Journal of Volcanology and Geothermal Research, 23 (1985) 299--335 299

Elsevier Science Publishers B.V., Amsterdam -- Printed in The Netherlands

T H E USE O F M I X I N G M O D E L S A N D C H E M I C A L G E O T H E R M O M E T E R S
F O R ESTIMATING U N D E R G R O U N D T E M P E R A T U R E S IN
G E O T H E R M A L SYSTEMS

STEFAN ARNORSSON
Science Institute, University of Iceland, Dunhagi 3, 107 ReykjavCk (Iceland)
(Received August 11, 1983; revised and accepted August 7, 1984)

ABSTRACT

ArnSrsson, S., 1985. The use of mixing models and chemical geothermometers for
estimating underground temperatures in geothermal systems. J. Volcanol. Geotherm.
Res., 23: 299--335.

Application of various chemical geothermometers and mixing models indicate under-

ground temperatures of 260°C, 280°C and 265°C in the Geysir, Hveravellir and Land-
mannalaugar geothermal fields in Iceland, respectively. Mixing of the hot water with cold
water occurs in the upflow zones of all these geothermal systems. Linear relations be-
tween chloride, boron and 61sO constitute the main evidence for mixing, which is further
substantiated by chloride, silica and sulphate relations in the Geysir and Hveravellir fields.
A new carbonate-silica mixing model is proposed which is useful in distinguishing boil-
ed and non-boiled geothermal waters. This model can also be used to estimate under
ground temperatures using data from warm springs. This model, as well as the chloride-
enthalpy model and the Na-Li, and CO~-gas geothermometers, invariably yield similar
results as the quartz geothermometer sometimes also does. By contrast, the Na-K and the
Na-K-Ca geothermometers yield low values in the case of boiling hot springs, largely due
to loss of potassium from solution in the upflow. The results of these geothermometers
are unreliable for mixed waters due to leaching subsequent to mixing.

INTRODUCTION

G e o t h e r m a l w a t e r w h i c h ascends f r o m g e o t h e r m a l reservoirs and emerges

at the surface in h o t springs m a y cool o n t h e w a y , either b y c o n d u c t i o n ,
boiling, or mixing with shallow cold water, or b y a n y c o m b i n a t i o n o f these
three processes. T h e c h e m i c a l c o m p o s i t i o n o f this w a t e r in surface discharge,
as well as the gas c o n t e n t in associated f u m a r o l e s , m a y be used t o evaluate
u n d e r g r o u n d t e m p e r a t u r e s , a p p l y i n g various chemical g e o t h e r m o m e t e r s and
mixing m o d e l s ( A r n 6 r s s o n , 1 9 7 0 a , b, 1 9 7 5 , 1 9 8 3 ; A r n 6 r s s o n et al., 1 9 8 3 a ;
Cusicanqui et al., 1 9 7 5 ; D ' A m o r e and Panichi, 1 9 8 0 ; Ellis, 1 9 7 0 , 1 9 7 9 ;
Fouillac and Michard, 1 9 8 1 ; F o u r n i e r , 1 9 7 3 , 1 9 7 7 , 1 9 7 9 ; F o u r n i e r and
R o w e , 1 9 6 6 ; F o u r n i e r and Truesdell, 1 9 7 3 ; F o u r n i e r et al., 1 9 7 4 , 1 9 7 5 ,
1 9 7 9 ; M a h o n , 1 9 7 5 ; Truesdell, 1 9 7 5 ; Truesdell and F o u r n i e r , 1 9 7 5 , 1 9 7 7 ;
White, 1970).

0377-0273/85/$03.30 © 1985 Elsevier Science Publishers B.V.

300

The present article focuses on the interpretation of chemical data of hot

spring water and fumarole steam from three geothermal fields in Iceland, at
Geysir, Landmannalaugar and Hveravellir (Figs. 1, 3 and 4) and special em-
phasis is put on assessing evidence for mixing processes in upflow zones, and
on evaluating chemical reactions between water and rock which set in as a
consequence of the mixing process. Comparison is made between the out-
come of the various chemical geothermometers (quartz, chalcedony, Na-K,
Na-K-Ca, Na-Li and COs) and mixing models. The sources of discrepancy are
discussed specifically and the overall results assessed with respect to under-
ground temperatures. A new mixing model is proposed, which is based on
the relation between the silica and carbon dioxide content of equilibrated
reservoir water. This model is useful in evaluating whether the geothermal
water has become degassed, i.e. if it has boiled, but this model may also be
used independently to estimate underground temperatures where mixed
non-boiled waters emerge in springs.
A brief description is given of the geology of the areas studied, as such
background information is considered to be essential for the reader's own
assessment of the interpretation given here. Chemical analyses of waters
from all three geothermal fields are given in Tables 1 to 3.

ANALYTICAL

For the silica-carbonate mixing model proposed in this contribution, the

method of sample collection and analysis for total carbonate is of major
importance. Alkalinity cannot be taken to represent carbonate. For hot
springs with a separate gas phase containing CO2 there is probably no way to
rigorously evaluate the carbonate content of the total discharge. For the
present study only the aqueous phase was collected. A funnel connected to
silicone tubing was submerged into the water. The tubing was fitted to a
cooling coil of stainless steel placed in a bucket of cold water. The water
from the spring was sucked up through the tubing and the cooling coil,
making sure that the far end of the coil was at a lower level than the water
level in the spring so that gravity flow would be established. A gas sampling
bulb was connected to the cooling coil with silicone tubing and filled with
cooled water (about 20°C) and the flow maintained through the tube for a
few minutes so that the water in the bulb, which was to be analyzed, should
not come into contact with the atmosphere. Total carbonate and pH were
analyzed in the sample in the gas bulb at the end of each field day. In deter-
mining total carbonate, pH was adjusted to 8.2 (practically all carbonate
occurs as HCO~ at this pH) with NaOH- or HCl-solution, as appropriate, and
the sample titrated with 0.1 N HC1 to a pH of 3.8 (all carbonate occurs as
CO2 at this pH). Correction for interference from weak acids other than
CO2 (silica, sulphide, boron, water) was made by calculation following
analysis of the respective components.
 301

GEOLOGY AND THERMAL MANIFESTATIONS

The three geothermal fields considered in the present study have been
classified as high-temperature (Arn6rsson, 1970a; P~lmason and Saemunds-
son, 1974). Two of them (Landmannalaugar and Hveravellir) are located
within the active volcanic belts and one (the Geysir field) close to the
eastern boundary of the main volcanic belt in southern Iceland (Figs. 1, 3
and 4). The most prominent thermal manifestations at Hveravellir and in the
Geysir field include geysers, boiling hot springs and considerable silica sinter
deposits. In the Landmannalaugar field fumaroles are, on the other hand, the
most prominent feature of surface thermal activity.

The Geysir field

The Geysir geothermal field is located in the uppermost part of the

southern lowlands of Iceland at an elevation of about 120 m. Most of the
geothermal activity occurs in an area which is only a few hundred metres
across, b u t thermal manifestations, mostly in the form o f warm springs, are
spread over an area of approximately 6 by 0.5 km, which is elongated in the
prevailing tectonic direction within this region (Fig. 1).
The rocks of the area within which the Geysir field is located belong to
the Brunhes magnetic epoch (less than 700.000 years). They consist of
interglacial basalt lavas, pillow lava and hyaloclastite formations, also of
basaltic composition, which have erupted subglacially, and four domes of
spherulitic rhyolite. The basaltic hyaloclastites are often rich in tachylyte
and palagonite. Pitchstone and tillite-like breccia are abundant in one of the
rhyolite domes, probably due to its subglacial extrusion.
High-temperature geothermal fields in Iceland are typically associated
with so-called central volcanoes (P~lmason and Saemundsson, 1974). One of
the characteristics of these volcanoes is relatively abundant acid volcanics, b u t
also intrusions and caldera structures, the latter often being represented b y a
dip of the lava flows towards the core of the volcano (Walker, 1963). The
area of the Geysir field may well represent a central volcano, although the
evidence for this is, admittedly, rather meager. The only evidence of intru-
sives is a gravity high south of the main hot spring area (P~lmason, un-
published data) and rather anomalously steeply dipping lavas (towards the
northeast) b y Stakks~ (Fig. 1).
Most of this area was submerged at the end of the last glaciation and
thick near-shore clastic sediments from that period cover the bedrock in the
southern part of the area (Fig. 1), forming extensive plains.
All the boiling hot springs within this field are situated within intensely
altered basalts just east of the rhyolite d o m e of Laugarfell (Fig. 1). Tepid
springs occur at the foot of the cliffs on the west side of Laugarfell and on
the alluvial plain to the south, as far as 4 km from the main hot spring area.
Warm and hot springs also occur in Haukadalur about 2 km to the north.
302

LEGEND:
ACID VOLCANICS
BASALTIC LAVASAND HYALOCLASTITES
STEEPLY DIPPINGTHOLEIITES
ALLUVIUM
• WATERSAMPLE WITH SAMPLE NO,
o FUMAROLESAMPLE
N
0 500m T

I
I

Fig. 1. Map of the Geysir field showing location of sampling points.

 303

Acid pools and small mud pots are found within the main hot spring area.
The higher ground on the lower slopes of the Laugarfell rhyolite d o m e is in-
tensely altered b y acid surface leaching. Here inconspicuous fumaroles
appear. The high fluoride content of the thermal waters indicates contact
with acid rocks (Arn6rsson et al., 1983b). This, and the distribution of the
thermal springs, suggests that the major upflow occurs either along perme-
able contacts between the Laugarfell rhyolite d o m e and the enveloping
rocks, or that the water ascends along permeable cracks within the rhyolite
itself. Many records exist of changes in the surface thermal manifestations
during earthquake episodes (Thoroddsen, 1925). This indicates rejuvenation
of permeability in the upflow caused b y tectonic movements.
One drillhole has been sunk within the Geysir field by the farm Nedridalur.
It is 850 m deep and struck an aquifer at 386 m depth with a temperature
of 68°C. The flow rate is 5 dm a s -I. B o t t o m hole temperature is 173°C and
there is a constant gradient below the producing aquifer equivalent to
220°C km -1 (Fig. 2).
As will be discussed m the following section, there is strong evidence that
the warm and tepid waters have formed by ~ixing of geothermal water with
Temperature °C
40 80 120 160

200
-/
i-

a
I)
aquifer
400

600

"4""44",,,\,,

800

i i r, i i I i I

Fig. 2. Temperature profile in well at Nedridalur. Based on unpublished data from the
National Energy Authority, Reykjavl"k.
304

cold groundwater. It appears particularly likely that mixing is prone to occur

when hot water emerges from the bedrock and ascends into unconsolidated
post-glacial sediments.
Total flow from the boiling hot springs is only 13 dm 3 s -1 and the flow
from all the warm springs is also rather low. Table 1 gives flow rates for those
springs analyzed for the present study. If reservoir temperatures are in the
range of 260°C (see later sections), adiabatic boiling in the upflow would
convert some 30% of the reservoir water into steam and, accordingly, a
steam discharge of 6 kg s -1 is expected to accompany the measured water
discharge of 13 dm 3 s -1 . The impression is that the steam flow is less, suggest-
ing that conductive heat loss in the upflow is significant. Cooling by con-
duction evidently occurs in pipes feeding some of the hot springs and
geysers, as shown by studies of the geyser activity of the Great Geysir
(Einarsson, 1937, 1949; Sigurgeirsson, 1949). These studies indicate surface
cooling and convection within the pipe below the geyser basin such that the
water at 20 m depth is about 130°C, but between 70°C and 90°C at the sur-
face, depending on weather conditions. No boiling occurs and the flow from
the spring is 2.2 dm 3 s -~ (Table 1).

