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. Stefán Arnórsson Institute of Earth Sciences, University of Iceland

Doctoral Committee
Prof. Stefán Arnórsson Institute of Earth Sciences, University of Iceland

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

Dr. Andri Stefánsson 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 Útdráttur (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 Námafjall . . . . . . . . . . . . . . . . . . . . . . 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. . . . . . .2. . 3. . . . . . . . . . . . . . . . . . . . . .6 3. . .8 Discussion . . . . . . . . . . . . . . . . . . .1 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . . . .6 Results . . . . . . . prehnite . Reykjanes and Svartsengi Fluid compositions . . epidote-clinozoisite. . .2. .11. . . . . . . . . . . . 3 Processes inuencing As. .5. . . .2 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .11 Individual mineral-solution equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Mineral solubility constants and gas solubilities . . . . . . . . . . . . . . . . . . .12 Discussion and conclusions . . . . . . . . 2. . . . . . . . . Arsenic. Sampling and analytical methods . . . . .7 3. . . . . 3. . . .6. . . . . . .2. . . . . . .1 3. . . . . . . . . . . . .5. . . . . . . . . . . . 4 Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld. .1 Calcite and wollastonite . . . . . . . . . . . . . . .2 3. . 3. . . . . 2. . . . . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv 74 74 . . . . . . . .3 Magnetite. Note on pH measurement . . .3 Calculation of aquifer uid composition . . . . . .9 2. . . . .5. . . . . . . . Nesjavellir . . . . . . . . . . . . . . 2. . . . . .3 . . . . . . . . . . . . . . Calculation of aquifer water compositions and aqueous speciation . . . . . . . .2 Andradite-grossular. . . . . . . Data handling . 19 21 21 21 23 23 27 30 30 32 33 33 35 Data handling . . . . . . . . . . . .9. . Rock derived concentrations . . . .2. . . . . . . . . . . . . . . . 3. B and Cl concentrations in uids of volcanic geothermal systems in Iceland 39 3. . . . . . . . . . . . . .1 2. . . . . Geological features . . . . . . . . B and Cl concentration in the aquifer uid Sources of As. . . .1 CO2 . .11. .6. . . .6. . . . . . . . . . . . . . . . . . . . . .2 H2 S and H2 . . . . . . . . . . . . .3 3. . . . . . . . .2. . . . .2. . . . . . . . . . . . . . . . .1 3. . . . . . . . . . . . . . . . . . . . . . . . . . .11. .4 3. . . . .1 3. . 2. . . . . . . .9.4 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 Mineral-gas equilibria 2. . . . . . . . B and Cl to geothermal uids Boron and Cl distribution in sampled waters As and Cl relationships 3.2. . . .3 3. . . . . . . . . . . . . . . . .2 3. . . . . . . . . . .10. . . . . . . Summary and conclusions . . . . . .4 N2 and Ar . .10. pyrite and pyrrhotite . . . Geology and hydrology . .5 3. . . . .2 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kraa and Námafjall . . .1 3. . . . . . . . . . . . . . 2. . . . . . . . . . . . . . .7 3. . . . . . . . . . . . . . Iceland 73 4. . . . . . . . 2. . . .1 4. . . . . . . . . . .2 Introduction .5 Overview . . . . . . 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 .11. . . . .8. . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4. .1 4. . . . . . . . . . . . . . . .7 4. . . . . . . 4. . . . . . . . .8 Changes in dissolved salts and pH Formation of the vapor cap 4. . . . . . . . . . . . . . .10 Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. . . . . . . .4 4. . . . .3 4.2 . . . . .6 Production history . . . .8. . . . . . . . . . . . . . . . . . . . .6. . . . . . . . . . . . . . . . Sampling. . . . . . . . 75 78 78 81 81 83 85 87 87 88 89 90 Evolution of gas concentrations . . . . .1 4. . . . . .9 Discussion . . . . .2 Results Vapor fraction calculations . . Wet-steam wells Dry-steam wells . . . . . . . . . . . . . . . . . . . . . . . . .8. . . . . . . . . . . . . . . . . . . . . . 4. . . . . .5 4. . . . . . .6. . . . . . . . analyses and calculations Fluid composition 4. . . . . . . . . . A Trace element analyses Bibliography 93 101 v . . . . . . . . . . . . . . . . .

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. .4 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9 Hot-spring and fumarole at Hveravellir . . Phase segregation excess enthalpy model . . . . . . . . . . . .List of Figures 1. 3. . .2 3. 5 6 10 17 25 28 29 31 32 34 34 42 47 53 Well testing at Kraa 3 Location map . . 54 55 59 60 3. . . . . . . . . . . . . . . . . . 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 . . . . . . . . . . . . . . . . .1 2. . 2+ /(H ) + 2 ratio versus temperature . .3 2. . . . . . . . . . . . . . . . .3 3. . . . . . . . . . . . .5 3. . . . . . . . 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 . .1 1.6 2. . . . vii . . . . . . . . . . . . . . . . . . . . Boron distribution between vapor and liquid phases discharging from wet-steam wells versus sampling temperature . . . . . . . . . . . . . . . . . . .1 3. .7 Measured Cl and B concentrations in liquid water samples from all the study areas . . . .2 2. . . . . . Map of Iceland showing the location of the studied high-temperature areas. . . . . .6 3. . . . . . . . . . . . . . . . . . .2 1. . . . . . . . . . . . . . . . . . . . . . . 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.4 Location map . . . . . . . . . . .7 2. . . . . . . . . . . . . . . . . . . . .5 2. . . . . . . . . .3 2. . . . . . . . . . . . . . . . . . . . . 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 . . . . . . . . . . . . . . . . Measured Cl and As concentrations in liquid water samples from all the study areas. B and Cl concentrations in aquifer liquid in Geysir and Hveravellir elds . . . . . . . . . . .8 2. Rock derived As. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.3 4. . . 4. . . . . . . . Cumulated discharge and injection Annual CO2 emissions from wet-steam and dry-steam wells at Svartsengi . . . . . 4. .9 Location map .11 Cl and B of non-marine origin . . .10 Mg +2 versus −2F− activities . . . . . . . . of the Námafjall area. . . . . . . . . . . . . . . . . B and Cl concentrations in aquifer liquid in Landmannalaugar and Hveragerdi elds . . . . 61 64 64 66 75 76 77 77 80 82 84 85 86 86 89 3. . . . Chloride concentration in the aquifer uid of wet-steam wells of wet-steam wells . . . . .8 4. .2 4. . . . .5 4. . . .8 3. Rock derived As. H2 S and H2 concentrations versus time in the aquifer uid . . . . . . . . . . . . . . Annual discharge and injection .6 4. . . . . . . . . . . . . . . . . . . . . . . . . . .1 4. . . . . . . . . . . . .11 Fraction of the total liquid that forms the vapor cap viii . . . . . . . . . . . . . . . . . . . . . . . B and Cl in aquifer liquid. . . . . . . . . CO2 . . . . . . . . . . . . . . . . . . . . . . .3. 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 .9 Rock derived As. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Fluoride concentration in the aquifer uid of wet-steam wells 4.4 4. . . . . . .7 4. . . . . . . . . . . . . . . CO2 . . . . . . . . . . . .10 Time evolution of non-marine B in the aquifer water of three wells 3. . . . . . . . . . . . . . .

. .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 vapor samples from wet-steam and drysteam wells . . . . .) . . . . . . . . Aquifer water composition . . . . . 96 95 ix . . . Arsenic. Mineral assemblages potentially controlling CO2 . .1 A. . . . . . . . . . . . . . Trace element analyses of vapor samples from wet-steam and drysteam wells (cont. .2 4. . . . . . . . . . . . . . . . . 57 52 4. . . . . .1 3. . . . .) . . . . . . . . . . . . . . . . . .3 Major and trace elements and major gas concentrations in aquifer liquid of wet-steam wells .1 A. . . . . . . . . . . . . . . . . . . . . . .4 2. . . . . . . . . Arsenic. . . . . . . . .2 14 16 20 24 26 K -temperature equations .1 2. . . . . . . H2 S and H2 concentrations and respective 3. . . Trace element analyses of liquid water samples from wet-steam wells (cont. . . . . . . . . . . . .1 A. . . . . . . . . . . . . . . . . . . . Gas concentrations and estimates of the fraction of vapor owing into wells 7 and 11 . . . . . . Concentrations in mg/kg. . .) . . . .1 4. . . . . . . . . . boron and chloride concentrations in spring waters from high-temperature areas . . . . . . . . . . . . . . . . . . . . . . .2 A. . . . . . . . . . Gas analyses of the sampled vapor phase .List of Tables 2. . . . . . . . . . . . . Gas concentrations in the vapor discharge from dry-steam wells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97 98 99 Trace element analyses of vapor samples from wet-steam and drysteam wells (cont. . . .) . . .5 Major elements analyses of the sampled waters.3 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B and Cl concentrations in liquid and vapor phases of wet-steam wells . . . . . . . . . . . . .2 A. . . . . . . . . . . . . . . . . . Individual minerals dissolution reactions . .2 2. . . . . 83 79 80 A. . . . . . . .

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l i me. 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 s 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 s (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 i in liquid water retained in aquifer i in vapor phase at conditions Pe xi . before it occurs aquifer and discharge of the uid.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.t M e.t md.List of Symbols Ai Ar As Ad Ae Af Ag Al Am As At Av al Ds fs hl ht hv Ks M d.v i me.t i md.l i md.l M f.

v X e.v s Pe Ps Te Tf V e.t X 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 .m i mf.t ) relative mass (to well discharge) of boiled (and degassed) water retained in aquifer f.t i ms i Ns ne.v concentration of component i 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 s ne.l (M /M d.l V f.l i mf.mf.t (M /M d.

and their state of equilibrium with various mineral assemblages. H2 S For most wells. 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. xiii . Such a vapor fraction strongly aects the H2 concentration in the aquifer uid but not so much the much more soluble H2 S. contain saline uid. 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 considered to be produced in the depressurization zone around wells. Excess well discharge enthalpy is not considered to reect such an enthalpy of the initial aquifer uid. whereas all the vapor ows into the wells. Nesjavellir. hydrogen sulde (H2 S). and hydrogen (H2 ). The rst three systems are of the dilute uid type. as well as the more soluble CO2 . The rst paper presented in this thesis focuses on the reactive gases carbon dioxide (CO2 ). where extensive boiling occurs. The high H2 aquifer uid H2 S concentrations are close to equilibrium with the assemblage epidoteprehnite-pyrite-pyrrhotite. thalpy. a fraction of the liquid is retained in the aquifer due to its adsorption onto mineral grain surfaces by capillary forces. The systems of Svartsengi and Reykjanes. Námafjall. the source uid is considered to be meteoric water. 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. The source water at Svartsengi is 70% seawater and 30% Some of the wells have excess enmeteoric water but seawater only at Reykjanes. that is the enthalpy of the discharged uid is higher than that of vapor saturated water at the aquifer temperature. concentrations are considered to reect the presence of a small fraction of equilibrium vapor in the aquifer uid. as well as the unreactive argon (Ar) and the relatively unreactive nitrogen (N2 ). Some of the wells in Kraa. whereas most of the wells at Nesjavellir show low CO2 concentrations. Svartsengi and Reykjanes. 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. likely because of high ux from the magmatic heat source. It is based on analytical data on water and vapor samples collected from wet. whereas H2 concentrations are often higher. however.Abstract Volatile species provide valuable information on physical and chemical processes occurring in high-temperature (volcanic) geothermal systems. on the other hand.and dry-steam well discharges. The elds considered are Kraa. are enriched in CO2 relative to equilibrium.

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. 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. The gas content of the vapor cap has decreased with time. deep uid has been dissolved from the host rock. In the young geothermal system at Kraa. The concentrations in the dilute uids are typically in the range 50150 ppb. boron (B) and chloride (Cl) using data from the ve above mentioned geothermal areas. due to rapid re-equilibration of the degassed water with Mg and OH-bearing minerals. 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.The main sources of N2 and Ar to the aquifer uid is air-saturated groundwater and seawater. 0. the At Nesjavellir. and 50150 ppm for As. Boron distribution between liquid and vapor is closely approached at the wellhead where samples were collected. 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.55 ppm. and from four wells in the Southern Lowlands low-temperature area. but B does. In 2006 the cumulated drawdown was 30 bar. magmatic gas or decaying organic matter. and Cl. 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. potentially entrapped air bubbles. Initially CO2 concentrations were ∼80. As is less mobile than B and Cl and is likely to be removed from solution into sulde minerals. In the saline uids. Boiling has reduced the gas content of the liquid reservoir and in turn increased and decreased aqueous uoride (F) and magnesium (Mg) concentrations. as well as samples from boiling and warm hot springs and hot water wells in four other high-temperature geothermal elds in Iceland. but a large fraction of the dissolved B has a magmatic source. of which 217 came from wet-steam wells (the liquid reservoir) and 25 Mt from dry-steam wells (the vapor cap). respectively. and Cl concentrations in geothermal uids in Iceland are low compared to such uids in many parts of the worlds. If virtually all the Cl in the Svartsengi and Reykjanes saline uids is of seawater origin. N2 /Ar ratios show that N2 has another source. 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. B. Arsenic does not partition signicantly into the vapor phase. xiv . Arsenic concentrations in the saline uids are similar. Arsenic. The uid is mostly depleted in both gases relative to the source water. period 19762006 amounts to 243 megatonnes (Mt). Boron and Cl are highly mobile on the ◦ whole range of water temperatures (10320 C) considered in this study.000ppm. The second paper aims at describing the sources and behavior of arsenic (As). which is considered likely. it is evident that a signicant fraction of the B in these uids is magmatic. respectively.000 ppm but at present they are ∼30. B. at least at vapor pressures as high as 40 bar. but B and Cl concentrations are much higher.

Efnagreining á uppleystum steinefnum í vatnssýnum og gösum í gufusýnum sem safnað úr renni blaut. Niðurstöður kvarsog alkalí-hitamælanna fyrir hávermisholur benda til þess að vatn og gufa í aðfærsluæð aðskiljist.og efnaræn ferli í háhitasvæðum. Hins vegar er styrkur H2 stundum of hár. Kröu. Svartsengi og Reykjanesi. Sumar blautgufuholurnr sem safnað var úr eru hávermisholur. Í djúpvökva margra borhola með lágseltu svarar styrkur CO2 vel til efnajafnvægis við steindafylkið epídót-prenít-kalsít-kvars en til jafnvægis við epídót-granat-kalsít-kvars í söltu svæðunum í Svartsengi og á Reykjanesi. Fyrsta greinin í þessari doktorsritgerð fjallar um hvarfgjarnar lofttegundir. en einnig um argon (Ar) og köfnunarefni (N2 ) en síðarnefnda lofttegundin er tiltölulega óhvarfgjörn.e. vermi holurennis er hærra en gufumettaðs vatns við þann hita sem ríkir í æð. Hún hefur hins vegar lítil áhrif á H2 S sem er miklu auðleystara í vatni en H2 og einnig lítil áhrif á CO2 sem er xv . þ. Hins vegar er styrkur CO2 í djúpvökva á Nesjavöllum lægri en svarar til jafnvægis. Líklegt er talið að styrkur H2 S og H2 í djúpvatni stýrist af efnajafnvægi við sama steindafylkið. Tilvist slíkrar djúpgufu hefur mikinn áhrif á styrk H2 í djúpvökva. Hinn hái styrkur H2 er ekki talinn ráðast af fráviki frá efnajafnvægi helfur af tilvist efnajafnvægisgufu í djúpvökva. Í sumum borholum í Kröu er styrkur CO2 í vökva í aðfærsluæð hærri en svarar til jafnvægis við nefnt steindafylki líklega vegna mikils streymis þessarar lofttegundar frá kviku undir jarðhitakernu. að hluta. Hluti vatnsins situr eftir í æðinni með því að hann loðir við yrborð steinda fyrir áhrif hápípukraa. Fyrir estar holur er svarar styrkur í æð vel til jafnvægis við fylkið epídót-prenít-pýrítpyrrótít. koltvíoxíð (CO2 ). Námafjalli. Hávermi í renni borhola er ekki talið endurspegla hávermi vökva í djúpvökva.m. Vökvinn í jarðhitakerfunum í Svartsengi og á Reykjanesi er saltur. Sú rannsókn sem hér er fjallað um lýsir athugun á nokkrum rokgjörnum efnum í vatni af íslenskum háhitasvæðum með áherslu á hvaða ferli ráða styrk þeirra í vatninu.k. Talið er að hávermisvökvi myndist við ákafa suðu í aðfærsluæð borhola. Í Svartsengi er upprunavatnið 70% sjór og 30% regnvatn en hreinn sjór á Reykjanesi.og þurrgufuhola var notuð til að reikna efnainnihald djúpvökva í mm háhitasvæðum. brennisteinsvetni (H2 S) og vetni (H2 ) og ástand efnajafnvægis þeirra við nokkur fylki ummyndunarsteinda. Upprunavökvinn er talinn vera úrkomuvatn. Gufan æðir hins vegar inn í borholurnar. og þannig myndist hávermisvökvi sem æðir inn í borholur.Útdráttur (in Icelandic) Ýmis rokgjörn efnasambönd veita mikilvægar upplýsingar um eðlis. Djúpvökvinn í þremur fyrst töldu svæðunum er snauður af uppleystum steinefnum. sennilega vegna takmarkaðs æðis þessa gass frá kviku. Nesjavöllum. a.

hefur yrleitt tapað báðum þessum gösum að hluta miðað við upprunavatnið. Styrkur As í ósöltu jarðhitavatni er sambærilegur við lágseltuvökva en miklu hærri fyrir B og Cl.000 ppm fyrir CO2 Holur hafa verið boraðar í Áætlað er að allt að 3% af djúpvatni efst í vatnskernu ha soðið til þessa til að mynda gufu fyrir gufupúðann.55 ppm og 50150 ppm. í kvikugösum eða jafnvel rotnandi lífrænu efni. er ljóst að verulegur hluti B í þessu vatni hefur borist í það frá kviku. Hlutföllin Cl/B og Cl/As í vatni á tiltölulega gömlum háhitasvæðum (liggja í útjaðri gosbeltanna) eru þau sömu og í basalti sem bendir til þess að þessi efni skolast úr berginu í sömu hlutföllum og þau eru í þessu bergi. Í hinu tiltölulega unga háhitasvæði (liggur á ekamótum) í Kröu er B og Cl í djúpvökva aðallega ættað frá kviku en aðeins tiltölulega lítill hluti er komin úr berginu sem vatnið hefur hvarfast við. loftmettuðu grunnvatni og loftmettuðum sjó. Sömu sögu er ekki að segja um B. gufupúðanum). komu 217 Mt frá blautgufuholum (úr vatnskernu) en 25 Mt úr þurrgufuholum (úr Árið 2006 samsvaraði uppsöfnuð þrýstilækkun í svæðinu 30 börum. B og Cl í lágseltuvökva á háhitasvæðum er 50150 ppb. Þriðja greininfjallar um gufupúðann í háhitasvæðinu í Svartsengi sem myndaðist yr 240 ◦ C heitu vatnsker vegna niðurdráttar í svæðinu í kjölfar vinnslu. í gufupúðanum hefur farið en er nú um 30. jafnvel þótt gufuþrýstingur sé 40 bör. Köfnunarefni í djúpvökva er aðallega komið út upprunaDjúpvökvinn vatninu og Ar eingöngu.og OH-steindir. lækkandi. en líklegt er talið að svo sé. Önnur greinin lýsir uppruna og hegðun arsens (As). hverum og heitavatnsholum af fjórum öðrum háhitasvæðum á Íslandi og í vatni úr fjórum borholum á lághitasvæðum á Suðurlandsundirlendi. Á Nesjavöllum er mestur hluti Cl í djúpvökva hins vegar ættaður úr bergi en stór hluti B er kvikuættaður. Arsen leitar ekki að neinu ráði yr í jarðgufu. Arsen er einnig mjög hreyfanlegt í upphaegum djúpvökva jarðhitasvæða en suða á þessum vökva og blöndun hans við kalt vatn leiðir til útfellinga á As og þá sérstaklega blöndun. Massataka vatns Af honum og gufu úr svæðinu á tímabilinu 19762006 nam 243 megatonnum (Mt). Í söltu djúpvatni er hreyfanleiki As lægri en B og Cl og tapast líklega úr lausn við upptöku þess í súlfíðsteindir. N2 /Ar hlutföll í einstökum sýnum benda til þess N2 geti átt uppruna víðar en í loftmettuðu vatni. H2 S út í andrúmsloftið á hverja framleidda raforkueiningu. Styrkur As. í lausn) við öll hitastig (10320 Bór og Cl eru mjög hreyfanleg efni (eftir að þau hafa borist í vatn haldast þau ◦ C) í íslenskum jarðhitakerfum. Suða í vatnskernu hefur leitt til lækkunar á gasstyrk í djúpvatninu sem aftur hefur orsakað hækkun á styrk úors (F) en lækkun á styrk magnesíums (Mg) vegna hraðrar nálgunar á efnajafnvægi hins afggasaða vatns við Mg. gufupúðann til raforkuframleiðslu með þeim aeiðingum að hækka útstreymi CO2 og xvi . Einkennandi styrkur As. bórs (B) og klóríðs (Cl) í jarðhitavökva fyrrnefndra háhitasvæða en einnig vatni í laugum.tiltölulega auðleyst í vatni. Styrkur gass Í uppha var hann um 80. hugsanlega loftbólum í þessu vatni.000 ppm. B og Cl í jarðhitavökva á Íslandi er lágur í samanburði við slíkan vökva í jarðhitasvæðum erlendis. 0. Jafnvægisdreing næst fyrir B milli vatns og gufu á holutoppi þar sem sýnum var safnað. Ef allt Cl í djúpvatni í Svartsengi og á Reykjanesi er sjávarættað.

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

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S... 3... which will be submitted for publication in international journals upon completion of the PhD thesis. Gunnarsson. Sampling and analysis of geothermal uids. Giroud. This doctoral thesis constitutes of the three following papers. and Arnórsson. Giroud. 2008. Analytica Chimica Acta 582 (1). the author participated in related research projects during his studies at the University of Iceland that are not part of this thesis: • • Arnórsson. 203216 Stefánsson. Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld. organic and total carbon in natural waters by Reagent-Free TM Ion Chromatography and inductively coupled plasma atomic emission spectrometry. A. 6974 1 . 2. I. N. Chapter 2.. A.. Cosmochimica Acta. N. Chapter 3. They are included here as Chapters: 1. Geothermics. temperature geothermal systems. J. Giroud. Iceland. Geouids 6 (3). N. 2007. and Arnórsson. Stefánsson. search. Bjarnason. New methods for the direct determination of dissolved inorganic.. S. 2008. Processes inuencing As. Ö. and Bjarnason... S. Arnórsson.. S. I. Geochimica et Gas chemistry in ve Icelandic high- Journal of Volcanology and Geothermal Re- In addition to these publications. Giroud. 2006. Gunnarsson. B and Cl concentrations in uids of volcanic geothermal systems in Iceland. N.. N. Giroud. Ö.Chapter 1 Introduction The main focus of this study is the behaviour of various volatile species in hightemperature volcanic geothermal uids in Iceland. Chapter 4.. J. 2008.

Estimation of long-term CO2 and H2 S release during operation of geothermal power plants. CO2 . while writing the present thesis. • Assess the processes that govern As.1. Poster at the Geoscience Society of Iceland Meeting During the last two years. In mature.1 Objectives Study of the geochemical characteristics of geothermal systems is of great importance. S. i. 2005. N. Formation of a steam-cap in the geothermal reservoir of Svartsengi. acts as essentially conservative component in the high-temperature geothermal systems in Iceland.. and Arnórsson. as Cl. their concentrations are largely or solely aected by physical processes and the respective solubilities of the gases. interactions of the uid with the host rock minerals. H2 S. The source of Ar to the uid in the high-temperature geothermal elds is airsaturated groundwater and seawater. H2 . 2004.. such as Kraa. The concentrations of reactive gases in the deep aquifer uid in geothermal systems is aected both by geochemical and physical processes. a large part of the aqueous B and Cl is derived from volatiles escaping from the underlying magma heat source. 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. 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. The results indicate that B. uxes from a magmatic source. H2 S. whereas several others are being developed. in 1969.e. Reykjanes peninsula. boiling/condensing and phase separation. and H2 ) in the uid are compared with predicted concentrations calculated by equilibrium with selected mineral assemblages. the presence or absence of equilibrium vapor. high-temperature 2 . B and Cl concentrations in uids of hightemperature geothermal systems. i.e. OBJECTIVES Parts of the work were also presented in various meetings. N2 and Ar. World Geothermal Congress 2005 paper 0233 • Giroud.e. on dierent projects related to geochemistry of ◦ high-temperature (> 200 C) and low-temperature geothermal systems. Results on this subject are presented in Chapter 2. including: • Giroud. once in solution it stays there. NE-Iceland. These are also the principal source for N2 although magmatic gases and decaying organic matter may contribute. Iceland. and to provide tools for an optimal use of geothermal resources. both to improve the knowledge of hydrothermal and volcanic systems. using thermodynamic data from the literature. 1. As a consequence. Arnórsson. In volcanically young elds. The concentrations of three of the reactive gases (CO2 .1. and trapped air bubbles.. at least in some elds. N. the author worked as a geochemist at Iceland GeoSurvey. Many of the high-temperature elds have been drilled for this purpose and six are being exploited today. S. chemical reactions within the uid. i.

Figure 1. it may be removed from solution into sulde minerals. Both liquid and vapor phases were sampled from wet-steam wells. together with samples collected specically for this study indicate progressive boiling within the liquid reservoir. For the present study. in particular when extensive boiling occurs and in particular when geothermal uid mixes with cold groundwater and ferric hydroxides are precipitated. wells producing a mixture of liquid water and vapor.1: Hot-spring and fumarole at Hveravellir elds. The details of this study are included in Chapter 3. As is highly mobile in the hightemperature geothermal systems. on the other hand. • Evaluate from geochemical data how extensively the 240 ◦ C liquid water reservoir at Svartsengi. Results of this study can be found in Chapter 4. the source of these elements to the water is the rock with which the geothermal uid has interacted. assessment of specic mineral-solution equilibria as well as consideration of the origin of the various component present in the geothermal uid. individual species activities in this uid. 1. which is based on data on the composition of well discharges. Additionally.CHAPTER 1.e. Samples of both phases were subsequently analyzed for major components at the University 3 . vapor was collected from four dry-steam wells at Svartsengi (see Chapter 4). i. Like B. has boiled to produce the above lying vapor cap. 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.2 Methods A very important part of research on geothermal uids. At present as much as 3% w/w of the liquid has boiled to yield vapor to the above lying vapor cap. southwest Iceland. Data on samples collected on a regular basis by Iceland GeoSurvey. is calculation of deep uid compositions. However.

