Quantifying mixing, boiling, degassing, oxidation and reactivity of

thermal waters at Vonarskard, Iceland

abstract

The chemical composition of geothermal fluids may be altered upon ascent from the reservoir to surface by processes including boiling, degassing, mixing, oxidation and water–rock
interaction. In an attempt to quantify these processes, a three step model was developed that includes: (1) defining the composition of the end-member fluid types present in the system,
(2) quantifying mixing between the end-members using non-reactive elemental concentrations and enthalpy and (3) quantifying the changes of reactive elements including degassing,
oxidation and water–rock interaction. The model was applied to geothermal water at Vonarskard, Iceland, for demonstration having temperatures of 3–98 °C, pH of 2.15–9.95 and TDS
of 323–2250 ppm, and was thought to be produced from boiled reservoir water, condensed steam and non-thermal water. Most geothermal water represented mixture of non-thermal
water and condensed steam whereas the boiled reservoir water was insignificantly mixed. CO2 and H2S degassing was found to be quantitative in steam-heated water, with oxidation of
H2S to SO4 also occurred. In contrast, major rock forming elements are enriched in steam-heated water relative to their mixing ratios, suggesting water–rock interaction in the surface
zone. Boiled reservoir water observed in alkaline hot springs have, however, undergone less geochemical changes upon ascent to surface and within the surface zone.

1. Introduction

The surface zone of active geothermal systems is characterized by chemical and physical changes resulting from various processes occur-ring in the systems.
These changes cause the varied appearance of the surface environment, typically including hot springs, mud pots, steam vents and altered ground. Some of these
features are the result of the geothermal activity at depth whereas others are the product of process-es occurring in the surface environment. At depth the
geothermal fluids are considered to be in equilibrium with secondary geothermal minerals (e.g. Giggenbach, 1981; 1988; Arnórsson et al., 1983; Reed and
Spycher, 1984; Stefánsson and Arnórsson, 2000, 2002). Upon ascent to the surface depressurization boiling may occur, leading to the formation of steam and
water. At the surface, the steam may form steam vents, or mix and condense with non-thermal oxygenated water and form steam-heated water. The boiled water
may also find its way to the surface, typically forming hot springs. The processes of boiling, cooling, mixing, oxidation and water–rock interaction lead to
chemical changes of the geothermal water (e.g. Brock, 1971; Giggenbach and Stewart, 1982; Arnórsson, 1985; Giggenbach, 1988; Fournier, 1989; Chiba, 1991;
Hedenquist, 1991; Goff and Janik, 2000; Hochstein and Browne, 2000; Takeno, 2000; Gherardi et al., 2002; Valentino and Stanzione, 2003; Arnórsson et al.,
2007; Nordstrom et al., 2009; Markússon and Stefánsson, 2011; Kaasalainen and Stefánsson, 2011, 2012). The system responds to these changes by reacting and
will do so until the system has approached chemical equilibrium.
Quantification of the geothermal fluid evolution on the way from the reservoir to the surface and in the surface zone of the geothermal systems is important for
various reasons: for example, to assess subsurface condi-tions from water composition at the surface and to evaluate the potential for geothermal utilization (e.g.
Truesdell and Fournier, 1977; Arnórsson, 1985; Ruggieri et al., 1999; Kaasalainen and Stefánsson, 2012), to quanti-fy chemical energy available for
chemolithotropic organisms (e.g. Shock et al., 2010; Cox et al., 2011; Swingley et al., 2012) and to assess possible environmental impact at the surface upon
geothermal fluid extraction from the geothermal reservoir (e.g. Kristmannsdóttir and Ármannsson, 2003; DiPippo, 2012), to name a few. Such quantification is,
however, often difficult due to multiple processes occurring in the surface zone of geothermal systems and chemical reactions occurring as a result of chem-ical
and physical changes in the systems.
In this study we attempt to quantify the various processes occurring in the surface zone of active volcanic geothermal systems, using the Vonarskard
geothermal system in central Iceland for demonstration. Using the concentrations of non-reactive and reactive compounds, enthalpy, pH and the inferred end-
member composition of boiled geo-thermal reservoir water, geothermal steam and non-thermal water we assess the effects of mixing, steam condensation,
volatile loss and oxida-tion, evaporation and water–rock interaction within the surface zone. The approach used here differs in many ways to many previously
sug-gested approaches for studying thermal fluid chemistry. More common-ly, chemical equilibrium (fluid–rock and/or gas–gas) is assumed for the reservoir
fluids and then mixing, cooling and boiling are investigated relative to the chemical composition of the reservoir fluids (e.g. Reed and Spycher, 1984; Arnórsson,
1985; Giggenbach, 1988). Here, the var-ious fluid chemistry and their mixing ratios of geothermal water are first assessed followed by investigation of chemical
reactivity including degassing, oxidation and water–rock interaction.

