/ Journal of Volcanology and Geothermal Research 346 (2017) 81–94

Contents lists available at ScienceDirect

Journal of Volcanology and Geothermal Research

journal homepage: www.elsevier.com/locate/jvolgeores

Gas chemistry of Icelandic thermal fluids

Andri Stefánsson
Institute of Earth Sciences, University of Iceland, Sturlugata 7, 101 Reykjavík, Iceland

a r t i c l e i n f o a b s t r a c t

Article history: The chemistry of gases in thermal fluids from Iceland was studied in order to evaluate the sources and processes
Received 14 November 2016 affecting volatile concentrations in volcanic geothermal systems at divergent plate boundaries. The fluids includ-
Received in revised form 15 March 2017 ed vapor fumaroles and two-phase well discharges with temperatures of ~100–340 °C. The vapor was dominated
Accepted 2 April 2017
by H2O accounting for 62–100 mol% and generally for N 99 mol%, with CO2, H2S and H2 being the dominant gases
Available online 7 April 2017
followed by N2, CH4, and Ar. Overall mineral-gas and gas-gas equilibria were not observed for the major gases,
Keywords:
including CO2, H2S, H2 and CH4 within the geothermal reservoirs. Instead the system proved to be controlled
Hydrothermal by source(s) and their ratios and various metastable equilibria along a fluid-rock reaction progress with gas con-
Fluid centrations controlled by such metastable equilibria varying at particular temperatures as a functional extent of
Equilibrium reaction. The concentrations of H2S and H2 closely reflect mineral-fluid metastable equilibria, whereas CO2 con-
centrations are controlled by the input of magma gas corresponding to N0.1 to b 5% mass input. With fluid ascent
to the surface, boiling and condensation may occur, further changing the gas concentrations and hence surface
fumaroles may not reflect the reservoir fluid characteristics but rather secondary processes.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
The chemistry of gases in thermal fluids has been extensively stud-
ied for over four decades, for the purpose of tracing the source(s) and
reactions of gases as well as for exploration and utilization of geother-
mal resources (e.g., D'Amore and Nuti, 1977; Giggenbach, 1980, 1987,
1993; D'Amore and Panichi, 1980; Arnórsson and Gunnlaugsson,
1985; Taran, 1986, 2011; Arnórsson et al., 1990; Chiodini and Cioni,
1989; Chiodini and Marini, 1998; Stefánsson and Arnórsson, 2002;
Scott et al., 2014). The major gases in thermal fluids include H2O, H2,
CO2, CH4, H2S and N2 as well as, sometimes, NH3, CO, He and Ar
(e.g., Giggenbach, 1975; Arnórsson et al., 2007). They are considered
to be derived from the atmosphere, mantle, and crust and often reflect
processes occurring within geothermal systems, such as fluid-rock and
fluid-fluid interaction and thermal decomposition of organic matter
(e.g., Giggenbach, 1992; Taran et al., 1995; Chiodini and Marini, 1998;
Hilton et al., 2002; Stefánsson et al., 2017a).
It has been suggested that local equilibria between geothermal min-
erals and gaseous species prevail in some geothermal systems
(e.g., Giggenbach, 1980; Chiodini and Marini, 1998). Local mineral-gas
and gas-gas equilibria are not always observed, however, as they are
thought to be influenced by the flux of gases and/or slow reaction kinet-
ics, particularly for oxidation and reduction reactions (e.g., Stefánsson
and Arnórsson, 2002; Lowenstern et al., 2015). The attainment of local
equilibria involving gases constitutes the basis for gas geothermometry.
E-mail address: as@hi.is.
These equilibria have been based on the concentration of a single reac-
tive gas, like CO2, H2S or H2 (Arnórsson and Gunnlaugsson, 1985), two
or more reactive gases like CO2-H2, H2S-H2 and CH4-CO2-CO
(Arnórsson and Gunnlaugsson, 1985; Chiodini and Cioni, 1989) or a
ratio of reactive and inert gas like CO2/Ar, H2/Ar and CO2/N2
(e.g., Arnórsson, 1987; Giggenbach, 1991), the last introduced to ac-
count for possible gas condensation in the fluid conduit in geothermal
systems.
Gases in thermal fluids in Icelandic geothermal systems have been a
subject of numerous studies, both their isotopes and chemical composi-
tions (e.g., Árnason, 1977; Ármannsson et al., 1982; Arnórsson and
Gunnlaugsson, 1985; Sano et al., 1985; Arnórsson, 1987; Arnórsson
et al., 1987, 2007; Marty et al., 1991; Poreda et al., 1992; Hilton et al.,
1998; Stefánsson and Arnórsson, 2002; Füri et al., 2010; Stefánsson
et al., 2011; Kaasalainen and Stefánsson, 2012; Barry et al., 2014; Scott
et al., 2014; Pope et al., 2015). Based on these studies it is evident that
the vapors of Icelandic geothermal systems are dominated by water,
in most cases N97%. From the δD and δ18O relationships, the source of
the water is considered to be meteoric and/or seawater (e.g.,
Sveinbjörnsdóttir et al., 1986; Pope et al., 2015). The non-reactive vola-
tiles in the source vapors, like Ar and N2, are considered to be dominant-
ly atmospheric, whereas recent data on δ15N isotopes have suggested a
minor mantle contribution in some cases (Óskarsson et al., 2015). A
deep-seated source for He has also been suggested (Poreda et al.,
1992; Hilton et al., 1998; Füri et al., 2010). With respect to reactive ele-
ments like CO2, H2S, CH4, H2 and Cl, melt degassing and/or rock leaching
have been suggested as a source of these elements (e.g., Ármannsson
et al., 1982; Arnórsson and Barnes, 1983; Poreda et al., 1992;

http://dx.doi.org/10.1016/j.jvolgeores.2017.04.002
0377-0273/© 2017 Elsevier B.V. All rights reserved.
82 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
Stefánsson and Arnórsson, 2002; Barry et al., 2014; Stefánsson et al.,
2015, 2016a; Stefánsson and Barnes, 2016). Based on thermodynamics,
it has been suggested that the major gas composition, i.e. CO2, H2S and
H2, is controlled close to equilibrium with secondary minerals. In con-
trast, overall gas-gas equilibria are not always observed (Arnórsson
and Gunnlaugsson, 1985; Stefánsson and Arnórsson, 2002). Moreover,
the ratio of magma gas to meteoric and/or seawater is also poorly
known, as well as the effects of progressive fluid-rock interaction on
the volatile concentrations.
In this study, the available data on the vapor composition of
Icelandic thermal fluids were summarized, including well discharges
and fumaroles, of data reported in scientific papers, reports and unpub-
lished data. From these data, the reservoir volatile concentrations and
mole fractions were used and compared with equilibrium mineral and
gas reactions, as well as reaction modeling involving gas-fluid-rock in-
teraction, in order to quantify the source(s) of the gases in the vapor
and the effects of mineral-gas and gas-gas reactions on their chemistry.
2. Geothermal activity in Iceland
Geothermal activity in Iceland has been divided into high- and low-
temperature systems (Bödvarsson, 1961; Fridleifsson, 1979). The high-
temperature geothermal activity is commonly associated with active
volcanic complexes located along the rift, whereas low-temperature
systems are associated with off-rift activity on the North American
and Eurasian plates (Fig. 1).
Icelandic thermal fluids are of meteoric and seawater origin or a
mixture of them, with temperatures between ~ 10 to ~ 450 °C, pH of
b2 to N10 and Cl concentrations of b1 to N20,000 ppm (Kaasalainen
and Stefánsson, 2012; Ármannsson, 2015; Kaasalainen et al., 2015;
Stefánsson et al., 2016b). They have been divided into two groups: pri-
mary and secondary type fluids (Arnórsson et al., 2007). Primary fluids,
sometimes referred to as reservoir fluids, are those reaching the deepest
level within the geothermal system. With ascent to the surface, they can
undergo chemical and physical changes leading to the formation of sec-
ondary geothermal fluids.
Deep wells, of up to N2500 m, have been drilled into many of the
geothermal systems in Iceland, thus allowing direct access to the
Fig. 1. Geology of Iceland and sampling locations. REY: Reykjanes, SVA: Svartsengi, KRÝ: Krýsuvík, HEL: Hellisheidi, HVER: Hveragerdi, NES: Nesjavellir, GEY: Geysir; SLL: Southern Low-
lands, TORF: Torfajökull, KERL: Kerlingarfjöll, HVERV: Hveravellir, VON: Vonarskard, KVER: Kverkfjöll, ASK: Askja, NÁM: Námafjall, KRA: Krafla and THEI: Theistareykir.
reservoir fluid to study their chemical characteristics. Based on such
well data, the primary or reservoir fluids have typically close to a neutral
pH value, with Na, Cl, S, C and Si being the dominant elements. The
chemical composition of secondary fluids is much more variable. Pro-
cesses like depressurization boiling, condensation and mixing may
alter their composition from the reservoir to the surface. The boiled liq-
uid that is typically discharged by hot springs is usually slightly enriched
in the non-volatile element concentrations and depleted in volatile con-
centration, like CO2 and H2S, relative to the primary fluids. As the fluids
have lost their main acids their pH is typically alkaline. In contrast, the
vapor phase formed upon boiling that is typically discharged at the sur-
face by fumaroles is enriched in the volatiles, including CO2, H2S, H2,
CH4, N2 and Ar relative to the boiled water and primary fluids. The
vapor may also mix and condense with non-thermal water at shallow
depths and surface steam-heated water, typically observed as mudpots
and bubbling springs. This means that secondary fluids may have un-
dergone various chemical and physical changes from the reservoir to
the surface, making their usage for assessment of reservoir chemical
characteristics more difficult compared with well fluids.
3. Methods
3.1. Collection and analysis of well and fumarole discharges
The dataset used in the present study comes from various sources,
spanning samples collected over six decades (Líndal and
Hermannsson, 1951; Ármannsson and Hauksson, 1980; Gíslason et al.,
1984; Ármannsson et al., 1985; Arnórsson and Gunnlaugsson, 1985;
Benjamínsson, 1985; Benjamínsson et al., 1985; Arnórsson, 1987;
Arnórsson et al., 1987, 1996; Ólafsson, 1991; Poreda et al., 1992;
Bjarnason, 1996, 2002; Bjarnason and Ólafsson, 2000; Gudmundsson
and Arnórsson, 2002, 2005; Hjartarson and Ólafsson, 2005a, 2005b;
Giroud, 2008; Benjamínsson and Hauksson, 2010, 2011; Stefánsson
et al., 2011, 2015; Kristinsson et al., 2013a, 2013b; Scott et al., 2014;
Kaasalainen et al., 2015; Stefánsson and Barnes, 2016). Various methods
were applied in collecting and analyzing the samples. However, in the
past ~40 years, a similar method has been applied in sample collection
and analysis for both fumarole gases and single and two-phase well
 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
discharges. These have been described in detail by Arnórsson et al.
(2006) and are only briefly summarized here.
For fumaroles, the common gases analyzed include H2O, CO2, H2S,
H2, CH4, N2 and Ar, whereas He, CO, NH3 and light hydrocarbons
(C2+) other than CH4 have not commonly been determined. Samples
for SO2 determination have rarely been collected, because of the low
sampling temperatures of fumaroles (~100 °C) and the non-magmatic
reservoir temperatures (b 350 °C) of geothermal systems in Iceland. In
fact SO2 is rarely observed in the thermal fluids except during and
soon after volcanic eruptions (e.g., Ármannsson et al., 1982).
In this study, the vapor, in each case, was collected by placing a plas-
tic funnel over or inserting a titanium tube into the vapor outlet and
connecting a gas bottle using a siliconee tube. The gas bottle ranged in
volume from 50 to 250 mL was evacuated prior to sampling and
contained ~ 10 mL of 50% KOH per 100 mL. The condensable gases,
CO2 and H2S, were then analyzed using modified alkalinity titration
(Stefánsson et al., 2007) and Hg-acetate precipitation titration with
dithizone as an indicator, respectively (Arnórsson et al., 2006). The
non-condensable gases (H2, CH4, N2 and Ar) were analyzed using gas
chromatography and the H2O determined by gravimetry and mass
balance.
For two-phase well discharges, the liquid and vapor phase were sep-
arated at the wellhead using a Webre separator. Vapor samples were
collected and analyzed in a similar manner as for fumarole vapor, as de-
scribed previously. The liquid phase samples were cooled down using a
stainless steel spiral connected to the Webre separator and then filtered
through a 0.2 μm cellulose acetate filter into polypropylene (for major
anion and cation analyses) or amber glass bottles (for CO2 analyses).
Samples for major cation analysis were acidified with 0.5 mL concen-
trated HNO3 (Suprapur®, Merck) per 100 mL sample and determined
using ICP-OES. Two samples for major anion analysis were collected,
Fig. 2. Sampling methods for two-phase well discharges and fumaroles. (A–B) The fumarole samples were collected by placing a funnel over or inserting a titanium tube into the vapor
stream, connecting the outflow by silicone tube to a gas bottle. (C–D) For the two-phase well discharges the liquid and vapor phases were separated using a Webre separator and the
two phases sampled, the vapor phase collected in the same manner as for fumaroles. For further details see Arnórsson et al. (2006).
83
one untreated and used for F, Cl and S2O3 determination and another
to which 2% Zn acetate solution was added to precipitate dissolved sul-
fide as zinc sulfide, leaving dissolved SO4 in solution for analysis. All
anion analyses were carried out using ion chromatography with the ex-
ception of CO2 in samples that were analyzed using the modified alka-
linity titration previously mentioned (Stefánsson et al., 2007).
Dissolved sulfide [ΣS-II = HS− and H2S(aq)] were titrated in situ using
the method previously described (Arnórsson et al., 2006). The pH was
analyzed in situ and in-line within a few seconds of sampling at
~20 °C using a flow-through pH cell.
A typical sampling setup for fumarole gas collection and two-phase
well discharges is shown in Fig. 2.
3.2. Calculation of reservoir fluid composition for well discharges
The WATCH program (Bjarnason, 2010) was used to calculate
the composition of geothermal reservoir fluids, aqueous speciation
and gas concentrations from data on two-phase well discharges. In the
case of vapor only fumarole discharges, the analytical data were directly
used. These calculations of reservoir fluid composition from the
chemical composition of vapor and liquid well discharges involve
solving together equations describing conservation of mass and
enthalpy (Arnórsson et al., 2007). The conservation of mass may be
expressed by,
 
