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Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur Erlangung des Doktorgrads der Naturwissenschaften (Dr. rer. nat.) am Fachbereich Geowissenschaften Universität Bremen vorgelegt von Budi Joko Purnomo Bremen March, 2015

Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

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Page 1: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

Geothermal systems in the Sunda volcanic island arc

Investigations on the islands of Java and Bali,

Indonesia

Dissertation

zur Erlangung des Doktorgrads der Naturwissenschaften (Dr. rer. nat.)

am Fachbereich Geowissenschaften

Universität Bremen

vorgelegt von

Budi Joko Purnomo

Bremen

March, 2015

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Gutachter:

Prof. Dr. Thomas Pichler

Prof. Dr. Peter La Femina

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E r k l ä r u n g

Hiermit versichere ich, dass ich

i. die Arbeit ohne unerlaubte fremde Hilfe angefertigt habe,

ii. keine anderen als die von mir angegebenen Quellen und Hilfsmittel

benutzt haben und

iii. die den benutzten Werken wörtlich oder inhaltlich entnommen Stellen

als solche kenntlich gemacht habe.

___________________ ,den ________________

______________________________

(Unterschrift)

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TABLE OF CONTENTS

Abstract .......................................................................................................................... ix

Zusammenfassung ....................................................................................................... xi

I. Introduction ................................................................................................................ 1

I.1. Thesis outline ................................................................................................................. 2

I.2. Research objectives ...................................................................................................... 4

I.3. Theoretical backgrounds .............................................................................................. 5

I.3.1. An overview of geothermal system ...................................................................... 5

I.3.2. Geothermal manifestations ................................................................................... 8

I.3.3. Geothermometry ..................................................................................................... 9

I.3.4. Boron isotope ........................................................................................................ 14

II. Geological setting, sampling and analyses ......................................................... 17

II.1. Geological setting ....................................................................................................... 17

II.2. Sampling and analyses .............................................................................................. 20

III. Geothermal systems on the island of Java, Indonesia ..................................... 23

Abstract ................................................................................................................................ 24

III.1. Introduction ................................................................................................................. 25

III.2. Sampling locations .................................................................................................... 25

III.3. Results ........................................................................................................................ 26

III.4. Discussion .................................................................................................................. 30

III.4.1. General considerations about geothermal systems on Java....................... 30

III.4.2. Geothermometry................................................................................................. 37

III.4.3. The heat sources of the fault-hosted geothermal systems .......................... 41

III.4.4. Oxygen and hydrogen isotope considerations .............................................. 44

III.5. Conclusions ................................................................................................................ 46

IV. Boron isotope variations in geothermal systems on Java, Indonesia ............49

Abstract ................................................................................................................................ 50

IV.1. Introduction ................................................................................................................ 51

IV.2. Sampling locations .................................................................................................... 52

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IV.3. Results ........................................................................................................................ 52

IV.4. Discussion .................................................................................................................. 56

IV.4.1. Boron in thermal waters and seawater input ................................................. 56

IV.4.2. The δ11B of acid sulfate and acid chloride crater lakes ................................ 60

IV.4.3. Processes affecting the δ11B value of thermal waters ................................. 62

IV.4.4. The δ11B of fault-hosted and volcano-hosted geothermal systems ........... 66

IV.5. Conclusions ................................................................................................................ 66

V. Geothermal systems on the island of Bali, Indonesia ........................................ 69

Abstract ................................................................................................................................ 70

V.1. Introduction.................................................................................................................. 71

V.2. Geological setting ....................................................................................................... 72

V.3. Results ......................................................................................................................... 74

V.4. Discussion ................................................................................................................... 75

V.4.1. Geochemistry of thermal waters ....................................................................... 75

V.4.2. Phase separation and seawater input ............................................................. 82

V.4.3. Geothermometry ................................................................................................. 84

V.4.4. Oxygen and hydrogen isotope considerations ............................................... 86

V.5. Conclusions ................................................................................................................. 88

VI. Conclusions and outlook ...................................................................................... 91

VI.1. Conclusions ................................................................................................................ 91

VI.2. Outlook........................................................................................................................ 92

Acknowledgements ..................................................................................................... 95

References .................................................................................................................... 97

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Abstract Geothermal systems located in a volcanic island arc are generally considered to be

exclusively influenced by Quaternary volcanic activities. Giving the complex geological

setting on the island of Java, the geothermal systems probably is not that simple. The

subduction of the Indo-Australian plate beneath the Eurasian plate formed three

volcanisms, Paleogene, Neogene and Quaternary, and faults. The subduction also

thinned the crust of the southern part of the island due to uplift and erosion. The

presence of geothermal systems hosted by a volcano and a fault zone, thus named as

volcano-hosted and fault-hosted, respectively, give an opportunity to study their

different physicochemical characteristics. The influence of Quaternary magma in the

fault-hosted geothermal systems distributed in two different volcanic belts, Quaternary

and Tertiary, were examined. Additionally, the contrast signatures of boron isotope

between two different crater lakes, acid sulfate and acid chloride, which likely has

been overlooked, were determined. Finally, the possibility of a carbonate sedimentary

basement as the host-rock of geothermal systems on the volcanic island of Bali was

investigated.

The physicochemical properties of geothermal waters were used in this study,

including major anion and cation, trace elements and stable isotope (2H and 18O). The

fractionation characteristics of boron isotope were used for further investigation on the

contrasting fault-hosted and volcano-hosted geothermal systems. The distinct boron

isotope composition of seawater was applied to confirm seawater input in some

geothermal systems.

The volcano-hosted and fault-hosted geothermal systems were chemically different:

the former had higher HCO3- concentrations and Mg/Na ratios compared to the latter.

This condition was caused by CO2 magmatic gas supply in the volcano-hosted, which

was insignificant or absent in the fault-hosted geothermal systems. The CO2 gas

supply produces slightly acid HCO3- thermal waters, hence together with its slower

ascent due to the longer flow path would elevate the Mg2+ content. Geothermal

systems hosted by faults located in the Quaternary magmatic belt were clearly

supplied by magmatic fluid, thus could not be classified as a fault-hosted geothermal

system. Although the Quaternary magmatic fluid input in the fault-hosted geothermal

systems located in the Tertiary volcanic belt are absent, the reservoir temperature and

lithium (Li) enrichment indicated a Quaternary magmatic heat source for the fault-

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hosted geothermal systems of Cilayu and Cisolok. Meanwhile, the other fault-hosted

geothermal systems are likely heated by a deep-seated magma. Magmatic fluid input

enriched the 2H and 18O isotope of some volcano-hosted geothermal systems,

something that was not identified in any of the fault-hosted geothermal systems.

Boron isotope further distinguished the volcano-hosted and fault-hosted geothermal

systems. The magmatic fluids input, favorable for minerals precipitation, and longer

thermal water ascent in the former geothermal system promoted δ11B enrichment. In

contrast, the fast thermal water ascent and absence of magmatic fluids input

maintained a light δ11B signature in the fault-hosted geothermal systems. Two

different types of thermal crater lakes, acid sulfate and acid chloride, had a contrast in

B isotope compositions. The acid chloride crater lake had a light δ11B value

representing magmatic origin, while the acid sulfate crater lakes had heavier δ11B

values, produced by a sequence of processes: vapor phase separation in the

subsurface, followed by evaporation and B adsorption into clay minerals on the

surface. B isotope confirmed seawater input in two fault-hosted geothermal systems:

Parangtritis and Krakal.

The geothermal systems on Bali were studied using the physicochemical properties of

surface thermal waters. The (Ca2+ + Mg2+)/HCO3- of approximately 0.4 and the visual

absence of 18O isotope enrichment ruled out a carbonate host rock type, instead the

K/Mg ratios indicated water-rock interaction with a calc-alkaline magmatic rocks. The

well correlation of HCO3- content with Ca2+, Mg2+, Sr2+ and K+ revealed water-rock

interaction influenced by carbonic acid. The B/Cl ratios revealed phase separation for

the Bedugul and Banjar geothermal systems. The heavy δ11B of +22.5 ‰ and a Cl/B

ratio of 820 confirmed seawater input in the Banyuwedang geothermal system.

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Zusammenfassung Es wird allgemein angenommen, dass Geothermale Systeme in vulkanischen

Inselbögen ausschließlich durch vulkanische Aktivität angetrieben werden. Die

komplexe geologische Struktur der Insel Java legt nahe, das dieses Erklärungsmodell

dort wahrscheinlich zu einfach ist. Durch Subduktion der indo-australischen unter die

eurasische Platte verursachter Vulkanismus, sowie dadurch entstandene

Grabensysteme, lassen sich chronostratigraphisch dem Paläogen, Neogen und

Quartär zuordnen. Die Mächtigkeit der Kruste ist durch Heraushebung und Erosion

während des Subduktionsprozesses verringert. Die geographische Nähe

geothermaler Systeme die sich an Vulkanen („volcano-hosted“) oder in Grabenbrüche

(„fault-hosted“) befinden, erlaubt es, die unterschiedlichen physiko-chemischen

Eigenschaften beider Systeme zu untersuchen. In den vorliegenden Arbeiten wurden

die Auswirkungen quartären Magmas auf “fault-hosted” geothermale Systeme

untersucht. In zwei Kraterseen wurde die Isotopenverteilung des Elements Bor (δ11B)

verglichen und die Konzentrationen von gelöstem Sulfat und Chlorid, die in vorherigen

Arbeiten häufig nicht betrachtet werden, bestimmt. Zusätzlich wurde untersucht, ob

karbonatisches Sediment als Untergrund in geothermalen Systemen der vulkanisch

entstandenen Insel Bali möglich ist.

Die physiko-chemischen Eigenschaften geothermalen Wassers, einschließlich

Anionen- und Kationenverteilungen, Konzentrationen von Spurenelementen sowie

Isotopengehalte (δ2H, δ18O) wurden untersucht. Die Isotopenverteilung des Elements

Bor (δ11B) wurde zur weiteren Charakterisierung der Unterschiede von „volcano-

hosted“ und „fault-hosted“ geothermalen Systemen genutzt. Die bekannte

Konzentration des δ11B in Meerwasser wurde zusätzlich genutzt, um das Einströmen

von Meerwasser in einige geothermale Systeme zu bestätigen.

„Volcano-hosted“ und „fault-hosted“ geothermale Systeme lassen sich aufgrund ihrer

chemischen Eigenschaften unterscheiden. Erstere haben höhere HCO3-

Konzentrationen und Mg2+/Na+-Verhältnisse verglichen mit Letzteren. Dieser Befund

lässt sich auf den Einfluss des CO2-Gehalts in magmatischen Gasen zurückführen,

der in “fault-hosted” Systemen vernachlässigbar gering bzw. nicht vorhanden ist.

Durch CO2-Eintrag wird in geothermalem „volcano-hosted“ Systemen

Hydrogenkarbonat gebildet und durch das dissoziierende Proton eine Senkung des

pH-Werts verursacht. Aufgrund der, durch die geologische Architektur bedingten,

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verlängerten Passage durch das Gestein erhöht sich der Mg2+-Gehalt. Die durch

Grabenbildung in quartären Vulkangürteln entstandenen geothermalen Systeme

werden eindeutig durch Wärmekonvektion magmatischer Flüssigkeit gespeist, was

dazu führt, dass diese nicht als „fault-hosted“ geothermales System im eigentlichen

Sinn beschrieben werden können. Obwohl ein Einströmen Quartär gebildeten

Magmas in die “fault-hosted” geothermalen Systeme, Cilayu und Cisolok, die in einem

im tertiär gebildeten Vulkangürtel lokalisiert sind, nicht gezeigt werden kann, kann

durch die Reservoir-Temperatur sowie die Anreicherung von Lithium (Li) Quartär

entstandenes Magma als Wärmequelle angenommen werden. Wahrscheinlich ist der

Ursprung anderer “fault-hosted” Systeme dieser Region die Wärme tiefliegender

Magmakörper. Durch magmatischen Einfluss werden 2H- und 18O-Isotope im Wasser

von “volcano-hosted” Systemen angereichert. Dieses Phänomen konnte in keinem

der “fault-hosted” Systeme beobachtet werden.

Eine weitere Möglichkeit der Unterscheidung geothermaler Systeme zwischen

“volcano-hosted” und “fault-hosted“ besteht in der Messung des δ11B. Durch

magmatische Flüssigkeit wird die Ausfällung von Mineralien unterstützt, und die oben

beschriebene längere Passage führt zu einer höheren Anreicherung von δ11B. Im

Gegensatz dazu führt eine schnelle Passage ohne Einströmen magmatischer

Flüssigkeit nur zu einer abgeschwächten Konzentration von δ11B in „fault-hosted“

geothermalen Systemen. Durch geothermale Systeme entstandene Kraterseen

können aufgrund ihrer δ11B-Konzetration der Genese charakterisiert werden.

Kraterseen mit hoher Cl--Konzentration haben einen niedrigen δ11B-Wert und lassen

auf magmatischen Ursprung schließen, während Kraterseen mit einer hohen Sulfat-

Konzentration ebenfalls einen hohen δ11B-Wert aufweisen aber im wesentlichen mit

Wasser meteorischen Ursprungs gefüllt sind. Dem hohen δ11B-Wert liegt der Ablauf

folgender Prozesse zugrunde: unterhalb der Oberfläche kommt es zu einer Trennung

der Dampfphase, durch anschließende Verdunstung adsorbiert Bor an Tonmineralien

der Oberfläche. Die hohen δ11B Werte bestätigen den Meerwassereintrag in die „fault-

hosted“ geothermalen Systeme von Parangtritis und Krakal.

Geothermale Systeme der Insel Bali wurden anhand der physiko-chemischen

Eigenschaften des geothermalen Oberflächenwassers untersucht. Ein ([Ca2+]+

[Mg2+])/HCO3- -Verhältnis von ~0,4 und eine nicht vorhandene Anreicherung von δ18O

schließen den Einfluss von Karbonat-Sediment aus. Die in den Untersuchungen

bestimmten K+/Mg2+-Verhältnisse deuten hingegen auf eine Einbeziehung von

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basischer Magma in den Reaktionskreislauf. Die beobachteten hohen Korrelationen

der HCO3- Gehalte mit Ca2+, Mg2+, Sr2+ und K+ lassen auf eine Kohlensäure vermittelte

Reaktion an der Phasengrenze Wasser-Stein schließen. Eine Phasentrennung in den

geothermalen Systemen von Bedugul und Banjar konnten durch die B/Cl-Ratios

gezeigt werden. Ein δ11B von +22.5‰ und ein Cl/B-Verhältnis von 820 bestätigten

den Meerwassereintrag in das geothermale System von Banyuwedang.

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INTRODUCTION

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I. Introduction Indonesia is known for having the biggest geothermal resources in the world,

mostly spread along the Sunda volcanic island arc, which extends from west to east,

from the island of Sumatera to the island of Damar. The island of Java located in the

middle of the island arc is the most geothermal exploited area due to the huge

demand of electricity. Based solely on the geological association, hosted by either a

volcano or fault, geothermal systems on Java can be divided into volcano-hosted and

fault-hosted, respectively. Concerning their potential as an electricity power source, to

date the geothermal development program has been only focused on the volcano-

hosted geothermal systems due to the assumption of low potential energy in the fault-

hosted geothermal systems.

Apart from the energy issue, the presence of fault-hosted geothermal systems

on Java provides an essential opportunity to determine the influence of the

Quaternary volcanoes to the systems. In a volcanic islands arc, the geothermal

systems are considered to be simply dominated by the Quaternary volcanic activities.

Therefore, less attention is given to the fault-hosted geothermal system located in this

geological setting. Several fault-hosted geothermal systems distributed in a

Quaternary volcanic arc, for instances in the Liquine-Ofqui fault zone, Chile and in the

Southern Apennines, Italy (Alam et al., 2010; Italiano et al., 2010), indicated

contrasting geochemical processes compared to volcano-hosted geothermal systems.

In the fault-hosted system deep circulated groundwater is simply conductive heated,

while in the volcano-hosted system involves condensation of volcanic steam (Alam et

al., 2010). On Java the geothermal systems are probably more complex due to the

geological setting. The island is mainly developed by three main volcanisms:

Paleogene volcanism formed the Tertiary volcanic belt, distributed along the southern

part, followed by Neogene volcanism shifted northward to the middle of the island and

finally Quaternary volcanism emerged along the Neogene volcanic (Soeria-Atmadja et

al., 1994). The relatively impermeable Tertiary volcanic rocks might inhibit the extent

of Quaternary magmatic fluids flow. The subduction in the south of Java developed

several major and minor faults that are distributed in the two volcanic belts, Tertiary

and Quaternary. The northward plates subduction has uplifted the southern part of the

island, followed by erosion, hence produced a thinner crust (Clements et al., 2009;

Hall et al., 2007). The thin crust enables deep penetrated groundwater through fault to

extract the heat. Considering these geological settings, different characteristics

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INTRODUCTION

2

between fault-hosted located in the Quaternary volcanic belt and the Tertiary volcanic

belt could be expected.

Two characteristics of boron (B) isotope fractionation might be beneficial for

further investigation on the contrast between volcano-hosted and fault-hosted

geothermal systems. Those characteristics are 1) the relatively conservative at

temperatures >65 °C (Aggarwal and Palmer, 1995; Palmer et al., 1987) and 2) the

significant fractionation due to B adsorption/coprecipitation onto clay, iron oxide and

calcite and evaporate minerals (Agyei and McMullen, 1968; Hemming and Hanson,

1992; Lemarchand et al., 2007; Oi et al., 1989; Palmer et al., 1987; Schwarcz et al.,

1969; Spivack and Edmond, 1987; Swihart et al., 1986; Vengosh et al., 1991a;

Vengosh et al., 1991b; Vengosh et al., 1992). The fast ascent of fault-hosted thermal

water through a fault and the absence of magmatic fluids input should result in a light

δ11B signature. Conversely the slow ascent and the presence of magmatic fluids input

might be favorable for δ11B enrichment. Additionally the presence of two contrasting

thermal crater lakes, acid-sulfate and acid-chloride, on Java provide an opportunity to

determine their distinct boron isotope signatures, which likely has been overlooked so

far.

Finally, the study on the characteristic of volcano-hosted and fault-hosted

geothermal systems was extended to the volcanic island of Bali. Apart from this

objective, the island is an ideal location to investigate the role of a carbonate rock

basement to the geothermal systems. In such a geological setting, the carbonate rock

was identified hosting the geothermal systems instead of volcanic rocks, e.g., in

Vicano-Cimino and Sabatini-Tolfa (Cinti et al., 2011; Cinti et al., 2014).

I.1. Thesis outline This thesis consists of six chapters with three main bodies. Chapter 1,

Introduction, provides the context of the research and overview of some theoretical

backgrounds. Chapter 2 explains the geological setting of the study areas, sampling

and analytical methods. Chapter 6 presents the overall conclusion answering the

research objectives and outlook related to the results of this study. Below the three

main chapters and my contributions on every chapter are briefly described.

Chapter 3

This chapter provides a classification of the geothermal systems on Java. The

systems were classified into volcano-hosted and fault-hosted based solely on their

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INTRODUCTION

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geological association, either in a volcano or fault zone. Subsequently the

physicochemistry of thermal waters clearly divided the two geothermal systems. The

possible role of Quaternary magma as a heat source for fault-hosted geothermal

system was investigated based on the reservoir temperatures and trace element

enrichments.

This research is published in Journal of Volcanology and Geothermal Research

(Purnomo, B.J. & Pichler, T., 2014).

My contributions on this article are:

- sampling and measurement of some physicochemical parameters in the field,

- preparing samples for laboratory analyses,

- quality control on the laboratory results,

- data interpretation, and

- writing the first draft of the published paper.

Chapter 4

In this chapter boron isotope was used to further investigate the distinct

geochemical characteristics between volcano-hosted and fault-hosted geothermal

systems. The contrast in B isotope signatures between two distinct thermal crater

lakes, acid-sulfate and acid-chloride, was determined. Boron isotope was also applied

to confirm seawater input in some geothermal systems on Java.

A part of the result was presented as a poster (Purnomo, B.J., Pichler, T. and

You, C.-F, 2014) in American Geophysical Union (AGU) Fall Meeting 2014. The final

version of this chapter has been submitted to Geochimica et Cosmochimica Acta

(Purnomo, B.J., Pichler, T. and You, C.-F, submitted in November 2014, current

status: under review).

My contributions on this article are:

- sampling and measurement of some physicochemical parameters in the field,

- preparing samples for laboratory analyses,

- data interpretation, and

- writing the first draft of the submitted manuscript.

Chapter 5

This chapter presents an overview of geothermal systems on Bali that were

classified into a volcano-hosted and fault-hosted. However, the main focus is to

investigate the host-rock, either carbonate or volcanic, considering the Quaternary

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INTRODUCTION

4

volcanoes have a carbonate sedimentary basement. The processes that govern the

chemical composition of the surface thermal waters, seawater input and

geothermometry of the reservoir were also determined.

The result of this study has been submitted to Journal of Volcanology and

Geothermal Research (Purnomo, B.J. and Pichler, T., submitted in February 2015,

current status: under review).

My contributions on this article are:

- sampling and measurement of some physicochemical parameters in the field,

- preparing samples for laboratory analyses,

- quality control on the laboratory results,

- data interpretation, and

- writing the first draft of the submitted manuscript.

I.2. Research objectives The main purpose of this study is to characterize the system of geothermal

fields located in the Sunda volcanic island arc. The geothermal system probably is

complicated by the complex geological setting formed by the dynamic plates

boundary. The presence of multiple volcanisms, fault zones and thin crust potentially

influence the geothermal system, instead of exclusively dominated by Quaternary

volcanic activities. Several specific objectives of the study are:

to define the geothermal systems into a volcano-hosted or fault-hosted systems,

to calculate the reservoir temperatures of the geothermal systems,

to characterize the contrast between volcano-hosted and fault-hosted

geothermal systems, including the physicochemical processes and fluids origin,

to investigate the role of Quaternary volcanoes to the fault-hosted geothermal

systems,

to determine the possible heat sources of the fault-hosted geothermal systems,

to apply boron isotope for further investigation on the contrast between fault-

hosted and volcano-hosted geothermal systems,

to investigate the boron isotope signatures of two distinct crater lakes, acid-

sulfate and acid-chloride,

to confirm seawater input in some geothermal systems, considering the location

close to sea, and

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INTRODUCTION

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to determine the role of a carbonate sedimentary basement on the volcanic

island of Bali.

I.3. Theoretical backgrounds I.3.1. An overview of geothermal system

Geothermal system is a heat transfer process from the Earth’s crust to the

surface. Generally the heat transfer involve meteoric water, hence it is called as

hydrothermal system (Hochstein and Browne, 2000). A geothermal system consists of

three main components: 1) heat source, 2) reservoir and 3) water (e.g., Goff and

Janik, 2000; Kuhn, 2004). The heat sources for geothermal systems include magmas

within the crust, intracrustal nonmagmatic and conductive heat flow (Hochstein and

Browne, 2000). The first can present as a convective magma fluid input or conductive

heat transfer from cooling magma, the second is present due to the anomaly thermal

gradient in areas with relatively thin crust and the third is formed in the sedimentary

basin where thick sediments generate heat and overpressure (Goff and Janik, 2000;

Kuhn, 2004; Nicholson, 1993). Faulds et al. (2010) introduced a term of ‘amagmatic’

heat source for a deep-seated magma, to distinguish it with Quaternary magma.

Apart from those heat sources, back to the experiment by Byerlee (1978), a frictional

heat source was proposed. However, its presence in natural geothermal systems has

never been proved, hence it is referred to ‘the stress-heat flow paradox’ (Lachenbruch

and Sass, 1980).

Several classifications of geothermal systems have been proposed. Simply

based on the reservoir temperature geothermal system was classified into three

(Hochstein and Browne, 2000):

1) High temperature (T >225 °C),

2) Intermediate temperature (125 to 225 °C), and

3) Low temperature (T <125 °C)

However the range of temperatures in the classification is not rigid, for an instance

Benderitter and Cormy (1990) suggested a low temperature geothermal system

accounted for temperatures below 100 °C.

Considering the geology, hydrology and engineering, Goff and Janik (2000)

classified geothermal system into:

1) Young igneous systems

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INTRODUCTION

6

Geothermal system hosted by Quaternary volcanic or intrusion. This system

generally spreads along plate boundaries and spreading centers.