Hveravellir

This geothermal field is located in central Iceland at an elevation of about

630 m between the icecaps of HofsjSkull and LangjSkull. The main hot
springs emerge in glacial outwash plains by the northern edge of the post-
glacial lava field of Kjalhraun (a lava shield), but fumarolic activity occurs
in the lava field (Fig. 3). Poor exposures on the glacial outwash plains indi-
cate that the rocks in the vicinity of the thermal field are basaltic hyalo-
clastites. Rhyolitic rocks outcrop in several localities in the marginal moun-
tains of LangjSkull some 5 km to the west.
This geothermal field is very small. The main area of alkaline hot springs is
only about 200 m across. Fumarolic activity extends about 1Ato 1 km to the
south into the Kjalhraun lava field and hydrothermal clay formed by acid
surface leaching has been found several hundred of metres northwest of the
main hot springs. The total quantity of water discharged from the hot
springs has been estimated to be some 15 dm 3 s -1 .
The thermal activity at Hveravellir bears close resemblance to that in the
Geysir field, that is, alkaline spring waters, geysers, extensive silica sinter
deposits, some mud pools and fumaroles and clayey hydrothermal soil. The
surface manifestations are spread on a north--south line coinciding with the
active tectonic fracturing of the region.

The Landmannalaugar field

The thermal activity in the vicinity of Landmannalaugar is a part of the

TorfajSkull geothermal field in southern Iceland. This is the largest (areally)
 305

,
*it+++++
+* +++++
+ i + + + + + + + + + t + + I + +
++++i++*++
++++***++*++++++++i’
‘-++++++*~+++++++++-++++++++~4
.l++++~t+++++++ +++~0,J6-++ + + + + A + + * ,
++~+++++++++++i
- , + + +‘++*++*++++++++++++
+ + + + + + + + + + + + + + +
*-i+++++++.++*++++++*+++++~+++
.t+++++**++++++++-
* * A + ++++++++++*’ * * + + *
+ + + + + + + + + + + + + +
+ + + + f + + + + + + + + + + i * + I + + + i+++++++++++
+*.++-+--++++++++~+t+++
. * + * * + + + + + + + + + + + * + A ++++++++*+t+++++
+++i+**++++tt++++++
..t--++*+r+++i+++++ 4 + + + I
**-A**-++++++++*+t++___++l++++
-.**‘f+.++i++i*+*
iii--~ -*tit+
- * _ - + + * + + _ - + * * + + + + + i _~.~. _ + + + + + f

/ . + ~~~- + * + + + +

--‘+
N +
+

+
L+*+++++++r+
+

+
+

3 * * +*++++++++*+

t-t++++++*+*
0 2oonl ++++++++++++
ii+-++-+++++
f+++++++i+++
T +++i+++++++*
+++++t++++++
LEGEND: +*+*t,++++++
+++++++++r+~
E=r;l SILICA SINTER +iii+it+++++
w KJALHRAUN POST-GLACIAL LAVA ~~~~~~+~+~+~+~++++++++~+
0 GROUND MORAINE + + + / + + / +-+++++*++
+-+++++tl&
. WATER SAMPLE +:4:-+-+++t+++++t+*+- +
WITHSAMPLEND.
0 FUMAROLE SAMPLE * + + * + + v + + + ++++
+-+++++++i*’
A TOURIST HUT +~+r++++++++
+t++t*+++*i+
I++++*++++*+
+++++++*++++

Fig. 3. Map of Hveravellir showing location of sampling points. Field location is shown in
Fig. 1.

geothermal field in the country, covering some 200-300 km2. It is, how-
ever, only in the Landmannalaugar area that alkaline spring waters of the
sodium chloride type are known and for that reason sampling for the present
study was limited to the Landmannalaugar field, but the main aim of the
study was to evaluate mixing processes and underground temperatures from
the composition of hot spring waters.
The Torfajijkull region constitutes the largest complex of acid volcanic
rocks in Iceland. Within the Landmannalaugar field only acidic rocks out-
crop and they include rhyolites, pitchstone and obsidian. It is considered
that all of the rocks exposed have formed by subglacial eruptions in late
Quaternary time, probably during the last glaciation (Saemundsson, 1972). A
young lava has been extruded from a short fissure on the slopes of the
rhyolitic dome of Brennisteinsalda. Tephrochronological evidence indicates
306

that this lava was erupted in the 14th century (G. Larsen, pets. commun.,
1984).
A large caldera or ring structure has been identified in the TorfajSkull
region (Saemundsson, 1972), which envelopes practically all the geothermal
manifestations and almost all the acid rocks. Fissure eruptions have simul-
taneously produced acid lavas within the caldera, basalt lavas outside it and
mixed lava at the caldera rim. This has been taken as evidence for the exis-
tence of acid magma at shallow depths within the caldera. A distinct positive
gravity anomaly in the TorfajSkull region has been taken as evidence for
basaltic magma intrusions below the eruptive acid rocks {Walker, 1974). It
appears thus that both acid and basic intrusives could constitute the heat
source for the geothermal system.
The terrain of the Landmannalaugar area is extremely rugged, as it is in
fact for a rather large part of the TorfajSkull region, being characterized by
steep-sided V-valleys and inassessable gorges. Valley bottoms, if there are
any, are covered by coarse alluvial gravel.
The thermal manifestations in the Landmannalaugar field differ greatly
from those at Hveravellir and Geysir. Fumarolic activity and hot ground,
altered by acid surface leaching, is much more prominent, especially on high
ground. Hot springs with alkaline sodium chloride waters occur in and near
the valley bottoms. They are widespread and numerous but the flow rate

r. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

0L__L- L ~ J ~500m
• 82-097 82-116,,
82-115"82"113 N
,~7~-099~82.098 82-114~
79-054
82-118•
82"119¢82-107

\
/s \
82-102
k
J 82-1001101
./ 82-1211122
•82-095
82-096 82-120/123
82-111 ]

J
/
82-103
LEGEND:

~
82-104- 82-108=82-110
[~ LAUGAHRAUN OBSIDIAN LAVA
82-109 94 ALLUVIUM WITH BRAIDED RIVERS
[~ ACID VOLCANICS [
82-105
• WATERSAMPLE ~WlTH SAMPLENO.
FUMAROLE SAMPLE
, TOURIST HUT
J

Fig. 4. Map of the Landmannalaugar field showing location of sampling points. Field lo-.
cation is shown in Fig. 1.
 307

from individual springs is low (generally less than 1 dm 3 s-'). Sinter deposits,
which most often show up as cementing of gravel, are not uncommon.
Alkaline spring waters and strong steam vents sometimes occur at a distance
of a few metres, suggesting that the two phases ascend together from the
deep reservoir.
Numerous warm springs with high flow rates issue from the edge of the
Laugahraun lava. When this lava flowed it blocked the main stream course
from the Vondugil area (Fig. 4). As discussed in the following section, there
is evidence indicating that these waters are of mixed origin and the hydrolog-
ical situation indicates that the mixing may occur below the lava, near its
base or at deeper levels in the inferred alluvium deposits or in the bedrock.
No estimate is available for the total heat o u t p u t from the Landmannalaugar
field.

EVIDENCE FOR MIXING

Water formed by mixing of geothermal water and cold ground- or surface

water possesses many chemical characteristics which serve to distinguish it
from unmixed geothermal water. The reason is that the chemistry of geo-
thermal waters is characterized by equilibrium conditions between solutes
and alteration minerals, whereas the composition of cold waters appears
mostly to be determined by the kinetics of the leaching process. The mixed
waters tend to acquire characteristics which may be said to be intermediate
between those just mentioned. It is, however, to be realized that the resi-
dence time in the bedrock after mixing and the temperature and salinity of
the mixed water have an influence on the final chemical composition in
spring discharges. Strong conductive cooling of geothermal waters in upflow
zones and subsequent reaction with the rock may produce compositional
affinities similar to those obtained by leaching subsequent to mixing. Since
geothermal waters are often, but not always, much higher in dissolved solids
than cold ground- and surface waters, the mixing process has often been
referred to in the literature as dilution.
The main chemical characteristics of mixed waters, which serve to distin-
guish them from equilibrated geothermal waters, include relatively high con-
centrations of silica in relation to the discharge temperature, low pH relative
to the water salinity (often in the range of 6--7 for C1 concentrations of less
than 100 ppm) and high total carbonate, at least if the mixing has prevented
boiling and the temperature of the hot water component exceeds some
200°C. Further, like cold waters, mixed waters tend to be calcite under-
saturated and with low calcium/proton activity ratios compared with geo-
thermal waters. Figure 5 shows the state of calcite saturation for water from
Hveravellir and the Geysir and Landmannalaugar fields as well as calcium/
proton activity ratios. As can be seen from this figure, some of the mixed
waters show affinities towards cold waters, whereas others approach equilib-
rium conditions.
308

""",, ,

9 ~: 7 "-.,. ,.
• •
"". .
• • ""-.
• %,

• I'I L~ 6
0 82 008

o • • •82 009
-10 • • 79 0 0 6 1 5
• • 82 0071

41

20" ~.0 6'o 8'0 2'o ;0 60 8'0

T e m p e r a t u r e °C T e m p e r a t u r e oC

Fig. 5. The state of calcite saturation and x/Ca~+/H ÷ activity ratios at discharge temper-
ature in waters from Hveravellir (triangles) and the Geysir (circles) and Landmannalaugar
(squares) geothermal fields. The broken curves indicate calcite saturation and x/Ca2÷/H ÷
activity relations for equilibrated waters according to Arn6rsson et al. (1983b).

A m u c h s t r o n g e r case is m a d e f o r m i x i n g in u p f l o w z o n e s w h e n t h e m i x i n g
can be q u a n t i f i e d b y considering a g r o u p o f spring w a t e r s r a t h e r t h a n relying
o n t h e c h e m i c a l characteristics o f individual discharges. H e r e near-linear rela-
t i o n s h i p s b e t w e e n c h l o r i d e c o n c e n t r a t i o n s o n t h e o n e h a n d and b o r o n con-
c e n t r a t i o n s and 5180 values o n t h e o t h e r are believed to be p a r t i c u l a r l y
valuable. S o m e t i m e s a linear r e l a t i o n b e t w e e n chloride and silica and
chloride and s u l p h a t e m a y also be useful.
Chloride and b o r o n levels in cold w a t e r are, as a rule, low b u t m u c h higher
in g e o t h e r m a l w a t e r s and, as these c o n s t i t u e n t s are n o t c o n s i d e r e d to be in-
c o r p o r a t e d in g e o t h e r m a l minerals, m i x i n g involves simple lowering o f con-
c e n t r a t i o n s w i t h o u t a f f e c t i n g t h e C1/B ratio. I f m i x i n g o f g e o t h e r m a l w a t e r
w i t h cold w a t e r is r e s p o n s i b l e f o r variable c h l o r i d e c o n c e n t r a t i o n s , it is t o b e
e x p e c t e d t h a t t h e i n t e r s e c t i o n at 0 p p m b o r o n o f a line t h r o u g h t h e d a t a
p o i n t s is in the range o f 10 p p m chloride, as cold w a t e r ( a n d p r e c i p i t a t i o n )
c o n t a i n s chloride in t h a t range and less t h a n 0.01 p p m b o r o n .
Figure 6 shows t h e c h l o r i d e - b o r o n r e l a t i o n f o r t h e w a t e r s f r o m Hveravellir
and the G e y s i r and L a n d m a n n a l a u g a r fields. In every case t h e r e is a r a t h e r
g o o d linear relation. F o r t h e Geysir and L a n d m a n n a l a u g a r fields t h e p o i n t o f
i n t e r s e c t i o n c o r r e s p o n d i n g w i t h 0 p p m b o r o n is s o m e 10 p p m f o r chloride.
T h u s t h e c h l o r i d e - b o r o n relationships o f w a t e r s f r o m t h e s e fields are t a k e n
to p r e s e n t a strong evidence f o r m i x i n g o f g e o t h e r m a l w a t e r and cold g r o u n d -
 309

water. For the Hveravellir waters the intersection of a regression line through
the data points at 0 ppm boron corresponds with 17 ppm chloride, or some-
what higher than anticipated. This appears to be, at least partly, due to
boiling prior to mixing.