2. The Vonarskard geothermal system

The Vonarskard geothermal system is associated with a central volcano of the same name, and is located in the rift zone of central Iceland, to the northeast of
the Vatnajökull icecap (Gudmundsson and Högnadóttir, 2007) (Fig. 1). The Vonarskard central volcano consists of a caldera of about 8 km in diameter, with the
western and the northeastern parts visible at the surface. The oldest exposed rock formations are about 300–500 thousand years old and the youngest are of
Holocene age. The formations consist mostly of interglacial lava flows and subglacial hyaloclastites and pillow lavas, all of basaltic composition, with rhyolites
found in the southern part of the caldera (Fridleifsson and Jóhannesson, 2005).
Fig. 1. The Vonarskard geothermal area together with sample locations (dots). The caldera structures, visible to the west and northeast, are also marked. The light blue areas (Vatnajökull and
Tungnafellsjökull) are glaciers. Based on Gudmundsson and Högnadóttir (2007). The black square in the insert shows the location of Vonarskard, whereas the dark gray areas indicate the volcanic
zones of Iceland. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

The Vonarskard central volcano hosts an active geothermal system with ongoing activity mostly found on the western side of the caldera. Surface
manifestations are widespread, characterized by steam vents, mud pots, hot springs and thermal streams, as well as argillic alteration similar to other geothermal
areas in Iceland (Sigvaldason, 1959; Markússon and Stefánsson, 2011; Kaasalainen and Stefánsson, 2012). The geothermal system has been active throughout
glacial and intergla-cial periods of the late Pleistocene and Holocene times. During interglacial periods, the geothermal fluids reach the surface and cause surface
geothermal alteration characterized by amorphous silica, anatase, pyrite, iron oxides and oxyhydroxides and clays (Markússon and Stefánsson, 2011). During
glacial periods, geothermal activity persisted under a glacier reaching up to 1–2 km thickness during the late Pleistocene (Norddahl et al., 2008). The pressure of
the glacial water column resulted in high-temperature geothermal alteration at the surface of the caldera floor characterized by actinolite, epidote, wollastonite
and K-feldspars (Fridleifsson and Jóhannesson, 2005). The high-temperature alteration led to highly altered and impermeable rock formations at shal-low levels
beneath the surface, resulting in a groundwater table at much higher altitude compared to other systems of similar nature in Iceland. As a consequence, the area is
characterized by an unusually high flow of thermal water that comprises very variable mixtures between non-thermal water, boiled geothermal water and
condensed geothermal steam. This results in geothermal water with a large range of temperatures, pH, and elemental composition.

3. Methods

3.1. Water and steam sampling and analysis

Samples of geothermal water and steam in Vonarskard were collect-ed and analyzed (Fig. 1). The sampling and analytical methods have been described in
details by Arnórsson et al. (2006). Water samples for major elemental analysis were filtered on-site through a 0.2 μm filter (cellulose acetate) into PP bottles.
Samples for the determination of major cations and anions were acidified to 1% (Merck, Suprapur®) and not further treated, respectively. Samples for total
dissolved inor-ganic carbon (∑CO2) and pH were collected into gas-tight amber glass bottles. Samples for the determination of SO4 were collected into
polypropylene bottles to which 2% Zn-acetate solution was added to precipitate H2S in solution.
Major cations including Na, K, Mg, Ca Al, Fe, Si and B were analyzed using ICP-AES whereas F, Cl, SO4 and ∑CO2 (total dissolved inorganic carbon) were
determined by ion chromatography (Stefánsson et al., 2007). Dissolved H2S was determined on site using spectrophotometry (APHA, 2005) or by precipitation
titration (Arnórsson et al., 2006). The pH was measured using a combination electrode usually within minutes to hours of sampling (Arnórsson et al., 2006). The
analytical precision of the chemical analysis based on repeated determination was ±3% at the 95% confidence level for all elements except Mg and Fe that had
±10% precision at the 95% confidence level.
Sample of steam from steam vents was collected into pre-evacuated 125 mL gas bulbs containing 10–15 mL 50% KOH solution. The non-condensable gases
(N2, H2, O2, Ar and CH4) were analyzed using gas chromatography whereas the condensable gases (∑CO2 and H2S) were analyzed by modified alkalinity
titration and precipitation titration, respectively (Arnórsson et al., 2006).

3.2. Geochemical modeling

Three sets of geochemical calculations were performed in this study with the aid of the WATCH program (Bjarnason, 2010) and the PHREEQC program
using the WATEQ database (Parkhurst and Appelo, 1999).
Firstly, the reservoir fluid composition was reconstructed from the chemical composition of alkaline hot springs. These calculations were conducted with the
aid of the WATCH program and involved correcting the dissolved solids content of the water phase taking steam loss into account, and adding the gases that
degassed upon boiling back into the liquid phase. For details about this approach, the reader is referred to Arnórsson et al. (2007). For these calculations, the
reservoir temper-atures were estimated using multicomponent geothermometry and gas and solute geothermometry (Reed and Spycher, 1984; Arnórsson, 2000;
Arnórsson et al., 2007, 1996).

Secondly, a model was developed to calculate the mixing properties of surface geothermal water from various end-member water composi-tions assuming
conservation of enthalpy and non-reactivity of Cl upon mixing. The three end-member water types taken into account were non-thermal water, condensed steam
and boiled reservoir water. Based on this model, volatile loss, oxidation, evaporation and water– rock interaction at surface was assessed.
Thirdly, the aqueous speciation and mineral saturation states of selected phases were calculated for the water samples at the measured temperatures using the
PHREEQC program, in order to assess the equilibrium between surface water composition and the observed alteration mineralogy.

