uids are shown in reactions 1 and 2 in Table 2.5.

23

Table 2.4: Aquifer water composition. Temperature is in

C,
SO4 Fe Al CO2 H2 S N2 Ar O2 CH4 H2

dissolved solid concentrations are in mg/kg but gases

in mmol/kg.
K Ca Mg Cl F B N2 /Ar

2.10. MINERAL-GAS EQUILIBRIA

Sample # Well Aquifer temp.b

SiO2

Na

N-12 N-9a K-13 K-15 K-16 K-17 K-20 K-21a K-24a K-27a

24

K-32 K-34 NJ-5 NJ-6 NJ-7a

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 04-3032 04-3029 04-3004 04-3006 05-3004 05-3003

NJ-9 NJ-10a NJ-11 NJ-13 NJ-14a NJ-16a

NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7a SV-8a SV-9a

SV-11a SV-18a SV-19a RN-12a RN-15a

268 232 222 273 263 268 293 238 199 247 299 263 276 285 268 283 278 282 297 275 273 293 274 291 296 292 239 240 241 239 240 239 287 284

536 421 411 598 521 596 614 458 337 485 648 461 582 600 563 602 598 587 638 596 589 601 573 609 655 624 429 442 448 431 427 421 613 567

115 139 232 182 153 108 185 137 195 206 176 135 134 123 144 133 138 111 109 141 130 103 142 110 117 108 6650 6380 6373 6394 6813 6809 9172 8511

21.1 0.35 17.9 2.38 25.3 4.26 32.0 1.68 25.8 0.69 18.1 0.18 37.5 1.40 18.1 1.08 15.5 3.17 30.0 2.31 40.3 1.16 25.6 0.99 25.6 0.28 25.5 0.19 25.2 0.33 26.8 0.29 26.2 0.26 21.1 0.22 24.4 0.10 25.8 0.24 23.5 0.35 23.0 0.06 26.8 0.37 24.3 0.23 25.5 0.16 23.0 0.31 961 1069 916 1033 915 1025 920 1032 1009 1023 994 1064 1294 1516 1220 1381

0.004 0.001 0.002 0.000 0.002 0.000 0.001 0.001 0.001 0.004 0.001 0.003 0.001 0.000 0.002 0.000 0.001 0.002 0.001 0.001 0.006 0.001 0.001 0.005 0.006 0.002 0.392 0.614 0.280 0.531 0.427 0.369 0.718 0.907

93.1 32.8 30.3 29.8 104.8 13.6 162.3 65.9 40.3 43.1 110.5 82.9 95.4 130.4 80.1 137.7 99.0 57.6 109.7 151.1 53.7 103.3 139.9 85.6 125.2 93.9 12664 12222 12054 12100 12912 12942 17402 16241

0.45 0.54 0.89 1.04 1.66 1.69 0.91 0.93 0.73 0.91 1.03 1.12 0.76 0.57 1.03 0.74 1.28 0.86 0.69 0.94 1.11 0.77 0.78 0.90 0.80 1.03 0.13 0.15 0.15 0.14 0.14 0.13 0.12 0.12

3.16 0.91 1.16 0.97 1.24 1.27 1.38 0.77 0.54 0.78 1.64 4.63 1.15 1.78 1.12 1.48 1.13 1.40 1.81 1.31 1.50 2.64 1.25 1.22 1.34 3.89 6.41 6.56 6.63 7.06 6.92 7.12 7.73 7.16

3.2 40.4 289.3 203.0 9.8 4.3 4.1 61.1 213.3 228.3 125.2 37.1 6.6 4.8 11.8 7.0 10.3 15.3 2.3 8.9 21.3 1.3 10.6 1.5 3.3 4.1 23.8 25.5 25.7 27.3 25.0 25.9 14.3 20.5

0.004 0.001 0.004 0.001 0.003 0.002 0.002 0.003 0.002 0.012 0.002 0.011 0.001 0.001 0.001 0.002 0.002 0.001 0.012 0.001 0.004 0.006 0.001 0.001 0.002 0.002 0.036 0.010 0.143 0.125 0.008 0.003 0.389 0.247

0.83 0.85 1.11 1.54 0.81 1.76 0.77 1.38 0.76 1.35 1.25 1.03 1.43 1.27 1.46 1.14 1.66 1.71 1.38 1.50 1.71 1.46 1.48 1.27 1.52 1.42 0.06 0.06 0.11 0.15 0.06 0.06 0.02 0.04

7.61 5.97 5.64 7.03 52.20 10.32 52.82 9.49 1.69 7.26 11.80 29.56 15.05 4.05 16.48 14.57 8.40 4.25 3.80 7.23 9.30 5.02 9.03 16.11 6.81 2.09 14.67 9.16 5.16 20.88 7.22 5.03 45.83 61.85

3.46 3.60 1.12 2.93 3.69 2.37 4.16 2.29 0.77 1.65 5.03 2.81 5.88 6.31 6.79 6.18 4.71 8.16 7.23 2.24 9.83 7.12 3.73 7.93 6.72 6.53 0.46 0.03 0.16 0.32 0.21 0.13 1.74 1.69

0.309 0.642 0.295 0.344 0.285 0.170 0.227 0.094 0.431 1.231 0.263 0.506 0.922 0.291 1.509 0.559 1.641 0.711 0.760 0.222 0.948 0.326 0.130 0.473 1.488 0.219 0.192 1.299 0.320 2.033 0.168 0.203 0.685 1.231

0.0169 0.0160 0.0050 0.0077 0.0077 0.0038 0.0060 0.0021 0.0105 0.0226 0.0057 0.0112 0.0146 0.0040 0.0232 0.0089 0.0285 0.0135 0.0106 0.0046 0.0141 0.0067 0.0014 0.0087 0.0223 0.0041 0.0038 0.0158 0.0051 0.0269 0.0035 0.0034 0.0106 0.0191

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0536 0.0605 0.0025 0.0056 0.0866 0.0293 0.0368 0.0212 0.0150 0.0667 0.0062 0.0218 0.1284 0.0062 0.3223 0.0810 0.3067 0.0823 0.0150 0.0268 0.1727 0.0137 0.0368 0.0430 0.0062 0.0150 0.0044 0.0037 0.0006 0.0056 0.0012 0.0012 0.0062 0.0106

7.411 8.438 1.067 1.255 6.245 1.528 4.594 0.461 0.015 0.893 3.299 7.034 3.239 3.041 9.901 3.477 0.303 6.176 4.584 0.268 8.994 4.767 1.389 4.360 2.947 4.217 0.189 0.020 0.020 0.228 0.010 0.010 0.084 0.134

18.3 40.2 58.6 44.6 36.8 44.5 37.7 44.2 41.1 54.4 45.8 45.3 63.2 72.1 65.1 62.9 57.6 52.7 71.9 48.5 67.1 48.8 91.6 54.5 66.8 53.9 49.8 82.2 62.6 75.5 48.2 60.2 64.5 64.4

a Liquid enthalpy wells b Selected, corresponds to the average of Na/K and quartz geothermometer temperatures, except for Reykjanes, where quartz geothermometer temperature was used (see text).

CHAPTER 2.

Figure 2.3: Potential mineral buers controlling CO2 gas concentrations in the initial aquifer uid. For the dilute uid activities of clinozoisite of 0.25 and 0.1 are shown. Prehnite activity was selected as 0.9. For the saline uids, the activities of clinozoisite, grossular and prehnite are 0.1, 0.2 and 0.82, respectively.

25

Table 2.5: Mineral assemblages potentially controlling CO2 , H2 S and H2 concentrations and respective

K -temperature

equations (Karingithi et al., 2008). Temperature equations are valid in the range 0350

at Psat . Unit activity was

selected for all minerals and liquid water.

# Species Reaction Log K (T) 3 3 1. CO2 czo + cal + 2 qtz = 2 pre + CO2,aq 1.831 22843/T2 1344.4/T + 0.00829T 0.455 log T 2 2. CO2 5 czo + cal + 3 qtz = 3 gro + 1 H2 O2l + CO2,aq 2.327 58215/T2 1829.2/T + 0.01059T 0.561 log T 5 5 5 1 2 3. H2 S 1 pyr + 1 pyrr + 3 pre + 21H2 Ol = 3 epi + H2 Saq 2.052 215218/T2 1658.7/T + 0.00856T 0.509 log T 3 3 3 1 H 2.020 188233/T2 1504.4/T + 0.00760T 0.528 log T 4. H2 S 4 pyr + 1 pyrr +1H2 Ol = 24 mt + 4 2 Saq 2 2 2 2 5. H2 S 3 gro + 13 pyr + 13 pyrr + 3 qtz + 3 H2 Ol = 3 epi + 3 wol + H2 Saq 1.862 253145/T2 1595.2/T + 0.00780T 0.452 log T 6. H2 S 2gro + 4 pyr + 2 mt + 2qtz 2 2H2 Ol = 2epi + 2wol + H2 Saq 1.549 383405/T2 1774.0/T + 0.00820T 0.303 log T + 4 2 7. H2 3 pyrr + 2 pre + 33H2 Ol =1 3 epi + 2 pyr + H2,aq 1.358 1420.4/T + 6.777 104 T + 5.611 106 T2 0.391 log T 3 3 3 8. H2 2 pyrr +4H2 Ol = 24 pyr +44 mt + H2,aq 2 1.436 1131.3/T 1.866 104 T + 5.377 106 T2 0.454 log T 2 9. H2 3 gro + 3 pyrr + 3 qtz + 3 H2 Ol = 2 epi + 3 wol + 2 pyr + H2,aq 1.241 1519.9/T + 8.818 104 T + 4.693 106 T2 0.336 log T 10. H2 6gro + 2mt + 6qtz + 4H2 Ol = 6epi3+ 6wol + H2,aq3 1.570 5346.3/T + 0.00880T 6.479 106 T2 + 1.113 log T

CHAPTER 2.
The equilibrium constant curves incorporate the average activities of the clinozoisite (0.25 and 0.1), Al-prehnite (0.9 and 0.82) and grossular (0.8) components in epidote, prehnite and garnet, respectively (see Fig. 2.3). Many of the data points for the dilute uids fall close to the equilibrium curve. Yet there are some systematic dierences between elds. At Kraa, three wells (16, 20 and 24) have high CO2 relative to equilibrium. The CO2 content of fumaroles and wells rose drastically in Kraa following an episode of magma intrusion into the roots of the geothermal system in the period 19751984 (rmannsson et al., 1989; Gudmundsson and Arnrsson, 2002). Since the magmatic event, the CO2 concentrations in the well discharges have declined in some wells (Gudmundsson and Arnrsson, 2002), but increased in others, depending on their location in relation to the newly intruded magma body. It is concluded that the high CO2 in wells 16, 20 and 24 is the consequence of high CO2 ux from the magma intrusion, too high for equilibrium with mineral assemblages to be closely approached in the respective aquifers. In the other wells at Kraa and at Nmafjall, the CO2 At Nesjavellir, concentration is close to equilibrium for a clinozoisite activity of 0.1.

the CO2 concentrations for most of the wells are lower than the equilibrium concentrations. Likely, this is a consequence of inadequate supply of CO2 from the magma heat source to the geothermal system, making calcite unstable. Equilibrium between +2 + 2 epidote, prehnite, quartz and solution xes aqueous Ca /(H ) activity ratios. From + +2 the following reaction CaCO3,calcite + 2H = Ca + CO2,aq + H2 Ol it is seen that +2 + 2 a specic CO2 partial pressure is required to stabilize calcite, if Ca /(H ) activity ratios are xed. For the saline uids at Svartsengi and Reykjanes comparison is made with another mineral assemblage, one including garnet rather than prehnite (see reaction 2 in Table 2.5). Garnet is abundant as hydrothermal mineral in these areas (Lonker et al., 1993) whereas prehnite is rare. Carbon dioxide concentrations at Reykjanes are very close to equilibrium with this buer. Two of the wells at Svartsengi show CO2 concentrations signicantly above the equilibrium curve but the four remaining are close to the curve.

2.10.2 H2 S and H2
These two gases are likely to equilibrate with the same mineral assemblage. The assemblages likely to be involved, as deduced from the hydrothermal minerals in the geothermal systems considered are given in Table 2.5 (reactions 3 to 6 for H2 S and 7 to 10 for H2 ). epidote or magnetite yield very similar equilibrium constants in the range 180320 The mineral assemblages involving pyrite and pyrrhotite and either prehnite + C for

the selected epidote and prehnite compositions, both for dilute and saline uid systems (Figs. 2.4 and 2.5). The dierence at 200 C is close to zero, increasing to about 0.3 logK units at 300 C. The dilute uids at Kraa, Nmafjall and Nesjavellir are close to equilibrium with these two assemblages. Overall, the match is, however, better for the prehnite-epidote bearing assemblage although it is not possible to determine for individual samples which assemblage may be involved. The average departure from equilibrium for the prehnite-epidote containing assemblage for Kraa and Nesjavellir is 0.05 and -0.04 log mol/kg with a standard deviation of 0.2. These deviations are within the error in the thermodynamic data of the minerals. A systematic dierence is observed

27

2.10. MINERAL-GAS EQUILIBRIA

Figure 2.4: Mineral buers controlling H2 S in the initial aquifer uid. Selected activities are 0.75 and 0.9 in the dilute uids for epidote and prehnite, respectively, and 0.9, 0.82 and 0.2 in the saline uids for epidote, prehnite and grossular, respectively.

between areas, the Nesjavellir samples tending to be the highest in H2 S in relation to the aquifer temperature. At Kraa and Nesjavellir, and in particular Nmafjall, a strong magnetic low is associated with the geothermal elds (Plmason, 1975; Bjrnsson et al., 1986). This has been taken to indicate that the primary magnetite of the basalt is unstable, dissolved by the geothermal uids. By this interpretation it seems likely that H2 Saq concentrations in the initial aquifer liquids are controlled by close approach to equilibrium with the pyrite, pyrrhotite, epidote and prehnite mineral assemblage (reaction 3 in Table 2.5). The H2 concentrations are similar to or higher than those predicted by equilibrium with the epidote-prehnite assemblage and by as much as 0.4 log mol/kg (Fig. 2.5). Three samples are close to equilibrium, two from Kraa (wells 21 and 27) and one from Nesjavellir (well 20). Another three aquifer uids are signicantly lower than the equilibrium values, two from Nesjavellir (wells 10 and 14) and one from Kraa (well 24). All these wells, except Nesjavellir 20 have liquid enthalpy. The apparent inconsistency

28

CHAPTER 2.

Figure 2.5: Mineral buers controlling H2 in the initial aquifer uid. The activity of epidote is 0.75 and 0.9 in the dilute and in the saline elds, respectively and the activity of prehnite is 0.9 and 0.82, respectively. For grossular, the selected activity is 0.2.

between H2 S and H2 is considered to result from the presence of vapor in the initial aquifer uid. The vapor fraction is apparently suciently large to signicantly raise the H2 concentrations but not those of the more soluble H2 S. This vapor fraction has been estimated on the assumption that both aqueous H2 S and H2 concentrations are xed by equilibrium with the mineral assemblage pyrite, pyrrhotite, epidote and prehnite. The highest vapor fraction value for excess enthalpy wells is 0.04 by mass and the average is 0.018. A value of 0.04 by mass at 300 C corresponds to 40% by volume and 0.018 corresponds to 22%. The H2 S concentrations in the saline uids are close to equilibrium with a mineral assemblage containing garnet, epidote and wollastonite (equation 5 in Table 2.5). Particular feature is the large variation in the H2 S temperatures in the Svartsengi aquifer uid, where both the Na/K and quartz geothermometers and the measured down-hole temperatures are very constant, around 240 C. One data point for Svartsengi (well 8), which yields the lowest aquifer uid H2 S concentration, involves an air contaminated

29

2.11. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA

vapor sample. Is is known that sulde reacts fast with O2 in alkaline medium, and therefore, it is concluded that the low H2 S temperature is faulty and due to air contamination of the sample. The remaining ve samples scatter around the equilibrium curve, the maximum departure being around 0.3 log mol/kg. Four of the samples in Svartsengi and both samples in Reykjanes show too low H2 equilibrium temperatures relative to that mineral assemblage.

2.11 Individual mineral-solution equilibria

If the aqueous concentrations of CO2 , H2 S and H2 are controlled by equilibria with particular mineral assemblages, the individual minerals in these assemblages should be in equilibrium with the solution. Below, we present results obtained for the state of mineral-solution equilibria for individual minerals. Mineral saturation is expressed in terms of saturation index (SI) dened as

SI = log
where

Q K

(2.11)

represents activity product and

the equilibrium constant.

2.11.1 Calcite and wollastonite

The majority of the aquifer uids are rather close to calcite saturation (Fig. 2.6). For Nmafjall and Kraa, the results indicate some over-saturation, the average SI values being 0.28 and 0.46, respectively. On average aquifer waters at Nesjavellir are very close to calcite saturation, average SI value is -0.11. At Svartsengi and Reykjanes, the aquifer water is systematically calcite under-saturated, or by -0.57 SI units in the case of Svartsengi and it falls down to -1.03 at Reykjanes. Monitoring studies at Svartsengi have indicated some depletion in the aquifer liquid concentration of CO2 and slight cooling (Steingrmsson, 1989). The cause is boiling and simultaneous formation of a steam cap over the liquid reservoir (Gudmundsson and Thrhallsson, 1986). The cooling has led to slight decrease in the pH of the aquifer water and this, together with the decrease in dissolved CO2 concentration has turned the aquifer liquid calcite under-saturated. The calculated pH of the aquifer water for the two samples from Reykjanes is 4.47 and +2 + 2 4.39. These values seem low. The Ca /(H ) activity ratios for the Reykjanes and Svartsengi aquifer waters are correspondingly low relative to those at equilibrium with mineral buers that potentially could control this activity ratio (Fig. reactions considered are: 2.7). The two

3 3 pre + 2H+ = czo + qtz + 2H2 Ol + Ca+2 2 2

and,

(2.12)

3 4 2 3 gro + 2H+ = H2 Ol + czo + qtz + Ca+2 5 5 5 5

(2.13)

+2 + 2 The low Ca /(H ) activity ratios correlate well with negative SI values for calcite.

The cause of the low calculated aquifer uid pH-value for Reykjanes and some of the

30

CHAPTER 2.

Figure 2.6: Saturation indices of selected alteration minerals. Endmember activities are the same as described in Fig. 2.3 to 2.5.

31

2.11. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA

Figure 2.7: Ca

2+

/(H )

+ 2

ratio versus temperature. Symbols for various areas are

the same as in Fig. 2.3 to 2.5. Mineral assemblages clinozoisite+prehnite+quartz and grossular+clinozoisite+quartz are also shown. Equations are modied from Karingithi et al. (2008), with activities of clinozoisite, prehnite and grossular of 0.1, 0.9 and 0.2, respectively.

Svartsengi samples is not known, nor is the calcite under-saturation observed at Reykjanes but equilibrium with calcite is rapidly attained at high temperatures (Zhang and Dawe, 1998). A process that could produce calcite under-saturated reservoir uid is degassing with respect to CO2 by depressurization boiling and rapid re-equilibration of pH, possibly by uptake of OH into layer silicates. The dilute aquifer waters are close to wollastonite saturation whereas the saline waters are signicantly under-saturated. As for calcite, the wollastonite under-saturation +2 + 2 in the saline aquifer uids is attributed to low aqueous Ca /(H ) activity ratios.

2.11.2 Andradite-grossular, epidote-clinozoisite, prehnite

A large scatter in SI values is observed for the endmembers of all these solid solution minerals. Part of the large scatter is the consequence of the stoichiometry of the respec+ tive mineral-solution reactions. As an example, in the garnets, H is raised to the power 4, which amplies in the same proportion the uncertainties on pH values. The results for the Fe endmembers of the garnet and epidote indicate systematic over-saturation. This is not considered real, but due to over-estimation of the Fe(OH)4 species activity due to faulty thermodynamic data on iron hydrolysis constants and possibly also in the selected thermodynamic properties of Fe(OH)4 as given by Diakonov et al. (1999). The saturation indices for all the Al-endmembers, grossular, clinozoisite and Alprehnite show an apparent over-saturation of the aquifer uids with respect to these phases. As for Fe-bearing minerals, one possible cause may be faulty thermodynamic +2 data on Al-species and in particular on the Al-Si dimer. Ca removal by calcite precipitation from the owing uid may also be involved if insucient time is allowed for re-equilibration.

32

CHAPTER 2.

2.11.3 Magnetite, pyrite and pyrrhotite

The over-estimation of the Fe(OH)4 due to faulty thermodynamic data leads to an 2+ under-estimation of the Fe species activity. This has an inuence on the equilibrium 2+ calculations of all Fe bearing minerals, i.e. pyrite and pyrrhotite and magnetite,

which all show a similar pattern of under-saturation, with more negative SI values at higher temperature (Fig. 2.6).