mif ;t ¼ md;t d;v d;v
i ¼ X mi þ 1−X
d;v
md;lq
i ð1Þ
and the conservation of enthalpy by,
 
f ;t d;t d;v d;lq
h ¼h ¼ X d;v h þ 1−X d;v h ð2Þ
84 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94

where mi denotes the molal concentration of the i-th component, X is pressures of gas species including H2O,
the vapor fraction, h is the enthalpy and f, t, d, v and lq are the fluid,
total, discharge, vapor and liquid, respectively. The vapor fraction can
be calculated from, P total ¼ ∑ P i ð5Þ
i

d;t d;lq
h −h
X d;v ¼ d
ð3Þ Vapor in geothermal systems is usually dominated by H2O, and has a
L relatively low gas partial pressure. Under these conditions it is reason-
able to assume the fugacity coefficients to be unity, i.e. Γi = 1 and that
where Ld is the latent heat of vaporization. The values for hd,t can fi = Pi and that,
either be obtained from the measured liquid to vapor fraction of
discharge fluids, here referred to as measured enthalpy (meas. h) or
evaluated from the reservoir temperature assuming a liquid only reser- xvapor
i ¼ P i =P total ¼ nvapor
i =nvapor
total
ð6Þ
voir, i.e. h f,t = hd,t = hTreslq where hTreslq is the enthalpy of liquid at the res-
ervoir temperature. The values for hd,t, hd,v and Ld can be obtained from where nvapor is the number of moles in the vapor phase including H2O.
i
the properties of liquid and vapor water (steam tables). In a two-phase liquid and vapor system (lq + v), the equilibrium sol-
Here, the two approaches were used to calculate the reservoir fluid ubility constant (Kh,i) of gas in the liquid phase is given by,
composition and vapor fraction at sampling and in the reservoir, i.e.
model 1 assumes a liquid only reservoir and hf , t = hd , t = hTreslq and
model 2 takes the measured discharge vapor fraction to calculate the K h;i ¼ ai = f i ¼ mi γi =P i Γ i ð7Þ
reservoir vapor fraction when hf,t = hd,t N hTreslq.
The reservoir temperatures for two-phase well discharges were cal-
where ai, mi and γi are the activity, molal concentration and activity co-
culated assuming quartz equilibrium (Gunnarsson and Arnórsson,
efficient of the i-th aqueous species, respectively.
2000). With respect to fumaroles, the reservoir temperature was calcu-
For vapor, the values of Pi, Ptotal, xi, mi and γi for the liquid and vapor
lated based on gas geothermometry involving CO2, H2S and H2
phases were calculated with the aid of the WATCH program (Bjarnason,
(Arnórsson and Gunnlaugsson, 1985). It should be pointed out that
2010). For these calculations the thermodynamic database of Arnórsson
equilibrium my not have been attained with respect to individual nor
et al. (1982) was used with updates on gas solubilities (Fernandez-Prini
gas ratios, i.e. the gas geothermometry temperatures need to be consid-
et al., 2003). The reaction equilibrium constants involving minerals and
ered with care.
gases were calculated with the aid of the Supcrt92 program and the
slop07.dat database (Johnson et al., 1992; http://geopig.asu.edu/tools).
3.3. Thermodynamic relations
The mineral-gas and gas-gas equilibrium constants used in the study
are summarized in Table 1. The reactions involve commonly observed
The equilibrium constant (Ki) of reactions involving gases can be de-
secondary minerals in Icelandic geothermal systems at N200 °C
scribed by the general equation,
including quartz, calcite, pyrite, pyrrhotite, magnetite, epidote,
clinozoesite, chlorite, prehnite, grossular, wollastonite and anhydrite
ν
K ¼ ∏ f i i ¼ ∏ xνi i Γ νi i P total ð4Þ (e.g., Kristmannsdóttir, 1978; Lonker et al., 1993). For the calculations
i i
the activities of minerals was assumed to be unity except for prehnite,
clinozoesite and epidote where the activity was taken to be equal to
where fi, xi and Γi are the gas fugacities, mole fractions and fugacity co- the mole fraction of the mineral in the solid solution (X = a) commonly
efficients for the i-th gas species, respectively, and vi are the reaction observed for these minerals of Xpre = 0.5, Xczo = 0.3 and Xepi = 0.7, re-
stoichiometric coefficients, positive for products and negative for reac- spectively (Sveinbjörnsdóttir, 1992; Lonker et al., 1993; Stefánsson and
tants. The total fluid pressure, Ptotal, is defined as the sum of all partial Arnórsson, 2002)

Table 1
Chemical reactions and equilibrium constants (logKi). Calculated based on Supcrt92, slop07.dat.a,b

Reactions Temperature (°C)

25 100 150 200 250 300 350

Gas-gas reactionsc
CO2(g) + 4H2(g) = CH4(g) + 2H2O(g) 19.73 14.04 11.23 8.98 7.14 5.59 4.29
pyr + H2(g) = pyrr + H2S(g) −4.54 −2.76 −1.91 −1.22 −0.65 −0.17 0.23
3pyr + 2H2(g) + 4H2O(g) = mt + 6H2S(g) −30.99 −22.93 −18.98 −15.87 −13.35 −11.26 −9.49

Gas-mineral reactions
czo + cc + 3/2qtz + H2O(g) = 3/2pre + CO2(g) −0.89 −0.95 −0.93 −0.90 −0.88 −0.86 −0.83
2/5czo + cc + 3/5qtz = 3/5gro + 1/5H2O(g) + CO2(aq) −6.91 −3.74 −2.27 −1.12 −0.19 0.58 1.22
2/3gro + 1/3pyr + 1/3pyrr + 2/3qtz + 4/3H2O(g) = 2/3epi + 2/3wo + H2S(g) −5.34 −5.23 −4.99 −4.73 −4.48 −4.21 −3.92
2gro + 1/2pyr + 1/2mt + 2qtz + 2H2O(g) = 2epi + 2wo + H2S(g) −2.28 −2.69 −2.77 −2.83 −2.88 −2.92 −2.96
1/4pyr + 1/2pyrr + H2O(g) = 1/4mt + H2S(aq) −5.40 −4.35 −3.79 −3.36 −3.01 −2.73 −2.49
6pyr + 1.5pre + 10H2O(g) = 2mt + 1.5qtz + czo + anh + 11H2S(g) −84.03 −63.66 −53.63 −45.72 −39.31 −33.99 −29.49
4/3pyrr + 2/3pre + 2/3H2O(g) = 2/3epi + 2/3pyr + H2(g) −1.74 −1.57 −1.49 −1.46 −1.46 −1.45 −1.46
2/3gro + 4/3pyrr + 2/3qtz + 4/3H2O(g) = 2/3epi + 2/3wo + 2/3pyr + H2(g) 0.18 −0.99 −1.49 −1.93 −2.28 −2.59 −2.85
6gro + 2mt + 6qtz + 4H2O(g) = 6epi + 6wo + H2(g) 8.67 3.41 1.17 −0.57 −1.96 −3.12 −4.12
3/2pyrr + H2O(g) = 3/4pyr + 1/4mt + H2(g) −0.94 −1.59 −1.87 −2.14 −2.37 −2.56 −2.72
1.5pyr + 4.5pre + 8H2O(g) = 0.5mt + 4.5qtz + 3czo + 3anh + 11H2(g) −81.65 −64.83 −56.50 −49.90 −44.52 −40.05 −36.27
a
geopig.asu.edu/tools.
b
pyr: pyrite; pyrr: pyrrhotite; mt: magnetite; czo: clinozoesite; cc: calcite; qtz: quartz; pre: prehnite; gro: grossular; epi: epidote; wo: wollastonite; anh: anhydrite.
c
apre = 0.5; aczo: 0.3 and aepi:0.7.
 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94 85