A thorough description of the calculation method is given in each chapter.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. the total well discharge composition equals that of the initial aquifer uid. These are Kraa and Námafjall.2). Geysir.1. Svartsengi and Reykjanes. silicic rocks occur in some areas. In the latter case. and may eventually evolve into low-temperature systems. and aqueous species distribution of the deep aquifer uid for each well. 1. Luleå. between the eastern and the western volcanic belts. and wells. like those on the Reykjanes peninsula.e. or to enhanced boiling of the liquid by heat-transfer from the aquifer rock. The Southern Lowlands are located on the Hreppar microplate. The geology of the areas shows an interesting variety of settings. As mentioned before. wells whose discharge enthalpy can be taken to be the same as that of the aquifer uid. However. 1. When this is the case. Sweden. and activity products from calculated species activities. have excess discharge enthalpy. directly above their magma heat source. i. composition. (2006). B and Cl. SELECTED GEOTHERMAL FIELDS of Iceland as described by Arnórsson et al. A more detailed description of the geology is presented in each chapter. (2006). The data interpretation involves calculation of solubility constants for minerals. Trace elements were analyzed by Analytica (ALS Laboratory Group). Analyzed liquid and vapor compositions were used to calculate the temperature. The rock type hosting the geothermal systems is mostly basaltic volcanics. All the areas except the Southern Lowlands are located within the active volcanic belts. but this is not the case if the cause of the excess enthalpy is phase segregation. southwest Iceland (Fig. Additionally. and Landmannalaugar) were studied with respect of As. some elds are located within the boundary of central volcanoes. astride the ssure swarms that intersect the central volcanoes. whereas others are located just outside such volcanoes. 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. as well as in Arnórsson et al. were also used. University of Iceland. A more detailed description of sampling and analytical methods can be found in each chapter. 4 . some elds. the axes of which represent the plate boundary between the Eurasian and NorthAmerican lithospheric plates. four wells in the Southern Lowlands were also sampled. however. due either to segregation in the aquifer of the vapor and liquid phases owing into wells.3. Additionally. northeast Iceland. Stability of various mineral phases in contact with the solution can thus be estimated. the total discharging uid is representative of the deep aquifer uid. The majority of the wells included in the present study. 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. This calculation is straightforward for liquid enthalpy wells. are not linked to any central volcano but have a sheeted dyke complex as heat source. southwest Iceland. and Nesjavellir. from four high-temperature areas (Hveravellir. data on samples from warm and boiling hot springs. Hveragerdi. These systems are considered to be mature.

5 . Figure 1.CHAPTER 1.2: Map of Iceland showing the location of the studied high-temperature areas.

3: Well testing at Kraa 6 .3. SELECTED GEOTHERMAL FIELDS Figure 1.1.

where the discharge enthalpy is higher than liquid enthalpy at the aquifer temperature due to phase segregation of the owing liquid and vapor. most likely because of insucient supply from the magma heat source. prehnite. and Svartsengi and Reykjanes where uids are saline. In the saline uids. Some wells at Kraa show excess CO2 due to recent magmatic activity. which are of dilute uid type. H2 S. epidote and wollastonite mineral assemblage. equilibrium generally seems to be closely approached with a grossular. CO2 concentrations are close to equilibrium with the clinozoisite. prehnite. pyrite and pyrrhotite assemblage. N2 and Ar concentrations in aquifer uids of ve liquid dominated volcanic geothermal elds. calcite and quartz assemblage. This study focuses on CO2 . However. CO2 appears to be controlled by equilibrium with the clinozoisite. the uids at Nesjavellir are generally depleted in CO2 relative to equilibrium.Chapter 2 Gas chemistry in ve Icelandic high-temperature geothermal systems Giroud. Other samples show higher H2 7 . Námafjall and Nesjavellir. In the saline uids. These are Kraa. H2 S concentrations correspond to equilibrium with a mineral assemblage containing epidote. This model yields consistent results for quartz and Na/K geothermometers. and Arnórsson S. pyrite and pyrrhotite. N. prehnite. grossular. In some of the dilute uids. In the dilute uids. The calculations account for the excess enthalpy of some wells. Dissolved solids and gas analyses of water and vapor samples were used to calculate aquifer uid compositions. Abstract Many processes control reactive and unreactive gas concentrations in aquifer uids of high-temperature geothermal systems. The same mineral buer is expected to control aquifer liquid H2 and H2 S concentrations. H2 . Indeed many samples of the dilute uids correspond well with equilibrium with the epidote. calcite and quartz assemblage.

Iceland and in the western part of Olkaria. The experimental solution pH is too high. The geothermal uid parameters can.. H2 concentrations are somewhat lower for Reykjanes than predicted by equilibrium with the epidote. 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. 1977).. 2002. 1995). Gudmundsson and Arnórsson.2. The median value for a total of 250 samples of lavas and dykes is 500 ppm CO2 (see Sveinbjörnsdóttir et al. Dissolution experiments involving basalt and pure water at temperatures > 250 ◦ C do not produce actual geothermal water compositions. Within a particular geothermal system. 1982. These minerals precipitated as a consequence of changes in the liquid water composition by its boiling. 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. In the saline uids..1 Introduction Many geochemical processes aect the concentrations and ratios of reactive and unreactive gases in uids of volcanic geothermal systems... In fresh undegassed basalt S and C concentrations are around 800 ppm (Moore and Fabbi. Fluids are mostly depleted in N2 and Ar relative to air-saturated water. whereas four have lower H2 . 2008). INTRODUCTION concentrations.. 1982). Modal calcite as high as 20% have been reported (Björnsson et al. This is considered to be due to the presence of equilibrium steam in the aquifer uid. 1972) which correspond to C concentrations in the rock in excess of 2%. variations in gas concentrations of the geothermal uid are also aected by gas-gas and mineral-gas reactions and boiling and phase separation. 1989. in other systems. The value of 1400 ppm is the average of 78 analyses of dyke samples from eastern Iceland. grossular and pyrrhotite assemblage. 1981. magmatic gas or decaying organic matter. however. 1989). These elements are hosted by sulde minerals and calcite (Gunnlaugsson. Kenya. Data from volcanic geothermal systems in Iceland hosted by basalt. potentially entrapped air bubbles. respectively. Arnórsson. most likely due to degassing of the aquifer liquid by boiling and consequent formation of the vapor cap above the liquid reservoir.. Two of the Svartsengi saline waters are close to equilibrium with this buer. N2 /Ar ratios show that N2 has another source than air-saturated water. However. wollastonite. H2 S and H2 ) in volcanic geothermal systems are often controlled by a close approach to equilibrium with hydrothermal mineral buers (Giggenbach. 1995). 2002. Karingithi et al. from the atmosphere and from the rock with which the geothermal uid interacts.1. Sulfur concentrations as high as 5% have been reported (Gunnlaugsson. be duplicated by addition of CO2 (Kacandes and Grandsta. the ux of CO2 from the magma heat source is considered to govern its concentration in aquifer uids (Ármannsson et al. 1985. Arnórsson. This lower value probably reects variable degassing of the lavas with respect to CO2 . 2. Ármannsson et al. 2006. Several studies have demonstrated that the aquifer water concentrations of the most abundant reactive gases (CO2 . 1971) and 1400 ppm as CO2 (Flower et al. Fridriksson et al. Gudmundsson and 8 . They include supply of gases from the magma heat source. Stefánsson and Arnórsson. such as at Kraa. 1977.

have been extensively drilled. the drilled reservoir rocks either contain no silicic rocks or they are very minor (Franzson. Silicic volcanics are typically associated with these complexes considered to have formed by partial melting of basalt at the base of the crust. Svartsengi and Reykjanes). H2 . Nesjavellir represents one of the wellelds within the In these systems. 2. The more visually conned emissions from fumarole or hot springs discharges are only a portion of the total emission (Fridriksson et al. In two of the systems the parent uid is essentially seawater but meteoric water in the other three systems.CHAPTER 2. 2005.2. calculated from the chemical analyzes of water and steam samples. Hengill system. however. either by reactions with other uid species or by reactions with the host rock minerals. 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. The aquifer rock is. The ve volcanic geothermal systems in Iceland (Kraa. 2. Hengill. Aiuppa et al. The methodology involves calculation of mineral equilibrium constants with thermodynamic data from the literature. Námafjall.. This study focuses on quantifying the geochemical and physical processes which govern the concentrations of the most abundant gases (CO2 . Arnórsson. these systems typically coincide with central volcanic complexes. The marginal volcanic geothermal systems are considered to be mature and have drifted away from their magma heat source within the active volcanic belts. One is modelling of initial aquifer uid compositions from data on liquid and vapor samples collected at the wellhead. Carbon dioxide emissions from active volcanic geothermal systems are largely diffuse and cover large areas. The volcanic belts represent the diverging boundary between the North-American and Eurasian plates. 2006. H2 S. Karingithi et al.1). 2008). 2. and comparison with the reaction quotient of the minerals. which are the subject of the present study.. CH4 .. largely 9 . Except for geothermal systems on the Reykjanes Peninsula. which represent points of maximum volcanic activity within the volcanic belts. which includes the reactive gases. 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. Chiodini et al. The other step. 2002.. N2 and Ar) in the aquifer uid of wet-steam wells drilled into ve volcanic geothermal elds in Iceland. 2004). 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.2 Geological background Volcanic geothermal systems in Iceland are located within the active volcanic belts. Essentially data interpretation involves two steps. most of them in the center of these belts but some close the their margins (Fig.1 Kraa and Námafjall The Kraa eld lies within the caldera of the Kraa central volcano which has erupted both basaltic and silicic magma (Jónasson. 1994). All these systems are hosted by basaltic rocks. 1998).

The 197584 volcanic episode suggests that the heat source to the Námafjall geothermal system is represented by the dykes formed by magma intrusion 10 . dolerite and gabbro. did not reach 3 the surface except on one occasion when a geothermal well erupted 3 m of magma (Larsen et al. 1978). particularly with respect to CO2 (Ármannsson et al. The drilled geothermal reservoir at Kraa has been divided into two main depth ◦ zones..2.. This magma.2. sub-aerially erupted lavas. GEOLOGICAL BACKGROUND Figure 2. 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. 1979). 1982. During periods of fracturing. magma sometimes owed to the south along the fractures from the magma chambers under Kraa. sub-glacially erupted hyaloclastites as well as small intrusive bodies of basalt. 1989). About twenty years after cessation of the 197584 volcanic episode.1: Map showing the active volcanic belts and high-temperature geothermal areas. 2002).. Degassing of the fresh magma was accompanied by an increase in gas uxes from the geothermal system. basaltic. This eld was also aected by the 1975-84 volcanic episode. many well discharges were still aected by this gas pulse (Gudmundsson and Arnórsson. 1978). Arnórsson.. 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. 1989. Intrusions of granophyre also occur. however. Geothermometer (quartz and Na-K) temperatures indicate that most aquifers producing into wells are ◦ below 300 C (Gudmundsson and Arnórsson. Ármannsson et al. 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. This subsurface discharge was witnessed by earthquake activity of deation of the Kraa caldera (Björnsson et al. The Námafjall eld.. 1995). 2002). may be regarded as a parasite system to the Kraa volcano. which lies 8 km south of Kraa. an upper sub-boiling zone at 190200 C and a lower two-phase zone with tem◦ peratures of up to 350 C (Ármannsson et al.

2. At Kraa. The two exploited geothermal systems are hosted by basaltic 11 .. the gas ux from the fresh magma may also have contributed to increased boiling. 1990).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. Fumarolic activity at both Kraa and Námafjall increased during the early part of the 1975-84 volcanic episode. 1978. As at Kraa. 2002).CHAPTER 2. The maximum recorded temperature is > 380 ◦ C.. Bull et al. 1992. In wells drilled in another part of the eld and after the 197584 volcanic episode. A volcanic ssure. Clifton and Kattenhorn.2 Nesjavellir The Nesjavellir eld lies in a tectonically active graben to the northeast of the Hengill central volcano. 2. which lies immediately to the north of the welleld erupted about 2000 years ago (Saemundsson.2. They lie astride two of the ve active ssure swarms on the Reykjanes peninsula. the temperature at the top of the reservoir is sub-boiling. The drilled geothermal system at Nesjavellir is two-phase. geothermometry indicates that aquifers producing into wells at Námafjall have considerably lower temperatures than this maximum (Gudmundsson and Arnórsson. at least to the depth penetrated by the deepest wells (∼2200 m). Intrusive formations dominate below about 1500 m depth. The increase in the fumarolic activity is likely caused by increased boiling by heat ux to already two-phase aquifer uid. 2002). at Námafjall no changes in the gas content of well discharge and fumarole steam was observed (Arnórsson and Gunnlaugsson. Granophyre is sporadic (Franzson. 2. The peninsula consists mostly of Holocene lavas protruded by hyaloclastite hills formed by sub-glacial eruptions during the last glaciation (Jakobsson et al. into tensional ssures from the magma body in the roots of the Kraa system. 1963. Maximum recorded temperatures in drillholes at Námafjall is 320 ◦ C (Gudmundsson and Arnórsson. 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. 19) temperatures follow the boiling point curve with depth. The apparent lack of increase in the gas content of the uid in the Námafjall system during the 1975-84 volcanic episode indicates that the magma intruded from the chambers below Kraa had already been largely degassed. Intrusions are dominant below some 1500 m depth. The drilled formations at depth are largely basalt lavas and basaltic hyaloclastites as wells as small intrusions of basalt and dolerite. These low temperatures are considered to be the consequence of cold shallow groundwater incursion along fractures that were activated during the 197584 volcanic episode.. the heat source to these systems are considered to be sheeted dyke complexes and the permeability is fracture controlled. In wells drilled at Námafjall prior to the 197584 volcanic episode (well nos. 1998). 2006). The aquifer rock at Námafjall is the same as at Kraa except that silicic rocks are absent. In view of their geological setting. However. 2005). The permeability is mostly fracture controlled (Bödvarsson et al. 1985).

All elds show a zonation with depth reecting the temperature stability range of the minerals within the system. The deuterium This has been content of the aquifer water is. breccias. 1978. due to the low K content of the host rocks. 1982) this explanation appears unlikely. The dierent salinity of the uid is not sucient to change drastically the alteration mineralogy from one system to another. In alphabetical order these are. subglacial hyaloclastites. pyrrhotite. (2008) conclude that the low δ 2H values of the geothermal seawater at Reykjanes is a consequence of equilibration of 12 . Magnetite is mostly present as primary mineral but is generally unstable in high-temperature geothermal systems. Hydrothermal sheet silicates are represented by smectite. Garnet. 1987. 1993). 1978). 1972... The aquifer is two-phase it is above ∼1000 m but subboiling at greater depths. In view of the low Cl content of basalt (Sigvaldason and Óskarsson. Floyd and Fuge. Mottl and Holland. and the solid-solutions epidoteclinozoisite and grossular-andradite. 1986). Abundance of intrusions increases with depth. However. Prehnite appears ◦ above 200 C and epidote at slightly higher temperature (Hreggvidsdóttir. the ◦ highest temperature recorded is ∼320 C at 2000 m depth. The present study focuses on ten alteration minerals that were considered as potential gas buers. of seawater (Sveinbjörnsdóttir. 1976. represented by the grossular-andradite solid solution is widely present in Reykjanes and Svartsengi (Lonker et al. Arnórsson. 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 (Árnason. 1993). They dominate the succession at the greatest depth reached by the wells. recent studies by Pope et al.3 Alteration mineralogy All systems considered in this study are located in basaltic environments and have similar mineralogy. Sveinbjörnsdóttir et al. The Cl concentrations of the unboiled aquifer water is thus close to that of seawater. and pillow lavas as well as tuaceous sediments. Quartz is assumed to be at equilibrium in all the geothermal systems considered in this study. discrete chlorite is formed. 1983. 2.2.. however. that is interstratied with chlorite above 200 ◦ C and above 230240 ◦ C. Albite is common. Calcite and pyrite are stable over the whole range of temperature. Ólafsson and Riley. Chalcedony is ◦ stable up to ∼180 C and above that temperature quartz is formed.3. Alteration mineralogy in the high temperature geothermal systems in Iceland has been summarized by Arnórsson (1995). 1995). The temperature in Svartsengi is very homogeneous. calcite. 1976. Lonker ◦ et al.. pyrite. especially at temperatures above 150 C. At Reykjanes. magnetite and wollastonite. 2.4 Fluid compositions The geothermal uid at Reykjanes represents seawater which has reacted with basalt (Björnsson et al. Between 500 and 2000 m depth ∼240 ◦ C. ALTERATION MINERALOGY rocks. reecting good vertical permeability in the system. whereas Kfeldspar (adularia) is scarce.

. As a result. 1993) and the deuterium content of this water is consistent with such an origin.1). 1984. Ragnarsdóttir et al.. the present geothermal uid source at Reykjanes is seawater that has reacted and experienced isotope exchange with alteration minerals. 1978). 1978. The Svartsengi geothermal system has a mixed meteoric-seawater uid origin with Cl content corresponding to about 2/3 that of seawater (Arnórsson. 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. Alteration mineralogy seems to 2 have formed from a glacial dominated uid source with a signicantly lower δ H signature than that of seawater. a slight decrease in Na but substantial increases in the concentrations of Ca and K. 13 . Silica is increased strongly but F decreased much (Table 2.CHAPTER 2. the geothermal uids with hydrous alteration minerals. Lonker et al. Experiments involving reaction of seawater with basalt have reproduced the uids at Reykjanes (Mottl and Holland.

906 1.67 8.0007 0.10.2 28.22/21.0017 0.0 21.12.6 47.0011 0.0022 0.7 0.12.b 1028a.1 15.2004 20.88/21.324 1.11/22.021 0.0 7.1 37.1 6.5 11.8 16.2 61.9 59.55/21.09.2004 SV-11 04-3004 10.2 29.072 1.008 0.003 7.3 7.004 0.9 12.188 17.678 7.129 0.828 1.416 1050 1167 1011 1141 1004 1125 982 1102 1114 1129 1093 1170 1434 1680 1447 1637 0.0005 0.718 a Liquid enthalpy wells b Selected.1331 0.6 04-3005 10.072 7.03 8.001 0.0 2.4315 0.92/22.5 0.0018 0.1 85.1 7.88/18.928 1.1568 0.8 1.0042 0.4 172.883 19. corresponds to enthalpy of steam-saturated liquid at 238 ◦ C c pH values above 8.1: Major elements analyses of the sampled waters.0071 0.1 8.9 7.550 1.5 15.027 0.9 83.0 49.9 9.5 16.77/21.933 1.9 51.104 9.0 15.087 32.28 8.162 0.4 90.8 99.0008 0.0 159.6 12.2004 15.3 69.9 47.0397 0.2 14.8 0.19/23.2 111.585 34.4 0.3 262.4063 0.603 0.936 0.12.9 12.6 58.6 28.397 33.160 0.0007 0.4 0.138 107.2004 19.2 16.001 0.723 1.445 31.12.7 9.431 1.1 110.7 72.847 1.7 9.1 9.0011 0.3068 0.54 8.2005 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.4 4.8 3.558 30.0110 0.1 2.991 1.522 0.34 8.58/20.550 0.002 0.5 88.12.693 1.3 621 457 432 730 662 653 859 502 381 558 867 554 713 758 671 753 739 796 881 721 713 861 693 786 859 829 468 488 492 460 471 463 679 672 133 151 244 222 194 118 259 150 221 237 235 162 164 156 171 167 171 150 150 171 157 147 172 142 153 144 7263 7043 6995 6825 7522 7490 10166 10089 24.745 1.0044 0.8 35.2004 15.8 13831 13493 13230 12916 14255 14235 19288 19251 3.4 0.9 227.271 2.674 1.2004 10.0018 0.10.5 15.0005 0.10.12.5 44.236 1.8 12.5 11.2004 SV-7 04-3003 10.4279 0.12.5 26.b 1316a 1256a 20.2004 21.1 89.9 46.2004 21.001 0.8 19.0 72.1 7.735 1.5 15.0 15.12.9 5.425 2.09.3 8. If present.5 3.7 20.9 108.0004 0.0003 0.3 17.8 1.6 67.45/22.46/22.09.12. 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 8.929 1.298 33.80 8.8 10.5 25.0031 0.7 46.10.0053 0.2004 SV-19 14.18 8.065 0.80/17.b 1028a.367 32.8 9.588 2.80/18.843 7.12.9 169.954 1.0010 0.147 0.341 0.619 0.8 67.9 8.003 0.4 0.093 1.3 15.2 1.1 8.002 0.6 15.6 8.0 7.7 19.01.581 26.6 8. pH pH corr.7 32.2004 10.290 28.322 28.5 0.063 0.8 0.40 8.2 10.4 0.0090 0.8 18.4 0.8 11.3 9.6 117.5 2.0017 0.1 27.8 8.0 0.10.6 2.95/21.0007 0.6 0.0035 0.890 3.9 1.650 6.530 7.3 122.70/22.767 8.004 0.210 30.2004 10.5 8.323 1.735 7.003 8.6780 0.6 4.6 103.424 32.0017 0.11 8.511 0.359 2.0010 0. Sampling meas.136 31.2004 10.25/22.9 0.0 25.582 1.0022 0.0 241.105 0.585 0.0020 0.2 0.786 6.2004 10.0 36.28 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 6.16/21.7 5.5 42.58 9.0 14.b 1028a.2004 15.0041 0.047 1.189 3.5 17.2004 21.0015 0.0012 0.541 0.0137 0.0027 0.7 43.8 59.128 7.2004 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 7.0014 0.3 78.128 1.232 0.855 1.825 1.4 1.9 56.2 6.134 6.6 46.7960 1.0137 0.09.523 2.3 0.0164 0.966 19.1 124.72/23.24/19.2004 15.Table 2.2004 SV-9 04-3029 01.7 65.654 53.7 38.4 158.9 303.2 62.2004 15.473 39.900 1.042 2.8 15.6 31.59/16.93/22.2 0.8 1.7 1.2930 0.4 2.0016 0.642 1.0748 0.066 0.8 95.10.54/22.10.818 2.2004 10.966 0.10.002 0.0049 0.158 0.008 0.0 147.0 8.0 14.26/18.0 15.023 0.2004 09.819 1.7 8.01.009 0.002 0.5 12.52 8.1 50.7 7.8 56.886 0.4 182.4 8.059 32.7 25.2004 20.42 8.605 1.163 0.003 0.1 151.147 0.3 5.790 1.047 1.334 32.2 24.002 0.2004 20.0 14.5 75.119 0.0023 0.008 7.633 6.0 28.002 0.4 0.10.0026 0.2004 20.0 14.2 1.400 2.891 2.070 0.0038 0.0 14.6 93.025 0.009 0.9 90.002 0.3 4.175 0.68 8.0 were corrected for silica polymerization.0012 0.12.361 0.6 8.749 1.052 2.878 1.8 9.7 8.4712 0.5 14.9 16.0037 0.999 9.10.5 15.7 15.8 24.006 0.246 30.3 0.017 0.10.5 14.66 8.09.398 19.8 8.2004 21.5668 0.5 25.9 4.43/18.944 1.13/21.1 31.12.90/18.3 38.2004 20.5 7.2004 10.51/19.5 164.2 45. the corrected value was used for the calculations.013 0.24/20.202 52.1 2.0 16.86/21.2004 SV-8 04-3032 01.3 49.7 8.380 1.632 7.b 1028a.4 133.19/21.09.10. .0016 0.157 1.005 0.2 3.8 36.3 5.4 167.59 8.0093 0.0009 0.1 72.0007 0.67 8.36/19.6 9.10/21.0 28.9 6.12.0037 0.3 69.0009 0.9 62.0 14.272 1.343 1.5 6.161 0.7 8. Concentrations in mg/kg.0009 0.24/20.0020 0.181 31.b 1028a.7 20.166 1.0009 0.136 1.308 33.1 28.5 147.209 1.27 8.724 0.8 1.5 15.8 86.2004 20.114 1.2004 SV-18 04-3006 05-3004 05-3003 10.067 2.9 12.045 0.0 164.41 8.89/19.29 9.923 1.0019 0.2005 R-12 14.2004 09.12.241 1.0080 0.001 0.2 14.673 1.026 1.9 247.0040 0.5 3.140 0.6 49.0 7.

1977). 1989). 2002.5 Well discharge enthalpy The enthalpy of the well uids sampled for the present study ranges between that of saturated vapor and liquid enthalpy. Ellis and Mahon. local or near local meteoric water according to At Kraa. (1971). as dened by White et al.e. Many of the studied wells have excess enthalpy. Carbon dioxide is generally the most abundant gas (18600 mmol/kg of condensate). All the geothermal elds considered for the present study are liquid-dominated.CHAPTER 2.1). 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 − (Arnórsson. the enthalpy of the discharged uid is higher than that of liquid enthalpy (Table 2. 1989. Thus. Capillary forces between mineral grain surfaces and liquid reduce partly or even completely the mobility of the liquid. 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. 1995). aquifer uid CO2 concentrations are relatively low. In the parasitic systems of Nesjavellir and Námafjall. Námafjall and Nesjavellir the source water to the geothermal uid is δ 2H data (Darling and Ármannsson. even in terms of volume. followed by H2 (<0. whereas those of H2 S and H2 are relatively high. the gas content of dilute aquifer uids is typically much higher than those of the dissolved solids. as measured at room temperature is typically below 7 for the saline water but above 8 for samples of dilute water. Systematic dierences are observed in the aquifer uid composition of the study areas. Methane concentrations are quite low. The pH of the unboiled and undegassed water in the aquifer is lower. 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. i. exploitation of the reservoir has led to the formation of a vapor cap on top of the hot water reservoir. meaning that the aquifer uid is liquid only or liquid with a small vapor fraction. the enthalpy of the discharged uid equals the enthalpy of vapor saturated liquid at the aquifer temperature. the most abundant + cation is Na and silica as SiO2 is typically the most abundant dissolved solid (Table 2. This CO2 anomaly is still quite strong in some of the Kraa wells (Gudmundsson and Arnórsson.1). 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 (Ármannsson et al. N2 /Ar ratios are most often between that of air-saturated water and that of air. At Svartsengi. The gas content of vapor samples is quite variable.g. The most important anions are Cl and SO4 . 1995). On a molar basis. 2.. 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 .e.2). 2005). The pH of water samples. the saline waters are low in both H2 S and H2 compared to the dilute waters. 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.5110 mmol/kg) or H2 S (<251 mmol/kg) (Table 2. i. Arnórsson.