2.11.4 N2 and Ar
In vapor samples, N2 /Ar molal ratios range between 18.4 and 92.1 (Table 2.2). In air saturated water (ASW) and seawater (ASS) at 5 C the N2 /Ar ratios are 37.2 and 39.4, respectively. If two samples are exempted (sample 04-3007 from well 12 at Nmafjall and sample 04-3050 from well 20 at Nesjavellir), N2 /Ar ratios range between 37.0 and 82.2 or between that of air-saturated water and air (Fig. 2.8). A possible explanation of these ratios is that the initial aquifer uid is represented by ASW containing minor amount of air bubbles. However, to produce a N2 /Ar ratio of 50, requires addition of 1.3 mmol of N2 from air to 1 kg of water and correspondingly 0.026 mmol for Ar. Fig. 2.9 shows the eect of addition of air bubbles to air-saturated water. As the Ar concentration increases, the N2 /Ar ratio approaches that of air. On the other hand, boiling of ASW and of a selected mixture of ASW and air with a N2 /Ar ratio of 70 produces higher N2 /Ar ratios, for a given Ar concentration, than allowed by air addition only. Two dierent types of boiling are shown. One that is a the uid is allowed to equilibrate with the total amount of steam at once, and an

system boiling,

closed system boiling, where open

step of temperature drop (0.01

which is in fact a multi-step boiling where the steam formed at each C in this case) is removed before the next fraction of

steam is formed. The latter model produces faster degassing of the aquifer uid for a given total mass fraction of steam. On the other hand, Fig. 2.9 shows that this boiling model yields higher N2 /Ar ratios for a given Ar concentration. The initial aquifer uid concentrations for N2 and Ar have been calculated for all the wells considered for the present study. For wells with discharge enthalpies close to liquid enthalpy (Table 2.1) the total well discharge composition was taken to represent the initial aquifer liquid composition. For excess enthalpy wells, two models were selected to calculate N2 and Ar concentrations in the initial aquifer uid. One of the models is the same as that used to calculate reactive gases in initial aquifer uid, the segregation model. The other model allows for addition of gas-free steam to the uid owing into wells (see Arnrsson et al., 2007, model 4). It is envisaged that evaporation of capillary water in the formation may add steam to the owing uid. Since all the wells considered for the present study have been producing for many years, it is considered reasonable that this capillary water has already been largely degassed. Model 4 yields higher N2 and Ar concentrations in the initial aquifer uid because it assumes dilution by addition of gas-free steam to the owing uid. The magnitude of this dilution is directly related to the amount of steam formed by vaporization of capillary water. The average aquifer Ar concentrations in the dilute uids producing into liquid enthalpy wells is 0.015 mmol/kg, the range being 0.002 to 0.028 mmol/kg. Two wells

33

2.11. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA

Figure 2.8: Argon versus N2 in initial aquifer uids for all elds. seawater (ASS, Weiss, 1970) at

Also shown

are air-saturated water (ASW, Fernndez-Prini et al., 2003) and air-saturated

5 C,

as well as ASW ratio and air ratio.

Figure 2.9: Inuence of air addition and boiling on the N2 /Ar ratio versus Ar concentration in aquifer uid. Continuous line shows addition of air bubbles to air-saturated water (ASW), broken and dotted lines show eect of boiling in a closed system and an open system, respectively, on the N2 /Ar ratio and Ar concentration in the boiled liquid (see text). Samples calculated in this study are also shown. Symbols for various areas have the same meaning as on Fig. 2.8, open and full symbols showing liquid and excess enthalpy wells, respectively.

34

CHAPTER 2.
are very low in Ar, well 21 at Kraa and well 14 at Nesjavellir (Table 2.4). These two wells are marginal to their respective well elds and may represent the degassed uid owing away from the major upow. If these two samples are exempted, the average Ar concentration is 0.019 mmol/kg, which is that of air-saturated water at 5 C, which is about the average annual air temperature at Nesjavellir. The saline aquifer water at Svartsengi is signicantly degassed with respect to Ar, due to its boiling and formation of a steam cap on the top of the liquid reservoir, the average being 0.010 mmol/kg. The geothermal seawater in producing aquifers at Reykjanes contains 0.015 mmol/kg of Ar, which corresponds very well with air-saturated seawater at 5 C. The segregation model yields Ar aquifer uid concentrations which are, with one exception, below that of air-saturated water, the average being 0.009 mmol/kg. By contrast, the model that allows addition of gas-free steam to the owing uid gives on average 0.021 mmol/kg, the range being 0.003 to 0.063 mmol/kg. In view of the modelling of aquifer uid Ar concentrations, it seems very likely that the combination of several processes explains the observed N2 /Ar ratios (Fig. 2.9). Possible processes causing the elevated ratios, above air-saturated water, are air enriched source water, boiling, contribution of N2 from the magma heat source or possibly decaying organic matter in paleosoils. Air contamination during sampling may also contribute, however in this case Ar concentrations would likely be higher than the observed values.

2.12 Discussion and conclusions

Wells drilled into liquid dominated geothermal reservoirs sometimes have liquid enthalpy but commonly excess enthalpy. The selection of a model to calculate the initial aquifer uid composition is likely one of the major sources of error in calculating the aquifer uid compositions from wellhead data on excess enthalpy wells. For wells with liquid enthalpy it is considered to be a reasonable assumption to take total well discharge composition to represent the initial aquifer uid composition. Excess enthalpy may be caused by phase segregation in producing aquifers or conductive heat transfer from the aquifer rock to the uid owing into wells. Aquifer uid compositions calculated for excess enthalpy well discharges applying the phase segregation model yield results consistent with compositions calculated from liquid enthalpy wells when assuming the total discharge composition of the latter to be equal to the total aquifer uid composition. The segregation model also yields consistent results for the quartz and Na/K geothermometers. It is therefore concluded that the excess enthalpy of the wells considered for the present study is for the most part produced by phase segregation although conductive heat ow from aquifer rock may also contribute. The composition of a well discharge may dier from that of the initial aquifer uid not only as a consequence of phase segregation but also by precipitation or dissolution reactions that can occur when extensive boiling causes changes in the chemical properties of the uid but also by reaction with casing and wellhead material. Elements present in low concentrations in the uid, which also are chemically reactive, are subject to the largest concentration changes between undisturbed aquifer and wellhead. They include Ca in dilute waters, Fe and possibly Al, along with many trace elements. Even if equilibria are upset between solution and individual mineral in assemblages that

35

2.12. DISCUSSION AND CONCLUSIONS

control the concentrations of components present in high concentrations in the uid, such as the major gases (CO2 , H2 S and H2 ), the well discharge composition will reect the correct concentrations of such components in the initial aquifer uid. Calculation of initial aquifer uid composition is only the rst step in assessing the state of equilibrium between particular species in the aqueous phase and minerals. The next step involves calculation of speciation distribution in the aquifer uid to obtain activity products (Q) for specic mineral-solution reactions and the nal step is to calculate equilibrium constants for these reactions from thermodynamic data. It is not possible to quantitatively assess the overall error. Yet, is is evident that the cumulative error on the minerals alone is greater that the departure from equilibrium of aqueous H2 S with the mineral assemblage pyrite, pyrrhotite, epidote and prehnite in the case of the dilute waters. Calculation of the equilibrium constant for this reaction assumed pure FeS and FeS2 . If the FeS is decient in iron, the equilibrium curve is shifted to 2 lower values. The presence of S in FeS2 has the same eect. Sulde mineral analysis is missing for quantitative estimation of the eect of the iron-sulde mineral composition on the equilibrium constant. Secondly, the uncertainties on the thermodynamic data on these mineral, as given by Robie and Hemingway (1995) may produce an error as high as 0.3 log mol/kg on the equilibrium H2 S concentration, in addition to the error produced by the silicate minerals, epidote and prehnite. In the saline waters at Svartsengi and Reykjanes, H2 S concentrations in the aquifer uids match well equilibrium with the mineral assemblage containing pyrite, pyrrhotite, quartz, garnet, epidote and wollastonite.

Aquifer uid CO2 concentrations in the dilute uids show larger variation than those of H2 S. The CO2 content of the Nesjavellir aquifer uids is low relative to equilibrium with the clinozoisite+prehnite+calcite+quartz assemblage. The selected activity of clinozoisite has a strong inuence on the value taken by the equilibrium constant because of the sensitivity of the clinozoisite activity to the composition of the epidote. The selected clinozoisite activity of 0.1 is within the measured clinozoisite composition in this area, or even 0.05 which brings the equilibrium curve close to the calculated aquifer uid CO2 concentration. On the other hand, low CO2 concentrations in the aquifer uid could be the consequence of insucient supply of CO2 to the geothermal system from the magma heat source. At Nmafjall and Kraa, CO2 aquifer uid concentrations match generally well equilibrium with the clinozoisite+prehnite+calcite+quartz assemblage. In a few instances it is higher due to rapid degassing of magma intruded into the roots of the geothermal system in the period 197584. At Reykjanes and Svartsengi, equilibrium with uid CO2 and clinozoisite+calcite+quartz+grossular rather than prehnite is closely approached. Grossular garnet is abundant in the reservoir rock in these elds but prehnite is rare. CO2 . The same mineral assemblage appears to control H2 and H2 S aquifer uid concentrations in the saline uid. Most of the wells at Kraa, Nmafjall and Nesjavellir have higher H2 aquifer uid concentrations than expected at equilibrium with the mineral assemblage involving H2 S. The uid concentrations of the gases were taken to represent liquid concentrations, when calculating the respective mineral-gas equilibrium Production from the Svartsengi reservoir has led to decreasing aquifer uid CO2 concentrations in some of the wells, whereas two wells have excessive

36

CHAPTER 2.
constants. The apparent high aquifer liquid H2 concentrations are considered to reect the presence of equilibrium vapor in the initial aquifer uid. This vapor has a clear eect on H2 because it is sparingly soluble in water but not on the more soluble CO2 and H2 S. The excess H2 indicates an equilibrium vapor fraction that varies between 0.04 and 4% by weight. Although the initial aquifer liquid concentrations of the reactive gases CO2 , H2 S and H2 seem to be generally controlled by close approach to equilibrium with specic mineral buers, the same does not appear to be the case for many of the minerals which form parts of these assemblages. This apparent discrepancy is considered to be partly due to changes in minor element concentrations in the uid between aquifer and wellhead due to precipitation reactions. In the case of Fe-bearing minerals it is also due to +2 faulty data on iron hydrolysis constants leading to under-estimation of the Fe species but over-estimation of Fe(OH)4 . The thermodynamic data selected for Fe(OH)4 to retrieve equilibrium constants may also contribute. Nitrogen and Ar concentrations in the initial aquifer uid were calculated according to a segregation model and model 4 in Arnrsson et al. (2007) which assumes that the excess enthalpy is due both phase segregation and addition of gas-free steam by evaporation of capillary water. The two models yield almost the same N2 /Ar ratios, but they dier in Ar and N2 concentrations, the latter giving higher gas concentrations in the initial aquifer uid. Our results show large variation of N2 and Ar concentrations and N2 /Ar ratios within elds. Most of the well discharges are depleted in Ar, indicating that the initial aquifer uid is represented by degassed uid. The observed N2 /Ar ratios cannot be produced only by boiling of air-saturated water. Boiling of such water causes decrease in the N2 /Ar ratio of the boiled liquid. 50. Early formed vapor that may mix with uid at higher levels in the reservoir can only produce N2 /Ar ratios up to around Liquid N2 /Ar ratios of up to 5060 can be produced by boiling of air-saturated However, higher ratios can only be explained by an water containing entrapped air.

additional source of N2 to the uid, either magmatic or organic.

37

Chapter 3 Processes inuencing As, B and Cl concentrations in uids of volcanic geothermal systems in Iceland
Giroud, N. and Arnrsson, S.

Abstract
The concentrations of arsenic, boron and chloride are relatively low in uids of hightemperature geothermal systems in Iceland. and 50150 ppm, respectively. In systems, where the convecting uid is meteoric by origin, As, B and Cl contents are typically 50150 ppb, 0.55 ppm The reason is low concentrations of these elements In the seawater systems of Reykjanes and in the basaltic volcanics of the country.

Svartsengi, As concentration levels are about the same as in the dilute uid systems. By contrast, B concentrations are substantially higher and those of Cl much higher due their presence in the source seawater uid. Boron and Cl act as incompatible in these geothermal systems. Arsenic in the deep uid is also highly mobile. During boiling and mixing of the geothermal water with cold groundwater, As is eectively removed from solution, probably mostly by its uptake into ferri-hydroxides and clay minerals but also into sulphide minerals, particularly when the liquid boils extensively. In hot spring waters of mature high-temperature systems, representing boiled deep water, Cl/B and Cl/As ratios are about the same as those of basalt indicating near stoichiometric basalt dissolution with respect to these elements. Arsenic does not partition signicantly into the vapor phase, at least at vapor pressures as high as 40 bar, but B does. From available experimental data on the distribution coecient for B between liquid and vapor, it is concluded that equilibrium distribution is closely approached at wellheads of wet-steam wells. In the high-temperature systems of Nmafjall and Kraa, B and Cl contents of the uid indicates that it is determined by the mixing of components from two sources. One

39

3.1. INTRODUCTION
is the basaltic rock with which the uid has interacted and the other magma volatiles. The rock interaction component represents uid that has reacted to a relatively limited extent. It is similar to the sub-boiling liquid in the upper Kraa reservoir. The Cl and B content of the magmatic component is some 200 and 30 ppm, respectively. Fresh magma was intruded into the roots of the Kraa geothermal systems during a volcanic episode in 197584 and magma from Kraa owed along ssures into the Nmafjall geothermal system. A substantial fraction of the B and Cl in the geothermal uid of the Kraa and Nmafjall systems is derived from the magmatic source. At Nesjavellir similar kind of mixing explains the B and Cl content of the uid. However, the rock interaction component is represented by quite extensively reacted water. Here little Cl appears to come from the magma but a substantial fraction of the B. The welleld at Nesjavellir is adjacent to a volcanic ssure that erupted

2000 years ago.

By comparison of data from

the seawater systems at Reykjanes and Svartsengi with the meteoric-water systems, it seems likely that a substantial fraction of the B in the uid of these seawater systems is of magmatic origin. The mobility of As is signicantly lower than those of Cl and B in aquifer uids producing into wet-steam wells. This is considered to be due to its removal from solution into sulphide minerals. Their formation is most intense in zones of extensive boiling. Magmatic volatiles contribute little if any As to the geothermal uid.

3.1 Introduction
Arsenic, boron and chloride are important components in geothermal uids. Both As and B are environmentally important (Smedley and Kinniburgh, 2002; Axtmann, 1975; Badruk and Kabay, 2003; Arnrsson, 2004). Arsenic is one of the most poisonous and carcinogenic element found in natural waters and elevated B concentrations in such waters may have adverse eects on the growth of many types of plants (Cengiz, 2007). Boron and Cl provide important information on the source uid to geothermal systems and various processes occurring within such systems including mixing and boiling (Giggenbach, 1991; Arnrsson, 1985; Ellis and Mahon, 1977). All these elements are highly mobile in geothermal systems. Chloride is generally taken to be conservative, i.e. once in solution it stays there (Giggenbach, 1991). Boron may also be conservative, depending on the type of minerals that form from solution and take up B. Arnrsson and Andrsdttir (1995) concluded that B essentially behaves as a conservative element in the basaltic environment of Iceland. Due to its correlation with Cl, As in geothermal systems has also been taken to be conservative although closer examination shows that it is not. Arsenic can be removed from solution by its uptake into sulphide minerals and iron hydroxides (Ballantyne and Moore, 1988; Smedley and Kinniburgh, 2002). In common types of volcanic rocks all these elements are present to some extent in easily soluble compounds. Thus hydrothermal experiments have demonstrated that they are largely transferred into solution without appreciable alteration of the rockforming minerals (Ellis and Mahon, 1964, 1967). Both As and B form volatile species at elevated temperatures (Kuritani and Nakamura, 2006; Glover, 1988; Ballantyne and Moore, 1988). The only types of minerals that eectively extract B from solution are clays, in particular illite (Harder, 1969). Such minerals may also incorporate As (Onishi, 1978) al-

40

CHAPTER 3.
though sulphides and ferri-hydroxides are more important (Bamford et al., 1980; Christensen et al., 1983). The ratios of Cl/B and Cl/As in seawater are much higher than in common types of igneous and metamorphic rocks due to uptake of As and B into marine sediments. The concentrations of As, B and Cl in oceanic basalts formed at diverging plate boundaries, such as Iceland, are much lower than in volcanic rocks formed on converging plate boundaries (Arnrsson, 2002; Arnrsson, 2003; Arnrsson and Andrsdttir, 1995; Sigvaldason and skarsson, 1976; Ellis and Mahon, 1964, 1967). The same applies to uids in volcanic geothermal systems. Thus B concentrations of less than a few ppm are typical for uids of volcanic geothermal systems in Iceland whereas they may be as high as 100 ppm in such systems by converging plate boundaries (Ellis and Mahon, 1977). Corresponding numbers for As are

<0.1

ppm and as much as 50 ppm, respectively It is likely that these elements are

(Arnrsson, 2003; Ballantyne and Moore, 1988).

added to andesitic and related magmas that form by partial melting of hydrated mantle rock, by transfer of volatile compounds rising from the heated underlying slab of marine sediments. Consequently rocks formed from this magma are rich in these elements as well as uids of geothermal systems forming over magmatic intrusions in this geological environment. Present interest to enhance development of geothermal resources to reduce emission of greenhouse gases into the atmosphere by fossil fuel combustion requires careful assessment of the long-term environmental impact of such development. One aspect of this is atmospheric and surface and groundwater contamination with respect to Cl but in particular B and As as well as an understanding of the geochemistry of these elements in volcanic and other types of geothermal systems. The present study focuses on the distribution of As, B and Cl in uids of nine volcanic geothermal systems in Iceland. Almost all known volcanic geothermal systems at diverging plate boundaries are sub-marine except those of Iceland. The uids of the Icelandic systems provide information of value for the understanding of the processes determining the content of these elements not only in basaltic environment at diverging plate boundaries but they also throw some light on the global cycle of these elements and therefore also their distribution in volcanic rocks and associated uids by converging plate boundaries.

3.2 Geological features

3.2.1 Overview
High-temperature volcanic geothermal systems in Iceland are located within the active belts of volcanism and rifting (Fig. 3.1). These volcanic belts represent the boundary of the American and European lithospheric plates. Yet, between them in South Iceland there is a triangular micro-plate, the Hreppar plate. The high-temperature systems that are marginal to the active volcanic belts (see Fig. 3.1) are most likely mature and in the process of cooling down as they drift out of these belts and are cut from their magmatic heat source. The high-temperature geothermal systems may be divided into groups This heat depending on their geological setting and the nature of their heat source.

41

3.2. GEOLOGICAL FEATURES

Figure 3.1: Map of Iceland showing the active volcanic belt systems and hightemperature areas.

source may be a sheeted dyke complex, high-level sills, cone-sheets, irregularly shaped small intrusive bodies and more deep-seated stocks in the roots of a major volcanic complex, typically associated with calderas. Parasitic systems to volcanic complexes are also known, where magma has been intruded laterally along ssures from a major magma body below the central volcano, such as Kraa (Bjrnsson et al., 1977). Due to crustal accretion at the plate boundary, geothermal systems initially on the plate boundary will drift with time out of the volcanic belts and become displaced from the magmatic heat source. In this way high-temperature geothermal systems can develop into low-temperature systems. For the present study, geothermal uids from springs and wells were collected from nine active high-temperature areas. They are Kraa, Nmafjall, Landmannalaugar, Further, Nesjavellir, Hveragerdi, Hveravellir, Geysir area, Svartsengi and Reykjanes.

several samples were collected from wells in the Southern Lowlands low-temperature area. The location of these areas is shown on Fig 3.1. Nmafjall is considered to be a parasitic system to the Kraa area. Nesjavellir and Hveragerdi are separate parts of the larger Hengill area. Below a brief description will be given of the geology of each area.

3.2.2 Kraa and Nmafjall

The Kraa geothermal eld in northern Iceland lies astride the plate boundary and is located within the caldera of the Kraa central volcanic complex (Stefnsson, 1981). The Nmafjall geothermal area lies outside this caldera, about 10 km to the south of the hill of Leirhnjkur which is located in the center of the Kraa caldera. An active ssure swarm runs through the Kraa caldera. The Nmafjall system lies across the eastern

42

CHAPTER 3.
part of this ssure swarm (Saemundsson, 1991) which is about 100 km long and 5 8 km wide (Saemundsson, 1974, 1978, 1983). The volcanic rocks in the area are mostly basaltic in composition although silicic magma has also been erupted (Jnasson, 1994). Basaltic and silicic eruptions have occurred in sub-glacial and Recent times in the area, both within and outside the Kraa central volcano (Saemundsson, 1991). Temperatures in deep drillholes (2000 m) at Kraa and Nmafjall are as high as 350 C and 320 C, respectively (rmannsson et al., 1987). A major volcanic-rifting episode started on the Kraa ssure swarm at the end of 1975. A total of nine volcanic eruptions took place during this episode that lasted until September 1984. Fresh magma was intruded into the roots of the Kraa volcano forming chambers at 37 km depth (Einarsson, 1978). Periodic discharge of magma from this chamber occurred into the ssure swarm to the north or south. On one occasion, 3 a geothermal well at Nmafjall erupted 3 m of magma (Larsen et al., 1978). The content of some common geothermal gases (CO2 and H2 ) rose in well uids and fumaroles at Kraa subsequent to the intrusion of the fresh magma but not at Nmafjall (rmannsson et al., 1982). These observations indicate that other components, which form fugitive compounds at magmatic temperatures, may have been added to the convecting geothermal uid at Kraa, e.g. As, B and Cl.

3.2.3 Landmannalaugar
The Landmannalaugar eld is part of the greater Torfajkull area in central south Iceland which is located at the plate boundary within the eastern active volcanic belt in South Iceland. Torfajkull hosts the largest geothermal area in the country, covering 2 some 200300 km . No drillings have been carried out in this area. Alkaline spring waters, representing the boiled fraction of the deep uid in the geothermal system, are only found in the Landmannalaugar part of the Torfajkull area. In most of the area, surface manifestations are characterized by fumaroles, steam-heated surface waters and hot altered ground. Geochemical geothermometers indicate temperatures as high as 300 C in the Landmannalaugar eld. At Landmannalaugar mixed water occurs in warm and hot springs (Arnrsson, 1985). The Torfajkull region constitutes the largest complex of silicic volcanics in Iceland. Within the Landmannalaugar eld only silicic volcanics are exposed. They include rhyolites and comendites as well as subglacially formed pitchstone and obsidian (varsson, 1992). It is considered that almost all the exposed volcanics formed by sub-glacial A large caldera structure characterizes the Torfajkull region, which eruptions during late Quaternary times, probably during the last glaciation (Saemundsson, 1972). envelopes practically all the thermal manifestations. The silicic formations produce a conspicuous gravity low within the area (Plmason, 1973). A distinct positive gravity anomaly occurs within gravity low taken to reect the existence of basaltic intrusives (Walker, 1974). Likely, the basaltic magma has been trapped under the less dense silicic volcanics forming the heat source to the geothermal system. By this model, it is expected that the chemical composition of the boiled hot spring water at Landmannalaugar is characterized by interaction with silicic rocks although volatile components from the basaltic magma heat source may inuence the gas chemistry of the uid in the geothermal system.