3.4. Geochemical simulation of gas-fluid-rock interaction
To gain further insight into gas-fluid-rock interaction and the effects
of gas (acid) supply source and reactions of C, S and H to the system, re-
action path simulations were conducted using the PHREEQC program
(Parkhurst and Appelo, 1999) and the llnl.dat database. The calculations
involve mixing non-thermal water with volcanic gas of different ratios
(0.1–10%), and reacting the liquid solution with basaltic rock in steps,
allowing secondary minerals to precipitate when saturated. The calcula-
tions were conducted at 275 °C and water vapor saturation pressure
(Psat). The secondary minerals included in the calculations were those
commonly associated with alteration of basalts at N200 °C and included
quartz, calcite, pyrite, pyrrhotite, magnetite, epidote, wollastonite, gros-
sular, clionzoestie, chlorite, prehnite, wairakite, albite, microcline and
anhydrite (e.g., Kristmannsdóttir, 1978; Lonker et al., 1993). The results
of the reaction path simulations were then compared with the observed
fluid composition in order to evaluate the role of volcanic gas input and
progressive mineral-fluid reactions in the gas chemistry. The input con-
ditions for the modeling, i.e. non-thermal water, basalt and volcanic gas
composition, are listed in Table 2. The basalt is the average Icelandic ba-
salt composition accounting for N80% of the rock type in Iceland
(Kaasalainen and Stefánsson, 2012), the non-thermal water is repre-
sented by typical surface water in Iceland and has been previously
used for modeling (Kaasalainen and Stefánsson, 2012), and the volcanic
gas is based on direct measurements of magma gases in Iceland
(Sigvaldason and Elísson, 1968; Gíslason et al., 2015; Gauthier et al.,
2016; Stefánsson et al., 2017b).
4. Gas concentrations of thermal fluids in Iceland
4.1. Fumaroles and well fluid discharges
The dataset compiled in the present study includes well fluid dis-
charges (n = 275) and fumarole vapor (n = 587) from over 15 geother-
mal systems in Iceland (Fig. 1). The geothermal systems include
Reykjanes, Svartsengi, Krýsuvík, Hengill including Hellisheidi,
Nesjavellir and Hveragerdi, Geysir, Southern Lowlands, Torfajökull,
Kerlingafjöll, Hveravellir, Vonarskard, Askja, Kverkfjöll, Námafjall, Krafla
and Theisareykir. All systems are located within the active volcanic zone
of Iceland with the exception of the systems on the Southern Lowlands.
Representative fluid composition for these geothermal systems are
given in Table 3 (the full ThermoFluid dataset, Stefánsson et al., 2016c,
can be obtained from Ríkey Kjartansdóttir, rikey@hi.is). The source
fluid for most of the geothermal systems is considered to be meteoric
water, whereas at Reykjanes and Svartsengi the source of the fluids is
both seawater and seawater-meteoric water (Arnórsson, 1995). Four
geothermal systems are associated with major silicic rock formations,
i.e. Geysir, Torfajökull, Kerlingafjöll and Askja, whereas the others are
dominated by basaltic rocks.
The well and fumarole vapor was dominated by H2O, accounting for
92.2 to 99.9 mol% and 62.3–100 mol%, respectively (Fig. 3). Carbon diox-
ide, H2S and H2 were the dominant gases with concentration ranges
(median in parenthesis) in well and fumarole vapor discharges of
0.01–37.8 (0.37) mol%, 7·10− 5-0.30 (0.06) mol% and 7·10−5-0.68
(0.05) mol% followed by N2, CH4, and Ar with concentrations, typically
b0.03 mol%, b0.002 and b 0.001 mol%, respectively.
Considerable differences in gas concentrations were observed be-
tween different geothermal systems. Elevated CO2 concentrations
were observed in some samples from Krafla, Askja, Krýsuvík and
Torfajökull, whereas vapor in Námafjall was high in H2 and CH4 relative
to fluids from most other geothermal systems. The concentrations of
H2S and H2 were generally lower for geothermal systems with a seawa-
ter source fluid than for systems with meteoric source fluids. Moreover,
fluids having low temperatures such as in the Southern Lowlands and at
Geysir and Hveravellir had lower gas concentrations in general com-
pared to geothermal systems having higher reservoir temperatures.
These observations suggest that multiple factors may affect gas concen-
trations in thermal fluids in Iceland, including the sources of gases, rock
and melt types and reactions within the geothermal systems and upon
fluid ascent to surface.
4.2. Reservoir fluids
The reservoir fluid composition was calculated based on the liquid
and vapor composition of the two-phase well discharges. For these cal-
culations, two approaches were used. Firstly, the geothermal reservoir
was assumed to be liquid only and the total fluid enthalpy calculated
based on the temperature and the liquid enthalpy of the reservoir.
This model is referred to as model 1 and calculated enthalpy
(i.e., model 1, calc. h). Secondly, the vapor fraction of the well discharge
and reservoir were calculated based on the measured enthalpy of the
fluid discharge and the reservoir temperature. This model is referred
to as model 2 and measured enthalpy (i.e., model 2, meas. h). The results
of the mole fractions of CO2, H2S and H2 as a function of reservoir tem-
perature have been plotted in Fig. 4.
The resulting reservoir vapor composition calculated based on well
liquid and vapor discharges was highly variable depending on the ap-
proach used to calculate the reservoir fluid composition. Assuming
only liquid in the geothermal reservoir (model 1, calc. h), the mole frac-
tions of gases for dilute fluids (b 500 ppm Cl), including CO2, H2S and H2,
were generally higher compared to when assuming two-phase liquid
and vapor reservoirs. It should be noted, however, that in the former
case the mole fraction of gases in the vapor phase was purely a thermo-
dynamic convention as there was no vapor phase present.

Table 2 5. Mineral-gas and gas-gas equilibria

Chemical compostion of basalt, non-thermal water and volcanic gas used in the geochem-
ical model calculations.
5.1. Mineral-gas equilibria
Basalta,b Non-thermal water a Volcanic gas c

SiO2 wt% 50.0 pH 7.45 H2O mol% 91.6 Mineral-gas equilibria have been suggested as a major factor con-
Al2O3 wt% 14.9 SiO2 ppm 11.5 CO2 mol% 4.95 trolling CO2, H2S and H2 concentrations in thermal fluids in Iceland
TiO2 wt% 1.52 Na ppm 7.79 SO2 mol% 3.22 (Arnórsson and Gunnlaugsson, 1985; Stefánsson and Arnórsson,
FeO wt% 10.8 K ppm 0.47 HCl mol% 0.23 2002), based on the composition of reservoir fluid composition and
MnO wt% 0.19 Ca ppm 3.89 HF mol% 0.05
mineral-gas equilibrium values. However, based on the comparison of
MgO wt% 7.86 Mg ppm 1.41
CaO wt% 12.3 CO2 ppm 19.3 the observed and calculated mole fractions (Fig. 4) it cannot be conclud-
Na2O wt% 2.14 Cl ppm 3.37 ed whether mineral-gas reactions controls CO2, H2S and H2 concentra-
K2O wt% 0.2 F ppm 0.14 tions in vapors in Icelandic geothermal systems; the scatter of data
S ppm 300 SO4 ppm 4.8
and equilibrium values is simply too great. Moreover, the uncertainties
Cl ppm 220
CO2 ppm 145b about the calculated reservoir fluid composition exceed in some cases
a
the range of equilibrium values calculated for the proposed mineral-
Kaasalainen and Stefánsson (2012) and references therein.
b
Barry et al. (2014).
gas reactions as well as the changes on boiling.
c
Based on Sigvaldason and Elísson (1968), Gíslason et al. (2015), Gauthier et al. (2016) Looking at the gas concentrations for a given geothermal system
and Stefánsson et al. (2017b). sometimes reveals a small range, for example at Hengill, whereas in
 86
Table 3
Selected discharge well and fumarole gas compostion.a,b

Sample # Location/well # Type c Tsampling model#1 (calc. h) d,e

model #2 (meas. h) d,e
Liquid phase (ppm) Vapor phase (μmol/mol)

Tres Xsampling Xres Tres Xsampling Xres Cl CO2 H2S H2O CO2 H2S H2 CH4 N2 Ar

Askja
1983–0001 f 311 971,089 26,537 1787 474 0.75 110 2.02
1983–0013 f 312 971,948 26,204 908 580 1.05 350 8.12
1983–0014 f 311 971,544 26,820 1012 471 149 2.77

Geysir
1982–0005 f 226 997,628 2335 17.1 0.027 18.6 0.34
1982–0006 f 248 995,077 2615 5.07 8.18 2248 47.2
1982–0007 f 256 997,232 2615 23.9 1.23 1.18 122 4.80
1982–0008 f 246 996,036 3434 6.74 0.326 513 10.7
1982–0097 f 263 996,645 1602 7.59 4.12 5.64 1703 33.5
1982–0098 f 259 996,448 1788 6.51 2.28 0.81 1706 48.5