2) Tectonic systems

Geothermal system associated with anomaly heat flows due to the relatively thin

crust. The heat is extracted by a deep penetrated groundwater hosted by faults.

3) Geopressured systems

This geothermal system distributed in sedimentary basins. Subsidences and thick

sediments form the heat and overpressure.

4) Hot dry rock systems

The heat stored in an impermeable rock is extracted by injecting water to the rock,

subsequently the resulting thermal water is pumped out to the surface.

5) Magma tap systems

The geothermal system taps the heat of a shallow magma by circulating water.

Nicholson (1993) proposed a classification of geothermal systems based on:

heat transfer, temperature, fluid composition and topographic (Fig. 1.1). Heat transfer

divides geothermal system into two, dynamic and static systems. The former involves

circulation of fluids from depth, where meteoric water circulated into the depth, extract

heat, then ascend to the surface. Meanwhile, in the latter system the thermal fluid is

trapped in the deep strata. The dynamic geothermal systems are distributed in plate

boundaries and spreading centers, while the static system are located in tectonic

stabile areas, for instances in Russia, Eastern Europe and Australia. Considering the

geological setting of the study areas is a subduction zone, only the dynamic system is

further elaborated. The dynamic geothermal system is divided into a high temperature

system, generally associated with Quaternary magmas, and a low temperature

system, associated with conductive heat transfer of anomaly heat flow. The high

temperature system is classified into a liquid-dominated and a vapor-dominated based

on the dominant phase in the reservoir. The contrast topographic of the liquid-

dominated geothermal systems divides the system into a low-relief and a high relief

system. The former is hosted by a silicic volcano, while the latter by an andesitic

volcano, which is a typical of volcanic island arc.

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INTRODUCTION

7

Fig. 1.1. Geothermal system classification by Nicholson (1993).

Exclusively based on the geological setting, Saemundsson (2009) classified

geothermal systems into:

1) Volcanic-geothermal system

Geothermal system associated with volcanoes, heated by intrusion or magma.

2) Convective system

Geothermal system generated due to the deep circulation of meteoric water

through fractures, extracted heat from an anomaly high temperature gradient.

3) Sedimentary system

Geothermal system hosted by thick sedimentary layers, heated by regional

thermal gradient.

Working in a complex of major fault and Quaternary volcanic arc geological

setting in the Liquiñe-Ofqui Fault Zone (LOFZ), Alam et al. (2010) divided the

Geothermal system

dynamic (convective)

static (conductive)

high temperature

liquid- dominated

low-relief high-relief

low temperature

geopressured low temperature

vapor- dominated

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INTRODUCTION

8

geothermal systems into a volcanic type, associated with stratovolcanoes, and a

structural (non-volcanic) type, hosted by the faults. This classification is adopted in

this study, however, the terms of volcano-hosted and fault-hosted geothermal systems

are preferred. Volcano rather than volcanic is used to avoid confusion with volcanic as

a rock type, while fault is applied to clarify its geological structures.

Although a volcanic arc is generally dominated by volcano-hosted geothermal

systems, fault-hosted geothermal systems might be present, for instances in the

Liquine-Ofqui fault zone, Chile and in the Southern Apennines, Italy (Alam et al.,

2010; Italiano et al., 2010). In the fault-hosted geothermal system a deep circulated

meteoric water through faults is conductive heated, while the volcano-hosted

geothermal system involves condensation of volcanic steam (Alam et al., 2010). The

heat sources of fault-hosted geothermal systems could be a deep seated magma.

This was named as ‘amagmatic’ heat source to distinguish it with shallow magmas of

Quaternary volcanoes, as has been applied in the Great Basin, USA and Western

Turkey (Faulds et al., 2010).

I.3.2. Geothermal manifestations

The existence of a geothermal system in the subsurface can be recognized by

the surface features (manifestation), which include solfatara, fumarole, acid crater

lake, hot spring, mud pool, steaming ground and altered ground (Fournier, 1989;

Giggenbach, 1988; Giggenbach and Stewart, 1982; Goff and Janik, 2000;

Hedenquist, 1990; Henley and Ellis, 1983; Hochstein and Browne, 2000; Nicholson,

1993). These manifestations are formed by a sequence of processes that briefly can

be explained as follow (Giggenbach, 1988; Nicholson, 1993). Volatile magmas

contain gases, H2O, CO2, H2S, HCl and HF, rise and react with deep circulated

groundwater producing acid water. The acid water-rock interaction subsequently

consumes H+ to form a neutral-chloride water, which then ascend to the surface.

During the ascent separation of fluid phases might occur due to a rapid drop in

temperature and pressure. The remaining chloride water discharges as a neutral

chloride hot spring on the surface. In a low relief topography the water emerges above

the upflow zone, close to the acid sulfate and bicarbonate hot springs, while in the

high relief topography (stratovolcano) it discharges far away from the upflow zone to

the flank of stratovolcano (Fig. 1.2). Meanwhile, the vapor phase resulted by the

phase separation usually is rich in CO2 and H2S gases, hence the condensation and

reaction with O2-rich groundwater produce a slightly acid bicarbonate (HCO3-) water

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INTRODUCTION

9

and an acid sulfate (SO4-) water, respectively. In a vapor-dominated geothermal

system, thermal water ascends exclusively as a steam phase that rich in CO2 and H2S

gases, therefore, the resulting manifestations are mud pools, acid sulfate and

bicarbonate hot springs (Fig. 1.3).

A geothermal system generally produces three types of hot springs: 1) neutral

chloride, 2) acid sulfate and 3) bicarbonate waters, however, mixtures between the

individual groups are common (Hedenquist, 1990; Hochstein and Browne, 2000;

Nicholson, 1993; White, 1957). The composition of these thermal springs is controlled

by two main factors: 1) reservoir condition and 2) secondary processes during ascent.

Host-rock type, temperature, residence time and magmatic fluid input govern the

geothermal brines. The physicochemistry of thermal waters might change during the

ascent due to phase separation, minerals precipitation, adsorption/desorption, water-

rock interaction, groundwater dilution and seawater input (in a coastal area). The

chemical composition of a thermal spring records the physicochemical processes in

the subsurface. Chemically inert constituent (tracers), Cl, B, Li, Rb and Cs, can be

used to track the source, while chemically reactive species (geoindicators), e.g., Na,

K, Mg, Ca and SiO2, record the physicochemical processes during thermal water

ascent (Ellis and Mahon, 1977; Giggenbach, 1991; Nicholson, 1993).

I.3.3. Geothermometry Solute geothermometers are commonly applied to estimate the reservoir

temperature of a geothermal system, by using either the absolute concentration,

solute ratio or solute relation. The geothermometers were formulated based on the

temperature dependency of a mineral-fluid reaction in the reservoir. This is preserved

on the surface due to the slow re-equilibrium of the minerals in a low temperature

system (Fournier, 1977). The successful application of solute geothermometers for

hot springs relies on five basic assumptions: 1) exclusively temperature dependent

mineral-fluis reaction; 2) abundance the mineral and/or solute; 3) equilibrium reaction

in the reservoir; 4) no re-equilibrium; and 5) no mixing or dilution (Ellis, 1979; Fournier,

1977; Fournier and Truesdell, 1973; Nicholson, 1993; Truesdell, 1975). The last

assumption can be overcome if the extent of dilution can be calculated. Below, solute

geothermometers that were used in this study are listed.

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Fig.

1.2

. Con

cept

ual m

odel

of l

iqui

d-do

min

ated

geo

ther

mal

sys

tem

in h

igh

relie

f top

ogra

phic

(stra

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lcan

o) (a

dopt

ed fr

om

H

enle

y an

d E

llis, 1

983)

.

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INTRODUCTION

11

Fig. 1.3. Conceptual model of vapor-dominated geothermal system (adopted from Nicholson, 2000).

a) Silica geothermometer

Silica geothermometer is deducted from the solubility of quartz in certain

temperatures and pressures. The thermometer is based on the absolute silica

concentration and thus sensitive to secondary processes such as mixing, boiling and

precipitation (Fournier and Rowe, 1966). Several silica geothermometers were

established for different conditions, such as:

- No steam loss T (°C) = {1309 / (5.19 – log SiO2)} – 273 (Fournier, 1977)

- Max. steam loss T (°C) = {1522 / (5.75 – log SiO2)} – 273 (Fournier, 1977)

In low temperatures the silica content is attributed to the solubility of chalcedony,

cristobalite and amorphous silica (Arnorsson, 1970; Arnorsson, 1975; Fournier and

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INTRODUCTION

12

Rowe, 1962; Fournier and Rowe, 1966). Therefore, the silica geothermometer, for an

example chalcedony, is stated as:

- Chalcedony T (°C) = {1032 / (4.69 – log SiO2)} – 273 (Fournier, 1977)

The application of silica geothermometers for hot springs usually calculates

underestimation temperatures, close to the discharge temperature, due to dilution by

shallow water. This can be overcome by calculating the silica ‘parent’ using the silica

mixing model of Truesdell and Fournier (1977) (Fig. 1.4).

Fig. 1.4. Silica vs. enthalpy diagram for silica parent calculation based on Truesdell and Fournier (1977).

b) Na/K geothermometer

The Na/K geothermometer was calculated using the Na2+ and K+ ratios. The

thermometer was formulated based on the temperature-dependent reaction of ion

exchange between albite and K feldspar (Fournier, 1979; Giggenbach, 1988).

NaAlSi3O8 + K+ (aq) = KAlSi3O8 + Na+ (aq) (albite) (K feldspar)

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INTRODUCTION

13

The Na/K gethermometer formula for instances are:

T (°C) = {1217 / (log (Na/K) + 1.483} – 273 (Fournier, 1979)

T (°C) = {1390/ (log (Na/K) + 1.750} – 273 (Giggenbach, 1988)

This geothermometer is suitable for reservoir temperatures ranging from 180 to 350

°C, but not for temperatures below 120 °C (Ellis, 1979; Nicholson, 1993). However,

the geothermometer has been indicated resulting in overestimation temperatures

when applied to thermal waters with high Ca2+ concentrations. This is considered due

to the competition of Ca2+, Na+ and K+ during ion exchange reaction (Nicholson,

1993).

c) Na/K/Ca geothermometer

The empiric Na/K/Ca geothermometer was developed by Fournier and Truesdell

(1973) for Ca-rich thermal waters, i.e., (√Ca / Na) >1. The thermometer was defined

as:

T (°C) = 1647 / {log (Na/K) + β[log(√Ca / Na) + 2.06] + 2.47} – 273

The thermometer is considered working well for reservoir temperatures above 180 °C.

However, the application to hot springs could be troublesome. During thermal water

ascent the Ca2+ content might be depleted by CO2 release, Mg2+ exchange and calcite

precipitation.

d) Na/K/Mg geothermometer

Giggenbach (1988) developed a ternary diagram of K/100-√Mg-Na/1000 as a

geothermometer and a tool to assess suitable hot springs for geothermometer

application (Fig. 1.5). In the diagram thermal waters are divided into three groups, fully

equilibrium, partially equilibrium and immature waters. Immature water potentially

produce inaccurate reservoir temperatures calculation.

e) Na/Li geothermometer

The Na/Li ratios of geothermal water were identified having an inverse correlation with

temperatures (Ellis and Wilson, 1960; Koga, 1970). The thermometer was formulated

based on the theoretical exchange reaction of Fouillac and Michard (1981):

Clay-Li + H+ = Clay-H + Li+

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INTRODUCTION

14

Fig. 1.5. Evaluation of Na-K-Mg geothermometer (Giggenbach, 1991).

with an equation:

T (°C) = 1000 / {log (Na/Li) + 0.389] – 273 (Fouillac and Michard, 1981)

Later, a new formula was established by Kharaka et al. (1982) as follow:

T (°C) = 1590 / {log (Na/Li) + 0.779] – 273

This thermometer was considered resulting the most reliable reservoir temperatures

for geothermal systems with a carbonate reservoir type (Minissale and Duchi, 1988).

I.3.4. Boron isotope Boron is a trace element, thus can be used to track the thermal water origin.

Dissolve boron is mainly present as B(OH)3 (boric acid, trigonal species) and B(OH)4

(borate anion, tetrahedral species) (Dickson, 1990; Hershey et al., 1986). At low pH

(<7) only B(OH)3 is present, and conversely at pH >10 boron is found as a B(OH)4

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INTRODUCTION

15

species. Boron has two stable isotopes, 10B and 11B, with an abundance of 19.8 ‰

and 80.2 ‰, respectively (e.g., Xiao et al., 2013; Bart, 1993). Boron isotope

composition is reported as δ11B per mil (‰) relative to the standard of NIST-SRM 951

(Catanzaro et al., 1970), with a formula:

δ11B (‰) = [(11B/10B)sample / (11B/10B)NIST-SRM-951 – 1] x 1000

Geothermal waters have a wide range of δ11B composition, from -9.3 to +44 ‰

(Aggarwal et al., 2000; Aggarwal et al., 1992; Barth, 1993; Leeman et al., 1990;

Musashi et al., 1988; Palmer and Sturchio, 1990; Vengosh et al., 1994b). The δ11B

composition of thermal water is mainly controlled by: 1) host-rock type, 2) fluid mixing,

3) B isotope fractionation and 4) steam phase separation. The last factor generally

only enriches the δ11B of up to 4 ‰ and thus is considered insignificant (Kanzaki et

al., 1979; Leeman et al., 1992; Nomura et al., 1982; Spivack et al., 1990; Yuan et al.,

2014). During thermal water-rock interaction, 11B is released into water, hence

reduces the 11B composition of the rock (Musashi et al., 1991; Palmer and Sturchio,

1990). Carbonate rocks have a wider range of δ11B composition compared to volcanic

rocks from island arc, respectively ranged from +1.5 to +26.2 ‰ (Hemming and

Hanson, 1992; Vengosh et al., 1991a) and from -2.3 to +7 ‰ (Ishikawa and

Nakamura, 1992; Palmer, 1991). B isotope fractionation at water temperatures above

65 °C was reported insignificant (Aggarwal and Palmer, 1995; Palmer et al., 1987),

thus relatively conservative during thermal water ascent. Groundwater generally has

heavier δ11B compositions than thermal water, thus groundwater dilution enriche the

δ11B of thermal water (Palmer and Sturchio, 1990; Vengosh et al., 1994a). Seawater

input has been reported elevating the δ11B value of thermal water, for instances at the

Reykjanes and Svartsengi, Iceland as well as at the Izu-Bonin arc, Kusatsu-Shirane

and Kagoshima, Japan (Aggarwal and Palmer, 1995; Aggarwal et al., 2000; Kakihana

et al., 1987; Millot et al., 2009; Musashi et al., 1988; Nomura et al., 1982; Oi et al.,

1993). Adsorption/coprecipitation of B into minerals leads to fractionation of the light 10B into minerals, thus increases the δ11B of water (Palmer et al., 1987; Schwarcz et

al., 1969; Xiao et al., 2013). B can be adsorbed/incorporated by clay minerals and iron

oxide (Lemarchand et al., 2007; Palmer et al., 1987; Schwarcz et al., 1969; Spivack

and Edmond, 1987; Vengosh et al., 1991b), calcite (Hemming and Hanson, 1992;

Vengosh et al., 1991a) and evaporite minerals (Agyei and McMullen, 1968; McMullen

et al., 1961; Oi et al., 1989; Swihart et al., 1986; Vengosh et al., 1992).

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INTRODUCTION

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GEOLOGICAL SETTING, SAMPLING AND ANALYSES

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II. Geological setting, sampling and analyses

II.1. Geological setting The geological features of the western part of the Indonesian archipelago was

started by the collision of the Sibumasu and Indochina–East Malaya, indicated by the

distribution of Triassic granite across the island of Sumatera (Hall, 2009). This event

pushed the continental active margin, which then ceased in the early Cretaceous due

to collision of the Australian microcontinental with the Java-Meratus subduction (Hall

et al., 2007; Smyth et al., 2008). The subduction can be detected by the presence of

metamorphic rocks, stretch along Sumatera to Central Java and turn to the north to

the Borneo island (Hall, 2009) (Fig. 2.1). In the middle Eocene the subduction

reactivated to the south due to the rapid northward movement, c.a., 6-7 cm/a, of the

Australian plate (Hall, 2009; Hamilton, 1979; Müller et al., 2000; Schellart et al., 2006;

Simandjuntak and Barber, 1996). This subduction generated a volcanic arc in the

active margin, marked by the distribution of the Tertiary volcanic belt along the

southern part of Java island (Soeria-Atmadja et al., 1994; Van Bemellen, 1949) (Fig.

2.2). In the early Miocene, the subduction ceased and resumed again in the middle

Miocene, indicated by the low volcanic activities, due to the further northward

movement of the subduction hinge (Macpherson and Hall, 1999; Macpherson and

Hall, 2002; Smyth et al., 2008). The volcanic activities increased again in the late

Miocene by the formation of the Neogene volcanic arc to the north of the Tertiary

volcanic belt (Hall, 2002; Hall et al., 2007; Macpherson and Hall, 2002; Soeria-

Atmadja et al., 1994). Later the Quaternary volcanic replaced the Neogene volcanic

arc, hence the current features on Java only have two volcanic belts, the Tertiary in

the south and the Quaternary in the middle (Hamilton, 1979; Soeria-Atmadja et al.,

1994).

The volcanisms on Java produced andesitic rocks, where the younger volcanic

(Quaternary) rocks are more alkaline (Soeria-Atmadja et al., 1994). The Quaternary

volcanism produced magmas ranging from tholeiites to high-K calc alkaline, named as

‘the normal island arc association’ (Whitford et al., 1979). The resulting magma type is

associated with the distance to the subduction trench/the depth of Benioff zone

(Wheller et al., 1987; Whitford et al., 1979). Volcanoes with deeper Benioff zones

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GEOLOGICAL SETTING, SAMPLING AND ANALYSES

18

produce richer K volcanic rocks. On Java, the Muria volcano has the highest K

content due to its location in the back arc (Wheller et al., 1987; Whitford et al., 1979).

Apart from the location relative to the subduction trench, the melting materials and

fluid flux also affect the typical magma produced in a volcanic island arc. Calc-alkaline

magma is produced by a high fluid flux as the result of melting of the mantle wedge

and sediment, while K-rich magma is associated with a lower fluid flux and melting of

a deeper mantle (Cottam et al., 2010). The basement of the Sunda volcanic arc are

vary from a continental crust in the West, Mesozoic accretionary complexes in the

central to east Java and an oceanic crust on Bali to Flores (Curray et al., 1977;

Hamilton, 1979). Avraham and Emery (1973) predicted the crustal thickness on Java

ranging from 20 to 25 km and thinner to the east, reached 15 km on Flores.

Fig. 2.1. Geographic and tectonic map of the Indonesian archipelago (after Hamilton, 1979 and Simandjuntak and Barber, 1996; the plates boundaries were based on Hall, 2009).

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GEO

LOG

ICAL

SET

TIN

G, S

AM

PLIN

G A

ND

AN

ALY

SES

Fig.

2.2

. G

eolo

gica

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tting

of

the

Java

isl

and

with

the

old

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cani

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ES ts.

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GEOLOGICAL SETTING, SAMPLING AND ANALYSES

20

The subduction in between the early Miocene to Pliocene thrust the Tertiary

volcanic belt to the north by more than 50 km (Hall et al., 2007). The continuous

subduction has also uplifted the southern part of Java. Followed by erosion, the

process thinned the crust and exposed the Tertiary (Paleogene) volcanic belt. In

Central Java the volcanic belt has been removed by excessive erosion, hence

outcropped the Cretaceous basement (Clements et al., 2009; Hall et al., 2007). This

block is the most thrust compared to the West Java and East Java due to the

presence of a couple two major strike-slip faults, the Central Java fault and Citandui

fault. The subduction pushed the East Java and West Java blocks to the north, hence

uplifted the southern part of Central Java (Bahar and Girod, 1983; Satyana, 2007;

Situmorang et al., 1976). Apart from these faults, two other major faults are present on

Java, namely the E-W backarc-thrust of Barabis-Kendeng and the NE-SW strike-slip

fault of Cimandiri (Hoffmann-Rothe et al., 2001). These faults have been generated

since the Neogene time by compressional forces (Hall, 2002; Simandjuntak and

Barber, 1996). The Cimandiri fault is an active fault with a slip rate of about 6 to 10

mm/a (Sarsito et al., 2011; Setijadji, 2010). Besides those major faults, there are

several smaller faults, which include the E-W Lembang fault in West Java, the NE-SW

Opak fault in Central Java and the NE-SW Grindulu fault in East Java.

II.2. Sampling and analyses The sampling of thermal and cold waters was performed in two periods, July to

September 2012 and October to November 2013. The first sampling covered almost

the whole area of Java, while the second was focused on Bali with some additional

samples from Java. The water samples were taken from hot spring, cold spring,

shallow thermal wells, deep geothermal well, steam vent, crater lake, freshwater lake

and seawater (e.g., Fig. 2.3).

Temperature, pH, conductivity, ORP and alkalinity, were measured in the field,

either by probe or acid titration (HACH, 2007). The samples were filtered through a

0.45 μm nylon membrane. A part of the filtered sample was used for alkalinity

measurement and two splits for the determination of anion, cation and isotopic

compositions were stored in pre-rinsed polyethylene bottles and transported to the

University of Bremen for further analyses. The cation split was acidified to 1%

concentrated HNO3 to avoid precipitation of metals. The anions, Cl-, SO42-, NO3

- and

Br-, were analyzed by ion chromatography using an IC Plus Chromathograph

(Metrohm). The cations, Ca2+, Mg2+, Na+ and K+, and Si were determined by

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GEOLOGICAL SETTING, SAMPLING AND ANALYSES

21

inductively coupled plasma-optical emission spectrometry (ICP-OES) using an Optima

7300 instrument (Perkin Elmer). Trace elements of B and As were measured by using

inductively coupled plasmamass spectrometry (ICP-MS) using an iCAP-Q instrument

(Thermo Fisher). Stable isotopes (18O and 2H) were determined on a LGR DLT-100

laser spectrometer (Los Gatos Research). The isotopes results were reported in δ per

mil (‰) relative to VSMOW with an analytical uncertainty of approximately ± 1 ‰ for

δ2H and ± 0.2 ‰ for δ18O.

The B isotope composition was analyzed using a multi-collector inductively

coupled plasma mass spectrometer (MC-ICP-MS, Neptune, Thermo Fisher Scientific)

at the Isotope Geochemistry Laboratory, National Cheng Kung University, Taiwan by

following the procedure of Wang et al. (2010). A volume of 0.5 or 1 mL sample

containing a minimum of 50 ng B was used in the measurement to ensure duplicated

analysis. Prior to measurement, the HNO3 in the samples was substituted with H2O to

minimize the memory effects. B was purified from the samples by micro-sublimation

technique at 98±0.1 °C in a thermostatic hot plate rack. The 11B data were reported in

δ per mil (‰) relative to the standard of SRM NBS 951 with an analytical uncertainty

of < 0.2 ‰.

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GEOLOGICAL SETTING, SAMPLING AND ANALYSES

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Fig. 2.3. (a) Kawah Sikidang acid crater lake, Dieng; (b) Cisolok geyser; (c) Kawah Kreta steam vent, Kamojang; (d) Dieng geothermal brines; (e) Yeh Panas hot spring, Bali; (f) Tirta Husada thermal shallow wells, Bali.

(a)

(d) (c)

(b)

(e) (f)

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

23

III. Geothermal systems on the island of Java, Indonesia

Modified from:

Budi Joko Purnomo * & Thomas Pichler *

* Geochemistry & Hydrogeology, Department of Geosciences, University of Bremen, Germany

Journal of Volcanology and Geothermal Research (2014) DOI: 10.1016/j.jvolgeores.2014.08.004

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

24

Abstract

This paper presents an overview of all known geothermal systems on the island

of Java by presenting physicochemical data for associated hot springs, cold springs

and acid crater lakes. A total of 69 locations were sampled and classified based on

their position in either a volcanic complex (volcano-hosted) or a fault zone (fault-

hosted). In particular the potential of a magmatic heat source for fault-hosted

geothermal systems was investigated. Volcano-hosted geothermal systems had

higher HCO3- concentrations and higher Mg/Na ratios than fault-hosted geothermal

systems. This geochemical difference is likely due to degassing and subsequent CO2-

water reaction in the volcano-hosted systems, which is absent in the fault-hosted

geothermal systems. The HCO3 vs. Cl and Mg/Na vs. SO4/Cl systematics indicated

that fault-hosted geothermal systems located in the active Quaternary volcanic belt

received shallow magmatic fluids, hence should be classified as volcano-hosted

geothermal systems. The heat source of fault-hosted geothermal systems located in

the old (Tertiary) volcanic belt were investigated by a combination of Li enrichment

and calculated reservoir temperatures. There a shallow magmatic heat source was

only indicated for the Cilayu and Cisolok geothermal systems. Thus, a deep seated

magma was considered to be the heat source for the fault-hosted geothermal systems

of Cikundul, Pakenjeng, Parangtritis and Pacitan.