73 2.045 0.000 0.052 0.2: Gas analyses of the sampled vapor phase in mmol/kg of condensate.22 3.000 0.8 44.8 413.50 1.4 72.42 34.757 3.6 43.9 21.1 48.51 1.788 0.5 49. The Na/K geothermometer results are independent of the process producing excess well discharge enthalpy because it is based on a component ratio.7 10.9 37.088 0.70 2.000 0.6 32. This is.2.8 7.4 41.144 0.060 2.236 0.0 96.035 0.82 46.110 0.5 64.0 600.097 0.52 9. including silica.7 24.8 31.8 50.14 61.99 11.08 3.6 64. 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 4.2 62.410 0.87 0.95 7. however.1 54. phase segregation is responsible for the excess enthalpy.15 4.9 122.95 1.09 0.000 0.333 0.7 58.06 12.49 31.12 3.160 0.000 0.4 139.95 105.0 18.081 0.9 12.60 51.000 0.000 0.19 0.062 0.154 0.174 0.8 0.89 40.012 0.2 49.000 0.0 53.07 13.00 30.2 14.0 1.8 37.1 11.067 103.5 67.000 0.055 1.0 142.8 82.10 2.110 0.353 0.006 0.000 0.072 0.8 93.00 8.089 0.40 5.27 32.30 41.4 40.41 1.000 0.2 57. 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.042 0. not the case for the quartz geothermometer.2 64. AQUIFER TEMPERATURES Table 2.4 2.147 0.8 74.9 44.2 3.38 2.4 3.026 0.000 0.7 25.2 51.040 0.036 0.2 59.012 0.0 44.4 3.3 18.081 0. These results indicate that phase segregation is largely the cause of excess enthalpy.511 0.12 3.000 0.18 41.000 0.3 167.6 40.2 27. although ◦ quartz equilibrium temperatures are systematically higher (13 C on average). For the Svartsengi wells.000 0.1 63.69 78.2 60. It is therefore reasonable to calculate component concentrations in the initial aquifer uid according to this model.000 0.039 0.4 446.1 44.3 8.7 32.040 0.8 49.35 110.73 9.7 25.083 0.97 1.99 9.47 1.35 6.175 0.025 0.35 8.5 37.222 0.88 0.153 0.59 3.9 389.1 33.6 40.000 0.000 0.010 0.4 30.240 0.63 5.9 1.0 165.344 1.8 18.7 67.091 0.201 0.82 5.98 1. If excess well discharge enthalpy is produced by conductive heat transfer from the aquifer rock to the uid owing into wells.000 0.000 0.26 5.145 0.22 3. which receive uids from sub-boiling aquifers.62 1.075 0.8 37.8 37.05 32. in the total well discharge are the same as in the aquifer uid.000 0. It is seen that the two geothermometers yield similar results by the phase segregation model. quartz equi- 16 .050 0.85 2.2 39.611 0.9 25.0 45. 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.150 0.46 1.4 46.2 18.86 24.000 0.684 0.21 13.0 95.2).000 0.12 0.45 19.741 1.038 0.47 5.2 41.8 157.000 0. 2.54 51.4 65.053 0.079 0.325 0.4 314.1 54.414 0.117 0.000 0.357 0.64 0.000 0.6 52.6 Aquifer temperatures Aquifer temperatures have been estimated by the quartz and Na/K geothermometers for all wells.9 72.33 30.011 0.5 4.9 92.5 48.5 56.6 63.000 0.000 0.02 7.5 72.5 43.6. on the other hand.044 0.628 0.6 23.000 0.000 0.87 92. If.3 48.122 0.17 7.024 0.0 79.000 0.60 30.1 54.26 0.8 44.043 0.6 24.109 0.90 9.22 0.000 0.000 0.6 75. component concentrations. Quartz equilibrium temperatures have been calculated according to both models for excess enthalpy wells together with the Na/K temperature (Fig.000 0.4 1.992 0.9 437.

17 .CHAPTER 2. Figure 2.2: Na/K and quartz geothermometers compared for both the phase segregation model and the heat transfer model.

The seawater source uid contains enthalpy wells. 2.2 sample was analyzed on a Reagent-Free µm cellulose acetate membrane using a Teon lter holder and collected into low-density polyethylene bottles. For liquid enthalpy wells discharging dilute waters (see Table 2. At Reykjanes. which is due to leaching from the basalt host rock. respectively.. For excess 13 ◦ C lower than quartz equilibrium ∼400 ppm K but the geothermal seawater 14001500 ppm. Mg. yield similar results ◦ ◦ in the temperature range of the wells under study.2. 1 and ◦ ◦ ◦ ◦ 17 C at 200 . Si. acidied sample was used for trace elements determination on an ICP-MS. Gudmundsson and Arnórsson. 1999. The calibration (quartz solubility constant) used here for the quartz geothermometer is that proposed by Gunnarsson and Arnórsson (2000). the dierence being only 6 . Sr). 2002). B.. 2. temperatures. A 200 ml sample was acidied with 2 ml Suprapur R HNO3 (E. Cl and SO4 . Hydrogen sulde was measured on 18 . average Na/K temperatures are 18 ◦ C lower than average quartz equilibrium temperatures. An untreated 200 ml TM ion-chromatograph (RFICTM . The cause is believed to be insucient supply of K from the basalt to the uid to saturate it with K-feldspar. however. 2. than the K content of fresh basalt in the Reykjanes area. Arnórsson et al. 2000. Na/K temperatures are signicantly lower than quartz equilibrium temperatures (Fig. is comparable. The calibration of Fournier and Potter (1982) is more widely used. 2000).1 Water phase Sample treatment Water samples were ltered through 0. (2006). Fe.00441) for major element analyses on an Inductively Coupled Plasma .7.2). in the temperature range of 200300 C.7.1). The two calibrations. Cl. Na/K temperatures are on average Such recharge has not been observed in Svartsengi. at least.Atomic Emission Spectrometer (ICP-AES) (Al. For further details. Merck Another 100 ml 1. Ca. see Arnórsson et al. or even higher. the average dierence for ◦ Svartsengi being 3. SAMPLING AND ANALYSIS librium and Na/K temperatures compare well (Fig. The dierence. The Na/K geothermometer equation used is based on thermodynamic data on low-albite and microcline solubility (Arnórsson and Stefánsson. Na. Glass bottles with air-tight cap were used for pH and total carbonate carbon determination in the laboratory shortly after sampling. 2.3 C suggesting that the calibration of the two geothermometers is ◦ internally consistent likely. 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 (Arnórsson et al. 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.7 Sampling and analysis Only a short description of the sampling and analytical techniques used in this study is given here. 250 and 300 C. Dionex 2000) for F.2).

O2 . Note on sulfate analysis Special samples were collected for sulfate determination. pyrite. pyrrhotite and calcite.32 (Bird and Spieler. (2008).5 were taken from ◦ ◦ ◦ ◦ Karingithi et al. Cp ) on the minerals from Holland and Powell (1998) except for pyrite. Upon sample storage the ZnS precipitate tends to dissolve. H2 S will cause an increase in the SO4 concentrations in the sample. Carbon dioxide and H2 S dissolve quantitatively in the hydroxide solution. gases in the gas phase. Data on the sulde minerals were taken from Robie and Hemingway (1995). sulfate concentrations were determined by RFIC TM .1 are maximum values. Activities of endmembers in solid solution have been retrieved from their analyzed composition 19 . Accordingly.. expressed as Xps . S . and OH are from SUPCRT92 (Johnson et al.8 Thermodynamic data 2. The calcite solubility constants is from Arnórsson et al. Ca . (1999) and Pokrovskii and Helgeson (1995). reported SO4 numbers in Table 2. the 2.3 and 2. the composition of epidote.1 Mineral solubility constants and gas solubilities Equilibrium constants for the reactions given in Tables 2. The thermodynamic properties of the aqueous species and liquid water entering the reactions in Table 2. respectively. They are based on thermodynamic data (∆Gf . garnet and prehnite). this measurement yields a value for sulfate. is in the range 0. Ar and CH4 were analyzed on a PerkinElmer-ARNEL 4019 gas-chromatograph.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. those on +2 +2 − H2 Ol . N2 . At Kraa and Nesjavellir. assuming ideal behavior. V .CHAPTER 2. One 1 ml of 1% Zn-acetate solution was added to 100 ml sample to remove H2 S. site by titration with standard mercuric acetate solution. 2..dat data set and those on Fe(OH)4 and Al(OH)4 from Diakonov et al. Condensate was analyzed for CO2 and H2 S by titration. (2003) assuming ideal behavior of the gases. magnetite. 1992) using the − − slop98. pyrrhotite. (1982). data on H4 SiO4 are from Gunnarsson and Arnórsson (2000). Fe . analysis.3 were taken from 0 various sources. Subsequently. 2006). using dithizone as endpoint indicator (Arnórsson et al. Sulfur was also analyzed by ICP-AES. The other minerals considered (calcite. quartz and prehnite) are taken to be pure. the mole fraction of pistacite (Ca2 Fe3 Si3 O12 OH). The standard Gibbs energy of the dissolved gases are based on the gas solubility constants given by Fernández-Prini et al. concentrating the non-condensable This allows a better precision of the non-condensable gas Hydrogen.8.7. In the absence of Subsequent oxidation of sulfur bearing species other than sulfate.180. Three of the hydrothermal minerals considered for the present study form extensive solid solutions (epidote.

44.2) (Lonker et al. we considered a full substitution of Al by Fe on this site.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.Al)Si3 O12 ) has only been reported from the saline uid elds in Svartsengi and Reykjanes. In Svartsengi and Reykjanes.19 and 0.3 is obtained for the grossular and andradite endmembers. The selected activities for the dilute aquifers is equal equal to 0.ideal is the activity of the endmember i. the M1 site can also accommodate some Fe. Mineral compositions used in this study are averages of chemical analyses from the cited authors. This gives an average epidote endmember (Ca2 FeAl2 Si3 O12 OH) activity of 0. The average mineral compositions were selected because it is the simplest one.ideal = X2 where ai. 2004). assuming ideal behavior. 11. Al-Fe substitution occurs on one site and the activity. Ca3 (Fe.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. 10. corresponding to an XF e of 0.Fe)Si3 O10 (OH)2 ). 3. Xps ranges between 0. From the average XAl in grossular and XF e in andradite. 1987) and 0. analyses are more likely to be performed on coarse-grained rather than ne-grained crystals that recently formed from solution.1 (Hreggvidsdóttir.75. In prehnite (Ca2 Al(Al. 1992). The substitution of Al by Fe in epidote occurs mostly in the M3 site. respectively. 6..8. which corresponds to an endmember epidote activity of 0. and to calculate the epidote and clinozoisite activities. The corresponding clinozoisite activity is therefore 0. In addition. Some minerals show a zonation and the core of those grains is not expected to be reacting with the present uid. activities of 0. 2. 4. so ai.2. Substitution occurs on two sites. assuming ideal solid-solution. is proportional to the ratio of Fe to one Al. 5. and X its mole fraction..25. neither will be the rim if the grain has ceased to grow.2 and 0. the uids sampled must be a mixture of many components and individual components likely have reacted with garnets of dierent compositions.3: Individual minerals dissolution reactions 1.8 (XF e elds. Also. Nevertheless. THERMODYNAMIC DATA Table 2.38 (Árnason and Bird. and + 4H+ + 8H2 O = 3Ca2+ + 2Fe(OH)− + 3H4 SiO0 4 4 cal + 2H+ = Ca2+ + H2 Ol + CO2. 1993). The question raises whether the numbers selected are representative of the mineral composition with which the present uid is reacting. 1992). 9. 7. respectively.140. 8. and this can lead to a modest overestimation of the calculated activities (Deer et al. 1993) for the saline 20 .9 (Bird and Spieler. Garnet (grossular-andradite..9. = 0. i The average Al mole fraction in the garnet at Svartsengi and Reykjanes is very variable (Lonker et al.

1 (Arnórsson et al. At high pH (above ∼9). model 3 in Arnórsson et al. 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 Arnórsson (2005). the phase segregation model was used to calculate initial aquifer uid compositions for excess enthalpy wells. Therefore.CHAPTER 2. version 2.. whereas the formation of oligomers has the opposite eect. oligomer formation dominates the pH change over decrease in silica As the acid dissociation constants for silica oligomers are monomer concentrations. when ionized silica concentrations are insignicant (pH below ∼8).9 Data handling 2. 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. which are stronger acids than silica monomers (Tossell and Sahai.1. only poorly known from ab initio calculations their eects on pH cannot be quantied. whereas other waters become supersaturated upon cooling to room temperature subsequent to sampling. 21 . i. 2000). it is reasonable to take total well discharge compositions to represent the initial aquifer uid.2 Calculation of aquifer water compositions and aqueous speciation As demonstrated in section 2. 2. When the measured pH was above 8. removal of monomers from solution tends to raise its pH.e.1). Silica polymerization aects the solution pH as it involves removal of silica monomers. decrease in silica monomer concentration by its polymerization dominates the pH change over oligomer formation and causes it to increase. from solution and the formation of silica oligomers. Besides their concentration cannot be measured and their concentrations change with time.9. The pH of the samples collected for the present study was measured when practically all silica in excess of amorphous silica polymerization had polymerized. For liquid enthalpy wells. which act as weak acid.9. In contrast. (2007). The initial temperature selected for calculating aquifer uid component compositions was the average of the quartz and Na/K geothermometers (Table 2. The pressure at which phase segregation occurs aects the composition of the initial aquifer uid in relation to the total well discharge. sometimes rapidly. Aquifer uid compositions and speciation distribution in this uid were calculated with the aid of the WATCH speciation calculation software. we selected this pressure to be halfway between aquifer and wellhead vapor pressures.6 above. 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. 2. Some of these waters are slightly amorphous silica supersaturated at sampling conditions. The results are shown in Table 2. when the dissolved silica is signicantly ionized.1 Note on pH measurement The waters sampled for the present study contain 380880 ppm of dissolved silica (as SiO2 ). the wellhead vapor pressure. the quartz and Na/K geothermometer results indicate that excess enthalpy of well discharges is essentially produced by phase segregation. Therefore.

v − hg. 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.v = h stands for specic enthalpy. For components that partition almost exclusively in the liquid d. it follows that s s Ds = 55. Therefore hd. (2.v so (2.9.v X g.6) (see Arnórsson et al. sulde sulfur and boron. the WATCH calculations involve two steps.v i i i i mi designates concentration on component i.508 Ks Ptot 22 (2.v X g.7) . (2.2) X g. For the rst step we have md. P g we have g Ds = At ng. respectively.v i s) vapor pressure describes its relative concentrations in the two phases at equilibrium.l (1 − X g. Gaseous species g are assumed to be present in both phases at P .l hg. v and l for initial aquifer uid.l (1 − X g.5) g Ds = mg. at sampling conditions.t = mg. hd.e. For liquid enthalpy wells.t = md.t = hg. The second step involves calculating aquifer uid composition from the liquid and vapor phase compositions at P g . t for total uid and f. d. In fact the only components analyzed in both phases are carbonate carbon.3) X g. the initial aquifer uid composition for component i is obtained from mf.5). 2007).v ) + mg. mi is taken to be zero by the WATCH program and for gaseous components that are present in insignicant concentrations in liquid samples. For excess enthalpy wells.v ) + md.2. Bjarnason. 1994).t − hg. mi is taken to be zero.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 . sampling pressures. 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.v s ng.l s and for dilute uids: (2. As before.v ) + hg. assuming that the owing uid enthalpy before phase segregation occurred is the same as that of vapor saturated liquid at the aquifer temperature.1) d stands for discharge. (2.. The superscript i.l and therefore not analyzed.l s s (2. vapor and liquid.l (1 − X d. DATA HANDLING 1982.v i i i where (2. The distribution coecient (Ds for species mg.v X d.1) through (3.v phase.v occurs.l (2.v s mg.1). n From denotes mole fraction and subscript s gaseous species Ps = xv Ptot and ml = Ks Ps .t = md.

10 Mineral-gas equilibria In the discussion below (section 2.t = mg.v uid. (2. The respective reactions for dilute and saline uids are shown in reactions 1 and 2 in Table 2. 23 .l X g.v i is taken to be zero. (2.8) allowing calculations of the concentrations of all components in both liquid and vapor g phases at pressure P .t = mg.12) it is assumed that the initial aquifer uid is represented by liquid only. and rewritten as g md.3 shows that the calculated aquifer liquid concentrations of carbon dioxide (CO2. together with the aquifer composition of uids feeding liquid enthalpy wells.l hg. is given in Table 2.2) can be (2.5. Now equation (2. such as H2 . 2. as calculated by the method just described. 2.9) mf. the calculated gas concentrations in the initial aquifer uid represent aqueous gas concentrations. particularly for the less water soluble gases.v i i i is the Henry's Law constant for gas s. i. The results for component concentrations in the initial aquifer uid of excess enthalpy wells. The s number 55.4.508 is the number of moles of water in one kg. This steam fraction is symbolized as X X e.10) mg.v − hg. Ks total pressure.v ) + mg. Also shown are equilibrium constants for two potential mineral assemblages that would x CO2.aq ) as a function of temperature.aq if equilibrium was attained.l (1 − X e.l and.v i i i As before for non-volatile species. Ps and Ptot are partial pressure of gas s and xv the mole fraction of gas s in the vapor phase.1 CO2 Figure 2.CHAPTER 2.e.10.l (1 − X g.v ) + Ds mg.v X e.t − hg. the true gas concentration in the aquifer liquid would be lower than assumed here. If some vapor is present in the aquifer uid.v = hf. 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. respectively.

303 6.020 0.5 3.35 1.245 1.53 0.78 0.Table 2.48 1.00 0.280 0.5 0.002 0.77 1.291 1.99 25.63 7.034 3.0150 0.8 0.7 27.61 5.3 2.3 65.001 0.3 20.78 1.004 0.0232 0.00 0.1 32.767 1.37 4.76 0.9 95.5 82.001 0.0087 0.0158 0.0067 0.24 1.8 91.392 0.16 0.0 1.008 0.907 93.11 1.0368 0.0150 0.2 72.002 0.63 1.004 0.25 3.54 0.509 0.13 0.31 1.0106 0.34 3.2 93.0146 0.00 0.29 26.3 63.8 104.9 49.3 4.0285 0.094 0.15 0.3 29.22 1.50 1.6 162.16 3.00 0.40 18.8 0.189 0.04 7.50 2.614 0.73 0.32 52.5 64.00 0.427 0.9 2.3 1.81 2.001 0.5 0.231 0.994 4.9 21.3 0.001 0.1 0.00 0.222 0.74 1.00 0.5 25.0057 0.69 18.1 65.00 0.41 6.00 0.23 25.1 110.010 0.10.389 4.0268 0.14 0.0810 0.73 7.192 1.0823 0.37 24.00 0.3 1.7 99.65 5.5 0.004 0. where quartz geothermometer temperature was used (see text).69 0.00 0.389 0.00 0.12 0.21 0.45 0.641 0.344 0.6 0.1 53.006 0.57 1.6 0.06 0.29 0.001 0.255 6.0014 0.94 1.31 961 1069 916 1033 915 1025 920 1032 1009 1023 994 1064 1294 1516 1220 1381 0.67 9.14 1.002 0.005 0.8 13.00 0.5 1.0223 0.001 0.002 0.6 54.6 75.0 9.32 0.0112 0.0430 0.0269 0.3 203.9 12664 12222 12054 12100 12912 12942 17402 16241 0.0536 0.036 0.91 1.477 0.69 7.00 0.8 11.16 2.6 36.16 5.369 0.85 3.084 0.5 37.23 2.22 24.8 7.001 0.0041 0.0034 0.69 2.1 213.012 0.3 10.11 0.002 0.02 9.03 52.5 66.1 48.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 21.12 3.92 7.38 0.24 23.91 0.2 41.506 0.9 14.00 0.295 0.1 137.0060 0.0077 0.203 0.02 0. K Ca Mg Cl F B N2 /Ar 2.3 25.2 58.69 0.7 44.76 1.00 0.0 0.4 289.0012 0.247 0.76 0.16 25.68 25.1284 0.9 48.0106 0.12 0.69 0.27 1.15 1.80 7.03 45.16 23.89 1.001 0.2 0. except for Reykjanes.06 0.26 21.231 0.20 10.49 1.28 25.0038 0.0051 0.00 0.77 1.54 0.0212 0.033 0.93 6.00 0.8 45.3067 0.90 0.73 7.4 80.000 0.83 61.130 0.71 8.8 25.17 30.0160 0.05 16.000 0.1 0.2 64.015 0.4 0.80 29.922 0.00 0.00 0.0141 0.0062 0.14 0.40 4.78 1.04 1.1 23.3 8.9 40.64 1.0062 0.28 0.0218 0.6 125.8 0. corresponds to the average of Na/K and quartz geothermometer temperatures.685 1.002 0.86 0.00 0.1 62.12 1.002 0.642 0.5 48.00 0.25 1.00 0.134 18.05 4.88 7.3 15.559 1.041 9.001 0.03 2.8 53.001 0.48 14.85 1.5 3.326 0.2 62.001 0.0 25.001 0.25 1.31 40.0025 0.66 1.003 0.13 1.83 0.285 0.0169 0.42 0.263 0.320 2.64 4.0012 0.000 0.26 11.0077 0.77 0.8 44.010 0.067 1.219 0.3 40.0056 0.57 8.901 3.0106 7.0605 0.89 6.012 0.268 8.227 0.40 1.0226 0.15 0.9 85.0056 0.002 0.19 25.0040 0.24 9. .06 0.760 0.03 16.1 6.1 61.60 1.3 43.33 26.03 0.46 1.8 30.0038 0.3 4.0044 0.360 2.06 6. Temperature is in ◦ C.431 1.000 0.35 17.66 1.718 0.12 3.001 0.411 8.1 54.006 0.12 2.299 7.38 1.1 0.001 0.77 0.0 0.003 0.08 15.594 0.217 0.43 1.00 0.2 60.0866 0.6 1.10 25.80 1.00 0.64 7.143 0.0050 0.0137 0.91 1.3 228.6 4.002 0.8 4.18 4.438 1.9 57.0 57.0135 0.03 1.001 0.2 40.93 0.88 6.83 7.002 0.5 67.170 0.6 44.004 0.71 1.16 0.16 20.0191 0.3 139.81 1.54 0.00 0.4 a Liquid enthalpy wells b Selected.531 0.0293 0.12 7.0105 0.1727 0.46 3.38 25.97 5.299 0.002 0.001 0.0062 0. SO4 Fe Al CO2 H2 S N2 Ar O2 CH4 H2 dissolved solid concentrations are in mg/kg but gases in mmol/kg.16 0.00 0.6 52.001 0.0089 0.0 2.0667 0.11 0.38 0.309 0.020 0.473 1.2 0.56 15.48 1.3223 0.13 1.93 3.3 4.0046 0.0037 0.4: Aquifer water composition.13 0.7 71.79 6.97 1.0 10.00 0.0035 0.003 0.461 0.00 0.6 109.31 6.0368 0.46 1.0062 0.003 0.001 0.27 1.23 9.06 0. MINERAL-GAS EQUILIBRIA Sample # Well Aquifer temp.46 0.947 4.00 0.1 1.528 4.11 6.0006 0.00 0.239 3.4 45.00 0.82 9.948 0.00 0.74 1.001 0.00 0.30 5.15 0.26 32.228 0.16 7.7 151.71 1.81 1.002 0.03 1.3 125.56 6.4 130.006 0.125 0.0021 0.03 0.22 5.010 0.001 0.09 14.27 1.004 0.002 0.2 37.488 0.06 26.5 0.584 0.168 0.18 37.8 0.176 4.0150 0.35 23.7 103.711 0.893 3.03 0.81 5.72 6.011 0.8 82.52 1.

2 and 0.9.CHAPTER 2.1. For the dilute uid activities of clinozoisite of 0. Figure 2. Prehnite activity was selected as 0.1 are shown. 25 . grossular and prehnite are 0. respectively.3: Potential mineral buers controlling CO2 gas concentrations in the initial aquifer uid. 0. For the saline uids. the activities of clinozoisite.82.25 and 0.

2/T + 0.3/T + 0.aq −2.528 log T 4.9/T + 8.391 log T 3 3 3 8. 2008).4/T + 0.5: Mineral assemblages potentially controlling CO2 . H2 S 3 gro + 13 pyr + 13 pyrr + 3 qtz + 3 H2 Ol = 3 epi + 3 wol + H2 Saq −1.358 − 1420.777 · 10−4 T + 5.570 − 5346.aq −1.aq3 1.aq 2 −1.00780T − 0.3/T − 1.693 · 10−6 T2 − 0.052 − 215218/T2 − 1658.377 · 10−6 T2 − 0.. Temperature equations are valid in the range 0350 ◦ C at Psat . # Species Reaction Log K (T) 3 3 1.509 log T 3 3 3 1 H −2. H2 2 pyrr +4H2 Ol = 24 pyr +44 mt + H2.Table 2.00880T − 6. H2 S 4 pyr + 1 pyrr +1H2 Ol = 24 mt + 4 2 Saq 2 2 2 2 5.303 log T + 4 2 7.020 − 188233/T2 − 1504.831 − 22843/T2 − 1344.4/T + 0. CO2 5 czo + cal + 3 qtz = 3 gro + 1 H2 O2l + CO2.2/T + 0.00856T − 0. H2 6gro + 2mt + 6qtz + 4H2 Ol = 6epi3+ 6wol + H2.611 · 10−6 T2 − 0.113 log T . H2 3 gro + 3 pyrr + 3 qtz + 3 H2 Ol = 2 epi + 3 wol + 2 pyr + H2. H2 S 2gro + 4 pyr + 2 mt + 2qtz 2 2H2 Ol = 2epi + 2wol + H2 Saq −1.455 log T 2 2.549 − 383405/T2 − 1774. H2 3 pyrr + 2 pre + 33H2 Ol =1 3 epi + 2 pyr + H2.aq −1.aq −1.818 · 10−4 T + 4.454 log T 2 9.336 log T 10.00829T − 0. CO2 czo + cal + 2 qtz = 2 pre + CO2.561 log T 5 5 5 1 2 3.7/T + 0.479 · 10−6 T2 + 1.241 − 1519.4/T + 6.01059T − 0.327 − 58215/T2 − 1829.0/T + 0.00760T − 0. H2 S 1 pyr + 1 pyrr + 3 pre + 21H2 Ol = 3 epi + H2 Saq −2.436 − 1131.00820T − 0.452 log T 6. H2 S and H2 concentrations and respective K -temperature equations (Karingithi et al.866 · 10−4 T + 5.862 − 253145/T2 − 1595. Unit activity was selected for all minerals and liquid water.