A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94

Hengill including Hellisheidi, Nesjavellir and Hveragerdi
08–3001 HE-07 w 171 263 0.20 0.00 261 0.31 0.14 199 7.4 76.1 998,729 536 436 234 4.45 59.5 0.97
08–3006 HE-05 w 173 268 0.21 0.00 268 0.22 0.01 77 33.1 37.7 998,242 1460 112 11.0 11.9 160 2.67
08–3007 HE-06 w 176 261 0.18 0.00 259 0.39 0.25 107 34.5 56.9 996,559 2808 348 251 3.91 29.7 0.52
09–5199 HE-17 w 188 260 0.16 0.00 284 0.76 0.70 216 15.4 68.7 997,532 1144 842 458 2.78 21.3 0.33
10–5168 HE-12 w 179 281 0.23 0.00 279 0.48 0.33 193 22.1 73.4 998,127 1027 495 331 4.10 16.6 0.34
10–5169 HE-07 w 179 262 0.18 0.00 260 0.29 0.14 185 16.4 73.6 998,552 671 400 234 3.39 138 1.69
10–5171 HE-42 w 179 292 0.26 0.00 301 0.85 0.81 169 13.6 35.0 998,782 310 546 348 1.19 12.5 0.33
1982–0017 f 294 984,611 13,401 1191 507 56.2 222 11.7
1982–0023 f 284 996,482 2931 52 42.3 474 18.0
1982–0025 f 300 993,097 4704 911 1201 11.2 73.5 2.38
2014–0010 f 293 994,512 4945 389 96.8 2.64 53.0 0.74
2014–0011 f 294 993,626 5849 369 103 3.25 50.2 0.74
2014–0012 f 266 998,574 1310 22.2 6.58 0.39 85.7 1.55
81–3017 HV-7 w 186 235 0.10 0.00 186 43.4 23.4 998,260 1260 109 21.1 2.48 331 16.3
81–3016 HV-6 w 178 232 0.11 0.00 171 28.6 23.4 998,534 1018 48.4 23.0 1.56 370 5.08
79–0136 G-2 w 147 191 0.07 0.00 142 44.2 18.4 999,633 338 16.1 11.6 1.20
78–0148 NJ-05 w 210 260 0.12 0.00 259 0.15 0.03 8 89.9 110.0 989,377 8328 850 977 85.0 382
04–3039 NJ-10 w 197 279 0.19 0.00 279 0.19 0.00 122 25.7 50.2 998,698 752 334 28.9 29.1 156 2.71
04–3048 NJ-11 w 168 281 0.25 0.00 278 0.59 0.46 78 15.1 111.7 997,473 590 898 921 12.3 105 1.98
04–3037 NJ-16 w 198 276 0.18 0.00 276 0.20 0.02 65 37.5 86.1 997,258 891 803 931 17.9 98.5 1.46
04–3050 NJ-20 w 200 274 0.17 0.00 273 0.27 0.13 169 32.9 49.9 998,061 1307 383 222 5.9 20.8 0.22
04–3046 NJ-21 w 200 286 0.21 0.00 290 0.80 0.75 111 51.2 83.8 995,713 2523 924 750 7.49 81.7 1.50

Hveravellir
1982–0101 f 258 998,841 1051 36.1 2.76 1.37 67.0 1.19
1982–0102 f 236 998,168 800 31.8 0.18 0.31 981 18.0
1982–0103 f 248 998,963 831 35.2 0.87 0.70 167 2.13
2004–0019 f 237 999,770 164 13.2 1.05 0.68 51.0 0.81
2004–0020 f 260 999,069 721 117 4.08 2.72 84.2 1.70

Kerlingarfjöll
1951–0002 f 284 997,780 1365 225 623 7.50
1982–0119 f 287 996,065 2880 393 433 1.05 225 3.40
2004–0006 f 294 996,075 2604 544 747 9.42 21.2 0.42
2004–0013 f 288 990,422 8298 806 452 4.10 17.2 0.33
2014–0044 f 287 996,839 2157 635 334 2.55 31.3 0.37
2014–0057 f 274 996,242 3331 215 165 8.65 37.8 0.64

Krafla
04–3010 K-13 w 198 234 0.08 0.00 230 0.56 0.53 32 67.9 72.6 995,840 2851 215 850 2.12 237 4.01
04–3015 K-15 w 195 277 0.19 0.00 275 0.33 0.18 36 16.0 93.2 998,455 1047 227 211 0.99 58 1.30
11-KRA-04 K-32 w 176 246 0.15 0.00 241 0.35 0.24 42 59.8 103.2 998,299 1028 424 228 1.43 19.5 0.41
11-KRA-08 K-24 w 137 213 0.14 0.00 213 0.14 0.00 44 45.7 28.4 999,116 792 23.1 4.37 5.08 57.6 1.32
77–1206 K-09 w 206 287 0.20 0.00 286 0.22 0.04 21 245.0 32.2 986,815 12,840 260 36.6 48.8
81–3036 K-16 w 165 259 0.20 0.00 256 0.43 0.29 65 158.5 53.7 993,278 5723 448 349 11.1 188 3.59
88–3245 K-12 w 143 305 0.35 0.00 304 0.86 0.79 110 162.8 44.2 991,890 6987 468 282 3.31 365 4.39
98–3203 K-20 w 189 284 0.22 0.00 285 0.79 0.73 155 204.6 53.5 982,690 15,924 715 625 8.09 36.3 0.77
98–3204 K-17 w 215 270 0.13 0.00 268 0.51 0.44 17 47.1 98.2 995,600 3331 478 538 14.5 38.7 0.91
1979–0001 f 298 835,694 161,051 1707 1515 32.9
1979–0013 f 287 995,296 3834 369 498 2.73
1983–0019 f 300 959,289 39,139 1056 374 0.48 138 2.21
1985–0024 f 279 950,064 49,606 91.9 102 7.22 123 5.17
1995–0018 f 298 972,880 20,460 45.6 6.11 6534 75.2
1995–0019 f 285 989,072 10,094 354 443 3.07 33.4 0.75
2009–0003 f 299 986,402 12,128 885 504 9.91 69.9 1.85
2011–0002 f 281 996,520 3057 190 182 4.90 42.8 1.89
2011–0005 f 314 914,586 81,134 2541 1224 60.8 445 8.92

Krýsuvík
1950–0001 f 281.0040960385 995,882 3538 294 279 7.53

A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94

1981–0008 f 273 994,442 5009 266 136 4.03 138 4.77
1981–0009 f 263 991,650 7822 250 61.2 7.11 204 5.94
1981–0033 f 266 993,864 5135 712 139 1.60 146 1.74
1984–0021 f 254 995,333 4301 297 15.0 1.23 50.6 2.32
1986–0003 f 285 971,349 20,825 1771 169 5792 93.21
2014–0005 f 274 996,323 3306 124 175 1.39 70.3 1.14

Kverkfjöll
1983–0008 f 277 992,964 5995 322 607 6.00 105
1983–0009 f 277 995,312 3658 378 610 2.91 39.2 0.61
1983–0015 f 277 992,155 6362 436 588 1.58 452 5.89
1983–0016 f 277 993,278 5635 450 593 2.80 40.7 0.98
1983–0017 f 278 994,455 3830 478 611 2.34 617 5.82
1983–0018 f 278 995,344 3509 472 614 4.00 55.9 1.72

Námafjall
79–3052 N-08 w 177 233 0.11 0.00 0.16 0.05 26 88.2 132.6 995,646 1703 787 1730 134
81–3022 N-11 w 214 236 0.05 0.00 0.76 0.75 31 10.9 97.8 994,732 1021 692 1439 2.84 2068 45.5
81–3023 N-12 w 216 241 0.05 0.00 0.77 0.76 35 18.1 136.1 995,489 1072 745 1572 5.12 1099 17.5
98–3215 N-04 w 143 236 0.18 0.00 0.19 0.02 40 11.4 10.6 997,134 559 227 17.1 2038 24.2
1950–0012 f 308 989,854 6837 2279 1007 22.7
1982–0109 f 260 998,257 1008 479 162 17.8 74.0 2.11
1982–0114 f 278 996,565 2013 540 619 3.72 255 4.21
1995–0024 f 317 987,584 9951 938 1486 15.1 25.3 1.17
1995–0025 f 315 993,787 3341 914 1910 12.5 34.8 1.03
1996–0016 f 303 993,544 3788 1077 1543 8.29 39.5 0.78
2012–0011 f 307 996,099 992 1125 1744 9.63 30.7 0.54
2013–0010 f 255 999,436 261 180 57 24.3 39.3 1.10
2013–0013 f 309 996,065 2079 1171 635 23.9 24.8 1.16

Reykjanes
1971–0083 RN-08 w 163 280 0.25 0.00 25,700 996,697 3182 100 22.0
1987–0005 RN-08 w 201 276 0.18 0.00 22,950 54.5 1.1 997,822 2079 79.1 2.27 0.27 17.5
1983–0225 RN-09 w 248 298 0.14 0.00 20,292 110.6 6.4 994,417 5310 188 29.3 0.98 55.6
2001–0461 RN-09 w 225 296 0.19 0.00 22,900 29.8 1.9 997,137 2729 119 3.14 11.6
05–3004 RN-12 w 252 285 0.09 0.00 19,288 103.9 11.5 991,437 8148 268 15.9 1.13 128 1.99
05–3003 RN-15 w 223 277 0.14 0.00 19,251 47.4 3.4 992,556 7094 188 15.8 1.22 143 2.22
1950–0002 f 255 997,641 2284 45.1 30.1
1982–0068 f 277 998,317 1604 19.9 4.79 0.13 48.8 5.83
1982–0070 f 292 985,661 13,388 196 63.3 5.60 648 37.5

Southern Lowlands

(continued on next page)

87
 88
Table 3 (continued)

Sample # Location/well # Type c Tsampling model#1 (calc. h) d,e

model #2 (meas. h) d,e
Liquid phase (ppm) Vapor phase (μmol/mol)

Tres Xsampling Xres Tres Xsampling Xres Cl CO2 H2S H2O CO2 H2S H2 CH4 N2 Ar

79–3028 Reykholt, w1 w 121 167 0.07 0.00 78 30.4 1.0 999,729 256 5.68 5.68 4.26
79–3030 Reykjaból, w1 w 143 191 0.08 0.00 42 54.3 4.1 999,017 946 17.1 11.4 8.55
88–3002 Efri-Reykir, w23 w 129 172 0.06 0.00 54 30.1 4.8 998,207 796 26.9 0.72 7.27 945 16.8
88–3204 Núpar w 113 172 0.09 0.00 356 49.7 1.7 997,572 1530 3.61 1.08 9.32 870 14.3
88–3206 Bakki w 102 142 0.04 0.00 669 5.9 0.2 995,235 701 0.090 4.34 4.30 4005 49.5
88–3207 Bakki, w2 w 107 136 0.02 0.00 679 6.0 0.3 996,000 529 1.26 1.45 15.3 3392 60.0
88–3208 Bakki, w1 w 111 143 0.03 0.00 811 5.7 0.2 997,073 589 5.06 1.44 16.8 2277 39.0
88–3211 Kotlaugar, w1 w 102 162 0.08 0.00 41 50.8 3.4 994,630 1027 0.18 4.88 5.44 4279 53.5
88–3237 Klausturhólar w 113 193 0.13 0.00 120 235.0 3.5 996,388 3123 25.0 0.36 5.54 452 6.44