In ten of the volcano-hosted geothermal systems, 2H and 18O isotopes

enrichments were found, but not in any of the fault-hosted geothermal systems. Stable

isotope enrichment due to evaporation was recognized in the Kawah Candradimuka

and Kawah Sileri, Kawah Hujan and Candi Gedong Songo geothermal systems. A

combination of intensive evaporation and magmatic gases input produced very heavy

stable isotopes in the hot acid crater lakes of the Kawah Kamojang, Kawah Sikidang

and Kawah Putih geothermal systems. The addition of substantial amounts of

andesitic water to the geothermal fluid was observed in the Candi Songgoriti,

Banyuasin and Pablengan geothermal systems.

Contrary to established belief fault-hosted geothermal systems on Java could be

considered a potential source for geothermal energy.

Keywords:

Java, volcano-hosted and fault-hosted geothermal systems, shallow and deep

magmatic heat sources, geochemistry, stable isotope

Page 39: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

25

III.1. Introduction At least 62 geothermal fields with the potential for exploitation are present on

the island of Java (Setijadji, 2010). Following Alam et al (2010) geothermal fields can

be divided into volcano-hosted and fault-hosted geothermal systems based on their

geologic association. The former is a geothermal system related to a volcanic

complex and the latter is a geothermal system located in a fault zone. To date, seven

volcano-hosted geothermal fields were developed and five of them produced

electricity. Fault-hosted geothermal fields were not developed and are rarely explored,

due to the assumption of insufficient energy. However, considering the geology of

Java, a volcanic (magmatic) influence on the fault-hosted geothermal systems is

likely.

In other volcanic arcs around the World, fault-hosted geothermal fields which

are located close to volcanic areas indicate a heating of deep circulated meteoric

water, e.g., in the Liquiñe-Ofqui fault zone of Chile and in the Southern Apennines of

Italy (Alam et al., 2010; Italiano et al., 2010). Using a trend of B enrichment, Alam et al

(2010) suggested for the Liquiñe-Ofqui fault zone (a) heating of meteoric water in

fault-zone hosted geothermal systems and (b) condensation of volcanic steam in

volcano-hosted geothermal systems. However, the authors did not indicate the heat

source of the fault hosted geothermal system. Arehart et al. (2003) identified a

magmatic heat source for the Steamboat geothermal system (Nevada, USA), based

on trace metal and gas data. Historically this geothermal system was considered as

an extensional geothermal type with anomalous heat flow as the heat source (Wisian

et al., 1999). Anomalous heat flow in the Alpine fault, New Zealand, for example, is

considered to be caused by uplift and erosion (Allis and Shi, 1995; Shi et al., 1996).

Here physicochemical processes, fluid sources and reservoir temperature of

volcano and fault-hosted geothermal systems on Java were examined, using chemical

and isotope (2H and 18O) data. The data indicated a magmatic influence on the fault-

hosted geothermal systems, and thus a hidden energy potential for some of the fault-

hosted geothermal systems on Java.

III.2. Sampling locations Water samples were collected from July to September 2012, the end of the dry

season on Java. The samples were taken from 25 geothermal systems: (1) Cisolok,

(2) Cikundul, (3) Batu Kapur, (4) Ciater, (5) Maribaya, (6) Tampomas, (7) Patuha, (8)

Pangalengan, (9) Darajat, (10) Kamojang, (11) Cipanas, (12) Kampung Sumur, (13)

Page 40: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

26

Ciawi, (14) Cilayu, (15) Pakenjeng, (16) Slamet Volcano, (17) Dieng, (18) Kalianget,

(19) Ungaran, (20) Candi Dukuh, (21) Parangtritis, (22) Lawu, (23) Pacitan, (24)

Arjuna-Welirang and (25) Segaran (Fig. 3.1). In total 70 samples were collected, 61

from hot springs, 4 from cold springs, 4 from hot crater lakes and 1 from the Indian

Ocean (Table 3.1). The locations of the 4 cold spring samples were chosen based on

their proximity to those hot springs which were sampled during this investigation.

III.3. Results The results of the field and laboratory measurements are presented in Table

3.1. Cold water springs in Java were slightly acid to slightly alkaline (pH= 6.2 to 7.8)

and conductivity ranged from 86 to 324 μS/cm. Compared to the hot spring samples,

the concentrations of Ca2+, Mg2+, Na+, K+ and Cl- of the cold spring waters were low (≤

31 mg/L). These cold spring waters had HCO3- and SO4

2- contents of 19.5 to 115.9

mg/L and 2.7 to 40.6 mg/L, respectively.

The volcano-hosted hot springs had a larger variety of temperature, pH,

conductivity, major anions (HCO3-, SO4

2-, and Cl-) and two major cations (Na+ and

Mg2+), but relatively a similar range of K+ and a smaller range of Ca2+, compared to

the fault-hosted hot springs. The temperatures of the volcano-hosted hot springs

ranged from 22 to 95 °C and those of the fault-hosted hot springs ranged from 47 to

102 °C. The volcano-hosted hot springs were very acid to slightly alkaline (pH= ~ 1 to

8.4), while of the fault-hosted hot springs were slightly acid to slightly alkaline (pH= 5

to 8.1). The conductivity of the volcano-hosted hot springs varied from 86 to 14600

μS/cm, compared to 1500 to 17340 μS/cm of the fault-hosted hot springs. The

concentration of HCO3- in the volcano-hosted hot springs ranged from below detection

to 1634.8 mg/L, SO42- ranged from below detection to 3005.5 mg/L, and Cl- ranged

from 6.9 to 8084 mg/L; and those of the fault-hosted hot springs had HCO3-

concentration ranged from 22 to 1085.8 mg/L, SO42- ranged from below detection to

1284.5 mg/L, and Cl- ranged from 122.1 to 6184.5 mg/L. The concentration of Mg2+ in

the volcano-hosted hot springs ranged from 2.6 to 211.9 mg/L, Na+ ranged from 2.2 to

2979 mg/L, K+ ranged from 1.4 to 119.8 mg/L, and Ca2+ ranged from 4.9 to 510.7

mg/L; while the concentration of Mg2+ in the fault-hosted hot springs ranged from

below detection to 97.7 mg/L, Na+ ranged from 115.8 to 1797.4 mg/L, K+ ranged from

below detection to 94.2 mg/L, and Ca2+ ranged from 32.8 to 2047.6 mg/L.

Page 41: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

Fig.

3.1

. Th

e di

strib

utio

n of

sam

pled

geo

ther

mal

sys

tem

s on

Jav

a, i

.e.,

(1)

Cis

olok

, (2

) C

ikun

dul,

(3)

Batu

Kap

ur,

(4)

Cia

ter,

(5)

Mar

ibay

a, (6

) Tam

pom

as, (

7) P

atuh

a, (8

) Pan

gale

ngan

, (9)

Dar

ajat

, (10

) Kam

ojan

g, (1

1) C

ipan

as, (

12) K

ampu

ng S

umur

, (13

) Cia

wi,

(14)

Cila

yu, (

15) P

aken

jeng

, (16

) Sla

met

Vol

cano

, (17

) Die

ng, (

18) K

alia

nget

, (19

) Ung

aran

, (20

) Can

di D

ukuh

, (21

) Par

angt

ritis

, (22

)

Law

u, (2

3) P

acita

n, (2

4) A

rjuna

-Wel

irang

and

(25)

Seg

aran

. Geo

logi

cal s

truct

ures

and

vol

cani

c be

lts w

ere

base

d on

Ham

ilton

(197

9),

Sim

andj

unta

k an

d Ba

rber

(199

6), H

offm

ann-

Rot

he e

t al.

(200

1) a

nd S

oeria

-Atm

adja

et a

l. (1

994)

.

(5)

awi,

(22)

79),

Page 42: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

Tabl

e 3.

1. S

ampl

ing

loca

tions

, phy

sico

chem

ical

and

sta

ble

isot

ope

com

posi

tions

of c

old

sprin

gs, h

ot s

prin

gs a

nd h

ot a

cid

crat

er la

kes

on J

ava.

Sam

ple

Loca

tion

Geo

. Te

mp.

pH

Ec

TD

S C

a M

g N

a K

C

l H

CO

3 SO

4 N

O3

Br

Si

B

Li

As

18O

2 H

ID

Ty

pe

(°C

) (u

S/c

m)

(mg/

L)

(μg/

L)

(‰)

Hot

Spr

ings

J1

Pan

cura

n 3

(Sla

met

vol

c.)

V

46.3

6.

2 40

70

3995

18

9.6

204.

2 35

8.0

75.4

73

2.5

652.

7 59

9.6

<dl

<dl

85.1

4.

01

19.6

12

.1

-8.6

-6

1.9

J2

Pan

cura

n 7

(Sla

met

vol

c.)

V

52.1

6.

9 42

80

3200

20

1.2

209.

2 37

1.5

75.3

77

7.3

722.

2 61

4.7

<dl

<dl

89.6

4.

33

76.8

12

.7

-9.1

-6

0.6

J3

Cia

wi 1

V

43

.2

6.5

1500

11

23

73.0

61

.3

169.

1 43

.0

152.

7 84

4.2

<dl

<dl

<dl

86.7

5.

90

478.

5 17

.8

-6.4

-3

6.4

J4

Cia

wi 2

V

53

.4

6.7

1860

13

00

85.8

72

.5

197.

9 48

.4

165.

3 97

6.0

<dl

<dl

<dl

91.3

6.

84

534.

4 18

.3

-6.2

-3

8.9

J6

Cie

ngan

g (C

ipan

as)

V

46.2

6.

2 15

25

1048

72

.6

90.7

12

1.9

25.0

11

3.6

362.

3 45

3.4

<dl

<dl

67.2

2.

16

96.7

5.

5 -7

.4

-48.

4 J7

C

ipan

as In

dah

(Cip

anas

) V

48

.3

6.3

1632

11

32

68.7

10

7.0

143.

8 28

.6

119.

0 38

3.1

486.

4 <d

l <d

l 68

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2.43

12

3.4

6.6

-7.5

-4

9.8

J8

Tirta

gang

ga (C

ipan

as)

V

49.3

6.

4 16

55

1170

80

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100.

3 13

8.2

27.2

11

9.0

397.

7 51

3.8

<dl

<dl

70.2

2.

51

96.3

4.

7 -7

.8

-49.

7 J1

0 K

awah

Huj

an (K

amoj

ang)

V

95

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4.9

618

409

25.1

5.

9 19

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6.9

7.2

22.0

13

3.4

0.8

<dl

83.9

4.

63

0.4

3.1

-1.3

-2

1.4

J11

Tirta

husa

da (P

acita

n)

F 51

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5.0

4262

30

55

417.

2 <d

l 20

0.2

<dl

308.

2 23

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1127

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<dl

<dl

16.4

0.

42

23.5

30

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-5.7

-3

9.5

J12

Tina

tar (

Pac

itan)

F

37.3

6.

9 28

62

2115

48

4.3

2.0

185.

3 <d

l 30

8.2

22.0

12

84.5

<d

l <d

l 16

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0.42

26

.6

23.2

-6

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-35.

8 J1

3 P

adus

an 1

(Arju

na-W

elira

ng v

olc.

) V

48

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6.5

2574

18

82

142.

4 10

8.5

239.

9 56

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246.

2 11

04.1

17

1.7

<dl

<dl

74.9

4.

97

166.

9 15

.1

-9.3

-6

2.4

J14

Pad

usan

2 (A

rjuna

-Wel

irang

vol

c.)

V

45.7

6.

3 23

77

1730

11

9.5

86.8

19

2.9

46.2

20

6.3

1000

.4

140.

4 3.

9 <d

l 65

.0

4.14

13

0.8

14.0

-9

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-59.

3 J1

6 C

anga

r 1 (A

rjuna

-Wel

irang

vol

c.)

V

46.1

6.

8 13

36

918

72.0

87

.3

116.

4 31

.0

48.1

69

5.4

82.6

14

.2

<dl

49.9

2.

62

1.6

2.6

-8.5

-6

0.9

J17

Can

gar 2

(Arju

na-W

elira

ng v

olc.

) V

42

.3

6.7

887

599

56.0

43

.9

78.2

21

.0

38.2

59

7.8

61.9

15

.8

<dl

48.8

2.

00

1.3

1.8

-9.1

-5

8.4

J18

Son

ggor

iti 1

(Arju

na-W

elira

ng v

olc.

) V

46

.4

6.3

5470

41

78

170.

3 12

4.8

765.

2 52

.9

1303

.5

1378

.6

<dl

<dl

<dl

84.9

50

.56

1710

.4

4448

.8

-5.9

-4

6.2

J19

Son

ggor

iti 2

(Arju

na-W

elira

ng v

olc.

) V

28

.4

7.0

5549

43

42

172.

2 13

0.9

797.

5 55

.6

1366

.8

1134

.6

<dl

<dl

<dl

86.2

51

.84

1784

.4

1423

.1

-4.8

-4

4.1

J20

Son

ggor

iti 3

(Arju

na-W

elira

ng v

olc.

) V

41

.5

6.3

4658

35

14

145.

0 10

5.3

635.

6 44

.7

1084

.4

1146

.8

<dl

<dl

<dl

80.0

42

.04

1437

.2

777.

6 -6

.1

-45.

3 J2

1 S

egar

an 1

(Lam

onga

n vo

lc.)

V

44.9

6.

5 39

07

2892

10

0.7

211.

9 40

5.3

79.3

55

0.5

1625

.0

<dl

<dl

<dl

73.9

21

.37

619.

2 46

.6

-5.0

-2

9.9

J22

Seg

aran

2 (L

amon

gan

volc

.) V

22

.3

6.3

3504

25

82

91.9

18

6.8

362.

7 71

.8

497.

9 14

57.9

<d

l 3.

9 <d

l 70

.5

18.7

4 54

9.0

50.8

-5

.0

-30.

2 J2

3 C

umpl

eng

(Law

u vo

lc.)

V

34.3

6.

2 23

01

1678

73

.3

33.0

39

4.5

12.2

30

0.0

971.

1 7.

4 <d

l <d

l 52

.5

4.08

68

2.8

21.9

-6

.4

-42.

9 J2

4 B

anyu

asin

(Law

u vo

lc.)

V

38.4

6.

1 13

800

1204

0 51

0.7

146.

2 29

79.0

11

9.8

5948

.7

835.

7 25

6.4

<dl

13.0

42

.9

93.2

3 11

060.

5 95

14.8

-4

.0

-42.

4 J2

6 P

able

ngan

(Law

u vo

lc.)

V

36.4

6.

3 14

600

1275

0 13

9.5

46.4

29

67.1

81

.4

4382

.4

1634

.8

<dl

<dl

11.3

49

.6

55.6

0 34

48.9

22

9.5

-3.4

-3

1.7

J27

Nge

rak

(Law

u vo

lc.)

V

34.4

6.

2 27

56

2032

19

6.0

84.1

19

1.8

39.9

66

8.9

151.

3 24

8.3

5.1

<dl

52.5

5.

22

108.

1 6.

8 -8

.9

-59.

4 J2

8 K

ondo

(Law

u vo

lc.)

V

33.2

6.

4 48

60

3745

15

9.4

46.7

84

1.8

22.4

90

4.9

878.

4 51

1.9

<dl

<dl

30.1

17

.37

1127

.6

49.5

-5

.4

-39.

6 J2

9 B

ayan

an (L

awu

volc

.) V

39

.8

6.8

2330

16

88

103.

6 69

.9

289.

8 29

.1

323.

8 98

8.2

<dl

<dl

<dl

69.4

3.

34

297.

6 0.

9 -6

.1

-36.

5 J3

0 N

gunu

t (La

wu

volc

.) V

41

.0

6.6

2451

17

84

98.2

77

.7

316.

6 25

.4

333.

1 10

30.9

<d

l <d

l <d

l 73

.1

3.47

35

9.6

0.9

-6.3

-3

7.0

J31

Can

di D

ukuh

(Am

bara

wa)

V

35

.9

7.2

1168

80

6 46

.0

38.0

16

2.9

14.0

17

1.3

377.

0 <d

l <d

l <d

l 37

.6

3.80

74

.6

35.8

-6

.5

-44.

6 J3

2 C

andi

Son

go (U

ngar

an v

olc.

) V

48

.5

3.0

870

582

24.2

10

.0

18.9

9.

3 14

.0

<dl

340.

6 1.

0 <d

l 83

.4

0.03

6.

1 3.

8 -4

.8

-36.

3 J3

3 G

ucci

(Sla

met

vol

c.)

V

40.5

6.

3 69

4 46

4 35

.0

41.6

57

.5

24.0

33

.5

319.

6 54

.2

8.9

<dl

59.9

2.

66

19.6

5.

3 -8

.7

-60.

4 J3

4 P

enga

siha

n (S

lam

et v

olc.

) V

53

.3

7.5

1206

81

9 46

.0

56.5

14

4.5

41.0

52

.6

556.

3 92

.0

<dl

<dl

75.4

7.

15

76.8

7.

9 -8

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-63.

8 J3

5 M

arib

aya

F 46

.5

6.2

2345

16

60

129.

0 97

.7

115.

8 26

.4

122.

1 10

17.5

<d

l <d

l <d

l 82

.5

1.94

11

6.5

1.2

-7.5

-5

0.1

J36

Cia

ter

V

46.6

2.

0 63

11

4850

88

.6

30.0

58

.7

41.4

82

2.5

<dl

659.

2 6.

0 <d

l 78

.7

2.07

37

.6

68.3

-6

.9

-44.

6 J3

7 Ba

tu K

apur

1

F 56

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6.7

2154

15

30

50.6

46

.2

310.

4 58

.5

280.

4 71

7.4

75.4

<d

l <d

l 87

.9

2.74

53

9.7

1.3

-7.1

-4

1.4

J38

Batu

Kap

ur 2

F

40.9

6.

4 24

86

1802

10

2.1

96.6

27

6.9

39.9

31

2.7

1085

.8

<dl

<dl

<dl

75.1

3.

12

703.

4 2.

5 -6

.4

-39.

3 J3

9 C

ibol

ang

(Pan

gale

ngan

) V

68

.9

7.1

988

650

77.0

43

.0

71.3

28

.0

24.0

21

9.6

236.

0 <d

l <d

l 95

.5

6.48

63

.8

14.2

-6

.5

-47.

3 J4

0 S

ukar

atu

(Pan

gale

ngan

) V

39

.8

6.4

1005

68

2 64

.0

53.2

97

.8

14.0

18

.6

475.

8 10

2.6

<dl

<dl

70.1

2.

12

61.5

6.

2 -8

.1

-56.

1 J4

1 K

erta

man

ah (P

anga

leng

an)

V

54.1

6.

4 32

08

553

54.0

35

.7

94.4

26

.0

17.6

43

3.1

91.8

<d

l <d

l 92

.5

1.06

56

.1

35.8

-8

.1

-53.

3

2 H‰

) -61.

9-6

0.6

-36.

4-3

8.9

-48.

4-4

9.8

-49.

7-2

1.4

-39.

5-3

5.8

-62.

4-5

9.3

-60.

9-5

8.4

-46.

2-4

4.1

-45.

3-2

9.9

-30.

2-4

2.9

-42.

4-3

1.7

-59.

4-3

9.6

-36.

5-3

7.0

-44.

6-3

6.3

-60.

4-6

3.8

-50.

1-4

4.6

-41.

4-3

9.3

-47.

3-5

6.1

-53.

3

Page 43: Geothermal systems in the Sunda volcanic island arc · Geothermal systems in the Sunda volcanic island arc Investigations on the islands of Java and Bali, Indonesia Dissertation zur

Ta

ble

3.1.

(con

tinue

d)

Sam

ple

Loca

tion

Geo

. Te

mp.

pH

Ec

TD

S C

a M

g N

a K

C

l H

CO

3 SO

4 N

O3

Br

Si

B

Li

As

18O

2 H

ID

Ty

pe

(°C

) (u

S/c

m)

(mg/

L)

(μg/

L)

(‰)

Hot

Spr

ings

J4

2 P

aken

jeng

F

59.9

7.

4 19

60

1367

22

5.5

<dl

224.

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l 12

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94

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<dl

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68

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Pak

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ng

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2048

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61

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<dl

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l <d

l 26

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ilayu

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4435

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11

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66

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58

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2233

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yu

F 45

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1014

0 83

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289.

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<dl

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27

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9 J4

6 K

alia

nget

V

38

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2611

19

27

118.

2 15

0.7

190.

1 45

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399.

1 84

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150.

8 <d

l <d

l 61

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20

3.4

135.

9 -9

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4 J4

7 K

alia

nget

V

40

.0

6.5

2657

19

54

128.

3 15

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197.

5 49

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424.

8 73

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163.

6 <d

l <d

l 66

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3.73

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8.3

189.

3 -9

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-59.

5 J4

8 C

ikun

dul

F 50

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7.8

1500

10

26

32.8

1.

1 26

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5.4

180.

2 61

.0

374.

2 <d

l <d

l 37

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10.7

2 94

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38.8

-5

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-39.

4 J4

9 C

isol

ok

F 10

2.0

8.1

1705

11

80

41.2

3.

0 28

5.8

10.3

30

5.6

129.

3 23

5.5

<dl

<dl

66.3

3.

58

290.

1 10

4.0

-5.9

-3

3.0

J50

Cis

olok

F

100.

0 8.

0 16

12

1078

52

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3.3

257.

6 8.

8 27

7.0

161.

0 22

2.7

<dl

<dl

58.9

3.

20

251.

9 96

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-6.0

-3

5.3

J52

Pat

uha

V

64.3

8.

4 71

5 46

8 41

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16.7

71

.4

16.5

35

.2

300.

1 46

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<dl

<dl

80.7

1.

29

44.9

43

.1

-8.9

-5

6.6

J53

Tam

pom

as

V

51.4

6.

9 19

12

1349

73

.2

50.8

24

1.9

22.8

28

0.2

705.

2 1.

6 <d

l <d

l 90

.8

4.95

49

0.5

0.7

-6.2

-4

2.8

J54

Tam

pom

as

V

48.5

7.

1 34

62

2526

83

.4

50.6

54

2.2

30.2

75

7.2

732.

0 <d

l <d

l 2.

8 82

.7

5.28

15

23.0

2.

1 -6

.6

-41.

2 J5

5 D

araj

at

V

60.0

2.

8 95

2 64

3 13

.7

5.3

7.9

2.9

13.3

<d

l 25

4.1

1.0

<dl

78.8

6.

97

2.9

87.2

-7

.9

-50.

6 J5

6 D

araj

at

V

54.0

3.

8 34

4 22

2 24

.0

4.3

10.9

5.

0 6.

9 <d

l 11

7.6

0.6

<dl

49.7

1.

11

5.8

17.1

-8

.7

-51.

9 J5

7 K

ampu

ng S

umur

V

35

.0

7.6

592

399

19.0

18

.1

85.9

14

.0

52.0

22

9.4

13.9

0.

9 <d

l 43

.0

0.95

33

.1

10.2

-7

.5

-47.

2 J5

8 Pa

rang

tritis

F

39.2

7.

6 17

340

1543

0 20

47.6

8.

7 16

40.0

21

.4

6184

.5

43.9

47

7.0

<dl

18.1

26

.2

9.51

28

2.3

15.6

-4

.3

-24.

2 J6

0 D

ieng

V

57

.4

6.3

1104

76

2 60

.0

19.5

11

2.4

27.0

77

.7

266.

0 20

2.9

0.8

<dl

49.5

6.

67

13.8

6.

1 -4

.3

-47.

4 J6

1 D

ieng

V

54

.0

6.2

1550

10

82

130.

4 40

.2

104.

1 59

.1

330.

6 18

3.0

67.8

<d

l 1.

0 10

3.5

6.41

52

.8

2.1

-8.0

-5

7.2

J62

Die

ng

V

70.1

6.

8 34

3 21

6 23

.8

11.2

16

.6

20.3

9.