A systematic dierence is observed 27 .5 (reactions 3 to 6 for H2 S and 7 to 10 for H2 ). the match is.04 log mol/kg with a standard deviation of 0. 2002). The dilute uids at Kraa. 2002).2. too high for equilibrium with mineral assemblages to be closely approached in the respective aquifers. quartz and solution xes aqueous Ca /(H ) activity ratios. Gudmundsson and Arnórsson.05 and -0. the CO2 At Nesjavellir. prehnite. 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. 1989. Yet there are some systematic dierences between elds. making calcite unstable.1.1). Carbon dioxide concentrations at Reykjanes are very close to equilibrium with this buer.2 H2 S and H2 These two gases are likely to equilibrate with the same mineral assemblage. 2. Two of the wells at Svartsengi show CO2 concentrations signicantly above the equilibrium curve but the four remaining are close to the curve.4 and 2. Al-prehnite (0. the CO2 concentrations in the well discharges have declined in some wells (Gudmundsson and Arnórsson.. 2.3 ◦ logK units at 300 C. but increased in others. depending on their location in relation to the newly intruded magma body. both for dilute and saline uid systems ◦ (Figs.9 and 0.3). increasing to about 0. Many of the data points for the dilute uids fall close to the equilibrium curve. three wells (16. one including garnet rather than prehnite (see reaction 2 in Table 2. Garnet is abundant as hydrothermal mineral in these areas (Lonker et al. Since the magmatic event. 2. Likely. For the saline uids at Svartsengi and Reykjanes comparison is made with another mineral assemblage.5). Equilibrium between +2 + 2 epidote. From + +2 the following reaction CaCO3. this is a consequence of inadequate supply of CO2 from the magma heat source to the geothermal system. The assemblages likely to be involved. The dierence at 200 C is close to zero. These deviations are within the error in the thermodynamic data of the minerals. respectively (see Fig. better for the prehnite-epidote bearing assemblage although it is not possible to determine for individual samples which assemblage may be involved. 20 and 24) have high CO2 relative to equilibrium. concentration is close to equilibrium for a clinozoisite activity of 0. however. 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 (Ármannsson et al. as deduced from the hydrothermal minerals in the geothermal systems considered are given in Table 2. 1993) whereas prehnite is rare. Námafjall and Nesjavellir are close to equilibrium with these two assemblages. At Kraa. It is concluded that the high CO2 in wells 16.10.5). In the other wells at Kraa and at Námafjall. The equilibrium constant curves incorporate the average activities of the clinozoisite (0.82) and grossular (0. prehnite and garnet.CHAPTER 2.8) components in epidote. Overall.calcite + 2H = Ca + CO2.25 and 0. if Ca /(H ) activity ratios are xed. The average departure from equilibrium for the prehnite-epidote containing assemblage for Kraa and Nesjavellir is 0. the CO2 concentrations for most of the wells are lower than the equilibrium concentrations. 20 and 24 is the consequence of high CO2 ux from the magma intrusion.aq + H2 Ol it is seen that +2 + 2 a specic CO2 partial pressure is required to stabilize calcite..

two from Kraa (wells 21 and 27) and one from Nesjavellir (well 20). dissolved by the geothermal uids. respectively.2. The apparent inconsistency 28 . All these wells. prehnite and grossular. 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.10. 0. At Kraa and Nesjavellir.5).. two from Nesjavellir (wells 10 and 14) and one from Kraa (well 24). The H2 concentrations are similar to or higher than those predicted by equilibrium with the epidote-prehnite assemblage and by as much as 0. 2. epidote and prehnite mineral assemblage (reaction 3 in Table 2.2 in the saline uids for epidote.82 and 0. 1975.9.4 log mol/kg (Fig. pyrrhotite.5). Three samples are close to equilibrium. a strong magnetic low is associated with the geothermal elds (Pálmason. 1986). the Nesjavellir samples tending to be the highest in H2 S in relation to the aquifer temperature. except Nesjavellir 20 have liquid enthalpy. Another three aquifer uids are signicantly lower than the equilibrium values.75 and 0. respectively. This has been taken to indicate that the primary magnetite of the basalt is unstable. between areas.9 in the dilute uids for epidote and prehnite. MINERAL-GAS EQUILIBRIA Figure 2. Selected activities are 0. Björnsson et al. and 0.4: Mineral buers controlling H2 S in the initial aquifer uid. and in particular Námafjall.

One data point for Svartsengi (well 8). epidote and wollastonite (equation 5 in Table 2. respectively. where both the Na/K and quartz geothermometers and the measured down-hole ◦ temperatures are very constant.5).018. between H2 S and H2 is considered to result from the presence of vapor in the initial aquifer uid. For grossular. around 240 C.5: Mineral buers controlling H2 in the initial aquifer uid.018 corresponds to 22%. 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. Figure 2. pyrrhotite. Particular feature is the large variation in the H2 S temperatures in the Svartsengi aquifer uid. epidote and prehnite. involves an air contaminated 29 .9 in the dilute and in the saline elds. the selected activity is 0.CHAPTER 2.2. The H2 S concentrations in the saline uids are close to equilibrium with a mineral assemblage containing garnet.04 by mass and the average ◦ is 0.75 and 0.04 by mass at 300 C corresponds to 40% by volume and 0. The activity of epidote is 0.9 and 0. respectively and the activity of prehnite is 0. A value of 0. which yields the lowest aquifer uid H2 S concentration. The vapor fraction is apparently suciently large to signicantly raise the H2 concentrations but not those of the more soluble H2 S.82. The highest vapor fraction value for excess enthalpy wells is 0.

the aquifer water is systematically calcite under-saturated. 2.6). Monitoring studies at Svartsengi have indicated some depletion in the aquifer liquid concentration of CO2 and slight cooling (Steingrímsson. respectively. we present results obtained for the state of mineral-solution equilibria for individual minerals.3 log mol/kg.03 at Reykjanes.11.57 SI units in the case of Svartsengi and it falls down to -1. Four of the samples in Svartsengi and both samples in Reykjanes show too low H2 equilibrium temperatures relative to that mineral assemblage. the average SI values being 0.1 Calcite and wollastonite The majority of the aquifer uids are rather close to calcite saturation (Fig. 2. and therefore. it is concluded that the low H2 S temperature is faulty and due to air contamination of the sample.46. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA vapor sample. 1986). These values seem low.11 Individual mineral-solution equilibria If the aqueous concentrations of CO2 .11) Q represents activity product and K the equilibrium constant. the individual minerals in these assemblages should be in equilibrium with the solution. together with the decrease in dissolved CO2 concentration has turned the aquifer liquid calcite under-saturated. reactions considered are: 2. The cooling has led to slight decrease in the pH of the aquifer water and this.39. The remaining ve samples scatter around the equilibrium curve. The two 3 3 pre + 2H+ = czo + qtz + 2H2 Ol + Ca+2 2 2 and.28 and 0. 1989). The calculated pH of the aquifer water for the two samples from Reykjanes is 4. On average aquifer waters at Nesjavellir are very close to calcite saturation. (2. For Námafjall and Kraa.11. At Svartsengi and Reykjanes.7).13) +2 + 2 The low Ca /(H ) activity ratios correlate well with negative SI values for calcite.12) 3 4 2 3 gro + 2H+ = H2 Ol + czo + qtz + Ca+2 5 5 5 5 (2. Is is known that sulde reacts fast with O2 in alkaline medium. the maximum departure being around 0.11. 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.2. 2. average SI value is -0.47 and +2 + 2 4. Below. Mineral saturation is expressed in terms of saturation index (SI) dened as „ SI = log where Q K « (2. H2 S and H2 are controlled by equilibria with particular mineral assemblages. or by -0. The cause of the low calculated aquifer uid pH-value for Reykjanes and some of the 30 . The cause is boiling and simultaneous formation of a steam cap over the liquid reservoir (Gudmundsson and Thórhallsson. the results indicate some over-saturation.

Endmember activities are the same as described in Fig. 31 .CHAPTER 2.6: Saturation indices of selected alteration minerals. Figure 2.3 to 2.5. 2.

7: Ca 2+ /(H ) + 2 ratio versus temperature. prehnite and grossular of 0. Part of the large scatter is the consequence of the stoichiometry of the respec+ tive mineral-solution reactions.3 to 2. 1998). The saturation indices for all the Al-endmembers.2.11. 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).5. Symbols for various areas are the same as in Fig. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA Figure 2. grossular. As an example.2. Mineral assemblages clinozoisite+prehnite+quartz and grossular+clinozoisite+quartz are also shown. (2008).11. H is raised to the power 4. Svartsengi samples is not known.1. epidote-clinozoisite. respectively. one possible cause may be faulty thermodynamic +2 data on Al-species and in particular on the Al-Si dimer. with activities of clinozoisite.2 Andradite-grossular. 32 . The dilute aquifer waters are close to wollastonite saturation whereas the saline waters are signicantly under-saturated. − This is not considered real. 2. As for Fe-bearing minerals. in the garnets. nor is the calcite under-saturation observed at Reykjanes but equilibrium with calcite is rapidly attained at high temperatures (Zhang and Dawe. 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. clinozoisite and Alprehnite show an apparent over-saturation of the aquifer uids with respect to these phases. Ca removal by calcite precipitation from the owing uid may also be involved if insucient time is allowed for re-equilibration. The results for the Fe endmembers of the garnet and epidote indicate systematic over-saturation. 0. the wollastonite under-saturation +2 + 2 in the saline aquifer uids is attributed to low aqueous Ca /(H ) activity ratios. prehnite A large scatter in SI values is observed for the endmembers of all these solid solution minerals. As for calcite.9 and 0. which amplies in the same proportion the uncertainties on pH values. Equations are modied from Karingithi et al. 2.

boiling of ASW and of a selected mixture of ASW and air with a N2 /Ar ratio of 70 produces higher N2 /Ar ratios. where open step of temperature drop (0. model 4).6).CHAPTER 2. 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. N2 /Ar ratios range between 37.1) the total well discharge composition was taken to represent the initial aquifer liquid composition. One that is a the uid is allowed to equilibrate with the total amount of steam at once. for a given Ar concentration.015 mmol/kg. Two dierent types of boiling are shown. However. On the other hand.0 and 82. which all show a similar pattern of under-saturation.026 mmol for Ar. 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. the N2 /Ar ratio approaches that of air.3 mmol of N2 from air to 1 kg of water and correspondingly 0. It is envisaged that evaporation of capillary water in the formation may add steam to the owing uid. the segregation model. closed system boiling. with more negative SI values at higher temperature (Fig.002 to 0. Since all the wells considered for the present study have been producing for many years.. On the other hand. 2.028 mmol/kg. Fig. The initial aquifer uid concentrations for N2 and Ar have been calculated for all the wells considered for the present study. As the Ar concentration increases. For wells with discharge enthalpies close to liquid enthalpy (Table 2. to produce a N2 /Ar ratio of 50. N2 /Ar molal ratios range between 18.8). One of the models is the same as that used to calculate reactive gases in initial aquifer uid. it is considered reasonable that this capillary water has already been largely degassed.9 shows that this boiling model yields higher N2 /Ar ratios for a given Ar concentration. than allowed by air addition only. 2. 2. The average aquifer Ar concentrations in the dilute uids producing into liquid enthalpy wells is 0.e. For excess enthalpy wells. respectively. The latter model produces faster degassing of the aquifer uid for a given total mass fraction of steam. The other model allows for addition of gas-free steam to the uid owing into wells (see Arnórsson et al.1 (Table 2. two models were selected to calculate N2 and Ar concentrations in the initial aquifer uid. If two samples are exempted (sample 04-3007 from well 12 at Námafjall and sample 04-3050 from well 20 at Nesjavellir). 2. i. 2. This has an inuence on the equilibrium 2+ calculations of all Fe bearing minerals.2).4 and 92. 2.01 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. requires addition of 1. Two wells 33 . the range being 0.4 N2 and Ar In vapor samples.11. A possible explanation of these ratios is that the initial aquifer uid is represented by ASW containing minor amount of air bubbles. The magnitude of this dilution is directly related to the amount of steam formed by vaporization of capillary water.9 shows the eect of addition of air bubbles to air-saturated water.4. and an system boiling. Fig.2 and 39.11. 2007.3 Magnetite. In air◦ saturated water (ASW) and seawater (ASS) at 5 C the N2 /Ar ratios are 37. pyrite and pyrrhotite and magnetite.2 or between that of air-saturated water and air (Fig.

2. INDIVIDUAL MINERAL-SOLUTION EQUILIBRIA Figure 2. Weiss. respectively.2. Samples calculated in this study are also shown.8: Argon versus N2 in initial aquifer uids for all elds. respectively. as well as ASW ratio and air ratio. seawater (ASS. Symbols for various areas have the same meaning as on Fig. 34 . Figure 2.11. 2003) and air-saturated 5 ◦ C. 1970) at Also shown are air-saturated water (ASW. on the N2 /Ar ratio and Ar concentration in the boiled liquid (see text). open and full symbols showing liquid and excess enthalpy wells.. Fernández-Prini et al.8.9: Inuence of air addition and boiling on the N2 /Ar ratio versus Ar concentration in aquifer uid. broken and dotted lines show eect of boiling in a closed system and an open system. Continuous line shows addition of air bubbles to air-saturated water (ASW).

Fe and possibly Al. These two wells are marginal to their respective well elds and may represent the degassed uid owing away from the major upow. boiling.12 Discussion and conclusions Wells drilled into liquid dominated geothermal reservoirs sometimes have liquid enthalpy but commonly excess enthalpy. it seems very likely that the combination of several processes explains the observed N2 /Ar ratios (Fig. which is about the average annual air temperature at Nesjavellir. are very low in Ar. 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. due to its boiling and formation of a steam cap on the top of the liquid reservoir.009 mmol/kg. 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. below that of air-saturated water.CHAPTER 2.021 mmol/kg. Possible processes causing the elevated ratios. 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. Even if equilibria are upset between solution and individual mineral in assemblages that 35 . Air contamination during sampling may also contribute. 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 average being 0. If these two samples are exempted. the range being 0. In view of the modelling of aquifer uid Ar concentrations. The geothermal seawater in producing aquifers at Reykjanes contains 0. above air-saturated water. are air enriched source water.063 mmol/kg. The segregation model also yields consistent results for the quartz and Na/K geothermometers. 2. however in this case Ar concentrations would likely be higher than the observed values.4). They include Ca in dilute waters. are subject to the largest concentration changes between undisturbed aquifer and wellhead.010 mmol/kg. The saline aquifer water at Svartsengi is signicantly degassed with respect to Ar.003 to 0. the average ◦ Ar concentration is 0. The segregation model yields Ar aquifer uid concentrations which are.019 mmol/kg. contribution of N2 from the magma heat source or possibly decaying organic matter in paleosoils. well 21 at Kraa and well 14 at Nesjavellir (Table 2. which also are chemically reactive. 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.015 mmol/kg ◦ of Ar.9). By contrast. 2. with one exception. the average being 0. which is that of air-saturated water at 5 C. which corresponds very well with air-saturated seawater at 5 C. 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. the model that allows addition of gas-free steam to the owing uid gives on average 0. Elements present in low concentrations in the uid. along with many trace elements.

in addition to the error produced by the silicate minerals. CO2 . 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. In the saline waters at Svartsengi and Reykjanes. The uid concentrations of the gases were taken to represent liquid concentrations. equilibrium with uid CO2 and clinozoisite+calcite+quartz+grossular rather than prehnite is closely approached. Yet. whereas two wells have excessive 36 .3 log mol/kg on the equilibrium H2 S concentration. 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.1 is within the measured clinozoisite composition in this area. H2 S concentrations in the aquifer uids match well equilibrium with the mineral assemblage containing pyrite. The same mineral assemblage appears to control H2 and H2 S aquifer uid concentrations in the saline uid. or even 0. as given by Robie and Hemingway (1995) may produce an error as high as 0. Aquifer uid CO2 concentrations in the dilute uids show larger variation than those of H2 S. The presence of S in FeS2 has the same eect. The selected clinozoisite activity of 0. the equilibrium curve is shifted to −2 lower values. Námafjall and Nesjavellir have higher H2 aquifer uid concentrations than expected at equilibrium with the mineral assemblage involving H2 S. the uncertainties on the thermodynamic data on these mineral. the well discharge composition will reect the correct concentrations of such components in the initial aquifer uid. 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. quartz. Secondly. 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. At Námafjall and Kraa. Most of the wells at Kraa. garnet. pyrrhotite. Calculation of the equilibrium constant for this reaction assumed pure FeS and FeS2 . such as the major gases (CO2 .12. epidote and wollastonite. DISCUSSION AND CONCLUSIONS control the concentrations of components present in high concentrations in the uid. 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. On the other hand.2.05 which brings the equilibrium curve close to the calculated aquifer uid CO2 concentration. 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. Grossular garnet is abundant in the reservoir rock in these elds but prehnite is rare. H2 S and H2 ). 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. pyrrhotite. If the FeS is decient in iron. epidote and prehnite in the case of the dilute waters. CO2 aquifer uid concentrations match generally well equilibrium with the clinozoisite+prehnite+calcite+quartz assemblage. The CO2 content of the Nesjavellir aquifer uids is low relative to equilibrium with the clinozoisite+prehnite+calcite+quartz assemblage. Sulde mineral analysis is missing for quantitative estimation of the eect of the iron-sulde mineral composition on the equilibrium constant. epidote and prehnite. At Reykjanes and Svartsengi.

The two models yield almost the same N2 /Ar ratios. The observed N2 /Ar ratios cannot be produced only by boiling of air-saturated water. additional source of N2 to the uid. 37 . the latter giving higher gas concentrations in the initial aquifer uid. but they dier in Ar and N2 concentrations. 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. Nitrogen and Ar concentrations in the initial aquifer uid were calculated according to a segregation model and model 4 in Arnórsson et al. indicating that the initial aquifer uid is represented by degassed uid. 50. either magmatic or organic. higher ratios can only be explained by an water containing entrapped air. H2 S and H2 seem to be generally controlled by close approach to equilibrium with specic mineral buers. The thermodynamic data selected for Fe(OH)4 to retrieve equilibrium constants may also contribute. 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. Most of the well discharges are depleted in Ar. 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. Our results show large variation of N2 and Ar concentrations and N2 /Ar ratios within elds. constants. Boiling of such water causes decrease in the N2 /Ar ratio of the boiled liquid.CHAPTER 2. The excess H2 indicates an equilibrium vapor fraction that varies between 0. 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 same does not appear to be the case for many of the minerals which form parts of these assemblages. (2007) which assumes that the excess enthalpy is due both phase segregation and addition of gas-free steam by evaporation of capillary water.04 and 4% by weight. Although the initial aquifer liquid concentrations of the reactive gases CO2 .

.

From available experimental data on the distribution coecient for B between liquid and vapor. Boron and Cl act as incompatible in these geothermal systems. As concentration levels are about the same as in the dilute uid systems. In hot spring waters of mature high-temperature systems. B concentrations are substantially higher and those of Cl much higher due their presence in the source seawater uid. particularly when the liquid boils extensively. and Arnórsson. During boiling and mixing of the geothermal water with cold groundwater. By contrast. In the high-temperature systems of Námafjall and Kraa. but B does. where the convecting uid is meteoric by origin.55 ppm The reason is low concentrations of these elements In the seawater systems of Reykjanes and in the basaltic volcanics of the country. N. Abstract The concentrations of arsenic. In systems. Arsenic in the deep uid is also highly mobile. One 39 . Cl/B and Cl/As ratios are about the same as those of basalt indicating near stoichiometric basalt dissolution with respect to these elements. B and Cl concentrations in uids of volcanic geothermal systems in Iceland Giroud. boron and chloride are relatively low in uids of hightemperature geothermal systems in Iceland. As. at least at vapor pressures as high as 40 bar. B and Cl contents are typically 50150 ppb. respectively. it is concluded that equilibrium distribution is closely approached at wellheads of wet-steam wells. and 50150 ppm.Chapter 3 Processes inuencing As. probably mostly by its uptake into ferri-hydroxides and clay minerals but also into sulphide minerals. representing boiled deep water. 0. As is eectively removed from solution. Svartsengi. S. B and Cl contents of the uid indicates that it is determined by the mixing of components from two sources. Arsenic does not partition signicantly into the vapor phase.

Arnórsson.e. 1988. 2006. The Cl and B content of the magmatic component is some 200 and 30 ppm. depending on the type of minerals that form from solution and take up B. 1985. Ballantyne and Moore. the rock interaction component is represented by quite extensively reacted water. Ellis and Mahon. Badruk and Kabay. respectively. 1988. 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. The welleld at Nesjavellir is adjacent to a volcanic ssure that erupted ∼2000 years ago. Both As and B are environmentally important (Smedley and Kinniburgh. 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. Smedley and Kinniburgh. A substantial fraction of the B and Cl in the geothermal uid of the Kraa and Námafjall systems is derived from the magmatic source. 1991). 1991. Arsenic can be removed from solution by its uptake into sulphide minerals and iron hydroxides (Ballantyne and Moore. 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 Námafjall geothermal system. boron and chloride are important components in geothermal uids.3. 1967). Arnórsson. 1975. 1964. 2004).1. 2003. once in solution it stays there (Giggenbach.1 Introduction Arsenic. 3. Their formation is most intense in zones of extensive boiling. INTRODUCTION is the basaltic rock with which the uid has interacted and the other magma volatiles. 2007). The mobility of As is signicantly lower than those of Cl and B in aquifer uids producing into wet-steam wells. In common types of volcanic rocks all these elements are present to some extent in easily soluble compounds. 1977). Here little Cl appears to come from the magma but a substantial fraction of the B. Magmatic volatiles contribute little if any As to the geothermal uid. Due to its correlation with Cl. Thus hydrothermal experiments have demonstrated that they are largely transferred into solution without appreciable alteration of the rockforming minerals (Ellis and Mahon. Glover. 1969). By comparison of data from the seawater systems at Reykjanes and Svartsengi with the meteoric-water systems. All these elements are highly mobile in geothermal systems. in particular illite (Harder. Both As and B form volatile species at elevated temperatures (Kuritani and Nakamura. Axtmann. it seems likely that a substantial fraction of the B in the uid of these seawater systems is of magmatic origin. It is similar to the sub-boiling liquid in the upper Kraa reservoir. 2002). Chloride is generally taken to be conservative. The only types of minerals that eectively extract B from solution are clays. However. Arnórsson and Andrésdóttir (1995) concluded that B essentially behaves as a conservative element in the basaltic environment of Iceland. As in geothermal systems has also been taken to be conservative although closer examination shows that it is not. Such minerals may also incorporate As (Onishi. At Nesjavellir similar kind of mixing explains the B and Cl content of the uid. 2002. This is considered to be due to its removal from solution into sulphide minerals. 1978) al- 40 . Boron may also be conservative. i. 1988). The rock interaction component represents uid that has reacted to a relatively limited extent.

1967). are much lower than in volcanic rocks formed on converging plate boundaries (Arnórsson. 3. 1964.1 Overview High-temperature volcanic geothermal systems in Iceland are located within the active belts of volcanism and rifting (Fig. 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. 3.2. 2002. between them in South Iceland there is a triangular micro-plate. Arnórsson. 1977). 3. Ballantyne and Moore. 1983). 1976. though sulphides and ferri-hydroxides are more important (Bamford et al.CHAPTER 3. 2003. Arnórsson and Andrésdóttir. 41 . Yet. B and Cl in oceanic basalts formed at diverging plate boundaries. 1995. Almost all known volcanic geothermal systems at diverging plate boundaries are sub-marine except those of Iceland. Sigvaldason and Óskarsson. 1980. 1988).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 same applies to uids in volcanic geothermal systems.. 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 high-temperature systems that are marginal to the active volcanic belts (see Fig. 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.1 ppm and as much as 50 ppm.2 Geological features 3. 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.1). The concentrations of As. B and Cl in uids of nine volcanic geothermal systems in Iceland. the Hreppar plate. Corresponding numbers for As are <0. Ellis and Mahon.. 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. These volcanic belts represent the boundary of the American and European lithospheric plates. The present study focuses on the distribution of As. Christensen et al. 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. such as Iceland. added to andesitic and related magmas that form by partial melting of hydrated mantle rock. respectively It is likely that these elements are (Arnórsson. 2003. The high-temperature geothermal systems may be divided into groups This heat depending on their geological setting and the nature of their heat source.