Svartsengi
04–3003 SV-08 w 193 243 0.11 0.00 13,493 16.9 1.2 998,067 1689 3.43 0.69 237 2.89
04–3004 SV-18 w 193 240 0.10 0.00 14,255 12.3 1.3 998,597 1336 34.3 1.62 0.20 30.7 0.63

A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94

04–3006 SV-19 w 195 239 0.09 0.00 14,235 8.6 0.8 998,973 963 21.6 2.16 0.22 39.1 0.65
04–3029 SV-11 w 208 241 0.07 0.00 12,916 46.6 3.8 993,581 5720 61.8 66.1 1.60 562 7.45
04–3032 SV-09 w 196 244 0.10 0.00 13,230 6.9 1.2 998,892 1018 25.3 3.97 0.18 60.1 0.96
79–3008 SV-04 w 141 242 0.20 0.00 17,010 32.6 999,504 484 3.96 0.50 0.50 6.44
95–0394 SV-12 w 191 239 0.10 0.00 13,379 38.7 0.3 998,731 1237 22.4 1.39 0.13 8.29
95–0396 SV-11 w 200 246 0.10 0.00 13,583 47.9 1.1 997,311 2600 53.0 7.40 0.21 28.7

Theistareykir
1950–0013 f 269 995,769 3440 482 301 7.53
1982–0099 f 293 987,205 10,277 1210 703 169 423 11.9
1985–0017 f 255 996,643 2783 456 31.5 5.32 79.8 1.59
1997–0022 f 237 993,774 6070 23.4 3.63 0.42 126 1.51
2012–0002 f 289 994,553 3076 995 1292 17.1 66.6 0.96
2012–0004 f 266 998,269 1023 428 265 1.15 13.2 0.22

Torfajökull
1950–0016 f 254 997,588 2194 90.2 128
1982–0078 f 267 996,972 2493 206 299 6.31 20.7 1.74
1982–0092 f 326 972,070 22,995 1022 3759 17.7 131 6.65
1994–0001 f 268 994,943 4515 232 306 2.45 0.98
1997–0001 f 324 806,391 191,621 885 1101 0.83 1.31
1997–0002 f 247 999,052 788 81.7 77.2 1.12 0.072 0.090
2014–0062 f 271 994,548 4788 141 474 7.29 41.9 0.51

Vonarskard and Köldukvíslarbotnar

1984–0018 f 251 994,509 4468 96.0 96.5 49.5 767 14.5
1985–0013 f 275 987,158 7313 595 575 29.7 4183 146
2012–0016 f 280 993,585 5006 552 706 4.77 144 2.46
2012–0017 f 270 996,888 2253 398 331 3.10 126 2.13
a
Based on: Líndal and Hermannsson (1951), Ármannsson and Hauksson (1980), Gíslason et al. (1984), Ármannsson et al. (1985), Arnórsson and Gunnlaugsson (1985), Benjamínsson (1985), Benjamínsson et al. (1985), Arnórsson (1987)
Arnórsson et al. (1987, 1996), Ólafsson (1991), Poreda et al. (1992), Bjarnason (1996, 2002), Bjarnason and Ólafsson (2000), Gudmundsson and Arnórsson (2002, 2005), Hjartarson and Ólafsson (2005a, 2005b), Giroud (2008), Benjamínsson and
Hauksson (2010, 2011), Stefánsson et al. (2011, 2015), Kristinsson et al. (2013a, 2013b), Scott et al. (2014), Kaasalainen et al. (2015), Stefánsson and Barnes (2016).
b
For full ThermoFluid dataset (Stefánsson et al., 2016c), contact Ríkey Kjartansdóttir (rikey@hi.is).
c
w: two-phase well fluids; f: fumarole vapor.
d
Calculated with the aid of the WATCH program (Bjarnason, 2010); model#1 referred to liquid only reservoir and calculated enthalpy, model#2 refers to two-phase reservoir and measured discharge enthalpy.
e
The reservoir temperature for two-phase well discharges referes to quartz geothermometry (Gunnarsson and Arnórsson, 2000) and for fumaroles gas geothermometry (Arnórsson and Gunnlaugsson, 1985).
 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94 89

Fig. 3. The relationship between H2O, CO2 and S mole ratios in thermal fluids in Iceland. Also shown are the trends with adiabatic boiling of typical reservoir fluids of meteoric origin (typ-
ical Krafla fluid: KRA) and seawater origin (typical Reykjanes fluid: REY) from the reservoir temperature to surface at 100 °C. Saline and dilute reservoir thermal fluids have similar CO2
concentration whereas the latter are enriched in H2S, resulting in higher CO2/H2S ratio for saline thermal fluids relative to dilute thermal fluids. Upon boiling the gas phase becomes in-
creasingly enriched in H2O as observed by the modelled boiling trend and the fumarole vapor samples.

other cases a large range is observed, for example for CO2 concentra-
tions at Torfajökull and Krafla. Given often a relatively narrow range in
temperature (~ 50 °C) for a given geothermal system and a generally
moderate slope with temperature of equilibrium gas concentrations
predicted by the mineral-gas reactions, the former case may indicate a
mineral-gas equilibrium. The latter case, however, is more characteristic
of a source-controlled system, i.e. the gas concentrations reflect the var-
iable input of gas to the system and/or are affected by progressive reac-
tion that may influence the gas concentrations rather than the mineral-
gas equilibria.
5.2. Gas-gas equilibria
Instead of looking at individual gas concentrations it is common to
look at gas ratios reflecting gas-gas interactions (e.g., Giggenbach,
1980, 1987; Chiodini and Marini, 1998). Gas-gas reactions involving
CO2, H2S, H2 and CH4 are shown as a function of reservoir temperature
in Fig. 5, together with the calculated equilibrium values (Table 1). A
large scatter of data was observed in all cases. The agreement between
the measured and calculated equilibrium ratios were close, particularly
for the reactions involving H2S and H2 (Fig. 5B and C), whereas the over-
all equilibrium values predicted between CO2, CH4 and H2 (Fig. 5A)
were ~ 5 log units offset relative to most data on vapor composition.
Moreover, boiling may have considerable effects on gas concentrations,
making it difficult to distinguish between reservoir conditions and sec-
ondary processes like boiling with fluid ascent.
Previously, Stefánsson and Arnórsson (2002) concluded that such
gas-gas equilibria may not prevail in Icelandic geothermal systems
based on comparing equilibrium and measured redox values (Eh) for
different half-reactions involving thermal gases. Such a comparison
does not imply that local equilibrium between some gases and/or gas-
reactions is not attained, simply that overall gas equilibria were not
observed.
Based on the observations of individual gas concentrations and gas-
gas ratios, it cannot be distinguished what processes control the gas
concentrations in the vapor in Icelandic geothermal systems and if gas
equilibrium were attained or not. Such an approach is simply insensi-
tive. Large uncertainties are related to calculation of reservoir fluid com-
position from two-phase well discharges. Moreover, data on fumarole
vapor composition do not allow for reconstruction of total reservoir
fluid properties, and distinguishing between reservoir characteristics
from later stage reactions may be difficult. Finally, uncertainties are re-
lated in calculating equilibrium constants at elevated temperatures.
6. Sources and reactions of gases in geothermal systems
The sources of the volatile gases can be many, including air, rock dis-
solution, organic matter decay and/or magma degassing. Nitrogen and
Ar are among the major gases in thermal fluids. Their source(s) have
been obtained through the respective isotope ratios. The reported Ar
isotope ratios (40Ar/36Ar) in thermal fluids in Iceland range from 295
to 313, i.e. close to the air ratio of 295 (Sano et al., 1985; Óskarsson
et al., 2015) suggesting air as the major source of Ar in thermal fluids
in Iceland. For N2, reported isotope ratios (δ15N) range from −10.5 to
+ 3.0‰ (Sano et al., 1985; Marty et al., 1991; Óskarsson et al., 2015),
considerably lower than air (0‰) but more similar to depleted MORB
mantle (DMM) of –5 ± 2‰ and the range found in Icelandic basalts
(− 2.3 to + 5.7‰) (Halldórsson et al., 2016b). This suggest multiple
sources of N2 in some thermal fluids, ranging from air to mantle N2,
with the range of values reflecting heterogeneity of the Iceland plume
source (Halldórsson et al., 2016a).
Ternary diagrams of N2-Ar-CO2-H2S relationships are shown in
Fig. 6. Many of the thermal gas samples indicate close to air saturated
N2/Ar ratio with a trend towards enrichment of CO2 and H2S. This is
taken to indicate air as the major source of N2 and Ar in these gases, to-
gether with the addition of CO2 and H2S. Inspection of the data in Fig. 6
suggests systematic enrichment of N2 relative to Ar and air-saturated
water. Either or both may indicate additional source(s) for N2, consis-
tent with the δ15N values in some of these fluids and/or air contamina-
tion during sampling. The latter is, however, considered highly unlikely
in the case of two-phase well discharges due to the high-discharge flow
rates and general lack of measurable O2 in such samples.
90 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94

0
A czo+cc+qtz+pre
czo+cc+qtz+gro

-1 boiling (dil. meas. h)

2
logx vCO

-2

-3

boiling (saline and

dil., calc. h)
-4

-2 B
boiling (dil. meas. h)
boiling (dil. calc. h)

-3
H2S
v
logx

-4

boiling (saline. calc. h)

-5 gro+pyr+pyrr+qtz+epi+wo
pyr+pre+mt+qtz+czo+anh

pyr+pyrr+mt
-6
C gro+pyr+pyrr+qtz+epi+wo
py+pyrr+pre+epi pyr+pyrr+mt
-1

-2
H2
logx v

boiling (dil. calc. h)

-3 boiling (dil. meas. h)

-4

-5
pyr+pre+mt+qtz+czo+anh
boiling (saline. calc. h)
-6
100 150 200 250 300 350
Temperature (°C)