GEYSlR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD

r , , , ,

////'
12 0.6 6

E
o. /
'~ / = n~"
,/
/
O~ /~:" 04 4

•//I / /
/
// •// #
/" /
/ /
0.4 " 02 /
/ •
/,/ /
/ • / • /
/ fo
/'O
h /
/"d" /
/
/
/L i
J 4'0 8 O J 120 20 40 ' 6'0 200 400 600
Cl. ppm CI, p p m CI, ppm

Fig. 6. Chloride and boron contents of cold and thermal waters from the Geysir field,
Hveravellir and the Landmannalaugar field. The broken lines shown were obtained by
linear regression of the data.

Figure 7 shows the relation between 6 D and 51sO values for the thermal
and non-thermal waters sampled from the fields under study. The Land-
mannalaugar data show a slight positive slope which is best explained by
steam loss. The Hveravellir data fall, with the exception of one sample, on
a line with a significant negative slope. The coolest waters with the largest
cold water component plot closest to the meteoric line. From the deuterium
content of the waters at Hveravellir/f~rnason (1976, 1977) concluded that
they are precipitation falling on high ground, on the LangjSkull and/or
Hofsjbkull ice-sheets to the west and east of the geothermal field. Mixing
of this distantly derived water and local meteoric water could explain the
distribution of data points in Fig. 7.
The data points from the Geysir field show a large scatter. Waters from
boiling hot springs show much oxygen shift and a gentle positive slope. As
for the Landmannalaugar waters, this slope may be explained by steam loss.
The deuterium levels indicate that the water is not local precipitation but
derived from the southern part of the LangjSkull ice-sheet some 50 km to
the north (see /~rnason, 1977). With two exceptions, the warm spring
waters from the Geysir field plot close to the meteoric line. According to
the deuterium precipitation map of/~rnason (1977), the deuterium content
of most of these warm waters (not 82-014 and 82-018) is compatible
310

with being largely local precipitation. One mixed water (82-018) is inter-
mediate between the boiling hot spring waters and the meteoric line, the
reason is considered to be that this water contains a rather large portion of
the hot water component, as indicated by the chloride content. Sample
82-014 issues from the alluvial plain in the southern extreme of the field
(Fig. 1). The cold water c o m p o n e n t in this water may not be local precipita-
tion but that of the through-flowing rivers which originate at the southern
edge of the LangjSkull ice-sheet, which would explain the relatively low 5 D
and 5~sO values for this water. Sample 82-012, which is from a tepid spring
some distance north from the main hot spring area, does not plot on the
meteoric line {Fig. 7) and is high in 5D relative to 51sO. The reason for this
is not known.

'//
82-012e /

-6(]

S
"
-80

J --:
-12 -10 -8
%0/~ 180

Fig. 7. Plot of 5 D versus 5~80 for cold and thermal waters from Hveravellir (triangles)
and the Geysir (circles) and Landmannalaugar (squares) geothermal fields.

Figure 8 shows that there is a good relation between chloride concentra-

tions and 51sO values for the Hveravellir and Landmannalaugar waters. This
relation is considered to reflect mixing of geothermal water with cold water.
The geothermal water has changed its 51sO value by reaction with the rock,
but the hydrogen and oxygen isotope composition of the tepid water corre-
sponds with that of the meteoric line (Fig. 7). A similar 8D/51sO pattern and
interpretation has been presented for the geothermal system at Long Valley,
California {Mariner and Willey, 1976; Fournier et al., 1979).
Two points in Fig. 8A and 8B show high 51sO values relative to their
chloride concentrations. A plausible explanation for the anomalous values
is that steam containing CO2 has condensed in this water, b u t CO2 is much
 311

enriched in the 1so isotope relative to water. The sample from the Geysir
field with the high 5 l s o value contains also anomalously high sulphate which
can be explained by the same process, namely oxidation of sulphide derived
from condensed steam.

GEYSIR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD

i i [ I i r

B C

-8 -8 I
•

o o

-10 -1C

I
~.
o •

-12 ~ -12

, i J i i /
40 80 120 2'0 ~ 40' ' 6'0 J 200 400 600
C ppm CI,ppm CI,ppm

Fig. 8. Plot o f chloride versus 6~sO in cold and t h e r m a l w a t e r f r o m Hveravellir and t h e

Geysir and L a n d m a n n a l a u g a r g e o t h e r m a l fields. Lines a and b designate mixing w i t h cold
w a t e r o f d i f f e r e n t 5180 c o n t e n t .

The waters from the Geysir field display a rather good linear relation be-
tween chloride and silica (Fig. 9). This relationship is not as clear for Hvera-
vellir and very poor for the Landmannalaugar waters. If the dilution process
is not followed by dissolution of silica from the rock, nor with precipitation,
a linear silica-chloride relation is to be expected and the line through the
data points should pass close to the point of origin in Fig. 9. If the unmixed
geothermal water was in equilibrium with quartz and re-equilibrium with
that phase occurred after mixing, considerable amounts of silica would have
to precipitate from the water.
The squares in Fig. 9 show the silica and chloride concentrations in the
reservoir water as deduced from chloride-enthalpy mixing model diagrams
discussed in a later section (see Fig. 17). The curves indicate silica/chloride
relations that result from mixing if the silica levels are always controlled by
quartz solubility. The broken and dotted lines indicate chloride-silica rela-
tions which result from mixing and steam loss respectively. For the Geysir
field and Hveravellir the data points in Fig. 9 tend to plot below the dilu-
tion/boiling line, indicating that some precipitation is associated with those
processes. The same holds for the Landmannalaugar field except for three
samples (82-113, 82-115 and 82-117) of water from the edge of the Laugah-
312

raun lava which contain high silica relative to chloride. It is considered that
leaching of silica from the rock after mixing is responsible. Data points
which plot below the quartz re-equilibration curve must have lost silica from
solution after mixing due to cooling by conduction or boiling. It is note-
worthy that the waters from Landmannalaugar which contain highest
chloride have lost the larger part of their original dissolved silica.

GEYSIR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD

r i I [ I + I I I q I

60(] 60O °: 60(]

E
o. •
@.
e~

0._
4 (£~1 .

O~ Ze •
40~
/
," •
•
40C +° /
,/ •
2413 /
/ ' ~2 2 117 ;
2-115 / • •

2OO // //"•82.018
/ 200 / e82127

/~4""V /
/ •
I I I I I I I 1 I I I 1
40 80 120 200 400 6OO
CI, p p m CI, p p m CI, p p m

Fig. 9. Plot of silica versus chloride in thermal and cold waters from the Geysir, Hveravel-
lir and Landmannalaugar geothermal fields. The squares represent deep water silica and
chloride concentrations as predicted by chloride-enthalpy mixing model plots (see Fig.
17). The broken and dotted lines indicate variations resulting from dilution and boiling
respectively. The curves show silica-chloride relations resulting from mixing and attain-
ment of quartz equilibrium. Practically all the data points plot below the mixing/boiling
lines, indicating that some silica precipitation generally occurs subsequent to these pro-
cesses. Data points with sample numbers are specifically discussed in text.

Sulphate concentrations show a good relation with chloride in waters

from Hveravellir and the Geysir field (Fig. 10): By contrast, no such rela-
tionship is observed for the Landmannalaugar waters. Yet, if waters issuing
from the edge of the Laugahraun lava and those in other parts o f the field
are considered separately, a positive and negative chloride-sulphate relation
respectively is apparent (Fig. 10).
It might be expected that the boiling hot spring waters, especially geysers
and pools with large surface areas, had relatively high sulphate content as a
result of sulphide oxidation by atmospheric oxygen. Indeed the 81sO value
for the sulphate indicates sulphide oxidation subsequent to isotopic equilibra-
tion (TruesdeU and Arn6rsson, unpublished work). An explanation, which
accounts for both the chloride-sulphate relationship and the 81sO values of
 313

the sulphate, assumes that sulphide oxidation occurs at depth before mixing.
It is conceivable that the waters emerging in the hot springs are mixed
waters, in which case atmospheric oxygen in the cold water component was
involved in converting the sulphide to sulphate.

GEYSIR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD

12(: • E 12( ~60 •

o.
ffl tN
'¢ 00
8G 8( 40 •

4C 4c 2E

40 80 t20 2b 4b 8b ~o 45o 660

CI. pprn Cl.ppm CI, pprn

Fig. 10. Plot of chloride versus sulphate in cold and thermal waters from Hveravellir and
the Geysir and Landmannalaugar geothermal fields. For the Landmannalaugar field
distinction is made between waters issuing from the edge of the Laugahraun lava (large
dots) and data from other parts of the field (small dots).

i...
"0
~-6
(.,-

0
0

-8

I ° oqw p

Temperature °C
Fig. 11. The state of anhydrite saturation in waters discharged from boiling hot springs
at Hveravellir (triangles) and in the Geysir (dots) and Landmannalaugar (squares) fields.
Quartz equilibrium temperature was selected for reference, assuming adiabatic steam loss.
314

TABLE 1

C o m p o s i t i o n of w a t e r s f r o m t h e Geysir g e o t h e r m a l field, s o u t h e r n Iceland ( c o n c e n t r a -

tions in p p m )

Sample Location Temp. Flow pH/°C SiO~ B Na K

No. (°C) d m 3 s -'

79-004 Geysir 72 2.2 9.36 '22 486.0 0.95 248.2 26.2

79-005 Sisjbdandi 95 1 9.57 '22 350.0 0.93 236.4 13.1
79-006 Smidur 98 0.1 8.93 '22 324.7 0.82 228.2 12.0
82-005 Blesi 90 2 9.38 '20 503.2 1.01 230.6 19.3
82-006 Otherrishola 94 0 8.92 '20 437.8 0.78 222.7 15.7
82-007 Litli S t r o k k u r 98 0 7.77 '20 404.2 0.76 216.1 12.2
82-008 Litli Geysir 70 0 8.73 '20 450.4 0.82 230.2 14.4
82-009 Strokkur 78 3 8.56 '20 457.2 0.96 225.4 14.4
82-010 Marteinslaug 78 0.4 7.88 '20 290.0 0.68 164.0 12.4
82-011 Kaldilaekur 5 8.01 '20 30.6 0.01 11.8 0.96
82-012 17 2 7.72 '20 35.2 0.01 9.4 0.61
82-013 Nedridalur 68 5 7.52 '20 146.2 0.22 223.2 44.2
82-014 Mfili 46 2 7.57 '20 167.0 0.18 180.9 21.1
82-015 24 2 7.76 '20 60.2 0.22 28.2 1.79
82-016 48 1 7.39 '20 145.7 0.25 83.8 5.72
82-017 Laugarfell 97 1 8.74 '20 355.1 0.66 194.4 8.68
82-018 39 0 7.44 '20 180.2 0.28 132.8 21.5
82-019 Helludalur 30 5 7.94 '20 79.7 0.13 84.6 9.76

a T o t a l c a r b o n a t e a n d t o t a l sulphide, respectively.