. Below a brief description will be given of the geology of each area. GEOLOGICAL FEATURES Figure 3. The Námafjall geothermal area lies outside this caldera. Hveravellir.2.1. such as Kraa (Björnsson et al.1: Map of Iceland showing the active volcanic belt systems and hightemperature areas. typically associated with calderas. where magma has been intruded laterally along ssures from a major magma body below the central volcano. In this way high-temperature geothermal systems can develop into low-temperature systems. irregularly shaped small intrusive bodies and more deep-seated stocks in the roots of a major volcanic complex. Nesjavellir. Geysir area. Further. geothermal systems initially on the plate boundary will drift with time out of the volcanic belts and become displaced from the magmatic heat source.2 Kraa and Námafjall The Kraa geothermal eld in northern Iceland lies astride the plate boundary and is located within the caldera of the Kraa central volcanic complex (Stefánsson. An active ssure swarm runs through the Kraa caldera. They are Kraa. Parasitic systems to volcanic complexes are also known. The Námafjall system lies across the eastern 42 . Svartsengi and Reykjanes. source may be a sheeted dyke complex. Hveragerdi. For the present study. Due to crustal accretion at the plate boundary. Nesjavellir and Hveragerdi are separate parts of the larger Hengill area. Landmannalaugar. several samples were collected from wells in the Southern Lowlands low-temperature area. high-level sills. Námafjall.2.3. 3. 1981). 1977). geothermal uids from springs and wells were collected from nine active high-temperature areas. cone-sheets. about 10 km to the south of the hill of Leirhnjúkur which is located in the center of the Kraa caldera. The location of these areas is shown on Fig 3. Námafjall is considered to be a parasitic system to the Kraa area.

may have been added to the convecting geothermal uid at Kraa. B and Cl. surface manifestations are characterized by fumaroles. Torfajökull hosts the largest geothermal area in the country.3 Landmannalaugar The Landmannalaugar eld is part of the greater Torfajökull area in central south Iceland which is located at the plate boundary within the eastern active volcanic belt in South Iceland. 1983). No drillings have been carried out in this area.. As. covering 2 some 200300 km . envelopes practically all the thermal manifestations. The silicic formations produce a conspicuous gravity low within the area (Pálmason. e. 1974. representing the boiled fraction of the deep uid in the geothermal system. In most of the area. On one occasion.. part of this ssure swarm (Saemundsson. 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. 1974). 1994). A distinct positive gravity anomaly occurs within gravity low taken to reect the existence of basaltic intrusives (Walker. which form fugitive compounds at magmatic temperatures. Periodic discharge of magma from this chamber occurred into the ssure swarm to the north or south. 1991).2. 1973). 1992). They include rhyolites and comendites as well as subglacially formed pitchstone and obsidian (Ívarsson. 3. 1985). both within and outside the Kraa central volcano (Saemundsson.CHAPTER 3. These observations indicate that other components. which eruptions during late Quaternary times. The volcanic rocks in the area are mostly basaltic in composition although silicic magma has also been erupted (Jónasson. Likely. Fresh magma was intruded into the roots of the Kraa volcano forming chambers at 37 km depth (Einarsson. 3 a geothermal well at Námafjall erupted 3 m of magma (Larsen et al. 1978.g.. the basaltic magma has been trapped under the less dense silicic volcanics forming the heat source to the geothermal system. 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 Námafjall (Ármannsson et al. respectively (Ármannsson et al. Within the Landmannalaugar eld only silicic volcanics are exposed. 1987). 1978). Basaltic and silicic eruptions have occurred in sub-glacial and Recent times in the area. The Torfajökull region constitutes the largest complex of silicic volcanics in Iceland. By this model. At Landmannalaugar mixed water occurs in warm and hot springs (Arnórsson. are only found in the Landmannalaugar part of the Torfajökull area. It is considered that almost all the exposed volcanics formed by sub-glacial A large caldera structure characterizes the Torfajökull region. 43 . 1978). 1991) which is about 100 km long and 5 8 km wide (Saemundsson. A total of nine volcanic eruptions took place during this episode that lasted until September 1984. Geochemical geothermometers indicate temperatures as high as 300 ◦ C in the Landmannalaugar eld. Temperatures ◦ ◦ in deep drillholes (∼2000 m) at Kraa and Námafjall are as high as 350 C and 320 C. 1982). A major volcanic-rifting episode started on the Kraa ssure swarm at the end of 1975. Alkaline spring waters. steam-heated surface waters and hot altered ground. probably during the last glaciation (Saemundsson. 1972).

Alteration in rocks at depth penetrated by wells in Hveragerdi is intense with minerals indicating temperatures higher than those measured today (Sigvaldason. Possibly the Hveragerdi system has drifted aside from its original magmatic heat source. on the other hand.4 Geysir area and Hveravellir These areas are described together because their surface manifestations have many things in common. Deposits of silica sinter are extensive around the hot springs in both areas. 1985). 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. By contrast. before the rising hot water becomes degassed as a consequence of boiling. rhyolitic rocks outcrop although most of the bedrock consists of basalts. Drill◦ hole data reveal a temperature of 180230 C (Arnórsson and Gunnlaugsson. Most of the geothermal activity in both elds occurs within an area that is only a few hundred meters across. 1963). as well as fumaroles and hot altered ground.e. 1985). 44 .3. The heat output in both areas is apparently low as deduced from the integrated ow from springs. Hot springs are abundant in the area. 3. such as high uoride and relatively high concentrations of Cl and B compared to thermal waters that have interacted with basalt only. The area is tectonically active although Hveragerdi lies outside the main zone of rifting. GEOLOGICAL FEATURES 3. 1985). The spring water at Geysir indeed reects reaction with silicic rocks. on the other hand. Both areas are quite small and marginal to the active volcanic belts (Arnórsson. Either the system has cooled down or erosion has brought high-temperature hydrothermal minerals closer to the surface. Silica sinter deposits are limited. the mixing occurs close to the surface between boiled and degassed water and cold groundwater (Arnórsson. this is not the case for the mixed waters. Underground ◦ temperatures in these area have been estimated as ∼250 C or a little higher (Arnórsson. The rocks in the vicinity of the Hveravellir eld are all basaltic. Some of these springs show geyser activity. At Geysir. 1985).2.2. 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. i.5 Hveragerdi The Hveragerdi eld is located at the southwestern boundary of the Hengill area. Such mixing leads to the formation of acidic water that is highly reactive (Arnórsson. 1985). At Geysir. At Hveravellir.2. The main uid upow feeding the hot springs at Geysir is considered to be along the contact of a rhyolite plug. Warm springs occur in both areas that represent a mixture of the geothermal water and cold groundwater. particularly when the mixing involves a gaseous hot water component. In valleys intersecting the hills north of Hveragerdi hydrothermally altered rocks are exposed containing minerals indicative of temperatures in excess ◦ of 200 C. It consists of hot springs with boiled deep water. the mixing occurs at depth.

1963). When more negative. being more than 60 and 80% of the rock below 1500 m depth at Svartsengi and Reykjanes.. The highest temperature recorded is about 320 C at 2000 m depth. the source water may be distantly derived 45 . respectively. subglacially erupted hyaloclastites. A volcanic ssure that erupted ∼2000 years ago forms the northwest side of the graben (Saemundsson.. 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. 1972). although sills may also be involved. Rare granophyric bodies have been identied within the intrusive complex.. 1986). The highest temperature recorded is > 380 C (the maximum measurable by the instrument) in a well drilled close to the volcanic ssure. breccias and pillow lavas and tuaceous sediments as well as lava ows formed during inter-glacial periods (Fridleifsson and Albertsson. 2000. In the deep geothermal reservoir at ◦ Svartsengi temperatures vary very little from 500 to 2000 m. It lies astride the plate boundary and is located within a tectonically active graben. Data on δ H for these water are similar to that of local precipitation or more negative. 1993).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.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. 3. This is the consequence of the low Cl content of the basalts with which the waters have interacted (Arnórsson and Andrésdóttir. the reservoir is two-phase above about 1000 m but sub-boiling at greater ◦ depths.6 Nesjavellir The Nesjavellir eld forms the northeasternmost part of the Hengill area in Southwest Iceland.CHAPTER 3.2. Tómasson and Kristmannsdóttir. Intrusive bodies also increase with depth and exceed 50% of the volume of the rock below 1500 m (Franzson. Intrusions become increasingly abundant with depth. 1988). The higher Cl content of waters from the Landmannalaugar and Geysir elds is due to interaction of the water 2 with silicic rocks. Sheeted dyke complexes are considered to serve as the magmatic heat source for the Reykjanes and Svartsengi geothermal systems. The rock exposed at the surface and penetrated by wells is solely basaltic. Permeability is fracture controlled (Bödvarsson et al. 3. 3. The reservoir uid is two-phase (liquid and vapor). at least down to the depths of the ◦ deepest wells in the area (∼2200 m). 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. 1995). At Reykjanes. being about 240 C. 1990). Permeability is fracture controlled. Both elds have been extensively drilled.2.

1978). were ltered through a 0. Water samples at wells. meteoric water (Arnórsson. the geothermal uid is relatively saline attributable to seawater recharge to the systems (Björnsson et al. 3. Ca. Non-condensable gases (H2 . 1995). SAMPLING AND ANALYTICAL METHODS precipitation from higher elevation and further inland or they contain a component or Pre-Holocene water (Arnórsson and Andrésdóttir. At Svartsengi Cl concentrations correspond to about recharges and 3. Reykjanes and Svartsengi.4 Sampling and analytical methods Only a brief description of sampling and analytical techniques is given here. 1994). 1978. (2006). 2002. 2006) containing 10 ml of 50% w/v KOH solution and condensed steam was collected into 100 ml polyethylene bottles and acidied with Suprapur R HNO3 for ICP-MS analysis in a manner similar to that for trace element samples of the water phase.. Fe. Arnórsson.500 1/3 and 23. Cl and SO4 . Si. Arnórsson.1 Calculation of aquifer uid composition Deep aquifer uid composition for wells and boiling hot springs was calculated using the WATCH speciation program (Arnórsson et al. Glass bottles with air-tight cap were used for collecting samples for pH and total carbonate carbon determination in the laboratory shortly after sampling. Stefánsson and Arnórsson. Sr). including As and B. Cl. Ragnarsdóttir et al. 1972... Carbon dioxide and H2 S. Steam phase was collected into evacuated Giggenbach bottles (see for example Arnórsson et al. water and steam samples were taken from two phase pipeline at the wellhead using a stainless steel (N316) Webre separator to separate the phases. Total carbonate carbon was determined by titration with standard (0. 1978. CH4 . using dithizone as endpoint indicator (Arnórsson et al. 46 . In the case of wet-steam wells.500 ppm (Arnórsson. 1995. Mg.Mass spectrometer (ICP-MS). Dionex 2000) for F.2 µm cellulose acetate membrane using a polypropylene or Teon lter holder and col- lected into low-density polyethylene bottles. measured 2/3 seawater ∼19. Ragnarsdóttir et al. the reader is referred to Arnórsson et al.. For a more detailed description. An untreated 200 ml sample was analyzed on a Reagent-Free TM ion-chromatograph (RFICTM . 1995. 1982). 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. were determined as in water samples. Ar) were analyzed by gas chromatography. 1984) The concentrations of the unreactive Cl of the deep unboiled Reykjanes geothermal uid is between ∼100% seawater (Lonker et al. N2 . (2006). Hydrogen sulde was measured on site by titration with standard mercuric acetate solution. Another 100 ml sample acidied with 1 ml of the same acid was used for trace elements determination on an Inductively Coupled Plasma . A R HNO3 (E. 1993).3 (Bjarnason. 1984).1 M) HCl solution as described by Arnórsson et al..4. In two areas. 2006).3. version 2.. which dissolved quantitatively in the alkaline solution. Na. as well as boiling hot springs.5 Data handling 3. Arnórsson.5.

When this model is selected. Other wells have excess enthalpy. 2004). the eects of capillary pressure (adhesive forces between mineral grain surfaces and liquid) and relative permeability (e. the enthalpy of the discharged uid is higher than the enthalpy of steam-saturated water at the aquifer temperature.. particularly when the 47 . in two-phase aquifers.e. the discharge enthalpy equals that of steam saturated water at the aquifer temperature. 2000. Li and Horne. Flowing liquid and vapor may separate. Figure 3. low quartz equilibrium temperatures are obtained. i. Excess well discharge enthalpy is the consequence of increase in the owing uid enthalpy in the depressurization zone around discharging wells. 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. conformity between the quartz and the Na/K geothermometers is good. If. at least partly (segregate). 3. it was assumed that the excess enthalpy was caused by conductive heat transfer from aquifer rock to the owing uid. 2007) Some of the wet-steam wells included in the present study have liquid enthalpy. By these processes the mobility of liquid is reduced relative to that of vapor (Fig. Pruess. even in terms of volume. 2002. Such separation results from the dierent ow properties of vapor and liquid. 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. Depressurization boiling in this zone lowers the temperature of the uid.. i.2: Phase segregation excess enthalpy model (modied from Arnórsson et al. Horne et al.CHAPTER 3. leading to an increase in the steam to water ratio (enthalpy) of the discharge.2). In this contribution it is assumed that excess well discharge enthalpy is produced by phase segregation. thus creating a temperature gradient between uid and aquifer rock and favoring conductive transfer of heat from rock to uid.g..e. Addition of heat to the two-phase uid will not aect its temperature but enhance boiling. on the other hand.

t yields V f. e..t · V f.5.4) and (3.l (3.t − me.l (3.l where (3.l i i i Common solution of equations (3.l · V e. l means liquid and t refers to total ow.l · V e.t = mf.l By selecting a value for h (the enthalpy of liquid water at which phase segregation f.l (V f. Superscript zone between f and the uid phase. Studies indicate that the steam fraction in the initial aquifer uid in hot-water volcanic geothermal systems is small.t − he.t − M e. 2002).2) enthalpy and mass we further have and md.6) V f. Kenya (Karingithi. 2002) and Olkaria. equations (3. 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. The second superscripts indicate Thus.t through 1 = V f. 1990.l .t = mf. the value of V can be obtained from equation (3. The steam fraction in the initial aquifer uid has been taken to be zero.t − V e.6) by elimination of V leads to md.t · M d. such as at Kraa.1) designate well discharge and M denotes mass ow rate. e stands for the intermediate d where phase segregation occurs.5) and isolation of (3.t = hd.t · M d. the mass ow rate of the well discharge is given by M d.t − he.l · M e.l i i i where (3.t d.t · V f.t − me.t value.1). DATA HANDLING discharge enthalpy is approaching that of dry steam.l Combination of equation (3.l Steam Tables give h for steam saturated water. SuM d. respectively.l · M e. Iceland (Gudmundsson and Arnórsson.3) leads to Dividing with component.l hf. because f.l hd.t it is assumed that the steam fraction in the initial aquifer uid is zero.t − he.t − he.3) h denotes specic enthalpy and mi concentration of the i-th perscripts have the same notation as in equation (3.t = mf.4) (3.1) to (3. even in terms of volume. so h = hf. f.t · M f.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.t · V f. From conservation of hd. When phase segregation occurs in producing aquifers.l the initial aquifer liquid (mi ) is controlled by a specic mineral buer (see Arnórsson et al.4) and (3.t = hf.t · M f.t = M f.7) since h is a measured f.7) e.t = hf.t occurs). The superscripts d and f initial aquifer uid of feed zone.3. 2007).5) (3.l md.t − me.8) and the distribution coecient Ds for species 48 .t − 1) i i i (3. h is known when a value for the aquifer temperature has been selected.

15) may be replaced by ml = Ks · Ps s Combining equations (4.9) Ds represents the distribution coecient for species v stands for vapor and n is the mole fraction given by ns = where Ns P NH 2 O + i Ni s.11) ms denotes molal concentration of species P i mi 55. between the liquid and vapor phases at the temperature at which phase segregation is taken to occur: Ds = where ne.16) Ds ∼ = The steam fraction (X boiling at temperature e. (3.l s s. then NH2 O = 55. superscript (3.15) al = Ks · fs s where Ks −1 −1 is the solubility constant (in moles kg bar ).16) yields (3.17) ) of the owing uid that has formed by depressurization but before phase segregation occurs is given by Te X e. If we consider a mass of uid containing 1 kg of H2 O. equation (3.t = hf.CHAPTER 3.v 55.13) The partial pressure s is given by Ps = nv · Ptot s where (3. (4.v s ne. The solubility constant (Henry's Law Coecient) of species s in aqueous solution is given by (3.14) Ptot is the total pressure of all gases including H2 O. (3.v − he.4).12).9) and (3. it follows hf.51 + i mi s.51 Ks · Ptot (3. For dilute uids.10) Ns stands for the number of moles of volatile species and and the sum is for all such species except H2 O.12) ms ns ∼ = 55.51 (3.18) that As it is assumed that the steam fraction of the initial aquifer uid is zero. (3. al s stands for the activity of species s in liquid water and fs its fugacity over the solution.51 ns = where so ms P 55. For dilute uids and moderate pressure. It also follows from conservation of mass that the concentration of 49 .l he.l (3.51 mv Ds ∼ s = l ms Ps of species and (3.l .v = hf.t − he.

v can be obtained from equations (3. For wells with liquid enthalpy.v ) r r as (3.8).l hd. the concentration i s in the liquid phase yields me.t −1 1−X e. i i hd.v ) i i i (3.21) me. Thus equation (3.e.24) and the concentration of component analogous to (3.v · X e. 50 .v + me.l (1 − X e. the concentrations of all components in the total discharge were taken to be equal to that of the initial aquifer uid.t = mf.t and md.8). Equations (3. mf.17) me.v ) i i i As for the enthalpy in equation (3.t − hd.22) X e. This gives the f. equation (3.19) mf.18).5.t .t = r V f.16)). or i in the initial aquifer uid is given by an equation mf.20) me.l .24) and (3.t r can be obtained by inserting equation (3.t − V f.t = me.18) and isolating Combination of equations (3.l (1 − X e. dividing into In the WATCH program this is done by Ks an arbitrary factor that can take a value between 0.l ) s can be obtained For non-volatile species.3.t r V f. mf. i. 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. In this case.25) For boiling hot springs.l = s Having obtained from equation (3.l .l enthalpy of the initial aquifer uid. 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 s mf.t (X e.l (3.v (D e − s r.18).1) reduces to M d.v i is zero. i i to (3.19) reduces to mf. 1)) + 1 (equal to (3. that does not partition signicantly into the vapor phase.t = md. the quartz equilibrium temperature was taken to represent f the temperature (T ) of the source aquifer to the hot spring water.21) into (3.t s f.v = and md.t From this it follows that: sampling conditions becomes (3.t = M f.t = mf.v · X d. increased.l s from equation (3.l (1 − X d. of species (3.19). h .01 and 1 (see This eectively means that the value of the solubility constant is The WATCH equation (3.t = hd. the gases are made more soluble than they really are.25) were thus used to calculate initial aquifer uid compositions.t = me.23) Thus the steam fraction at h f.19) by inserting equation (3.7) and (3. respectively.20). V md.v (3. mf.v − hd.v + md.t X d.17) into (3.

in the initial aquifer uid. program was run until the arbitrary factor gave a CO2 concentration that matched calcite saturation. 51 . 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. The concentrations of As in vapor samples is with two exceptions low. which do not partition signicantly into the vapor phase. 1978. were derived from equation (3. B and Cl concentration in the aquifer uid Boron and As were determined in both liquid and vapor samples of wet-steam wells (Table 3.2 Arsenic.8% of the concentration in liquid samples and no more than would be expected for carry-over of liquid to vapor. Arnórsson et al.. on the other hand. 3.1). 1983). measured B concentrations are signicant in vapor samples and they increase with sampling pressure relative to B liquid concentrations. as well as those of Cl.5.1). less than 0. 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 (Arnórsson.21) has been used to obtain As concentrations.20). The of B concentrations in this uid. For these reasons equation (3. On the other hand. indicating that B partitions signicantly in the vapor phase (Table 3.CHAPTER 3.

6 139. NJ=Nesjavellir.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 18.5 17.1 6.5 26.10.1 3.2e 0.5 20.5 11.2005 14.7 107.86 6.69 239 12916 5.05 <0.3 87.0 4061 155 205 350 697 93.6 46.05 <0.5 17.3 74.0 88.329 0.9 140.8 87.4 172.3 15.2004 09.12.6 40.1 29.6 80.6 39.05 <0.10.38 6.0 183.2 20.186 0.7 138.4 12. b Average of quartz and Na/K geothermometer temperatures.3 74.05 0.1 11.75 7.9 35.22 7.10.1: Arsenic.12.05 12800 41.4 2.0 40.2004 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 10.9 22.0 57.8 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 37.8 22.5 6.05 <0.1 11.6 177.8 35.7 134.2004 15.2004 10.2004 30.1 6.4 15.10 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 0.94 6.1 16.8 95.12.0 24.68 7.8 213.1 53.5 53. Cl B B As As Cl B As Cl B As Aquifer temp.3 157.7 20.61 239 125 151 137 155 14235 44.12.2004 SV-09 04-3029 01.6 15.9 114.05 <0.3 79.1 151.0 15.10.8 19.0 88.4 38.6 134.0 80.9 20.10.3 83.11.0 40.1 96.3 69.2004 10.4 78.2 45.5 15.1 57.0 119.7 51.1 124.3e nonnonmarinec.9 12.05 <0.3 69. It is expected to be less than the analytical error of the Cl determination.f marinef marinef mg/kg µg/kg µg/kg <0.7 33.0 28.01. B and Cl leached from the rock in the deep aquifer liquid are also shown.2004 20.0 148.7 23.3 88.5 16.0 84.6 141.4 15.05 7.4 27.88 4.0 25.1 93.5 129.6 29.0 156.10.3 27.317 14.2004 15.05 <0.1 8.3 122.2004 SV-19 Bödmódstadir Efri Reykir S-24 Reykholt S-1 Reykjaból S-1 1028d 525 637 576 654 14.5 0.5 15.8 0.8 102.0 6.0 14.77 7.3 84.2 20.0 14.1 43.1 28.09.01 6.4 42.0 1.3 0.Table 3.12.86 239 13831 7000 172.5 42.5 11.05 <0.7 133.8 11.5 14.8 22.7 20. N=Námafjall.6 36.5 147.86 6.5 27.8 92.2004 10.10.8 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. quartz equilibrium temperature was used and chalcedony equilibrium temperature in the case of the Southern Lowlands.62 7.0 0.4 139.10.5 164.2004 30.11.4 48.193 0.3 1.10.5 11.0 7.0 2.6 107.12.18 241 13230 7340 7540 5.1 25.283 15.9 131.0 84.89 6.348 1.37 6.1 50.1 43.2004 14.4 27.7 33.12.7 98.8 10. d Selected.1 23.7 1.86 6.04 6.5 29.0 129.2 173.4 73.09.05 0.0 15.9 16.1 16.0 16.4 90.05 <0.5 92.6 29.0 38. SV=Svartsengi.4 2.99 6.9 15.4 1.5 103.10.2004 20.9 86.2004 21. .10 240 13493 7260 4.5 164.0 14.1 182.3 14.3 62.3 0.1 30.6 114.7 65.79 6.10.0 15.0 0.8 15.9 52.0 14.2004 15.72 6.8 96.7 69.1 16. Discharge enthalpy kJ/kg bar-g liquid pH pressure aquifer liquid sample mg/kg sample µg/kg sample µg/kg sample µg/kg sample µg/kg uid mg/kg uid uid liquid vapor liquid vapor aquifer aquifer aquifer nonSampling Calc.0 72.1 47.1 83.3 113.0 12542 12041 11853 12024 12723 6407 6556 6633 7057 6922 71.5 164.0 7125 126 160 340 534 94.0 120.0 60.5 98.2004 21. B and Cl concentrations in liquid and vapor phases of wet-steam wells.125 12.0 5.8 72.2004 30.11.2004 15.6 36.9 22. f Amount of Cl added to uid by rock dissolution and/or from magma.05 <0. For Reykjanes.056 <0.1 43.21 240 14255 4.0 105.9 227.0 125.05 <0.05 <0.0 37.01.b Sample # Sampling Locationa date ◦C µg/kg µg/kg <0.2004 SV-08 04-3032 01.1 15.05 <0.87 6.4 91.2 16.2004 19.05 <0.2004 21.2 176.03 6.6 142.2004 19.6 36.5 14.2004 10.0 173.8 04-3005 1028d 1028d 1028d 1028d 01. Caused by carry-over of liquid into vapor sample.12.3 83.05 <0.1 71.6 89.8 77.2 14.2004 15.3 113.5 231.7 53.8 36.1 55.8 72.10.6 111.05 <0.061 0.0 30.1 110.6 112.2004 10.37 222 273 263 268 289 238 199 247 299 263 268 232 276 285 268 282 278 282 297 274 273 293 274 291 296 292 261 260 31.73 4.4 57.0 7660 210.8 99. c It is not possible to calculate the non-marine derived Cl in the Reykjanes and Svartsengi systems.6 46.7 136.0 60.91 7.7 94.2004 10.0 15.9 24.0 a K=Kraa.4 38. except for Reykjanes and Southern Lowlands.5 129.6 49.11.8 23.12.2004 30.0 197.10.0 164.6 146.6 23.2004 20.4 133.0 147.4 143.05 <0.9 169.8 101.2004 09.05 0.12.922 0.2005 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 15.8 11.1 52.90 6. Calculated concentrations of As.55 6.6 5.1 23.3 78.2004 SV-18 04-3006 04-3027 04-3026 04-3025 04-3024 09.0 2.0 87.4 28.7 110.1 14.12.7 58.3 24.84 7.3 65.0 52.09.8 5.2 <0.12.00 6.4 148.0 7.1 76.4 7840 132 163 350 541 105.8 23.2004 10.5 2.1 9.6 107.12.2004 20.36 7.051 0.8 77. The number indicate well number.7 91.6 32.1 91.3 53.4 39.10.9 47.12.92 6.0 57.0 15.80 6.5 104.0 42.9 136.12.2004 SV-11 04-3004 09. S=Southern Lowlands.9 79.2004 20. corresponds to enthalpy of steam-saturated liquid at 238 ◦ C e Suspect. RN=Reykjanes.3 87.90 78.2004 21.7 32.74 6.