Fig. 4. The mole fractions (xi) of (A) CO2, (B) H2S and (C) H2 as a function of temperature.
Shown are the mole fractions of the various samples in reservoir fluids calculated from the
two-phase well discharges and for the two approaches applied, i.e. measured discharge
enthalpy (meas. h) and calculated reservoir enthalpy assuming liquid only reservoir
(calc. h) as well as the mole fractions in fumarole vapor. The various mineral-gas
equilibria are further shown (Table 1) and the effect of adiabatic boiling from the
reservoir conditions to surface at 100 °C for saline (N500 ppm Cl) and dilute (b500 ppm
Cl) fluids. For explanation of symbols see Fig. 3. A) The concentrations of CO2 are
observed to be scatter within ±1 log units for dilute and saline thermal fluids, the exact
composition mostly depending on the model applied to calculate the reservoir fluids.
Gas-mineral reactions show greater variability with temperature and between different
reactions suggesting that equilibrium of a given gas-mineral reaction may not control
xCO2 in the thermal fluids. Boiling of reservoir fluids results in decreased xCO2 but these
changes are insignificant relative to the scatter of the data. B) With respect to H2S, dilute
thermal fluids have generally higher concentrations than saline fluids. Moreover, xH2S is
observed to decrease with decreasing temperature, similar to the calculated equilibrium
values with respect to various gas-mineral reactions suggesting H2S to by fluid-mineral
equilibrium. Boiling results in decreased xH2S, these changes being less than the scatter
of the data. C) For H2, dilute fluids generally display higher concentrations than saline
fluids, similar to H2S. The predicted xH2 values by the gas-mineral buffers show great
variability for different reactions making it difficult to conclude if a fluid-mineral
equilibrium controls H2 concentration in the thermal fluids.
Fig. 5. The relationship between gas ratios of (A) CH4-H2O-CO2-H2, (B) H2S-H2, (C) H2S-
H2-H2O and temperature. Shown are the ratios of the various samples in reservoir fluids
calculated from the two-phase well discharges and for the two approaches applied, i.e.
measured discharge enthalpy (meas. h) and calculated reservoir enthalpy assuming
liquid only reservoir (calc. h) as well as the mole fractions in fumarole vapor. The
various mineral-gas ratios equilibria are further shown (Table 1) and the effect of
adiabatic boiling from the reservoir conditions to surface at 100 °C for saline (N500 ppm
Cl) and dilute (b500 ppm Cl) fluids. For explanation of symbols see Fig. 3. A) The
reservoir fluids and fumarole vapors are not observed to correspond to the predicted
equilibrium conditions for the reaction CO2(g) + 4H2(g) = CH4(g) + 2H2O(g),
suggesting that an overall equilibrium between CH4, H2O, CO2 and H2 is not attained for
Icelandic thermal fluids. In contrast, close to equilibrium conditions are observed between
H2(g), H2S(g) and H2O corresponding to the reactions B) pyrite + H2(g) =
pyrrhotite + H2S(g) and C) 3pyrite + 2H2(g) + 4H2O(g) = magnetite + 6H2S(g). How-
ever, it should be pointed out that in all cases large scatter of the data is observed and that
the calculated reservoir fluid composition from data on well discharges is in all cases very
dependent on the model applied making any conclusion if gas-gas and/or gas-mineral
equilibrium controls gas composition of thermal fluids in Iceland.
 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
Fig. 6. The mole distribution of (A) CO2, N2 and Ar and (B) H2S, N2 and Ar in two-phase
well discharges and fumarole vapor. The source of Ar and N2 correspond to the ratios
between air and air saturated water, whereas the thermal fluids show progressive
enrichment with respect to Co2 and H2S suggesting addition of these gases to the fluids
to various degree.
The sources of CO2 and H2S may be the basalt and progressive fluid-
rock interaction and/or degassing of basaltic melts, either at great depth
upon partial melting within the upper mantle and lower crust or at
shallower levels within the crust. Both types of source(s) have been sug-
gested, particularly evidenced in the case of CO2 (e.g., Stefánsson et al.,
2016a), whereas H2S is considered to originate predominantly from ba-
salt upon rock leaching (Stefánsson et al., 2015; Gunnarsson-Robin
et al., 2017).
In order to study the effects of progressive fluid-rock interaction and
magma gas addition, geochemical model calculations were conducted.
The calculations involve mixing non-thermal water with volcanic gas
of different ratios (0.1–10% volcanic gas) and reacting the liquid solution
with basaltic rock in steps, allowing secondary minerals commonly ob-
served in geothermal systems in Iceland to precipitate when saturated.
The results of the geochemical calculations with respect to pH, CO2, H2S
and H2 are shown in Fig. 7. Additionally, the range of concentration of
gases of the reservoir fluids are shown (as box plot). With progressive
fluid-rock interaction, the pH of the thermal solutions increases due to
consumption of H+ associated with basalt dissolution (e.g., Stefánsson,
2010; Gysi and Stefánsson, 2011). For fluids with a low-acid supply,
i.e. low volcanic gas input, the pH increases rapidly to N 8 at low reaction
progress (ξ b 0.l), whereas at high volcanic gas input, more basaltic rock
is needed to raise the pH. With respect to the gases, a very specific trend
91
Fig. 7. The result of the gas-fluid-rock interaction modeling as a function of progressive
fluid rock interaction (ξ) for initial 0.1%, 1% and 10% volcanic gas mass input into
meteoric water. Shown are (A) pH, (B) CO2 concentrations, (C) H2S concentrations and
(D) H2 concentrations. Also shown are the range of pH, CO2, H2S and H2 values in dilute
reservoir fluids (b500 ppm Cl) hosted by basaltic rocks and assuming liquid only
reservoir and calculated enthalpy. With progressive fluid-rock interaction the pH of the
solution increases due to consumption of H+ with basalt leaching with the exact pH
value determined by the input of volcanic gas (acid) and extent of reaction (ξ). H2S and
H2 are observed to become controlled by metastable fluid-mineral equilibria at
insignificant to moderate reaction progress (ξ = 0.01 to 0.5), the changes in the
metastable equilibria and mass of minerals resulting in insignificant variations for H2S
concentrations but being important for H2 concentrations with increasing
concentrations with increasing pH. In contrast, CO2 is not controlled by metastable fluid-
mineral equilibria except at a very high reaction progress, low gas input and alkaline pH,
thus suggesting that the CO2 concentrations are controlled by the ratio of volcanic gas to
source water in the geothermal reservoir in most cases.
is observed. At low volcanic gas input (b 0.1%), the H2S is rapidly miner-
alized into sulfides, resulting in a rapid decrease of H2S whereas with
considerable gas input, the H2S concentrations become buffered by
mineral-gas reactions at a low to moderate reaction progress (ξ 0.01
92 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
to 0.2 at 1 to 10% volcanic gas input). In contrast, CO2 does not seem to
be controlled by mineral-gas reactions but rather by the relative amount
of gas input, except at low CO2 gas input, whereas the pH increases due
to fluid-rock interaction resulting in calcite formation and decreased
CO2 concentration. In the case of H2, the thermal fluid concentration is
controlled by mineral-gas equilibrium, the minerals involved as well
as their relative masses depending on the pH of the solution. At alkaline
pH, considerable H2 may form under hydrothermal conditions, such
conditions either produced by low volcanic gas input and insignificant
to extensive fluid-rock interaction or high-volcanic gas input and exten-
sive fluid-rock interaction.
The results of the gas-fluid-rock interaction simulations clearly indi-
cate the key variables in controlling the concentrations of reactive vola-
tiles in geothermal systems are degree of volcanic gas input and
progressive fluid-rock interaction or fluid to rock ratio. An overall gas-
gas and mineral-gas equilibrium is not attained; instead the system is
in metastable equilibrium along the reaction progress (e.g., Anderson,
2002). The concentrations of H2S and H2 seem to reflect close to
mineral-gas metastable equilibria at low to high-volcanic gas input,
the absolute concentration of the gases, however, depending on the
mass movement in the system controlled by the gas input and extent
of fluid-rock interaction. In contrast, the concentrations of CO2 do not
seem to be controlled by fluid-rock equilibria but rather the ratio of vol-
canic gas to source water. For the Icelandic systems, a close to ~1% vol-
canic gas and 99% source water seems to correspond closely to the
Fig. 8. A summary of the sources and processes affecting volatile concentrations in thermal fluids in Iceland.
values observed for CO2, and H2S and the variable extent of the reactions
(ξ b0.01 to N1). The corresponding values for H2 indicate either some-
what lower volcanic gas input and/or greater extent of reaction ξ N 1.
The results of the simulations demonstrated that overall mineral-gas
equilibria of the systems do not control the concentrations of reactive
volatiles like CO2, H2S and H2 in geothermal systems. For multicompo-