43

3.2. GEOLOGICAL FEATURES

3.2.4 Geysir area and Hveravellir

These areas are described together because their surface manifestations have many things in common. Both areas are quite small and marginal to the active volcanic belts (Arnrsson, 1985). Most of the geothermal activity in both elds occurs within an area that is only a few hundred meters across. It consists of hot springs with boiled deep water. Some of these springs show geyser activity. Warm springs occur in both areas that represent a mixture of the geothermal water and cold groundwater. At Geysir, the mixing occurs at depth, i.e. before the rising hot water becomes degassed as a consequence of boiling. At Hveravellir, on the other hand, the mixing occurs close to the surface between boiled and degassed water and cold groundwater (Arnrsson, 1985). The heat output in both areas is apparently low as deduced from the integrated ow from springs. The rocks in the vicinity of the Hveravellir eld are all basaltic. At Geysir, on the other hand, rhyolitic rocks outcrop although most of the bedrock consists of basalts. The main uid upow feeding the hot springs at Geysir is considered to be along the contact of a rhyolite plug. The spring water at Geysir indeed reects reaction with silicic rocks, such as high uoride and relatively high concentrations of Cl and B compared to thermal waters that have interacted with basalt only. Underground temperatures in these area have been estimated as 250 C or a little higher (Arnrsson, 1985). Deposits of silica sinter are extensive around the hot springs in both areas. It is

considered likely that such deposits cover fracture surfaces in upow channels below the hot springs limiting interaction between water and rock and thus impeding changes in the chemical composition of the rising uid. By contrast, this is not the case for the mixed waters, particularly when the mixing involves a gaseous hot water component. Such mixing leads to the formation of acidic water that is highly reactive (Arnrsson, 1985).

3.2.5 Hveragerdi
The Hveragerdi eld is located at the southwestern boundary of the Hengill area. Drill hole data reveal a temperature of 180230 C (Arnrsson and Gunnlaugsson, 1985). Hot springs are abundant in the area, as well as fumaroles and hot altered ground. Silica sinter deposits are limited. The area is tectonically active although Hveragerdi lies outside the main zone of rifting. In valleys intersecting the hills north of Hveragerdi hydrothermally altered rocks are exposed containing minerals indicative of temperatures in excess of 200 C. Alteration in rocks at depth penetrated by wells in Hveragerdi is intense with minerals indicating temperatures higher than those measured today (Sigvaldason, 1963). Either the system has cooled down or erosion has brought high-temperature hydrothermal minerals closer to the surface. Both explanations are consistent with the geological location of the eld that indicates that it is mature and is in the process of drifting out of the active volcanic belt. Possibly the Hveragerdi system has drifted aside from its original magmatic heat source.

44

CHAPTER 3.

3.2.6 Nesjavellir
The Nesjavellir eld forms the northeasternmost part of the Hengill area in Southwest Iceland. It lies astride the plate boundary and is located within a tectonically active graben. A volcanic ssure that erupted

2000

years ago forms the northwest side of

the graben (Saemundsson, 1963). Permeability is fracture controlled (Bdvarsson et al., 1990). Faults running through the area can be traced through the Hengill mountainous area and towards northeast across the bottom of Lake Thingvallavatn and farther north. The reservoir uid is two-phase (liquid and vapor), at least down to the depths of the deepest wells in the area (2200 m). The highest temperature recorded is > 380 C (the maximum measurable by the instrument) in a well drilled close to the volcanic ssure. This high temperature is perhaps related to proximity to a magmatic intrusion below the 2000 year old eruptive ssure. The geological formations at Nesjavellir above 600 m depth consist primarily of basaltic hyaloclastites and basaltic lavas with the latter becoming more abundant below 600 m (Franzson et al., 1986). Intrusive bodies also increase with depth and exceed 50% of the volume of the rock below 1500 m (Franzson, 1988). Rare granophyric bodies have been identied within the intrusive complex.

3.2.7 Reykjanes and Svartsengi

The Svartsengi and Reykjanes elds lie astride the divergent plate boundary where it is intersected by active ssure swarms that form an angle of about 50 to the plate boundary (Lonker et al., 1993). Sheeted dyke complexes are considered to serve as the magmatic heat source for the Reykjanes and Svartsengi geothermal systems, although sills may also be involved. The rock exposed at the surface and penetrated by wells is solely basaltic, subglacially erupted hyaloclastites, breccias and pillow lavas and tuaceous sediments as well as lava ows formed during inter-glacial periods (Fridleifsson and Albertsson, 2000; Tmasson and Kristmannsdttir, 1972). Intrusions become increasingly abundant with depth, being more than 60 and 80% of the rock below 1500 m depth at Svartsengi and Reykjanes, respectively. Both elds have been extensively drilled. Permeability is fracture controlled. In the deep geothermal reservoir at Svartsengi temperatures vary very little from 500 to 2000 m, being about 240 C. At Reykjanes, the reservoir is two-phase above about 1000 m but sub-boiling at greater depths. The highest temperature recorded is about 320 C at 2000 m depth.

3.3 Fluid compositions

In seven of the nine high-temperature elds sampled the waters are meteoric by origin and low in dissolved solids compared to most high-temperature geothermal waters in the world. This is the consequence of the low Cl content of the basalts with which the waters have interacted (Arnrsson and Andrsdttir, 1995). The higher Cl content of waters from the Landmannalaugar and Geysir elds is due to interaction of the water 2 with silicic rocks. Data on H for these water are similar to that of local precipitation or more negative. When more negative, the source water may be distantly derived

45

3.4. SAMPLING AND ANALYTICAL METHODS

precipitation from higher elevation and further inland or they contain a component or Pre-Holocene water (Arnrsson and Andrsdttir, 1995; Arnrsson, 1995). In two areas, Reykjanes and Svartsengi, the geothermal uid is relatively saline attributable to seawater recharge to the systems (Bjrnsson et al., 1972; Arnrsson, 1978; Ragnarsdttir et al., 1984) The concentrations of the unreactive Cl of the deep unboiled Reykjanes geothermal uid is between

100% seawater (Lonker et al., 1993), measured 2/3

seawater

19,500 1/3

and 23,500 ppm (Arnrsson, 1995; Stefnsson and Arnrsson, 2002; meteoric water (Arnrsson, 1978; Ragnarsdttir et al., 1984).

Arnrsson, 1978). At Svartsengi Cl concentrations correspond to about recharges and

3.4 Sampling and analytical methods

Only a brief description of sampling and analytical techniques is given here. For a more detailed description, the reader is referred to Arnrsson et al. (2006). In the case of wet-steam wells, water and steam samples were taken from two phase pipeline at the wellhead using a stainless steel (N316) Webre separator to separate the phases. Water samples at wells, as well as boiling hot springs, were ltered through a 0.2

m cellulose acetate membrane using a polypropylene or Teon lter holder and col-

lected into low-density polyethylene bottles. An untreated 200 ml sample was analyzed on a Reagent-Free

TM ion-chromatograph (RFICTM , Dionex 2000) for F, Cl and SO4 . A R HNO3 (E. Merck 100441) for major 200 ml sample was acidied with 1 ml Suprapur
element analyses on an Inductively Coupled Plasma - Atomic Emission Spectrometer (ICP-AES) (Al, Ca, Cl, Fe, Mg, Na, Si, Sr). Another 100 ml sample acidied with 1 ml of the same acid was used for trace elements determination on an Inductively Coupled Plasma - Mass spectrometer (ICP-MS), including As and B. Glass bottles with air-tight cap were used for collecting samples for pH and total carbonate carbon determination in the laboratory shortly after sampling. Hydrogen sulde was measured on site by titration with standard mercuric acetate solution, using dithizone as endpoint indicator (Arnrsson et al., 2006). Total carbonate carbon was determined by titration with standard (0.1 M) HCl solution as described by Arnrsson et al. (2006). Steam phase was collected into evacuated Giggenbach bottles (see for example Arnrsson et al., 2006) containing 10 ml of 50% w/v KOH solution and condensed steam was collected into 100 ml polyethylene bottles and acidied with Suprapur

HNO3 for ICP-MS analysis in a manner similar to that for trace element samples of the water phase. Carbon dioxide and H2 S, which dissolved quantitatively in the alkaline solution, were determined as in water samples. Non-condensable gases (H2 , N2 , CH4 , Ar) were analyzed by gas chromatography.

3.5 Data handling

3.5.1 Calculation of aquifer uid composition
Deep aquifer uid composition for wells and boiling hot springs was calculated using the WATCH speciation program (Arnrsson et al., 1982), version 2.3 (Bjarnason, 1994).

46

CHAPTER 3.

Figure 3.2: Phase segregation excess enthalpy model (modied from Arnrsson et al., 2007)

Some of the wet-steam wells included in the present study have liquid enthalpy, i.e. the discharge enthalpy equals that of steam saturated water at the aquifer temperature. Other wells have excess enthalpy, i.e. the enthalpy of the discharged uid is higher than the enthalpy of steam-saturated water at the aquifer temperature. All the geothermal systems considered here are hot-water (liquid dominated) systems (see White et al., 1971) implying that the aquifer uid is liquid water only or liquid water with a small vapor fraction, even in terms of volume, so the enthalpy of the initial aquifer uid is equal to or only slightly higher than that of steam saturated water at the aquifer temperature. Excess well discharge enthalpy is the consequence of increase in the owing uid enthalpy in the depressurization zone around discharging wells. Depressurization boiling in this zone lowers the temperature of the uid, thus creating a temperature gradient between uid and aquifer rock and favoring conductive transfer of heat from rock to uid. Addition of heat to the two-phase uid will not aect its temperature but enhance boiling. Flowing liquid and vapor may separate, at least partly (segregate), in two-phase aquifers, leading to an increase in the steam to water ratio (enthalpy) of the discharge. Such separation results from the dierent ow properties of vapor and liquid, the eects of capillary pressure (adhesive forces between mineral grain surfaces and liquid) and relative permeability (e.g. Horne et al., 2000; Pruess, 2002; Li and Horne, 2004). By these processes the mobility of liquid is reduced relative to that of vapor (Fig. 3.2). In this contribution it is assumed that excess well discharge enthalpy is produced by phase segregation. When this model is selected, conformity between the quartz and the Na/K geothermometers is good. If, on the other hand, it was assumed that the excess enthalpy was caused by conductive heat transfer from aquifer rock to the owing uid, low quartz equilibrium temperatures are obtained, particularly when the

47

3.5. DATA HANDLING

discharge enthalpy is approaching that of dry steam. The steam fraction in the initial aquifer uid has been taken to be zero. This steam fraction can be obtained from data on the concentrations of two gases in the total discharge (preferably H2 and H2 S) and by assuming that their concentrations in f,l the initial aquifer liquid (mi ) is controlled by a specic mineral buer (see Arnrsson et al., 1990, 2007). Studies indicate that the steam fraction in the initial aquifer uid in hot-water volcanic geothermal systems is small, even in terms of volume, such as at Kraa, Iceland (Gudmundsson and Arnrsson, 2002) and Olkaria, Kenya (Karingithi, 2002). When phase segregation occurs in producing aquifers, the mass ow rate of the well discharge is given by

M d,t = M f,t M e,l

where

(3.1) designate well discharge and

denotes mass ow rate. The superscripts

d and f

initial aquifer uid of feed zone, respectively. Superscript zone between

and

the uid phase.

e stands for the intermediate d where phase segregation occurs. The second superscripts indicate Thus, l means liquid and t refers to total ow. From conservation of hd,t M d,t = hf,t M f,t he,l M e,l
(3.2)

enthalpy and mass we further have

and

md,t M d,t = mf,t M f,t me,l M e,l i i i

where

(3.3)

denotes specic enthalpy and

mi

concentration of the

i-th

perscripts have the same notation as in equation (3.1). equations (3.1) to (3.3) leads to

Dividing with

component. SuM d,t through

1 = V f,t V e,l hd,t = hf,t V f,t he,l V e,l md,t = mf,t V f,t me,l V e,l i i i
Common solution of equations (3.4) and (3.5) and isolation of

(3.4) (3.5) (3.6)

V f,t

yields

V f,t =

hd,t he,l hf,t he,l

(3.7)

e,l By selecting a value for h (the enthalpy of liquid water at which phase segregation f,t d,t occurs), the value of V can be obtained from equation (3.7) since h is a measured f,t value, h is known when a value for the aquifer temperature has been selected, because f,t it is assumed that the steam fraction in the initial aquifer uid is zero, so h = hf,l . f,l Steam Tables give h for steam saturated water. e,l Combination of equation (3.4) and (3.6) by elimination of V leads to

md,t = mf,t V f,t me,l (V f,t 1) i i i

(3.8)

The concentrations of individual analyzed components in the deep unboiled aquifer uid can be obtained from analytical data on liquid and vapor samples collected at the surface with the aid of equation (3.8) and the distribution coecient

Ds

for species

48

CHAPTER 3.
between the liquid and vapor phases at the temperature at which phase segregation is taken to occur:

Ds =
where

ne,v s ne,l s s,
superscript

(3.9)

Ds

represents the distribution coecient for species

stands for

vapor and

is the mole fraction given by

ns =
where

Ns P NH 2 O + i Ni s,

(3.10)

Ns

stands for the number of moles of volatile species and

and the sum is for all

such species except H2 O. If we consider a mass of uid containing 1 kg of H2 O, then

NH2 O = 55.51

ns =
where so

ms P 55.51 + i mi s.
For dilute uids,

(3.11)

ms

denotes molal concentration of species

mi

55.51
(3.12)

ms ns = 55.51 mv Ds s = l ms Ps
of species

and

(3.13)

The partial pressure

is given by

Ps = nv Ptot s
where

(3.14)

Ptot

is the total pressure of all gases including H2 O. The solubility constant

(Henry's Law Coecient) of species

in aqueous solution is given by (3.15)

al = Ks fs s
where

Ks

1 1 is the solubility constant (in moles kg bar ),

al s

stands for the activity

of species

in liquid water and

fs

its fugacity over the solution. For dilute uids and

moderate pressure, equation (3.15) may be replaced by

ml = Ks Ps s
Combining equations (4.4), (3.12), (4.9) and (3.16) yields

(3.16)

Ds =
The steam fraction (X boiling at temperature
e,v

55.51 Ks Ptot

(3.17)

) of the owing uid that has formed by depressurization but before phase segregation occurs is given by

Te

X e,v =

hf,t he,l he,v he,l

(3.18)

that

As it is assumed that the steam fraction of the initial aquifer uid is zero, it follows hf,t = hf,l . It also follows from conservation of mass that the concentration of

49

3.5. DATA HANDLING

species

s in the liquid and vapor phases at temperature T e

is related to its concentration

in the aquifer uid by

mf,t = me,v X e,v + me,l (1 X e,v ) i i i

As for the enthalpy in equation (3.18), of species

(3.19)

mf,t = mf,l . i i

to (3.19) by inserting equation (3.17) into (3.18) and isolating

Combination of equations (3.17) me,l , the concentration i

in the liquid phase yields

me,l = s
Having obtained from equation (3.8).

md,t s f,t (X e,v (D e s r,

1)) + 1
(equal to

(3.20)

me,l s

from equation (3.20),

mf,t s

mf,l ) s

can be obtained

For non-volatile species,

that does not partition signicantly

into the vapor phase, equation (3.19) reduces to

mf,t = me,l (1 X e,v ) r r

as

(3.21)

me,v i

is zero. In this case,

mf,t r

can be obtained by inserting equation (3.21) into (3.8).

mf,t = r V f,t
and

md,t r V f,t
V f,t 1 1X e,v

(3.22)

X e,v

can be obtained from equations (3.7) and (3.18), respectively.

For wells with liquid enthalpy, the concentrations of all components in the total discharge were taken to be equal to that of the initial aquifer uid. Thus equation (3.1) reduces to

M d,t = M f,t
From this it follows that: sampling conditions becomes

(3.23) Thus the steam fraction at

f,t

= hd,t X d,v =

and

md,t = mf,t . i i

hd,t hd,l hd,v hd,l

(3.24)

and the concentration of component analogous to (3.19), or

in the initial aquifer uid is given by an equation

mf,t = md,v X d,v + md,l (1 X d,v ) i i i

(3.25)

For boiling hot springs, the quartz equilibrium temperature was taken to represent f the temperature (T ) of the source aquifer to the hot spring water. This gives the f,l enthalpy of the initial aquifer uid, h . Equations (3.24) and (3.25) were thus used to calculate initial aquifer uid compositions. Degassing of the deep aquifer uid during its boiling in the upow zones was adjusted to such a degree that it matched calcite saturation in the unboiled aquifer water. dividing into In the WATCH program this is done by

Ks

an arbitrary factor that can take a value between 0.01 and 1 (see This eectively means that the value of the solubility constant is The WATCH

equation (3.16)).

increased, i.e. the gases are made more soluble than they really are.

50

CHAPTER 3.
program was run until the arbitrary factor gave a CO2 concentration that matched calcite saturation. It is reasonable to assume calcite saturation in the unboiled water below hot springs because studies of drillhole data reveal that calcite saturation is closely approached in the aquifer of hot water (> 50 C) and wet-steam wells in Iceland (Arnrsson, 1978; Arnrsson et al., 1983).

3.5.2 Arsenic, B and Cl concentration in the aquifer uid

Boron and As were determined in both liquid and vapor samples of wet-steam wells (Table 3.1). The concentrations of As in vapor samples is with two exceptions low, less than 0.8% of the concentration in liquid samples and no more than would be expected for carry-over of liquid to vapor. The high As concentration in the vapor of two samples (04-3014 and 04-3032) is considered to be due to carry over as these samples also contain relatively high concentrations of trace elements such as Br and Ti, which do not partition signicantly into the vapor phase. On the other hand, measured B concentrations are signicant in vapor samples and they increase with sampling pressure relative to B liquid concentrations, indicating that B partitions signicantly in the vapor phase (Table 3.1). For these reasons equation (3.21) has been used to obtain As concentrations, as well as those of Cl, in the initial aquifer uid. The of B concentrations in this uid, on the other hand, were derived from equation (3.20).