Table 1
Chemical composition of surface geothermal water in Vonarskard. Units are in ppm.
 # Location t/°C pH/°C B SiO2 Na K Ca Mg Al Fe F Cl ΣCO2 H2S SO4

Alkaline water
12-VON-07 Gráni 97 9.93/15 2.05 375 207 8.17 1.54 0.018 0.15 0.046 0.74 128 93.6 3.93 19
12-VON-08 Gráni 61 9.95/15 1.99 367 207 8.11 1.60 0.015 0.14 0.037 0.75 129 93.3 13.70 19
12-VON-10 Stóri Grámann 60 9.76/16 1.96 318 184 6.55 2.17 0.08 0.37 0.087 0.58 121 84.4 0.75 23
12-VON-11 Litli Grámann 63 9.35/18 1.82 301 176 6.12 1.60 0.10 0.36 0.10 0.61 112 100 5.47 24
12-VON-13 Theysandi 98 9.34/19 2.03 261 210 5.44 1.14 0.10 0.14 0.10 0.67 119 94.8 4.20 25
12-VON-15 Geysandi 98 9.45/18 1.81 263 190 6.07 1.75 0.36 1.10 0.88 0.67 117 86.2 1.29 47
11-VON-18 94 9.33/23 2.03 263 199 5.50 1.36 0.13 0.43 0.063 1.09 136 75.3 44.3 49

Steam heated acid water

11-VON-14 Steam heated mud pot 87 3.59/23 0.018 154 37.0 6.51 21.1 7.78 0.51 1.80 0.22 1.03 31.6 12.6 178
11-VON-16 Red-two-color stream 43 3.46/23 0.022 157 21.3 10.2 8.64 3.06 0.90 3.05 0.22 2.04 29.4 b0.01 114
11-VON-17 White-two-color stream 42 3.48/23 0.102 225 39.7 12.9 13.5 4.09 0.49 4.49 0.26 6.63 8.21 0.50 166
12-VON-03 72 2.58/14 0.02 160 19.1 2.22 35.1 15.7 12.4 11.8 0.03 0.97 69.2 0.08 468
12-VON-04 46 3.14/14 b0.01 139 13.7 1.86 28.7 15.8 8.29 6.63 0.03 1.25 121 0.01 280
12-VON-16 Litli Gosi 81 3.12/19 0.03 127 12.5 2.06 40.0 11.2 3.03 17.9 0.02 0.67 38.1 0.05 263
12-VON-19 Grámi 75 2.34/19 0.39 229 12.9 1.32 21.7 14.7 34.5 96.8 0.01 0.29 42.5 0.03 719
12-VON-24 85 2.93/19 0.15 118 19.7 2.77 11.9 5.94 2.80 7.09 0.06 7.67 35.3 0.03 164
12-VON-26 43 3.49/19 b0.01 159 24.9 12.8 8.96 2.99 0.98 2.10 0.05 1.63 75.0 3.55 113
12-VON-27 91 2.66/20 0.04 100 7.01 1.82 8.55 5.35 10.9 9.44 0.03 1.37 34.0 0.01 247
12-VON-28 83 2.15/20 0.67 232 8.43 1.41 29.2 22.3 114 168 0.00 0.33 35.3 0.02 1639

Steam heated neutral water

11-VON-1 Red-pool outflow 62 6.86/16 0.065 178 68.6 6.43 42.3 6.81 b0.02 0.309 0.78 4.45 170 b0.01 87
11-VON-2 Red-pool 45 7.68/15 0.062 175 67.0 6.46 45.7 7.96 b0.02 0.189 0.71 4.15 140 b0.01 89
11-VON-3 Red-pool 40 7.99/18 0.049 171 67.4 6.22 35.4 7.05 b0.02 0.256 0.87 4.50 123 b0.01 90
11-VON-4 Small hot pool 64 6.91/16 0.062 176 67.3 6.59 50.4 8.28 b0.02 0.343 0.72 4.02 198 b0.01 89
11-VON-6 Red-pool 64 6.77/17 0.059 180 68.6 6.85 49.9 8.26 b0.02 0.363 0.73 4.08 204 b0.01 90
11-VON-8 Hærulangur 73 5.98/23 0.014 237 67.9 12.8 30.0 7.53 b0.02 0.007 0.44 1.32 189 22.6 167
11-VON-9 Hærulangur 50 6.05/23 0.008 221 64.8 12.4 28.7 6.98 b0.02 0.106 0.45 1.11 72.2 3.27 193
11-VON-10 Hærulangur 44 6.71/23 0.010 222 65.1 12.3 29.1 7.25 b0.02 0.093 0.46 1.40 36.7 0.058 193
11-VON-11 Hærulangur 41 6.94/23 0.011 224 65.4 12.4 29.7 7.31 b0.02 0.100 0.42 1.02 32.6 0.044 194
11-VON-13 Hærulangur 44 6.8/23 0.019 216 66.9 12.5 28.8 7.43 b0.02 0.061 0.36 1.53 49.7 0.19 177
11-VON-15 Hærulangur 95 7.7/23 0.061 228 81.6 17.7 29.2 7.73 0.02 0.050 0.47 4.41 77.3 14.4 162
12-VON-05 63 5.67/14 b0.01 83 8.66 1.32 21.6 11.5 0.04 0.08 0.06 1.52 115.7 10.21 70
12-VON-06 67 5.98/14 0.02 101 25.8 2.03 39.0 15.5 0.09 4.28 0.05 1.68 123.8 3.71 167
12-VON-12 Kolur 88 6.59/18 0.11 171 29.9 5.19 22.8 7.03 0.11 0.19 0.14 8.30 97.5 1.29 46
12-VON-25 74 6.56/19 0.11 164 28.0 4.29 25.7 7.87 0.15 0.23 0.14 9.11 97.1 3.54 45
12-S-VON-01 Hærulangur 72 5.79/16 b0.01 245 69.5 13.7 30.1 7.90 b0.02 0.003 0.34 1.06 117 16.63 189
12-S-VON-02 Hærulangur 49 6.51/16 b0.01 228 66.8 17.1 29.7 7.57 0.03 0.050 0.33 0.86 85.6 0.04 196
12-S-VON-03 Hærulangur 44 6.68/16 b0.01 230 67.4 15.8 29.6 7.61 0.02 0.029 0.32 0.87 79.6 b0.01 203
12-S-VON-04 Hærulangur 41 7.05/16 b0.01 228 66.9 13.1 29.0 7.44 0.03 0.021 0.32 0.89 66.5 b0.01 211
12-S-VON-05 Hærulangur 51 6.55/16 b0.01 224 66.2 13.0 29.0 7.49 0.02 0.020 0.31 0.87 79.6 0.36 206
12-S-VON-06 Hærulangur 42 6.69/16 b0.01 226 66.7 17.4 29.9 7.85 0.03 0.041 0.27 0.98 80.6 1.30 185
12-S-VON-07 Hærulangur 40 6.75/16 b0.01 224 66.5 13.7 30.2 7.98 0.07 0.083 0.26 1.43 75.1 0.01 183
12-S-VON-08 Hærulangur 35 6.84/15 b0.01 220 67.7 13.5 29.9 7.58 0.11 0.095 0.26 1.83 74.9 0.44 182
12-S-VON-09 Hærulangur 29 6.58/16 b0.01 219 67.2 13.5 29.6 7.65 0.30 0.21 0.25 1.78 64.7 0.01 189
12-S-VON-10 Hærulangur 26 6.85/16 b0.01 213 65.7 13.0 28.7 7.58 0.25 0.17 0.25 2.05 63.2 0.05 190
12-S-VON-11 Svartskeggur 85 6.96/16 0.03 225 78.5 17.2 27.0 7.44 0.02 0.04 0.25 4.45 94.0 0.35 148