The value of P e . Equilibrium distribution (Glover. above) is also shown. As already pointed out. Here it is assumed that the T − 729 149. of pressures.CHAPTER 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. 3.26) Figure 3. 1988) is also shown. It is. was taken to be half way between the aquifer vapor pressure and the vapor pressure at the wellhead at which samples were collected. 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. 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. The equilibrium distribution (equation (3. For 53 . 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. the vapor pressure at which phase segregation occurs. however. between liquid water and vapor samples.26) log(DB ) = where T is in K.5 DB value refers to the H3 BO3 species and Fig.3: Boron distribution between vapor and liquid phases discharging from wet-steam wells versus sampling temperature. particularly when the discharge enthalpy of wells is close to that of saturated steam. Fig. The choice of segregation pressure aects the calculated concentration of B in the initial aquifer uid. 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.

when these areas were transgressed by the ocean. respectively. It ranges from over 10 ppm for high-temperature systems in coastal areas to about 3 ppm in those systems located farthest inland. the calculated concentration of e B in the initial aquifer uid is not sensitive to the choice of P . we have used the information provided by Sigurdsson and Einarsson (1988) on Cl in precipitation in Iceland.0009 ppb. By contrast.3. According to Arnórsson and Andrésdóttir (1995). such inltration also occurred around the end of the last glaciation in many other lowland areas.5..00030. If the segregation occurred at 20 bar abs. 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). For 54 . 3. 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. the choice of P is only important for wells with discharge enthalpy close to that of dry steam.3 Sources of As. In order to estimate the contribution of Cl from precipitation. such as at Svartsengi and Reykjanes. As for B.5. such as As and e Cl. Seawater inltration into geothermal systems may occur under present-day hydrological conditions. the rock with which the uid has interacted and magma volatiles.4 ppb and 0. The only high-temperature system considered here that may contain an old seawater component is Hveragerdi. inltration of seawater into the bedrock.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. the calculated aquifer B concentration would be 4540 ppb. Corresponding numbers for B and As are 0. Figure 3. Selection of phase segregation vapor pressure also aects the calculated concentrations of non-volatile components in the initial aquifer uid. B and Cl to the uids of the high-temperature geothermal systems in Iceland include precipitation.72. but 3360 ppb if it occurred at 60 bar abs. B and Cl to geothermal uids The principal sources of As. DATA HANDLING wells with discharge enthalpy below about 1800 kJ/kg.

at least for some areas. Included are samples from Arnórsson and Andrésdóttir (1995) a Cl/B rock dissolution ratio of 38.5 ppb B. In the case of the seawater systems at Reykjanes and Svartsengi. a gaseous phase from the magma heat source. >99% for B and 9098% in the case of Cl. The solid line corresponds to seawater Cl/B ratio. The average Cl and B concentrations of these tholeiites are 177 and 1. The data given by Arnórsson and Andrésdóttir (1995) show considerable scatter. the sources of As. Figure 3.5. 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. as given by Krauskopf and Bird (1994).1 Boron and Cl distribution in sampled waters The relation between analyzed Cl and B concentrations is shown in Fig. B and Cl from magma volatiles to high-temperature uids.5: Measured Cl and B concentrations in liquid water samples from all the study areas. In a later section an attempt is made to evaluate the contribution of As. The selected Cl/B ratio is based on data on Cl and B in Icelandic tholeiites as reported by Arnórsson and Andrésdóttir (1995). 3. and 2 ppm Cl and 0. B and Cl to the deep. respectively.43 ppm.2 ppb B. Accordingly the selected Cl/B ratio carries considerable error.6.CHAPTER 3. or ∼100% for As. the Cl marine groundwater component accounts for 4258% of the total Cl in the area. undiluted geothermal uid are dominantly non-marine. respectively. 3.6 Results 3. Very likely almost all the Cl is marine (>99%) but trivial part of As. a large proportion of the B in the waters is of marine origin. The sources include the rock with which the uid has interacted and. 55 . In the dilute water systems. 59% at Reykjanes and 44% at Svartsengi.

The observation that the data points in Fig. have much lower Cl/B ratios than seawater. Since it is generally accepted that Cl displays conservative behavior. in particular those from Námafjall and Kraa. Their B concentrations lie in the range from ∼500 ppb to almost 6800 ppb.2 ppb B serves as a good proxy for the concentrations of these elements in the local precipitation in the study areas. 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. 230 ppm.e. whereas it is somewhat lower in Kraa and at Hveravellir (∼3 ppm) and higher (∼10 ppm) in Hveragerdi and the Southern Lowlands. However.5 for the elds of Geysir. It is 56 . 3. the amount of B added to the water from other sources is 3.1 and 3. All samples. 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 (Arnórsson and Andrésdóttir. The average Cl/B ratio for all these areas is almost the same. 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. both for basalts and silicic rocks. Landmannalaugar. At this time. Samples from hot springs in the Geysir. i. Hveragerdi and most of the Southern Lowlands were transgressed by the ocean in early Holocene times. local precipitation in the Geysir. Nesjavellir and Námafjall areas contains ∼5 ppm Cl. This is attributed to a small component of seawatergroundwater component in these waters. 3. Hveravellir and Landmannalaugar. Data on Cl and B from Arnórsson and Andrésdóttir (1995) have been plotted in Fig. Hveravellir and Landmannalaugar areas plot a little below the Cl-B dissolution line. Therefore a value of 5 ppm Cl and 1.3. once in solution it stays there. Cl/B ratios are half that of seawater. spring waters from Hveragerdi and discharges from three of the four wells from the Southern Lowlands have higher Cl/B ratios. 1995). 3640. Many of the dilute waters from wet-steam wells in high-temperature areas have lower Cl/B ratios than basalt. if one heavily diluted sample from the Geysir area is excluded. i.e. except those from the seawater systems of Reykjanes and Svartsengi. In view of the uncertainty in the Cl/B leaching ratio.4 ppm (Arnórsson and Andrésdóttir. This water is from a well in an elevated part in this area that was not submerged in early Recent times.1) that does not contain a marine groundwater component. Hveravellir. This is higher than the average for the dilute waters.5 together with the data presented in Tables 3. it is concluded that B also acts as conservative. The average B content of tholeiites in Iceland is close to 1. When the marine derived B content of the geothermal seawaters at Reykjanes and Svartsengi are subtracted from the total B. The most common The corresponding number for Cl is 15 concentration is. Compared to the waters at Geysir. yet within the same range. RESULTS According to Sigurdsson and Einarsson (1988). however 10002000 ppb. It is thus evident that many high-temperature waters contain higher B concentrations than the rock with which they have reacted.54 ppm in the case of Svartsengi and ∼3 ppm for Reykjanes. 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. 1995).6. In the seawater systems.2. it is considered that the slightly low Cl/B ratios of the most reacted Landmannalaugar waters are not signicant. some samples from Landmannalaugar have lower Cl/B ratios.

07565 64.00 0. Aquif.29934 64.17 0.21 6.7 3.0 35.2 98.3 0.0 30.01 7.70 0.10836 63.39 4.31793/-20.9 162.4 37.9 49.85908/-19.11305 64.00 0.00 0.0 148.7 18.9 18.00 0.3 276.9 5.1 4.0 36.3 52.1 7.6 32.5 2036 126.1 53.06 0.3 2221 107.4 60. VI 01-3235 Skriduhver 01-3236 Bóluhver 01-3237 Litli-Sullur 01-3238 Svartaauga 01-3239 Svuntuhver 01-3240 Eyrarauga 01-3241 Eyrarhver 01-3243 Raudanefskelda 01-3244 Graenalaug 01-3245 Stefánsauga 01-3246 Landmannal.5 86.7 58.8 305 312 454 173 476 420 288 152 64 476 571 0.25 0.0 51.25 6.31280/-20.2 46.2 90.3 92.10875 64.4 1123 17. B and Cl concentration originating from rock dissolution (leached).5 2.1 211.24 7.4 60.2 68.00 0.16 0. III 01-3232 Landmannal.6 0.5 88 0.01900 63.31269/-20. aquif.8 17.9 45.7 498.3 277.00 0.0 125.5 42.5 1704 17.59 7.0 252.7 138.4 49.31115/-20.6 16.5 a The quartz and chalcedony geothermometer were used for boiling and sub-boiling springs.1 4.7 61.5 62.00397/-21.59 7.5 84.3 4.2: Arsenic.0 2.5 120 0.0 88.0 64.0 148. V 01-3234 Landmannal.96988/-19.9 34.11083 64.9 73.4 71.9 78.2 0.91 6.9 60.0 87. IV 01-3233 Landmannal.31390/-20.55545 64.3 0.9 96.00064/-21.55502 64.10858 63.9 38.3 96.9 125.55489 64.2 45.21 0.8 61.82 6.0 254.3 132.05761 63.55328 63.75 8.2 0.3 1.0 47.26 7.63 6.6 84.7 50.85904/-19. mg/kg µg/kg µg/kg mg/kg µg/kg µg/kg mg/kg µg/kg µg/kg 64.00402/-21.11228 64.30 7.3 1.5 287.2 200 2.35 7.51 6.5 21.2 95.8 103.73 7.7 36.00 0.00 0.0 93.7 54.1 0.9 55.41 7.0 64.5 99.3 2220 107.48 6.3 32.8 35.7 33.8 113.34 7.a liq.30826 64.7 90.4 0.8 26.72 6.28 0.2 2.26 6.1 15.4 85 0.7 64.98899/-19.30 0.22 7.3 66.5 37.6 242.55479 64.9 85.8 1209 17.85895/-19.00 0.0 123.9 43. Table 3.7 135.8 35.04 0.00 124.1 345 1.5 70.2 0.31352/-20.05783 63.1 58.29345 64.7 111.8 1705 17.29 6.10031 63.1 1. Cl B As Cl B As Cl B As temp.33033 64.10896 64.5 609 6.7 1480 36.5 96.00149/-21.0 65.2 77.7 95.05774 63.00 0.2 96.4 26.98776/-19.91 6.9 47.98901/-19.6 0.0 2.9 20.10 0.2 98.2 80.00250/-21.3 0.9 114.2 160.00067/-21.30126 64.4 600 6.21 0.8 69.0 92.11 0.1 13.9 82.85 6.6 88.0 93. 8 02-3210 Spring Hverag.1 5. Sample Spring name Coordinates N/E Deg.77 7.1 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. Also shown are calculated aquifer water pH and As.1 4.7 55.8 0.11089 64. II 01-3231 Landmannal.28 0.8 105.98840/-19.31180/-20.68 7.3 46.11053 64.32108 64.1 73.0 96.5 2.11728 63.7 74.1 577 4. I 02-3211 Spring Hverag.5 0.7 64.12764 64.6 182.1 64.8 1208 17.2 5.0 95.3 59.0 17. Geysir 01-3201 Geysir 01-3202 Blesi 01-3203 Ótherrishola 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 Beiná 01-3212 Laugarfell east 01-3213 Strokkur 01-3214 Nedridalur 1 01-3215 Múli 1 01-3216 Nyihver Hveravellir 01-3217 Hveravellir I 01-3218 Graenihver 01-3219 Braedrahver 01-3220 Bláhver 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.3 41.3 14.5 49.20 0.9 64.8 6.4 1122 17.55370 64.0 19.30230 64.5 83.4 52.16 0. leach.18 0.85900/-19.4 6.2 773 789 774 831 734 800 772 113 256 102 21 752 793 203 227 796 387 387 386 404 379 415 353 276 386 369 339 265 62.5 5.7 93.10622 63.0 36.0 83.7 0.5 5.2 0.1 99.6 233 231 231 214 207 204 226 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 6.0 11.18 6.6 75.1 17.10923 64.3 272.3 52.6 222.2 7.6 70.0 135.7 61.0 87.3 43.06 6.6 97.34 7.7 148.55578 64.4 36.00349/-21.4 6.30280/-20.6 56.9 7.9 2.26 0.98862/-19.1 99.6 62.9 0.8 0.32171/-20.5 2.CHAPTER 3.00 0.5 2035 126.1 578 4.01514/-21.78 7.7 178.61 6.7 45.4 3.5 1.8 416.31386/-20.98779/-19.8 61.6 218.7 153.1 775 790 776 832 735 801 774 114 257 103 22 754 795 204 228 797 388 387 387 405 380 415 354 276 386 369 339 266 62.27408/-20.0 55.8 86.31387/-20.22 0.3 48.30 0.9 166.31039/-20.18 0.2 5.7 14.18 0.5 122.0 90.5 62.4 6.85917/-19.30140 64.4 61.98873/-19.9 1275 45.2 4.18 0.97107/-19.7 17.9 18.2 124.7 36. VII Hveragerdi 02-3201 Hverag.7 22.3 154.00 0.5 24 1.2 4286 212.8 58.5 37.22 0. temp.19 7.00 0.27 7.8 87.3 122.00 0.4 20.4 0.05752 63.2 51.2 49.5 93.6 58.7 28.10689 63.1 54.4 45.31208/-20.1 2.29 0.9 0.38 5.2 48.2 93.5 2.63 7.1 93.3 1.6 77.1 344 1. I 01-3230 Landmannal.5 25 1.5 117.2 68.98734/-19.57 6.15 0.5 84 0.85986/-19.7 14.9 7.48 6.6 96.11291 87.5 5.5 5.2 0.2 4.2 76.98767/-19.9 1276 45.31057/-20.9 90.98814/-19.12 0.62 7. boron and chloride concentrations in spring waters from high-temperature areas.55500 64.6 50.4 2.9 36.8 89.2 51.9 158.00 0. aquif.0 44.8 44.2 4.3 0.4 599 6.16 0.00 0.0 64.7 33.2 4285 212.8 0.0 51.25 7.1 20.30155 64.8 302 309 452 171 474 418 285 150 61 473 569 0.0 182.00091/-21.98686/-19. ◦C ◦C pH fract.30478 64.77 6.12 7.2 0.98877/-19.00 0.0 115.85924/-19.8 65.7 36.0 37.7 43.6 238.55 7.11 7.71 6.6 21.30607 64. II Spring Aquif.30184 64.3 46.0 98.4 76.7 30.55430 64.5 20.8 48. leach.7 1481 36.6 83.5 17.8 50.9 2.16 0. 57 .8 69.0 44.16 0.0 1.6 50.23 0.5 610 6. Calc.4 35.30095 64.85930/-19.6 59.31019 64.00 0.5 81. waterfall II 02-3203 By swimming pool 02-3204 By well nr.5 38.1 215.9 24.05774 63.2 99.4 15.2 38.3 46.02 7.4 2.31833/-20.00 0.0 2.5 92.8 271.5 0.31 6.5 98.0 99.4 0.5 42.55620 64.4 4.8 44.55622 64.1 0.8 68.85966/-19.1 38.0 0.8 65.25 0.00898/-21.8 420.3 124.97322/-19.5 6.7 42.85904/-19. waterfall I 02-3202 Hverag.9 22.25 0.9 75.4 3.2 8. leach.7 88.05776 63.5 38.4 6.9 97.30237 64.9 48.85906/-19.85 7. Bóluhver 02-3209 By well nr.92 7.0 127.55567 64.00397/-21.4 37.10857 63.5 5.1 96.0 92.3 60.98848/-19. respectively.8 81.27 0.1 53.5 6.11051 64.65 6.51 6.5 88.13 0.60 7.6 1.4 99.1 2.7 96.0 120.02336 63.5 121 0.02608 63.4 35.4 5.97236/-19.85943/-19.1 88.6 1.2 14.5 40.7 157.2 199 2.30186 64.31 7.5 89 0.9 36.2 43.9 15.25 0.00 0.4 164.6 0.21 0. steam sample sample sample aquif.0 46.9 173.39 7.9 36.2 66. 3 02-3205 By Frosti&Funi 02-3206 Bóluhver 02-3207 Above Bóluhver 02-3208 By river.

Boron-containing minerals and Bminerals have been found as sublimates around volcanic fumaroles (Garavelli and Vurro. like Cl.. 1967).5 ppm (Sigvaldason and Óskarsson. as well as Landmannalaugar. The Cl/As ratio of the geothermal seawater at Reykjanes and Svartsengi are almost two orders of magnitude higher than that of seawater. The Reykjanes and Svartsengi areas. 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. Námafjall and Kraa waters could be due to lower ratios of these elements in the rock. 3. and a Cl/As leaching ratio of 3129. Likely. 3. Like B. 1963).6 show how aqueous Cl/As ratios change by basalt dissolution for precipitation containing 5 and 2 ppm Cl. The Reykjanes and Svartsengi uids have received considerable B in addition to that from the parent seawater. the low Cl/B ratios of the Nesjavellir.6. the Cl-As relationship diers in some respect from that of Cl-B. On 58 . the release of Cl from magma is limited relative to B due to its relatively high solubility in melt. RESULTS further concluded that the source of Cl and B to these waters is essentially the rock with which these waters have reacted. Boron is known to form volatile compounds at magmatic and lower temperatures and most of the B in basalt is readily extractable. The welleld at Nesjavellir is adjacent to a volcanic ssure that erupted 1880±65 years ago (Saemundsson. 1994. Such compound is believed to form by sublimation of volatile B compounds after the magma has consolidated. 3. Sigvaldason and Óskarsson (1976) concluded that only a small fraction of the Cl in basaltic magma is lost as a volatile during its consolidation. who demonstrated that As. The As-Cl values show more scatter than those of B-Cl (Fig. This ratio is based on the average Cl content of Icelandic basalts of 177. For other elds.6 shows the As-Cl relationship in water samples. This assumption is supported by the dissolution experiments of Ellis and Mahon (1964. loss of Cl from solution relative to B or preferential addition of B relative to Cl from a magmatic heat source.. Theoretically. It occurs mostly as HCl in magmatic gases. The latter number represents the average As content of tholeiites in the Skagafjördur area of northern Iceland. Fresh magma was intruded into the roots of the Kraa caldera immediately below the present wellelds during a volcanic episode in 197584 (Björnsson et al. 1977) and this magma owed along ssures into the Námafjall area (Larsen et al. Like Cl-B. 1967).. It is thus assumed that basalt dissolves congruently with respect to As and Cl. 1976) and an As content of 0. The dotted and broken curves in Fig. All these areas are closely associated with recent volcanism.3. 2006). 1978). is easily extractable and almost quantitatively leached from basalt and other types of volcanic rocks by hydrothermal solutions. Landmannalaugar is marginal to the Torfajökull geothermal area and may not be overlying a magmatic heat source.6. 1997) and on cooling new lava (Kuritani and Nakamura.12 ppm. 3. Cl forms volatile compounds at magmatic temperatures. undiluted waters from the Geysir area and Hveravellir fall more or less on the basalt dissolution curve.2 As and Cl relationships Fig.5). as indicated by the leaching experiments of Ellis and Mahon (1964. are also in areas of young volcanism but the other study areas are not. presumably because it exists in a soluble compound on mineral grain surfaces. Garavelli et al.

6. the other hand mixed waters from these areas containing a large cold water component. 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. 2002) and on Arnórsson and Andrésdóttir (1995) for Cl and B as before. except for the most diluted sample. which is the average As content of Tertiary tholeiites in northern Iceland (Arnórsson. In the case of Landmannalaugar.3 Rock derived concentrations Fig. Landmannalaugar. have As concentrations that plot above the Cl/As dissolution curve.8 show the relationships between the rock-derived concentrations of As. 3. Figure 3. Hveragerdi and Hveravellir.CHAPTER 3. this is considered to be due to precipitation of As from solution. (Fig. For Hveragerdi. they are based on Arnórsson and Andrésdóttir (1995) but for Cl/As and B/As they are based on a value of 0. The broken lines represent the respective elemental ratios in Icelandic tholeiites. The third plot (part C) shows the rock-derived As concentration versus aquifer temperature. For Cl/B. versus the calculated rock-derived Cl concentration. whereas this ratio is higher in the case of the Nesjavellir waters. The waters at Kraa and Námafjall possess Cl/As ratios which typically are lower than that of basalt.6: Measured Cl and As concentrations in liquid water samples from all the study areas. the low Cl/As ratios can be accounted for by the presence of the high marine Cl content. 3. which has a marine Cl content of 50100 ppm. 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.6).7 and 3.12 ppm for As. B and Cl for the elds of Geysir. 3. 59 .

The broken line represents the respective elemental ratios in Icelandic tholeiites according to Arnórsson and Andrésdóttir (1995). B and Cl concentrations in aquifer liquid in Geysir and Hveravellir elds. 60 .6. RESULTS Figure 3.3.7: Rock derived As.

CHAPTER 3. The broken line represents the respective elemental ratios in tholeiites from various parts of Iceland (Arnórsson and An- 61 . 1995).8: Rock derived As. drésdóttir. Figure 3. B and Cl concentrations in aquifer liquid in Landmannalaugar and Hveragerdi elds.

B and Cl concentration may or may not represent undiluted reservoir uid. respectively. 3.e. Landmannalaugar Arsenic. As is highly depleted in all the extensively diluted warm spring waters and in all but two samples of mixed boiling spring waters (Fig. It is possible that removal of As from boiling waters involves its incorporation 62 . B and Cl concentrations variations are larger in this eld than in other areas considered for the present study.0 ppb for four samples from Hveravellir. The results for the mixed waters indicate that As is removed to substantial degree from solution subsequent to mixing. represent extensively diluted geothermal waters. which also have high ow rates. with an average of 2. The same kind of pattern appears on the As versus calculated aquifer temperature graph. 3.7B) show two dierent groups. The relationship between Cl and B All is linear and the ratio is almost the same as in Icelandic tholeiites (Fig. mixing leads to a decrease in pH. particularly if mixing involves unboiled and therefore undegassed geothermal water. 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. A line passing through the data points goes through the point of origin. groundwater. The water sample containing the highest As. 54500 ppb and 1 220 ppb for Cl. and therefore also B.1 ppb As for six samples from the Geysir area and 7. RESULTS Geysir and Hveravellir The relationship between Cl and B is linear for the elds of Geysir and Hveravellir. they contain a large cold water component. described above.8) indicating its removal from solution subsequent to mixing. The Cl/B ratios of the waters are very similar to the average Cl/B ratio of Icelandic tholeiites. The other group plots above the mixing line. 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. except one water from boiling hot springs show considerable mixing with cooler or cold Warm springs. Unlike the results for the areas of Geysir and Hveravellir. The decrease in pH enhances dissolution of the primary mac basalt minerals leading to increased formation of secondary iron-hydroxides and clays. The waters of this group which contain a large cold water component are highly depleted in As relative to Cl. This leads to the conclusion that the high As. we observe As precipitation not only for mixed sub-boiling waters but also for mixed boiling waters. the range being 10400 ppm. B and Cl content of the geothermal waters is the consequence of reaction of these waters with silicic volcanics. As demonstrated by Arnórsson (1985).6. Relative to Cl. The group with the high Cl and As contents probably represents undiluted geothermal water. 3. Geothermal waters at Landmannalaugar dier from those at Geysir and Hveravellir by their higher H2 S content. The As versus Cl graphs for the Geysir and Hveravellir elds (Fig. B and As. The bedrock exposed in the Landmannalaugar area is all composed of silicic volcanics. 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.3. Likely the As coprecipitates with these minerals. i. This line is the consequence of mixing between the geothermal water and cold water.8).

by contrast. B concentrations have clearly decreased with time (Fig. At Námafjall.8. Cl/B ratios are ∼45 (molal) or a little higher than such ratios in geothermal waters at Geysir. whether limited or extensive leads to precipitation of As from solution. CO2 and H2 S raises the pH of the boiling water. Both decrease of temperature and increase in pH reduce sulde mineral solubilities. Data are lacking to verify this. Mixing of the deep water with shallower water. whereas the average for the Icelandic tholeiites is 38. both within and between elds (Fig. but in two of the wells. Kraa. Hveravellir and Landmannalaugar. B and Cl in dilute wet-steam well uids from the elds of Kraa. the relative concentrations of As. possibly due to variable production from more than one aquifer. into suldes that precipitate from solution upon extensive boiling due to cooling and degassing. being around 80 (molal) for the waters containing the highest Cl (100130 ppm). Arsenic is very low and the Cl/As ratio is the highest compared to uids from other elds considered for the present study. Hveragerdi At Hveragerdi. Námafjall and Nesjavellir show much greater scatter. 3. Studies of hydrothermal alteration at depth in Hveragerdi show that it is very pervasive (Sigvaldason. 1963). the aqueous Cl/B ratio is higher. 2 ppb B) as would be expected if this line represented mixing.9). Arnórsson (1969) demonstrated that Mo and Ge are excessively depleted from the altered rock at Hveragerdi. 63 . Landmannalaugar and Hveragerdi. However. At Nesjavellir Cl/B ratios vary between 8 and 39 (molal) whereas those from Kraa have a range of 639. Cl has stayed constant but in the third well it is erratic. In the most dilute waters. In these elds Cl/B ratios are similar to those of Icelandic tholeiites and the hot spring waters or lower. Hveravellir. 2002.10). The primary basalt minerals have been totally replaced by hydrothermal minerals and extensive removal of As from the initial basalt accompanied the hydrothermal alteration. 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 (Arnórsson and Andrésdóttir. the Cl-B data points form a curve. rather than a line. 339 and 124 for Kraa and Námafjall. 3. Degassing with respect to the acid gases. 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. relative to fresh basalt. As can be seen from Fig. 1985). Arnórsson and Gunnlaugsson. the range is even larger. 1995). and a linear regression through these data points does not pass through the point representing local precipitation (10 ppm Cl. respectively. Námafjall and Nesjavellir Unlike the results just presented for the hot spring data from Geysir. When considering older data on Cl and B from Námafjall and Kraa (Gudmundsson and Arnórsson. The Cl/B ratios increase with increasing concentrations. the average being 68 (molal).CHAPTER 3. 3.

9: Rock derived As.6.10: Time evolution of non-marine B in the aquifer water of three wells of the Námafjall area. RESULTS Figure 3. Figure 3. B and Cl in aquifer liquid. 64 .3.

yields a B concentration of 0. They include wells 16. 3. particularly those south of Kraa mountain. The low B end-member for the low-slope mixing line represents geothermal uid that has reacted to a relatively limited extent with basalt.75 ppm and 94 ppm for Cl.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. It is therefore concluded that calculated aquifer uid B concentrations cannot be explained e by use of an erroneous selection of P .11) indicating that the Cl and B contents of the aquifer uid in these geothermal systems are determined. Assuming a Cl/B ratio (molal) of 38 for the other component. exceptions. the magmatic component has mixed with relatively little reacted water. The selected Cl/B ratio is the average Cl/B ratio of Icelandic tholeiites. There are. however. The low B end-member for the mixing line (not shown in Fig. Selection of too a low e value for P leads to over-estimation of the aquifer uid B concentration. for each line.CHAPTER 3.1) do not contain anomalously high B whereas other wells have high B but not very high discharge enthalpy (e. 3. see Table 3. A plot of Cl/B against 1/B of data from Nesjavellir. one of these components is taken to be that at the intersection point of the two lines. for well locations). 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 ).11) with the lower slope gives 0. 2 in Gudmundsson and Arnórsson. 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. Well 21 is located some 2 km to the south of other productive wells. 3.15 ppm B and 19.5. on the other hand. Some of the wells with the highest B concentrations discharge almost dry steam. in a shadow of the Kraa 65 . By contrast. Essentially. 20. like that discharged from boiling hot springs in the Geysir area. considered to be represented by the upper sub-boiling reservoir of the Kraa system. Kraa and Námafjall shows that most of the data points scatter around two lines (Fig.2 above.15 ppm B corresponds to 1/B = 70 (molal).g.11. 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. 2002. A large groundwater current ows from the north to the west of the mountain of Kraa. The component which corresponds to the point of intersection of the two mixing lines.2 ppm Cl for a Cl/B molal ratio of 38.g. is considered to contain a relatively high proportion of magmatic volatiles.2 ppm B and 188 ppm Cl. by mixing of two components. as well as one sample from well 13. the two component mixing always involves substantial addition of B to the geothermal uid from a magmatic source. The value of 0. It contains Cl in concentrations quite similar to that of water in aquifers in the upper Kraa reservoir. 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. are outside the main groundwater current. well 12 at Námafjall and well 19 at Nesjavellir). The wells to the east. As discussed in section 3. For the line with the steeper slope in Fig. the low B end-member for the high-slope line represents quite extensively reacted water. 16. 21 and 32 at Kraa. 3. 17 and 20 at Kraa. The data depicted in Fig. At Kraa and Námafjall. (see Fig. Some wells with discharge enthalpy close to that of dry steam (e. This component contains 26.