0 12

4.4

16.6

<d

l <d

l 97

.9

0.09

2.

5 91

.1

-8.6

-5

7.6

J63

Die

ng

V

56.1

6.

7 74

5 48

7 41

.9

25.1

76

.0

26.5

27

.3

270.

8 11

9.7

<dl

<dl

91.6

4.

55

22.6

2.

3 -7

.3

-55.

6 J6

4 D

ieng

V

60

.0

7.3

744

487

41.7

14

.3

95.5

32

.2

21.5

32

9.4

82.8

0.

9 <d

l 81

.4

2.08

45

.0

6.6

-8.0

-5

7.1

J65

Die

ng

V

81.0

7.

3 15

75

1046

16

.3

6.6

4.0

2.2

14.7

10

4.9

298.

5 1.

3 <d

l 13

.2

0.54

6.

7 1.

2 0.

6 -2

1.0

J66

Die

ng

V

31.6

5.

9 42

7 28

3 35

.6

21.6

15

.7

11.2

15

.7

201.

3 22

.4

0.5

<dl

55.8

0.

27

11.2

3.

8 -8

.2

-54.

8 J6

8 D

ieng

V

23

.4

2.5

1748

12

60

4.9

2.6

2.2

1.4

13.1

<d

l 43

4.0

0.9

<dl

45.4

0.

15

3.6

2.4

-8.6

-5

4.3

J69

Die

ng

V

26.6

6.

0 40

0 26

7 35

.2

24.3

10

.9

8.1

16.8

17

9.3

41.2

<d

l <d

l 52

.0

0.17

4.

4 0.

3 -9

.3

-62.

3 H

ot C

rate

r Lak

es

J9

Kam

ojan

g V

40

.0

2.9

1185

82

6 63

.0

23.5

15

.9

23.0

12

.8

<dl

406.

8 <d

l <d

l 16

8.8

1.39

13

.3

1.3

7.7

-4.1

J5

1 P

atuh

a V

32

.9

1.0

86

115

75.0

32

.1

34.2

33

.0

8084

.2

<dl

3005

.5

0.7

20.5

12

2.4

94.4

0 41

.7

236.

5 7.

9 -4

.0

J59

Die

ng

V

86.8

2.

5 25

69

1851

18

.3

14.5

11

.4

5.9

14.4

<d

l 90

0.6

<dl

<dl

161.

5 73

.29

12.6

1.

4 7.

5 -7

.6

Col

d Sp

rings

J5

C

iaw

i -

25.2

6.

5 16

9 10

8.1

15.0

9.

5 2.

9 <d

l 9.

1 97

.6

2.7

0.9

<dl

36.0

0.

01

2.7

0.9

-6.1

-4

2.0

J15

Arju

na-W

elira

ng

- 22

.6

6.3

324

215.

0 31

.0

13.6

16

.0

5.0

22.0

11

5.9

30.4

8.

2 <d

l 30

.7

0.27

2.

6 2.

9 -7

.6

-52.

5 J2

5 La

wu

- 21

.9

6.2

86

55.3

5.

0 1.

6 9.

5 <d

l 9.

5 19

.5

12.7

2.

2 <d

l 20

.5

0.10

22

.0

73.2

-7

.9

-52.

8 J6

7 D

ieng

-

18.1

7.

6 28

6 19

0.4

28.8

6.

6 13

.5

4.8

15.6

15

.9

40.6

48

.4

<dl

21.6

0.

97

1.4

0.9

-8.8

-5

5.6

Seaw

ater

SW

In

dian

Oce

an

- nm

nm

nm

nm

36

9.7

1372

.8

1068

3 36

0 19

191

151

2183

<d

l 60

.3

nm

9.96

11

.6

nm

nm

nm

*V=

volc

ano-

host

ed, F

= fa

ult-h

oste

d, v

olc.

= vo

lcan

o, <

dl=

belo

w d

etec

tion

limit,

nm

= no

t mea

sure

d

2 H) -3

5.6

-35.

8-4

0.8

-33.

9-5

8.4

-59.

5-3

9.4

-33.

0-3

5.3

-56.

6-4

2.8

-41.

2-5

0.6

-51.

9-4

7.2

-24.

2-4

7.4

-57.

2-5

7.6

-55.

6-5

7.1

-21.

0-5

4.8

-54.

3-6

2.3

-4.1

-4.0

-7.6

-42.

0-5

2.5

-52.

8-5

5.6

nm

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

30

Both the volcano- and fault-hosted hot springs were characterized by relatively

large variation of B, Li and As concentrations. The B concentration of the volcano-

hosted systems ranged from 0.03 to 94.4 mg/L, Li ranged from 0.4 μg/L to 11.06 mg/L

and As ranged from 0.3 μg/L to 9.5 mg/L. In the fault-hosted systems, the B

concentrations ranged from 0.42 to 58.2 mg/L, Li ranged from 23.5 μg/L to 2.23 mg/L

and As ranged from 1.2 μg/L to 3.5 mg/L. Most of the hot springs with high B, Li and

As concentrations were chloride water. This phenomenon is common in geothermal

systems, because neutral chloride waters ascend directly from the reservoir and thus

are generally enriched in selected trace elements, i.e., the geothermal suite of

elements (Goff and Janik, 2000; Nicholson, 1993; White et al., 1971).

In addition to physicochemical parameters, stable isotopes of 2H and 18O were

determined. The stable isotope composition of hot spring waters from the volcano-

hosted systems had a larger variation than those from the fault-hosted systems. The 18O isotope composition of the cold springs ranged from -8.8 to -6.1 ‰, the volcano-

hosted hot springs waters ranged from -9.3 to 7.9 ‰ and the fault-hosted hot springs

waters ranged from -7.5 to -4.3 ‰ (Table 3.1). The 2H isotope composition of the cold

springs ranged from -55.6 to -42.0 ‰, the volcano-hosted hot springs waters ranged

from -62.3 to -4.1 ‰ and the fault-hosted hot springs waters ranged from -50.1 to -4.2

‰ (Table 3.1).

III.4. Discussion III.4.1. General considerations about geothermal systems on Java

As mentioned above, geothermal systems on Java were classified into volcano-

hosted and fault-hosted. Based on this classification, from a total of 25 sampled

geothermal systems, 8 were considered fault-hosted (i.e., Pacitan, Maribaya, Batu

Kapur, Pakenjeng, Cilayu, Cikundul, Cisolok, and Parangtritis) and 17 were

considered volcano-hosted (i.e., Segaran, Arjuna-Welirang Volcano, Lawu Volcano,

Ungaran Volcano, Candi Dukuh, Dieng, Kalianget, Slamet Volcano, Ciawi, Kampung

Sumur, Tampomas, Cipanas, Ciater, Darajat, Kamojang, Pangalengan, and Patuha)

(Fig. 3.1). All of the volcano-hosted geothermal systems were in the Quaternary

volcanic belt, while most of the fault-hosted geothermal systems were in the Tertiary

volcanic belt (Fig. 3.1).

Several of those fault-hosted geothermal systems are located in major fault

zones, e.g. the Cisolok and Cikundul geothermal systems in the Cimandiri fault, the

Maribaya geothermal system in the Lembang fault, the Parangtritis geothermal

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

31

system in the Opak fault, and the Pacitan geothermal system in the Grindulu fault.

The Batu Kapur, the Pakenjeng and the Cilayu geothermal systems are associated

with minor faults (Fig. 3.1). Contrast with the other fault-hosted geothermal systems,

the Maribaya and the Batu Kapur were located in the active Quarternary volcanic belt,

thus probably are heated by volcanic activity. According to the geologic maps of Java

(Alzwar et al., 1992a; Effendi et al., 1998a; Samodra et al., 1992; Silitonga, 1973a;

Sujatmiko and Santosa, 1992a), the Pacitan, the Pakenjeng, the Cilayu, the Cisolok

and the Parangtritis geothermal systems are situated close to the zones of the

Tertiary intrusive rocks. The position of a fault-hosted geothermal field nearby an

intrusive rock could be an indication of a magmatic heat source, an assumption that

was further investigated using geochemical tools.

The origin and physicochemical history of hydrothermal fluids can be explored in

a Cl, SO4 and HCO3 ternary diagram (Chang, 1984; Giggenbach, 1991; Giggenbach,

1997; Nicholson, 1993). Based on their position in the diagram, hydrothermal waters

can be divided into neutral chloride, acid sulfate and bicarbonate waters, but mixtures

between the individual groups are common. On Java, bicarbonate was the dominant

water type for the volcano-hosted hot springs, followed by acid sulfate and neutral

chloride waters, while for the fault-hosted hot springs the water types were distributed

more or less evenly (Fig. 3.2). The occurrence of different water types in a given

hydrothermal system is common, indicating the different physicochemical processes,

such as, phase separation and mixing in the shallow subsurface (Ellis and Mahon,

1977; Giggenbach, 1997; Hedenquist, 1990; Henley and Ellis, 1983; McCarthy et al.,

2005). Although the bicarbonate water type seems to be more abundant in the

volcano-hosted hydrothermal systems, a definite difference between the volcano- and

fault-hosted systems is difficult to be assessed in a ternary diagram alone. Thus,

following the procedure of Valentino and Stanzione (2003), the hot waters from Java

were plotted in HCO3 vs. Cl and Mg/Na vs. SO4/Cl diagrams (Figs. 3.3 and 3.4).

These diagrams show that the volcano-hosted thermal waters have a higher HCO3-

content and a higher Mg2+/Na+ ratio. This observation could result due to magmatic

degassing and thus addition of CO2 to the volcano-hosted hot springs, which is likely

absent or minor in the fault-hosted hot springs. The reaction between H2O and CO2

increases acidity and thus intensifies water-rock interaction (Giggenbach, 1984;

Giggenbach, 1988; White, 1957). Acid conditions and low temperature, due to slow

upward migration or a long flow path of the ascending thermal waters, increases the

solubility of Mg2+ (Allen and Day, 1927), hence producing Mg-rich waters.

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

32

Fig. 3.2. SO4-HCO3-Cl ternary diagram of cold and hot springs. Most of the volcano-hosted hot springs were of the HCO3

- water type, whereas the fault-hosted hot springs were distributed evenly between the SO42-, HCO3

- and Cl- types. Open circle = cold spring, gray filled triangle = volcano-hosted hot spring and open square = fault-hosted hot spring.

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

33

Fig. 3.3. HCO3 vs. Cl (in mg/L basis) diagram of cold and hot springs for: (A) and (B) formed in the margin of the ‘primary neutralization’, where (A) are closer than (B), (C) thermal waters from shallow depth, thus undergone major dilution by groundwater, (D) volcanic H2S gas oxidized by O2-rich groundwater, (E) and (F) fault-hosted hot springs, where (E) were less diluted by groundwater than the (F). (E) is likely influenced by seawater input. (Symbols are as in Fig. 3.2).

Fig. 3.4. Mg/Na vs. SO4/Cl (in meq/L basis) diagram of cold and hot springs. The interpretation of groups A, B, C, D, E and F are similar to those in Fig. 3.4. (Symbols are as in Fig. 3.2).

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

34

Four groups of the volcano-hosted thermal waters are shown in the HCO3 vs. Cl

and the Mg/Na vs. SO4/Cl diagrams, i.e., A, B, C and D (Fig. 3.3 and 3.4). The group

A samples had the highest HCO3- and Cl- concentrations, but the lowest SO4/Cl ratios.

Conversely, the group D samples had the lowest HCO3- and Cl- concentrations but the

highest SO4/Cl ratios. Meanwhile, the group B and C had HCO3- and Cl-

concentrations and SO4/Cl ratios in between of the group A and D. However, the

group C was split from the group B due to its lower HCO3- and Cl- contents. The

groups A and B are thought to have formed at the margin of the ‘primary

neutralization’ zone (Giggenbach, 1988). There separation of CO2 and its reaction

with groundwater produces HCO3-rich thermal waters, while the Cl- content remains

high due to the lesser dilution by groundwater. The group A samples originated closer

to the ‘primary neutralization’ zone than the group B samples and thus had a higher

Cl- concentration. In the Mg/Na vs. SO4/Cl diagram, two acid thermal waters, J51

(Kawah Putih) and J36 (Ciater), are exceptions in group B. The moderate SO42-/Cl-

ratios in these two samples were likely caused by H2S and HCl addition to shallow

groundwater (Delmelle and Bernard, 1994; Delmelle et al., 2000; Giggenbach, 1988;

Sriwana et al., 2000). The resulting low pH enhances water-rock interaction, thus

causing the high Mg2+/Na+ ratio in those two samples. The group C samples were

considered thermal waters formed in the shallow subsurface and thus were diluted by

groundwater, which lowered their HCO3- and Cl- contents. The group D samples were

interpreted to be thermal waters influenced by primary H2S-rich magmatic vapor in the

shallow subsurface, hence producing acid sulfate waters. In this group, J65 (Dieng)

was an exception (Fig. 3.4), because the hot spring had a neutral (pH= 7) and was Cl-

poor (14.7 mg/L). This thermal water is likely a mixture of HCO3-rich and SO4-rich

water, which can occur in low relief liquid-dominated geothermal systems (Kuhn,

2004). Meanwhile, the thermal waters of the fault-hosted geothermal systems were

divided into two groups, E and F, where the former had a higher Cl- content than the

latter. Chloride is a conservative element and thus the Cl- variation in the fault-hosted

thermal waters could be caused by either varying degrees of mixing with shallow

groundwater or reflect the initial Cl- content of the hydrothermal fluid. Based on that

assumption, group E thermal waters should have undergone less mixing with shallow

groundwater than group F. This is also indicated in the Na-K-Mg ternary diagram

(Giggenbach, 1988), where the group E thermal waters (J45 and J58) plot closer to

equilibrium than the group F thermal waters (Fig. 3.6). The high Cl- concentration in

sample J58 from the Parangtritis hot spring is unusual, but can be explained by

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GEOTHERMAL SYSTEMS ON THE ISLAND OF JAVA, INDONESIA

35

seawater addition to the geothermal system, because of its proximity to the Indian

Ocean. Most of the acid sulfate waters had HCO3- concentrations, which were below

detection and thus less samples could be plotted as group D in the HCO3 vs. Cl

diagram than in the Mg/Na vs. SO4/Cl diagram. Conversely, many neutral chloride

waters were below the detection limit of SO42- and therefore more thermal waters

plotted as group A in the HCO3 vs. Cl diagram than in the Mg/Na vs. SO4/Cl diagram.

Several anomalies and discrepancies were found in both the HCO3 vs. Cl and

Mg/Na vs. SO4/Cl diagrams. In the HCO3 vs. Cl diagram, the fault-hosted hot springs

of Maribaya (J35) and Batu Kapur (J37 and J38) plot within the group B of the

volcano-hosted thermal waters, whereas the volcano-hosted hot springs of J27

(Lawu) and J61 (Dieng) plot as a group of fault-hosted thermal waters (Fig. 3.3). As

mentioned previously, the HCO3- abundance in the Maribaya and Batu Kapur hot

springs was likely caused by addition of magmatic CO2, due to their location within the

active Quaternary volcanic belt. Meanwhile, the lower HCO3- concentrations in

samples J27 (Lawu) and J61 (Dieng) were likely the result of carbonate mineral

precipitation. That sample J28 plots below group B in the Mg/Na vs. SO4/Cl diagram

should be due to the formation of clay minerals and the associated depletion of Mg2+.

The discrepancy that samples J23 and J53 plot in group B in the HCO3 vs. Cl diagram

and in group A in the Mg/Na vs. SO4/Cl diagram can be attributed to the removal of

SO4 due to precipitation of sulfate minerals. The same process is the likely cause for

the location of sample J57, a dilute thermal water, in group B in the Mg/Na vs. SO4/Cl

diagram.

The Cl/B ratios of hydrothermal waters can be used to identify subsurface

processes, such as, water-rock interaction, magma degassing and seawater feeding

in a geothermal system (Arnorsson and Andresdottir, 1995; Valentino and Stanzione,

2003). The Cl/B ratios found in the samples from Java indicated three dominant

processes for the volcano-hosted thermal waters, i.e., groundwater mixing, water-rock

interaction with the andesitic host rock and phase separation. On the other hand, the

Cl/B ratios of fault-hosted hot springs were generally affected by water-rock

interaction with the andesitic host rock (Fig. 3.5).

Geothermal water in the Dieng, Kamojang and Darajat geothermal fields had

lower Cl/B ratio than the andesitic rock (Fig. 3.5), something that can be caused by

phase separation in high temperature (>300 °C) reservoirs (Truesdell et al., 1989).

This process removes B from the geothermal reservoir, thus relatively increasing the

Cl- concentration of the remaining hydrothermal fluid (Arnorsson and Andresdottir,

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1995; Truesdell et al., 1989). One volcano-hosted hot spring, J36 (Ciater), and three

fault-hosted hot springs, J11 (Pacitan), J12 (Pacitan) and J58 (Parangtritis), plotted

closed to the seawater-precipitation line. The J58 (Parangtritis) sample also plotted in

the HCO3 vs. Cl and Mg/Na vs. SO4/Cl diagrams in a way which would indicate

seawater addition. However, seawater addition is not likely for the J12 and J13 hot

springs due to their low Cl- concentration. Hence, the low B/Cl ratio of these hot

springs could have been caused by B removal due to adsorption by clay minerals,

particularly illite (Harder, 1970).

Fig. 3.5. Cl vs. B diagram of cold waters and geothermal waters. The Cl/B ratio of seawater from the Indian Ocean (this research) and andesitic rock from Trompetter et al. (1999) are used. The Cl/B ratio of volcano-hosted and fault-hosted hot springs were considered to be controlled by water-rock interaction. The Dieng, Kamojang and Darajat volcano-hosted geothermal systems underwent phase separation. Though J58 (Parangtritis), J11 and J12 of Pacitan and J36 (Ciater) plotted close to seawater, but only for J58 seawater mixing was indicated. (Symbols are as in Fig. 3.2).

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III.4.2. Geothermometry Solute geothermometers, such as listed in Table 3.2, can provide powerful tools

to estimate subsurface conditions. Their successful application has been extensively

discussed in the geothermal literature and relies on five basic assumptions: 1)

exclusively temperature dependent mineral-fluid reaction; 2) abundance of the mineral

and/or solute; 3) chemical equilibrium; 4) no re-equilibration; and 5) no mixing or

dilution (e.g., Nicholson, 1993). The no mixing or dilution assumption, however, can

be circumvented if their extent and/or influence on solute ratios (e.g., Na/K) are

known. Several geothermometers were applied in order to analyze the

physichochemical processes encountered by the hydrothermal fluids during their

ascent to the surface. These processes include dilution by shallow water, conductive

cooling, adiabatic cooling, mineral precipitation, adsorption/desorption, water-rock

interaction and re-equlibrium (Fournier, 1977; Kaasalainen and Stefánsson, 2012).

Different geothermometers record different equilibria and disagreement does not

immediately eliminate the use of one or the other. Careful application and evaluation

of calculated temperatures may provide important clues to the overall hydrology of the

geothermal system (Pichler et al., 1999).

Silica geothermometers, which are commonly applied to hot springs (Fournier,

1977) predicted a temperature range from 100 to 140 °C for most samples (Table

3.2). Lower temperatures were calculated for J60 (Kampung Sumur), J31 (Candi

Dukuh), and J24 and J28 (Lawu). The J60 and J31 hot springs were located at the

edge of a pool and a lake, respectively and thus, should be diluted by surface water.

The two hot springs, J24 and J28, were Cl-rich, which would preclude dilution by

surface or groundwater dilution. That lead to the conclusion that the J24 and J28 hot

springs lost silica due to the precipitation of silicate minerals during ascent, causing

the low silica geothermometer temperatures.

When applied to hot springs, silica thermometers are known to predict closer to

the discharge temperature, rather than the reservoir temperature (e.g., Pichler et al.,

1999). This inherent problem can be overcome by calculating the silica ‘parent’

concentration using the silica mixing model of Fournier (1977). After application, the

silica geothermometers predicted much higher reservoir temperatures of 258 °C for

Slamet, 188 °C for Ciawi, 180 °C for Batu Kapur and 221 °C for Pangalengan. These

temperatures were in the range of those, predicted by the Na/K and Na/K/Ca

geothermometers (see below).

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Table 3.2. Calculated reservoir temperatures.

Location Samples Geothermal T Field Geothermometers (°C)

ID Types (oC) Quartz Quartz Chalcedony Quartz Na/K Na-K-Ca

(steam

loss) (parents)

Slamet

J1

V

46.3 128 125 101

258

290 217 J2 52.1 131 128 104 286 215 J33 40.5 110 110 81 380 241 J34 53.3 122 120 94 326 232

Ciawi J3 V 43.2 129 126 102 188 313 223 J4 53.4 132 128 105 308 222

Cipanas J6

V 46.2 116 115 87

nd 287 203

J7 48.3 117 116 88 284 205 J8 49.3 118 117 90 283 202

Arjuna-Welirang

J13

V

48.3 122 119 93

nd

304 219 J14 45.7 114 113 85 305 217 J16 46.1 102 102 72 318 218 J17 42.3 101 102 71 319 213 J18 46.4 128 125 101 187 169 J19 28.4 129 126 101 188 180 J20 41.5 125 122 97 189 168

Segaran J21 V 44.9 121 119 93 nd 282 222 J22 22.3 118 117 90 283 221

Lawu

J23

V

34.3 104 104 74

nd

133 128 J24 38.4 95 96 64 150 155 J26 36.4 101 102 71 127 147 J27 34.4 104 104 74 289 203 J28 33.2 79 83 48 125 126 J29 39.8 118 116 89 217 176 J30 41.0 120 118 92 199 166

Candi Dukuh J31 V 35.9 89 91 58 nd 204 165

Pangalengan J39

V 68.9 135 131 108

221 371 232

J40 39.8 118 117 90 250 180 J41 54.1 133 129 106 323 219

Kalianget J46 V 38.9 112 111 83 nd 305 216 J47 40.0 115 114 86 310 219

Patuha J52 V 32.9 125 123 98 nd 301 205

Tampomas J53 V 64.3 132 128 105 nd 212 172 J54 51.4 127 124 99 171 158

Kampung Sumur J57 V 35.0 95 96 64 nd 263 196

Dieng

J60

V

57 101 102 71

nd

306 213 J61 54 139 134 113 431 261 J62 70 136 132 109 599 296 J63 56 132 129 105 354 233 J64 60 126 123 98 349 236 J66 32 107 107 77 474 248 J69 27 104 104 74 481 242

Pacitan J11 F 51.3 56 62 24 nd nd nd J12 37.3 54 63 24 Maribaya J35 V 46.5 127 124 99 nd 299 203

Batu Kapur J37 V 56.3 130 127 103 180 278 221 J38 40.9 122 120 93 250 195

Pakenjeng J42 F 59.9 75 79 44 nd nd nd J43 43.1 74 79 43

Cilayu J44 F 70.3 125 122 97 nd 177 176 J45 45.1 127 124 99 167 167

Cikundul J48 F 50.5 89 91 58 nd 111 111

Cisolok J49 F 102.0 115 114 87 nd 143 133 J50 100.0 110 109 80 139 128

Parangtritis J58 F 39.2 74 78 42 nd 88 55 *V= volcano-hosted, F= fault-hosted, nd= not defined

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Reservoir temperature calculations with the Na/K and Na/K/Ca

geothermometers were conducted according to Giggenbach (1988), by first evaluating

if equilibrium between host-rock and hydrothermal fluid was attained. Only six

samples, J24 and J26 (Lawu volcano), J44 and J45 (Cilayu), J48 (Cikundul), and J58

(Parangtritis) were in partial equilibrium, and four samples, J23 and J28 (Lawu), and

J49 and J50 (Cisolok) were close to partial equilibrium with their respective host rocks

(Fig. 3.6). The Na/K geothermometer was then applied for these ten samples and

calculated reservoir temperatures were 127 to 150 °C for Lawu, 167 to 177 °C for

Cilayu, 111 °C for Cikundul, 88 °C for Parangtritis and 139 to 143 °C for Cisolok.

Fig. 3.6. Na-K-Mg ternary diagram Giggenbach (1988) for the Java hot springs. Several fault-hosted and a few of volcano-hosted hot springs were close to or in partial equilibrium with the host-rock. (Symbols are as in Fig. 3.2).