nent and multiphase (solid, liquid and gas) systems where the compo-
nents react within and between phases in an incongruent manner, the
concentrations of components may change as a function of the extent
of reaction even though under given conditions the system is at meta-
stable equilibrium. An overall equilibrium will not be attained until
the system is closed off to inputs from all sources and has reacted to
achieve its final thermodynamic stability. It follows that the concentra-
tions of components of such open systems reflect metastable equilibria
for some components like H2 and H2S and non-equilibrium source con-
trolled concentrations for other components like CO2, the metastability
of the system being controlled by the ratio of the entry of elements into
the system and the extent of reactions occurring within the system.
7. Summary and conclusions
The available data on gas concentrations in thermal fluids in Iceland
have been summarized. The samples included two-phase well dis-
charges and single phase vapor fumaroles, for a total of 862 samples
from 18 geothermal areas. The vapor was dominated by H2O, generally
 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
accounting for N 99 mol%. Carbon dioxide, H2S and H2 were the other
dominant gases, followed by N2, CH4, and Ar. An overall gas-gas and
mineral-gas equilibrium is not attained within geothermal systems in
Iceland; instead the thermodynamic system occurs at various metasta-
ble equilibria along a reaction progress. The concentrations of H2S and
H2 seem to reflect close to mineral-gas metastable equilibria, whereas
the concentration of CO2 does not seem to be controlled by either
mineral-gas or gas-gas reactions but rather by the ratio of volcanic gas
to source water with the input of magma gas corresponding to N 0.1 to
b5 mass%. An overall equilibrium is not reached in the geothermal sys-
tems until they are closed off to inputs of all sources and have reacted to
its final thermodynamic stability. Moreover, the concentrations of gases
controlled by metastable equilibria may vary as a function of extent of
reaction, for example progressive fluid-rock interaction. With fluid as-
cent to surface, boiling and condensation may occur, further changing
the gas concentrations and hence surface fumaroles may not reflect
the reservoir fluid characteristics but rather these secondary processes
(Fig. 8).
Acknowledgments
I would like to thank Jóhann Gunnarsson-Robin for his help in com-
piling the data and assisting in sample collection and analysis.
Gudmundur Sverrisson and Hjörtur Andrason are also thanked for their
help in the field. The ThermoFluid dataset can be obtained from Ríkey
Kjartansdóttir (rikey@hi.is). I would also like to thank the guest editor,
Yuri Taran and two reviewers, Jacob Lowenstern and an anonymous re-
viewer for their constructive comments which have improved this
contribution.
References
Anderson, G.M., 2002. Stable and metastable equilibrium: The third constraint. In: Water-
rock interactions, ore deposits and Env. Geochem A tribute to D.A. Crerar, Hellmann,
R., Wood, S.A. (eds.). Geochem. Soc. Spec. Publ. 7, 181–189.
Ármannsson, H., 2015. The fluid geochemistry of Icelandic high temperature geothermal
areas. Appl. Geochem. 66, 14–64.
Ármannsson, H., Benjamínsson, J., Sigurdsson, K.H., 1985. Krafla: chemical composition of
steam in fumaroles. July 1984. Report OS-85058/JHD-23 (in Icelandic).
Ármannsson, H., Gíslason, G., Hauksson, T., 1982. Magmatic gases aid the mapping of the
flow pattern in a geothermal system. Geochim. Cosmochim. Acta 46, 167–177.
Ármannsson, H., Hauksson, T., 1980. Krafla: chemical composition of steam in fumaroles.
Report OS80027/JHD16 (in Icelandic).
Árnason, B., 1977. Hydrothermal systems in Iceland traced by deuterium. Geothermics 5,
125–151.
Arnórsson, S., 1995. Geothermal systems in Iceland: structure and conceptual models - I.
High-temperature areas. Geothermics 24, 561–602.
Arnórsson, S., Björnsson, S., Muna, Z.W., Bwire-Ojiambo, S., 1990. The use of gas chemistry
to evaluate boiling processes and initial steam fractions in geothermal reservoirs with
an example from the Olkaria field, Kenya. Geothermics 19, 497–514.
Arnórsson, S., 1987. Gas chemistry of the Krísuvík geothermal field, Iceland, with special
reference to evaluation of steam condensation in upflow zones. Jökull 37, 31–48.
Arnórsson, S., Barnes, I., 1983. The nature of carbon dioxide waters in Snæfellsnes, west-
ern Iceland. Geothermics 12, 171–176.
Arnórsson, S., Bjarnason, J.Ö., Giroud, N., Gunnarsson, I., Stefánsson, A., 2006. Sampling
and analysis of hydrothermal fluids. Geofluids 6, 203–216.
Arnórsson, S., Fridriksson, Th., Gunnarsson, I., 1996. Krafla and Námafjall: gases in wells
and fumaroles in 1995–1996. Report RH 12–96 (in Icelandic).
Arnórsson, S., Gunnlaugsson, E., 1985. New gas geothermometers for geothermal
exploration–calibration and application. Geochim. Cosmochim. Acta 49, 1307–1325.
Arnórsson, S., Ívarsson, G., Cuff, K.E., Sæmundsson, K., 1987. Geothermal activity in the
Torfajökull field, South Iceland: summary of geochemical studies. Jökull 37, 1–10.
Arnórsson, S., Sigurdsson, S., Svavarsson, H., 1982. The chemistry of geothermal waters in
Iceland. I. Calculation of aqueous speciation from 0° to 370°C. Geochim. Cosmochim.
Acta 46, 1513–1532.
Arnórsson, S., Stefánsson, A., Bjarnason, J.Ö., 2007. Fluid-fluid interaction in geothermal
systems. Rev. Min. Geochem. 65, 259–312.
Barry, P.H., Hilton, D.R., Füri, E., Halldórsson, S.A., Grönvold, K., 2014. Carbon isotope abun-
dance systematics of Icelandic geothermal gases, fluids and subglacial basalts with
implications for mantle plume- related CO2 fluxes. Geochim. Cosmochim. Acta 134,
74–99.
Benjamínsson, J., 1985. Krafla: comparison of gases in fumaroles between 1979 and 1984/
85. Report OS-85061/JHD-26 (in Icelandic).
Benjamínsson, J., Hauksson, T., 2010. Kröflusvædi and Bjarnarflag: environmental moni-
toring 2009. Report LV-2010/110 (in Icelandic).
93
Benjamínsson, J., Hauksson, T., 2011. Kröflusvædi and Bjarnarflag: environmental moni-
toring 2010. Report LV-2011/119 (in Icelandic).
Benjamínsson, J., Sigurdsson, K.H., Hjaltadóttir, V., Tómasson, S., 1985. Krafla: composition
of gas in fumaroles, June 1985. Report OS-85-060/JHD-25 (in Icelandic).
Bjarnason, J.Ö., 2010. The chemical speciation program WATCH, version 2.4. ÍSOR –
Iceland Geosurvey, Reykjavík, Iceland (Accessible at: http://www.geothermal.is/
software).
Bjarnason, J.Ö., Ólafsson, M., 2000. Torfajökll: chemistry of steam and thermal water. Re-
port OS-2000/030 (in Icelandic).
Bjarnason, J.Ö., 1996. Svartsengi, chemical monitoring, 1988–1995. Report OS-96082/
JHD-10 (126 pp).
Bjarnason, J.Ö., 2002. Reykjanes, chemistry of geothermal seawater and steam, 1971–
2001. Report OS-2002/038 (69 pp).
Bödvarsson, G., 1961. Physical characteristics of natural heat resources in Iceland. Jökull
11, 29–38.
Chiodini, G., Marini, L., 1998. Hydrothermal gas equilibria: the H2O-H2-CO2-CO-CH4 sys-
tem. Geochim. Cosmochim. Acta 62, 2673–2687.
Chiodini, G., Cioni, R., 1989. Gas geobarometry for hydrothermal systems and its applica-
tion to some Italian geothermal areas. Appl. Geochem. 4, 465–472.
D'Amore, F., Nuti, S., 1977. Notes on the chemistry of geothermal gases. Geothermics 6,
39–45.
D'Amore, F., Panichi, C., 1980. Evaluation of deep temperature of hydrothermal systems
by a new gas-geothermometer. Geochim. Cosmochim. Acta 44, 549–556.
Fernandez-Prini, R., Alvarez, J.L., Harvey, A.H., 2003. Henry's constants and vapor–liquid
distribution constants for gaseous solutes in H2O and D2O at high temperatures.
J. Phys. Chem. Ref. Data 32, 903–916.
Fridleifsson, I.B., 1979. Geothermal activity in Iceland. Jökull 29, 47–56.
Füri, E., Hilton, D.R., Halldórsson, S.A., Barry, P.H., Hahm, D., Fischer, T.P., Grönvold, K.,
2010. Apparent decoupling of the he and ne isotope systematics of the Icelandic man-
tle: the role of he depletion, melt mixing, degassing fractionation and air interaction.
Geochim. Cosmochim. Acta 74, 3307–3332.
Gauthier, P.J., Sigmarsson, O., Gouhier, M., Haddadi, B., Moune, S., 2016. Elevated gas flux
and trace metal degassing from the 2014–2015 fissure eruption at the Bárdarbunga
volcanic system, Iceland. J. Geophys. Res. Solid Earth http://dx.doi.org/10.1002/
2015JB012111.
Giggenbach, W.F., 1975. A simple method for the collection and analysis of volcanic gas
samples. Bull. Volcanol. 39, 132–145.
Giggenbach, W.F., 1980. Geothermal gas equilibria. Geochim. Cosmochim. Acta 44,
2021–2032.
Giggenbach, W.F., 1987. Redox processes governing the chemistry of fumarolic gas dis-
charges from White Island, New Zealand. Appl. Geochem. 2, 143–161.
Giggenbach, W.F., 1991. Chemical techniques in geothermal exploration. In: D'Amore, F.
(Ed.), Application of Geochemistry in Geothermal Reservoir Development. UNITAR,
pp. 119–144.
Giggenbach, W.F., 1992. Isotopic shift in waters from geothermal and volcanic systems
along convergent plate boundaries and their origin. Earth Planet. Sci. Lett. 113,
495–510.
Giggenbach, W.F., 1993. Redox control of gas compositions in Philippine volcanic-
hydrothermal systems. Geothermics 22, 575–587.
Giroud, N., 2008. A Chemical Study of Arsenic, Boron and Gases in High-Temperature
Geothermal Fluids in Iceland. (Ph.D. thesis). University of Iceland.
Gíslason, G., Johnsen, G.V., Ármannson, H., Torfason, H., Árnason, K., 1984. Theistareykir.