51

Table 3.1: Arsenic, B and Cl concentrations in liquid and vapor phases of wet-steam wells. Calculated concentrations of As,

B and Cl leached from the rock in the deep aquifer liquid are also shown.
Discharge enthalpy kJ/kg bar-g liquid pH pressure aquifer liquid sample mg/kg sample g/kg sample g/kg sample g/kg sample g/kg uid mg/kg uid uid liquid vapor liquid vapor aquifer aquifer aquifer nonSampling Calc. Cl B B As As Cl B As Cl B As Aquifer temp.b

Sample #

Sampling

Locationa

date

C g/kg g/kg <0.05

0.061 0.056 <0.05 <0.05 <0.05 0.329 0.125 12.3e

nonnonmarinec,f marinef marinef mg/kg g/kg g/kg

<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05
0.186 0.10

04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3007 04-3008 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 05-3004 05-3003 0.348 1.90 78.3 157.0 0.0 183.0 7660 210.0 173.0 7.1 9.7 98.6 89.4 57.5 104.0 0.193 0.317 14.2e 0.051 0.922 0.283 15.5 14.0 14.8 19.0 14.0 5.21 240 14255 4.69 239 12916 5.18 241 13230 7340 7540 5.10 240 13493 7260 4.86 239 13831 7000 172.0 12542 12041 11853 12024 12723 6407 6556 6633 7057 6922 71.0 88.0 80.1 53.5 92.9

20.10.2004 20.10.2004 21.10.2004 21.10.2004 21.10.2004 20.10.2004 21.10.2004 20.10.2004 20.10.2004 20.10.2004 19.10.2004 19.10.2004 10.12.2004 10.12.2004 10.12.2004 10.12.2004 10.12.2004 15.12.2004 09.09.2004 15.12.2004 10.12.2004 09.09.2004 15.12.2004 15.12.2004 15.12.2004 10.12.2004 14.01.2005 14.01.2005

K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 N-12 N-09 NJ-05 NJ-06 NJ-07 NJ-09 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 RN-12 RN-15

15.5 14.5 11.0 28.5 11.0 15.0 2.9 12.0 14.5 17.5 20.0 14.0 15.5 15.8 15.5 15.3 15.0 7.8 10.5 16.1 15.5 6.0 16.2 16.0 15.6 15.5 42.0 25.0

6.84 7.03 6.22 7.01 6.55 6.91 7.05 7.04 6.99 6.37 6.86 6.87 6.72 6.74 6.89 6.62 7.00 6.80 6.92 6.90 6.94 6.38 6.86 6.79 6.86 6.88 4.73 4.37

222 273 263 268 289 238 199 247 299 263 268 232 276 285 268 282 278 282 297 274 273 293 274 291 296 292 261 260

31.8 36.4 133.2 14.9 227.0 72.2 45.6 49.5 147.8 99.6 107.8 35.6 177.0 164.8 95.4 172.3 122.3 78.1 151.1 182.7 65.0 147.9 169.1 110.5 164.1 124.8 19288 19250

1230 1200 1670 1400 2200 845 615 896 2000 6220 3680 984 1429 2310 1330 1860 1390 1950 2550 1580 1810 3830 1510 1710 1760 6790 7890 7860

18.8 22.8 23.1 55.4 27.4 12.8 5.5 11.5 231.9 114.0 84.5 17.8 22.1 43.7 23.1 30.9 24.1 11.4 28.5 27.7 51.4 27.7 32.1 25.9 35.1 83.0 197.0 119.0

38.8 102.0 105.0 42.3 88.9 16.8 0.8 23.8 213.0 129.0 148.0 24.3 24.4 90.3 14.1 57.1 8.1 50.6 80.5 53.1 28.3 84.0 88.6 40.4 48.1 93.4 139.0 156.0

30.5 29.7 110.1 14.2 176.3 65.6 39.4 42.6 114.0 87.7 94.6 32.6 146.9 136.4 78.6 139.1 96.7 58.6 112.4 148.1 52.8 101.7 138.8 92.0 125.5 103.8 18951 17517

1161 971 1240 1272 1382 771 544 779 1642 4633 3162 907 1153 1780 1120 1477 1130 1401 1806 1311 1504 2645 1251 1224 1342 3894 7728 7157

37.3 83.3 87.0 40.3 69.0 15.3 0.7 20.5 164.3 113.5 129.9 22.2 20.3 74.8 11.6 46.1 6.4 38.0 60.1 43.1 23.0 57.8 72.7 33.6 36.8 77.7 136.6 142.3

27.5 26.7 107.1 11.2 173.3 62.6 36.4 39.6 111.0 84.7 91.6 29.6 141.9 131.4 73.6 134.1 91.7 53.6 107.4 143.1 47.8 96.7 133.8 87.0 120.5 98.8

1160 970 1239 1271 1381 770 544 779 1642 4632 3162 906 1152 1779 1119 1476 1129 1399 1805 1310 1503 2644 1250 1223 1341 3893 3192 2964 3405 3674 3796 4179 3877

37.3 83.3 87.0 40.3 69.0 15.3 0.7 20.5 164.3 113.5 129.9 22.2 20.3 74.8 11.6 46.1 6.4 38.0 60.1 43.1 23.0 57.8 72.7 33.6 36.8 77.7 134.9 140.7 69.9 86.9 79.0 52.4 91.8

04-3005 1028d 1028d 1028d 1028d

01.12.2004

SV-07

1941 1499 2451 2547 2543 1167 887 1199 1910 2636 1759 1060 1800 2136 1182 1700 1133 1948 1937 1195 1252 1711 1400 2400 1612 2662 1316 1256 1028d

04-3003

10.09.2004

SV-08

04-3032

01.12.2004

SV-09

04-3029

01.12.2004

SV-11

04-3004

09.10.2004

SV-18

04-3006 04-3027 04-3026 04-3025 04-3024

09.10.2004 30.11.2004 30.11.2004 30.11.2004 30.11.2004

SV-19 Bdmdstadir Efri Reykir S-24 Reykholt S-1 Reykjabl S-1

1028d 525 637 576 654 14.5 0.0 2.7 1.1 3.6 5.36 7.77 7.75 7.68 7.61 239 125 151 137 155

14235 44.3 53.3 79.1 29.4

7840 132 163 350 541

105.0 1.5 2.1 16.9 15.2

<0.05 <0.05

12800 41.9 52.1 76.6 29.0

7125 126 160 340 534

94.4 1.4 2.1 16.4 15.0

37.9 47.1 71.6 23.0

4061 155 205 350 697

93.3 1.4 2.1 16.4 15.0

a K=Kraa, N=Nmafjall, NJ=Nesjavellir, RN=Reykjanes, SV=Svartsengi, S=Southern Lowlands. The number indicate well number. b Average of quartz and Na/K geothermometer temperatures, except for Reykjanes and Southern Lowlands. For Reykjanes, quartz equilibrium temperature was used and chalcedony equilibrium temperature in the case of the Southern Lowlands. c It is not possible to calculate the non-marine derived Cl in the Reykjanes and Svartsengi systems. It is expected to be less than the analytical error of the Cl determination. d Selected, corresponds to enthalpy of steam-saturated liquid at 238 C e Suspect. Caused by carry-over of liquid into vapor sample.

f Amount of Cl added to uid by rock dissolution and/or from magma.

CHAPTER 3.
The value of

P e , the vapor pressure at which phase segregation occurs, was taken to

be half way between the aquifer vapor pressure and the vapor pressure at the wellhead at which samples were collected. Glover (1988) summarized experimental results on the distribution coecient (DB ) for B between liquid water and vapor. He proposed the following equation for

DB
(3.26)

log(DB ) =
where T is in K. Here it is assumed that the

T 729 149.5 DB

value refers to the H3 BO3 species and Fig. 3.3 shows the analyzed B ratio

that practically all the B in both the liquid and vapor phases at sampling conditions and higher temperatures occurs as this species. above) is also shown. between liquid water and vapor samples. The equilibrium distribution (equation (3.26)

Figure 3.3: Boron distribution between vapor and liquid phases discharging from wet-steam wells versus sampling temperature. Equilibrium distribution (Glover, 1988) is also shown.

As already pointed out, phase segregation is assumed to occur at a vapor pressure which is halfway between the sampling vapor pressure and the vapor pressure of the initial aquifer uid. of pressures. It is, however, likely that phase segregation occurs over a range The choice made here is therefore This pressure range is not known.

reasonable because it is the simplest one. The choice of segregation pressure aects the calculated concentration of B in the initial aquifer uid, particularly when the discharge enthalpy of wells is close to that of saturated steam. Fig. 3.4 shows how calculated B concentrations in the initial aquifer uid vary with the selected vapor pressure value for phase segregation for three selected wells. For

53

3.5. DATA HANDLING

wells with discharge enthalpy below about 1800 kJ/kg, the calculated concentration of e B in the initial aquifer uid is not sensitive to the choice of P . By contrast, this is not the case for well NJ-23 that has an enthalpy of 2662 kJ/kg (the enthalpy of dry steam at atmospheric pressure is 2676 kJ/kg). If the segregation occurred at 20 bar abs., the calculated aquifer B concentration would be 4540 ppb, but 3360 ppb if it occurred at 60 bar abs. Selection of phase segregation vapor pressure also aects the calculated concentrations of non-volatile components in the initial aquifer uid, such as As and e Cl. As for B, the choice of P is only important for wells with discharge enthalpy close to that of dry steam.

Figure 3.4:

Example of the inuence of the selected vapor pressure at which

phase segregation occurs on the calculated aquifer B concentration for three highenthalpy wells.

3.5.3 Sources of As, B and Cl to geothermal uids

The principal sources of As, B and Cl to the uids of the high-temperature geothermal systems in Iceland include precipitation, inltration of seawater into the bedrock, the rock with which the uid has interacted and magma volatiles. In order to estimate the contribution of Cl from precipitation, we have used the information provided by Sigurdsson and Einarsson (1988) on Cl in precipitation in Iceland. It ranges from over 10 ppm for high-temperature systems in coastal areas to about 3 ppm in those systems located farthest inland. Corresponding numbers for B and As are 0.72.4 ppb and 0.00030.0009 ppb, respectively. From this it is considered that Cl contribution from precipitation to the hightemperature uids is insignicant and trivial in the case of B and As. Seawater inltration into geothermal systems may occur under present-day hydrological conditions, such as at Svartsengi and Reykjanes. According to Arnrsson and Andrsdttir (1995), such inltration also occurred around the end of the last glaciation in many other lowland areas, when these areas were transgressed by the ocean. The only high-temperature system considered here that may contain an old seawater component is Hveragerdi. For

54

CHAPTER 3.

Figure 3.5: Measured Cl and B concentrations in liquid water samples from all the study areas. Included are samples from Arnrsson and Andrsdttir (1995)

a Cl/B rock dissolution ratio of 38, the Cl marine groundwater component accounts for 4258% of the total Cl in the area. In the case of the seawater systems at Reykjanes and Svartsengi, a large proportion of the B in the waters is of marine origin, 59% at Reykjanes and 44% at Svartsengi. Very likely almost all the Cl is marine (>99%) but trivial part of As. In the dilute water systems, the sources of As, B and Cl to the deep, undiluted geothermal uid are dominantly non-marine, or

100%

for As,

>99%

for B

and 9098% in the case of Cl. The sources include the rock with which the uid has interacted and, at least for some areas, a gaseous phase from the magma heat source. In a later section an attempt is made to evaluate the contribution of As, B and Cl from magma volatiles to high-temperature uids.

3.6 Results
3.6.1 Boron and Cl distribution in sampled waters
The relation between analyzed Cl and B concentrations is shown in Fig. 3.5. The solid line corresponds to seawater Cl/B ratio, as given by Krauskopf and Bird (1994), whereas the dotted and broken curves show relationship between Cl and B for Cl/B molal rock dissolution ratio of 38 (molal) and an initial concentration of 5 ppm Cl and 1.2 ppb B, and 2 ppm Cl and 0.5 ppb B, respectively. The selected Cl/B ratio is based on data on Cl and B in Icelandic tholeiites as reported by Arnrsson and Andrsdttir (1995). The average Cl and B concentrations of these tholeiites are 177 and 1.43 ppm, respectively. The data given by Arnrsson and Andrsdttir (1995) show considerable scatter. Accordingly the selected Cl/B ratio carries considerable error.

55

3.6. RESULTS
According to Sigurdsson and Einarsson (1988), local precipitation in the Geysir, Landmannalaugar, Nesjavellir and Nmafjall areas contains

ppm Cl, whereas it

is somewhat lower in Kraa and at Hveravellir (3 ppm) and higher (10 ppm) in Hveragerdi and the Southern Lowlands. Therefore a value of 5 ppm Cl and 1.2 ppb B serves as a good proxy for the concentrations of these elements in the local precipitation in the study areas. Data on Cl and B from Arnrsson and Andrsdttir (1995) have been plotted in Fig. 3.5 together with the data presented in Tables 3.1 and 3.2. All samples, except those from the seawater systems of Reykjanes and Svartsengi, have much lower Cl/B ratios than seawater. In the seawater systems, Cl/B ratios are half that of seawater. Samples from hot springs in the Geysir, Hveravellir and Landmannalaugar areas plot a little below the Cl-B dissolution line. The average Cl/B ratio for all these areas is almost the same, 3640, if one heavily diluted sample from the Geysir area is excluded. However, some samples from Landmannalaugar have lower Cl/B ratios, i.e. those samples that have reacted the most with the rocks as well as mixed waters from warm springs that contain a large cold water component. In view of the uncertainty in the Cl/B leaching ratio, both for basalts and silicic rocks, it is considered that the slightly low Cl/B ratios of the most reacted Landmannalaugar waters are not signicant. Compared to the waters at Geysir, Hveravellir and Landmannalaugar, spring waters from Hveragerdi and discharges from three of the four wells from the Southern Lowlands have higher Cl/B ratios. This is attributed to a small component of seawatergroundwater component in these waters. Hveragerdi and most of the Southern Lowlands were transgressed by the ocean in early Holocene times. At this time, seawater must have inltrated the bedrock and this old seawater is still seeping into permeable tectonically active fractures in which more recent water of meteoric origin is convecting (Arnrsson and Andrsdttir, 1995). The Cl/B ratio of the Hveragerdi and Southern Lowlands waters can be explained by assuming that Cl of marine origin in these waters is 2040% of the total Cl except for one sample (04-3024 in Table 3.1) that does not contain a marine groundwater component. This water is from a well in an elevated part in this area that was not submerged in early Recent times. Many of the dilute waters from wet-steam wells in high-temperature areas have lower Cl/B ratios than basalt, in particular those from Nmafjall and Kraa. Their B concentrations lie in the range from

500

ppb to almost 6800 ppb. The most common The corresponding number for Cl is 15

concentration is, however 10002000 ppb.

230 ppm. When the marine derived B content of the geothermal seawaters at Reykjanes and Svartsengi are subtracted from the total B, the amount of B added to the water from other sources is 3.54 ppm in the case of Svartsengi and

ppm for Reykjanes. This is

higher than the average for the dilute waters, yet within the same range. The average B content of tholeiites in Iceland is close to 1.4 ppm (Arnrsson and Andrsdttir, 1995). It is thus evident that many high-temperature waters contain higher B concentrations than the rock with which they have reacted. The observation that the data points in Fig. 3.5 for the elds of Geysir, Hveravellir, Hveragerdi and Landmannalaugar fall quite close to the basalt Cl-B dissolution curve is taken to indicate that these elements are dissolved from the rock in stoichiometric proportions. Since it is generally accepted that Cl displays conservative behavior, i.e. once in solution it stays there, it is concluded that B also acts as conservative. It is

56

CHAPTER 3.
Table 3.2: Arsenic, boron and chloride concentrations in spring waters from high-temperature areas. Also shown are calculated aquifer water pH and As, B and Cl concentration originating from rock dissolution (leached).
Sample Spring name Coordinates N/E Deg. Geysir 01-3201 Geysir 01-3202 Blesi 01-3203 therrishola 01-3204 Litli-Geysir 01-3205 Litli-Strokkur 01-3206 Smidur 01-3207 Konungshver 01-3208 Helludalur 1 01-3209 Laugarfell west 01-3210 82-015 01-3211 Spring by Bein 01-3212 Laugarfell east 01-3213 Strokkur 01-3214 Nedridalur 1 01-3215 Mli 1 01-3216 Nyihver Hveravellir 01-3217 Hveravellir I 01-3218 Graenihver 01-3219 Braedrahver 01-3220 Blhver 01-3221 Eyvindarhola 01-3222 Hveravellir II 01-3223 Hveravellir III 01-3224 Hveravellir IV 01-3225 Fagrihver 01-3226 Hveravellir V 01-3227 Hveravellir VI 01-3228 Hveravellir VII Landmannalaugar 01-3229 Landmannal. I 01-3230 Landmannal. II 01-3231 Landmannal. III 01-3232 Landmannal. IV 01-3233 Landmannal. V 01-3234 Landmannal. VI 01-3235 Skriduhver 01-3236 Bluhver 01-3237 Litli-Sullur 01-3238 Svartaauga 01-3239 Svuntuhver 01-3240 Eyrarauga 01-3241 Eyrarhver 01-3243 Raudanefskelda 01-3244 Graenalaug 01-3245 Stefnsauga 01-3246 Landmannal. VII Hveragerdi 02-3201 Hverag. waterfall I 02-3202 Hverag. waterfall II 02-3203 By swimming pool 02-3204 By well nr. 3 02-3205 By Frosti&Funi 02-3206 Bluhver 02-3207 Above Bluhver 02-3208 By river, Bluhver 02-3209 By well nr. 8 02-3210 Spring Hverag. I 02-3211 Spring Hverag. II Spring Aquif. Aquif. Calc. Cl B As Cl B As Cl B As temp. temp.a liq. steam sample sample sample aquif. aquif. aquif. leach. leach. leach. C C pH fract. mg/kg g/kg g/kg mg/kg g/kg g/kg mg/kg g/kg g/kg

64.31387/-20.29934 64.31352/-20.30140 64.31208/-20.30237 64.31180/-20.30126 64.31115/-20.30230 64.31057/-20.30184 64.31386/-20.30186 64.32171/-20.30826 64.31280/-20.31019 64.31833/-20.30478 64.31793/-20.29345 64.31390/-20.30607 64.31269/-20.30095 64.30280/-20.33033 64.27408/-20.32108 64.31039/-20.30155 64.85924/-19.55620 64.85908/-19.55500 64.85906/-19.55479 64.85900/-19.55502 64.85895/-19.55567 64.85930/-19.55578 64.85904/-19.55622 64.85904/-19.55545 64.85917/-19.55489 64.85943/-19.55430 64.85966/-19.55370 64.85986/-19.55328 63.98779/-19.05774 63.98776/-19.05783 63.98767/-19.05774 63.98814/-19.05776 63.98848/-19.05761 63.98873/-19.05752 63.98862/-19.10836 63.98840/-19.11728 63.98899/-19.10857 63.98901/-19.10858 63.98686/-19.10689 63.98734/-19.10622 63.98877/-19.10031 63.96988/-19.01900 63.97107/-19.02336 63.97322/-19.02608 63.97236/-19.07565 64.00064/-21.10875 64.00149/-21.10923 64.00250/-21.10896 64.00898/-21.11228 64.00349/-21.11051 64.00397/-21.11089 64.00402/-21.11083 64.00397/-21.11053 64.01514/-21.12764 64.00067/-21.11305 64.00091/-21.11291

87.0 87.5 98.0 93.0 88.0 99.0 95.0 30.1 38.8 26.0 19.6 97.5 86.0 65.2 48.0 98.0 96.0 93.3 96.2 90.2 95.5 81.6 62.2 80.6 84.0 92.9 82.5 38.6 77.2 14.5 5.8 58.3 60.0 55.6 96.2 96.7 96.9 96.9 97.1 96.5 96.0 11.7 55.6 75.9 18.0 90.2 99.5 99.8 65.1 99.2 98.1 99.4 99.9 75.3 92.2 66.6

233 231 231 214 207 204 226 81 101 72 39 208 214 142 123 210 246 251 250 229 219 240 183 193 245 243 195 78 184 84 53 152 154 151 132 94 180 123 195 182 182 72 145 194 88 158 163 182 104 191 185 169 154 126 196 187

6.91 6.92 7.12 7.25 6.59 7.34 7.11 7.77 7.39 7.60 7.73 7.01 7.31 7.68 7.35 7.31 6.91 6.72 6.63 6.65 6.8 6.57 6.39 4.29 6.71 6.77 6.62 7.85 6.61 6.48 6.26 6.51 6.51 6.55 7.75 8.85 7.02 7.34 7.22 7.26 7.38 5.59 7.06 6.18 6.82 6.63 7.41 7.24 7.25 7.19 7.30 7.21 6.48 6.78 7.27 7.70

0.26 0.25 0.25 0.22 0.21 0.20 0.25 0.00 0.00 0.00 0.00 0.21 0.22 0.00 0.00 0.21 0.29 0.30 0.30 0.25 0.23 0.27 0.16 0.00 0.28 0.28 0.18 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.06 0.00 0.15 0.04 0.18 0.16 0.16 0.00 0.00 0.18 0.00 0.11 0.12 0.16 0.00 0.17 0.16 0.13 0.10 0.00 0.18 0.00

124.3 124.8 105.5 122.7 111.5 117.0 123.4 20.5 42.5 21.2 7.9 114.0 120.5 20.7 33.2 124.8 68.6 70.7 64.2 68.3 59.5 70.1 54.3 32.6 56.4 61.0 46.5 37.3 277.0 64.0 17.5 49.7 58.0 51.9 173.0 182.0 254.4 164.8 271.5 287.7 498.3 4.2 4.5 6.9 22.2 76.5 84.0 148.7 36.2 160.7 135.8 86.2 38.3 14.9 166.0 148.1

1047 1061 1040 1068 926 1001 1025 114 257 103 22 953 1019 204 228 1012 543 551 549 540 493 572 421 277 540 513 415 266 1706 345 122 600 610 577 1356 1208 1746 1174 2483 2631 5082 25 89 104 200 342 354 539 173 577 502 331 169 64 582 571

84.5 83.4 71.0 83.2 77.9 55.8 81.5 2.0 2.3 1.2 0.3 66.8 89.6 0.4 6.4 76.2 51.6 50.4 52.6 59.2 46.6 50.5 17.0 0.7 50.8 65.2 8.9 5.8 17.1 1.5 0.4 6.5 6.1 4.9 48.7 17.7 42.9 18.3 154.0 127.0 252.0 1.5 0.4 0.2 2.8 0.4 0.5 2.4 0.4 4.7 3.1 2.2 0.7 0.1 5.5 5.5

92.0 92.9 78.7 95.6 88.5 93.7 93.1 20.5 42.6 21.1 7.9 90.1 93.9 20.7 33.2 98.3 48.9 49.7 45.2 51.2 45.8 50.9 45.6 32.5 40.3 43.9 38.0 37.3 276.9 64.1 17.4 49.6 58.0 51.9 162.6 182.1 215.7 157.6 222.6 242.8 420.2 4.2 4.5 5.7 22.2 68.1 73.9 125.4 36.3 132.8 113.7 74.9 34.4 15.0 135.7 148.1

775 790 776 832 735 801 774 114 257 103 22 754 795 204 228 797 388 387 387 405 380 415 354 276 386 369 339 266

62.5 62.1 53.0 64.8 61.8 44.7 61.5 2.0 2.3 1.2 0.3 52.8 69.8 0.4 6.4 60.0 36.8 35.4 37.0 44.4 35.9 36.7 14.3 0.7 36.3 46.9 7.2 5.8

87.0 87.9 73.7 90.6 83.5 88.7 88.1 15.5 37.6 16.1 2.9 85.1 88.9 15.7 28.2 93.3 46.9 47.7 43.2 49.2 43.8 48.9 43.7 30.5 38.3 41.9 36.0 35.3 272.9 60.1 13.4 45.7 54.0 47.9 158.7 178.1 211.7 153.6 218.6 238.8 416.2 0.2 0.5 1.7 18.1 58.1 64.0 115.4 26.3 122.8 103.7 64.9 24.4 5.0 125.7 138.2

773 789 774 831 734 800 772 113 256 102 21 752 793 203 227 796 387 387 386 404 379 415 353 276 386 369 339 265

62.5 62.1 53.0 64.8 61.8 44.7 61.5 2.0 2.3 1.2 0.3 52.8 69.8 0.4 6.4 60.0 36.8 35.4 37.0 44.4 35.9 36.7 14.3 0.7 36.3 46.9 7.2 5.8

1705 17.1 345 1.5 121 0.4 600 6.5 610 6.1 578 4.9 1276 45.8 1209 17.7 1481 36.4 1123 17.5 2036 126.3 2221 107.2 4286 212.5 25 1.5 89 0.4 85 0.2 200 2.8 305 312 454 173 476 420 288 152 64 476 571 0.3 0.4 2.1 0.4 3.9 2.6 1.9 0.6 0.1 4.5 5.5

1704 17.1 344 1.5 120 0.4 599 6.5 609 6.1 577 4.9 1275 45.8 1208 17.7 1480 36.4 1122 17.5 2035 126.3 2220 107.2 4285 212.5 24 1.5 88 0.5 84 0.2 199 2.8 302 309 452 171 474 418 285 150 61 473 569 0.3 0.4 2.1 0.4 3.9 2.6 1.9 0.6 0.1 4.5 5.5

The quartz and chalcedony geothermometer were used for boiling and sub-boiling springs, respectively.