TABLE 2

C o m p o s i t i o n of waters f r o m t h e Hveravellir g e o t h e r m a l field, c e n t r a l Iceland ( c o n c e n t r a -

t i o n s in p p m )

Sample Location Temp. Flow b pH/°C SiO~ B Na K

No. (°C) ( d m 3 s -1)

82-124 Braedrahver 96 1 9.75 '10 606.5 0.51 169.6 16.7

82-125 Fagrihver 93 0.1 9.59 '10 595.5 0.54 159.6 15.7
82-126 Eyvindarhola 97 0.3 9.26 '10 478.8 0.46 147.5 8.56
82-127 97 2 9.48 '10 196.9 0.34 115.8 4.81
82-128 92 9.60 ~10 564.5 0.51 158.0 16.2
82-129 35 0.5 8.73 ¢20 42.3 0.10 45.5 2.32
82-130 40 2 8.80 ~20 78.4 0.14 74.7 3.00
82-131 65 0.1 9.12 f20 280.9 0.26 105.3 8.86
82-132 89 0.5 9.41 ~20 384.8 0.38 132.6 10.4
82-133 20 7.34 t20 50.6 0.10 45.9 1.76

a T o t a l c a r b o n a t e and t o t a l s u l p h i d e , respectively.
bEstimated.
 315

Ca Mg Li CO2a SO, H2S a CI F 5 D°/oo 6180o/00

0.76 0.002 0.340 136.8 117.0 0.86 132.4 8.66 -75.6 --7.60
0.72 0.002 0.201 109.6 101.5 1.56 122.9 12.18 --82.5 --8.65
0.68 0.006 0.194 92.1 150.2 0.59 115.0 10.90 --74.0 -6.14
0.86 0.010 0.348 99.0 103.5 1.34 132.2 9.90 --77.9 8.46
1.47 0.015 0.296 126.1 93.8 1.99 124.4 11.00 --78.7 --8.50
0.85 0.012 0.236 180.2 80.2 2.61 118.2 13.20 --81.4 9.04
0.71 0.010 0.308 146.8 104.8 0.28 131.3 13.10 --75.4 --7.81
0.73 0.011 0.285 159.0 104.6 0.25 132.2 12.90 --77.4 --7.77
4.48 0.120 0.262 180.0 61.1 0.72 86.6 5.06 /-80.3 --10.18
3.22 0.461 0.001 16.6 0.5 <0.01 7.4 0.07 --66.0 --9.78
4.93 0.980 0.001 36.5 0.3 <0.01 10.6 0.13 --46.2 --8.50
7.72 0.611 0.017 462.5 28.3 0.04 46.4 5.88 --68.4 --9.54
15.5 4.08 0.016 399.6 34.8 0.07 36.0 1.92 --78.1 --10.90
12.7 1.58 0.008 73.8 9.8 <0.01 18.9 1.24 --60.6 --9.37
4.00 0.530 0.006 94.9 22.4 <0.01 43.6 7.93 --64.3 --9.39
1.19 0.018 0.210 160.5 79.3 1.81 105.5 15.20 --84.4 --9.33
10.2 3.11 0.044 243.2 47.8 <0.01 64.5 6.02 --71.6 --8.88
2.90 0.540 0.013 147.8 13.2 <0.01 26.4 2.53 --60.7 --9.35

Ca Mg Li CO2 a SO, H2S a C1 F 5 D°/oo ~1~0°/oo

2.28 0.053 0.315 16.8 137.3 3.51 70.0 3.12 --91.0 --11.00
2.17 0.020 0.293 26.9 142.1 2.10 73.0 3.12 --91.1 --10.69
3.22 0.042 0.165 47.3 142.8 1.92 67.2 2.20 --96.3 --9.49
4.04 0.020 0.083 25.7 118.7 0.38 54.5 1.34 --91.4 --11.45
2.93 0.015 0.277 23.5 145.8 2.50 74.0 3.12 --94.2 --10.60
9.63 0.559 0.024 30.6 55.3 <0.01 29.0 0.33 88.0 --11.97
8.56 0.800 0.042 42.5 86.8 <0.01 38.6 0.50 --88.8 11.83
3.52 0.080 0.140 41.7 81.3 3.22 39.6 1.58 --97.2 --12.21
2.56 0.049 0.169 23.3 121.8 1.07 59.0 2.39 --11.37
7.77 1.046 0.033 40.0 51.8 <0.01 26.4 0.40 --88.8 --11.97
316

TABLE 3

Composition of waters from the Landmannalaugar geothermal field central south Iceland
(concentrations in ppm)

Sample Location Temp. Flow b pH/°C SiO 2 B Na K

no. (°C) (dm3s -' )

79-053 Sullur 94 1 8.80 r24 210.2 1.63 263.0 11.6

79-054 Landm. laugar 82 3 6.10 ~23 258.4 1.72 252.6 35.3
82-093 94 1 9.27 r14 207.1 6.14 363.6 17.3
82-095 Graenagil 45 2 6.64 t14 160.6 1.25 151.6 14.0
82-097 Eyrarhver 95 1 9.96 /14 271.8 4.21 413.9 16.1
82-099 Vondugil 94 3 9.58 t14 145.4 1.27 208.2 8.97
82-106 Vondugil 94 1 9.93 '14 299.1 1.96 291.9 15.1
82-113 Landm. laugar 59 10 6.32 f14 186.0 0.39 65.4 13.0
82-114 Landm. laugar 24 20 6.57 f13 81.8 0.25 57.6 8.74
82-115 Landm. laugar 58 5 6.62 '13 165.5 0.36 70.8 14.5
82-116 Landm. laugar 10 100 7.34 ~13 36.9 0.06 17.9 3.54
82-117 Landm. laugar 45 10 7.91 r13 173.1 0.36 61.7 13.4
82-118 Vondugil 93 0.2 9.82 r14 265.4 2.61 278.9 13.6
82-119 Vondugil 96 1 9.91 ~14 297.3 2.32 273.4 22.6

aTotal carbonate and total sulphide, respectively.

bEstimated.

The Geysir and the Hveravellir waters are in general c o n s i d e r a b l y higher

in sulphate t h a n waters f r o m t h e L a n d m a n n a l a u g a r field (Tables 1--3).
C o m p u t e r analysis indicates a n h y d r i t e u n d e r s a t u r a t i o n at d e p t h for the
waters feeding boiling h o t springs in all t h r e e fields (Fig. 11). The lack o f
chloride-sulphate relationship f o r the L a n d m a n n a l a u g a r waters c a n n o t ,
t h e r e f o r e , be explained b y the c o n t r o l o f a n h y d r i t e solubility u p o n sulphate
m o b i l i t y . It m a y be t h a t r e d o x equilibrium involving h y d r o g e n , sulphide and
pH is t h e c o n t r o l l i n g f a c t o r :
H~S + 4 H 2 0 = SO/, 2 + 4H2 + 2H +

REDISTRIBUTION OF CATIONS

In t h e m i x e d w a r m waters t h e m a j o r c a t i o n (Na, K, Ca, and Mg) c o n c e n -

trations d o n o t s h o w a n y regular variation w i t h t h o s e o f chloride, indicating
t h a t t h e mixing process is f o l l o w e d b y r e d i s t r i b u t i o n o f these ions. Dissolu-
t i o n f r o m the r o c k following c o n v e r s i o n o f CO2 t o HCO~ is m o s t i m p o r t a n t ,
b u t u p t a k e in alteration minerals m a y also be involved.
T h e boiling h o t spring waters f r o m all t h r e e fields are l o w e r in c a l c i u m and
m a g n e s i u m t h a n b o t h c o l d and m i x e d waters. Calcium is highest in t h e w a r m
waters o f m i x e d origin. Magnesium levels also t e n d t o be highest in t h e mix-
ed waters. Potassium c o n c e n t r a t i o n s are highly variable. F o r t h e Geysir and
L a n d m a n n a l a u g a r fields, waters o f m i x e d origin m a y be higher or l o w e r in
 317

Ca Mg Li CO2 a SO 4 H2S a CI F 6 D°/oo 81sO°/o,

1.39 0.076 0.222 106.2 54.7 16.3 200.5 19.7 --69.2

10.86 2.28 0.604 280.3 70.0 0.07 307.0 7.15 --68.6
12.3 0.059 0.114 11.4 18.2 4.58 534.7 9.63 --70.6 --8.49
15.8 5.17 0.097 99.1 37.7 <0.01 192.0 4.51 --73.7 --10.52
0.83 0.077 0.228 68.7 26.2 17.5 416.0 25.2 --71.4 --9.20
1.61 0.039 0.199 68.6 58.8 10.9 149.8 15.1 72.4 10.68
1.17 0.006 0.381 38.3 37.8 18.3 264.4 21.4 --67.5 --9.61
9.94 4.30 0.074 153.4 5.0 <0.01 51.8 3.75 --72.2 -10.86
6.14 2.23 0.386 19.9 36.2 <0.01 79.3 2.20 --76.4 --10.99
10.5 4.68 0.057 183.9 4.7 <0.01 49.8 4.07 --77.2 --11.10
6.00 2.33 0.034 56.3 13.7 <0.01 13.6 1.87 ~72.6 --10.89
10.1 4.53 0.046 127.1 5.2 <0.01 45.0 3.83 --76.8 --10.98
1.67 0.124 0.719 52.3 41.2 23.2 280.3 21.0 P72.8 --9.81
1.80 0.036 0.775 24.5 40.9 25.1 274.6 21.9 --74.9 --10.04

potassium than waters in the boiling hot springs. At Hveravellir the mixed
waters are much lower in potassium than the boiling hot spring waters, but
in this field mixing occurs subsequent to boiling.
Sodium is the d o m i n a n t cation with the exception o f the cold waters and
those waters which contain a very high fraction of the cold water compo-
nent. Here calcium may contribute significantly to the total cation content.
Sodium concentrations bear no relation to chloride. In those instances where
mixing prevented boiling, the ratio of bicarbonate to total anions is much
higher in the warm waters and sodium, being the d o m i n a n t cation, matches
most of the anions in solution.
Special description of the water discharged from the drillhole at Nedridalur
in the Geysir field is illustrative for the general change caused by the leach-
ing process after mixing when the hot water component has not been de-
gassed by boiling prior to mixing. The water discharged from the hole con-
tains 46.4 ppm chloride (Table 1) and, according to the results of the
chloride-enthalpy mixing model in Fig. 17, the deep hot water contains 114
ppm chloride and has a temperature of 260°C. For the path of cooling and
mixing in Fig. 17 this indicates that the hot water component in the drill-
hole water is 0.37 and that the temperature after mixing is estimated at
73°C (assuming that sample 82-011 represents the cold water component).
The sodium content, 223 ppm, is similar to that of the boiling hot spring
waters in the area but, calculated from the dilution factor of 0.37 indicated
by the chloride, a sodium concentration of some 80 ppm, is expected. The
318