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Fournier (1989) respectively proposed the use of the Na/K geothermometer

and the Na-K-Ca geothermometer for the prediction of the highest and the lowest

reservoir temperatures in a geothermal system. Following this approach, calculated

temperatures ranged from 205 to 301 °C in Patuha and 219 to 323 °C in Pangalengan

geothermal systems. These results were in good agreement with the predicted

reservoir temperatures by direct measurement, i.e., 209 to 241 °C for Patuha (Layman

and Soemarinda, 2003) and 250 to 300 °C for Pangalengan (Abrenica et al., 2010;

Layman and Soemarinda, 2003). Reliable reservoir temperature prediction with those

two geothermometers was also indicated in the Dieng geothermal system, where

calculated temperatures ranged from 236 to 349 °C. These temperatures were

relatively similar to the predictions by Prasetio et al. (2010) (i.e, 240 to 333 °C), who

used gas geothermometers. Therefore, based on those observation, the two

geothermometers were applied to the remaining geothermal systems and calculated

temperatures in Arjuna-Welirang ranged from 217 to 305 °C, in Cipanas from 202 to

277 °C, in Segaran from 221 to 283 °C, in Kalianget from 216 to 305 °C, in Tampomas

from 172 to 212 °C and in Maribaya from 203 to 299 °C.

The K+ concentration in the Pacitan and Pakenjeng hot springs waters were

below detection limit, thus the Na/K and Na/K/Ca geothermometers could not be

applied. Silica geothermometers resulted in a maximum temperature of 63 °C for

Pacitan and 79 °C for Pakenjeng geothermal systems. Those temperatures although

likely lower than the actual reservoir temperatures indicated reservoir temperatures

below 100 °C. A compilation of all calculated reservoir temperatures on Java are

presented in Table 3.3.

In the Darajat and Kamojang geothermal systems, the only surface expressions

were acid sulfate-type hot springs. That type of hydrothermal fluid reacts extensively

with near surface rocks, hence chemical geothermometers could not be applied (e.g.

Nicholson, 1993). A reservoir temperature of 280 °C was predicted by Hadi (1997) for

the Darajat geothermal system, based on the alteration minerals observed in drill

cores and Sudarman et al. (1995) reported a shallow reservoir temperature

measurement of 232 °C for the Kamojang geothermal system.

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Table 3.3. Compilation of calculated geothermal reservoir temperatures on Java.

Geothermal Geothermal T (oC) Geothermometer systems Types

Slamet M. V 258 to 380 Si parent and Na-K

Ciawi V 188 to 313 Si parent and Na-K

Cipanas V 202 to 287 Na-K and Na-K-Ca

Arjuna-Welirang M. V 217 to 305 Na-K and Na-K-Ca

Segaran V 221 to 283 Na-K and Na-K-Ca

Lawu M. V 127 to 150 Na-K

Candi Dukuh V 165 to 204 Na-K and Na-K-Ca

Pangalengan V 221 to 323 Si parent and Na-K

Kalianget V 216 to 310 Na-K and Na-K-Ca

Patuha V 205 to 301 Na-K and Na-K-Ca

Tampomas V 172 to 212 Na-K and Na-K-Ca

Kampung Sumur V 196 to 263 Na-K and Na-K-Ca

Dieng V 236 to 349 Na-K and Na-K-Ca

Pacitan V <100 Si

Maribaya F 203 to 299 Na-K and Na-K-Ca

Batu Kapur F 180 to 278 Si parent and Na-K

Pakenjeng F <100 Si

Cilayu F 125 to 177 Na-K

Cikundul F 111 Na-K

Cisolok F 139 to 143 Na-K

Parangtritis F 88 Na-K

*V= volcano-hosted, F= fault-hosted

III.4.3. The heat sources of the fault-hosted geothermal systems

The Quaternary volcanic arc could be the heat source for the fault-hosted

geothermal systems. That case was investigated by comparing the enrichment of

conservative trace elements and reservoir temperatures between the volcanic and

fault-hosted geothermal fields. A similar procedure was applied to the Steamboat

geothermal system (Arehart et al., 2003), which pointed towards a magmatic heat

source rather than just enhanced heat flow. Lithium was considered as the most

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conservative trace element in this study, because the B concentration in several hot

spring waters were affected by phase separation.

The Li vs. Cl diagram shows that some of the fault-hosted hot springs have

similar high trends of Li enrichment as the volcano-hosted hot springs (Fig. 3.7). The

slopes of Li enrichment of the volcano-hosted hot springs are ~0.003, but ~0.003 and

~ 0.0001 for the fault-hosted hot springs. The similarity of high Li enrichment between

the fault-hosted and volcano-hosted geothermal fields could be an indication of the

same type of heat source, i.e, magmatic. Nevertheless, this assumption has to be

corroborated, because the trace element enrichment in hot springs can be generated

by several other processes, i.e., (1) high trace element concentration of the host rock,

(2) intermediate age and (3) high temperature of the geothermal system (Arehart et

al., 2003). The first point was ruled out, because the geothermal host rocks on Java

are basically identical, i.e., andesitic rocks. However, the second and the third points

were evaluated by considering the calculated reservoir temperatures. The similarity of

the high Li enrichment trend and the similarity high reservoir temperatures of fault-

hosted and volcano-hosted geothermal systems was considered an indication of a

magmatic heat source for both. Meanwhile, an intermediate age of a fault-hosted

geothermal system can be concluded when its reservoir temperature is lower than

that of a volcano-hosted geothermal system and its Li enrichment is as high that of a

volcano-hosted geothermal system. An intermediate age geothermal system has a

relatively higher trace element concentration due to the extended period of water-rock

interaction. Young geothermal systems have less time of water-rock interaction and

old geothermal systems have already leached most trace elments from their host

rocks, thus both systems have relatively low trace element concentrations (Arehart et

al., 2003). Considering those assumptions, the fault-hosted geothermal systems of

Cilayu, Batu Kapur, Maribaya and Cisolok should be heated by a magmatic heat

source. In contrast, such heat source was not likely for the Cikundul and Pakenjeng

fault-hosted geothermal systems. Hence, the high Li enrichment of these two fault-

hosted geothermal systems was caused by their intermediate age.

All of the low temperature and Li-poor fault-hosted geothermal systems,

Cikundul, Pakenjeng, Parangtritis and Pacitan, are located in the southern part of the

Java island. This area consists of the Tertiary volcanic belt, where volcanism ceased

in the last Paleogene. The volcanism then shifted northward forming the Neogene and

Quaternary volcanic belts in the central part of the island (Soeria-Atmadja et al.,

1994). Under those geological conditions, the heat source of those fault-hosted

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geothermal system was likely similar to those described as ‘amagmatic’ heat source in

the Great Basin (USA) and Western Turkey (Faulds et al., 2010). An ‘amagmatic’ heat

source is a deep seated magma, which remained after volcanism ceased. The name

was used to distinguish this heat source from the shallow magmatic heat sources of

the Quaternary. As indicated by the exposure of the Cretaceous basement, the

southern part of the Java island underwent uplift and erosion due to the subduction of

Indo-Australia and Eurasian plates (Clements et al., 2009). As a result the crust

became thinner, which in turn increased the heat gradient, causing thermal circulation

of groundwater along faults, thus generating the fault-hosted geothermal systems.

The same heating mechanism was suggested for geothermal systems along the

Alpine fault, New Zealand (Allis and Shi, 1995; Shi et al., 1996).

Fig. 3.7. Li vs. Cl diagram of volcano-hosted and fault-hosted hot springs. Most of fault-hosted hot springs had similar trends of Li enrichment to those of volcano-hosted hot springs. (Symbols are as in Fig. 3.2).

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III.4.4. Oxygen and hydrogen isotope considerations The deuterium and oxygen isotopic composition of hot springs can be used to

investigate their origin (Arnason, 1977; Craig, 1963; Craig et al., 1956; Giggenbach,

1978; Giggenbach et al., 1983; Majumdar et al., 2009; McCarthy et al., 2005; Pichler,

2005). All of the fault-hosted hot springs and most of the volcano-hosted hot springs

plotted close to the Local Meteoric Water Line (LMWL), indicating meteoric water as

the source of the hydrothermal fluids (Fig. 3.8).

Ten volcano-hosted geothermal waters, J9, J10, J19, J24, J26, J32, J51, J59

and J65, show stable isotope enrichment. This could be caused by either evaporation,

water-rock interaction, the input of magmatic fluids input or any combination of the

above (Craig, 1966; D'Amore and Bolognesi, 1994; Giggenbach and Stewart, 1982;

Ohba et al., 2000; Varekamp and Kreulen, 2000). Using the formulas from Gonfiantini

(1986) and Varekamp and Kreulen (2000), a theoretical evaporation line was

calculated for 90 °C lake temperature, 22 °C ambient temperature, 80% atmosphere

humidity and a δ18O of -6.9 ‰ and δ2H of -45 ‰ for meteoric water. Samples J10,

J26, J32 and J65 plotted close to the evaporation line although only J10, J32 and J65

were affected by evaporation, while the stable isotope enrichment in J26 was likely

caused by addition of andesitic water of Taran et al. (1989) and Giggenbach (1992).

The hot acid crater lakes of Kawah Kamojang (J9), Kawah Putih (J51) and

Kawah Sikidang (J59) have the heaviest isotope composition and plotted above the

field of andesitic water (Fig. 3.8). Connecting the hot crater lakes with their respective

meteoric water (δ18O = -6.9 ‰ and δ2H = -45 ‰) generates a line, which is flatter than

the evaporation line (Fig. 3.9). The slope of this line is close to the slope of other hot

acid crater lakes lakes, such as, Khusatsu-Shirane volcano (Ohba et al., 2000), Poas

volcano (Rowe Jr, 1994), Kelimutu (Varekamp and Kreulen, 2000) and Kawah Ijen

(Delmelle et al., 2000). Thus, the isotopic composition indicated that the hot crater

lake fluids likely underwent substantial evaporation and some reaction with magmatic

gas.

The presence of andesitic water in the geothermal systems was indicated for

samples J19 (Candi Songgoriti 2), J24 (Banyuasin) and J60 (Kawah Sileri), which plot

on or near the mixing line between local groundwater and andesitic water (Fig. 3.8).

However, Figure 3.10 only indicates andesitic water input for J19, J24 and J26, but

not for J60. The plot of J26 on the theoretical evaporation line in Figure 3.9 is caused

by its lighter stable isotope composition compared to the other hot springs with

andesitic water mixing. Andesitic water input was also found, for example, for the

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Meager Creek (Clark et al., 1982), Larderello (D'Amore and Bolognesi, 1994), Geyser

(D'Amore and Bolognesi, 1994), Tongonan (Gerardo et al., 1993), El Chicon volcano

(Taran et al., 2008) and Tutum Bay (Pichler et al., 1999) geothermal systems (Fig.

3.9). In addition, the elevated Cl- concentration in samples J19, J24 and J26

corroborate the presence of andesitic water in those geothermal systems. In contrast

to these three samples, the presence of andesitic water could not be confirmed for

sample J60, due to its low Cl- concentration. Hence, similar to the J10, J32 and J65

hot springs, stable isotope enrichment of J60 should have been caused by

evaporation. The fact that J60 plots below the evaporation is likely due to a lighter

stable isotope composition of its meteoric source water compared to that of the

meteoric source water, which was used for the calculation of the theoretical

evaporation line.

Fig. 3.8. δ2H and δ18O compositions of cold and hot springs. LMWL and GMWL were taken from (Wandowo et al., 2001) and (Craig, 1961), respectively. All of fault-hosted and most of volcano-hosted hot springs had a meteoric water origin. Three stable isotope enrichments were identified, i.e., evaporation, combination of magmatic gases input with evaporation and andesitic water input. (Symbols are as in Fig. 3.2).

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Fig. 3.9. δ2H and δ18O correlation lines between hot springs (gray filled) to their associated cold springs (open) from Java. The dashed lines are stable isotope correlation between thermal waters and their respective meteoric waters from other locations around the World.

III.5. Conclusions Based on the geological setting, two types of geothermal systems were

identified on Java, volcano-hosted and fault-hosted. Contribution of CO2 to the

geothermal fluid in volcano-hosted geothermal system, which was absent/minor in

fault-hosted geothermal system, led to a different water chemistry. Volcano-hosted hot

springs had higher HCO3- concentration and a higher Mg2+/Na+ ratio than fault-hosted

host springs. While the B concentration of fault-hosted hot springs was only affected

by water-rock interaction, volcano-hosted hot springs were influenced by phase

separation, water-rock interaction and groundwater mixing. Seawater addition was

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identified in the Parangtritis, which was considered a fault-hosted geothermal system.

Calculated reservoir temperatures of volcano-hosted geothermal systems ranged from

125 to 338 °C and those of fault-hosted geothermal systems ranged from 74 to 299

°C.

Several geothermal systems on Java, although fault-hosted are likely heated by

shallow magmas, i.e., Batu Kapur, Maribaya, Cilayu and Cisolok. The addition of

volcanic fluids in Batu Kapur and Maribaya, which are located in the active

Quarternary volcanic belt, indicated that these two geothermal systems in fact are

volcano-hosted geothermal systems. Those fault-hosted geothermal fields that were

located in the old (Neogene) volcanic belt did not experience any addition of volcanic

fluids. Shallow magmas heat sources were not indicated in fault-hosted geothermal

systems of Cikundul, Pakenjeng, Pacitan and Parangtritis. Thus, deep seated magma

heat sources were suggested for those four geothermal systems.

Stable isotope enrichments were found in ten of the volcano-hosted geothermal

systems, but not in any of the fault-hosted geothermal systems. Stable isotope

enrichment due to evaporation was recognized in the Kawah Candradimuka and

Kawah Sileri, Kawah Hujan and Candi Gedong Songo geothermal systems. A

combination of intensive evaporation and magmatic gases input produced very heavy

stable isotopes in the hot acid crater lakes of the Kawah Kamojang, Kawah Sikidang

and Kawah Putih geothermal systems. The addition of substantial amounts of

Andesitic water to the geothermal fluid was observed in the Candi Songgoriti,

Banyuasin and Pablengan geothermal systems

Those finding reject the general assumption of a low energy potential of fault-

hosted geothermal systems, since although fault-hosted their heat source can be

magmatic as seen for several of the fault-hosted geothermal systems on Java. This

should give a new perspective for geothermal exploration on Java, where to date,

fault-hosted geothermal system were excluded from the geothermal energy

development program.

Acknowledgements A part of this study was supported by the Ministry of Energy and Mineral

Resources of Indonesia in a form of PhD scholarship grants. Thanks to Seto and

Maman for their help in the sampling campaign. TP acknowledges funding from the

German Research Foundation (DFG). M. Rowe and two anonymous reviewers are

thanked for their fruitful input and comments on the first version of this manuscript.

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IV. Boron isotope variations in geothermal systems on Java, Indonesia

Modified from: Budi Joko Purnomo a, Thomas Pichler a, & Chen-Feng You b

a Geochemistry & Hydrogeology, Department of Geosciences, University of

Bremen, Germany b Department of Earth Sciences, National Cheng Kung University, Tainan,

Taiwan, ROC

Submitted to:

Geochimica et Cosmochimica Acta

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Abstract

This paper presents δ11B data for hot springs, hot acid crater lakes, geothermal brines

and a steam vent from Java, Indonesia with emphasis to investigate the difference

between boron (B) isotope compositions in volcano-hosted geothermal systems and

fault-hosted geothermal systems, as well as differences between sulfate crater lakes

and acid-chloride crater lakes. The possible seawater input into geothermal systems

and the mechanisms of B isotope fractionation were also investigated. The δ11B

values of hot springs ranged from -2.4 to +28.7 ‰ and hot acid crater lakes ranged

from +0.6 to +34.9 ‰. The δ11B and Cl/B values in waters from the Parangtritis and

Krakal geothermal systems indicated seawater input. The δ11B values of acid sulfate

crater lakes ranged from +5.5 to +34.9 ‰ and were higher than the δ11B of +0.6 ‰ of

the acid chloride crater lake. The heavier δ11B in the acid sulfate crater lakes was

caused by a combination of vapor phase addition and further enrichment due to

evaporation and B adsorption onto clay minerals. In contrast, the light δ11B of the acid

chloride crater lake was a result of continuous magmatic fluid input. The fluids in

volcano-hosted geothermal systems had a lighter δ11B signature than those in fault-

hosted geothermal systems. The faster ascent and the insignificant input of magmatic

fluids in the fault-hosted geothermal systems resulted in a light δ11B signature. In

contrast, the input of magmatic fluids and the slower ascent in volcano-hosted

geothermal systems were favorable for B isotope fractionation towards heavier

values.

Keywords:

Java, boron isotope, volcano- and fault-hosted geothermal systems, crater lake,

seawater input

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IV.1. Introduction Geothermal waters are known to have a large range of δ11B, from -9.3 to +44 ‰

(Aggarwal et al., 2000; Aggarwal et al., 1992; Barth, 1993; Leeman et al., 1990;

Musashi et al., 1988; Palmer and Sturchio, 1990; Vengosh et al., 1994b). This range

is caused by the δ11B signature of the geothermal host-rock, seawater input,

groundwater mixing and B isotope fractionation. Different sources of rocks were

identified producing a variety of δ11B in geothermal fluids at the Argentine Puna

Plateau (Kasemann et al., 2004). The heavy δ11B of seawater, +39.6 ‰ (Foster et al.,

2010), was successfully used to identify seawater components in geothermal waters

on Iceland (the Reykjanes and Svartsengi geothermal fields) and in Japan (the Izu-

Bonin arc, Kusatsu-Shirane area, and Kagoshima) (Aggarwal and Palmer, 1995;

Aggarwal et al., 2000; Kakihana et al., 1987; Millot et al., 2009; Musashi et al., 1988;

Nomura et al., 1982; Oi et al., 1993). Shallow groundwater dilution potentially

increases the δ11B composition of thermal waters (Palmer and Sturchio, 1990; Yuan

et al., 2014). Fractionation of B isotopes in thermal waters occurred due to

adsorption/incorporation of B onto clay minerals and iron oxide (Lemarchand et al.,

2007; Palmer et al., 1987; Schwarcz et al., 1969; Spivack and Edmond, 1987;

Vengosh et al., 1991b), calcite (Hemming and Hanson, 1992; Vengosh et al., 1991a)

and evaporite minerals (Agyei and McMullen, 1968; McMullen et al., 1961; Oi et al.,

1989; Swihart et al., 1986; Vengosh et al., 1992). These processes enrich the 10B

isotope in the solid phases and thus increase the δ11B of thermal waters. Thermal

waters which condensated from the vapor phase of a geothermal system are

potentially enriched in δ11B as a consequence of 11B fractionation into the vapor

phase. The δ11B enrichment during this process was generally considered

insignificant (Kanzaki et al., 1979; Leeman et al., 1992; Nomura et al., 1982; Spivack

et al., 1990; Yuan et al., 2014), but potentially should not be neglected in vapor-

dominated geothermal systems.

Java has many hot springs, steam vents, mud pools, hot acid crater lakes and

altered grounds. Purnomo and Pichler (2014) divided the geothermal systems into

fault-hosted and volcano-hosted geothermal systems, based on their location, either

in a volcanic complex or a fault zone. While in fault-hosted geothermal systems deep

circulating groundwater is simply heated, volcano-hosted geothermal systems seem

to be more complex due to the addition of magmatic fluids to the geothermal water

(Alam et al., 2010; Purnomo and Pichler, 2014).

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The focus of previous B isotope studies in geothermal systems were generally

the mechanisms of B isotopes fractionation, while in this paper B isotope signatures

were rather used as tracers to investigate contrasting systems, i.e., (1) volcano-

hosted vs. fault-hosted geothermal systems, (2) acid sulfate vs. acid chloride crater

lakes and (3) meteoric vs. seawater influenced.

IV.2. Sampling locations Thermal water samples for this study were taken from 21 geothermal systems

on Java consist of 15 volcano-hosted and 6 fault-hosted geothermal systems (Fig.

4.1). All fault-hosted geothermal systems are distributed in the Tertiary volcanic belt.

The Cikundul and the Parangtritis geothermal systems are hosted in the major fault

zones of Cimandiri and Opak, respectively (Effendi et al., 1998; Rahardjo et al., 1995).

Other fault-hosted geothermal systems, i.e., Cisolok, Cilayu, Pakenjeng and Krakal,

are hosted in minor fault zones (Alzwar et al., 1992; Asikin et al., 1992; Silitonga,

1973; Sujatmiko and Santosa, 1992). Meanwhile, all volcano-hosted geothermal

systems on Java are within the Quaternary volcanic complex. The Kamojang, Darajat

and Wayang-Windu are located in the Kendang volcanic complex (Rejeki et al., 2005).

The Patuha geothermal system is located in the flat volcanic highland of the Patuha

volcano (Layman and Soemarinda, 2003). The Sari Ater geothermal system is hosted

by the Tangkuban Prahu volcano, Cileungsing by the Tampomas volcano and

Segaran by the Lamongan volcano. The Gucci and Baturaden geothermal systems

are hosted by the Slamet volcano. Another single volcano, the Lawu volcano is

hosting the Lawu geothermal system. The Songgoriti and Padusan geothermal

systems are located in the Arjuna-Weilrang volcano complex and the Dieng

geothermal system is located in the Dieng caldera.

IV.3. Results The temperature, pH, Cl-, B, HCO3

-, Fe data and δ11B values are reported in

Table 4.1. Except for δ11B, this data is from Purnomo and Pichler (2014). The

physicochemical data and δ11B values of new samples from the Kawah Kreta steam

vent (J73), the Krakal hot spring (J74), the Kawah Domas acid sulfate crater lake

(J72) and two geothermal brines of well AFT-28 (J70) and PAD-7C (J71) from the

Dieng geothermal field are reported separately in Table 4.2.

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Fig.

4.1

. The

sam

plin

g lo

catio

n of

geo

ther

mal

fiel

ds o

n Ja

va, i

.e.,

(1)

Cis

olok

, (2)

Cik

undu

l, (3

) Ba

tu K

apur

, (4)

Tan

gkub

an P

arah

u, (

5)

Tam

pom

as, (

6) P

atuh

a, (7

) Pan

gale

ngan

, (8)

Dar

ajat

, (9)

Kam

ojan

g, (1

0) C

ipan

as, (

11) C

iaw

i, (1

2) C

ilayu

, (13

) Pak

enje

ng, (

14) S

lam

et,

(15)

Kra

kal,

(16)

Die

ng, (

17)

Kalia

nget

, (18

) Pa

rang

tritis

, (19

) La

wu,

(20

) A

rjuna

-Wel

irang

and

(21

) S

egar

an. G

eolo

gica

l stru

ctur

es a

nd

volc

anic

bel

ts w

ere

base

d on

Ham

ilton

(197

9), S

iman

djun

tak

and

Bar

ber (

1996

), H

offm

ann-

Rot

he e

t al.

(200

1) a

nd S

oeria

-Atm

adja

et a

l. (1

994)

. Mod

ified

from

Pur

nom

o an

d P

ichl

er (2

014)

.

) t, d l.