4. Chemical composition of geothermal water and steam At Vonarskarð, Central Iceland

The sampled water at Vonarskard had temperatures of 3–98 °C, pH of 2.15–9.95 and total dissolved solids (TDS) of 323–2250 ppm. The major elemental
composition of the sampled water and steam is given in Tables 1 and 2, respectively.
Based on the major element composition, pH, and temperature the water samples were classified into: alkaline water, steam-heated acid water and steam-
heated neutral water (Fig. 2). Alkaline water samples, typically discharged by hot springs, had pH of 9.33–9.95 and elevated Na, SiO2, Cl and CO2
concentrations and very low Mg concentrations. Steam-heated acid water samples typical of mud pots and some streams had acid pH of 2.15–3.59, elevated SO4
and many metal concentra-tions and very low Cl concentrations. Steam-heated neutral water had pH of 5.67–7.99, low Cl concentrations and often high CO2
con-centrations compared to steam-heated acid water. The metal con-centration of neutral steam-heated water also differs from alkaline water with much higher
Ca, Mg and Fe concentrations and lower Na concentrations.
Table 2
Gas composition of steam-vents in Vonarskard. Units are in mmol kg−1 condensate.

Sample # H2 CO2 H2 S CH4 N2 Ar O2

12-VON-GAS-1 141 344 49.1 6.63 25.4 0.44 0.72

12-VON-GAS-2 45.1 265 39.6 0.30 5.26 0.09 0.00
12-VON-GAS-3 66.1 322 38.8 0.22 10.2 0.22 0.02
12-VON-GAS-4 38.9 276 30.4 0.26 7.94 0.14 0.72
12-VON-GAS-5 18.3 125 22.0 0.17 6.96 0.12 0.65
12-VON-GAS-6 10.1 105 27.1 0.10 5.35 0.10 0.43

5. Reconstruction of reservoir fluid composition

The reservoir fluid composition was reconstructed from the compo-sition of alkaline water, based on an adiabatic boiling model and assum-ing alkaline water
to be representative of the boiled fraction of the reservoir fluid. The calculations involved correcting the dissolved solids content of the water phase for steam loss
and adding the gases that degassed upon boiling back into the liquid phase, applying a model referred to as the boiling hot-spring model (Arnórsson et al., 2007).
The calculations were conducted with the aid of the WATCH program assuming equilibrium steam loss (Arnórsson et al., 2007) and using the multicomponent
geothermometry method for estimating reservoir temperature (Reed and Spycher, 1984) similar to that of the GeoT pro-gram
(http://esd1.lbl.gov/research/projects/geot/). The average reser-voir composition is reported in Table 3.

20 80

40 60

60 40

80 20

Ca+Mg 20 40 60 80 Na

SO4

20 80

40 60

60 40

80 20

ΣCO2 20 40 60 80 Cl

Fig. 2. The relationship between Na–K–Ca + Mg and Cl–∑CO2–SO4 in the geothermal waters at Vonarskard. Open dots represent steam-heated neutral water, closed dots represent steam-heated
acid water and closed triangles alkaline water.
Table 3
Composition of various water types and steam, as measured or modeled. Units are in ppm.