difference has been leached from the rock. Leaching of potassium is even
more extensive, as the drillhole water has twice as high a potassium content
as the boiling hot spring waters. Some potassium may, and is thought to have
been lost from solution in the upflow below the boiling springs (see later
section) which could reduce the calculated quantity of 33 ppm potassium
leached from the rock after mixing. For calcium and magnesium it is calculated
that the Nedridalur well water should contain 2.3 and 0.27 ppm respectively,
which is to be contrasted with the analyzed concentrations of 7.7 and 0.6
ppm. The difference in these two sets of figures is a measure of the a m o u n t
of calcium and magnesium leached after mixing. For these calculations it was
assumed that the hot water component contained 1 ppm calcium and 0.01
ppm magnesium.
In contrast with the major cations, lithium appears to be precipitated
from solution subsequent to mixing, as indicated by the overall convex
(downwards) relation between chloride and lithium concentrations in waters
from each field. This fact is important for geothermometry purposes as dis-
cussed in the following section.
Equilibrated waters in geothermal reservoirs, at least when their temper-
ature is above some 200°C, will contain substantial concentrations of carbon-
ate which is mostly as carbon dioxide (Arn6rsson et al., 1983b). Upon mix-
ing, and if boiling does not occur, a slightly acid solution is produced. This
is demonstrated in Fig. 12 for selected samples (82-013--82-117) from the
Geysir and Landmannalaugar fields. The composition of the hot water compo-
nent was derived from analysis of samples 82-005 and 82-093 (Table 3) and
the results for chloride concentrations and temperatures of reservoir waters
according to Fig. 17. The cold water component was taken to be represent-
ed by sample 82-011. As can be seen from the data points in Fig. 12, the
initial diluted waters containing unboiled hot water components, depart
strongly from equilibrium and protons must be lost from solution for attain-
ment of equilibrium. The actual mixed waters have approached the equilib-
rium state to a considerable degree.
As protons are lost from the mixed water during the change of the system
towards equilibrium, the carbon dioxide will be partly, or mostly, converted
into bicarbonate. The formation of the bicarbonate ion requires dissolution
of cations from the rock for maintainance of electric neutrality. The final pH
at equilibrium must satisfy the cation/proton equilibrium ratios in Fig. 12 at
the respective temperature and the equivalent sum of cations must in turn
satisfy electric neutrality where conversion of carbon dioxide into bicarbon-
ate is affected by pH changes.
Mixing does not lead to strong departure from equilibrium with respect to
cation/proton ratios when the hot water component has been degassed (by
boiling) before mixing, as demonstrated by sample 82-130 from Hveravellir
in Fig. 12. Consequently, leaching does not m o d i f y the water composition
nearly as much as in those instances when the hot water component has not
boiled.
 319

The Na/K ratios in cold water and in the warm mixed waters, especially
when containing undegassed hot water components, tend to be similar to or
lower than those in the boiling hot springs and similar to the ratio in
c o m m o n basaltic and acid volcanic rocks. This suggests that the Na/K ratios
of the mixed waters may be dominated by the leaching process and not by
the composition of the hot water component.
The Na/Li ratios in the warm and cold waters from the Geysir field and
Hveravellir tend to be similar to those of basaltic rocks and much higher than
in boiling hot spring waters. The difference cannot be explained by leaching
of sodium from the rock and precipitation of lithium must be assumed. The
situation is different for the Landmannalaugar waters. Broadly speaking, the
Na/Li ratios show a similar range for mixed warm waters and boiling hot
spring waters.

~8 ~6
¢o 82.130

_o
82-130
82-1/ ~2 013 2

2~ 4b ~ 8~ 2'o 4b 6b 8b
Temperature°C Temperature°C
+-r

L~ 1=6
~ 2 130

117 (~2 013

4

~ ~o ~o 2b 4'0 do 80
Temperature °C Temperature °C

Fig. 12. Cation/proton activity ratios in selected mixed waters from the Geysir, Hvera-
vellir and Landmannalaugar geothermal fields. The curves indicate relations in equilibrat-
ed geothermal waters according to Arn6rsson et al. (1983b). Open circles refer to mea-
sured discharge temperatures and analyzed compositions and filled circles to calculated
temperatures and calculated compositions of mixed waters (see text). These calculations
are based on the chloride content of the mixed water and chloride levels and temper-
atures in the hot water component as deduced from chloride-enthalpy mixing model
plots. Lines connect data points for individual samples and the figures refer to sample
numbers (see Tables 1 to 3).
320

TABLE 4

G e o t h e r m o m e t r y results
a,b a,b b
Sample tmeas tqt z tqt z tch a tNa K tNaKC a tNaLi
no.

Geysir field
79.004 72 236/273 227/255 209/227 201 224 267
79-005 95 210/234 205/223 184/197 142 185 221
79-006 98 204/226 200/217 179/190 137 182 220
82-005 90 239/278 230/258 211/230 178 206 277
82-006 94 227/260 220/244 200/217 162 190 264
82-007 98 221/251 214/236 194/210 143 182 244
82-008 70 230/263 222/247 203/220 152 191 264
82-009 78 231/265 223/248 204/221 153 191 259
82-010 78 --/215 --/208 --/181 168 178 284
82-011 5 81 c 52 c 175 c 43 76
82-012 17 87 57 154 23 86
82-013 68 --/160 --/132 276 237 72
82-014 46 T/168 --/141 211 193 79
82-015 24 --/111 82 153 43 156
82-016 48 --/160 --/132 159 162 210
82-017 97 211/236 206/225 1851198 125 165 243
82-018 39 --/173 --/146 257 210 150
82-019 30 --/125 96 210 193 103

Hve~vellir
82-124 96 255]304 244/283 227/250 193 200 301
82-125 93 253/301 243/280 225/248 193 199 300
82-126 97 235/268 226/253 207/226 145 165 246
82-127 97 169/179 146/152 120 144 206
82-128 92 249/293 239/273 221/242 197 199 295
82-129 35 95 65 135 59 183
82-130 40 --/124 96 117 74 186
82-131 65 1931211 190/205 169/179 178 178 264
82-132 89 217/245 211/232 191/205 172 182 259
82-133 20 --/103 74 114 55 204

Landmannalaugar field
79-053 94 172/184 173'184 150~157 124 168 220
79-054 82 --/203 --'199 --'172 232 214 333
82-093 94 171/183 172r183 149 '156 130 159 146
82-095 45 --~166 --'138 187 176 189
82-097 95 190/208 188'203 166'176 115 174 185
82-099 94 153'160 128'132 122 162 231
82-106 94 198/218 194'210 173'184 136 180 262
82-113 59 --f176 --'148 277 209 248
82-114 24 --~126 98 241 194 ?
82-115 58 --t168 --/140 279 211 216
82-116 10 89 59 276 72 305
82-117 45 --/171 --/143 285 212 209
82-118 93 189/206 187/201 165/174 132 173 343
82-119 96 197/217 194/210 172/183 177 202 357
 321

UNDERGROUND TEMPERATURE ESTIMATES

C h e m i c a l g e o t h e r m o m e try

Table 4 shows the calculated results for the silica, Na-K, Na-K-Ca and Na-
Li geothermometers. Results for quartz are presented for both the newly
presented solubility curves of Fournier and Potter (1982a, b) and Ragnars-
dSttir and Walther (1983). In the discussion that follows reference is always,
if not otherwise specified, made to the curve of Ragnarsd6ttir and Walther
(1983). This does not imply that the present author considers this curve
better for geothermometry purposes. The difference between the two
solubility curves is small. The curve of Fournier and Potter (1982a, b) indi-
cates higher solubility, thus yielding lower quartz geothermometry temper-
atures. Solubility at 200 and 205°C is 262 ppm silica. Corresponding figures
for 673 ppm silica are 300 and 322°C.
For convenience of presentation and calculation of quartz equilibrium
temperatures, new equations have been derived to describe the results of
Ragnarsd6ttir and Walther (1983) and Fournier and Potter (1982a) and the
form selected for the equations is that used b y the latter authors:
t(°C) = K1 + K 2 C + K 3 C ~ + K 4 C 3 + K s log C (1)
where C is silica (SiO2) in ppm. The constants for the respective functions
are presented in Table 5 and they show quartz solubility at the vapor pres-
sure of the solution and, after correction for steam loss, by adiabatic boil-
ing to 100°C.
In calculating the quartz and chalcedony temperatures total silica, i.e.
analyzed silica, was taken to represent undissociated silica (H4SiO °) in the
deep water. In many of the boiling hot spring waters the pH is very high so
a large portion of the dissolved silica is ionized, but the solubility of the
silica minerals refers to the activity of unionized silica in solution:
SiO2 ,solid + 2H20 = H4SiO ° (2)
The reason for taking analyzed silica to represent H4SiO ° is that boiling
in the upflow and the accompanying degassing is taken to be the cause of
the high pH and below the level of first boiling the pH is expected to be low
enough to prevent significant ionization of the dissolved silica. If quartz
equilibrium is assumed at depth, a relatively accurate determination of reser-
voir water pH can be obtained from the temperature dependence of the log
asa÷/aH+ ratio, as shown by Arn6rsson et al. (1983b). The calculation in-

a T h e first t w o c o l u m n s are based o n q u a r t z s o l u b i l i t y a c c o r d i n g to R a g n a r s d S t t i r and Wal-

t h e r ( 1 9 8 3 ) a n d F o u r n i e r and P o t t e r
b T h e figures a b o v e a n d b e l o w t h e
cooling, respectively.
CThis is surface w a t e r a n d is n o t
mineral.
( 1 9 8 2 a , b), respectively.
solidus refer to a d i a b a t i c s t e a m loss a n d c o n d u c t i v e
e x p e c t e d to have e q u i l i b r a t e d w i t h a n y g e o t h e r m a l
322

TABLE 5

Constants in eq. 1 describing quartz solubility

Function K~ K2 K3 K4 Ks

ia -42.198 0.28831 -3.6686X 10 -4 3.1665x 10 -7 77.034

2a 39.536 0.58127 -6.1713 X 10-* 3.7499x 10 -7 19.985
3b --53.500 0.11236 - 0.5559 X 10 -4 0.1772 ~ 10 -7 88.390
4b 121.627 0.10483 -0.4541 X 10 -4 0.0890 x 10 -7 117.810

aQuartz solubility along the three phase boundary quartz + water + steam. Function 1 is
that reported by Fournier and Potter (1982a). Function 2 was derived from equation 5
in Ragnarsd6ttir and Walther (1983).
bSilica concentrations in water initially in equilibrium with quartz at the vapor pressure
of the solution corrected for adiabatic steam loss to 100°C. Function 3 is based on the
data of Fournier and Potter (1982a) and function 4 on quartz solubility according to
Ragnarsd6ttir and Walther (1983).

volves s u b s t i t u t i o n of the a n a l y z e d s o d i u m c o n t e n t and t h e c o n s t a n t KNa

for the s o d i u m / p r o t o n ratio into t h e equilibrium describing silica i o n i z a t i o n

aH+aH,sio,- /an4sio0 = KH,SiO, (3)

and s i m u l t a n e o u s s o l u t i o n o f eqs. 2 and 3. T h e c o n s t a n t s in b o t h e q u a t i o n s
are t e m p e r a t u r e d e p e n d e n t and the s i m u l t a n e o u s s o l u t i o n o f t h e t w o equa-
tions involves an iteration process. I n s p e c t i o n s h o w s t h a t f o r t e m p e r a t u r e s in
excess o f 200°C ( c o r r e s p o n d i n g with a b o u t 300 p p m dissolved silica) an in-
significant f r a c t i o n o f the silica is ionized for s o d i u m c o n c e n t r a t i o n s as low
as 50 p p m .
A l t h o u g h c h a l c e d o n y equilibrium t e m p e r a t u r e s are r e p o r t e d in Table 4, it
is c o n s i d e r e d , in line with results f r o m drillhole d a t a ( A r n 6 r s s o n , 1975), t h a t
q u a r t z is the phase-controlling silica activity in the u n m i x e d g e o t h e r m a l
waters w h e n t e m p e r a t u r e s in excess o f 180°C are indicated. It seems, h o w -
ever, conceivable t h a t s o m e o f t h e m i x e d waters have equilibrated m e t a s t a b l y
with c h a l c e d o n y .
F o r boiling h o t spring waters t h e q u a r t z g e o t h e r m o m e t e r always yields
higher t e m p e r a t u r e s t h a n the Na-K and Na-K-Ca g e o t h e r m o m e t e r s , even f o r
t h e m o s t conservative case w h i c h assumes adiabatic steam loss and uses the
solubility curve o f F o u r n i e r and P o t t e r ( 1 9 8 2 a , b). T h e relationship b e t w e e n
chloride o n o n e h a n d and s o d i u m and p o t a s s i u m o n t h e o t h e r indicates t h a t
t h e lower Na-K t e m p e r a t u r e s , c o m p a r e d with q u a r t z , are d u e to loss o f
p o t a s s i u m f r o m s o l u t i o n in t h e u p f l o w , at least f o r the Geysir and Hveravellir
fields (Fig. 13). F o r these fields t h e r e is a p p r o x i m a t e l y a linear relation be-
t w e e n s o d i u m and chloride and e x t r a p o l a t i o n passes close to t h e p o i n t o f
origin (Fig. 13), suggesting t h a t the s o d i u m variations in the boiling spring
waters are due to d i l u t i o n a n d / o r steam loss. P o t a s s i u m c o n c e n t r a t i o n s are
lower t h a n w o u l d be e x p e c t e d if o n l y the processes o f d i l u t i o n / b o i l i n g were
 323

operative. Extrapolation of the data points for potassium and chloride (Fig.
13) intersects the chloride axis (zero potassium concentrations) at rather
high chloride concentrations. Potassium appears thus to have been lost from
solution, perhaps by precipitation of K-feldspar, but absorption onto clays
is also possible.