57

3.6. RESULTS
further concluded that the source of Cl and B to these waters is essentially the rock with which these waters have reacted. Theoretically, the low Cl/B ratios of the Nesjavellir, Nmafjall and Kraa waters could be due to lower ratios of these elements in the rock, loss of Cl from solution relative to B or preferential addition of B relative to Cl from a magmatic heat source. All these areas are closely associated with recent volcanism. Fresh magma was intruded into the roots of the Kraa caldera immediately below the present wellelds during a volcanic episode in 197584 (Bjrnsson et al., 1977) and this magma owed along ssures into the Nmafjall area (Larsen et al., 1978). The welleld at Nesjavellir is adjacent to a volcanic ssure that erupted 188065 years ago (Saemundsson, 1963). The Reykjanes and Svartsengi areas, as well as Landmannalaugar, are also in areas of young volcanism but the other study areas are not. The Reykjanes and Svartsengi uids have received considerable B in addition to that from the parent seawater. Landmannalaugar is marginal to the Torfajkull geothermal area and may not be overlying a magmatic heat source. Thus geological setting of areas and their link with volcanic activity favor that the low uid Cl/B ratios are due to supply of this element from magma in excess of Cl. Boron is known to form volatile compounds at magmatic and lower temperatures and most of the B in basalt is readily extractable, as indicated by the leaching experiments of Ellis and Mahon (1964, 1967), presumably because it exists in a soluble compound on mineral grain surfaces. Such compound is believed to form by sublimation of volatile B compounds after the magma has consolidated. Boron-containing minerals and Bminerals have been found as sublimates around volcanic fumaroles (Garavelli and Vurro, 1994; Garavelli et al., 1997) and on cooling new lava (Kuritani and Nakamura, 2006). Like B, Cl forms volatile compounds at magmatic temperatures. It occurs mostly as HCl in magmatic gases. Likely, the release of Cl from magma is limited relative to B due to its relatively high solubility in melt. Sigvaldason and skarsson (1976) concluded that only a small fraction of the Cl in basaltic magma is lost as a volatile during its consolidation.

3.6.2 As and Cl relationships

Fig. 3.6 shows the As-Cl relationship in water samples. The As-Cl values show more scatter than those of B-Cl (Fig. 3.5). The dotted and broken curves in Fig. 3.6 show how aqueous Cl/As ratios change by basalt dissolution for precipitation containing 5 and 2 ppm Cl, and a Cl/As leaching ratio of 3129. This ratio is based on the average Cl content of Icelandic basalts of 177.5 ppm (Sigvaldason and skarsson, 1976) and an As content of 0.12 ppm. The latter number represents the average As content of tholeiites in the Skagafjrdur area of northern Iceland. It is thus assumed that basalt dissolves congruently with respect to As and Cl. This assumption is supported by the dissolution experiments of Ellis and Mahon (1964, 1967), who demonstrated that As, like Cl, is easily extractable and almost quantitatively leached from basalt and other types of volcanic rocks by hydrothermal solutions. The Cl/As ratio of the geothermal seawater at Reykjanes and Svartsengi are almost two orders of magnitude higher than that of seawater. For other elds, the Cl-As relationship diers in some respect from that of Cl-B. Like Cl-B, undiluted waters from the Geysir area and Hveravellir fall more or less on the basalt dissolution curve. On

58

CHAPTER 3.

Figure 3.6: Measured Cl and As concentrations in liquid water samples from all the study areas.

the other hand mixed waters from these areas containing a large cold water component, have As concentrations that plot above the Cl/As dissolution curve. In the case of Landmannalaugar, this is considered to be due to precipitation of As from solution. For Hveragerdi, which has a marine Cl content of 50100 ppm, except for the most diluted sample, the low Cl/As ratios can be accounted for by the presence of the high marine Cl content. (Fig. 3.6). The waters at Kraa and Nmafjall possess Cl/As ratios which typically are lower than that of basalt, whereas this ratio is higher in the case of the Nesjavellir waters.

3.6.3 Rock derived concentrations

Fig. 3.7 and 3.8 show the relationships between the rock-derived concentrations of As, B and Cl for the elds of Geysir, Landmannalaugar, Hveragerdi and Hveravellir. The term rock-derived (or leached) represents the dierence between analyzed concentration in samples and the estimated concentration of these elements in the parent precipitation. The two rst plots from the top (parts A and B) for each area show the calculated rockderived (or leached) B and As concentrations in the aquifer liquid water, respectively, versus the calculated rock-derived Cl concentration. The third plot (part C) shows the rock-derived As concentration versus aquifer temperature. The broken lines represent the respective elemental ratios in Icelandic tholeiites. For Cl/B, they are based on Arnrsson and Andrsdttir (1995) but for Cl/As and B/As they are based on a value of 0.12 ppm for As, which is the average As content of Tertiary tholeiites in northern Iceland (Arnrsson, 2002) and on Arnrsson and Andrsdttir (1995) for Cl and B as before.

59

3.6. RESULTS

Figure 3.7: Rock derived As, B and Cl concentrations in aquifer liquid in Geysir and Hveravellir elds. The broken line represents the respective elemental ratios in Icelandic tholeiites according to Arnrsson and Andrsdttir (1995).

60

CHAPTER 3.

Figure 3.8: Rock derived As, B and Cl concentrations in aquifer liquid in Landmannalaugar and Hveragerdi elds. drsdttir, 1995). The broken line represents the respective elemental ratios in tholeiites from various parts of Iceland (Arnrsson and An-

61

3.6. RESULTS
Geysir and Hveravellir
The relationship between Cl and B is linear for the elds of Geysir and Hveravellir. A line passing through the data points goes through the point of origin. This line is the consequence of mixing between the geothermal water and cold water. The Cl/B ratios of the waters are very similar to the average Cl/B ratio of Icelandic tholeiites. From this it is concluded that B behaves conservatively as Cl in these areas and that dissolution of Cl and B from the basalt is stoichiometric. The As versus Cl graphs for the Geysir and Hveravellir elds (Fig. 3.7B) show two dierent groups. The group with the high Cl and As contents probably represents undiluted geothermal water. The other group plots above the mixing line. The waters of this group which contain a large cold water component are highly depleted in As relative to Cl, with an average of 2.1 ppb As for six samples from the Geysir area and 7.0 ppb for four samples from Hveravellir. The same kind of pattern appears on the As versus calculated aquifer temperature graph. This temperature corresponds to the last temperature of equilibrium with quartz for high As samples but to the temperature of last equilibrium with chalcedony in the case of the mixed waters. The results for the mixed waters indicate that As is removed to substantial degree from solution subsequent to mixing. As demonstrated by Arnrsson (1985), mixing leads to a decrease in pH, particularly if mixing involves unboiled and therefore undegassed geothermal water. The decrease in pH enhances dissolution of the primary mac basalt minerals leading to increased formation of secondary iron-hydroxides and clays. Likely the As coprecipitates with these minerals.

Landmannalaugar
Arsenic, B and Cl concentrations variations are larger in this eld than in other areas considered for the present study, the range being 10400 ppm, 54500 ppb and 1 220 ppb for Cl, B and As, respectively. The highest observed Cl and As concentrations are higher than in other areas and the highest B concentrations are similar to the highest values observed in wet-steam well discharges. The bedrock exposed in the Landmannalaugar area is all composed of silicic volcanics. This leads to the conclusion that the high As, B and Cl content of the geothermal waters is the consequence of reaction of these waters with silicic volcanics. The relationship between Cl and B All is linear and the ratio is almost the same as in Icelandic tholeiites (Fig. 3.8). groundwater.

except one water from boiling hot springs show considerable mixing with cooler or cold Warm springs, which also have high ow rates, represent extensively diluted geothermal waters, i.e. they contain a large cold water component. The water sample containing the highest As, B and Cl concentration may or may not represent undiluted reservoir uid. Relative to Cl, and therefore also B, As is highly depleted in all the extensively diluted warm spring waters and in all but two samples of mixed boiling spring waters (Fig. 3.8) indicating its removal from solution subsequent to mixing. Unlike the results for the areas of Geysir and Hveravellir, described above, we observe As precipitation not only for mixed sub-boiling waters but also for mixed boiling waters. Geothermal waters at Landmannalaugar dier from those at Geysir and Hveravellir by their higher H2 S content. It is possible that removal of As from boiling waters involves its incorporation

62

CHAPTER 3.
into suldes that precipitate from solution upon extensive boiling due to cooling and degassing. Degassing with respect to the acid gases, CO2 and H2 S raises the pH of the boiling water. Both decrease of temperature and increase in pH reduce sulde mineral solubilities.

Hveragerdi
At Hveragerdi, the aqueous Cl/B ratio is higher, the average being 68 (molal), whereas the average for the Icelandic tholeiites is 38. As can be seen from Fig. 3.8, the Cl-B data points form a curve, rather than a line, and a linear regression through these data points does not pass through the point representing local precipitation (10 ppm Cl, 2 ppb B) as would be expected if this line represented mixing. The Cl/B ratios increase with increasing concentrations, being around 80 (molal) for the waters containing the highest Cl (100130 ppm). In the most dilute waters, by contrast, Cl/B ratios are

45

(molal) or a little higher than such ratios in geothermal waters at Geysir, Hveravellir and Landmannalaugar. The curvature of the Cl/B ratios of the Hveragerdi waters can be explained by continuous mixing of rising geothermal water with progressively less reacted water in which Cl/B ratios equal that of Icelandic tholeiites. The high Cl/B ratios of the deep geothermal water at Hveragerdi are probably due to the presence of a seawater-groundwater component that inltrated the bedrock around the end of the last glaciation when the area was transgressed by the ocean (Arnrsson and Andrsdttir, 1995). Arsenic is very low and the Cl/As ratio is the highest compared to uids from other elds considered for the present study. Mixing of the deep water with shallower water, whether limited or extensive leads to precipitation of As from solution. Studies of hydrothermal alteration at depth in Hveragerdi show that it is very pervasive (Sigvaldason, 1963). The primary basalt minerals have been totally replaced by hydrothermal minerals and extensive removal of As from the initial basalt accompanied the hydrothermal alteration. Data are lacking to verify this. However, Arnrsson (1969) demonstrated that Mo and Ge are excessively depleted from the altered rock at Hveragerdi, relative to fresh basalt.

Kraa, Nmafjall and Nesjavellir

Unlike the results just presented for the hot spring data from Geysir, Hveravellir, Landmannalaugar and Hveragerdi, the relative concentrations of As, B and Cl in dilute wet-steam well uids from the elds of Kraa, Nmafjall and Nesjavellir show much greater scatter, both within and between elds (Fig. 3.9). In these elds Cl/B ratios are similar to those of Icelandic tholeiites and the hot spring waters or lower. At Nesjavellir Cl/B ratios vary between 8 and 39 (molal) whereas those from Kraa have a range of 639. When considering older data on Cl and B from Nmafjall and Kraa (Gudmundsson and Arnrsson, 2002; Arnrsson and Gunnlaugsson, 1985), the range is even larger, 339 and 124 for Kraa and Nmafjall, respectively. At Nmafjall, B concentrations have clearly decreased with time (Fig. 3.10), but in two of the wells, Cl has stayed constant but in the third well it is erratic, possibly due to variable production from more than one aquifer.

63

3.6. RESULTS

Figure 3.9: Rock derived As, B and Cl in aquifer liquid.

Figure 3.10: Time evolution of non-marine B in the aquifer water of three wells of the Nmafjall area.

64

CHAPTER 3.
Some of the wells with the highest B concentrations discharge almost dry steam. As discussed in section 3.5.2 above, the calculated value for aquifer uid B concentration from analyzed concentrations in liquid and vapor samples collected at the wellhead e depends on the value selected for the segregation pressure (P ). Selection of too a low e value for P leads to over-estimation of the aquifer uid B concentration. Some wells with discharge enthalpy close to that of dry steam (e.g. 16, 17 and 20 at Kraa, see Table 3.1) do not contain anomalously high B whereas other wells have high B but not very high discharge enthalpy (e.g. well 12 at Nmafjall and well 19 at Nesjavellir). It is therefore concluded that calculated aquifer uid B concentrations cannot be explained e by use of an erroneous selection of P . A plot of Cl/B against 1/B of data from Nesjavellir, Kraa and Nmafjall shows that most of the data points scatter around two lines (Fig. 3.11) indicating that the Cl and B contents of the aquifer uid in these geothermal systems are determined, for each line, by mixing of two components. For the line with the steeper slope in Fig. 3.11, one of these components is taken to be that at the intersection point of the two lines. This component contains 26.2 ppm B and 188 ppm Cl. Assuming a Cl/B ratio (molal) of 38 for the other component, yields a B concentration of 0.75 ppm and 94 ppm for Cl. The selected Cl/B ratio is the average Cl/B ratio of Icelandic tholeiites. The low B end-member for the mixing line (not shown in Fig. 3.11) with the lower slope gives 0.15 ppm B and 19.2 ppm Cl for a Cl/B molal ratio of 38. The value of 0.15 ppm B corresponds to

1/B = 70

(molal).

The low B end-member for the low-slope mixing line represents geothermal uid that has reacted to a relatively limited extent with basalt. It contains Cl in concentrations quite similar to that of water in aquifers in the upper Kraa reservoir. By contrast, the low B end-member for the high-slope line represents quite extensively reacted water, like that discharged from boiling hot springs in the Geysir area. The component which corresponds to the point of intersection of the two mixing lines, is considered to contain a relatively high proportion of magmatic volatiles. Essentially, the two component mixing always involves substantial addition of B to the geothermal uid from a magmatic source. Addition of Cl is limited to uids falling on the steep slope mixing line but large in the case of uids dening the low-slope line. The data depicted in Fig. 3.11 indicate that the Nesjavellir well uids are represented by liquid that has reacted extensively with the basalt either before or subsequent to mixing with the component rich in magmatic volatiles. At Kraa and Nmafjall, on the other hand, the magmatic component has mixed with relatively little reacted water. There are, however, exceptions. They include wells 16, 20, 21 and 32 at Kraa, as well as one sample from well 13. Wells 16 and 20 are located south of the Kraa mountain but wells 13 and 32 in the easternmost part of the Leirbotnar welleld by the lower slopes on the west side of Kraa mountain. Well 21 is located some 2 km to the south of other productive wells. (see Fig. 2 in Gudmundsson and Arnrsson, 2002, for well locations). A large groundwater current ows from the north to the west of the mountain of Kraa, considered to be represented by the upper sub-boiling reservoir of the Kraa system. Wells drilled through the upper reservoir and into the lower two-phase zone at Kraa discharge uid represented by a mixture of the magmatic volatile component and little reacted water of the upper reservoir. The wells to the east, particularly those south of Kraa mountain, are outside the main groundwater current, in a shadow of the Kraa

65

3.6. RESULTS

Figure 3.11: A plot of Cl and B of non-marine origin. Filled symbols represent samples from this study, open symbols represent data from Gudmundsson and Arnrsson (2002),Arnrsson and Gunnlaugsson (1985). The solid and the broken lines represent the linear regression of data from Nesjavellir and the lower Kraa reservoir and data from the upper Kraa reservoir and Nmafjall, respectively. These two lines represent mixing of two end-members, a magma-volatile component and liquid meteoric that has reacted to a dierent extend with the rock (see text).

66

CHAPTER 3.
mountain. The mixed uid in these wells contain a component of water that has reacted extensively with the basalt, just as is the case at Nesjavellir. The uid discharged from well 21 represents a mixture of moderately reacted water containing a fair contribution of the magmatic volatile component. Four samples have been plotted for well 13 in Fig. 3.11. Initially this well had two feed zones, one from the deeper two-phase reservoir and one from the upper sub-boiling reservoir. The sample with the high Cl/B ratio from well 13 was collected in 1981 during the early years of production when the deeper feed zone was active. The three samples collected at a later date (1988 to 2004), are all derived from the shallower subboiling zone because at that time the deeper zone had become inactive due to its low permeability. As already mentioned, B concentrations have decreased in aquifers producing into wells at Nmafjall. Such decrease has also been observed for couple of wells at Kraa but most show no change or erratic variation with time. magmatic gas component of the well discharge. Decrease with time in the concentration of B in the aquifer uid of a particular well indicates a decrease in the

A correlation is not observed between As and Cl concentrations in uids discharged from the wet-steam wells at Kraa, Nmafjall and Nesjavellir (Fig. 3.9). This is to The be contrasted with the results described previously for the hot spring waters.

undiluted hot springs waters have relatively constant concentrations of Cl and As, and therefore also of Cl/As ratios. In the wet-steam wells, concentration variation for Cl is roughly 15-fold but 25-fold for As. Cl/As ratios in the Nesjavellir uids are with few exceptions higher than those at Kraa and Nmafjall. On average they are 4600 (molal) and 2800 for these elds, respectively, if a total of four samples are omitted that have very high Cl/As due to low As concentrations. These four samples also have high B/As ratios suggesting that the cause of these high ratios is removal of As from solution through its incorporation into precipitating suldes.

If four samples are omitted, there is a signicant positive correlation between the concentrations of As and B in the aquifer uids at Kraa plus Nmafjall and Nesjavellir, respectively (Fig. 3.9). The four exempted samples all have anomalously high B relative to Cl (Fig. 3.9), attributable to large supply of B to the uid by magmatic volatiles. As for Cl/As ratios, those of B/As are higher at Nesjavellir than at Kraa. The dierence in the Cl/As and B/As ratios of the uids at Nesjavellir on one hand and Kraa and Nmafjall on the other, indicate lower mobility of As at Nesjavellir than at Kraa and Nmafjall. This is, however, not conclusive due to limited data on the As content of basaltic to silicic igneous rocks in Iceland that would permit B/As and Cl/As ratios of these rocks to be well established and correlated with these elemental ratios in geothermal uids. There may be several reasons for the lower mobility of As relative to those of Cl and B. They include loss of As from solution by its incorporation into precipitating sulde minerals at depth, which precipitate, in particular in zones of extensive boiling, and variable addition of As to the geothermal uids from magmatic volatiles.

67

3.7. DISCUSSION
Reykjanes and Svartsengi
The concentrations of As, B and Cl in the aquifer uid at Svartsengi lie in the range of 5293 ppb, 6.47.1 ppm and 11,85012,800 ppm, respectively (Table 3.1 and Fig. 3.9). For the two samples from Reykjanes, average As and B concentrations are somewhat higher, 139 ppb and 7.4 ppm, respectively. The concentrations of As and B from the non-marine source have been estimated from the reported As, B and Cl in seawater using

mf,m = i
where

mf,m Cl ms i ms Cl i

(3.27)

represents concentration.

Subscript

denotes either As or B. Superscripts

stand for the marine component in the initial aquifer uid and seawater, f,l f,m respectively. The dierence between mi and mi is the concentration of component i in the initial aquifer uid of non-marine origin. Almost all the As in the Reykjanes and Svartsengi uids is of non-marine origin (Table 3.1) and 41% (3.1 ppm) and 56% (3.8 ppm) of the B. Practically all the Cl is taken to be of marine origin. Both As and B concentrations are generally higher in the saline Reykjanes and Svartsengi uids than observed for the drilled dilute-water hightemperature areas. At Svartsengi, B/As relationship is similar to that of the high B samples from Nesjavellir and Kraa, whereas the same relationships for the Reykjanes uids compares with those at Nesjavellir. Fig. 3.9 also shows that the As concentrations relative to the aquifer temperature are higher than for the other areas. This could either be due to more extensive rock leaching or a higher fraction of magmatic volatiles in the saline uids.

f, m

and

3.7 Discussion
The concentrations of As and B in uids of volcanic geothermal systems in Iceland are low compared to uids in geothermal systems located on converging plate boundaries. An important fraction of the B and As present in the oceans is trapped within the oceanic sediments, mostly adsorbed on clay minerals (Spivack et al., 1987) and iron oxyhydroxides (Sullivan and Aller, 1996; Pierce and Moore, 1982). Some of the trapped As and B is remobilized on converging plate boundaries at the high temperature in the subducted plate below the mantle wedge (James and Palmer, 2000; You and Gieskes, 2001), which explains the high concentrations of these elements in volcanic rocks and associated geothermal systems in this environment. The amount of Cl in the meteoric geothermal uids derived from the parent precipitation has been estimated from data on Cl in precipitations in Iceland given by Sigurdsson and Einarsson (1988). Subsequently, precipitation derived B and As were estimated by assuming that the Cl/B and Cl/As ratios of the precipitation were the same as that of seawater. For individual samples, they represent rounded values in specic areas rather than being evaluated for individual samples, as e.g. described by Arnrsson and Andrsdttir (1995). This may produce a large error for heavily diluted geothermal spring waters but not for little or undiluted waters as almost all the As, B and Cl are of non-marine origin.

68

CHAPTER 3.
Calculation of the deep aquifer uid composition from wellhead data involves some assumptions and approximations. The uid source of a geothermal well or spring is taken to be chemically homogeneous and with a xed temperature. In formations of heterogeneous permeability, the discharge of hot springs and wells will be composed of many components that have owed over dierent distances at dierent rates from their point of origin to the well or hot spring. These components may dier, both in composition and temperature. Strictly speaking, therefore, there is no large body of aquifer uid with a specic temperature and composition.

