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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.
INTRODUCTION
ANALYTICAL
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.
LEGEND:
ACID VOLCANICS
BASALTIC LAVASAND HYALOCLASTITES
STEEPLY DIPPINGTHOLEIITES
ALLUVIUM
• WATERSAMPLE WITH SAMPLE NO,
o FUMAROLESAMPLE
N
0 500m T
I
I
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
Hveravellir
,
*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.
""",, ,
9 ~: 7 "-.,. ,.
• •
"". .
• • ""-.
• %,
• I'I L~ 6
0 82 008
o • • •82 009
-10 • • 79 0 0 6 1 5
• • 82 0071
41
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.
////'
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.
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.
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
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.
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.
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.
o.
ffl tN
'¢ 00
8G 8( 40 •
4C 4c 2E
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
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
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
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
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)
REDISTRIBUTION OF CATIONS
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
~ ~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
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-
TABLE 5
Function K~ K2 K3 K4 Ks
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).
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.
:;:,
z z 40C • 20
30C ]0 15C 15
3O(]
20C • n 10C
t
20C • 10
10(] 10 50
;1
10C
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.
TABLE 6
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
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
500 500
E 400 E 400
f~
o= O.
~5 3OO
V 300
oolI.
200 200
/
e:
e,'
100 - i
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.
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
• 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.
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
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
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