GEYSIR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD

E E
E . . . . . E

:;:,
z z 40C • 20
30C ]0 15C 15

3O(]

20C • n 10C
t
20C • 10

10(] 10 50
;1
10C

40 80 120 20 40 60 200 4.00 600

CI ppm CL p p m CI ppm

Fig. 13. Plot of chloride versus sodium (dots) and potassium (squares) for waters from
boiling hot springs at Hveravellir and in the Geysir and Landmannalaugar fields.

The Na-K-Ca geothermometer usually gives slightly higher temperatures

than the Na-K geothermometer for the boiling hot spring waters. Loss of
potassium from solution will, of course, lower the Na-K-Ca temperatures,
but this tends to be counteracted when boiling occurs by loss of calcium
through calcite precipitation. The different results obtained by these two
cation geothermometers are not necessarily due to the net effect of the two
counteracting processes, loss of potassium and loss of calcium. Systematic
deviation relating to their calibration may just as well be the cause.
The CO2 geothermometer of ArnSrsson et al. (1983a) always gives higher
temperatures than the Na-K and Na-K-Ca geothermometers, whereas the
silica and the Na-Li geothermometers yield similar or higher temperatures
(see Tables 4 and 6). The CO2 geothermometry results are not entirely com-
parable with those of the solute geothermometers as they are not based on
the same fluid discharge. However, for the assumption on which the geo-
thermometry is based, the CO2 and other geothermometers should yield
comparable results for close-by hot springs and fumaroles.
The results of the gas geothermometer of D'Amore and Panichi (1980)
are given in Table 6. The results compare rather well with the CO2 geo-
thermometer for some samples from the Landmannalaugar field but for the
Geysir field and Hveravellir the gas geothermometer of D'Amore and Panichi
(1980) yields considerably lower temperatures. This can be attributed to
low H2S and H2 in the steam from these fields, the reason probably being
that oxidation occurs in the upflow. This interpretation is in line with that
of the 51sO content of sulphate discussed at the end of the previous section.
324

TABLE 6

Gas geothermometry results (°C)

Sample no. too ~ t~ Ad

Geysirfield
82-020 267 _b 82-007
82-021 270 _6 82-005
82-034 270 174 82-005
82-035 276 _b 82-005
82-134 259 185 82-005
82-135 261 185 79-004
Hveravellir
82-136 248 221
82-137 239 175 82-124

Landmanna~ugar field
82-094 243 _c 82-093
82-096 262 _c
82-098 245 232 82-106
82-100 e 269 353
82-102 279 329
82-103 245 340
82-104 248 326
82-105 268 334
82-107 242 179 82-119
82-108 249 391
82-109 263 318
82-110 255 371
82-111 263 395
82~120 e 307 372
82-121 e 291 410
aBased on the gas geothermometer of D'Amore and Panichi (1980).
bHydrogen or methane were not detected in the sample.
cSamples were air contaminated.
dThis column gives sample no. for nearby springs.
eAverage of the following duplicate samples: 100/101, 120/123, and 121/122.

The relation between the chemical geothermometry results differs for the
warm springs (mixed waters) from that of boiling springs. The Na-K temper-
a t u r e s a r e e q u a l t o o r h i g h e r t h a n t h e q u a r t z e q u i l i b r i u m t e m p e r a t u r e s in t h e
warm waters and they are also about equal to or higher than the Na-K tem-
peratures of the boiling hot spring waters (Fig. 14). In view of the inter-
p r e t a t i o n in t h e p r e v i o u s s e c t i o n t h a t t h e m a j o r c a t i o n c o n c e n t r a t i o n s in t h e
w a r m , m i x e d w a t e r s a r e g o v e r n e d b y l e a c h i n g a f t e r m i x i n g , it is c o n c l u d e d
t h a t t h e N a - K t e m p e r a t u r e s , as w e l l as t h e N a - K - C a t e m p e r a t u r e s , a r e u n -
r e a l i s t i c f o r t h e w a r m w a t e r s as t h e a s s u m p t i o n o f m i n e r a l / s o l u t e e q u i -
librium with respect to sodium and potassium does not seem to be valid. The
 325

Na-K-Ca g e o t h e r m o m e t e r w o u l d be e x p e c t e d to yield m o r e reliable esti-

m a t e s , as i n d e e d i n d i c a t e d f o r s o m e w a r m w a t e r s (Table 4). H o w e v e r , o t h e r
s a m p l e s yield high and, it is believed, d u b i o u s t e m p e r a t u r e estimates. Like
t h e Na-K-Ca g e o t h e r m o m e t e r , the Na-Li g e o t h e r m o m e t e r o f Fouillac and
Michard ( 1 9 8 1 ) t e n d s to give less misleading results for w a t e r s o f m i x e d
origin t h a n t h e N a - K g e o t h e r m o m e t e r , the r e a s o n p r o b a b l y being t h a t the
s o d i u m / l i t h i u m ratios in basaltic a n d acidic r o c k s are c o m p a r a b l e with t h o s e
o f e q u i l i b r a t e d w a r m waters.

I/I/
[] O[~5 //
/
0 s/"
[] //
Z [] /
/
O O //
200 / •
[] /
0 ,,"~1 •

o o ,,'g •e A

,]I",
100 J SI
~J
~J
~J
/
/"
/t
/t
/
/
/"
/•
eo

;do 26o
tqtz °C
Fig. 14. Relation between quartz equilibrium and Na-K temperatures. The data used on
quartz solubility are from Ragnarsd6ttir and Walther (1983), assuming total pressure to
be the vapour pressure of the solution and adiabatic steam loss to 100°C. The function
given by Arndrsson et al. (1983a) was used for the Na-K geothermometer. Open symbols
indicate warm, mixed waters but filled symbols boiling hot springs discharges. Circles,
triangles and squares represent data from Geysir, Hveravellir and Landmannalaugar,
respectively.

A n e w silica-carbonate mixing m o d e l

A r n 6 r s s o n et al. ( 1 9 8 3 b ) f o u n d t h a t t h e c o n c e n t r a t i o n s o f c a r b o n d i o x i d e
in w a t e r s in g e o t h e r m a l reservoirs w e r e o n l y d e p e n d e n t o n t h e t e m p e r a t u r e
o f t h e s e waters. T h e y c o n c l u d e d t h a t this was t h e result o f overall s o l u t e /
m i n e r a l e q u i l i b r a t i o n in t h e s e reservoirs. At t e m p e r a t u r e s a b o v e a b o u t
200°C, m o s t o f t h e dissolved t o t a l c a r b o n a t e is in t h e f o r m o f c a r b o n d i o x i d e ,
so it is a s a t i s f a c t o r y a p p r o x i m a t i o n t o t a k e a n a l y z e d c a r b o n a t e t o r e p r e s e n t
c a r b o n d i o x i d e . It is well k n o w n t h a t silica levels in h i g h - t e m p e r a t u r e w a t e r s
326

are determined by quartz solubility. It follows, therefore, that it is a satis-

factory approximation to assume a fixed relation between silica and total
carbonate in high-temperature geothermal reservoir waters. Boiling of such
waters will lead to drastic reduction in its carbonate content but mixing
without boiling will, on the other hand, produce waters with high carbon-
ate/silica ratios relative to the equilibrated waters, due to the curvature of
the silica/carbonate relationship {Fig. 15).

GEYSIR FIELD LANDMANNALAUGAR FIELD

500 500

E 400 E 400
f~
o= O.

~5 3OO
V 300

oolI.
200 200
/
e:
e,'

100 - i

400 800 12'00 16'00 40'0 8oo 1 oo 16'oo

Total carbonate, ppm Total carbonate, ppm

Fig. 15. A plot of silica versus total carbonate (silica-carbonate mixing model) for cold
and thermal waters from the Geysir and Landmannalaugar fields. The curves represent
silica/carbon-dioxide relationship in equilibrated geothermal waters. The temperature
dependence of silica was assumed to be controlled by quartz solubility according to the
data of Ragnarsdbttir and Walther (1983). The temperature dependence of carbon
dioxide was derived from the respective function in table 5 of Arnbrsson et al. (1983b).
Data points plotting above the equilibrium curve represent degassed waters, whereas data
points which plot below correspond with mixed waters. The broken lines indicate evaluat-
ed silica-carbonate relationship in mixed, undegassed waters and their intersection with
the equilibrium curve is a measure of the temperature of the hot water component.

The silica-carbonate diagram in Fig. 15 may be used in two ways to aid

geothermometry interpretation. Firstly, it serves to distinguish boiled waters
from conductively cooled waters and mixed waters which contain an un-
degassed (and therefore unboiled) hot water component, assuming that the
boiling occurs between the points of last equilibrium with quartz and sam-
pling. Secondly, if there are sufficient data on warm waters containing an
unboiled water component, the diagram may be used to evaluate the tem-
perature of the hot water component. The diagram is useful as a supple-
 327

m e n t to interpretation of the silica-enthalpy warm spring mixing model

because a choice often needs to be made as to whether it should be as-
sumed that boiling had occurred before mixing or not. Little steam forma-
tion suffices to deplete the original h o t water almost quantitatively in total
carbonate.
Relationship between chloride and total carbonate might also be used to
aid distinguishing boiled and non-boiled hot spring waters, as was demon-
strated by Fournier (1981) for the Geyser Hill and Black Sand waters of the
Upper Basin, Yellowstone National Park.
Estimation of underground temperatures by the silica-carbonate mixing
model involves extrapolation of a line through the data points for mixed and
undegassed warm waters and determination of the point of intersection with
the silica-carbonate curve for equilibrated waters. From the silica concentra-
tion corresponding with this point, the temperature may be derived from the
quartz geothermometer.
I r I

311°C
. o~

E
o..
f (I)
o.