In the studied wet-steam wells, all the As and Cl occupies the liquid phase at wellhead conditions but a fraction of the B is in the vapor phase and this fraction increases with increasing vapor pressure, indicating that the amount of B in the vapor phase is higher at aquifer pressure conditions than at wellhead conditions. Analysis of B in both liquid and vapor phases sampled at wellheads shows that the B partitioning between the two phases corresponds well with equilibrium distribution according to experimental data compiled by Glover (1988). This implies that B concentration in steam discharged from wet-steam wells can be calculated with reasonable condence from its concentration in the water when data on B in steam are lacking. Segregation of vapor and liquid in producing aquifers of wet-steam wells was assumed to be the cause of excess well discharge enthalpy. The segregation was assumed to occur at a particular vapor pressure, taken to be half way between the wellhead and initial aquifer vapor pressures. pressures. Likely, phase segregation occurs over a range of Therefore the selection of a single value for phase segregation involves an

approximation. This approximation, however, does not produce a signicant error in calculating elemental concentrations in the initial aquifer uid except when the discharge enthalpy is approaching that of dry steam as can be inferred from Fig. 3.3.

Mixing of geothermal uid with cold groundwater, particularly if it has not been degassed by boiling prior to mixing, produces an acid solution leading to enhancement of primary basalt mineral dissolution, particularly olivine, pyroxene and glass and subsequent precipitation of ferric hydroxides. Chloride and B act as incompatible during the mixing process as indicated by their linear concentration relationship in variably mixed waters from specic geothermal areas. On the other hand, As is largely removed from solution. The cause is considered to be its co-precipitation with ferric hydroxides, or even clays, or adsorption onto such minerals. Limited data are available on the contents of As, B and Cl in Icelandic basalts, and especially silicic volcanics. Values selected for Cl/B ratios of Icelandic tholeiites are based on data on Cl from Sigvaldason and skarsson (1976) and B data on the same samples presented by Arnrsson and Andrsdttir (1995). From the average Cl content of 177 ppm in these basalts and 1.43 ppm B, an average Cl/B molal ratio of 38 is obtained. The range of the Cl and B concentrations in individual samples is, however, considerable, leading to an uncertainty in the Cl/B basalt ratios. Cl/B ratios of hot springs waters from the studied high-temperature areas are almost the same on average (40), as that obtained for the basalts. Estimated Cl/As and B/As ratios in basalt carry a large uncertainty. They are based on the average As content of tholeiites (0.12 ppm) from the province of Skagafjrdur in

69

3.8. SUMMARY AND CONCLUSIONS

northern Iceland and Cl and B data on dierent samples (Sigvaldason and skarsson, 1976; Arnrsson and Andrsdttir, 1995). More extensive data on all these elements in Icelandic rocks, in particular in the studied high-temperature elds would permit a more accurate evaluation of whether these elements are dissolved from basalts and silicic volcanics in stoichiometric proportions, or whether rock dissolution is incongruent with respect to them.

3.8 Summary and conclusions

The concentrations of As, B and Cl in meteoric uids of volcanic geothermal systems (high-temperature > 200 C) in Iceland are low compared to such uids in volcanic geothermal systems by converging plate boundaries. They typically lie in the range of 20140 ppb, 5005000 ppb and 30150 ppm, respectively, when the host rock is basalt. The reason for the low concentrations of these elements in the Icelandic uids is their low content in the host basalt and the parent basaltic magma.When the meteoric uids have reacted with silicic volcanics, which formed by remelting of basaltic crust, their contents of As, B and Cl are higher. In the seawater geothermal systems of Reykjanes and Svartsengi, As and B concentrations are similar to those of the meteoric water systems when correction has been made for the marine contribution which is signicant for B but trivial for As. Many of the wells included in this study have higher discharge enthalpy than that of the initial aquifer uid. In calculating the aquifer uid composition from analysis of liquid and vapor samples collected at the wellhead, it was assumed that the enthalpy increase was produced by phase segregation, i.e. partial or complete retention of the liquid in the aquifer due to its absorption onto mineral grain surfaces by capillary forces. The phase segregation model was selected because it yields consistent results for the quartz and Na-K geothermometers. Boron partitions signicantly into the vapor phase of wet-steam well discharges but As does not, at least at vapor pressures as high as 40 bar. Equilibrium distribution is closely approached for B between liquid and vapor phases. The calculated concentrations of As, B and Cl in the initial aquifer uid are aected by the value selected for the initial aquifer temperature values as well as the selected vapor pressure at which phase segregation is assumed to occur. The eect of the latter selection is, however, small (a few percent) except for wells with enthalpy approaching that of dry steam. In view of this, the aquifer uid concentrations of As, B and Cl, reported in Table 3.1 are considered to be accurate within several percent with possibly two exceptions (samples nos. 04-3012 and 04-3041). Chloride and B are dissolved from the rock in stoichiometric proportions and both elements display conservative behavior; once dissolved they stay in solution. In hot spring areas that are mature, as indicated by their location outside the zones of active rifting within the volcanic belts, the Cl/B uid ratios are very similar to those of basalt except in one eld (Hveragerdi) where the uid contains a small fraction of seawater groundwater thought to have inltrated the bedrock around the end of the last glaciation. In young systems with meteoric uid, located at the divergent plate boundary, Cl/B uid ratios are lower than those of basalt due to excessive supply of B

70

CHAPTER 3.
to the geothermal uid from the magmatic heat source in relation to Cl. Such magmatic ux of B also occurs in the seawater systems of Svartsengi and Hveragerdi. When fresh magma is being degassed Cl/B ratios may be as low as 1 (molal). Arsenic possesses relatively high mobility in aquifer uids like Cl and B. Frequently its concentration in deep aquifers is comparable to that of tholeiitic basalt. However, some As is considered to be removed from solution at depth due to its incorporation into secondary sulde minerals. When hot uid rises from depth and mixes with cold groundwater at shallow levels, As is eectively removed from solution by its coprecipitation with or adsorption onto ferric hydroxide and possibly also clays.

71

Chapter 4 Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld, Iceland

Giroud, N., Arnrsson, S. and Bjarnason, J. .

Abstract
Production from the Svartsengi geothermal eld, SW-Iceland, started in 1976. At present, the installed electric capacity of the geothermal plant is 76 MW and the installed thermal capacity for direct use is 150 MW. The total uid mass withdrawn from the reservoir at the end of 2006 was 243 megatonnes (Mt) of which 217 came from wet-steam wells and 25 Mt from dry-steam wells. Production has led to a pressure drawdown of approximately 30 bar in the 240 C liquid reservoir. A vapor cap has formed above the liquid reservoir as a consequence of enhanced boiling by the pressure drawdown that presently extends down to over 400 m depth. Boiling of the liquid has reduced its gas content. This in turn has caused an increase and decrease of liquid F and Mg concentrations, respectively, due to re-equilibration of the boiled water with Mg and OH-bearing minerals. Initially, the vapor cap was very rich in gas, but it has decreased with time, i.e. continued boiling of the underlying liquid water. Shallow wells have been drilled to tap the vapor cap for electricity production. This is economically attractive but not environmentally favorable due to the high content of CO2 and H2 S in the vapor. It is estimated that to date as much as 3% w/w of the initial liquid water has boiled to supply vapor to the vapor cap.

73

4.1. INTRODUCTION

4.1 Introduction
Vapor-dominated geothermal systems are considered to have formed by boiling down of liquid-dominated geothermal systems (Go and Janik, 2000). In the East Production Field of Olkaria geothermal eld in Kenya, a vapor zone existed under natural conditions on top of a two-phase liquid-dominated reservoir (Arnrsson et al., 1990, and references therein). At Wairakei in New Zealand and Svartsengi and Reykjanes in Iceland a vapor cap has formed over liquid-dominated reservoirs as a consequence of a productioninduced pressure drawdown (Clotworthy, 2000; Gudmundsson and Thrhallsson, 1986, and unpubl. data). At Wairakei, as well as Svartsengi, production from the steam cap by the drilling of shallow holes into it has proved to be economic. Environmentally, on the other hand, it is not so favourable due to the high CO2 content of the vapor. Plans are under way at Reykjanes to drill into the steam cap for its exploitation. At Svartsengi the best permeability is associated with near-vertical active tectonic fractures and also with scoriaceous tops of lava ows and minor contraction fractures. The formation of the steam cap at Svartsengi has been associated with much increased fumarole activity, which was minor prior to exploitation. In the light of data on hydrothermal alteration from the nearby eld at Reykjanes (Pope et al., 2008), it seems unlikely that such alteration can lead to the formation of a self-sealing cap on top of the Svartsengi reservoir that would impede escape of vapor to the surface. Tectonic movements are frequent, as witnessed by earthquake activity, and formation of hydrothermal minerals is unlikely to cope with opening of fractures by the these movements. It appears more likely that ascent of vapor is restricted by volume expansion of the rising vapor. The chemistry of the uids discharged from all the wells at Svartsengi has been monitored by Iceland GeoSurvey, formerly part of the National Energy Authority, since the beginning of production. This has resulted in a database of nearly 30 years of chemical data that allows assessment of the various processes that have caused uid compositions to vary as a consequence of pressure drawdown by production. The present article is based on these monitoring data as well as on 10 samples specically collected for the present study. These data provide important information about the mode of formation of the vapor cap at Svartsengi and allow predictions to be made regarding changes in the gas content of the vapor cap.

4.2 Geology and hydrology

The Svartsengi high-temperature geothermal eld is one of ve high-temperature geothermal elds on the Reykjanes peninsula, in South-West Iceland (Fig. 4.1). It is located in the Grindavk ssure swarm, one of ve ssure swarms that lie across the plate boundary on the Reykjanes peninsula (Jakobsson et al., 1978). The rocks consist predominantly of sub-glacially erupted hyaloclastites, breccias and pillow-lavas, intercalated with Pleistocene and Holocene lava ows and dyke intrusions. At depths greater than 1500 m, dykes, and to a lesser extent sills, predominate. et al., 1978; Arnrsson, 1995). Abundant vertical fractures provide very high permeability across the reservoir with The heat source of the geothermal system is considered to consist of a shallow (13 km) sheeted dyke complex (Arnrsson

74

CHAPTER 4.

Figure 4.1: Map of the Reykjanes peninsula with the Svartsengi, Eldvrp and Reykjanes high-temperature geothermal elds (modied from Fridriksson et al., 2006).

values up to 100150

1015 m2

(Arnrsson, 1995). The reservoir in its natural state

was liquid-dominated and the temperature across the eld is very uniform at about 240 C. The deep groundwater consists of seawater-groundwater. Drillings in the western part of the Reykjanes peninsula outside the geothermal elds reveal the existence of a fresh water lens oating on top of that seawater-groundwater (Sigurdsson, 1986). groundwater level at In the middle of the peninsula, north of Svartsengi, the lens is about 50 m thick and the

2 m above sea level.

The fresh water lens thins towards the coast

in south, west and north. The producing eld is hydrologically connected to the high-temperature area of Eldvrp, located about 6 km to the southwest (Fig. 4.1), as shown by resistivity surveys (Stefnsson et al., 1976), geochemical studies (Bjarnason, 1984), as well as by pressure monitoring, subsidence measurements, and gravity surveys. The total area of the eld 2 is considered to be close to 7 km and shaped like a rectangle extending in an eastwest direction (Gudmundsson and Thrhallsson, 1986). liquid-dominated aquifer extends from 600 to at least The depth of the producing m depth (Bjrnsson and

2000

Steingrmsson, 1992). The volume of the total geothermal system has been estimated 3 as 1525 km (Bjarnason, 1996).

4.3 Production history

Production from the Svartsengi high-temperature eld started in 1976. Delivery of hot-water for district heating was followed shortly by electric power generation. The installed generating capacity was 2 MW in 1977, increasing to 8 MW in 1980, 11.6 MW

75

4.3. PRODUCTION HISTORY

Figure 4.2: Annual discharge and injection in million tonnes of uid.

in 1989, 16.4 MW in 1993, 46.4 MW in 1999, and nally to 76.4 MW in April 2008 (Arnrsson et al., 2008). The annual and cumulated uid withdrawal from the reservoir from 1976 to 2006 is shown in Fig. 4.2 and Fig. 4.3, respectively. The total uidliquid and vaporwithdrawn from wet-steam wells increased sharply in the rst years of 9 production up to a maximum of 9.84 Mt (megatonnes, 10 kg) in 1986. Since then, uid withdrawal from wet-steam wells has ranged between 6.0 and 9.7 Mt/year. Reservoir pressure drawdown caused by production from the eld has led to the formation of a vapor cap at the top of the reservoir. Well 10, which is only 425 m deep, stopped discharging liquid water in 1984 and became the rst well to produce dry steam from the vapor cap. Three other wells were drilled into the vapor cap and brought on stream in 1996, 1999 and 2001, respectively. The spent uid has been mostly disposed o at the surface, but a fraction of it was injected irregularly between 1984 and 1999. Injection was resumed in 2001 and has been continued since, reaching 4.40 Mt in 2006 (Fig. 4.2). The total mass of uid withdrawn from the aquifer between 1976 and 2006 is 243 Mt, and the cumulated mass of injected liquid is 27 Mt. The net mass extraction from the 3 eld is thus 216 Mt, corresponding to a volume of 0.26 km of liquid water at 238 C. Regular downhole pressure measurements carried out by Iceland GeoSurvey show that the pressure drawdown in monitored wells ranges between 25 and 32 bar. If we 3 assume a uid density of 816 kg/m , the corresponding water level drawdown is 312 to 400 m. Between 96 and 98% of the gas discharged from the wells at Svartsengi is CO2 . The emissions from the wet-steam wells have been relatively constant over time, ranging between 2,700 and 4,700 tonnes per year (Fig. production from these wells. declined since, to 4.4). Emissions from the dry-steam wells, on the other hand, are much higher, and they have increased with increasing Carbon dioxide emissions from the four wells tapping steam from the vapor cap reached a maximum in 2002 (60,000 tonnes) but have

43,000

tonnes in 2006 (Fig. 4.4).

76

CHAPTER 4.

Figure 4.3: Cumulated discharge and injection in million tonnes of uid.

Figure 4.4: Annual CO2 emissions (in tonnes) from wet-steam and dry-steam wells at Svartsengi (Fridriksson et al., 2007).

77

4.4. SAMPLING, ANALYSES AND CALCULATIONS

4.4 Sampling and analytical techniques and calculation of aquifer uid compositions
Ten of the Svartsengi wells were sampled for the present study, six wet-steam wells and four dry-steam wells. The sampling and analytical methods used were those described by Arnrsson et al. (2006). Monitoring samples, which were extracted from Iceland Initially gases and condensate were GeoSurvey reports to Sudurnes Regional Heating Company, were collected as described by Arnrsson et al. (2006) except for the gases. collected separately as described by Arnrsson et al. (2000) but later by the method given by Arnrsson et al. (2006). However, gas analytical methods have been the same throughout the monitoring period. Dissolved solids in monitoring water samples have been analyzed by a variety of methods. For wet-steam wells, the total discharge composition is taken to represent the aquifer liquid composition. The vapor fraction of the discharge was calculated from the measured sampling pressure, taking the discharge enthalpy to be that of vapor-saturated liquid at the aquifer temperature. We have

X d,v =
where

hf,l hd,l hd,v hd,l

(4.1)

f,l is the vapor fraction of the discharge at sampling conditions, h is the d,l d,v specic enthalpy of the aquifer liquid, and h and h are the specic enthalpies of

X d,v

the liquid and the vapor at sampling conditions, respectively. For any component i, we have

mf,l = md,l (1 X d,v ) + md,v X d,v i i i

where

(4.2)

denotes concentration.

The aquifer liquid compositions including pH were

calculated with the aid of the WATCH speciation program (Arnrsson et al., 1982), version 2.1 (Bjarnason, 1994). The results are shown in Table 4.1. Vapor samples from dry-steam wells are taken to represent the composition of the vapor cap.

4.5 Fluid composition

The deep reservoir uid at Svartsengi is sub-boiling and consists of a mixture of twothirds seawater and one-third meteoric water (Arnrsson, 1978; Ragnarsdttir et al., 1984; Bjarnason, 1988, 1996; Lonker et al., 1993). The composition of the reservoir liquid is remarkably uniform, with a Cl content of 1213,000 mg/kg. Slight but systematic dierences are observed in the aquifer uid Cl content of individual production wells (Fig. 4.5). The deuterium content of the aquifer uid is consistent with its origin, as deduced from its Cl content (Lonker et al., 1993; Pope et al., 2008). The fresh water component in the Svartsengi reservoir uid is considered to originate from the fresh water lens mentioned in section 4.2. Relative to seawater and its Cl content, the Svartsengi brine is enriched in Si, K, Ca and B, practically devoid of Mg and SO4 , much depleted in F and slightly in Na (Table 4.1). The in situ aquifer water pH is around 5, as calculated by the WATCH speciation program. The trace element composition of the Svartsengi brine generally

78

CHAPTER 4.
Table 4.1: Major and trace elements and major gas concentrations in aquifer liquid of wet-steam wells. Sampling pressure and vapor fraction are also shown. Concentrations of major components and trace elements in mg/kg and respectively.

g/kg,

Well Sample #

SV-7 04-3005

SV-8 04-3003 10.09.2004 14.0 9.91 5.11 442 6380 916 1033 0.614 12222 0.15 6.56 25.5 0.010 0.06 7.84 403 1.1 0.04 36.4 0.00 0.63 0.060 95.1 89.3 0.010 1721 39,856 0.043 0.065 0.495 54.5 <1 0.218 14.1 0.0111 110.5 2,790 210 7.89 2.23 <10 <0.1 2,736 1.522 <0.5 <0.02 1.97 7.81 <0.005 2.09 0.651 2.53
<0.05

SV-9 04-3032 01.12.2004 14.8 9.38 5.20 448 6373 915 1025 0.280 12054 0.15 6.63 25.7 0.143 0.11 7.63 227 5.3 0.04 9.0 0.00 0.20 0.010 169.5 81.5 <0.001 1203 40,999 0.091 0.156 1.367 53.7 <1 0.436 19.2 0.0312 119.4 2,342 118 5.62 3.50 13.85 <0.1 2,806 1.403 <0.5 <0.02 1.38 6.17 <0.005 7.34 <0.5 <2
79

SV-11 04-3029 01.12.2004 19.0 7.40 4.72 431 6394 920 1032 0.531 12100 0.14 7.06 27.3 0.125 0.15 7.53 919 10.9 0.46 56.9 0.00 1.08 0.090 123.7 53.9 0.012 1415 41,220 0.117 0.155 3.279 55.5 1.2 0.609 20.9 <0.0020 72.4 2,557 191 5.56 3.58 10.59 0.154 2,857 0.541 <0.5 <0.02 3.61 6.66 <0.005 3.75 <0.5 3.63
<0.05

SV-18 04-3004 10.09.2004 14.0 9.91 5.22 427 6813 1009 1023 0.427 12912 0.14 6.92 25.0 0.008 0.06 7.74 318 7.3 0.02 4.7 0.00 0.14 0.020 110.5 94.2 0.013 1920 45,290 0.134 0.100 1.839 57.6 <1 0.063 12.5 0.0092 120.5 2,699 185 9.15 2.27 <10 <0.1 2,980 1.667 <0.5 <0.02 3.65 8.43 <0.005 3.4 0.572 <2
<0.05

SV-19 04-3006 10.09.2004 14.5 9.57 5.37 421 6809 994 1064 0.369 12942 0.13 7.12 25.9 0.003 0.06 8.00 221 4.5 0.02 5.7 0.00 0.13 0.020 119.1 95.5 0.023 1573 47,275 0.072 <0.05 0.559 56.0 <1 <0.05 15.1 0.0088 99.1 2,518 156 5.85 1.96 12.00 <0.1 2,927 1.682 <0.5 <0.02 1.42 7.56 <0.005 4.01 <0.5 2.25
<0.05

Sampling date 10.09.2004 Pd (bar-g) 15.5 Xd,v (% w/w) 8.93 pH (at 238 C) 4.88 SiO2 429 Na 6650 K 961 Ca 1069 Mg 0.392 Cl 12664 F 0.13 B 6.41 SO4 23.8 Fe 0.036 Al 0.06 Sr 8.00 CO2 646 H2S 15.8 H2 0.38 N2 5.4 O2 0.00 Ar 0.15 CH4 0.070 Ag Al As Au Ba Br Cd Co Cr Cs Cu Ga Ge Hg I Li Mn Mo Ni P Pb Rb Sb Sn Th Ti Tl U V W Zn

Trace elements

102.5 71.7 0.011 1474 44,865 0.124 0.127 1.227 54.8 <1 0.615 16.1 0.0066 70.6 2,371 139 7.03 4.93 9.71 0.110 2,765 0.890 <0.5 <0.02 2.02 7.73 <0.005 2.77 0.539 1.95

<0.05

<0.05

4.5. FLUID COMPOSITION

Figure 4.5: Chloride concentration in the aquifer uid of wet-steam wells. Open and full symbols represent data from Iceland GeoSurvey and samples collected for this study, respectively.

diers much from that of seawater, in particular the concentrations of As, Ba, Fe, Ge, Mo, Rb and Sr. The major dissolved gas is CO2 . It accounts for 9698% of the total gas, the remainder being mostly H2 S, H2 and N2 . At present, CO2 concentrations are 200 800 mg/kg in the liquid reservoir, but some 20,000 mg/kg in the vapor cap (Table 4.2). The dierence in the compositions of the geothermal brine and the source uid is the consequence of interaction of the source uid with the basaltic rock. Additionally, some of the CO2 and the As may be derived from a magmatic source (Giroud and Arnrsson, 2008a,b).