Filled symbols represent samples from this study. 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 Námafjall. open symbols represent data from Gudmundsson and Arnórsson (2002).3.6. respectively. RESULTS Figure 3. 66 .11: A plot of Cl and B of non-marine origin. These two lines represent mixing of two end-members.Arnórsson and Gunnlaugsson (1985). a magma-volatile component and liquid meteoric that has reacted to a dierent extend with the rock (see text).

respectively. They include loss of As from solution by its incorporation into precipitating sulde minerals at depth. 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. undiluted hot springs waters have relatively constant concentrations of Cl and As. in particular in zones of extensive boiling. This is to The be contrasted with the results described previously for the hot spring waters. Námafjall and Nesjavellir (Fig. 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. indicate lower mobility of As at Nesjavellir than at Kraa and Námafjall. There may be several reasons for the lower mobility of As relative to those of Cl and B. 3. Initially this well had two feed zones. however. The mixed uid in these wells contain a component of water that has reacted extensively with the basalt. which precipitate. are all derived from the shallower subboiling zone because at that time the deeper zone had become inactive due to its low permeability. B concentrations have decreased in aquifers producing into wells at Námafjall. 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. The uid discharged from well 21 represents a mixture of moderately reacted water containing a fair contribution of the magmatic volatile component. On average they are 4600 (molal) and 2800 for these elds.11. In the wet-steam wells.9). and variable addition of As to the geothermal uids from magmatic volatiles. if a total of four samples are omitted that have very high Cl/As due to low As concentrations. magmatic gas component of the well discharge. mountain. there is a signicant positive correlation between the concentrations of As and B in the aquifer uids at Kraa plus Námafjall and Nesjavellir.9). As already mentioned. The dierence in the Cl/As and B/As ratios of the uids at Nesjavellir on one hand and Kraa and Námafjall on the other. Four samples have been plotted for well 13 in Fig. attributable to large supply of B to the uid by magmatic volatiles. one from the deeper two-phase reservoir and one from the upper sub-boiling reservoir. 3. The three samples collected at a later date (1988 to 2004). respectively (Fig. Such decrease has also been observed for couple of wells at Kraa but most show no change or erratic variation with time. 67 . concentration variation for Cl is roughly 15-fold but 25-fold for As. If four samples are omitted. The four exempted samples all have anomalously high B relative to Cl (Fig.9).CHAPTER 3. and therefore also of Cl/As ratios. 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. 3. This is. those of B/As are higher at Nesjavellir than at Kraa. 3. just as is the case at Nesjavellir. As for Cl/As ratios. Cl/As ratios in the Nesjavellir uids are with few exceptions higher than those at Kraa and Námafjall.

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)

m

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

s

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 Arnórsson and Andrésdóttir (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 Óskarsson (1976) and B data on the same samples presented by Arnórsson and Andrésdóttir (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 Skagafjördur in

69

3.8. SUMMARY AND CONCLUSIONS
northern Iceland and Cl and B data on dierent samples (Sigvaldason and Óskarsson, 1976; Arnórsson and Andrésdóttir, 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

.

N. Ö. SW-Iceland. 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. J. 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. i. the installed electric capacity of the geothermal plant is 76 MW and the installed thermal capacity for direct use is 150 MW. started in 1976. but it has decreased with time. Boiling of the liquid has reduced its gas content. and Bjarnason. 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. This in turn has caused an increase and decrease of liquid F and Mg concentrations. Initially. Arnórsson. continued boiling of the underlying liquid water. This is economically attractive but not environmentally favorable due to the high content of CO2 and H2 S in the vapor.e. Shallow wells have been drilled to tap the vapor cap for electricity production. respectively.. the vapor cap was very rich in gas. Production has led to a pressure ◦ drawdown of approximately 30 bar in the 240 C liquid reservoir. Abstract Production from the Svartsengi geothermal eld. S. At present. Iceland Giroud.Chapter 4 Formation of a vapor cap subsequent to production in the Svartsengi geothermal eld. 73 . due to re-equilibration of the boiled water with Mg and OH-bearing minerals.

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. 2008).1 Introduction Vapor-dominated geothermal systems are considered to have formed by boiling down of liquid-dominated geothermal systems (Go and Janik. 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. Plans are under way at Reykjanes to drill into the steam cap for its exploitation. 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 (Arnórsson 74 . At depths greater than 1500 m. INTRODUCTION 4. breccias and pillow-lavas. predominate. and formation of hydrothermal minerals is unlikely to cope with opening of fractures by the these movements. 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. Gudmundsson and Thórhallsson. and references therein).2 Geology and hydrology The Svartsengi high-temperature geothermal eld is one of ve high-temperature geothermal elds on the Reykjanes peninsula. It is located in the Grindavík ssure swarm.. intercalated with Pleistocene and Holocene lava ows and dyke intrusions. The rocks consist predominantly of sub-glacially erupted hyaloclastites.4. 1990... and to a lesser extent sills. one of ve ssure swarms that lie across the plate boundary on the Reykjanes peninsula (Jakobsson et al. a vapor zone existed under natural conditions on top of a two-phase liquid-dominated reservoir (Arnórsson et al. The formation of the steam cap at Svartsengi has been associated with much increased fumarole activity. 4. Arnórsson. et al. It appears more likely that ascent of vapor is restricted by volume expansion of the rising vapor. dykes. 1978). since the beginning of production. 2000). 2000. 1986. 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. formerly part of the National Energy Authority. Environmentally. it is not so favourable due to the high CO2 content of the vapor.1.. At Wairakei. 4. and unpubl. 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. 1978. In the East Production Field of Olkaria geothermal eld in Kenya. on the other hand. data). in South-West Iceland (Fig. Tectonic movements are frequent.1). The chemistry of the uids discharged from all the wells at Svartsengi has been monitored by Iceland GeoSurvey. The present article is based on these monitoring data as well as on 10 samples specically collected for the present study. which was minor prior to exploitation. as well as Svartsengi. In the light of data on hydrothermal alteration from the nearby eld at Reykjanes (Pope et al. 1995). as witnessed by earthquake activity. production from the steam cap by the drilling of shallow holes into it has proved to be economic.

3 Production history Production from the Svartsengi high-temperature eld started in 1976. north of Svartsengi. 1976).CHAPTER 4. 1995). as shown by resistivity surveys (Stefánsson et al. 4. values up to 100150 · 10−15 m2 (Arnórsson.6 MW 75 . increasing to 8 MW in 1980. groundwater level at In the middle of the peninsula. 1984). geochemical studies (Bjarnason. liquid-dominated aquifer extends from 600 to at least The depth of the producing m depth (Björnsson and ∼2000 Steingrímsson. The deep groundwater consists of seawater-groundwater. the lens is about 50 m thick and the ∼2 m above sea level. The volume of the total geothermal system has been estimated 3 as 1525 km (Bjarnason. west and north. Delivery of hot-water for district heating was followed shortly by electric power generation.1).. The installed generating capacity was 2 MW in 1977. Eldvörp and Reykjanes high-temperature geothermal elds (modied from Fridriksson et al.. subsidence measurements. 1996).1: Map of the Reykjanes peninsula with the Svartsengi. 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. The producing eld is hydrologically connected to the high-temperature area of Eldvörp. 4. located about 6 km to the southwest (Fig. The reservoir in its natural state was liquid-dominated and the temperature across the eld is very uniform at about 240 ◦ C. as well as by pressure monitoring. 1992). 1986). 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 Thórhallsson. Figure 4. The fresh water lens thins towards the coast in south. and gravity surveys. 11. 2006). 1986).

ranging between 2. The emissions from the wet-steam wells have been relatively constant over time.700 tonnes per year (Fig. Well 10. The total uidliquid and vaporwithdrawn from wet-steam wells increased sharply in the rst years of 9 production up to a maximum of 9. If we 3 assume a uid density of 816 kg/m . 4.4 MW in April 2008 (Arnórsson et al.3. 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. corresponding to a volume of 0. 16. are much higher. respectively.000 tonnes) but have ∼43.3. and nally to 76.. 4.4. The net mass extraction from the 3 ◦ eld is thus 216 Mt.4).000 tonnes in 2006 (Fig. 1999 and 2001.4).4 MW in 1993. 76 . 4.7 Mt/year.4 MW in 1999.84 Mt (megatonnes.40 Mt in 2006 (Fig. 2008).2 and Fig. Reservoir pressure drawdown caused by production from the eld has led to the formation of a vapor cap at the top of the reservoir. and the cumulated mass of injected liquid is 27 Mt. which is only 425 m deep. PRODUCTION HISTORY Figure 4. Regular downhole pressure measurements carried out by Iceland GeoSurvey show that the pressure drawdown in monitored wells ranges between 25 and 32 bar. Three other wells were drilled into the vapor cap and brought on stream in 1996. on the other hand. The spent uid has been mostly disposed o at the surface. production from these wells. 46. declined since. Since then. reaching 4. to 4. The total mass of uid withdrawn from the aquifer between 1976 and 2006 is 243 Mt. Emissions from the dry-steam wells.2). respectively. in 1989. the corresponding water level drawdown is 312 to 400 m.0 and 9. stopped discharging liquid water in 1984 and became the rst well to produce dry steam from the vapor cap. Injection was resumed in 2001 and has been continued since. 4. but a fraction of it was injected irregularly between 1984 and 1999. 10 kg) in 1986. uid withdrawal from wet-steam wells has ranged between 6.700 and 4.2: Annual discharge and injection in million tonnes of uid.26 km of liquid water at 238 C. Between 96 and 98% of the gas discharged from the wells at Svartsengi is CO2 . The annual and cumulated uid withdrawal from the reservoir from 1976 to 2006 is shown in Fig.

Figure 4. 77 .3: Cumulated discharge and injection in million tonnes of uid.. Figure 4.CHAPTER 4. 2007).4: Annual CO2 emissions (in tonnes) from wet-steam and dry-steam wells at Svartsengi (Fridriksson et al.

were collected as described by Arnórsson et al. 1984. The in situ aquifer water pH is around 5. Bjarnason.1).l (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 (Arnórsson.v X d. Monitoring samples. collected separately as described by Arnórsson et al.4 Sampling and analytical techniques and calculation of aquifer uid compositions Ten of the Svartsengi wells were sampled for the present study.l (1 − X d. as calculated by the WATCH speciation program.5). Relative to seawater and its Cl content. The aquifer liquid compositions including pH were calculated with the aid of the WATCH speciation program (Arnórsson et al.4. We have X d. 2008). taking the discharge enthalpy to be that of vapor-saturated liquid at the aquifer temperature.2) m denotes concentration.4. ANALYSES AND CALCULATIONS 4. the Svartsengi brine is enriched in Si. However. we have mf.1) f.v i i i where (4. Lonker et al. Pope et al. Ragnarsdóttir et al.. Ca and B.v = where hf. h is the d. The deuterium content of the aquifer uid is consistent with its origin.v ) + md.1 (Bjarnason. (2006).l d.. practically devoid of Mg and SO4 .l = md.. For wet-steam wells. version 2. (2006) except for the gases. For any component i. gas analytical methods have been the same throughout the monitoring period. 1996. 1993). 1982). 1994).v the liquid and the vapor at sampling conditions.v specic enthalpy of the aquifer liquid. much depleted in F and slightly in Na (Table 4. Vapor samples from dry-steam wells are taken to represent the composition of the vapor cap. 1993.1.v − hd. respectively. The composition of the reservoir liquid is remarkably uniform. (2006). The fresh water component in the Svartsengi reservoir uid is considered to originate from the fresh water lens mentioned in section 4. and h and h are the specic enthalpies of X d.. The results are shown in Table 4.l is the vapor fraction of the discharge at sampling conditions. SAMPLING. 4. The trace element composition of the Svartsengi brine generally 78 . six wet-steam wells and four dry-steam wells. Slight but systematic dierences are observed in the aquifer uid Cl content of individual production wells (Fig. The vapor fraction of the discharge was calculated from the measured sampling pressure. (2000) but later by the method given by Arnórsson et al. which were extracted from Iceland Initially gases and condensate were GeoSurvey reports to Sudurnes Regional Heating Company.000 mg/kg. The sampling and analytical methods used were those described by Arnórsson et al. as deduced from its Cl content (Lonker et al. 1978. the total discharge composition is taken to represent the aquifer liquid composition.. with a Cl content of 1213. K. 1988.2. 4.l hd. Dissolved solids in monitoring water samples have been analyzed by a variety of methods.l − hd.

0 9.134 0.63 <0.25 <0.97 7.1 2.857 0.0111 110.008 0.5 <1 0.92 25.58 10.003 0.56 3.00 0.518 156 5.9 0.2 0.15 2.42 7.5 <0.117 0.5 0.522 <0.08 0.218 14. Sampling pressure and vapor fraction are also shown.023 1573 47.0 <1 <0.043 0.005 7.00 CO2 646 H2S 15.005 3.00 0.427 12912 0.56 <0.806 1.1 95.011 1474 44.38 N2 5.1 89.5 <0.1 0.367 53.403 <0.62 3.74 318 7.53 919 10. Table 4.539 1.5 <0.0020 72.06 7.154 2.20 448 6373 915 1025 0.5 81.005 2.02 1.667 <0.02 2.81 <0.5 <0.5 <2 79 SV-11 04-3029 01.15 6.572 <2 <0.143 0.0066 70.0 7.50 13.20 0.010 1721 39.03 4.11 442 6380 916 1033 0.615 16.5 9.89 2.85 <0.09 0.09.12.63 0.93 pH (at 238 ◦ C) 4.14 6.5 71.0 0.00 Ar 0.1 2.04 36.651 2.06 Sr 8.7 0.56 25.5 <0.790 210 7.1: Major and trace elements and major gas concentrations in aquifer liquid of wet-steam wells.85 1.12.04 9.110 2.57 5.5 2.559 56.06 8.005 2.7 53.1 2.96 12.065 0.05 0.2004 14.11 7.02 5.14 7.4 2.15 6.927 1.4 0.02 1.05 15.5 3.290 0.02 7.127 1.13 0.91 5.7 <1 0.5 2.63 25.001 1203 40.77 0.557 191 5.3 0.609 20.156 1.005 3.9 0.09.12 25.05 <0.890 <0.155 3.91 5.43 <0.9 0.010 169.72 431 6394 920 1032 0.4 O2 0.38 6.65 8.091 0.88 SiO2 429 Na 6650 K 961 Ca 1069 Mg 0.541 <0.036 Al 0.7 0.0092 120.125 0.1 0.342 118 5.013 1920 45.8 9.227 54.61 6.005 4.980 1.010 0.3 0.5 <0.05 SV-18 04-3004 10.280 12054 0.00 <0.1 0.23 <10 <0.CHAPTER 4.09.856 0.060 95.02 3.17 <0.2004 19.5 2.100 1.5 0.95 <0.371 139 7.41 SO4 23.2 0.682 <0.2004 14.012 1415 41.1 2.71 0.124 0.37 421 6809 994 1064 0.38 5.6 <1 0.0 9.01 <0.02 3.00 1.34 <0.9 0.2004 Pd (bar-g) 15.2 0.06 7.0 0.020 110.614 12222 0.839 57.14 0.5 1.5 0.063 12.46 56. Well Sample # SV-7 04-3005 SV-8 04-3003 10.05 .220 0.495 54.5 94.1 2.531 12100 0.9 <0.13 B 6.13 7.5 Xd.7 0.59 0.53 <0.v (% w/w) 8.15 CH4 0.275 0.865 0.93 9.279 55.8 Fe 0.072 <0.02 1.392 Cl 12664 F 0.15 7.00 0.3 0.0312 119.5 0.5 <0.2004 14.2004 14.0088 99.369 12942 0. µg/kg.22 427 6813 1009 1023 0.84 403 1.765 0.8 H2 0.75 <0.6 2.09.8 <1 0. Concentrations of major components and trace elements in mg/kg and respectively.436 19.02 4.020 119.05 SV-9 04-3032 01.05 SV-19 04-3006 10.4 0.66 <0.699 185 9.1 0.63 227 5.27 <10 <0.00 0.090 123.7 0.3 0.40 4.070 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 102.06 27.73 <0.999 0.736 1.05 Sampling date 10.4 2.00 221 4.

467 418 9.00 2.47 461. FLUID COMPOSITION Figure 4.00 8.2004 CO2 29.52 1.41 1.33 91.2004 21.2). diers much from that of seawater. Fe.77 Sampling date 01. CO2 concentrations are 200 800 mg/kg in the liquid reservoir.1 O2 0. 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. some of the CO2 and the As may be derived from a magmatic source (Giroud and Arnórsson. Table 4.00 Ar 8.01. The major dissolved gas is CO2 . 2008a.12. Ba.12. Well Sample # SV-10 05-3001 SV-14 04-3030 01.8 0.00 CH4 2.18 SV-16 05-3002 14.625 349 11. Ge. At present.4. Mo.1 0.12. It accounts for 9698% of the total gas.82 SV-20 04-3031 01. in particular the concentrations of As. Additionally.5: Chloride concentration in the aquifer uid of wet-steam wells. Rb and Sr.00 2. respectively.292 H2 S 411 H2 9.2004 19.000 mg/kg in the vapor cap (Table 4. Concentrations in mg/kg.b).60 2. but some 20.12 80 . Open and full symbols represent data from Iceland GeoSurvey and samples collected for this study.94 N2 391.698 179 6.2 0. the remainder being mostly H2 S. H2 and N2 .2005 26.66 93.2: Gas concentrations in the vapor discharge from dry-steam wells.5.

Since 19901991. H2 S and H2 ) in the aquifer uid feeding wetsteam wells (nos.4).1 Wet-steam wells Until 1990. from 0. led to a further increase in the gaseous vapor of wells 7 and 11.6. 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. CO2 concentrations remain mostly stable in the period 19901999. Some samples show almost no H2 S. wells 7 and 11 show an increase. As a result.6). Small air contamination of the vapor upon sampling leads to high N2 and Ar concentrations. After 1990 large dierences are on the other hand seen between wells. particularly in an alkaline medium like that used by Iceland GeoSurvey for vapor sampling in recent years (see section 4. Indeed. As in wells 7 and 11. and After 1990. A smaller increase is observed for wells 8 and 9. particularly when its concentrations are low. become dierent between wells in a manner comparable to that for CO2 . samples low in H2 S tend to be high in N2 . The vapor fractions calculated with 81 . The pressure drawdown will cause the depth level of rst boiling in the liquid-dominated reservoir to migrate downwards. 4. The H2 S concentrations in the aquifer uid of wet-steam wells range mostly between 5 and 10 mg/kg until 1990 (Fig. 4. an increase is also seen between 1999 and 2000 in wells 8 and 9. Analyzed H2 concentrations are close to the detection limit of the analytical method used.7% to 2.6). concentrations do not vary with time.6 shows that the CO2 concentration decreases between 1982 and 1990 in all of the wet-steam wells.3% in wells 7 and 11. Analyzed H2 S concentrations are sensitive to air contamination upon sampling. again just as for CO2 and H2 S (Fig. as for CO2 and H2 S. gas concentrations (CO2 . well 11 showing the highest concentrations. In well 8. 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 . changed little until about 2005. 9 and 11) are on the whole about the same (Fig. particularly between 1991 and 2000.CHAPTER 4. The slight excess vapor in the discharge of wells 7 and 11 may come from the vapor cap. No clear trend is observed before 1990 for any of the wells.3 shows a three-fold increase in the vapor mass fraction between 19961997 and 20062007. Then. Fig.6). This increase coincides with increased production from the reservoir when wells 18 and 19 were put on line. when wells 18 and 19 came on line. an increase is observed in the CO2 concentration in wells 7 and 11.9% to 3. 8. depending on the depth level of producing horizons intersected by these wells. H2 S and H2 in the other four wet-steam wells and in the dry-steam wells. The CO2 in well 9 continues to decrease. but in the last few years. respectively. concentrations have stabilized and vary between 500 and 800 mg/kg. specially after 2003. because H2 S reacts rapidly with O2 . There is complete overlap between wells. 4. This increase becomes very sharp between 1999 and 2000. but it is not as sharp. as well as that of wells 8 and 9. H2 S concentrations apparently. 4. 4. Table 4. air contamination likely leads to an underestimate of the H2 S content of the vapor. or from rising vapor bubbles in the liquid reservoir. and such vapor also appeared in wells 8 and 9. 7.1% and from 0. Enhanced drawdown in the reservoir in 1999 to 2000.6 Evolution of gas concentrations 4. but has decreased since. The CO2 content of the discharge of these two wells.

6: CO2 . H2 S and H2 concentrations versus time in the aquifer uid of wet-steam wells. 82 .4.5.6. Symbols have the same meaning as in Fig. EVOLUTION OF GAS CONCENTRATIONS Figure 4. 4.

34 % v/v 26. Concentrations are averages (in mg/kg) of all samples taken in the periods 19961997 and 20062007.700 mg/kg per year.225 0.37 2.CHAPTER 4.54 3. is likely to be due to boiling of previously undegassed reservoir liquid.6.68 18. Well 7 Well 11 Other wet-steam wells Dry-steam wells CO2 19961997 453 473 215 37.422 7.10 2.060 0.18 0.3 31.65 0.37 mg/kg.828 % w/w 1.86 0.013 8.70 2.7 15.60 6.385 mg/kg. well 16 showing usually the highest CO2 concentrations.67 0.843 % w/w 0.6 38.6 11.030 8. 4.49 2.60 0. the average H2 S and H2 concentrations decreased from 365 to 308 mg/kg.68 0. but since 1984 it has produced dry steam only.020 mg/kg in the period 20062007. The increase in the gas content in wells 8 and 9 around the year 2000.8 30.97 9. as mentioned above.26 433.06 285.6 21.3: Gas concentrations and estimates of the fraction of vapor (in % w/w and % v/v) owing into wells 7 and 11. 83 . Table 4.7). 4.54 0.000 mg/kg on average (Fig. A very similar trend is observed for H2 S and H2 : Between 19992000 and 20062007.2 10.89 % v/v 11.98 4.Initially.69 1.0 12.2 Dry-steam wells At the outset. There is a small dierence between wells. 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.9 41.7 49. decreasing to 15.3) are higher than those calculated from CO2 and H2 .94 4.22 2. and well 20 the lowest. and from 6. The average CO2 concentration in the four wells in the period 19992000 was 20.253 0. 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. respectively.9 15. CO2 concentrations in the vapor cap were close to 50. well 10 discharged wet steam.6 20062007 546 778 236 18.32 0. They have been decreasing since at a rate of about 1.3 33. respectively.070 0.5 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 4.33 to 5.445 12.4 12.2 34.

respectively.7: CO2 .6. EVOLUTION OF GAS CONCENTRATIONS Figure 4. 84 . 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.4.

2007) in wells producing from the liquid reservoir have not changed with time over the 25 years covered by this study.7 Changes in dissolved salts and pH The concentration of Cl (Fig. 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. 4. The concentrations of Mg have decreased. 4.2 mg/kg. 4. 4. as can be seen from MgO + 2H+ = H2 O + Mg+2 (4. They observed that F /OH activity ratios were constant at any particular temperature. K.15 to 0.3) where MgO represents the magnesium oxide component in a Mg-silicate mineral.5).9). Ca and SiO2 (Fridriksson et al. and those of F have increased (Figs. In seawater.CHAPTER 4.10 to fall on a line with unit slope. A decrease of Mg concentrations by a factor of 2 to 4 corresponds to an increase in pH +2 − of 0. Fig.10 shows a plot of log(Mg ) activity versus -2log(F ) activity.3.8 and 4. 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.5. but they have increased to about 0. This is 85 . Arnórsson et al. F concentrations are 1. 1993). In the Svartsengi geothermal brine.0 mg/kg and therefore 0. 4. Symbols have the same meaning as in Fig. see Lonker et al. F concentrations were about 0. however.8: Magnesium concentration in the aquifer uid of wet-steam wells.7 mg/kg in the source uid to the Svartsengi geothermal system. (1983) suggested that F concentrations in geothermal uids reacting with basaltic rock are controlled by exchange equilibria with OH-bearing minerals. Figure 4.. Na.1 mg/kg during the early years of production. such as chlorite and − − smectite. then H activity would have decreased by a factor of 2.3 units. 4.. +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. If it is assumed that the increase in F − + concentration is accompanied in an equal change in OH . that is pH increased by 0.

5.4. Symbols have the same meaning as in Fig.9: Fluoride concentration in the aquifer uid of wet-steam wells. CHANGES IN DISSOLVED SALTS AND PH Figure 4.5. Symbols have the same meaning as in Fig. 86 .7. Figure 4.10: Mg +2 versus −2F− activities in the aquifer uid of wet steam wells. 4. 4. The line represents the unit slope.

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

s

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

v

and

l

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 (Arnórsson et al., 2007).

where

m

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

s

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

s

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

f

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 Fernández-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

Such an increase has not been observed. It is likely that this eect. 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. of Mg and F concentrations with time in the liquid reservoir. The eect of injected waste water should also increase the Cl content of the well uid. together with enhanced boiling by pressure drawdown. 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. 4. 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. respectively an increase. gravity in the area. Removal of CO2 and H2 S decreases the pH of the remaining liquid. because the only source of these gases to the geothermal uid is air-saturated meteoric water and seawater. As a consequence. are the causes of the formation of the vapor cap.4. The gas concentrations in the vapor cap are several orders of magnitude higher than those in the liquid reservoir.e. both natural and by injection. Unfortunately. rapid equilibration with Mg and OH-bearing minerals leads to a decrease. 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. i. A self-sealing zone by hydrothermal mineral formation or impermeable strata. Recharge into the Svartsengi reservoir.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 geothermal eld at Svartsengi has 70% natural recharge. many of the vapor samples collected for the monitoring studies are air-contaminated.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. This volume increase will impede uid ow. certainly in relation to the frequency of tectonic movements. Extensive boiling in the reservoir also leads to degassing of the liquid water. 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. increases the activity of − the OH ion. It would be particularly interesting to have data on the noble gases for such an assessment. are not needed for the formation of such a cap whether it forms under natural conditions or by exploitation. 90 . may cause the gas content of the uid discharged from wells to decrease. 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. Boiling of the According to Eysteinsson (2000). or to a lesser extent. indicating that the eect of used brine on decrease in the gas content of the well uid is not signicant.