0
A
f 262 °C

Ul

"D

"0
o

"o
i-
• °'///s
I A X"
2o0 ..... /
~ 0~t....
• ~,"

2-013 ~)~v/
D ^~,~ / ( I )

I I I I I
400 800 1200
Enthalpy, J/g
Fig. 16. A p l o t of undissociated silica versus enthalpy of spring discharges. The dots,
triangles and squares designate data from the Geysir, Hveravellir and Landmannalaugar
fields respectively. The undissociated silica c o n c e n t r a t i o n s were calculated f r o m total
silica, the measured pH reported in Tables 1 to 3 and the values for KI-I SiO 4 given by
Arn6rsson et al. (1982). Quartz saturation curves are based on: (1) Fourn]er and Potter
(1982a); and (2) Ragnarsd6ttir and Walther (1983). The broken line represents silica-
enthalpy relationship for cold water and the water from the Nedridalur well in t h e Geysir
field (these waters have a relatively low pH so undissociated silica equals total silica) and
the intersection (open squares) with the quartz saturation curves represents the enthalpy
of the hot water c o m p o n e n t .
328

The curve describing the silica-carbonate relationship can be drawn from

the temperature functions for quartz solubility in Table 5 and the CO2-
temperature function in table 5 of Arn6rsson et al. (1983b).
In the Geysir and Landmannalaugar geothermal fields the silica-carbon-
ate relation indicates that the hot water component in the mixed waters has
not boiled (Fig. 16), whereas the warm Hveravellir waters are a mixture of
cold water and degassed hot water. In the Geysir field most of the cold and
warm waters show a linear relation between silica and carbonate and an
extrapolation of a line through the data points indicates that the hot water
component is at some 260°C {Fig. 15). Two waters show relatively low
carbonate (samples 82-010 and 82-018). As deduced from the temperature
of the first water, near surface degassing may be responsible, and for the
second sample the hot water component may be, at least partly, boiled be-
cause this sample is located relatively close to the main area of boiling hot
springs. In the Landmannalaugar field the silica-carbonate relationship in-
dicates a temperature of 231°C for the hot water component.
A silica-carbonate plot is not presented for Hveravellir as all waters issued
at the surface in this field have been degassed.

The silica-enthalpy warm spring mixing model

Silica concentrations versus discharge enthalpy show the same general

pattern for waters from all three geothermal fields (Fig. 16). Cold and tepid
waters are undersaturated with amorphous silica. Warm waters tend to be
saturated or slightly undersaturated. Boiling spring waters at Hveravellir and
in the Geysir field range from significant supersaturation to undersaturation,
whereas waters in boiling springs in the Landmannalaugar field are always
considerably undersaturated. When plotting the data for the boiling hot
spring waters, which generally have a pH of more than 9, correction was
made for the fraction in solution that is ionized.
It may be that the solubility of an amorphous aluminium silicate sets an
upper limit to silica levels in the springs at Landmannalaugar. Precipitates of
this kind are known from geothermal waters in Iceland that are conducted
through asbestos pipes in a few district-heating systems (ThSrhallsson et al.,
1975). The Landmannalaugar waters issue either through alluvial gravel or
altered rhyolite, so the water has good access to the aluminium in the rock.
As all the cold waters are amorphous silica undersaturated and waters in
high-temperature geothermal reservoirs axe k n o w n to equilibrate with quartz,
it follows that mixing alone never produces amorphous silica-saturated
water. For attainment of such saturation, cooling by boiling or conduction
is necessary, or leaching of silica from the rock subsequent to mixing. Con-
ductive cooling beyond amorphous silica saturation will lead to precipitation
of this phase, which in turn will give low silica relative to chloride in the
mixed water. Such is the case for samples 82-010 and 82-018 from the
Geysir field, samples 79-054 and 82-095 from Landmannalaugar and sample
82-131 from HveraveUir.
 329

In selecting data for estimation of the enthalpy of the hot c o m p o n e n t in

mixed waters by the silica-enthalpy model it is useful to study silica-chloride
relations (Fig. 5) and the state of amorphous silica saturation at the dis-
charge temperature. For undegassed waters showing low silica relative to
chloride, as well as amorphous silica saturation, it can be inferred that con-
ductive cooling has occurred and the silica-enthalpy plot is liable to yield
high estimates for the temperature of the hot water component.
The water issuing from the Nedridalur well in the Geysir field may not
have cooled significantly by conduction after mixing, as deduced from the
relatively high discharge rate (5 dm 3 s -1) and the depth level of the producing
aquifer (390 m), although cooling during ascent amounts to 5°C (Fig. 2).
Taking sample 82-011 to represent the cold water component, a silica
enthalpy plot intersects the quartz saturation curves of Fournier and Potter
(1982a) and Ragnarsd6ttir and Walther (1983) at 1145 and 1408 J g-',
respectively. These values correspond with a temperature of 262 ° and 311°C.
If the temperature (73°C) in the well at the point of inflow had been select-
ed, instead of the discharge temperature, to derive the enthalpy of the hot
water component, the corresponding temperatures are 248 and 288°C. This
shows how sensitive the temperature estimate is to the selection of the
enthalpy value for the mixed water, the reason being the large extrapolation
of the line through the data points onto the quartz solubility curve.
From the chloride-enthalpy diagram in Fig. 17 it is deduced that water at
260°C in the Geysir field will contain 114 ppm C1. Using these values for
temperature and chloride to represent the hot water component, as well as
the indicated path of cooling and mixing in Fig. 17 and sample 82-011, to
represent the cold water component, the initial temperature and the degree
of conductive cooling of warm waters in the Geysir field has been evaluated
from their chloride content. It is found that only samples 82-010, 82-018
and 82-016 have cooled significantly after mixing, or by 65, 66 and 20°C,
respectively. Other warm spring waters are calculated to have cooled after
mixing by less than 10°C.
If water at a temperature of about 260°C or higher mixes to give water
with a temperature in the range of 50°C, one would expect the mixing to
occur at a depth of less than a few hundreds of metres, as the temperature
gradient in the region of the Geysir field is probably 100--150°C km -1 (P~il-
mason et al., 1979). The steam pressure exerted by water at 262--311°C (the
temperature estimates from the silica-enthalpy plot Fig. 16) is 48--100 bar
abs., so boiling of this water, if it exists, would be expected to begin at some
600--1200 m depth. The only real possibility for mixing would be that it
either occurs in a series of steps or that the cold water encountered two-
phase flow where the total fluid discharge enthalpy was 1145--1408 J g-~
and that the steam was condensed in the process.
The assumption generally made in using the silica-enthalpy mixing model
may not always be valid, namely that the temperature and the silica content
of the hot water c o m p o n e n t corresponds with quartz saturation. Cooling of
330
GEYSIR FIELD HVERAVELLIR LANDMANNALAUGAR FIELD
1
352'
/
1600 160( 160(

• 311

287
~_120C =
j: ( ") ~262

/
8®l • ! 80C
.¢'
400 i ' //
, /,
/~
! t 40C
, ~! "L(9 0 5 4

c k
40 80 120 160 ~oo 20 40 60 ' - -

Clppm CI, p p m CI p p m

Fig. 17. Chloride-enthalpy mixing model diagram. For boiling hot spring waters (filled
symbols) the enthatpy was derived from the silica content, assuming equilibrium with
quartz and adiabatic steam loss. For warm springs, represented by open symbols, the
enthalpy was obtained from measured discharge temperatures. Large triangles represent
enthalpy derived from the silica-enthalpy warm spring mixing model using the curves of
Fournier and Potter (1982a) and Ragnarsd6ttir and Walther (1983), respectively (see
Fig. 16 ). Half-filled symbols represent the boiling springs with the highest chloride in each
field at the discharge temperature and at the quartz equilibrium temperature, assuming
conductive heat loss. Broken, dotted and slim solid lines indicate mixing, adiabatic boil-
ing and conductive cooling, respectively. The thick solid line shows the most likely evolu-
tionary path for the deep hot water. The large circles represent the estimated chloride and
enthalpy (corresponding temperature is reported) for the deep hot water in each field.

the water by conduction prior to mixing, without sufficient silica precipita-

tion to restore equilibrium, may well have occurred as indicated schematical-
ly by the broken line on the chloride-enthalpy diagram in Fig. 17. From a
hydrological point of view this mixing process is more acceptable than the
one described above which involved mixing of cold water with rising hot
water and steam.
The silica-enthalpy mixing model cannot be applied with confidence to
the data from HveraveUir and the Landmannalaugar field. For Hveravellir
the only waters which are undersaturated with amorphous silica are the tepid
ones and sample 82-127. The chloride-silica relationship (Fig. 9) indicates
precipitation of silica from solution prior to, or subsequent to, mixing.
At Landmannalaugar all the warm waters are close to amorphous silica
saturation. For samples 82-113, 82-115 and 82-117 this saturation has evi-
dently been attained by dissolution of silica from the rock, as indicated by
the chloride-silica relationship in Fig. 9. For sample 79-054 conductive
cooling may be important. The silica-carbonate relationship in Fig. 15 shows
that saturation with amorphous silica cannot have resulted from mixing after
boiling (which means degassing) of the hot water c o m p o n e n t for any of the
warm waters.
 331

The chloride-enthalpy mixing model

This mixing model takes into account both mixing and boiling processes.
Its application involves basically relating analyzed chloride levels to water
enthalpy which can be derived in a number of ways, such as from measured
discharge temperatures, geothermometry temperatures, and silica-enthalpy
mixing model temperatures.
The silica-enthalpy mixing model indicated that the temperatures of the
hot water c o m p o n e n t in the mixed warm waters from the Geysir field was as
high as 262°C if the quartz solubility curve of Fournier and Potter (1982b)
was used and 311°C if the curve of RagnarsdSttir and Walther (1983) was
used. By conventional use of the chloride-enthalpy diagram these temper-
ature values imply, if there was a unique hot water phase with respect to
temperature and chloride, that the unmixed hot water was as much as 352°C
(Fig. 17) and that the hot water c o m p o n e n t in the mixed water had boiled
to 311°C before mixing, whereas the boiling hot spring waters had cooled by
mixing to some 260°C and then boiled. This model is not compatible with
the present interpretation of the silica-carbonate relations from which it was
concluded that the hot water c o m p o n e n t in the mixed water had not been
degassed and had, therefore, not boiled. The discrepancy is thought to result
from an erroneous conclusion of the silica-enthalpy mixing model of a hot
water c o m p o n e n t at 311°C. An explanation which is compatible with the
combined silica-chloride-carbonate-enthalpy relations and anticipated
maximum depth of mixing is that the equilibrated hot water c o m p o n e n t has
an enthalpy and chloride indicated by the large circles in Fig. 17, and that
conductive cooling of this water followed by mixing produced the warm
waters. Boiling, but also some conductive cooling and mixing, caused changes
in the composition of the water in the upflow below the boiling hot springs.
It seems logical that conductive cooling is more extensive if it is followed
by mixing as one factor -- low permeability -- increases the probability for
and the magnitude of both processes. Where permeability is highest the
chances for hot water to reach the surface are at maximum and mixing at
minimum.
For Hveravellir the chloride-enthalpy mixing model yields underground
temperatures similar to those of the quartz geothermometer (Fig. 17), indi-
cating that the boiling hot spring waters, which are highest in chloride, have
n o t mixed with surficial water, and that significant silica had not precip-
itated during cooling in the upflow.
In the Landmannalaugar field chloride-enthalpy relations indicate substan-
tial loss of silica from solution for the waters highest in chloride. Conse-
quently, this mixing model yields higher underground temperatures than the
quartz geothermometer and also higher than the Na-K and Na-K-Ca geo-
thermometers. Comparison of Fig. 17 with the results in Tables 4 and 6
shows that the Na-Li and CO2 geothermometry results spread around the
temperature values indicated by the chloride-enthalpy mixing model, both
for Hveravellir and the Landmannalaugar field.
332