Geothermal Non-thermal Boiled reservoir Condensed

reservoir watera water (ntw)b water (brw)c steam (cs)
t/°C 217 2.8 100 100
pHT 6.74 7.65 8.58 3.85
B 1.65 0.0070 2.09 0
SiO2 300 6.72 381 0
Na 165 2.16 209 0
K 5.52 0.67 7.01 0
Ca 1.14 1.82 1.45 0
Mg 0.054 0.46 0.069 0
Al 0.179 0.27 0.227 0
Fe 0.050 0.13 0.064 0
F 0.664 0.17 0.843 0
Cl 104 2.12 131.99 0
ΣCO2 532 1.40 78.7 2215
H2S 49.25 b0.01 16.68 170/0d
SO4 22.79 7.86 28.95 0/480d
a
Modeled reservoir water taking into account equilibrium vapor and gas loss upon adiabatic boiling, assuming single phase geothermometry liquid reservoir and applying quartz.

b
The composition of non-thermal water taken to represent the average composition various surface water samples collected (n = 5).
c
Boiled water and steam at 100 °C and 1 bar based on alkaline water composition boiling and equilibrium degassing and the modeled reservoir water composition and taken into account adiabatic.
d
All H2S in steam assumed to have oxidized to SO4.

The multicomponent geothermometry approach results in equilibri-um convergence at temperature 217 °C. For comparison, the reservoir temperatures were
also estimated using various gas and solute geothermometry (Arnórsson et al., 2007) and the Na–K–Mg ternary diagram (Giggenbach, 1988) (Fig. 3). The gas
geothermometry when taken into account possible steam condensation (CO2/N2, H2S/Ar and H2/Ar) resulted in reservoir temperature of ~ 265 °C whereas single
gas geothermometry gave much higher temperatures. Such a trend suggests open system boiling and phase segregation in the up-flow zone (Arnórsson et al.,
2007). In contrast, the Na–K–Mg ternary diagram resulted in reservoir fluid temperature of b170 °C, this is considered to be incorrect and caused by increased K
and/or Mg in the up-flow and surface zone relative to Na due to fluid–rock interaction.

6. Geothermal water composition

The approach demonstrated below to quantify the formation mech-anisms of surface geothermal water and the respective chemical charac-teristics is based
on major elemental composition and enthalpy. The approach is divided into three steps: (1) defining the composition of the end-member water types, (2) setting
up a mathematical model for the non-reactive mixing between these water types and (3) quantifying the reactive behavior of major elements including degassing,
oxidation and water–rock interaction.

6.1. End-member water composition

The end-member water types forming surface geothermal water include boiled reservoir water (brw), condensed steam (cs) and non-thermal water (ntw). The
composition of these end-members can be defined in two ways. One way is by defining the composition of various water types based on analytical data for
sampled water and steam. Alternatively, the boiled geothermal liquid water and the steam at 100 °C and 1 bar can be modeled based on reservoir fluid
composition and applying adiabatic boiling from the reservoir temperatures to sur-face. The two approaches differ in the way the volatile concentra-tions (CO2,
H2S) in steam are obtained and therefore mixing ratios of steam condensates with other end-member water types. Here the end-member steam composition was
selected based on the boiled
 A. Stefánsson et al. / Journal of Volcanology and Geothermal Research 309 (2016) 53–62 57

A Na/1000 B 4
reservoir
temperature solutes
wai

Q/
K)
g(
2

lo
20
80 czo
qtz
0
pre
alb
40 60 chl
150°C mic
-2
200°C 100°C
laum
re-equilibration in C
60 250°C
T
40 NaK
T reservoir
300°C qtz temperature gases
80 T
reservoir non H2S/Ar
T
temperature gases
temperature solutes -
reactive
re-equilibration in
and/or mixing H2/Ar phase segregation
T
reservoir 20 CO2/N2

mixing T
H2S TH
2

K/100
T
CO2

20 40 60 80 Mg 100 200 300 400

Temperature (°C)

Fig. 3. The results of estimation of reservoir temperatures using alkaline water composition. A) The Na–K–Mg ternary diagram (Giggenbach, 1988) results in reservoir temperatures of ~165 °C. This
is considered to be too low estimate resulting from re-equilibration of reservoir fluids upon ascent to surface causing increased Mg and/or K concentration relative to Na,
B) the results of multicomponent geothermometry method (Reed and Spycher, 1984) show convergence in mineral equilibrium at 217 °C, this temperature considered to represent the true reservoir
temperatures. Note K and Mg containing minerals (microcline and chlorite) do not show the respective equilibrium temperature. C) The results of various solutes and gas geothermometry, the gas
geothermometry temperatures suggesting temperatures of ~270 °C when taken into account steam condensation. The apparent higher temperatures for single gas geothermometry are considered to
indicate open system boiling and phase segregation (Arnórsson et al., 2007). Open dots represent steam-heated neutral water, closed dots represent steam-heated acid water and closed triangles
alkaline water.

reservoir water rather than steam vent composition due to possible steam 6.2. Mixing
segregation and steam condensation affecting the latter.
The composition of the three end-members is given in Table 3. The non- The surface geothermal water is thought to represent various degrees of
thermal water composition is represented average non-thermal water of the mixture of non-thermal water, condensed steam and boiled reservoir water.
area based on the samples of surface river and stream water (n = 5). For the To quantify the degree of mixing, we present a mixing model based on Cl, an
boiled reservoir water and condensed steam, the composition of alkaline element thought to be non-reactive upon mixing (Arnórsson and Andrésdóttir,
water samples was used whereas the com-position of steam was based on 1995), and assuming conservation of enthalpy upon mixing. Enthalpy may be
adiabatic boiling of the reservoir water assuming equilibrium degassing. used as an indicator of mixing as long as no significant heat is lost to the
surrounding environment.