CHAPTER 4. The much enhanced vapor formation and volume increase in relation to permeability may be sucient for the vapor cap to form. 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. 91 .

.

93 .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.

01 0.125 0.546 1.460 6.3 38.001 989 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 54 476 191 544 148.001 <0.073 <0.265 1.615 0.520 1.0005 0.660 6.0010 0.0012 0.1 57.623 0.100 0.002 <0.007 <0.000 1730.002 <0.057 0.05 <0.005 <0.002 <0.005 <0.0008 0.018 0.0054 0.223 0.005 <0.200 1.002 <0.081 0.105 0.005 <0.900 3.229 0.139 0.05 <0.005 <0.002 0.278 0.5 3.047 0.0 42.920 4.005 0.117 0.001 0.006 0.005 0.9 16.014 0.0127 0.0001 0.064 0.3 88.0 129.290 15. 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 Bödmódstadir Efri Reykir S-24 Reykholt S-1 Reykjaból S-1 0.005 0.4 48.002 <0.9 15.002 <0.0094 0.002 <0.005 <0.0311 0.193 0.005 <0.610 3.5 104. Concentrations in µg/kg.241 0.0054 0.0118 0.052 0.024 <0.001 0.001 <0.6 89.508 0.2 0.8 0.4 90.04 0.086 0.002 <0.923 <0.0642 0.579 3.005 <0.417 0.190 <0.4 57.479 0.089 0.026 0.000 6480.001 0.005 <0.3 98.0001 0.119 0.268 0.1: Trace element analyses of liquid water samples from wet-steam wells.0645 0.002 <0.027 0.080 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 0.13 0.900 59.005 0.038 2.001 0.135 0.390 6.660 5.013 <0.007 <0.020 59.005 <0.002 <0.05 <0.374 0.005 <0.001 <0.002 <0.0021 0.8 213.6 80.047 0.088 0.0114 <0.3 84.150 7.0026 0.171 0.050 7.006 <0.002 <0.300 0.005 0.0051 0.05 0.210 3.005 <0.0115 0.102 0.001 0.0092 0.000 6650.001 <0.0 24.820 6.4 78.910 4.010 0.002 <0.940 4.660 4.5 2.120 3.000 2120.880 2.600 62.0255 0.069 0.0 24.148 0.1 50.1 16.640 1.1 93.000 1320.05 <0.002 <0.0102 0.140 2.3 14.0008 0.002 <0.05 0.010 8.010 1.114 0.569 1610.600 0.5 2.900 60.895 0.035 0.200 58.6 40.600 61.008 0.002 <0.1 8.600 61.0103 0.000 1510.002 <0.002 0.920 0.036 0.660 0.0 1.484 0.005 0.0325 <0.000 0.001 0.0242 0.0139 0.001 <0.0005 <0.001 0.171 0.0059 0.200 63.05 <0.0333 0.005 <0.5 53.110 <0.423 0.05 <0.34 0.118 0.608 0.0 139.086 <0.002 <0.1 28.015 <0.140 3.342 .006 0.0 105.002 <0.0014 0.045 0.361 1.001 0.005 0.320 0.072 0.210 6.291 0.005 <0.0098 0.0111 0.814 0.900 0.002 <0.Table A.0038 0.019 0.8 23.770 0.0 88.0 105.001 <0.002 0.904 2.045 0.002 0.002 <0.002 0.004 0.000 1900.101 0.005 <0.002 <0.113 0.0051 0.386 0.0 156.8 102.002 <0.370 0.010 0.488 0.758 0.002 <0.165 0.002 0.790 8.280 3.03 0.002 <0.340 0.003 <0.111 1.08 0.001 0.0258 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 0.005 <0.002 <0.005 <0.830 7.460 9.095 0.

120 <0.49 23.0 194.133 <0.0020 0.9 43.0 225.05 0.29 1.7 27.05 <0.011 0.269 <0.0020 0.0020 <0.92 6.40 92. .67 0.26 6.68 1.7 23.85 6.60 <10 15.5 17.92 5.021 0.98 1.008 <0.00 131.9 28.318 0.787 0.61 4.1 29.0 49.006 <0.10 9.0 474.0 3080.16 1.0 2980.66 3.80 6.43 2.61 2.101 0.07 <0.23 1.405 0.68 8.050 0.38 1.52 1.0020 <0.0020 0.12 6.660 2.77 0.0 274.158 0.96 1.05 <0.6 22.590 0.65 0.80 24.48 1.139 0.25 2.010 0.068 <0.01 0.8 16.90 2.7 33.0 146.57 7.30 5.740 0.510 2.760 0.1 <0.18 7.90 0.105 0.56 3.08 5.72 7.280 <1 <1 <1 1.03 <1 1.90 34.1 <0.011 0.55 5.633 0.01 0.6 22.48 0.13 1.40 4.395 0.0020 0.05 <0.007 <0.019 0.089 <0.038 0.0020 <0.21 1.155 0.10 5.013 0.653 1.0 283.21 <1 1.003 <0.12 3.01 0.7 23.0020 <0.300 2.1: (cont.0020 0.14 2.14 7.0 381.60 5.018 <0.09 4.00 77.19 4.05 <0.59 2.47 5.05 5.2 43.0 223.000 204.16 5.542 0.50 8.10 6.034 <0.52 6.160 0.0 277.21 1.38 4.158 0.88 2.46 11.018 <0.0 2770.461 <1 <1 <1 1.05 7.000 130.059 CHAPTER A.000 204.417 0.0 215.627 0.840 3.91 0.06 5.17 1.698 0.00 6.126 0.5 2.05 <0.1 <0.026 0.81 77.0 2730.0020 <0.2 28.68 11.210 1.6 40.011 <0.0 234.00 2.21 213.47 30.05 <0.372 0.270 0.226 0.140 0.0 32.1 <0.0 186.023 0.0020 <0.34 2.330 0.28 3.005 <0.85 11.56 3.47 8.308 0.48 1.223 0.6 285.20 3.05 <0.328 0.015 0.6 44.164 <0.7 16.115 0.3 8.460 3.156 3.62 0.40 6.0020 0.37 3.05 <0.053 0.299 0.820 2.7 36.10 1.90 5.605 0.00 7.35 5.0 312.055 <0.30 133.91 1.042 0.0020 0.175 0.50 10.74 6.730 0.91 1.13 1.21 4.34 5.000 2210.3 10.012 0.755 0.95 5.380 2.10 122.023 0.11 8.337 0.142 <0.535 1.61 11.17 5.0 247.7 51.0 187.540 0.967 1.000 232.02 1.31 1.6 21.31 5.01 0.209 0.090 0.71 6.0 370.58 10.00 300.25 1.0 156.375 1.070 1.05 0.1 0.05 0.1 0.58 2.1 40.70 12.05 <0.6 15.7 46.05 0.6 31.0 182.05 <0.000 172.36 25.480 1.68 5.7 39.000 1500.257 0.4 9.70 <1 <1 2.000 0.864 0.40 6.0 197.240 1.617 0.910 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 Bödmódstadir Efri Reykir S-24 Reykholt S-1 Reykjaból S-1 0.0 112.0020 0.446 1.004 <0.0 25.245 0.0 7.00 109.01 0.32 1.87 4.0 264.802 <0.15 4.28 11.29 4.0020 Well Cu Ga Ge Hg I Li Mn Mo Ni P 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 0.021 <0.004 <0.295 <0.2 31.87 1.0 188.393 0.271 0.44 64.70 2.08 <1 1.0020 <0.0020 0.72 4.0020 <0.00 292.0 278.260 0.96 5.) Sample <0.20 21.09 6.773 0.94 10.027 0.0020 0.631 3.0 3840.24 0.3 23.754 152.05 <0.20 4.18 1.50 15.0 3930.9 29.271 0.17 3.23 1.010 0.7 10.257 0.540 0.531 0.116 0.007 0.57 8.1 42.241 0.078 <0.2 47.05 <0.80 4.20 11.0020 0.1 0.01 0.10 8.003 <0.9 40.30 <10 13.Table A.1 22.05 5.003 <0.0 33.0 2570.107 0.87 3.0 91.966 0.2 24.322 0.3 13.02 1.526 0.718 0.017 0.0 2590.663 1.

610 0.780 0.05 <0.0005 <0.470 16.05 <0.5 <0.002 0.00 8140.05 <0.060 1.05 <0.020 5.002 <0.74 3.00 7.005 <0.639 1.33 8050.80 9.0 18.485 0.720 0.130 2.05 <0.019 <0.046 0.095 0.021 0.147 0.890 0.6 137.002 <0.2 19.1: (cont.750 0.012 0.781 0.002 <0.002 <0.310 8.854 1.05 <0.005 8.210 2.570 5.0005 <0.05 <0.590 2.0 127.) Sample Well Rb Sb Sn Sr Th Ti Tl U V W Zn 96 <0.110 9.510 0.178 0.499 1.5 0.0005 <0.002 <0.190 6.2 0.828 0.065 0.18 2.100 2.00 7660.05 <0.05 <0.350 4.00 7820.320 9.002 <0.12 1.0 71.599 2.174 0.0005 <0.002 <0.0 210.50 10.170 0.005 0.301 0.577 1.85 3.05 2.41 2.150 <0.236 1.006 0.055 0.392 0.470 6.93 12.170 1.410 2.015 0.05 <0.719 <0.730 1.005 0.0 121.05 <0.5 <0.811 0.930 5.0005 <0.730 5.020 0.002 <0.700 0.005 0.990 4.270 2.410 3.10 5.00 8410.154 0.2 3020.0005 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 Bödmódstadir Efri Reykir S-24 Reykholt S-1 Reykjaból S-1 0.0005 <0.5 <0.002 <0.020 2.921 1.480 5.505 0.0005 <0.00 9010.28 1.0005 <0.245 0.640 1.790 <2 3.019 <0.05 <0.190 1.0005 <0.005 <0.070 2.0005 <0.310 8.0005 <0.20 28.198 0.05 <0.05 <0.272 0.544 0.72 16.300 0.770 2.350 0.011 0.05 <0.8 161.5 0.0 4150.7 24.05 <0.02 <0.005 <0.6 30.150 0.770 7.002 <0.890 1.005 <0.312 0.068 0.440 8.02 <0.02 <0.008 0.002 <0.87 1.002 <0.23 2.633 2.5 <0.031 0.200 4.0 184.0 3290.4 1.240 6.940 4.5 <0.650 6.002 <0.509 0.664 0.002 <0.0 3050.870 6.310 0.00 8160.05 <0.020 1.90 22.05 <0.153 0.140 4.030 1.848 .600 <0.840 1.760 3.060 4.676 0.005 <0.940 17.880 0.707 2.137 0.097 0.400 0.00 11.6 104.158 1.0 113.42 5.246 0.214 1.87 2.077 0.840 0.1 0.750 4.910 1.120 1.680 1.870 6.220 4.064 0.011 0.464 0.02 <0.0 152.0 206.0 124.002 <0.005 <0.19 2.844 <0.020 0.760 2.0 142.0 3080.850 1.730 0.05 <0.884 1.060 0.880 1.600 0.992 0.05 <0.05 <0.410 9.0 97.0005 <0.602 1.210 2.400 1.970 0.0 167.0 3220.017 0.002 <0.640 4.97 6.0 173.005 0.210 0.155 0.0005 <0.20 2.Table A.0 150.0 3020.692 11.0005 <0.631 <0.880 7.05 <0.002 <0.897 0.0005 <0.02 <0.130 0.002 <0.620 6.500 4.500 5.0 196.16 0.0005 <0.002 <0.5 <0.560 6.009 0.324 0.0005 <0.589 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 <0.140 0.150 0.334 0.163 0.5 <0.70 16.0 339.680 1.480 5.02 <0.000 4.283 0.007 <0.162 0.0005 <0.960 1.141 0.052 0.370 0.746 0.002 <0.0 4200.524 0.900 0.54 0.002 <0.55 32.05 <0.006 <0.002 <0.015 0.440 4.0005 <0.0005 <0.075 0.432 0.0 143.90 6.850 4.002 <0.002 <0.002 <0.0005 <0.0005 <0.254 0.300 50.5 <0.000 3.00 9120.005 <0.492 1.015 <0.563 0.060 2.16 2.444 0.320 4.653 <0.010 7.050 6.003 93.510 3.0005 <0.05 <0.19 0.283 0.0 176.080 4.859 0.506 0.02 <0.751 1.570 1.34 <0.0005 <0.200 0.5 <0.0 153.221 0.870 5.0005 <0.0005 <0.002 <0.100 3.05 <0.0 93.05 <0.05 <0.210 3.030 3.590 3.147 0.05 <0.0 156.002 <0.002 <0.540 0.160 3.923 0.2 0.090 1.970 9.272 0.05 <0.972 1.02 <0.880 <2 2.011 0.0 245.002 <0.005 <0.005 0.0005 <0.720 5.

82 5.0001 <0.001 <0.1 43.140 1.002 <0.501 35.168 0.236 0.001 <0.0 342.100 <0.9 35.005 <0.060 0.5 27.200 6.002 <0.7 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 Reykjaból 0.0 98.003 <0.055 0.001 <0.730 0.002 <0.010 <0.99 3.001 <0.922 0.0001 <0.710 6.7 183.292 <0.0001 <0.34 2.187 0.252 0.021 4.202 2.017 0.006 0.10 7.1 25.050 <0.0001 <0.043 0.740 113.95 9.5 17.649 1.003 <0.022 0.395 0.359 1.325 0.915 0.008 <0.0001 <0.005 0.022 0.689 0.033 0.76 147.0001 <0.001 0.015 0.051 <0.300 0.04 2.83 0.0001 <0.142 0.309 1.065 0.1 55.54 4.001 <0.317 0.001 <0.0011 CHAPTER A.346 1.0 66.045 0.001 <0.4 As Au B Ba Cd Co Cr Cs Sample Well Ag <0.339 0.1 30.125 <0.050 <0.001 <0.670 1.002 0.023 0.970 0.001 <0.756 0.002 <0.89 4.001 <0.660 0.0001 <0.0010 <0.65 5.010 0.244 6.005 <0.017 0.002 0.030 0.485 0.0001 <0.450 0.001 <0.735 0.447 0.010 0.002 0.1 9.007 0.005 <0.001 <0.005 <0.0001 <0.110 0. Concentrations in µg/kg Al 84.0001 <0.005 <0.0001 <0.0001 <0.050 <0.45 5.005 0.259 0.840 0.050 <0.394 1.21 2.510 11.0001 <0.104 0.004 <0.001 <0.150 0.240 2.005 0.4 169.0001 <0.001 <0.245 0.015 0.001 0.4 28.13 9.79 3.7 32.64 12.008 <0.050 <0.050 1.001 <0.489 0.0001 <0.8 23.001 <0.520 8.089 0.002 0.7 51.003 <0.001 <0.0001 <0.203 0.0001 <0.272 0.0001 <0.002 <0.2: Trace element analyses of vapor samples from wet-steam and dry- steam wells.769 0.053 0.00 4.167 0.002 <0.232 0.359 0.19 4.001 <0.002 <0.620 0.050 <0.001 <0.0001 <0.001 <0.050 <0.016 0.001 <0.360 1.002 0.0001 <0.40 11.008 0.55 2.261 1.0 46.050 <0.068 <0.330 0.424 2.127 0.258 1.446 0.007 0.129 0.0001 <0.1 11.363 0.198 0.005 <0.050 0.41 3.7 23.002 <0.511 <0.002 <0.009 0.001 <0.294 0.193 0.681 5.030 0.002 <0.185 0.0001 <0.533 0.0 114.57 3.61 2.001 <0.175 0.433 0.050 <0.005 <0.050 <0.472 0.050 <0.001 <0.65 3.0001 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 0.186 <0.283 0.68 4.0001 0.0001 <0.000 9.250 0.90 6.72 8.090 0.150 0.267 0.002 0.142 0.600 0.003 0.0001 <0.050 <0.1 83.5 11.002 <0.068 0.900 <0.790 0.4 27.001 97 <0.006 0.800 31.0 172.171 0.002 <0.0001 <0.830 1.00 8.002 <0.001 0.060 1.0001 <0.765 0.80 5.180 0.500 2.005 <0.001 <0.10 6.001 <0.230 0.840 0.001 <0.318 0.005 <0.001 <0.0001 <0.002 <0.969 <0.169 0.175 0.384 0.005 0.083 0.005 0.10 1.43 3.178 0.050 0.553 0.693 1.461 0.920 12.0 7.007 <0.773 0.5 188.740 .056 <0.0001 <0.023 0.041 0.050 0.130 0.65 2.050 <0.0001 <0.002 <0.028 0.348 1.001 <0.0001 <0.613 0.001 <0.12 7.445 0.203 0.321 0.55 2.229 0.050 0.0001 5.0001 <0.008 <0.500 1.44 4.0001 <0.050 <0.0 27.014 0.241 0.177 0.0 74.050 <0.00 10.0001 <0.537 0.471 0.005 <0.350 1.90 9.8 18.061 0.8 22. 0.361 0.3 197.062 0.39 22.0001 <0.001 0.002 <0.002 <0.17 1.0 157.3 210.56 6.005 0.141 0.050 <0.001 0.9 24.002 0.050 0.007 <0.420 3.0 173.050 <0.050 <0.Table A.201 0.405 0.910 2.066 0.050 0.753 10.030 0.002 0.0001 <0.788 16.005 <0.002 <0.050 <0.002 0.360 0.003 3.8 22.001 <0.0 119.005 <0.

021 <0.050 <0.188 0.28 3.010 0.1430 0.300 0.80 1.730 0.0114 3.005 0.006 0.013 0.2: (cont.1680 0.100 <0.970 1.478 0.001 0.038 0.060 0.014 0.100 1.219 1.008 0.010 0.001 0.03 9.2810 0.201 0.391 0.105 <0.100 <0.910 7.050 <0.001 0.050 0.336 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 Reykjaból 0.008 0.700 1.0147 0.003 0.661 0.99 3.) Sample <0.760 1.278 0.090 0.233 1.022 0.6840 0.001 0.Table A.7500 1.001 <0.020 0.012 <0.9000 9.84 3.1710 2.088 0.050 <0.022 0.0915 0.408 17.013 0.173 0.0176 0.050 <0.080 0.1870 1.016 0.317 0.153 <0.130 0.1000 0.056 0.8000 1.178 0.012 0.100 <0.016 0.646 0.033 0.021 0.868 0.955 3.140 0.2880 0.050 <0.80 14.104 <0.040 0.0278 0.4900 0.894 2.647 0.050 <0.025 0.50 13.80 58.050 <0.004 0.78 3.26 6.100 0.146 0.2400 0.018 0.00 5.063 0.50 5.008 <0.029 0.096 0.887 1.100 0.1040 0.1570 0.008 0.02 2.362 0.154 1.290 0.475 2.80 4.036 0.010 0.473 <0.060 0.114 0.014 0.609 0.10 12.0827 0.816 0.109 0.181 0.217 0.151 0.882 0.025 0.136 0.012 0.013 0.060 0.100 <0.217 0.0240 0.050 <0.001 <0.050 <0.0773 0.050 <0.100 0.050 <0.045 0.018 0.048 0.71 25.038 0.049 0.011 0.032 0.006 0.043 0.060 0.030 0.1800 .164 0.517 1.491 3.061 0.100 0.019 0.66 10.045 0.0180 0.4930 0.510 <0.007 0.560 0.039 0.037 0.043 0.011 0.32 0.140 0.023 0.50 5.017 0.018 <0.340 <0.2700 0.007 0.043 0.102 <0.100 <0.100 <0.102 0.490 2.059 2.420 0.100 <0.177 0.427 0.8700 0.000 0.6280 128.89 2.035 0.1060 0.108 0.119 <0.66 2.013 0.0731 11.477 0.010 0.099 15.95 7.026 0.437 0.050 <0.057 0.100 <0.026 0.049 0.036 0.050 0.650 7.460 8.578 1.100 0.348 <0.406 0.723 1.157 0.050 Well Cu Ga Ge Hg Li Mn Mo Ni Pb 0.630 0.034 0.300 0.10 0.806 0.033 0.014 0.040 0.2940 0.050 0.0000 1.145 0.745 0.050 <0.100 0.40 1.025 0.037 0.050 0.050 <0.100 0.041 0.354 0.714 0.055 0.250 0.57 1.030 0.050 <0.041 0.145 0.6600 1.100 <0.41 4.076 0.808 0.021 0.610 0.061 0.585 0.173 <0.016 0.100 0.32 5.0506 0.007 0.014 0.004 0.47 15.015 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 0.1270 0.896 0.055 0.80 2.009 0.017 0.47 14.196 0.30 2.051 0.026 0.037 0.506 0.40 7.011 0.350 0.679 <0.160 0.031 0.184 0.470 1.0233 0.436 0.310 383.432 0.001 0.035 0.065 0.050 <0.100 1.100 0.008 0.050 <0.40 2.104 0.3700 0.460 0.001 0.588 1.117 <0.624 12.091 0.050 <0.354 0.000 0.100 0.253 1.100 <0.018 <0.027 0.328 0.068 <0.56 42.015 0.024 0.2520 0.488 0.009 0.88 4.93 8.015 0.90 3.011 0.1950 1.528 0.1260 0.16 11.034 0.190 0.188 <0.99 6.343 0.760 2.95 41.55 1.036 0.100 <0.533 0.063 0.018 0.010 0.

353 0.0005 <0.026 0.0170 0.420 0.010 <0.380 1.005 <0.0249 0.0005 0.521 1.012 CHAPTER A.005 <0.1130 0.0005 <0.010 0.0005 <0.0742 0.0005 <0.0144 0.0633 0.300 7.0005 <0.005 <0.500 4.330 0.177 0.350 3.0621 0.241 0.3210 0.005 <0.470 6.0291 0.0005 <0.131 0.106 0.0544 0.005 <0.0555 0.0064 0.0149 0.0005 <0.244 0.0334 0.169 0.0005 <0.005 <0.0866 0.010 10.005 <0.0005 <0.209 0.836 0.300 <0.0579 0.005 <0.544 0.005 <0.0648 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 Reykjaból 1.345 0.010 <0.950 2.703 0.0355 0.200 0.710 5.0005 <0.530 1.0005 <0.500 2.010 <0.460 3.0179 0.010 <0.910 4.089 0.0312 <0.010 0.424 1.350 1.0005 <0.656 0.0005 <0.790 0.0539 0.880 18.800 2.010 <0.040 3.0482 0.010 <0.005 0.005 <0.0571 0.330 4.005 <0.790 4. 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 0.0849 0.320 0.720 4.210 5.0596 0.0005 <0.051 0.0470 0.0005 <0.040 0.0303 0.1060 0.010 <0.005 <0.0612 0.0005 <0.010 <0.430 15.360 0.010 <0.500 9.5150 0.0005 <0.0508 0.210 0.0005 <0.018 0.0583 0.005 <0.280 5.059 0.0123 0.0777 0.121 0.090 2.005 <0.097 0.0188 0.005 <0.951 1.674 2.110 5.200 0.0106 0.010 <0.130 0.005 <0.499 7.050 3.Table A.010 <0.542 3.0395 0.315 <0.539 0.300 8.1300 0.0577 0.721 0.0284 0.650 1.0005 0.200 0.231 0.005 <0.005 <0.0005 <0.0829 0.106 0.005 <0.010 <0.0046 1.120 0.190 0.0186 0.640 1.069 0.010 <0.0102 0.000 10.0591 2.005 <0.0336 0.0005 <0.110 0.005 <0.300 2.436 0.010 <0.010 <0.0005 <0.1010 0.090 2.000 0.005 <0.700 0.0005 <0.281 2.010 <0.101 0.0005 <0.005 <0.735 1.0825 0.584 13.3030 0.670 2.860 5.0005 <0.0005 <0.362 0.730 10.0758 0.005 <0.0191 0.010 <0.010 <0.0005 <0.021 0.530 6.0601 0.245 0.054 0.0737 0.414 0.6750 0.187 0.000 0.350 3.005 <0.0005 <0.0175 0.086 0.185 2.119 0.0005 <0.005 <0.0005 <0.281 0.0005 0.590 3.010 <0.280 0.560 5.005 <0.005 <0.0732 0.134 0.010 <0.0640 0.702 0.0005 <0.494 6.380 <0.441 0.005 <0.100 0.093 0.950 7.010 <0.457 3.0005 <0.005 <0.0007 <0.911 0.010 <0.155 2.010 <0.010 <0.005 <0.540 9.010 <0.150 5.0050 0.540 4.385 0.0005 <0.200 17.0219 0.970 .1250 0.0054 0.0371 0.010 <0.181 0.663 0.437 0.355 21.0005 <0.0448 0.224 0.430 4.005 <0.010 <0.400 1.0005 <0.930 1.010 <0.1630 0.160 7.0008 <0.120 1.010 <0.0395 0.520 0.010 <0.010 <0.4780 0.385 0.000 4.020 <0.010 <0.120 0.500 9.090 0.005 <0.570 1.862 0.0236 0.010 <0.005 <0.312 2.475 0.0149 0.3600 0.130 0.010 <0.360 8.1090 0.510 7.640 0.913 0.065 0.0548 0.005 <0.0487 0.070 0.0727 0.0295 0.000 0.005 <0.) Sample Well Rb Sb Sr Te Ti Tl U V Zn 99 <0.024 0.999 0.091 0.540 0.910 3.0005 <0.046 0.005 <0.0368 0.892 0.111 11.260 3.890 0.0223 0.530 0.0620 0.2: (cont.0102 0.005 <0.117 0.010 <0.320 0.640 9.010 <0.010 <0.047 0.0569 0.0277 0.0195 0.0005 <0.0089 0.

.

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