SUMMARY AND CONCLUSIONS

Interpretation of chemical analyses of hot spring waters and fumaroles

with respect to predicting underground temperatures should integrate as
m a n y parameters as possible into a single model rather than considering in-
dividual geothermometers and mixing models in isolation. In the present
study use was made of almost all the chemical components for which results
are presented in Tables 1--3.
Relation of chloride concentrations to boron and 5180 appears to be
particularly useful to evaluate mixing processes. If mixing has occurred, a
linear relation between these parameters should be observed. Linear, or near-
linear, relations between chloride and silica and sulphate may also be useful
to strengthen evidence for mixing.
It was found unreliable to apply the cation geothermometers, except for
Na-Li, to mixed waters. The reason is that leaching after mixing tends to
dominate the relative cation concentrations. Na-K ratios become similar to
those in the associated rocks. Mixing involving hot water relatively rich in
carbon dioxide produces slightly acid solutions, but the carbon dioxide con-
tent of the hot water is determined by its temperature, if boiling has not
occurred. The leaching process occurs mostly in response to increasing pH
of the mixed water and conversion of carbon dioxide to bicarbonate. The
effect of the leaching process on the validity of the Na-K and the Na-K-Ca
geothermometers will, it is believed, depend on water salinity or, to be more
precise, on the ratio of total cations to carbon dioxide. When carbon dioxide
concentrations are low in relation to total cation concentrations, the leach-
ing process will not greatly affect the relative amounts of cations in solution.
The Na-K and the Na-K-Ca geothermometers give lower results for boiling
hot spring waters than do the quartz and the Na-Li geothermometers and the
mixing models. This results from loss of potassium from solution during
cooling in the upflow. The Na-K-Ca temperatures tend to be somewhat
higher than the Na-K temperatures, probably because the effect of potassium
loss is to some extent counter-balanced by loss of calcium from solution
through calcite precipitation.
Usually some silica is precipitated from solution as a consequence of mix-
ing, but occasionally it may be leached from the rock to an extent dictated
by amorphous silica solubility.
The Na-Li and CO2-gas geothermometry temperatures are similar to those
obtained from chloride-enthalpy mixing models, at least if enthalpy values
for warm spring waters and boiling hot spring waters are based on discharge
temperatures and quartz geothermometry temperatures respectively. The
quartz geothermometer also yields similar results for the Geysir and Hvera-
vellir fields, but lower temperatures for the Landmannalaugar, the reason
being precipitation in the upflow.
The new carbonate-silica mixing model proposed here is useful to esti-
mate underground temperatures if the mixing process prevents boiling and,
 333

therefore, degassing. For the Geysir field this mixing model yields results
comparable to those of the chloride-enthalpy mixing model and the Na-Li
and CO2 gas geothermometers, but for the Landmannalaugar field these geo-
thermometers tend to yield somewhat higher values.

ACKNOWLEDGEMENTS

The writer wishes to acknowledge Dr. Valgardur Stef~nsson of the Nation-

al Energy Authority, Reykjavik, for making available the downhole temper-
ature data for the well at Nedridalur. Special thanks are due to Halld6r .~r-
mansson and Thorsteinn Thorsteinsson for providing facilities and assistance
in carrying out the lithium analyses, and to my daughter, Harpa, for making
all the drawings. Dr. Sigffls Johnson is also thanked especially for arranging
the oxygen isotope analyses at the Geophysical Isotope Laboratorium in
Copenhagen.
The hydrogen isotope analyses were carried out at the International
Atomic Energy Agency in Vienna under the supervision of Dr. Bryan Payne.
Most of the analyses of waters from the Geysir geothermal field were carried
out by Mr. Oliver Jordan as a part of his work at the United Nations Uni-
versity Geothermal Programme operated by the National Energy Authority.
This study has been supported by the Icelandic Science Foundation.

REFERENCES

.~rnason, B., 1976. Groundwater Systems in Iceland Traced by Deuterium. Publ. Societas
Scientiarum Islandica, Reykjav~, 236 pp.
,~rnason, B., 1977. Hydrothermal systems in Iceland traced by deuterium. Geothermics,
5: 125--152.
Arn6rsson, S., 1970a. Underground temperatures in hydrothermal areas in Iceland as de-
duced from the silica content of the thermal water. Geothermics, 2: 536--541.
Arn6rsson, S., 1970b. Geochemical studies of thermal waters in the southern lowlands of
Iceland. Geothermics, 2: 547--552.
Arn6rsson, S., 1975. Application of the silica geothermometer in low-temperature hydro-
thermal areas in Iceland. Am. J. Sci., 275: 763--784.
Arn6rsson, S., 1983. Chemical equilibria in Icelandic geothermal systems -- implications
for chemical geothermometry investigations. Geothermics, 12: 119--128.
Arn6rsson, S., Sigurdsson, S. and 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.
Arn6rsson, S., Gunnlaugsson, E. and Svavarsson, H., 1983a. The chemistry of geothermal
waters in Iceland. III. Chemical geothermometry in geothermal investigations. Geo-
chim. Cosmochim. Acta, 47: 567--577.
Arn6rsson, S., Gunnlaugsson, E. and Svavarsson, H., 1983b. The chemistry of geothermal
waters in Iceland. II. Mineral equilibria and independent variables controlling water
compositions. Geochim. Cosmochim. Acta, 47: 547--566.
Cusicanqui, H., Mahon, W.A.J. and Ellis, A.J., 1975. The geochemistry of the E1 Tatio
geothermal field, northern Chile. Proceedings of the Second United Nations Sympo-
sium on the Development and Use of Geothermal Resources, San Francisco 20--29
May, 1975, 1: 703--711.
334

D'Amore, F. and Panichi, C., 1980. Evaluation of deep temperatures in hydrothermal

systems by a new gas geothermometer. Geochim. Cosmochim. Acta, 44: 549--556.
Einarsson, T., 1937. t~ber die neuen Eruptionen des Geysir in Haukadatur. Publ. Societas
Scientiarum Islandica, Ser. 1, 2: 149---166.
Einarsson, T., 1949. The eruptions of Geysir in Haukadalur. N~itt6rufraedingurinn, 19:
20--26 (in Icelandic).
Ellis, A.J., 1970. Quantitative interpretation of chemical characteristics of hydrothermal
systems. Geothermics, 2: 516--527.
Ellis, A.J., 1979. Chemical geothermometry in geothermal systems. Chem. Geol., 25:
219--226.
Fouillac, C. and Michard, G., 1981. Sodium]lithium ratio in water applied to geother-
mometry of geothermal reservoirs. Geothermics, 10: 55--70.
Fournier, R.O., 1973. Silica in thermal waters: laboratory and field investigations. Pro L
ceedings International Symposium on Hydrochemistry and Biochemistry, Japan, pp.
122--139.
Fournier, R.O., 1977. Chemical geothermometers and mixing models for geothermal sys-
tems. Geothermics, 5: 41--50.
Fournier, R.O., 1979. Geochemical and hydrologic considerations and the use of enthalpy-
chloride diagrams in the prediction of underground conditions in hot-spring systems.
J. Volcanol. Geotherm. Res., 5: 1--16.
Fournier, R.O., 1981. Application of water chemistry to geothermal exploration and
reservoir engineering. In: L. Rybach and L.J.P. Muffler (Editors), Geothermal Sys-
tems: Principles and Case Histories. Wiley, New York, N.Y., pp. 109--143.
Fournier, R.O. and Potter, R.W. II, 1982a. A revised and expanded quartz geothermom-
eter. Geotherm. Resour. Council Bull., Nov., 1982: 3--9.
Fournier, R.O. and Potter, R.W. II., 1982b. An equation correlating the solubility of
quartz in water from 25 ° to 900°C at pressures up to 10,000 bars. Geochim. Cosmo-
chim. Acta, 46: 1969--1974.
Fournier, R.O. and Rowe, J.J., 1966. Estimation of underground temperatures from
the silica content of water from hot springs and wet-steam wells. Am. J. Sci., 264:
685---697.
Fournier, R.O. and Truesdell, A.H., 1973. An empirical Na-K-Ca geothermometer for
natural waters. Geochim. Cosmochim. Acta, 37: 1255--1275.
Fournier, R.O., White, D.E. and Truesdell, A.H., 1974. Geochemical indicators of sub-
surface temperature, 1. Basic assumptions. J. Res. U.S. Geol. Surv., 2: 259--262.
Fournier, R.O., White, D.E. and Truesdell, A.H., 1975. Convective heat flow in Yellow-
stone National Park. Proceedings Second United Nations Symposium on the Develop-
ment and Use of Geothermal Resources, San Francisco, 1: 731--739.
Fournier, R.O., Sorey, M.L,, Mariner, R.H. and Truesdell, A.H., 1979. Geochemical
prediction of aquifer temperatures in the geothermal system at Long Valley, California.
J. Volcanol. Geotherm. Res., 5: 17--34.
Mahon, W.A.J., 1975. Review of hydrogeochemistry of geothermal systems--prospecting,
development and use. Proceedings Second United Nations Symposium on the Develop-
ment and Use of Geothermal Resources, San Francisco, 1: 775--783.
Mariner, R.H. and Willey, L.M., 1976. Geochemistry of thermal waters in Long Valley,
Mono Country, California. J. Geophys. Res., 81: 792--800.
P~lmason, G. and Saemundsson, K., 1974. Iceland in relation to the Mid-Atlantic Ridge.
Annu. Rev. Earth Planet. Sci., 2: 25--50.
P~lmason, G., ArnSrsson, S., Fridleifsson, I.B., Kristmannsd6ttir, H., Saemundsson, K.,
Stef~insson, V., Steingrfmsson, B., T6masson, J. and Kristj~nsson, L., 1979. The Ice-
land crust: evidence from drillhole data on structure and processes. Ewing Series, AGU
(1979), pp. 43--65.
Ragnarsd6ttir, K.V. and Walther, J.W., 1983. Pressure sensitive "silica geothermometer"
determined from quartz solubility experiments at 250°C. Geochim. Cosmochim. Acta,
47 : 941--946.
 335

Saemundsson, K., 1972. On the geological features of the Torfajbkull region, N~tttiru-
fraedingurinn, 42: 81--99.
Sigurgeirsson, Th., 1949. Temperature measurements in Geysir. N~ttfirufraedingurinn,
1 9 : 2 7 - - 3 3 (in Icelandic).
Th6rhallsson, S., Ragnars, K., Arn6rsson, S. and Kristmannsd6ttir, H., 1975. Rapid
scaling of silica in two district heating systems. Proceedings Second United Nations
Symposium on the Development and Use of Geothermal Resources, San Francisco,
2: 1445--1449.
Thoroddsen, Th., 1925. Die Geschichte der isl~/ndischen Vulkane. Kgl. Danske Vidensk.
Selsk. Skr., Ser. 8, 9 : 4 5 8 pp.
Truesdell, A.H., 1975. Summary of section III -- geochemical techniques in exploration.
Proceedings Second United Nations Symposium on the Development and Use of
Geothermal Resources, San Francisco, 1: liii--lxiii.
Truesdell, A.H. and Fournier, R.O., 1975. Calculation of deep temperatures in geo~
thermal systems from the chemistry of boiling spring waters of mixed origin. Pro-
ceedings Second United Nations Symposium on the Development and Use of Geo-
thermal Resources, San Francisco, 1 : 837--844.
Truesdell, A.H. and Fournier, R.O., 1977. Procedure for estimating the temperature of
hot water component in a mixed water using a plot of dissolved silica vs enthalpy. J.
Res., U.S. Geol. Surv., 5: 49--52.
Walker, G.P.L., 1963. The Breiddalur central volcano, eastern Iceland. Q.J. Geol. Soc.
London, 119: 29--63.
Walker, G.P.L., 1974. Eruptive mechanisms in Iceland. In: Geodynamics of Iceland and
the North-Atlantic Area. Reidel, Dordrecht, pp. 189--202.
White, D.E., 1970. Geochemistry applied to the discovery, evaluation and exploitation of
geothermal energy resources. Geothermics, 1: 58--80.