160

A Boiled reservoir water (brw)

B 100
140
%
120
brw 80%
20 80boiled
100%

100
cs 0% 20% 40% 60% 80%

(ntw)
Cl (ppm)

reservoir
80 60% water 40 60

60 water
40%
thermal 60
40
40 -
(brw)
20%
non
20 Non-thermal water (ntw) Condensed steam (cs)
%
80 20

100
0 20 40 60 80 100 20 40 60 80 100
Temperature (°C) % condensed steam (cs)

Fig. 4. A) The relationship between measured chlorine and surface temperature of surface geothermal water at Vonarskard. The end-member water compositions are also shown, including non-
thermal water (ntw), condensed steam (cs) and boiled reservoir water (brw) (Table 3). The mixing lines between these three end-member water types are also shown, assuming non-reactivity of Cl
and conservation of enthalpy. Open dots represent steam-heated neutral water, closed dots represent steam-heated acid water and closed triangles alkaline water. B) Mixing ratios forming the surface
geothermal water at Vonarskard calculated using the end-member compositions given in Table 3 and Eqs. (1) to (10). Open dots represent steam-heated neutral water, closed dots represent steam-
heated acid water and closed triangles alkaline water.
58 A. Stefánsson et al. / Journal of Volcanology and Geothermal Research 309 (2016) 53–62

Table 4 where X is the fraction, T is temperature and mCl is the Cl concentration of

Results of the mixing model between boiled reservoir water, condensed steam and non-thermal condensed steam, boiled reservoir water, and non-thermal water. Applying
water.
Cramer's rule we obtain,

# Xcs Xbrw Xntw

Alkaline water
12-VON-07 0.00 0.97 0.03 Xcs ¼ Dcs=D ð4Þ
12-VON-08 0.00a 0.97 0.03b
12-VON-10 0.00a 0.91 0.09b
12-VON-11 0.00a 0.84 0.16b
12-VON-13 0.00 0.91 0.09
300
12-VON-15 0.00 0.89 0.11
A
brw

a c b
0.00 1.00 0.00

80%
11-VON-18

%
1
0
0
0% 20 % 40 % 60 %

Steam heated acid water 250 (cs)

steam
11-VON-14 0.86 0.01 0.14 10%
condensed

2
11-VON-16 0.41 0.01 0.59
200
11-VON-17 0.36 0.04 0.60

Σ CO (ppm)
12-VON-03 0.71 0.00 0.29
12-VON-04 0.44 0.00 0.56
150
12-VON-16 0.80 0.00 0.20
12-VON-19 0.74 0.00 0.26 cs
5%
12-VON-24 0.79 0.06 0.15 100
12-VON-26 0.41 0.00 0.59
12-VON-27 0.90 0.01 0.09
12-VON-28 0.82 0.00 0.18 50 Boiled reservoir water (brw)
Non-thermal water (ntw)
Steam heated neutral water
11-VON-1 0.58 0.03 0.39 CO2 loss
11-VON-2 0.41 0.02 0.57 0
11-VON-3 0.35 0.02 0.62 0 20 40 60 80 100
11-VON-4 0.61 0.02 0.37 50
11-VON-6 0.60 0.02 0.37
B
) brw

%
1
0
0
11-VON-8 0.71 0.01 0.28
20% 40 % 60% 80 %

0%

11-VON-9 0.49 0.00 0.51

40
11-VON-10 0.42 0.00 0.58
Sm
p
p

11-VON-11 0.40 0.00 0.60

(

cs
20%
11-VON-13 0.42 0.00 0.57
11-VON-15 0.92 0.03 0.05 30
H

12-VON-05 0.61 0.01 0.38 Boiled reservoir water (brw)

12-VON-06 0.65 0.01 0.34
12-VON-12 0.82 0.06 0.12 20 10% cs
2

12-VON-25 0.67 0.06 0.27

12-S-VON-01 0.71 0.00 0.29
12-S-VON-02 0.48 0.00 0.52
10
12-S-VON-03 0.42 0.00 0.58 Non-thermal water (ntw) H2S loss
12-S-VON-04 0.39 0.00 0.61
12-S-VON-05 0.50 0.00 0.50
12-S-VON-06 0.40 0.00 0.60 0
12-S-VON-07 0.38 0.00 0.62
12-S-VON-08 0.33 0.00 0.67 0 20 40 60 80 100
12-S-VON-09 0.27 0.00 0.73 1800
12-S-VON-10 0.23 0.00 0.76
C
condensation

12-S-VON-11 0.81 0.03 0.15

1700
a Negative values assigned to be 0.
b Values recalculated assuming the total sum of Xcs, Xbrw and Xntw to be equal to unity.
4

c Value greater than 1 assigned to be 1. 1600

800
(ppm)

acumlative steam

600 Condensed steam (cs)

SO

This may not always be the case particularly for springs with very low 400 cs 80%
brw
flow rate. Since the enthalpy of a liquid water between 0 and 100 °C is 0%
20%40% 60% 80% 60%

linearly dependent on temperature, the latter is a convenient proxy 200 40%

for enthalpy, given that temperature is a parameter measured routinely, 20%

unlike enthalpy. Non-thermal water (ntw)

The mixing between the three end-member water components may 0 Boiled reservoir water (brw)
be expressed by the equations, 0 20 40 60 80 100

þ Xbrw þ Xntw
mmCl ¼ XcsmcsCl þ XbrwmbrwCl þ XntwmntwCl
1¼

Tm ¼ XcsTcs þ XbrwTbrw þ XntwTntw X

cs
 avior and conservation of enthalpy.
T Note that in figures A and B, the condensed steam
endmember composition is offe scale. For H2S and SO4, the composition of fully reduced and
ð1Þ
oxidized steam is presented, respectively. Open dots represent steam-heated neutral water,
m
closed dots represent steam-heated acid water and closed triangles alkaline water.
p
ð2Þ e
r
a
ð3Þ t
u
r
e