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Table 4.1. Temperature, pH, Cl-, HCO3-, B and Fe data and δ11B of hot springs, hot

acid crater lakes and cold springs from Java. Sample Location Geo. Temp. pH Cl HCO3 B Fe δ11B

ID Type °C mg/L ‰

Hot springs J2 Baturaden (Slamet volc.) V 52 6.9 777.3 722.2 4.3 3.0 5.9

J4 Ciawi V 53 6.7 165.3 976.0 6.8 0.6 -0.7

J7 Cipanas V 48 6.3 119.0 383.1 2.4 0.01 4.6

J10 Kawah Hujan (Kamojang) V 95 4.9 7.2 22.0 4.6 0.1 2.3

J13 Padusan (Arjuna-Welirang volc.) V 48 6.5 246.2 1104.1 5.0 1.7 12

J18 Songgoriti (Arjuna-Welirang volc.) V 46 6.3 1303.5 1378.6 50.6 6.2 7.1

J21 Segaran (Lamongan volc.) V 45 6.5 550.5 1625.0 21.4 0.03 6.7

J24 Banyuasin (Lawu volc.) V 38 6.1 5948.7 835.7 93.2 9.4 8.1

J28 Kondo (Lawu volc.) V 36 6.3 4382.4 1634.8 55.6 1.9 4.5

J30 Ngunut (Lawu volc.) V 33 6.4 904.9 878.4 17.4 0.02 1.3

J34 Gucci (Slamet volc.) V 53 7.5 52.6 556.3 7.2 0.2 7.8

J36 Sari Ater (Tangkuban Parahu volc.) V 47 2.0 822.5 <dl 2.1 21.6 2.4

J38 Batu Kapur V 41 6.4 312.7 1085.8 3.1 1.3 -2.4

J39 Cibolang (Pangalengan) V 69 7.1 24.0 219.6 6.5 0.01 0.4

J42 Pakenjeng F 60 7.4 126.0 40.3 7.2 0.06 0.0

J44 Cilayu F 70 8.1 1387.2 372.1 58.2 0.1 0.2

J47 Kalianget V 40 6.5 424.8 732.0 3.7 1.1 8.9

J48 Cikundul F 51 7.8 180.2 61.0 10.7 0.01 9.3

J49 Cisolok F 102 8.1 305.6 129.3 3.6 0.01 -0.7

J54 Cileungsing (Tampomas) V 49 7.1 757.2 732.0 5.3 1.8 -1.0

J55 Darajat V 60 2.8 13.3 < dl 7.0 8.6 12.8

J58 Parangtritis F 39 7.6 6184.5 43.9 9.5 0.2 24.8

J60 Kawah Sileri (Dieng) V 57 6.3 77.7 266.0 6.7 0.02 0.3

J61 Pulosari (Dieng) V 54 6.2 330.6 183.0 6.4 0.1 4.6

J64 Bitingan (Dieng) V 60 7.3 21.5 329.4 2.1 0.01 3.2

Hot acid crater lakes

J9 Kawah Kamojang (Kamojang) V 40 2.9 12.8 <dl 1.4 4.9 9.3

J51 Kawah Putih (Patuha) V 33 1.0 8084.2 <dl 94.4 35.3 0.6

J59 Kawah Sikidang (Dieng) V 87 2.5 14.4 <dl 73.3 7.6 34.9

Cold springs J5 Ciawi 25 6.5 9.1 97.6 0.01 0.01 nm

J15 Cangar (Arjuna-Welirang volc.) 23 6.3 22.0 115.9 0.3 0.01 11.1

J67 Bimo Lukar (Dieng) 18 6.2 17.3 7.3 0.01 0.01 nm

*V= volcano-hosted, F= fault-hosted, nm= not measured, <dl= below detection limit

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Tabl

e 4.

2. P

hysi

coch

emic

al d

ata

and δ11

B va

lues

of t

he K

raka

l hot

spr

ing,

the

Kaw

ah D

omas

cra

ter l

ake,

the

Kaw

ah K

reta

ste

am v

ent

and

geot

herm

al b

rines

of t

he D

ieng

geo

ther

mal

fiel

d.

Sam

ple

Loca

tion

Geo.

Te

mp.

pH

O

RP

Cond

TD

S Ca

M

g N

a K

Cl

HCO

3 SO

4 Si

Sr

Al

B

Mn

Fe

δ11B

ID

Type

°C

m

V uS

/cm

m

g/L

Hot s

prin

gs

J74

Krak

al, K

ebum

en

F 39

8.

2 -8

6 21

470

2017

0 20

82.9

<d

l 24

36.4

3.

8 86

71.8

31

.2

21.6

<d

l 8.

8 0.

4 14

.5

< dl

< dl

28

.7

Hot a

cid

crat

er la

kes

J72

Kaw

ah D

omas

V

85

1.8

94

6935

56

08

38.1

8.

5 17

.9

10.9

<d

l <d

l 20

40

86.4

0.

1 70

.9

2.7

1.2

17.4

5.

5

(T.

Para

hu)

Geo

ther

mal

brin

es

J70

GW A

FT-2

8 (D

ieng

) V

150

6.3

-196

59

500

6400

0 89

3.5

<dl

1053

6.3

3016

.5

2224

2.5

39.0

<d

l 39

4.3

8.9

<dl

593.

6 12

.21.

3 0.

3

J71

GW P

AD-7

C (D

ieng

) V

150

5.8

-117

37

110

3850

0 37

1.6

<dl

6504

.5

1933

.4

1338

4.0

14.6

38

.8

457.

9 5.

6 <d

l 26

2.5

8.2

2.3

0.0

Stea

m v

ent

J73

Kaw

ah K

reta

(K

amoj

ang)

V

nm

nm

nm

nm

nm

2.0

<dl

0.8

<dl

<dl

nm

4.7

<dl

<dl

0.14

3.

5 <d

l<d

l 3.

8

*V=

volc

ano-

host

ed, F

= fa

ult-

host

ed, n

m=

not m

easu

red,

<dl

= be

low

det

ectio

n lim

it

11B

‰ 8.7

5.5

0.3

0.0

3.8

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The B concentrations of hot springs and acid crater lakes had a similar large

range, from 2.1 to 93.2 mg/L and from 1.4 to 94.4 mg/L, respectively. The two

geothermal brines from the Dieng geothermal field had B contents of 262.5 and 593.6

mg/L. The Kawah Kreta steam vent (J73) had a B content of 3.5 mg/L, which is

enriched relative to its Cl- concentration, which was below detection. The B

concentration in the acid sulfate crater lakes ranged from 1.4 to 73.3 mg/L, while the

Kawah Putih (J51) acid chloride crater lake had a slightly higher value of 94.4 mg/L.

The δ11B of the Cangar cold spring (J15) was +11.1 ‰, within the range of the

thermal waters of -2.4 to +34.9 ‰, but heavier than the Kawah Kreta steam vent of

+3.8 ‰ and the Dieng geothermal brines of 0 to 0.3 ‰. In accordance with the B

concentration, the hot springs and hot crater lakes had relatively similar ranges of δ

11B, i.e., -2.4 to +28.7 ‰ and +0.6 to 34.9 ‰, respectively. In contrast to the B

content, acid sulfate crater lakes had relatively heavy δ11B values from +5.6 to 34.9

‰compared to the acid chloride crater lake, which had a value of +0.6 ‰. The fault-

hosted and volcano-hosted geothermal systems had a relatively similar large ranges

of δ11B, i.e., -2.4 to +28.7 ‰ and -1.0 to +34.9 ‰, respectively. The J74 and J58 fault-

hosted hot springs as well as J59 acid sulfate crater lake had a δ11B value close to

that of seawater, i.e., +39.6 ‰ (Foster et al., 2010). The δ11B of the thermal waters

were poorly correlated with their temperature, pH, Cl-, B, HCO3- and Fe (Fig. 4.2).

Thermal waters with temperatures above 65 °C generally had relatively light δ11B

values, close to 0 ‰, while below this temperatures most of the thermal waters were

δ11B enriched (Fig. 4.2a). This indicates more significant of B isotope enrichment at

low temperatures, as suggested by others, e.g., Palmer et al. (1987) and Aggarwal

and Palmer (1995).

IV.4. Discussion IV.4.1. Boron in thermal waters and seawater input

Following the procedure of Arnorsson and Andresdottir (1995) the B content of

thermal waters on Java was used to identify steam separation for J9, J10, J34, J39,

J55, J59 and J64; andesitic host-rock leaching for most of the thermal waters;

seawater input for J58; and B adsorption for J2, J36, J38, J47, J49 and J54 (Purnomo

and Pichler, 2014). The Krakal (J74) fault-hosted hot spring plotted close to the

seawater line, similar to J58, indicating seawater input, while the Kawah Domas acid

sulfate crater lake (J72) plotted in the vapor phase separation and the geothermal

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brines from Dieng, J70 and J71, plotted close to the andesitic rock leaching line (Fig.

4.3).

Fig. 4.2. a) δ11B vs. T, b) δ11B vs. pH, c) δ11B vs. Cl, d) δ11B vs. B, e) δ11B vs. HCO3 and f) δ11B vs. Fe diagrams of thermal waters on Java show poor correlations of δ11B with T, pH, Cl-, B, HCO3

- and Fe. The δ11B vs. T indicates generally lower δ11B enrichment at temperatures above 65 °C.

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Fig. 4.3. Cl vs. B diagram of thermal waters (modified from Purnomo and Pichler, 2014). Thermal waters underwent seawater input, B depletion, steam phase separation and andesitic rock leaching. Seawater input is indicated for two fault-hosted geothermal systems, J58 and J74, while most thermal waters were resulted by andesitic rock leaching.

The boron isotope composition can be a powerful tool to detect seawater input

into geothermal systems, as demonstrated for two geothermal fields on Iceland (the

Reykjanes and Svartsengi) and three areas in Japan (the Izu-Bonin arc, Kusatsu-

Shirane area, and Kagoshima) (Aggarwal and Palmer, 1995; Aggarwal et al., 2000;

Kakihana et al., 1987; Millot et al., 2009; Musashi et al., 1988; Nomura et al., 1982; Oi

et al., 1993). A similar approach was used to investigate seawater input in the fault-

hosted thermal waters at Krakal (J74) and Parangtritis (J58). These two thermal

waters plot close to the mixing line between seawater and groundwater (Fig. 4.4),

which proves the presence of seawater. The acid sulfate crater lake of Kawah

Sikidang (J59) also had a heavy δ11B of +34.9 ‰. However, this acid sulfate crater

lake had a Cl/B ratio five magnitudes lower than seawater (Fig. 4.4), thus seawater

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input could be excluded. The fluid source of Kawah Sikidang, which is the deep

reservoir of the Dieng geothermal field, J70 and J71, also showed the absence of

seawater input. The geothermal brines had a light δ11B of approximately 0 ‰ and Cl/B

ratios two magnitudes lower than seawater (Fig. 4.4). If there was seawater input

during the vapor phase ascent, the resulting thermal water should have a higher Cl-

content corresponding to the vapor/seawater mixing ratio.

Fig. 4.4. δ11B vs. B/Cl diagram of thermal waters, groundwater and geothermal brines. Seawater input is confirmed for two fault-hosted thermal waters, J58 and J74, but not for the Kawah Sikidang (J59) acid sulfate crater lake. The δ11B value of +39.6 ‰ for seawater (Foster et al., 2010) and B/Cl ratio of the Indian Ocean (Purnomo and Pichler, 2014) are used in this diagram.

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IV.4.2. The δ11B of acid sulfate and acid chloride crater lakes Two species of B, B(OH)3 and B(OH)4

- exist in natural waters and only the

former species is present at a pH of less than 7 (Dickson, 1990; Xiao et al., 2013).

B(OH)3 species produce a higher degree of B isotope fractionation than B(OH)4-,

hence B isotope fractionation is stronger at low pH (Palmer et al., 1987). The four acid

crater lakes, Kawah Kamojang (J9), Kawah Domas (J72), Kawah Putih (J51) and

Kawah Sikidang (J59) had low pH values ranging from 1 to 2.9 and thus were

favorable for B isotope fractionation.

The B/Cl ratios indicate that, except for Kawah Putih, the three other crater

lakes were formed due to condensation of the geothermal vapor phase (Fig. 4.3). The

δ11B of vapor phase is generally enriched by up to 4 ‰ relative to the remaining liquid

phase (Kanzaki et al., 1979; Leeman et al., 1992; Nomura et al., 1982; Spivack et al.,

1990; Yuan et al., 2014). The difference in δ11B between the Dieng geothermal brines

and the Kawah Kreta vapor phase was approximately 3.8 ‰ confirming condensation

as the main process of fractionation. Assuming steam condensation from a similar

vapor phase as Kawah Kreta, the Kawah Domas, Kawah Kamojang and Kawah

Sikidang crater lakes were enriched in δ11B by 1.7 ‰, 5.5 ‰ and 31.1 ‰,

respectively. The Kawah Kreta steam vent had a B concentration of 3.5 mg/L, which

was slightly higher than Kawah Kamojang with 1.4 mg/L and Kawah Domas with 2.7

mg/L. Smith et al. (1987) reported for the Geyser geothermal field (USA) that the

water of the vapor trap was approximately 50 times enriched in B concentration

compared to the steam phase. Accordingly, an acid crater lake originated from vapor

phase condensation is expected to have a higher B concentration than the vapor

phase. Therefore, the low B concentration of the Kawah Kamojang and Kawah

Domas crater lakes in comparison to the vapor phase should indicate additional

processes which lowered the B concentration. This could have been caused either by

precipitation of a B-rich mineral phase or adsorption by clay minerals. Both processes

reduce the B concentration of the remaining water and thus enrich 11B due to

adsorption of 10B by the solid phases (Agyei and McMullen, 1968; McMullen et al.,

1961; Oi et al., 1989; Palmer et al., 1987; Schwarcz et al., 1969; Spivack and

Edmond, 1987; Swihart et al., 1986; Vengosh et al., 1991b; Vengosh et al., 1992).

Palmer and Sturchio (1990) reported more significant B isotope fractionation at low

temperature and thus the high temperature of Kawah Domas (85 °C) should allow

only little B isotope fractionation, causing the lighter δ11B values compared to Kawah

Kamojang, where the temperature was 40 °C. Meanwhile, the heavy δ11B value in

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Kawah Sikidang, which was by 31 ‰ heavier than the vapor phase, cannot be

explained exclusively by steam phase separation. Other mechanisms must have

produced such a B-rich and heavy δ11B signature in this acid sulfate crater lake.

Apart from the heavy δ11B, the Kawah Sikidang crater lake had a noticeable B

enrichment of 73.3 mg/L. This value is higher than that of the other acid sulfate crater

lakes and only comparable to the acid chloride crater lake Kawah Putih, which had a

B concentration of 94.4 mg/L. However, Kawah Putih was Cl-rich (8084 mg/L) and its

δ11B was +0.6 ‰, whereas Kawah Sikidang in contrast was Cl-poor (14.4 mg/L) with a

δ11B of +34.9 ‰. Delmelle and Bernard (1994) explained that the chemical

composition of an acid chloride crater lake is the result of condensation and oxidation

of magmatic gases, such as, SO2, H2S and HCl, upon contact with oxygenated

groundwater followed by water-rock interaction. Fumaroles in Japan (Kanzaki et al.,

1979; Nomura et al., 1982) and Vulcano Island, Italy (Leeman et al., 2005), for

example, had light δ11B, representing the magmatic fluids. Accordingly, the vapor

phase of Kawah Putih should have been derived from magmatic fluids and thus

inherited the light δ11B of an andesitic island arc magma of -2.3 to +3.5 ‰ (Palmer,

1991). After discharge at the surface, B isotope enrichment was moreless absent

though the water was very acidic (pH = ~1) and relatively cold (T = 32.9 °C), probably

was caused by continuous magmatic fluid input. The crater lake had a dimension of

approximately 350 x 290 m2 (Sriwana et al., 2000) and the ambient air temperature

was 16 °C at the time of sampling, that the fluid was cooled down rapidly.

The main mechanism that produces heavy δ11B (+34.9 ‰) of Kawah Sikidang

probably was evaporation. Vengosh et al. (1992) reported that during the latest stage

of evaporation the δ11B of seawater could be enriched up to 30 ‰ due to incorporation

of 10B into evaporate minerals, e.g., halite. Kawah Sikidang had a temperature of 87

°C without outflow to the nearby river, hence excessive evaporation could be

expected. The condition is contrary to the Kawah Domas acid sulfate crater lake

which had a temperature of 85 °C but the water drained to the adjacent river and thus

the effect of evaporation was less significant than at Kawah Sikidang. Evaporation

should have lowered the B concentration of Kawah Sikidang due to incorporation of B

into evaporites. Therefore, the elevated B content of 73.3 mg/L of the crater lake has

to be sustained by constant addition of subsurface B. The reservoir vapor phase

probably had an initial B content comparable to the Kawah Kreta steam vent of 3.5

mg/L, however, in the shallow depth the vapor was B enriched due to interaction with

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B-rich minerals. This assumption was supported by the elevated B concentration of

altered ground surrounding Kawah Sikidang which was up to 25.5 mg/Kg, compared

to the less than 0.02 mg/Kg of unaltered ground in Dieng.

IV.4.3. Processes affecting the δ11B value of thermal waters

Mixing with groundwater in the shallow subsurface prior to discharge leads to a

heavier δ11B signature, because groundwater has generally a heavier δ11B signature

than thermal water (Palmer and Sturchio, 1990; Vengosh et al., 1994b). A binary

mixing model can be applied to estimate the effect of groundwater mixing for the B

concentration and δ11B signature of thermal waters (Vengosh et al., 1991b; Yuan et

al., 2014). To set up the model, the groundwater of Cangar (J15) and the geothermal

brine from the Dieng geothermal field (J70) were used as end members. Groundwater

dilution was evident for eight thermal waters, i.e., J10 (Kawah Hujan), J30(Ngunut),

J36 (Sari Ater), J39 (Cibolang), J42 (Pakenjeng), J44 (Cilayu), J60 (Kawah Sileri) and

J64 (Bitingan) (Fig. 4.5). However, most of the thermal waters plot above the mixing

line and four thermal waters, J4 (Ciawi), J38 (Batu Kapur), J49 (Cisolok) and J54

(Cileungsing), plot below the mixing line (Fig. 4.5), indicating that the B concentration

and δ11B signature in those waters is more complex than just groundwater mixing.

Those samples plotting above ther mixing line are relatively enriched, which could

have been caused by adsorption, phase separation, water-sediment interaction or any

combination of these processes (Hemming and Hanson, 1992; Lemarchand et al.,

2007; Palmer et al., 1987; Schwarcz et al., 1969; Spivack and Edmond, 1987;

Vengosh et al., 1991a; Vengosh et al., 1991b; Vengosh et al., 1992; Xiao et al., 2013;

Yuan et al., 2014). The four thermal waters plotting below the mixing line either had

initially a light δ11B signature or desorbed B from solid phases. Although J36, J10, J39

and J64 plotted close to the groundwater mixing line (Fig. 4.5), groundwater mixing

cannot be the only process responsible for their final δ11B composition. Based on their

B/Cl ratios, J36 was relatively B depleted, while J10, J39 and J64 were relatively B

enriched (Fig. 4.3). The B concentration in J36 was lowered due to adsorption onto

clay minerals, which at the same time increased the δ11B value to +2.4 ‰. Since J36

was of the acid chloride type with a pH of 2, it likely had an initial δ11B value similar to

the geothermal brines of approximately 0 ‰. In contrast, the higher B/Cl ratios of J10,

J39 and J64 compared to the andesitic rock were a result of steam phase separation

(Fig. 4.3). Thermal waters generated by condensation of a vapor phase in

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Fig. 4.5. δ11B vs. B diagram of thermal waters and geothermal brines with a theoretical binary mixing line of groundwater (J15) and geothermal brine (J70). Groundwater dilution is dominant for J10, J30, J36, J39, J42, J44, J60 and J64 thermal waters.

a geothermal system generally undergo δ11B enrichment of up to 4 ‰ (Leeman et al.,

1992; Spivack et al., 1990). J10 and J64 had a δ11B of +2.3 ‰ and +3.2 ‰,

respectively, which were close to the Kawah Kreta steam vent of +3.8 ‰. The slightly

lower δ11B of those two thermal waters compared to the steam vent could be due to

addition of 10B from carbonate mineral dissolution, because J10 and J64 were under

saturated with respect to carbonate minerals (Table 4.3). In the case of J64

desorption of B from iron oxide could have been possible as well, since iron oxides

were also undersaturated (Table 4.3). In comparison, J39 was saturated with respect

to goethite, carbonate and clay minerals and its temperature of 68.9 °C would

dampen B isotope fractionation after discharge. Therefore, the light δ11B of J39 must

be derived from its vapor phase leading to the conclusion that B isotope fractionation

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Table 4.3. Saturation indices with respect to carbonate, clay and goethite minerals were calculated using PHREEQC (Parkhurst and Appelo, 1999).

Sample Location Saturation Index

ID Calcite Dolomite Strontianite Illite Smectite Goethite

J2 Baturaden (Slamet volc.) 0.64 2.74 -0.20 - - 1.56

J4 Ciawi 0.33 2.12 -0.61 - - 1.81

J7 Cipanas -0.81 -0.02 - - - 2.04

J10 Kawah Hujan (Kamojang) -4.27 -7.78 -5.49 2.12 -2.54 1.40

J13 Padusan (Arjuna-Welirang) 0.22 1.81 -0.71 - - 1.50

J18 Songgoriti (Arjuna-Welirang) 0.03 1.45 -0.31 6.96 3.48 0.62

J21 Segaran (Lamongan volc.) 0.15 2.13 -0.33 - - -1.31

J24 Banyuasin (Lawu volc.) -0.28 0.38 -0.08 - - 1.16

J28 Kondo (Lawu volc.) -0.25 0.51 0.37 - - -1.03

J30 Ngunut (Lawu volc.) -0.27 0.33 -0.08 - - 0.77

J34 Gucci (Slamet volc.) 0.73 3.06 -0.21 4.03 4.48 4.79

J74 Krakal, Kebumen 1.14 - 0.39 - - -

J38 Batu Kapur -0.14 1.19 -0.26 - - 0.29

J39 Cibolang (Pangalengan) 0.35 1.89 -0.69 1.40 2.29 4.74

J42 Pakenjeng 0.09 - -0.65 - - 3.82

J44 Cilayu 1.32 3.42 0.92 -3.13 1.81 7.01

J47 Kalianget -0.12 1.31 -1.15 - - 0.81

J48 Cikundul -0.14 -0.36 - 3.69 2.02 -0.01

J49 Cisolok 1.18 2.62 0.42 - - 4.49

J54 Cileungsing (Tampomas) 0.54 2.39 0.51 - - 2.01

J58 Parangtritis 0.76 0.64 0.01 - - 4.00

J60 Kawah Sileri (Dieng) -0.80 -0.60 -1.75 3.02 -0.14 -4.36

J61 Pulosari (Dieng) 0.08 1.20 -0.64 0.50 0.80 3.78

J64 Bitingan (Dieng) -1.28 -1.61 -2.07 4.03 -0.98 -4.27

during vapor phase separation must have been insignificant. The isotope fractionation

of B is considered unimportant at reservoir temperatures above 400 °C (Leeman et

al., 1992; Spivack et al., 1990) or high reservoir pressure (Liebscher et al., 2005). The

reservoir temperature of J39 ranged from 221 to 323 °C, similar to J10 and J64 of

approximately ranging from 220 to 350 °C (Purnomo and Pichler, 2014; Sudarman et

al., 1995), hence temperature cannot be responsible for the light δ11B of the J39 vapor

phase. Meanwhile, the reservoir pressure of J39 (Wayang-Windu geothermal field)

was recorded up to 84 bar (Mulyadi and Ashat, 2011), higher than J10 (Kamojang

geothermal field) and J64 (Dieng geothermal field) of up to 36 and 40 bar, respectively

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(Bachrun et al., 1995; Zuhro, 2004). Therefore, the light δ11B of the J39 vapor phase

was more likely caused by high reservoir pressure.

Twelve thermal waters, J2, J7, J13, J18, J21, J24, J28, J34, J47, J48, J55 and

J61, were δ11B enriched, thus plotted above the mixing line (Fig. 4.5). The increasing

δ11B in a hot spring where adsorption/coprecipitation of B occurs should coincide with

a decrease of the B/Cl ratio. However, as seen in the Cl vs. B diagram only J2

underwent B depletion, while J55 plotted in the steam separation group and J7, J13,

J18, J21, J24, J28, J34, J48 as well as J61 plotted close to andesitic rock leaching

(Fig. 4.3). Compared to the Kawah Kreta steam vent, J55 was δ11B enriched by 9 ‰,

a result of B adsorption onto clay minerals due to its acidic condition (pH = 2.8). This

process lowered the B/Cl ratio of J55, however, the thermal water still plotted in the

steam separation group due to its initial higher B/Cl ratio, formed by the high

temperature geothermal system. Meanwhile, J7, J13, J18, J21, J24, J28, J34, J48

and J61 plot close to the andesitic line, which might be caused by Cl- depletion during

ascent or initially higher B/Cl ratios. In a mud volcano, for example, Cl- depletion was

considered due to NaCl filtration by clay minerals during clay dehydration (Dahlmann

and Lange, 2003; Dia et al., 1999; Hensen et al., 2004; Kastner et al., 1991; You et

al., 2004). This mechanism, however, is unlikely in a geothermal system, clay

minerals along the fluid pathway should be hydrated instead. Vapor phase separation

and reaction with B-rich minerals potentially increase the B/Cl ratio of a thermal water.

However, the former could be ruled out because those nine thermal waters had higher

Cl- contents compared to the thermal waters generated by steam separation.