Table 4.2: Gas concentrations in the vapor discharge from dry-steam wells. Concentrations in mg/kg.

Well Sample #

SV-10 05-3001

SV-14 04-3030 01.12.2004 21,698 179 6.47 461.1 0.00 8.41 1.18

SV-16 05-3002 14.01.2005 26,467 418 9.66 93.8 0.00 2.60 2.82

SV-20 04-3031 01.12.2004 19,625 349 11.33 91.2 0.00 2.52 1.77

Sampling date 01.12.2004 CO2 29,292 H2 S 411 H2 9.94 N2 391.1 O2 0.00 Ar 8.00 CH4 2.12

80

CHAPTER 4.

4.6 Evolution of gas concentrations

4.6.1 Wet-steam wells
Until 1990, gas concentrations (CO2 , H2 S and H2 ) in the aquifer uid feeding wetsteam wells (nos. 7, 8, 9 and 11) are on the whole about the same (Fig. 4.6). After 1990 large dierences are on the other hand seen between wells. Fig. 4.6 shows that the CO2 concentration decreases between 1982 and 1990 in all of the wet-steam wells. Since 19901991, an increase is observed in the CO2 concentration in wells 7 and 11. This increase becomes very sharp between 1999 and 2000, but in the last few years, concentrations have stabilized and vary between 500 and 800 mg/kg, well 11 showing the highest concentrations. In well 8, CO2 concentrations remain mostly stable in the period 19901999. The CO2 in well 9 continues to decrease. As in wells 7 and 11, an increase is also seen between 1999 and 2000 in wells 8 and 9, but it is not as sharp. This increase coincides with increased production from the reservoir when wells 18 and 19 were put on line. The CO2 content of the discharge of these two wells, as well as that of wells 8 and 9, changed little until about 2005, but has decreased since. The H2 S concentrations in the aquifer uid of wet-steam wells range mostly between 5 and 10 mg/kg until 1990 (Fig. 4.6). There is complete overlap between wells, and After 1990, H2 S concentrations apparently, concentrations do not vary with time.

become dierent between wells in a manner comparable to that for CO2 . Some samples show almost no H2 S, specially after 2003. Analyzed H2 S concentrations are sensitive to air contamination upon sampling, because H2 S reacts rapidly with O2 , particularly in an alkaline medium like that used by Iceland GeoSurvey for vapor sampling in recent years (see section 4.4). As a result, air contamination likely leads to an underestimate of the H2 S content of the vapor, particularly when its concentrations are low. Small air contamination of the vapor upon sampling leads to high N2 and Ar concentrations. Indeed, samples low in H2 S tend to be high in N2 . Analyzed H2 concentrations are close to the detection limit of the analytical method used. No clear trend is observed before 1990 for any of the wells. Then, wells 7 and 11 show an increase, particularly between 1991 and 2000, as for CO2 and H2 S. A smaller increase is observed for wells 8 and 9, again just as for CO2 and H2 S (Fig. 4.6). The increase in the gas concentrations in wells 7 and 11 after 19901991 is believed to be a consequence of the drawdown of the water level and a corresponding downward migration of the interface between the vapor cap and the liquid reservoir. The pressure drawdown will cause the depth level of rst boiling in the liquid-dominated reservoir to migrate downwards. The slight excess vapor in the discharge of wells 7 and 11 may come from the vapor cap, or from rising vapor bubbles in the liquid reservoir, depending on the depth level of producing horizons intersected by these wells. Enhanced drawdown in the reservoir in 1999 to 2000, when wells 18 and 19 came on line, led to a further increase in the gaseous vapor of wells 7 and 11, and such vapor also appeared in wells 8 and 9. The fraction of vapor forming the vapor cap in the total uid discharge from wells 7 and 11 has been estimated using average concentrations of CO2 , H2 S and H2 in the other four wet-steam wells and in the dry-steam wells. Table 4.3 shows a three-fold increase in the vapor mass fraction between 19961997 and 20062007, from 0.7% to 2.1% and from 0.9% to 3.3% in wells 7 and 11, respectively. The vapor fractions calculated with

81

4.6. EVOLUTION OF GAS CONCENTRATIONS

Figure 4.6: CO2 , H2 S and H2 concentrations versus time in the aquifer uid of wet-steam wells. Symbols have the same meaning as in Fig. 4.5.

82

CHAPTER 4.
Table 4.3: Gas concentrations and estimates of the fraction of vapor (in % w/w and % v/v) owing into wells 7 and 11. Concentrations are averages (in mg/kg) of all samples taken in the periods 19961997 and 20062007, respectively.

Well 7 Well 11 Other wet-steam wells Dry-steam wells

CO2

19961997 453 473 215 37,422 7.97 9.94 4.26 433.67 0.060 0.070 0.013 8.843 % w/w 0.60 0.86 0.54 0.68 0.69 1.32 0.65 0.89 % v/v 11.7 15.2 10.0 12.4 12.6 21.6 11.9 15.6

20062007 546 778 236 18,445 12.68 18.60 6.06 285.18 0.225 0.253 0.030 8.828 % w/w 1.70 2.37 2.22 2.10 2.98 4.49 2.54 3.34 % v/v 26.3 33.3 31.8 30.6 38.7 49.2 34.9 41.5

H2 S

Well 7 Well 11 Other wet-steam wells Dry-steam wells

Well 7 Well 11 Other wet-steam wells Dry-steam wells

H2

Well 7

Vapor fraction

CO2 H2 S H2 Average CO2 H2 S H2 Average

Well 11

H2 S (Table 4.3) are higher than those calculated from CO2 and H2 . This is likely to be due to an underestimate of the H2 S concentration in the wet-steam well uids due to air contamination of the sample, as mentioned above. The decrease in gas concentrations of well 9 is most likely due to inow of progressively more degassed liquid due to its boiling and subsequent segregation of the boiled liquid and the vapor. The increase in the gas content in wells 8 and 9 around the year 2000, is likely to be due to boiling of previously undegassed reservoir liquid.

4.6.2 Dry-steam wells

At the outset, well 10 discharged wet steam, but since 1984 it has produced dry steam only.Initially, CO2 concentrations in the vapor cap were close to 50,000 mg/kg on average (Fig. 4.7). They have been decreasing since at a rate of about 1,700 mg/kg per year. There is a small dierence between wells, well 16 showing usually the highest CO2 concentrations, and well 20 the lowest. The average CO2 concentration in the four wells in the period 19992000 was 20,385 mg/kg, decreasing to 15,020 mg/kg in the period 20062007. A very similar trend is observed for H2 S and H2 : Between 19992000 and 20062007, the average H2 S and H2 concentrations decreased from 365 to 308 mg/kg, and from 6.33 to 5.37 mg/kg, respectively.

83

4.6. EVOLUTION OF GAS CONCENTRATIONS

Figure 4.7: CO2 , H2 S and H2 concentrations versus time in the discharging vapor from the dry-steam wells. Open and full symbols represent data from Iceland GeoSurvey and samples collected for this study, respectively.

84

CHAPTER 4.

Figure 4.8:

Magnesium concentration in the aquifer uid of wet-steam wells.

Symbols have the same meaning as in Fig. 4.5.

4.7 Changes in dissolved salts and pH

The concentration of Cl (Fig. 4.5), Na, K, Ca and SiO2 (Fridriksson et al., 2007) in wells producing from the liquid reservoir have not changed with time over the 25 years covered by this study. The concentrations of Mg have decreased, however, and those of F have increased (Figs. 4.8 and 4.9). It is thought that the cause of these changes is loss of CO2 from the reservoir liquid due to boiling, and rapid re-equilibration between solution and OH-bearing minerals (chlorite and smectite, see Lonker et al., 1993). Arnrsson et al. (1983) suggested that F concentrations in geothermal uids reacting with basaltic rock are controlled by exchange equilibria with OH-bearing minerals, such as chlorite and smectite. They observed that F /OH activity ratios were constant at any particular temperature. In seawater, F concentrations are 1.0 mg/kg and therefore 0.7 mg/kg in the source uid to the Svartsengi geothermal system. In the Svartsengi geothermal brine, F concentrations were about 0.1 mg/kg during the early years of production, but they have increased to about 0.2 mg/kg. If it is assumed that the increase in F + concentration is accompanied in an equal change in OH , then H activity would have decreased by a factor of 2, that is pH increased by 0.3 units. The decrease in Mg + 2 concentration by a factor of 2 to 4 could result from an equal decrease in (H ) activity +2 + 2 if hydrolysis reactions controlled the Mg /(H ) ratio, as can be seen from MgO

+ 2H+ = H2 O + Mg+2

(4.3)

where MgO represents the magnesium oxide component in a Mg-silicate mineral. A decrease of Mg concentrations by a factor of 2 to 4 corresponds to an increase in pH +2 of 0.15 to 0.3. Fig. 4.10 shows a plot of log(Mg ) activity versus -2log(F ) activity. +2 If a change in solution pH was the cause of changes in both Mg and F activities, one would expect the data points in Fig. 4.10 to fall on a line with unit slope. This is

85

4.7. CHANGES IN DISSOLVED SALTS AND PH

Figure 4.9: Fluoride concentration in the aquifer uid of wet-steam wells. Symbols have the same meaning as in Fig. 4.5.

Figure 4.10: Mg

+2

versus

2F

activities in the aquifer uid of wet steam wells.

Symbols have the same meaning as in Fig. 4.5. The line represents the unit slope.

86

CHAPTER 4.
indeed the case with most of the data points. Notable exceptions are data from wells 7 and 11, the discharges of these wells contain gaseous steam. This gaseous steam would not aect signicantly the true pH of the boiled liquid, but it aects the calculated in situ pH and therefore underestimates F activity and correspondingly overestimates the activity of the HF species. It is thus concluded that the calculated F activity for wells 7 and 11 are in error (too low F ) when the discharge of these wells contains signicant gaseous steam. As a consequence, the calculated pH does not reect the actual increase in the OH concentration, but shows instead a slow decrease with time (Fridriksson et al., 2006).

4.8 Formation of the vapor cap

As mentioned in section 4.3, the pressure drawdown in the liquid reservoir at Svartsengi of more than 25 bar has led to the formation of a vapor cap above the liquid reservoir. The pressure drawdown has enhanced boiling in the upper part of the liquid reservoir. The vapor formed subsequently separates from the liquid by gravity to accumulate at higher levels. Some of the steam escapes to the surface but apparently most of it cumulates in the bedrock. Evidently, gravity separation becomes operative at low vapor fractions, even in terms of volume (considerably less than 10%). The fraction of the liquid body which has vaporized to form the vapor cap has been estimated from the gas content of the discharges wet-steam and dry-steam wells. The calculation procedure is given below.

4.8.1 Vapor fraction calculations

Progressive boiling of liquid water in the Svartsengi reservoir leads to a decrease in its gas content. It also leads to a decrease in the gas content of the vapor cap; during the early stages of boiling, the vapor of the vapor cap is rich in gas, but it decreases with continued vapor formation. If equilibrium distribution is closely approached between liquid and vapor, the distribution coecient describes the relative concentration of gas

in the two phases. The distribution coecient

Ds

is dened as

Ds =
where superscript

nv s nl s n

(4.4) mole fraction. When gas

and

designate vapor and liquid, and

pressures are low, relative to vapor pressure, we have

ns =

ms 55.508 mv Ds s = l ms gas s in a al s fs

so :

(4.5)

(4.6) kg of vapor (Arnrsson et al., 2007).

where

designates concentration of

The solubility constant (Henry's Law constant) for gas

s, Ks ,

dened as

Ks =
87

(4.7)

4.8. FORMATION OF THE VAPOR CAP

where

al s

and

fs

are the activity of species

in the liquid and its fugacity over the solu-

tion, respectively, can be expressed in the following way for dilute uids and moderate pressures:

ml = Ks Ps s
where

(4.8)

Ps

is the partial pressure of species

s,

dened as (4.9)

Ps = ns Ptot
where

Ptot

is total pressure. Combining equations (4.5), (4.4), (4.8) and (4.9), leads to

55.508 Ds = Ks Ptot

(4.10)

Vapor fractions were calculated from an initial temperature of 240 C, with cooling steps due to adiabatic boiling of 0.01 C in an open system where the vapor produced at g each temperature step is immediately removed. The steam fraction X at temperature g T < 240 C, is expressed as, hf,t hg,l (4.11) X g,v = g,v h hg,l

where

are the enthalpy of the total uid at 240 C, and the enthalpy g of the liquid and vapor at T , the temperature of phase separation, respectively.

hf,t , hg,l

and

hg,v

A mass balance for gas

in the reservoir liquid and vapor cap is given by (4.12)

g

mf,l = mg,l (1 X g,v ) + mg,v X g,v s s s

where superscript

denotes initial reservoir liquid,

and vapor separate. Superscripts

g temperature T at which liquid l and v have the same notation as before. Combination

of equation (4.10) and (4.12) gives

55.508 mf,l = mg,l 1 + X g,v s s Ks P tot

(4.13)

We have selected the average gas content (CO2 , H2 S and H2 ) of the initial reservoir liquid to be represented by the average composition of the samples collected from wetf,l g,l steam wells in the period 19831985. From the selected ms , ms has been calculated g,v for selected X values with the aid of equation (4.13) and subsequently ms from equation (4.6). Values for the gas solubility constants were taken from Fernndez-Prini et al. (2003).

4.8.2 Results
The decline of the CO2 concentration in the uid of well 9 before 1999, before the sharp increase of the mass of uid withdrawn from the reservoir, amounts to 310 mg/kg (from 432 down to 122 mg/kg). If this decline in gas concentration is taken to be solely a consequence of adiabatic boiling, the fraction of steam produced from the boiling of the liquid during this period would be close to 0.85% w/w. As mentioned in section 4.6.1, the changes in the H2 S and H2 content of the liquid aquifer do not show trends that are as clear as for CO2 , mostly because of their overall lower concentrations.

88

CHAPTER 4.

Figure 4.11: Fraction of the total liquid that forms the vapor cap. Each point is an average of all data available that year for all four dry-steam wells.

Fig. 4.11, shows how the vapor fraction forming the vapor cap has increased with time. As based on the analyzed gas concentrations in the dry-steam wells. The results for CO2 and H2 S compare reasonably, but those for H2 are low. As already mentioned, the H2 data are not very reliable, particularly those in the initial aquifer liquid, because analyzed concentrations are close to the detection limit of the analytical method used. According to the results in Fig. 4.11, about 1% w/w (or 17% v/v) of the initial liquid had boiled in 1990, to yield steam for the vapor cap, this number had increased to 3% w/w (or 49% v/v) in 2006. Vapor formation amounting to 1% w/w assuming adiabatic boiling would cool the reservoir liquid by 4 C, that is from 240 to 236 C. 3% w/w vapor formation produces cooling by 11 C. This latter gure is signicantly higher than measured cooling in producing wells below the depth level of rst boiling. The reason for this is considered to be escape of early formed vapor to the surface and withdrawal of vapor from the vapor cap through the dry-steam wells. Both escape routes will cause the actual gas in the vapor cap to be lower than that calculated for adiabatic boiling.

4.9 Discussion
The best permeability at Svartsengi is provided by near-vertical ssures and faults as indicated by the geological structure and the homogeneity of reservoir temperature over large depth ranges. Distribution of hydrothermal minerals does not indicate a selfsealing zone on top of the reservoir. Also renewal of permeability by tectonic movements is frequent relative to the growth rate of hydrothermal minerals. At the nearby hightemperature eld at Reykjanes, epidote, which formed in Pre-Holocene times from fresh water geothermal uid has not yet re-equilibrated with seawater that has been circulating through the system for the last

10,000

years (Pope et al., 2008). Isotopic

89

4.10. SUMMARY AND CONCLUSIONS

exchange equilibria are relatively rapid so the results from Reykjanes suggest that the rate of hydrothermal mineral formation by alteration of the basaltic rock is very slow, certainly in relation to the frequency of tectonic movements. Recharge into the Svartsengi reservoir, both natural and by injection, may cause the gas content of the uid discharged from wells to decrease. The eect of injected waste water should also increase the Cl content of the well uid. Such an increase has not been observed, indicating that the eect of used brine on decrease in the gas content of the well uid is not signicant. gravity in the area. or to a lesser extent. Boiling of the According to Eysteinsson (2000), the geothermal eld at Svartsengi has 70% natural recharge. These results are based on monitoring of These result indicate that cold recharge into the reservoir could cause a decrease in the gas content of the reservoir liquid but hot recharge would not,

240 C

volume as the specic volume of

reservoir liquid at Svartsengi causes much expansion of uid 240 C vapor is about 20 times that of liquid at the

same temperature. This volume increase will impede uid ow. It is likely that this eect, together with enhanced boiling by pressure drawdown, are the causes of the formation of the vapor cap. A self-sealing zone by hydrothermal mineral formation or impermeable strata, are not needed for the formation of such a cap whether it forms under natural conditions or by exploitation. Unfortunately, many of the vapor samples collected for the monitoring studies are air-contaminated, so it is not possible to use the unreactive gases like N2 and Ar to assess boiling processes and the fraction of liquid that has boiled to generate vapor for the vapor cap. It would be particularly interesting to have data on the noble gases for such an assessment, because the only source of these gases to the geothermal uid is air-saturated meteoric water and seawater, and the dierent noble gases have dierent solubilities in liquid so limited vapor formation by boiling will fractionate these gases to a dierent extent between boiled liquid and vapor.

4.10 Summary and conclusions

The pressure drawdown and subsequent enhanced boiling in the geothermal reservoir at Svartsengi due to important uid withdrawal for electricity production led to the formation of a vapor cap on top of the liquid dominated reservoir. The study of the changes in gas concentrations with time in both the liquid aquifer and the vapor cap allows us to estimate to up to 3% w/w the fraction of the liquid that has vaporized to form the vapor cap. Extensive boiling in the reservoir also leads to degassing of the liquid water. Removal of CO2 and H2 S decreases the pH of the remaining liquid, i.e. increases the activity of the OH ion. As a consequence, rapid equilibration with Mg and OH-bearing minerals leads to a decrease, respectively an increase, of Mg and F concentrations with time in the liquid reservoir. The gas concentrations in the vapor cap are several orders of magnitude higher than those in the liquid reservoir. The amount of CO2 released into the atmosphere per unit of electricity produced is therefore less favourable when the uid is withdrawn from the vapor cap rather than from the liquid dominated reservoir.

90

CHAPTER 4.
The presence of a cap rock or of a self-sealing process at the top of the aquifer may not be required for the formation of a vapor cap. The much enhanced vapor formation and volume increase in relation to permeability may be sucient for the vapor cap to form.

91

Appendix A Trace element analyses

Trace elements were analyzed on liquid water and vapor samples collected from most of the wells considered in this study. Results of the analyses are presented in the following tables.

93

Table A.1: Trace element analyses of liquid water samples from wet-steam wells.

Concentrations in

g/kg.
Ag Al As Au B Ba Br Cd Co Cr Cs

Sample

Well

94

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 04-3032 04-3029 04-3004 04-3006 05-3004 05-3003 04-3027 04-3026 04-3025 04-3024

N-12 N-09 K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-9 SV-11 SV-18 SV-19 RN-12 RN-15 Bdmdstadir Efri Reykir S-24 Reykholt S-1 Reykjabl S-1

0.019 0.002 0.001 <0.001 0.001 <0.001 0.002 <0.05 <0.001 0.002 0.001 0.002 0.003 <0.001 0.007 <0.001 0.005 0.002 0.013 <0.001 0.027 0.014 0.010 0.001 0.008 0.001 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 0.113 0.073 <0.001 <0.001 <0.001 <0.001

989 1040 1200 1660 969 1690 1060 1540 877 1390 1850 1340 1560 1360 1590 1150 1860 2160 1540 1680 1930 2280 1500 1420 1770 1720 112 105 186 132 122 131 61 92 54 476 191 544

148.0 24.3 38.8 102.0 105.0 42.3 88.9 16.8 0.8 23.8 213.0 129.0 24.4 90.3 14.1 57.1 8.1 50.6 80.5 53.1 28.3 84.0 88.6 40.4 48.1 93.4 78.3 98.6 89.4 57.5 104.0 105.0 139.0 156.0 1.5 2.1 16.9 15.2

0.0311 0.0051 0.0051 0.0092 0.0094 0.0005 0.0242 0.0008 0.0008 0.0014 0.0103 0.0026 0.0054 0.0038 0.0118 0.0054 0.0098 0.0059 0.0642 0.0010 0.0333 0.0258 0.0102 0.0111 0.0645 0.0021 0.0115 0.0114 <0.001 0.0127 0.0139 0.0255 0.0012 0.0325 <0.0001 0.0005 <0.0001 0.0016

3680 984 1230 1200 1670 1400 2200 845 615 896 2000 6220 1420 2310 1330 1860 1390 1950 2550 1580 1810 3830 1510 1710 1760 6790 7000 7260 7340 7540 7660 7840 7890 7860 132 163 350 541

0.904 2.200 1.640 1.920 0.623 0.265 1.340 0.895 0.579 3.940 4.010 1.900 0.479 0.423 0.608 0.484 0.508 0.361 1.300 0.370 0.488 0.814 0.374 0.386 0.278 0.569 1610.000 1900.000 1320.000 1510.000 2120.000 1730.000 6480.000 6650.000 0.223 0.171 0.241 0.066

350 115 82 72 260 39 440 260 114 97 240 120 430 600 370 620 490 260 510 680 230 550 590 320 670 420 49000 44000 45000 44000 50000 52000 74000 78000 140 150 250 83

0.004 0.035 0.024 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 0.135 0.047 0.100 0.125 0.148 0.080 0.417 0.923 <0.002 <0.002 <0.002 <0.002

0.190 <0.005 <0.005 0.015 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 0.006 <0.005 <0.005 <0.005 <0.005 0.007 <0.005 0.006 0.010 0.139 0.072 0.171 0.165 0.110 <0.05 0.119 0.320 0.005 0.005 <0.005 0.006

0.13 0.052 0.081 0.089 0.117 0.105 0.04 0.036 0.018 0.045 0.047 0.102 0.08 0.045 0.118 0.193 0.095 0.088 0.086 0.064 0.229 0.114 0.057 0.069 0.101 0.111 1.34 0.546 1.5 3.5 2.03 0.615 0.291 0.268 0.026 0.086 <0.01 0.038

2.520 1.150 7.790 8.460 9.660 5.290 15.900 3.920 4.010 8.460 6.830 7.210 3.120 3.910 4.280 3.210 6.140 3.050 7.390 6.880 2.660 4.660 6.610 3.820 6.140 2.020 59.900 60.200 58.900 59.200 63.600 61.600 62.600 61.600 0.770 0.660 0.758 0.342

Table A.1: (cont.)