(
°
C
)

Fig.
5.
The
rela
tion
ship
bet
wee
n
CO
2,
H2
S
and
SO
4
and
tem
per
atur
e
for
vari
ous
wat
er
typ
es
tog
ethe
r
wit
h
end
-
me
mb
er
wat
er
co
mp
osit
ion
(Ta
ble
3)
and
mix
ing
rati
os
bet
wee
n
the
end
-
me
mb
ers
ass
umi
ng
non
-
reac
tive
beh
 A. Stefánsson et al. / Journal of Volcanology and Geothermal Research 309 (2016) 53–62 59

20 6.3. Volatile loss, oxidation and evaporation processes

lt dissolution
Upon boiling o f res ervoir geothermal wate r the

16.4mg NaCl dissolved in kg water s team phas e becomes progres s ively enriched in volatiles including CO 2 , H 2 S and H 2 . As a part o f

15 97% evaporation (vap)

sa
500
A

evaporation
10 Boiled reservoir amorphous silica solubility
Cl (ppm)

95% vap 400 water (brw)

and/or
8.2mg NaCl
boiling
brw 80%
300

(ppm)
5 90% vap
4.1 mg NaCl
No evaporation/NaCl dissolution

2
200

w
a

n
r
(

)
t

t
SiO
0 qurtz solubility
40%

0 20 40 60 80 100
100 cs

0%
10
0%

Temperature (°C)
20% 40%

the
No
20%

rm
n-

al
water-rock interaction
Fig. 6. The effects of evaporation and/or salt dissolution on the Cl content of steam-heated
water. Most water samples have very similar Cl concentrations as predicted by mixing between 0 Condensed steam (cs)
non-thermal water and condensed steam (shaded area). Upon evaporation and/ or salt 0 50 100 150 200 250
dissolution, the Cl concentration may increase. Insignificant halite (NaCl) dissolution is needed
to raise the Cl concentration whereas evaporation to near dryness is needed to raise the Cl 250
significantly. Open dots represent steam-heated neutral water, closed dots represent steam-
heated acid water and closed triangles alkaline water. B
Boiled

reservoir water (brw)

200
boiling
Xbrw ¼ Dbrw=D ð5Þ Na (ppm)

Xntw ¼ Dntw=D ð6Þ

where,

D mClcs T brw−Tntw −Tcs mClbrw−mClntw mClbrwTntw−mClntwTbrw 7

¼ þ ðÞ

Dcs mClm T brw−Tntw −Tm mClbrw−mClntw mClbrwTntw−mClntwTbrw 8

¼ þ ðÞ

Dbrw ¼ mClcs T m−Tntw −Tcs mClm−mClntw þ mClmTntw−mClntwTm ð9Þ

Dntw mClcs T brw−Tm −Tcs mClbrw−mClm mClbrwTm−mClmTbrw : 10
¼ þ ð Þ

With this approach negative values are possible as well as values greater
than 1. Such values have no physical relevance. The reason for such negative
values is thought to be temperature decrease due to conductive cooling, loss
of water mass through evaporation, natural variability of the end-member
fluid composition and/or uncertainties associated with the chemical analysis
of individual water samples. The above approach is general and can be
applied to any geothermal area. Mixing between more end-member water
types is also possible; this requires additional mixing equation(s) for more
non-reactive elements and the mathematical solution of a matrix of the fourth
or higher order.
The results for the mixing of various waters at Vonarskard are shown in
Fig. 4 and listed in Table 4. Two populations are seen, mixing between
condensed steam and non-thermal water whereas boiled reservoir water seems
mixed to insignificant degree. The reason for this could be related to the
geohydrology of the system with boiled reservoir water commonly discharged
through highly permeable fractures whereas the steam-heated water is more
distributed over the area through the ground.
60 A. Stefánsson et al. / Journal of Volcanology and Geothermal Research 309 (2016) 53–62

the steam condenses and mixes with non-thermal water, these vola-tiles may surface conditions. The alteration mineralogy in the surface zone has been
be lost due to degassing, the degassing depending on the partial pressure of demonstrated to be dependent on the intensity of the geo-thermal activity with
the dissolved gas, temperature and pH of the liq-uid phase. amorphous silica, anatase, pyrite and native

Insignificant CO2 loss is observed for boiled reservoir water whereas

steam-heated waters are largely degassed. This is seen by comparing the
mixing ratios based on Cl and temperature (Fig. 4) with those observed in Fig. 4
5. A similar trend is observed for H2S with almost complete loss of H2S for 3 Kaolinite
most steam-heated water. Assuming the mixing ratios of steam-heated water
being representative from the Cl and temperature rela-tionship, the degassing 2

of CO2 for steam-heated acid and neutral water is 86–99%. The degassing of

logQ/K
1
CO2 for boiled alkaline water is, however, 0–5% or insignificant. With Equilibrium
0
respect to H2S, the loss for steam-heated water is usually N99%.
-1
In addition to degassing, H2S may also oxidize to sulfuric acid when -2
exposed to atmospheric O2. This results in the loss of H2S from the steam-
heated water, enrichment of SO4 and subsequent decrease in the water pH. -3
2 4 6 8 10
The relationship between SO4 and temperature is shown in Fig. 5 together
with the mixing lines used previously. Significant oxidation 0.6