Therefore, it could be suggested that they underwent B enrichment due to interaction

with B-rich minerals in the subsurface. The minerals supplied B into the ascending

thermal water and thus increased the B/Cl ratio. Post discharge at the surface, the

water underwent B adsorption/coprecipitation that reduced the B/Cl ratio but

increased the δ11B.

In order to identify the mineral phases that potentially adsorb/desorp B in hot

springs, the saturation indices of carbonate, clay and iron oxide minerals were

calculated using PHREEQC of Parkhurst and Appelo (1999) (Table 4.3). Lemarchand

et al. (2007) reported a higher B isotope fractionation during adsorption onto iron

oxide than onto clay and carbonate minerals. The saturation index calculation

indicates that B coprecipitation with goethite could be expected for most of the hot

springs, but not for J21, J28, J74, J48, J60 and J64 (Table 4.3). In hot springs J21

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and J74 B likely coprecipitated with calcite, in J48, J60 and J64 B adsorbed onto clay

minerals and in J28 it coprecipitated with dolomite and strontianite.

IV.4.4. The δ11B of fault-hosted and volcano-hosted geothermal systems

The magmatic fluid input in volcano-hosted geothermal systems, which is

absent/minor in fault-hosted geothermal systems, distinguishes their chemical

characteristics (Purnomo and Pichler, 2014). The presences of magmatic gases (CO2,

H2S, HCl, SO2) in volcano-hosted geothermal systems produces reactive thermal

waters, favorable for clay, carbonate and sulfate mineral precipitation. These minerals

then can preferentially adsorb 10B over 11B causing the δ11B of thermal waters to

increase. In addition, the longer flow path and thus ascent time of volcano-hosted

thermal waters compared to fault-hosted geothermal systems enhances B isotope

fractionation. Considering these two factors, volcano-hosted thermal waters should

have a heavier δ11B signature than fault-hosted thermal waters. By excluding thermal

waters influenced by seawater and acid crate lakes, this assumption could be

confirmed.

With the exception of J48 (Cikundul), the fault-hosted thermal waters had δ11B

values ranging from -0.7 to +0.2 ‰, while volcano-hosted thermal waters were

generally heavier and ranged from -2.4 to +12.8 ‰. Figure 4.6 indicates that most of

the volcano-hosted thermal waters were δ11B enriched, while for the fault-hosted such

indication was only found in J48. Five volcano-hosted thermal waters, J4, J38, J39, 54

and J60, which had light δ11B signatures were saturated with carbonate minerals and

goethite (Table 4.3). The addition of 10B to those thermal water due to mineral

dissolution can be dismissed and thus sources of those thermal waters should have

had a lighter δ11B signature than the geothermal reservoir at Dieng. Meanwhile, the

relatively heavy δ11B (+9.3 ‰) and high B value (10.7 mg/L) of the fault-hosted hot

spring J48 are considered a result of water-sediment interaction, since this hot spring

was located at the bottom of the Cimandiri river. The relatively high B value and a

temperature of 51 °C indicate insignificant mixing with river water prior to sampling.

IV.5. Conclusions Hot springs and hot crater lakes on Java had a range of δ11B from -2.4 to +34.9

‰, relatively similar to other geothermal systems in the World (Barth, 1993). Seawater

input was detected for two fault-hosted geothermal systems, Parangtritis and Krakal,

and is considered a source of the heavy δ11B. The Kawah Sikidang acid sulfate crater

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Fig. 4.6. δ11B vs. B diagram indicates most volcanic-hosted thermal waters were δ11B enriched, while δ11B enrichment for fault-hosted thermal waters were moreless absent.

lake had a δ11B indicating seawater addition to its geothermal source, although the

low Cl/B ratio excluded seawater as a source for 11B.

Two types of hot acid crater lakes, Cl-poor (Cl- < 15 mg/L) and Cl-rich (Cl- =

8084 mg/L), showed a contrasting δ11B composition. The Cl-poor crater lakes had

relatively heavy δ11B values ranging from +5.5 to 34.9 ‰, while the Cl-rich lake had a

lighter δ11B of +0.6 ‰, similar to the Dieng geothermal brines. The heavier δ11B

values of the acid sulfate crater lakes are a combination of vapor phase separation,

evaporation after discharge and preferential adsorption of 10B by clay minerals. The

heavy δ11B (+34.9 ‰) of the Kawah Sikidang acid sulfate crater lake was mainly

caused by evaporation, while its B content of 73.3 mg/L was due to water-rock

interaction with B-rich minerals in the shallow subsurface. Meanwhile, the light δ11B of

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the Kawah Putih acid chloride crater lake was a result of continuous magmatic gases

input.

The initial division of the geothermal systems on Java into fault-hosted and

volcano-hosted (Purnomo and Pichler, 2014) was confirmed by their different δ11B

signatures. In general, fault-hosted systems had lighter δ11B values ranging from -0.7

to +0.2 ‰, while the volcano-hosted systems had heavier δ11B values of above 1 ‰.

The comparably faster ascent to the surface and the absence of magmatic fluids in

fault-hosted geothermal systems should not facilitate B isotope fractionation, hence

the lower δ11B values. In volcano-hosted geothermal systems, the ascent time is

relatively longer and the condensation of magmatic gas, as well as the formation of

clay, carbonate, sulfate and iron oxide minerals should facilitate B isotope

fractionation, hence the higher δ11B values.

Acknowledgments A part of this study was funded by the Ministry of Energy and Mineral Resources

of Indonesia through PhD scholarship grants number: 2579 K/69/MEM/2010 for B.J.

Purnomo. Thanks to Laura Knigge for the laboratory assistance and to Britta Hinz-

Stolle for an editorial review.

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V. Geothermal systems on the island of Bali, Indonesia

Modified from:

Budi Joko Purnomo and Thomas Pichler *

* Geochemistry & Hydrogeology, Department of Geosciences, University of

Bremen, Germany

Submitted to:

Journal of Volcanology and Geothermal Research

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Abstract This paper presents an overview of geothermal systems on the island of Bali,

Indonesia by presenting physicochemical data for shallow thermal wells, hot springs,

cold springs and volcanic lakes. A total of 4 locations were sampled and classified

based on their position in either as a volcano-hosted or a fault-hosted geothermal

system. A carbonate host rock for the geothermal reservoirs could not be confirmed,

because the characteristic δ18O shift to the right for carbonate reservoir fluids was not

observed. The HCO3- of the thermal waters was well correlated with Ca2+, Mg2+, Sr2+

and K+ indicating water-rock interaction in the presence of carbonic acid. The (Ca2+ +

Mg2+)/HCO3- molar ratios were approximately 0.4 and K/Mg ratios were typical for

interaction with calc-alkaline magmatic rocks. The B/Cl ratios indicated steam phase

separation for the Bedugul and Banjar geothermal systems. The heavy δ11B of +22.5

‰ and a Cl/B ratio of 820 confirmed seawater input into the Banyuwedang geothermal

system. Comparison of the Si, Na/K, Na/K/Ca and Na/Li geothermometers with actual

reservoir temperature measurements and physicochemical considerations led to the

conclusion that the Na/Li thermometer provided the best results for geothermal

systems on Bali. Using this thermometer, the following reservoir temperatures were

calculated: (1) Penebel (Bedugul) from 235 to 254 °C, (2) Batur 240 °C, (3) Banjar

255 °C and (4) Banyuwedang below 100 °C. The 2H and 18O isotope compositions of

the geothermal fluids indicated meteoric water as a source of all thermal waters

studied.

Keywords: Bali, carbonate, volcanic, host-rock, seawater input, geothermal system,

geothermometer, 2H and 18O isotope

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V.1. Introduction The island of Bali, Indonesia is host to several hot springs and geothermal

systems, of which some are of interest for geothermal exploitation. The Bedugul

geothermal field, located near Lake Bratan, was identified to cover an area of

approximately 8 km2 with an estimated annual electric energy potential of 80 MWe for

30 years (Hochstein et al., 2005; Hochstein and Sudarman, 2008; Mulyadi et al.,

2005). However, the development was suspended due to environmental and cultural

concerns. In addition to Bedugul, other geothermal prospects on Bali are the Batur,

Banyuwedang and Banjar geothermal systems.

Bali is dominantly covered by volcanic rocks, overlying the Tertiary carbonate

rocks that outcrop in the southern and western part of the island (Hadiwidjojo et al.,

1998). The Bedugul geothermal field was reported producing brines dominated by

CO2 of approximately 97 wt. % and the reservoir was assumed to be hosted in

carbonate rocks (Mulyadi et al., 2005). To the contrary Geiger (2014) concluded that

the reservoir was in volcanic rocks and that the carbonate basement was leached by

shallow magma, 2 to 7 km depth, in the Batur and Agung volcanoes based on the

thermobarometric study. The dissolution of carbonate rock by magma releases large

amounts of CO2 gas due to the breakdown of CaCO3 into CO2 gas and CaO (Allard,

1983; Chadwick et al., 2007; Deegan et al., 2010; Gertisser and Keller, 2003;

Marziano et al., 2007; Marziano et al., 2009). The rich in CO2 volatile magma

subsequently ascends to the geothermal reservoir and promotes vaporization, which

in turn produces a CO2-rich vapor phase (Lowenstern, 2001).

It is possible that geothermal systems on Bali could be hosted by carbonate

rocks, but CO2 content alone would be insufficient for that conclusion. The carbonate

rocks were determined as the reservoir rock in some volcanic areas in Italy, e.g.,

Vicano-Cimino and Sabatini- Tolfa (Cinti et al., 2011; Cinti et al., 2014). There the

thermal is characterized by a (Ca2+ + Mg2+)/HCO3- molar ratio of ~1 as a result of

calcite and/or dolomite dissolution (Capaccioni et al., 2011; Cinti et al., 2011; Cinti et

al., 2014; Gemici and Filiz, 2001; Goff et al., 1981; Grassa et al., 2006; Levet et al.,

2002; Pasvanoglu and Chandrasekharam, 2011; Pasvanoglu and Gultekin, 2012).

Another characteristic of thermal waters hosted by carbonate rocks could be the

relative 18O isotope enrichment due to the heavier δ18O of the carbonate host rock, as

indicated at Balikesir and Cesme, Turkey; Lanzarote, Spain; and the Salton Sea, USA

(Arana and Panichi, 1974; Craig, 1966; Gemici and Filiz, 2001). Although some

carbonate rock associated geothermal systems also showed depletion of 18O isotope

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due to exchange with CO2, for instances at Vicano-Cimino, Sabatini, and Sicily, Italy

(Cinti et al., 2011; Cinti et al., 2014; Grassa et al., 2006).

This paper presents new physicochemical and isotope (18O, 2H and 11B) data for

hot springs and shallow thermal wells on Bali with the objective to investigate the host

rocks of the geothermal systems. Additionally, boron isotopes were applied to identify

seawater input and solute geothermometers to predict the reservoir temperatures.

V.2. Geological setting Bali is a part of the Sunda-Banda volcanic islands arc, which extends for

approximately 4700 km east to west, from the island of Damar to the island of

Sumatera. The arc is caused by the convergence of the Indo-Australian and Eurasia

plates, with a rate of c.a. 6 to 7 cm/a (Hamilton, 1979; Simandjuntak and Barber,

1996). This process caused volcanisms on Bali since the late Tertiary (Hadiwidjojo et

al., 1998; Hamilton, 1979; Van Bemellen, 1949) and produced a vast distribution of

volcanic rocks. The Jembrana volcanic complex occupies the western part of the

island, the Buyat-Bratan-Batur volcanic complex the central part, and the Agung and

Seraya volcanic complexes the eastern parts. Underlying the volcanic rocks are

sedimentary rocks of Tertiary age, which are minimally exposed in the east, south and

west part of the island (Fig. 5.1) (Hadiwidjojo et al., 1998).

The volcanic rocks on Bali are calc-alkaline characterized by a medium

concentrations of K (Nicholls and Whitford, 1983; Whitford et al., 1979). Based on the

thermobarometric results of clinopyroxene and plagioclase at Batur volcano, Geiger

(2014) suggested the existence of a shallow magma in 2 to 4 km depth, associated

with a carbonate sedimentary crust. This is corroborated by InSar satellite data

indicating shallow magma at 2 to 4 km depth (Chaussard and Amelung, 2012) and by

earthquake focal zones at 1.5 to 5 km depth (Hidayati and Sulaeman, 2013).

Volcanoes where carbonate assimilation takes place generally have an explosive

eruption behavior (Deegan et al., 2010).

Explosive eruptions formed two large calderas on Bali, the Batur and the Bratan

calderas (Reubi and Nicholls, 2004; Watanabe et al., 2010; Wheller and Varne, 1986).

Both calderas are geothermal prospects, due to the presence of thermal water in the

shallow subsurface. Although a geothermal reservoir was confirmed beneath the

Bratan lake, (Mulyadi et al., 2005), surface features of geothermal systems, such as

hot springs are virtually absent in the Bratan caldera. Outside of the caldera to the

south, however, several hot springs are present in the Penebel area (Fig. 5.1). On the

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northwestern side of the Buyat-Bratan volcano, the Banjar hot spring discharges at

the contact between the Buyat-Bratan-Batur volcanic complex and the Tertiary Asah

Formation. At the western end of the island, the Banyuwedang hot spring is located in

carbonate rocks of the Prapatagung Formation.

Fig. 5.1. Geological map of Bali showing the sampling locations (modified from Hadiwidjojo et al., 1998).

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V.3. Results The physicochemical and stable isotopes (18O, 2H and 11B) data of the water

samples from Bali are presented in Table 5.1. The temperatures of thermal waters

ranged from 37.2 to 45.2 °C, while the selected cold waters ranged from 24 to 30.1

°C. The thermal waters had slightly acid to neutral pH, while cold springs neutral and

lake waters were slightly alkaline. The thermal and cold waters had relatively similar

ranges of TDS, Cl-, Na+ and K+ concentrations. Meanwhile the thermal waters had

wider ranges of Ca2+, Mg2+ and HCO3- contents compared to the cold waters. The

Ca2+ concentration of the thermal waters ranged from 51.3 to 211.5 mg/L, Mg2+ from

51.5 to 243.8 mg/L and HCO3- from 31.7 to 2235 mg/L, while for cold waters the Ca2+

and Mg2+ were lower than 100 mg/L and HCO3- ranged from 19.5 to 761.3 mg/L. The

Cl- content of thermal waters ranged from 17.3 to 902.1 mg/L and for cold waters from

under detection limit to 1025.7 mg/L. The Cl-rich cold waters were found in B12 (Batur

Lake) and B8 (Pejarakan), with Cl- contents of 188.6 and 1025.7 mg/L, respectively.

Thermal waters of B1, B2, B3, and B4 had Ca2+, Mg2+ and HCO3- concentrations a

magnitude higher than the other thermal waters. However, B4 differed from B1, B2

and B3 due to its higher SO42- and lower Cl- concentrations. B4 had a SO4

2- content of

111.7 mg/L and a Cl- content of 61.2 mg/L, compared to SO42- of below detection limit

and Cl- ranged from 377 to 443.9 mg/L in B1, B2 and B3. Thermal waters of B6 and

B13 had TDS of <1000 mg/L and Cl- < 20 mg/L, lower than the other thermal waters,

which varied between 1430 to 2600 mg/L and from 61.2 to 902.1 mg/L, respectively.

The two thermal waters probably were more diluted by shallow groundwater. The

thermal water located near the coastline, B7, had the highest TDS and Cl- contents

and the lowest HCO3- concentration.

The thermal waters had δ2H and δ18O values ranging from -42.4 to -33.2 ‰ and

from -6.8 to -5.6 ‰, respectively. This was probably a result of the range in elevation

from close to 0 (seawater) to approximately 1200 m above sea level. The δ2H of cold

springs and a shallow well ranged from 36.9 to -30.0 ‰ and δ18O ranged from -6.0 to -

5.4 ‰. In contrast, cold waters from two freshwater lakes, Batur and Bratan, had

heavier δ2H, ranging from -16.4 to -14.6 ‰, and δ18O, from –2.3 to -1.7 ‰. The

selected thermal waters had a wide range of δ11B compositions, from +1.3 to +22.5

‰. In accordance to the TDS and Cl- contents, the heaviest δ11B value was found in

sample B7, might be due to seawater input.

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V.4. Discussion V.4.1. Geochemistry of thermal waters

A geothermal system generally produces three types of hot springs, neutral

chloride, acid sulfate and bicarbonate waters, but mixtures between the individual

groups are common (Hedenquist, 1990; Hochstein and Browne, 2000; Nicholson,

1993; White, 1957). The discharge composition of thermal springs is controlled by two

sets of processes: 1) deep reservoir conditions (deep reservoir = reaction zone

immediately above the heat source), and 2) secondary processes during ascent. In

the deep reservoir, host rock composition, temperature, direct magmatic contributions

and residence time are the controlling factors. During ascent a drop in pressure and

temperature can initiate phase separation and mineral precipitation, causing a

dramatic change in fluid composition. Mixing with other hydrothermal fluids and/or

groundwater is possible at any depth. In near-shore and submarine environments

mixing with seawater cannot be ruled out. The chemical composition of a

hydrothermal fluid, sampled at the surface, generally contains an imprint of its

subsurface history and chemically inert constituents (tracers) provide information

about their source, whereas chemically reactive species (geoindicators) record

physico-chemical changes (Ellis and Mahon, 1977; Giggenbach, 1991; Nicholson,

1993). Classification of thermal waters on Bali using the Cl-SO4-HCO3 ternary

diagram (Chang, 1984; Giggenbach, 1991; Giggenbach, 1997) indicated a

bicarbonate (HCO3-) type for B1, B2, B3, B4, B6 and B13, a mixing type for B9, B10

and B11, and a neutral chloride (Cl-) type for B7 (Fig. 5.2). Neutral chloride waters are

usually thought to represent the deep reservoir fluid, while acid sulfate and

bicarbonate waters form by underground absorption of vapors separated from a

neutral chloride water into cooler ground water. Whether acid sulfate or bicarbonate

waters are formed depends on the gas content of the vapor and redox conditions in

the shallow subsurface (Ellis and Mahon, 1977; Giggenbach, 1997; Hedenquist, 1990;

Henley and Ellis, 1983).

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Tabl

e 5.

1. S

ampl

ing

loca

tions

, phy

sico

chem

ical

and

sta

ble

isot

opes

(2 H, 18

O a

nd 11

B) d

ata

of th

erm

al a

nd c

old

wat

ers

on B

ali.

The ρC

O2 w

as

calc

ulat

ed u

sing

the

com

pute

r cod

e P

HR

EEQ

C (P

arkh

urst

and

App

elo,

199

9).

ID

Loca

tion

T pH

O

RP

Con

d.

TDS

Ca

Mg

Na

K C

l H

CO

3 S

O4

Si

Al

Li

B S

r Fe

δ18

O

δ2 H

δ11B

Lo

g

°C

mV

uS/c

m

mg/

l ‰

ρC

O2

Hot

spr

ings

B

1 Y

eh P

anas

1

38.8

6.

5 25

30

16

2238

12

2.4

161.

6 26

3.4

50.1

37

7.0

1466

.4

<dl

76.0

0.

2 1.

3 8.

0 0.

4 <d

l -6

.5

-33

- -0

.5

Pen

ebel

B

2 Y

eh P

anas

2

38.8

6.

6 0

3052

22

72

122.

5 16

4.0

270.

3 51

.2

363.

7 15

25.0

<d

l 76

.0

0.2

1.3

7.6

0.4

<dl

-6.1

-3

6 -

-0.5

P

eneb

el

B3

Yeh

Pan

as 3

42

.6

6.4

-41

3282

24

53

135.

1 16

1.2

309.

4 58

.4

443.

9 15

55.5

<d

l 80

.8

0.2

1.4

9.1

0.4

<dl

- -

10.4

-0

.4

Pen

ebel

B

4 Be

lula

ng

41.8

6.

5 -4

7 34

02

2555

21

1.5

243.

8 23

4.5

67.2

61

.2

2235

.0

111.

7 72

.8

0.2

1.4

4.3

0.8

<dl

-6.8

-4

1 4.

0 -0

.2

Pen

ebel

B

6 A

ngse

ri 45

.2

6.1

1 13

63

943

54.3

81

.7

123.

0 40

.0

16.6

63

4.4

166.

0 97

.3

0.1

0.7

5.4

0.2

0.7

-5.8

-3

3 -

-0.6

P

eneb

el

B7

Ban

yuw

edan

g 44

.6

7.8

-310

34

53

2600

51

.3

51.6

52

6.8

14.8

90

2.1

31.7

20

0.2

11.7

0.

2 1.

2 1.

1 0.

3 <d

l -6

-3

6 22

.5

-3.2

B

13

Ban

jar

37.2

6.

2 -4

1 12

65

873.

6 68

.4

66.2

10

9.2

23.6

17

.3

773.

5 2.

2 73

.1

0.1

0.6

1.9

0.2

1.3

-6.1

-3

7 1.

7 -0

.6

Ther

mal

sha

llow

wel

ls

B9

Toya

Bon

gkah

39

.9

7.5

163

2122

15

23

46.0

75

.8

294.

2 24

.0

159.

3 46

3.6

370.

3 56

.6

0.2

1.3

1.9

0.1

<dl

-6.4

-4

2 1.

3 -1

.8

Bat

ur

B10

Ti

rta H

usad

a 43

.1

7.3

191

2007

14

30

46.6

69

.7

277.

8 22

.8

136.

2 45

8.7

325.

2 62

.0

0.2

1.3

2.0

0.1

<dl

-6

-42

- -1

.6

Bat

ur

B11

To

ya D

evas

ya

40.6

7.

4 16

3 20

55

1478

47

.4

71.1

28

1.6

22.8

14

7.0

488.

0 32

8.7

57.2

0.

3 1.

3 2.

0 0.

1 <d

l -6

.8

-42

- -1

.7

Bat

ur

Lake

sB

12

Bat

ur L

ake

27.2

8.

5 13

5 21

22

1525

31

.8

67.2

32

1.2

26.0

18

8.6

336.

7 48

8.6

1.3

0.3

1.4

1.7

0.0

<dl

-1.7

-1

6.4

- -3

.0

B15

B

rata

n La

ke

24

8.7

195

49.1

2 32

.2

4.6

0.3

<dl

0.8

<dl

19.5

2.

7 0.

0 0.

2 0.

6 0.

4 <d

l <d

l -2

.3

-14.

5 -

-4.4

C

old

sprin

gs a

nd s

hallo

w w

ell

B5

Belu

lang

30

.1

7.0

36

1057

72

7.9

48.9

49

.5

48.6

13

.4

4.3

575.

8 28

.0

27.5

0.

1 0.

6 1.

0 0.

2 <d

l -6

-3

0 -

-1.3

B

8 P

ejar

akan

29

7.

4 93

49

74

3891

40

.0

74.5

87

4.9

68.9

10

25.7

76

1.3

361.

5 31

.0

0.2

1.2

1.1

1.0

<dl

-5.7

-3

7 -

- B

14

Ban

jar

30.9

7.

7 14

3 87

6.2

598.

5 55

.4

41.2

64

.2

15.6

2.

6 56

1.2

4.7

52.3

0.

1 0.

6 1.

1 0.

3 <d

l -5

.4

-31

- -1

.9

was

og CO

2

0.5

0.5

0.4

0.2

0.6

3.2

0.6

1.8

1.6

1.7

3.0

4.4

1.3 -

1.9

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Fig. 5.2. Cl-SO4-HCO3 ternary diagram (Giggenbach diagram). Most of the thermal waters were of the bicarbonate type. The samples from Batur (B9, B10 and B11) were a mixing type and B7 a chloride type. The plots of the Pejarakan cold well (B8) and Lake Batur (B12) as mixing water type probably were caused by seawater and thermal water inputs.

The TDS value of 1525 mg/L of B12 was relatively similar to those of the Batur

thermal waters (B9, B10 and B11), probably due to major discharge of thermal water

into the lake. However, it should be noted that B12 was sampled from a site relatively

close to of Batur thermal waters, hence considering the large dimension of the lake of

approximately 6.6 km length and 2.5 km width, the sample probably does not

represent the general chemistry of the lake water. Meanwhile, the higher Cl-

concentration of the shallow well (B8) was likely caused by seawater input due to its

location close to sea.

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Solely based on their geological setting geothermal systems on Bali can be

divided into two groups, volcano-hosted are Batur (B9, B10 and B11) and Penebel

(B1, B2, B3, B4 and B6), while Banyuwedang (B7) and Banjar (B13) are fault-hosted.