Sample
<0.0020

Well

Cu

Ga

Ge

Hg

Li

Mn

Mo

Ni

Pb

95

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 04-3032 04-3029 04-3004 04-3006 05-3004 05-3003 04-3027 04-3026 04-3025 04-3024 0.006 <0.0020 <0.0020 <0.0020 <0.0020 <0.0020 <0.0020 <0.0020 0.003 <0.0020 <0.0020 0.003 <0.0020 0.004 <0.0020 0.005 <0.0020 0.008 <0.0020 0.013 0.007 <0.0020 <0.0020 0.003 <0.0020 0.007 0.012 0.034 <0.0020 0.010 0.010 0.101 0.068 <0.0020 0.004 <0.0020 0.019

N-12 N-09 K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-9 SV-11 SV-18 SV-19 RN-12 RN-15 Bdmdstadir Efri Reykir S-24 Reykholt S-1 Reykjabl S-1

0.631 3.910 0.446 1.730 0.175 0.542 0.116 0.526 0.107 0.257 0.395 0.605 0.271 0.271 0.966 0.241 0.627 0.617 0.787 0.417 0.663 1.260 0.270 0.257 0.318 0.461 <1 <1 <1 1.280 <1 <1 <1 1.740 0.802 <0.1 0.115 0.156

3.21 4.28 3.85 6.15 4.92 6.92 5.68 5.12 3.38 4.74 6.61 4.30 5.72 4.08 5.09 4.26 6.18 7.80 4.95 5.05 7.09 6.96 5.06 5.31 5.90 5.77 0.67 0.24 0.48 0.65 0.07 <0.05 5.70 2.29 4.52 6.16 5.40 4.49

23.7 23.7 23.7 27.2 24.7 16.2 28.6 22.1 29.9 28.7 33.2 31.7 46.9 40.1 42.0 33.7 51.0 49.9 43.0 32.2 47.7 39.6 31.9 29.7 36.6 40.5 17.6 15.6 21.1 22.3 13.8 16.6 22.3 23.0 7.4 9.3 8.3 10.7

10.20 4.25 2.61 2.35 5.68 1.10 9.68 11.20 3.17 3.00 6.87 3.11 8.50 10.40 6.61 11.10 8.55 5.46 11.70 12.10 5.28 11.90 34.80 6.85 11.00 7.81 77.10 122.00 131.00 77.30 133.00 109.00 292.00 300.00 2.43 2.60 5.87 1.21

213.0 112.0 156.0 283.0 264.0 247.0 370.0 182.0 91.6 285.0 474.0 215.0 186.0 194.0 225.0 188.0 278.0 187.0 381.0 274.0 146.0 312.0 223.0 234.0 277.0 197.0 2590.0 3080.0 2570.0 2730.0 2980.0 2770.0 3840.0 3930.0 25.2 43.6 44.1 40.5

2.240 1.070 1.210 1.480 1.590 0.967 1.760 0.755 0.337 0.653 1.660 2.540 0.372 0.698 0.155 0.773 0.158 0.328 0.405 0.209 0.158 0.864 0.393 0.531 0.223 0.754 152.000 232.000 130.000 204.000 204.000 172.000 2210.000 1500.000 0.308 0.299 0.540 0.633

0.91 0.34 2.88 2.56 3.87 4.58 2.57 8.13 1.34 5.59 2.19 4.21 1.47 5.98 1.12 6.17 1.48 1.37 3.72 7.48 1.56 3.47 8.91 1.90 2.66 3.14 7.68 8.71 6.17 5.94 10.10 6.44 64.40 92.50 8.57 7.36 25.80 24.90

0.718 0.090 0.053 0.269 <0.05 <0.05 0.078 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 0.133 <0.05 <0.05 0.295 <0.05 0.139 0.089 <0.05 <0.05 <0.05 <0.05 5.380 2.460 3.840 3.820 2.510 2.160 0.535 1.330 0.245 0.322 0.375 1.300

2.21 <1 1.02 1.38 1.25 1.14 2.32 1.08 <1 1.21 1.96 1.31 1.03 <1 1.23 1.23 1.16 1.29 1.91 1.02 1.47 30.10 1.18 1.13 1.52 1.58 10.60 <10 15.20 11.30 <10 13.20 21.50 15.40 6.70 <1 <1 2.62

0.042 0.105 0.038 0.018 <0.01 0.011 0.011 0.050 0.023 0.027 0.017 0.019 0.011 <0.01 0.021 <0.01 0.018 <0.01 0.126 0.015 0.140 0.142 <0.01 0.026 0.055 <0.01 0.120 <0.1 <0.1 0.164 <0.1 <0.1 <0.1 <0.1 0.226 0.021 0.023 0.059

CHAPTER A.

Table A.1: (cont.)

Sample

Well

Rb

Sb

Sn

Sr

Th

Ti

Tl

Zn

96

<0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005

0.001

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3019 04-3009 04-3023 04-3011 04-3014 04-3012 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 04-3032 04-3029 04-3004 04-3006 05-3004 05-3003 04-3027 04-3026 04-3025 04-3024
<0.0005 <0.0005 <0.0005

N-12 N-09 K-13 K-15 K-16 K-17 K-20 K-21 K-24 K-27 K-32 K-34 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-9 SV-11 SV-18 SV-19 RN-12 RN-15 Bdmdstadir Efri Reykir S-24 Reykholt S-1 Reykjabl S-1 0.003

93.6 104.0 210.0 196.0 206.0 124.0 339.0 156.0 167.0 176.0 245.0 184.0 121.0 153.0 150.0 127.0 142.0 97.8 161.0 173.0 93.6 137.0 152.0 113.0 143.0 71.2 3020.0 3020.0 3080.0 3050.0 3290.0 3220.0 4150.0 4200.0 18.6 30.7 24.2 19.4

1.170 0.854 1.020 1.880 1.680 1.210 2.310 0.811 0.236 1.160 3.030 3.730 0.499 1.130 0.506 0.840 0.563 0.751 1.750 0.676 0.640 1.060 1.970 0.746 0.880 0.664 0.972 1.680 1.540 0.577 1.840 1.850 1.090 1.370 0.065 0.163 0.334 0.653

<0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.05 <0.05 <0.05 <0.05

2.55 32.90 22.50 10.10 5.16 0.97 6.93 12.20 28.70 16.80 9.42 5.41 2.20 2.23 2.74 3.18 2.28 1.87 1.16 2.19 2.19 0.85 3.12 1.54 0.87 2.33 8050.00 8410.00 7660.00 8140.00 7820.00 8160.00 9010.00 9120.00 11.00 7.72 16.90 6.34

<0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.002 <0.002 <0.002 <0.002

0.283 0.312 0.324 0.272 0.178 0.245 0.198 0.246 0.064 0.153 0.254 0.301 0.077 0.137 0.140 0.221 0.162 0.141 0.392 0.150 0.154 0.300 0.174 0.147 0.155 0.599 2.210 2.170 1.510 3.850 4.030 1.560 6.150 <0.1 0.283 0.068 0.075 0.147

0.017 0.020 0.052 0.055 0.011 0.011 0.021 0.046 0.020 0.095 0.097 0.019 <0.005 0.006 <0.005 0.007 <0.005 <0.005 0.031 0.009 0.012 0.015 <0.005 0.006 0.019 <0.005 8.440 8.620 6.770 7.110 9.310 8.320 9.940 17.600 0.015 0.008 0.015 0.011

0.781 0.158 1.060 2.120 1.730 1.570 1.890 1.150 0.492 1.880 7.940 4.590 2.270 2.700 0.602 1.760 2.190 1.960 1.760 3.060 0.639 1.770 2.910 1.500 4.100 2.100 3.020 2.310 8.060 4.000 3.750 4.410 9.970 9.080 4.400 1.890 0.921 1.410

2.070 2.220 4.650 6.870 6.410 3.870 6.990 4.210 3.640 4.470 6.590 3.500 5.730 5.350 4.480 5.050 6.020 5.200 4.930 5.440 4.140 4.870 5.320 4.720 5.570 5.210 0.589 0.719 <0.5 <0.5 0.631 <0.5 0.884 1.000 4.480 5.010 7.190 6.400

0.432 0.992 0.844 <0.2 0.505 0.509 0.272 0.214 1.600 <0.2 0.544 0.350 0.720 0.464 0.923 0.485 0.780 0.610 0.444 0.692 11.200 0.897 0.707 2.240 6.510 0.633 2.130 2.790 <2 3.880 <2 2.470 16.300 50.900 0.859 0.828 0.524 0.848

Table A.2: Trace element analyses of vapor samples from wet-steam and dry-

steam wells. Concentrations in

g/kg
Al 84.5 17.8 18.8 22.8 23.1 55.4 169.0 27.4 As Au B Ba Cd Co Cr Cs

Sample

Well

Ag

<0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001

97

<0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0010 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001 <0.0001

0.0011

CHAPTER A.

0.0001

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3018 04-3019 04-3009 04-3023 04-3011 04-3017 04-3020 04-3012 04-3013 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 05-3001 04-3029 05-3002 04-3004 04-3006 04-3031 05-3004 05-3003 04-3026 04-3024 0.0001 5.5 11.5 188.0 342.0 114.0 98.8 22.1 43.7 23.1 30.9 24.1 11.4 28.5 27.7 51.4 27.7 32.1 25.9 35.1 83.0 172.0 157.0 46.7 183.0 74.3 210.0 173.0 66.3 197.0 119.0 7.1 9.7

N-12 N-9 K-13 K-15 K-16 K-17 K-19 K-20 K-21 K-24 K-27 K-30 K-31 K-33 K-35 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-10 SV-11 SV-16 SV-18 SV-19 SV-20 RN-12 RN-15 Efri Reykir Reykjabl

0.003 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0.001 <0.001 <0.001 <0.001 <0.001 0.003 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0.010 <0.001 <0.001 0.001 <0.001 <0.001 <0.001 <0.001 <0.001 0.003

3.21 2.95 9.54 4.41 3.10 1.61 2.64 12.00 4.90 9.13 9.43 3.89 4.80 5.65 5.65 3.68 4.34 2.99 3.12 7.79 3.82 5.45 5.76 147.00 8.65 2.55 2.56 6.19 4.57 3.44 4.39 22.10 7.17 1.72 8.40 11.90 6.04 2.55 2.00 10.10 6.83

0.100 <0.050 <0.050 0.061 0.056 <0.050 <0.050 <0.050 <0.050 0.359 0.125 <0.050 0.969 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 0.186 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 0.193 0.317 0.055 0.051 <0.050 0.922 0.283 0.083 0.348 1.900 <0.050 <0.050

1.180 0.533 0.252 0.203 0.198 0.250 0.294 0.445 0.395 0.068 0.142 0.185 0.241 0.339 0.471 0.168 0.167 0.245 0.203 0.142 0.309 1.840 0.346 1.350 1.620 0.236 0.318 0.446 0.053 0.735 0.537 0.261 1.110 0.175 0.461 0.910 2.730 0.394 1.660 0.244 6.840

0.030 0.003 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 0.005 <0.002 0.008 <0.002 <0.002 0.002 <0.002 <0.002 0.005 <0.002 <0.002 <0.002 <0.002 0.015 0.002 <0.002 <0.002 <0.002 <0.002 0.028 0.007 0.050 <0.002 <0.002 0.017 0.004 <0.002 0.015 0.005 <0.002 0.003

0.009 0.007 0.007 <0.005 <0.005 <0.005 <0.005 <0.005 0.008 <0.005 0.014 0.008 0.008 <0.005 <0.005 <0.005 0.007 <0.005 <0.005 0.010 0.006 0.068 <0.005 0.178 0.005 <0.005 <0.005 0.006 0.045 0.022 0.023 0.169 0.066 0.023 0.104 0.017 0.010 0.022 0.016 0.021 4.510

11.500 2.790 0.765 0.175 0.177 0.915 0.359 1.140 1.060 0.202 2.970 0.150 0.613 0.693 1.670 1.240 2.420 3.230 0.649 1.360 0.788 16.300 0.501 35.200 6.090 0.553 0.681 5.330 0.424 2.710 6.740 113.000 9.920 12.800 31.500 1.360 1.830 1.520 8.450 0.753 10.600

0.089 0.127 0.201 0.258 1.130 0.267 0.272 0.689 0.062 0.756 0.187 0.259 0.447 0.171 0.405 0.363 0.321 0.232 0.384 0.361 0.229 0.150 0.325 0.065 0.769 0.433 0.485 0.043 0.129 0.489 0.141 0.033 0.292 <0.030 0.472 0.773 0.511 <0.030 0.041 0.060 1.740

Table A.2: (cont.)

Sample
<0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050

Well

Cu

Ga

Ge

Hg

Li

Mn

Mo

Ni

Pb

0.069

98

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3018 04-3019 04-3009 04-3023 04-3011 04-3017 04-3020 04-3012 04-3013 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 05-3001 04-3029 05-3002 04-3004 04-3006 04-3031 05-3004 05-3003 04-3026 04-3024 0.177 0.340 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 <0.050 0.119 <0.050 <0.050 0.105 <0.050 0.068 <0.050 <0.050 <0.050 <0.050 <0.050 0.076 0.154 1.060 0.091 0.253 1.060 0.164 0.065 0.217 0.217 0.196 0.293

N-12 N-9 K-13 K-15 K-16 K-17 K-19 K-20 K-21 K-24 K-27 K-30 K-31 K-33 K-35 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-10 SV-11 SV-16 SV-18 SV-19 SV-20 RN-12 RN-15 Efri Reykir Reykjabl

0.104 0.114 0.153 <0.100 <0.100 <0.100 <0.100 <0.100 <0.100 0.140 0.188 <0.100 1.510 <0.100 <0.100 0.145 0.102 <0.100 0.679 <0.100 <0.100 0.104 <0.100 0.145 0.348 <0.100 <0.100 <0.100 <0.100 0.173 0.362 0.816 0.117 <0.100 0.646 0.173 <0.100 0.473 <0.100 <0.100 1.420

0.031 0.017 0.051 0.063 0.055 0.004 0.009 0.026 0.049 0.036 0.039 0.013 0.015 0.032 0.038 0.090 0.037 0.043 0.060 0.056 0.027 0.080 0.041 0.146 0.060 0.040 0.043 0.061 0.151 0.013 0.010 0.016 0.024 0.001 0.011 0.040 0.022 0.011 0.010 0.034 0.037

0.020 0.016 0.012 <0.001 0.008 <0.001 <0.001 0.013 0.018 <0.001 0.021 <0.001 <0.001 0.018 <0.001 0.036 0.026 0.043 0.025 0.063 0.048 0.038 0.029 0.096 0.109 0.049 0.015 0.030 0.045 0.033 0.021 0.035 0.023 0.009 0.045 0.025 0.007 0.026 0.021 0.018 0.057

0.006 0.008 0.005 0.014 0.015 0.012 0.010 0.006 0.008 0.010 0.008 0.013 0.003 0.011 0.008 0.014 0.034 0.019 0.036 0.018 0.014 0.007 0.033 0.022 0.004 0.016 0.017 0.011 0.018 0.041 0.010 0.007 0.102 0.055 0.037 0.088 0.035 0.025 0.061 0.014 0.201

0.157 0.427 0.585 0.887 1.350 0.181 0.714 0.882 0.808 0.647 0.432 0.745 0.328 0.300 0.219 1.130 0.723 1.030 0.578 1.160 0.290 0.354 0.488 0.475 2.100 0.336 0.477 0.012 0.894 2.100 0.868 0.188 0.437 0.059 2.970 1.630 0.478 0.233 1.460 0.896 0.408

17.50 13.00 5.57 1.55 1.28 3.41 4.95 7.80 14.10 0.66 2.99 3.88 4.03 9.66 10.40 2.80 2.78 3.90 3.89 2.32 5.56 42.50 5.47 14.80 58.80 4.02 2.93 8.32 0.84 3.99 6.26 6.10 12.30 2.16 11.50 5.47 15.40 1.71 25.40 7.95 41.80

1.730 0.806 0.533 0.108 0.136 0.343 0.278 0.491 3.250 0.517 1.610 0.184 0.354 0.528 0.506 0.436 0.560 0.661 0.406 0.391 0.624 12.000 0.099 15.300 0.317 0.178 0.190 0.609 0.588 1.760 2.910 7.460 8.760 1.650 7.700 1.490 2.470 1.140 0.955 3.310 383.000

0.4930 0.6840 0.2810 0.0915 0.1680 0.0147 0.0233 0.0278 0.2940 0.1950 1.2400 0.1260 0.1570 0.1060 0.0773 0.1430 0.1040 0.1270 0.2880 0.1000 0.0240 0.0176 0.0114 3.7500 1.3700 0.0180 0.0506 0.0827 0.0731 11.9000 9.8000 1.8700 0.2520 0.6280 128.0000 1.2700 0.1870 1.6600 1.4900 0.1710 2.1800

Table A.2: (cont.)

Sample

Well

Rb

Sb

Sr

Te

Ti

Tl

Zn

99

<0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010

<0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005

0.010

<0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010 <0.010

0.010

0.018

0.012

CHAPTER A.

04-3007 04-3008 04-3010 04-3015 04-3022 04-3021 04-3018 04-3019 04-3009 04-3023 04-3011 04-3017 04-3020 04-3012 04-3013 04-3040 04-3042 04-3038 04-3043 04-3039 04-3048 04-3001 04-3049 04-3037 04-3002 04-3050 04-3046 04-3045 04-3041 04-3005 04-3003 05-3001 04-3029 05-3002 04-3004 04-3006 04-3031 05-3004 05-3003 04-3026 04-3024 0.020
<0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005 <0.005

N-12 N-9 K-13 K-15 K-16 K-17 K-19 K-20 K-21 K-24 K-27 K-30 K-31 K-33 K-35 NJ-5 NJ-6 NJ-7 NJ-9 NJ-10 NJ-11 NJ-13 NJ-14 NJ-16 NJ-19 NJ-20 NJ-21 NJ-22 NJ-23 SV-7 SV-8 SV-10 SV-11 SV-16 SV-18 SV-19 SV-20 RN-12 RN-15 Efri Reykir Reykjabl

1.560 5.150 5.860 5.430 15.300 2.460 3.950 7.330 4.640 9.710 5.210 5.000 4.910 3.910 4.010 10.300 7.300 8.730 10.500 9.790 4.590 3.530 6.350 1.540 9.160 7.510 7.500 2.430 4.880 18.800 2.930 1.110 5.000 0.584 13.200 17.500 9.090 0.951 1.570 1.350 3.950

2.640 1.280 0.911 0.241 0.181 0.320 0.475 0.650 1.330 0.091 0.520 0.353 0.380 1.120 1.210 0.441 0.437 0.362 0.436 0.244 0.494 6.120 0.674 2.470 6.110 0.539 0.385 0.721 0.155 2.720 4.420 0.281 2.890 0.185 2.540 4.280 5.530 0.312 2.400 1.090 2.540

0.117 0.065 0.414 0.134 0.046 0.024 0.086 0.021 0.231 0.999 0.224 0.106 0.169 0.040 0.130 0.089 0.320 0.097 0.051 0.703 0.130 0.120 0.111 11.000 0.093 0.026 0.121 0.385 0.059 0.047 0.040 3.100 0.187 0.101 0.054 0.131 0.106 0.119 0.069 0.177 0.281

0.0123 0.0054 0.0295 0.0470 0.0571 0.0102 0.0170 0.0179 0.0188 0.0355 0.0236 0.0186 0.0149 0.0106 0.0149 0.0577 0.0223 0.0334 0.0648 0.0249 0.0144 0.0102 0.0064 0.0312 <0.0050 0.0089 0.0579 0.0191 0.0395 0.0866 0.0368 0.0737 0.0195 0.0777 0.1630 0.3030 0.0596 0.1010 0.0277 0.0046 1.3600

0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 0.0007 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 0.0008 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005

0.1250 0.0569 0.1300 0.0732 0.0303 0.0395 0.0175 0.0621 0.0727 0.0633 0.0849 0.0508 0.0544 0.0742 0.0482 0.0548 0.1060 0.0371 0.0620 0.0829 0.0601 0.0612 0.1090 0.5150 0.0219 0.0284 0.1130 0.6750 0.0555 0.0487 0.0448 0.3210 0.0758 0.0640 0.4780 0.0583 0.0825 0.0291 0.0539 0.0336 0.0591

2.070 0.457 3.300 <0.200 0.315 <0.200 0.209 0.245 0.355 21.000 0.640 0.424 1.380 <0.200 0.345 0.656 0.663 0.836 0.913 0.702 0.544 0.892 0.499 7.360 0.862 0.530 1.090 2.190 0.521 1.260 3.000 10.500 4.670 2.050 3.790 0.735 1.360 8.350 3.700 0.542 3.970

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