Surface study of a high-temperature geothermal area. Report OS-84089/JHD-16 (in
Icelandic).
Gíslason, S.R., Stefánsdóttir, G., Pfeffer, M.A., Barsotti, S., Jóhannsson, Th., Galeczka, I., Bali,
E., Sigmarsson, O., Stefánsson, A., Keller, N.S., Sigurdsson, Á., Bergsson, B., Galle, B.,
Jacobo, V.C., Arellano, S., Aiuppa, A., Jónasdóttir, E.B., Eiríksdóttir, E.S., Jakobsson, S.,
Gudfinsson, G.H., Halldórsson, S.A., Gunnarsson, H., Haddadi, B., Jónsdóttir, I.,
Thordarson, Th., Riishuus, M., Högnadóttir, Th., Dürig, T., Pedersen, G.B.M.,
Höskuldsson, Á., Gudmundsson, M.T., 2015. Environmental pressure from the 2014-
15 eruption of Bárdarbunga volcano, Iceland. Geochem. Persp. Lett. 1, 84–93.
Gudmundsson, B.Th., Arnórsson, S., 2002. Geochemical monitoring of the Krafla and
Námafjall geothermal areas, N-Iceland. Geothermics 31, 195–253.
Gudmundsson, B.Th., Arnórsson, S., 2005. Secondary mineral-fluid equilibria in the Krafla
and Námafjall geothermal systems, Iceland. Appl. Geochem. 20, 1607–1625.
Gunnarsson, I., Arnórsson, S., 2000. Amorphous silica solubility and the thermodynamic
properties of H4SiO4 in the range of 0 to 350°C at Psat. Geochim. Cosmochim. Acta
64, 2295–2307.
Gunnarsson-Robin, J., Stefánsson, A., Ono, S., Torssander, P., 2017. Sulfur isotopes in
Icelandic thermal fluids. J. Volcanol. Geotherm. Res. 346, 161–179.
Gysi, A.P., Stefánsson, A., 2011. CO2-water–basalt interaction. Low temperature experi-
ments and implications for CO 2 sequestration into basalts. Geochim. Cosmochim.
Acta 81, 129–152.
Halldórsson, S.A., Barnes, J.D., Stefánsson, A., Hilton, D.R., Hauri, E.H., Marshall, E.W.,
2016a. Subducted lithosphere controls halogen enrichments in the Iceland mantle
plume source. Geology 44, 679–682.
Halldórsson, S.A., Hilton, D.R., Barry, P.H., Füri, E., Grönvold, K., 2016b. Recycling of crustal
material by the Iceland mantle plume: new evidence from nitrogen elemental and
isotope systematics of subglacial basalts. Geochim. Cosmochim. Acta 176, 206–226.
Hilton, D.R., Fischer, T.P., Marty, M., 2002. Noble gases and volatile recycling at subduction
zones. Rev. Min. Geochem. 47, 319–370.
Hilton, D.R., Grönvold, K., Sveinbjörnsdóttir, A.E., Hammerschmidt, K., 1998. Helium iso-
tope evidence for off-axis degassing of the Icelandic hotspot. Chem. Geol. 149,
173–187.
Hjartarson, Á., Ólafsson, M., 2005a. Kerlingarfjöll: Study and mapping og a high-
temperature geothermal area. Report ISOR-2005/012 (in Icelandic).
94 A. Stefánsson / Journal of Volcanology and Geothermal Research 346 (2017) 81–94
Hjartarson, Á., Ólafsson, M., 2005b. Hveravellir: study and mapping of a high-temperature
geothermal area. Report ISOR-2005/014 (in Icelandic).
Johnson, J.W., Oelkers, E.H., Helgeson, H.C., 1992. Supcrt92 – a software package for calcu-
lating the standard molal thermodynamic properties of minerals, gases, aqueous spe-
cies, and reactions from 1 bar to 5000 bar and 0°C to 1000°C. Comput. Geosci. 18,
899–947.
Kaasalainen, H., Stefánsson, A., 2012. The chemistry of trace elements in surface geother-
mal water and steam, Iceland. Chem. Geol. 330–331, 60–85.
Kaasalainen, H., Stefánsson, A., Giroud, N., Arnórsson, S., 2015. The geochemistry of trace
elements in geothermal fluids, Iceland. Appl. Geochem. 62, 207–223.
Kristinsson, S.G., Fridriksson, Th., Ólafsson, M., Gunnarsdóttir, H.G., Níelsson, S., 2013a.
High-temperature areas at Theistareykir, Krafla and Námafjall: monitoring of surface
activity and groundwater. Report LV-2013-091 (in Icelandic).
Kristinsson, S.G., Óskarsson, F., Ólafsson, M., Óladóttir, A.A., Tryggvason, H.H., Fridriksson,
Th., 2013b. High-temperature areas at Theistareykir, Krafla and Námafjall: monitor-
ing of surface activity and groundwater in 2013. Report LV-2013-132 (in Icelandic).
Kristmannsdóttir, H., 1978. Alteration of bedrock in the Krafla geothermal system. Nation-
al Energy Authority Report (OS-JHD-7854).
Líndal, B., Hermannsson, S., 1951. Chemical Analysis of hot Springs. Jarðboranir ríkisins
(95 pp.).
Lonker, S.W., Franzson, H., Kristmannsdóttir, H., 1993. Mineral–fluid interaction in the
Reykjanes and Svartsengi geothermal systems, Iceland. Am. J. Sci. 293, 605–670.
Lowenstern, J.B., Bergfeld, D., Evans, W.C., Hunt, A.G., 2015. Origins of geothermal gases at
Yellowstone. J. Volcanol. Geotherm. Res. 302, 87–101.
Marty, B., Gunnlaugsson, E., Jambon, A., Oskarsson, N., Ozima, M., Pineau, F., Torssander, P.,
1991. Gas geochemistry of geothermal fluids, the Hengill area, southwest rift zone of
Iceland. Chem. Geol. 91, 207–225.
Ólafsson, M., 1991. Geothermal fluids in Krýsuvík: Sampling of fumaroles, spring 1990 Re-
port MÓ-91-06.
Óskarsson, F., Fridriksson, Th., Thorbjörnsson, D., 2015. Geochemical monitoring of the
Reykjanes geothermal reservoir 2003 to 2013. Proc. World. Geotherm. Cong. 1-9.
Parkhurst, D.L., Appelo, C.A.J., 1999. User's guide to PHREEQC (Version 2) - A computer
program for speciation, batch-reaction, one-dimensional transport, and inverse geo-
chemical calculations. Report 99-4259, U.S. Geological Survey, Water-Resources
Investigations.
Pope, E.C., Bird, D.K., Arnórsson, S., Giroud, N., 2015. Hydrogeology of the Krafla geother-
mal system, northeast Iceland. Geofluids 16, 1–23.
Poreda, R.J., Craig, H., Arnórsson, S., Welhan, J.A., 1992. Helium isotopes in Icelandic geo-
thermal systems: I. 3He, gas chemistry, and 13C relations. Geochim. Cosmochim. Acta
56, 4221–4228.
Sano, Y., Urabe, A., Wakita, H., Chiba, H., Sakai, H., 1985. Chemical and isotopic composi-
tions of gases in geothermal fluids in Iceland. Geochem. J. 19, 135–148.
Scott, S., Gunnarsson, I., Arnórsson, S., Stefánsson, A., 2014. Gas chemistry, boiling and
phase segregation in a geothermal system, Hellisheidi, Iceland. Geochim. Cosmochim.
Acta. 124, 170–189.
Sigvaldason, G.E., Elísson, G., 1968. Collection and analysis of volcanic gases at Surtsey.
Iceland. Geochim. Cosmochim. Acta 32 (797-80).
Stefánsson, A., 2010. Low-temperature alteration of basalts–the effects of temperature,
acids and extent of reaction on mineralization and water chemistry. Jökull 60,
165–184.
Stefánsson, A., Arnórsson, S., 2002. Gas pressures and redox reactions in geothermal fluids
in Iceland. Chem. Geol. 190, 251–271.
Stefánsson, A., Arnórsson, S., Gunnarsson, I., Kaasalainen, H., Gunnlaugsson, E., 2011. The
geochemistry and sequestration of H2S into the geothermal system at Hellisheidi.
J. Volcanol. Geotherm. Res. 202, 179–188.
Stefánsson, A., Barnes, J.D., 2016. Chlorine isotope geochemistry of Icelandic thermal
fluids: implications for geothermal system behavior at divergent plate boundaries.
E. Planet. Sci. Lett. 449, 69–78.
Stefánsson, A., Gunnarsson, I., Giroud, N., 2007. New method for the direct determination
of dissolved inorganic, organic and total carbon in natural water by reagent-free ion
chromatography and inductively coupled plasma atomic emission spectrometry.
Anal. Chim. Acta 582, 69–74.
Stefánsson, A., Keller, N.S., Gunnarsson-Robin, J., Ono, S., 2015. Multiple sulfur isotope sys-
tematics of Icelandic geothermal fluids and the source and reactions of sulfur in vol-
canic geothermal systems at divergent plate boundaries. Geochim. Cosmochim. Acta
165, 307–323.
Stefánsson, A., Sveinbjörnsdóttir, Á.E., Heinemeier, J., Arnórsson, S., Kjartansdóttir, R.,
Kristmannsdóttir, H., 2016a. Mantle CO2 degassing through the Icelandic crust evi-
denced from carbon isotopes in groundwater. Geochimica. Cosmochimica Acta 191,
300–319.
Stefánsson, A., Arnórsson, S., Kjartansdóttir, R., Gunnarsson-Robin, J., Sveinbjörnsdóttir,
Á.E., Kaasalainen, H., Keller, N.S., 2016c. GeoFluids database 2016. Chemical composi-
tion of Icelandic fluids and gases. Sci. Inst. Report RH-10-2016.
Stefánsson, A., Hilton, D.R., Sveinbjörnsdóttir, Á.E., Torssander, P., Heinemeier, J., Barnes,
D.J., Ono, S., Halldórsson, S.A., Fiebig, J., Arnórsson, S., 2017a. Isotope systematics of
Icelandic thermal fluids. J. Volcanol. Geotherm. Res. 337, 146–164.
Stefánsson, A., Stefánsson, G., Keller, N.S., Barsotti, S., Sigurdsson, Á., Thorláksdóttir, S.B.,
Pfeffer, M.A., Eiríksdóttir, E.S., Jónasdóttir, E.B., Löwis, S., Gíslason, S.R., 2017b. Major
impact of volcanic gases on the chemical composition of precipitation in Iceland dur-
ing the 2014–2015 Holuhraun eruption. J. Geophys. Res. Atmos. 122, 1971–1982.
Stefánsson, A., Keller, N.S., Gunnarsson-Robin, J., Kaasalainen, H., Björnsdóttir, S.,
Pétursdóttir, S., Jóhannesson, H., Hreggvidsson, G.Ó., 2016b. Quantifying mixing, boil-
ing, degassing, oxidation and reactivity of thermal waters at Vonarskard, Iceland.
J. Volcanol. Geotherm. Res. 309, 53–62.
Sveinbjörnsdóttir, Á.E., 1992. Composition of geothermal minerals from saline and dilute
fluids—Krafla and Reykjanes, Iceland. Lithos 27, 301–315.
Sveinbjörnsdóttir, A.E., Coleman, M.L., Yardley, B.W.D., 1986. Origin and history of hydro-
thermal fluids of the Reykjanes and Krafla geothermal fields, Iceland: a stable isotope
study. Contrib. Mineral. Petrol. 94, 99–109.
Taran, Y.A., 1986. Gas geothermometers for hydrothermal systems. Geochem. Int. 23,
111–126.
Taran, Y.A., Hedenquist, J.W., Korzhinsky, M.A., Tkachenko, S.I., Shmulovich, K.I., 1995.
Geochemistry of magma gases from Kudryavy volcano, Itrup, Kuril Island. Geochim.
Cosmochim. Acta 59, 1749–1761.
Taran, Y.A., 2011. N2, Ar and He as a tool for discriminating sources of volcanic fluids with
application to Vulcano, Italy. Bull. Volcanol. 73, 395–408.