0.4 Amorphous silica

of H2S is observed for steam-heated neutral and acid water. This is based on
the assumption of complete oxidation of H S in the steam to SO in the
2 4
0.2
condensed steam. Partial oxidation is, however, very difficult to quantify with

logQ/K
this approach demonstrated here. Some steam-heated acid water samples are 0.0
highly enriched in SO4, suggesting cumulative steam conden-sation and
oxidation. -0.2
The steam heating of the surface environment may also enhance
-0.4
evaporation of geothermal water and, upon evaporation to almost dry-ness,
salts may precipitate followed by dissolution during the next rain period. -0.6
2 4 6 8 10
These two factors may be qualitatively assessed looking at the detailed Cl and
temperature relationship (Fig. 6). Evaporation and salt dissolution of steam- 6
heated water may result in enrichment of Cl relative to the mixing ratio of the 4 Ferrihydrite
two. As observed, most of the steam-heated water at Vonarskard shows 2
insignificant signs of evaporation or salt disso-lution. Only few samples are
0
logQ/K

enriched in Cl relative to the mixing line, suggesting either evaporation to

near dryness (90–95% evaporation) or insignificant salt dissolution. -2
-4
-6
6.4. Water–rock interaction in the surface zone
-8
In addition to volatile degassing, oxidation, evaporation and possible salt -10
dissolution, the water may react with the surrounding rocks, thus changing the 2 4 6 8 10
composition of the geothermal water. Such water–rock interaction is, for
example, thought to cause argillic alteration commonly observed at the
0
surface of active volcanic and geothermal systems (e.g. Bignall and Browne,
1994; Markússon and Stefánsson, 2011). Water– rock interaction can be -5
assessed by investigating specific elements known to be sensitive to water–
logQ/K

-10
rock interaction. SiO2, Na and Mg are examples of such elements, and are
shown in Fig. 7. Upon depressuriza-tion boiling of the reservoir water the -15
concentrations of non-volatiles in the boiled water fraction increase.
Deviation from the boiling trend suggests loss or gain of an element upon -20
Pyrite
ascent to surface. With respect to the boiled reservoir water at Vonarskard
represented by alkaline water at the surface, moderate to insignificant loss is -25
2 4 6 8 10
observed for most major elements.
10

For steam-heated acid and neutral water, significant enrichment of SiO2, 8 Montmorillonite
Na and Mg is observed relative to the mixing ratios calculated from the Cl 6
and temperature mixing model. The same is true for other rock forming 4
elements including K, Ca, Fe and Al, indicating water–rock interaction within
logQ/K

2
the surface zone. At reservoir condi-tions, the composition of the geothermal
water is thought to be con-trolled by close to equilibrium with respect to 0
secondary minerals (Giggenbach, 1981; Arnórsson et al., 1983). Upon ascent -2
to the sur-face and associated cooling, boiling and mixing with non-thermal
water followed by degassing and oxidation, the various water types become -4
out of equilibrium with the surrounding rocks, leading to rock dissolution and -6
2 4 6 8 10
formation of secondary minerals stable at
pH
Fig. 8. Mineral saturation state with respect to alteration minerals commonly observed at the
surface of Icelandic geothermal systems. Open dots represent steam-heated neutral water,
closed dots represent steam-heated acid water and closed triangles alkaline water.
sulfur in most active areas and associated with water with pH b4 whereas kaolinite, iron oxyhydroxides and oxides and montmoril-lonite become predominant
with decreasing activity and associated with water with pH N4 (Sigvaldason, 1959; Markússon and Stefánsson, 2011). In order to assess whether the composition
of the steam-heated acid and neutral water reflects the interaction with the host rock at the surface and formation of secondary minerals typically as-sociated with
surface alteration, the saturation state of some secondary minerals commonly observed in the surface zone are shown in Fig. 8. As can be seen in this figure,
amorphous silica and pyrite are saturated in steam-heated acid water whereas Al–Si minerals like kaolinite and mont-morillonite as well as iron-oxyhydroxides
(using ferrihydrite as an exam-ple) become saturated associated with steam-heated neutral water. These saturation state calculations are in good agreement with
observations in the field, and suggest that water–rock interaction is the main controlling process affecting the concentration of Si, Na, K, Ca, Mg, Fe and Al in
steam-heated water, rather than mixing between various water types. In contrast, the boiled reservoir water represented by the alkaline water bear the remnants of
the reservoir conditions rather than reactions occurring within the surface zone.

7. Conclusions

In this study a mixing model was developed in order to quantify the source and reactions of geothermal water at the surface. Such quantifi-cation is essential
in order to assess subsurface conditions from water composition at the surface for potential geothermal utilization for instance. This approach was demonstrated
for the geothermal water at the Vonarskard geothermal system in central Iceland. It involves three steps including: (1) defining the composition of the end-
member water, here thought to be non-thermal water (ntw), boiled reservoir water (brw) and condensed steam (cs), (2) defining the non-reactive mixing between
these water types based on non-reactivity of Cl and conservation of enthalpy and (3) defining the possible reactive behavior of other major elements in processes
such as degassing, oxidation and water–rock inter-action. The model can be used for any surface geothermal area as long as the end-member composition can be
assessed. Moreover, such informa-tion may be used to gain insight into geochemical processes occurring at depth and those occurring within the surface zone as
well as insight into the geohydrology of the system. When applied before and after geo-thermal exploitation and with time during geothermal utilization, possi-
ble geochemical and geohydrological changes occurring in the system may also be investigated.