Following the interpretation of Purnomo and Pichler (2014) only Banyuwedang (B7)

was considered a truly fault-hosted geothermal system. This thermal water differs

from the others due to its poor of HCO3- content and thus plots as group C, fault-

hosted geothermal system in Figure 5.3. The volcanic-hosted thermal waters are

divided into group A, diluted thermal waters, and group B, originated from the margin

of the ‘primary neutralization’ zone of Giggenbach (1988). In this zone, the elevated

HCO3- content is produced by separation of CO2 and the subsequent reaction with

groundwater. The extent of groundwater mixing governs the Cl- concentration of

thermal waters. The HCO3- content of thermal waters was well correlated (R2 ~ 0.9)

with the Ca2+, Mg2+,Sr2+ and K+ (Fig. 5.4), hence indicated rock dissolution by carbonic

acid. The rocks dissolution was triggered by the formation of weak acid, H2CO3, at

temperatures below 300 °C due to oxidation of CO2 by groundwater (Bischoff and

Rosenbauer, 1996; Giggenbach, 1997; Lowenstern, 2001). The (Ca2+ + Mg2+)/HCO3-

molar ratios of the thermal waters of approximately 0.4 (Fig. 5.5) are lower than the

ratios for thermal waters hosted by carbonate rocks of 1, as reported for the

geothermal systems of Vicano-Cimino, Sabatini-Tolfa and Sicily, Italy; Cesme,

Nevsehir and Terme-Karakurt, Turkey, Bagneres de Bigorre, France; and Jemez

springs, USA (Capaccioni et al., 2011; Cinti et al., 2011; Cinti et al., 2014; Gemici and

Filiz, 2001; Goff et al., 1981; Grassa et al., 2006; Levet et al., 2002; Pasvanoglu and

Chandrasekharam, 2011; Pasvanoglu and Gultekin, 2012). Following this

interpretation a carbonate type host rock for the geothermal systems on Bali could be

ruled out. The thermal waters are more likely hosted by magmatic rocks of calc-

alkaline origin as indicated in the K/Mg vs. Na/K diagram (Fig. 5.6). This type of

magma is generally produced by volcanoes located in the middle of a volcanic island

arc, in between tholeiitic and high-K calc-alkaline magmatic regions (Whitford et al.,

1979).

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Fig. 5.3. HCO3 vs. Cl diagram. Groups A and B were volcano-hosted thermal waters originated from the ‘primary neutralization’ zone, where group B was less diluted by groundwater compared to group A. Group C was fault-hosted thermal water, hence underwent insignificant magmatic fluid input.

The final pH of the thermal water was governed by addition of CO2, hence

H2CO3 formation, and subsequent water-rock interaction. While addition of CO2 lowers

the pH, water-rock interaction causes an increase due to the comsuption of H+. The

effect of CO2 addition in Penebel group (B1, B2, B3, B4 and B6) and Banjar (B13)

dominated water-rock interaction and thus kept a slightly acid pH (Fig. 5.7a).

Meanwhile, the CO2 supply in Batur group (B9, B10 and B11) and thus decreasing pH

was neutralized by water-rock interaction. However, the lower ρCO2 and higher pH of

Batur group compared to the other thermal waters also could be caused by calcite

precipitation, which also releases CO2, indicated by the saturation condition with

respect to calcite (Fig. 5.7b).

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Fig. 5.4. a) Ca vs. HCO3, b) Mg vs. HCO3, c) K vs. HCO3 and d) Sr vs. HCO3 diagrams. The well correlations of HCO3

- with Ca2+, Mg2+, K+ and Sr2+ indicated rock dissolution by carbonic acid.

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Fig. 5.5. The (Ca2+ + Mg2+)/HCO3- molar ratios of thermal waters were approximately

0.4, an indication of non-carbonate host-rocks. For comparison (Ca2+ + Mg2+)/HCO3-

molar ratios of the carbonate-hosted thermal waters plotted using data from Cinti et al. (2014), Capaccioni et al. (2011) and Levet et al. (2002).

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Fig. 5.6. K/Mg vs. Na/K diagram indicates dissolution of calc-alkaline volcanic rocks of Batur volcano. Data of calc-alkaline volcanic rocks of Batur are from Reubi and Nicholls (2004) and high-K volcanic rocks of Muria volcano from Whitford et al. (1979).

Fig. 5.7. a) log ρCO2 vs. pH and b) SI calcite vs. pH diagrams. Thermal waters with high ρCO2 had lower pH, a typical of CO2 fed thermal waters. The water pH probably was also buffered by calcite precipitation.

V.4.2. Phase separation and seawater input The Cl/B ratio of thermal waters can be used to identify water-rock interaction,

steam separation and seawater input in the subsurface (Arnorsson and Andresdottir,

1995; Purnomo and Pichler, 2014; Valentino and Stanzione, 2003). The Cl vs. B

diagram of thermal waters from Bali indicates reaction with andesitic rock for the Yeh

Panas group (B1, B2 and B3) and the Batur group (B9, B10 and B11) of thermal

waters. Either B depletion or seawater input is indicated for Banyuwedang (B7) and

steam phase separation for Belulang (B4), Angseri (B6) and Banjar (B13) (Fig. 5.8).

The last process elevates the B/Cl ratio of the thermal water by scavenging B into the

steam phase, thus relatively increasing the Cl content of the residual water (Arnorsson

and Andresdottir, 1995; Truesdell et al., 1989). That steam phase separation occurred

for B4 and B6 was confirmed due to the existence of two phases, liquid and vapor,

zone in the liquid-dominated reservoir of the Bedugul geothermal field (Hochstein et

al., 2005).

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The distinct δ11B composition of seawater of +39.61 ‰ (Foster et al., 2010) is

heavier than other fluid sources and thus can be used to investigate seawater input or

B adsorption onto minerals to explain the B/Cl ratio observed for Banyuwedang (B7).

This method was successfully applied for some geothermal systems on Java island,

Indonesia (Parangtritis and Krakal), Iceland (the Reykjanes and Svartsengi) and three

areas in Japan (the Izu-Bonin arc, Kusatsu-Shirane area, and Kagoshima) (Aggarwal

and Palmer, 1995; Aggarwal et al., 2000; Kakihana et al., 1987; Millot et al., 2009;

Musashi et al., 1988; Oi et al., 1993; Purnomo et al., 2015). Adsorption of B by

minerals also increases the δ11B of the thermal water due to the preferentially

fractionation of 10B into the solid phase (Palmer et al., 1987; Schwarcz et al., 1969;

Xiao et al., 2013). The magnitude, however, is lower than what can be observed due

to seawater input. Banyuwedang (B7) had a δ11B composition of +22.5 ‰ and a Cl/B

ratio of 806; therefore, it plots close to the mixing line between seawater and thermal

water in the δ11B vs. B/Cl diagram (Fig. 5.9), which would confirm seawater input. The

thermal water shift away from the seawater point in the B vs. Cl diagram was caused

by groundwater mixing that lowered its B and Cl- concentrations.

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Fig. 5.8. Cl vs. B diagram illustrates four processes in the sub surface, i.e., a steam phase separation for B4, B6 and B13; an andesitic rock leaching for B1 to B3 and B9 to B11; and either a B depletion or seawater input for B7.

Fig. 5.9. The plot of Banyuwedang close to the mixing line of seawater-thermal water in the δ11B vs. B/Cl diagram confirms seawater input.

V.4.3. Geothermometry

The reservoir temperatures of geothermal systems on Bali were calculated

using solute geothermometers, SiO2, Na-K-Ca, Na-K and Na-Li (Table 5.2) (Fournier,

1977; Fournier, 1979; Fournier and Truesdell, 1973; Kharaka and Mariner, 1989).

These geothermometers record their temperature-dependent equilibrium reactions,

hence application of multiple geothermometers can be used to evaluate secondary

processes during thermal water ascent from the reservoir to the surface. These

processes include shallow water dilution, conductive cooling, adiabatic cooling,

mineral precipitation, water-rock interaction and re-equlibration (Fournier, 1977;

Kaasalainen and Stefánsson, 2012). Such an evaluation has been successfully

applied, for instances, on Java, Indonesia and Ambitle island, Papua New Guinea

(Pichler et al., 1999; Purnomo and Pichler, 2014).

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The silica geothermometer calculated lower reservoir temperatures compared to

the Na-K, Na-K-Ca and Na-Li geothermometers, which is common for samples taken

at the surface from hot springs, rather than directly from the geothermal reservoir.

That geothermometer predicted reservoir temperatures ranging from 44 to 136 °C,

while those predicted by the Na/K thermometer ranged from 257 to 773 °C, those

predicted by the Na/K/Ca thermometer from 130 to 236 °C and those predicted by the

Na/Li thermometer from 162 to 254 °C (Table 5.2). The calculation of silica

geothermometry is based on absolute silica content, hence sensitive to boiling,

precipitation and dilution (e.g. Nicholson, 1993). This deficiency can be overcome by

calculating the silica parent using the silica mixing model of Fournier (1977). However,

this method could not be used on Bali because the thermal waters in a given

geothermal system had relatively similar temperatures and silica contents, for

example the Penebel group (B1, B2, B3, B4 and B6). Meanwhile, the Na/K

temperatures are likely overestimations caused by competition of Ca2+, Na+ and K+

during ion exchange (Nicholson, 1993). The use of the Na/Li geothermometer resulted

in reservoir temperatures ranging from 235 to 254 °C for the Penebel thermal waters

(B1, B2, B3, B4 and B6), which were relatively similar to actual reservoir temperatures

at 1800 m below ground of the nearby Bedugul geothermal field of 243 °C (Mulyadi et

al., 2005). This indicates the applicability of the Na/Li geothermometer as has been

proposed by, e.g., Fouillac and Michard (1981). Based on this, the reservoir

temperatures of the other geothermal systems on Bali, with an exception of

Banyuwedang (B7), were predicted using Na/Li geothermometer. Therefore, the

reservoir temperature of the Batur geothermal system was approximately 240 °C and

Banjar was 255 °C. However, due to the input of seawater in Banyuwedang (B7),

there a geothermometer based on Na+ content is unreliable. The silica

geothermometer predicted a temperature of 44 °C for B7, similar to the discharge

temperature and hence a likely underestimation. Therefore, the reservoir temperature

of B7 could not be reliably calculated, but probably is lower than 100 °C, a

temperature similar to most of the fault-hosted geothermal system on Java (Purnomo

and Pichler, 2014).

Calcite precipitation during thermal water ascent was predicted by comparing

the result of Na/Li and Na/K/Ca geothemometers. Precipitation of calcite during

thermal water ascent reduces the Ca2+ concentration and thus should result in lower

calculated Na/K/Ca temperatures. Calculated temperatures ranged from 209 to 236

°C for the Penebel group of thermal waters and thus were similar to those calculated

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the Na/Li geothermometer, which would indicate insignificant calcite precipitation

during fluid ascent. In contrast, the difference between 170 °C (Na/K/Ca) and 240 °C

(Na/Li) for the Batur group of thermal waters indicates that calcite precipitated during

ascent. This is corroborated by the lower ρCO2 and higher pH compared to the

Penebel thermal waters (Fig. 5.7).

Table 5.2. Calculated reservoir temperatures using solute geothermometers.

Location Sample Geothermometers (°C) ID Silica Na/K/Ca Na/K Na/Li

(Truesdell, 1975)

(Fournier and Truesdell, 1973)

(Fournier, 1979)

(Kharaka et al., 1982)

Penebel

B1 122 209 568 244 B2 122 209 567 242 B3 126 211 566 235 B4 120 227 688 254 B6 136 236 733 254

Banyuwedang B7 44 130 257 190

Batur B9 108 172 395 236 B10 122 171 396 240 B11 108 171 394 239

Banjar B13 120 205 602 255

V.4.4. Oxygen and hydrogen isotope considerations The deuterium and oxygen isotopic composition of thermal waters has been

successfully applied to investigate the fluid origin, i.e., meteoric, marine or magmatic,

mixing and physicochemical processes, such as, water-rock interaction and water-

CO2 isotope exchange (Arnason, 1977; Cinti et al., 2014; Craig et al., 1956; Gemici

and Filiz, 2001; Giggenbach et al., 1983; Pichler, 2005; Purnomo and Pichler, 2014).

The δ2H and δ18O composition of water is generally a good indicator of its origin.

Hydrothermal fluids normally plot to the right of the LMWL due to exchange of 18O

during water-rock interaction (Craig, 1966) or due to subsurface mixing with an

andesitic water, as defined by (Giggenbach, 1992). In the δ2H vs. δ18O diagram all

thermal waters, except the two lake waters, plot close to the local meteoric water line

(LMWL) and weighted mean annual value for precipitation in the region, indicating

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local rainwater as the ultimate fluid source (Fig. 5.10). With the exception of sample

B10 the thermal waters from Bali did not shift to the right of the LMWL indicating

neither water-rock isotope exchange or mixing with an andesitic water. Neither

process, however, can be completely ruled out because an initial 18O-shift to the right

may have been later reversed by a subsequent isotope exchange between CO2 and

H2O. Such isotope shifts were observed in several CO2-rich aquifers and

hydrothermal waters (Chiodini et al., 2000; Cinti et al., 2011; Cinti et al., 2014; Grassa

et al., 2006; Vuataz and Goff, 1986). The Tirta Husada hot spring (B10) from the Batur

group plots slightly right shifted from Toya Devasya (B11), potentially signaling some

water-rock interaction. However, the TDS of B10 was relatively similar to B11 and B9

(Fig. 5.11). Although shallow magma is present at the Batur volcano (Geiger, 2014),

an isotope isotope enrichment by magmatic input was not observed. The absence of a

pronounced δ18O shift to heavier values also points towards a non-carbonate

reservoir. Due to water-rock interaction in carbonate reservoirs heavier δ18O values

are generally observed at such locations (Pasvanoglu and Chandrasekharam, 2011).

Fig. 5.10. δ2H vs. δ18O diagram with the local meteoric water line (LMWL) from Wandowo et al. (2001), GMWL from Craig (1961) and the mean annual value for

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precipitation in Jakarta from IAEA (2008). The thermal waters were of meteoric water origin. B10 is slightly horizontal right shifted from B11, probably was caused by water-rock interaction. The heavy water isotope of Lake Bratan and Lake Batur were caused by evaporation.

Fig. 5.11. TDS vs. δ18O diagram shows relatively similar TDS for the Batur thermal waters, B9, B10 and B11, hence indicating an insignificant 18O enrichment due to water-rock interaction.

The elevated δ2H and δ18O compositions of Lake Batur (B12) and Lake Bratan

(B15), which were studied in detail by Varekamp and Kreulen (2000), were a result of

evaporation in a cold lake. B12 was slightly enriched in δ18O compared to B15, likely

due to the significant input of thermal waters into the lake that elevated its

temperature. A lake with a higher temperature would produce a heavier δ18O due to

evaporation (Gonfiantini, 1986; Varekamp and Kreulen, 2000).

V.5. Conclusions Two types of geothermal systems are present on Bali, the fault-hosted for

Banyuwedang geothermal system and the volcano-hosted Penebel, Batur and Banjar

geothermal systems. Contrary to assumptions by others we conclude that, although

Bali is underlain by a carbonate basement, the geothermal reservoir rocks are of calc-

alkaline magmatic origin. Steam phase separation occurred in Penebel and Banjar

geothermal systems, while seawater input was confirmed for the fault-hosted

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geothermal system of Banyuwedang. Comparison of several geothermometers with

actual reservoir temperature measurements and physicochemical considerations led

to the conclusion that the Na/Li thermometer provided the best results for geothermal

systems on Bali. Using this thermometer, the following reservoir temperatures were

calculated: (1) Penebel (Bedugul) from 235 to 254 °C, (2) Batur 240 °C, (3) Banjar

255 °C and (4) Banyuwedang below 100 °C. The deuterium and oxygen isotopic

composition indicated the thermal water were of meteoric water origin without

significant of water-rock interaction and/or mixing with an andesitic magmatic fluid. Acknowledgments

B.J. Purnomo likes to thank the Ministry of Energy and Mineral Resources of

Indonesia for the PhD scholarship grants number: 2579 K/69/MEM/2010. Thanks to

Chen-Feng You for the boron isotope measurement, to Laura Knigge for the

laboratory assistance, to Ketut Suardana for the help during fieldwork and to Britta

Hinz-Stolle for an editorial review.

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VI. Conclusions and outlook

VI.1. Conclusions

Geothermal systems in the Sunda volcanic island arc are mostly a volcano-

hosted system. In this geological setting, the geothermal systems are considered

mainly influenced by Quaternary volcanic activities. However, a closer look at the

geothermal systems on Java showed that a fault-hosted geothermal system could

exist exclusively, without any influence from the Quaternary magma. Specific

conclusions coming from this study are:

1. The geothermal systems on Java could be classified into two types, volcano-

hosted and fault-hosted. However, the classification could not be solely based on

the location, either in a volcano or fault, magmatic fluids input has to be taken into

account. Geothermal systems hosted by fault distributed in the Quaternary volcanic

belt were supplied by magmatic fluids, thus could not be classified as a fault-

hosted geothermal system.

2. The presence of magmatic fluids input in the volcano-hosted geothermal system

elevated the HCO3-, Mg/Na ratios and stable isotope (2H and 18O). These

characteristics were not identified in the fault-hosted geothermal systems.

3. In the fault-hosted geothermal systems deep circulated groundwater is conductive

heated. Quaternary magma fluids input are absent due to the relatively

impermeable Tertiary volcanic rocks. However, the Quaternary magma could be

the heat source for the fault-hosted geothermal system, as indicated in the Cilayu

and Cisolok geothermal systems.

4. Another heat source for the fault-hosted geothermal systems located in the Tertiary

volcanic belt was considered a deep-seated magma, like has been identified

elsewhere, e.g., the Alpine fault, New Zealand (Allis and Shi, 1995; Shi et al.,

1996). The plates subduction in the south of Java has uplifted and thinned the

crust of the sourthern part of the island, hence deep circulated groundwater can

extract a deep-seated magma.

5. The boron isotope composition of thermal waters further distinguished volcano-

hosted and fault-hosted geothermal systems. The fast ascent and absence of

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magmatic fluids input kept a light δ11B value of the fault-hosted geothermal systems

and conversely, slow ascent and magmatic fluids input, which is favorable for

minerals precipitation, promoted δ11B enrichment in the volcano-hosted geothermal

systems.

6. The contrasting processes between acid chloride and acid sulfate crater lakes

produced different B isotope signatures. The former had light δ11B values

representing direct magmatic fluids supply from the subsurface. In contrast, the

latter were δ11B enriched by vapor phase separation in the subsurface, followed by

evaporation and B adsorption into clay minerals after discharge.

7. The study of geothermal systems on Bali identified two types of geothermal

systems, a fault-hosted for Banyuwedang and a volcano-hosted for Penebel

(Bedugul), Batur and Banjar. The thermal waters had (Ca2+ + Mg2+)/HCO3- ratios of

approximately 0.4 and stable (2H and 18O) isotope typical of meteoric water origin,

hence ruled out a carbonate host rock type. The host rocks are volcanic of calc-

alkaline magma, as indicated by the K/Mg. Vapor phase separation was identified

occurring in Penebel (Bedugul) and Banjar geothermal systems. The fault-hosted

geothermal system of Banyuwedang is influenced by seawater input.

VI.2. Outlook This study reveals a complex geothermal systems in the Sunda volcanic island

arc. The fault-hosted geothermal systems are not necessarily influenced by the

Quaternary volcanic activities. Since every location has unique geological

characteristics, the methods used in this study could be applied in other volcanic

islands arcs, e.g., Japan, Philippines and New Zealand. The studies will benefit for

better understanding the geothermal systems in such a geological setting, hence the

model can be established. The absence of Quaternary magmatic fluid should be

corroborated in the next studies by incorporating sulfur (34S of SO42-) and carbon (13C

of CO2) isotopes to trace the origin. Sulfur in a geothermal water can be sourced from

1) seawater, 2) magmatic gases (H2S and SO2) and 3) oxidation of sulfide minerals

(Pichler, 2005). 13C isotope of CO2 was applied to trace the contribution of mantle

degassing and rock leaching, e.g., in Tutum Bay, Papua New Guinea by Pichler

(2005) and the Sabatini volcanic area, Italy by Cinti et al. (2011). The geochemical

study can be supported by details geological mapping and geophysical measurement

to configure the subsurface condition in the boundary of the Quaternary volcanic belt

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and Tertiary volcanic belt. Although the Tertiary volcanic rocks are relatively

impermeable, the presence of fractures potentially circulating fluids.

Concerning on the boron isotope signature of the two contrast thermal crater

lakes, acid sulfate and acid chloride, this study shows an overview of their different

boron isotope signatures and provides the possible explanations. More samples

representing both acid crater lakes from different location would corroborate this

finding. The distinct characteristic of the two crater lakes, the Kawah putih, rich in B

and light in δ11B values, and Kawah Sikidang, rich in B and heavy in δ11B values,

deserve for a more detail study. A time series of sampling should be done to

understand the fluctuation of δ11B isotope value. The behavior of B isotope after

discharge can be determined by performing experiments of B isotope fractionation

during evaporation and clay adsorption for low pH water with high and low Cl-

concentrations, representing acid sulfate and acid choride, respectively. To date the

effect of pH on B isotope fractionation during water-clay interaction is only known for

higher pH (> 5), e.g., Yingkai and Lan (2001).

The study on Bali provides evidences of a non carbonate reservoir type, thus

the rich of CO2 in the geothermal brines likely was resulted by CO2-rich magma

volatile due to a carbonate assimilation, as was proposed by Geiger (2014). 13C

isotope of CO2 has to be incorporated in the upcoming studies. Access to the

geothermal brines of the Bedugul geothermal field could be used to examine its

contrasting physicochemical properties compared to the geothermal brines from Java

(Bogie et al., 2008; Mulyadi et al., 2005; Purnomo and Pichler, 2014). The indication

of significant thermal water supply into the Lake Batur needs to be confirmed by a

systematic sampling. The sampling also can be applied to map the physicochemical

characteristic distribution, leading to an identification of thermal water sources. The

significant thermal water input might be originated from underwater thermal water

discharge, hence a survey of underwater hot spot is needed.

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Acknowledgements

This PhD was made possible by funding from the Ministry of Energy and Mineral

Resources of Republic Indonesia and University of Bremen.

I would like to first thank my supervisor, Prof. Dr. Thomas Pichler for the opportunity to

do PhD, something beyond my imagination before you invited me. I learned the

passion of doing fieldwork as a geoscientist from the experience working along with

you during sampling campaign across Java in 2012. Words will not be enough to

express my gratitude for your advices, supports and critical discussions during my 4

years doing PhD.

I thank to Prof. Dr. Peter LaFemina for the agreement to review and examine my PhD

thesis. Thanks to Prof. Dr. Chen-Feng You for the boron isotope analysis. The fourth

chapter of this thesis would not be possible without your contributions.

Special thank to Laura Knigge, Christine Albert and Christian Breuer for the help

during laboratory analyses, also Britta Hinz-Stolle for your much effort and time on the

editorial review of my manuscripts. Wisanukorn Poonchai is thanked for your German

to English translation during our PHREEQC summer course. I also thank to Dr. Kay

Hamer and Dr. Lars-Eric Heimburger for the fruitful advices, discussions and inputs.

Pak Ketut, Maman and Seto are thanked for the assistance during sampling campaign

on Java and Bali.

My fellow PhD students in the Geochemistry and Hydrogeology group, Wu Debo, Qi

Pengfei and Ali Mozafarri, for the support, sharing, discussion and encouragement.

Special for my office mates, Debo and Pengfei, thanks for always keep a warm

atmosphere in our beloved office.

I thank to my fellow ‘Cator’-ers (Indonesian PhD students in Bremen): Riza Setiawan,

Mba Asty, Mba Hesty, Teh Rima, Kang Ayi, Condro, Yusup, Haliq, Mba Enab, Mba

Meity, and Rovi. Our togetherness kept my motivation and spirit on finishing this

study.

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Finally, my beloved wife, Novi, and daughter, Inca, deserve very special thank. I

dedicate this for you both. Thanks to my big family, my father and mother (in heaven),

my 9 brothers and sisters, Mas Kentut, Mba Pon, Mba Iten, Mba Sri, Mas Tris, Mba

Nik, Mas Cipto, Mba Yani and Ulin. I could not achieve this level without all of you. My

parents in law are thanked for taking care my small family during I stay in Germany.

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