Journal o f Volcanology and Geothermal Research, 15 (1983) 167--186 167

Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

THERMODYNAMIC PARAMETERS AND EXPERIMENTAL DATA FOR

THE Na-K-Ca GEOTHERMOMETER*

TIMOTHY BENJAMIN, ROBERT CHARLES, and ROSEMARY VIDALE

Los Alamos National Laboratory, Los Alamos, NM 8 7545 (U.S.A.)
(Received May 4, 1982)

ABSTRACT

Benjamin, T., Charles, R. and Vidale, R., 1983. Thermodynamic parameters and experi-
mental data for the Na-K-Ca geothermometer. In: G. Heiken and F. Goff (Editors),
Geothermal Energy from Hot Dry Rock. J. Volcanol. Geotherm. Res., 15: 167--186.

The standard literature values for the thermodynamic parameters of a quartz--two-

feldspar reaction are not consistent with the constants of Fournier and Truesdell. The
constants in the geothermometer expression have been re-evaluated by the method of least
squares using both the data compiled by Fournier and Truesdell and new experimental
data. The resultant thermodynamic parameters also eliminate feldspar-quartz as the
controlling phase assemblage and, in conjunction with experimental observations, suggest
that many different alteration phase reactions involving thermodynamically similar clays
and zeolites may buffer the solution to the observed compositions. A single formulation
of the Na-K-Ca geothermometer may, therefore, be appropriate over a given temperature
range for dilute aqueous systems in a number of different altered rocks containing frame-
work silicates.
The new constants using the least-squares fit of the Fournier and Truesdell data yield
the following revised Na-K-Ca geothermometer equations:
log (Na+/K +) - 6.3 log ( ~ N a +) = 22200/T + 64.2 for T < 100°C
log(Na÷/K +) + 0 . 0 5 5 1 o g ( C , , ~ / N a ÷) = 1 4 1 6 / T - 1 . 6 9 for T > 100°C

INTRODUCTION

Direct maximum-temperature m e a s u r e m e n t in g e o t h e r m a l r e s e r v o i r s c a n
be difficult if not impossible. Accurate, indirect measurement methods must
b e u s e d . O n e m e t h o d is a c h e m i c a l g e o t h e r m o m e t e r b a s e d o n t h e c h e m i s t r y
of the emergent aqueous fluid. Fournier {1981) has tabulated the pertinent
literature on use of water chemistry to determine underground temperatures
with emphasis on applications to geothermal energy utilization. We wish to
focus upon one such geothermometer, the Na-K-Ca chemical geothermometer

*Prepared under the auspices of the Division of Geothermal Energy, U.S. Department of
Energy.
168

developed by Fournier and Truesdell (1973) and empirically expressed by:

log (Na+/K ÷) +/3 log (x/c-aT+/Na÷) = 1647/T(°K) - 2.24
where ~ is 4/3 for T -~ 100°C and 1/3 for T > 100°C.
The Na-K-Ca geothermometer, which is used in geothermal systems to
determine the maximum temperature in the geothermal reservoir from the
concentrations of Na ÷, K ÷ and Ca 2÷ in the emergent aqueous solution, is
assumed to operate by equilibration of the aqueous solution with a mineral
phase assemblage at depth. The constants of the empirical expression derived
by Fournier and Truesdell (1973) should be a function of the thermodynamic
parameters of the controlling mineral reaction or reactions. ~Ihe Na-K-Ca
geothermometer is useful in many rock--fluid systems, principally systems
with dilute fluids in contact with rocks containing feldspar and quartz.
Attempts to improve this geothermometer empirically to take into account
other ions in solution (Mg - Fournier and Potter, 1979) have lent further
versitility to it.
The major problem in the use of the Na-K-Ca geothermometer lies in
knowing over what temperature range it applies and to what rock composi-
tions. A basic understanding of the reactions controlling the chemical
potentials of the principal cations in solution would give this information.
Although reasonably successful in estimating temperature, the graphically
determined values used in the Fournier and Truesdell (F & T) geothermometer
provide little insight into the actual thermodynamics of the equilibrium
reactions. This paper examines field and experimental w a t e r - r o c k inter-
action data and their implications about the magnitudes of the relevant
thermodynamic parameters. The calculated parameters presented in this
paper are no less empirical than those used by Fournier and Truesdell;
the differences are between a least-squares mathematical fit and an esti-
mated graphical fit to the data.

THERMODYNAMIC PARAMETERS

The following analysis is similar to that of Michard and Fouillac (1976)

but with two important differences. They assumed that the graphically
derived value of ~ = 1/3 is correct and that the feldspars are in equilibrium
with the aqueous solution. We will show that neither is correct.
The thermodynamic parameters implicit in the F & T geothermometer
model are developed below. The F & T geothermometer is:
log (Na+/K ÷) +/3 log (x/-C~/Na ÷) = 1647/T(°K) - 2.24 (1)
where the cation concentrations are in molal units.
If, following Fournier and Truesdell (1973), the feldspar end-members are
the solid phases in equilibrium with the solution bearing the Na-K-Ca cations,
the following reaction is typical of reactions that can be written. The use of
 169

mineral names is a convenience that will be discussed further below. Similar

reactions may be written for other K-, Na-, and Ca-bearing phases:

(x + 2 y ) K ÷ + x Ab + y An + 4y SiO2 = x Na ÷ + y C a 2÷ + (x+2y)Or (2)

All reactions are balanced so that only 1 mole of K ÷ is involved. That is,
in this example:
(x+2y) - 1 (3)
For any equilibrium reaction:
-AGr/2.303RT = log Keq (4)

where:
y X
[x/-~] 2y [Na] x [Na] 2y ~'Ca~'NaaOr
Keq = [K]X+2Y [Na]2Y a YnaXAb~t K a ~t z
So, for the example:
X
~'~aTNaaOr
-AG/2.303RT = log (Na÷/K ÷) + 2y log (x/-C-a~/Na ÷) + log (5)

where a and 7 are activities and activity coefficients, respectively. Rearranging

and separating the free-energy term into its enthalpy and entropy compo-
nents, yields:
-AH
log (Na+/K +) - 2y log ( ~ / N a +) -
2.303RT
7~aV~aaOr AS
- log + _ (6)
a~na~b7Ka~t z 2.303R

Although graphically obtained, the Fournier and Truesdell constants

have the following correspondence with thermodynamic parameters:
-AH
1647 - -* AH = - 3 1 5 3 0 J-M -1 (K +) (7a)
2.303R

This AH value should be considered an average over the temperature range

of the data used for its determination. Fortunately, AH of reaction does not
vary rapidly over the relatively restricted temperature range of interest.
/3 = 2y (the stoichiometry constraint) (7b)
x
AS ~/~aTNaaOr
-2.24 - log (7c)
2.303R a~,na~,b TKa~t z
170

Calculations indicate that the cation activity coefficient product ratio for
the dilute solutions under consideration is on the order of magnitude of unity
and, with the assumption of pure feldspar end m em ber solids (in this example!.
the log (activities) term in eq. 7c is approximately equal to log t unityt or
zero. This approximation is substantiated by the observed consistency of
the empirical (Fournier and Truesdell, 1973) constant (the entropy terni)
over a 3 orders of magnitude range in cation concentration. This observation
"also indicates that feldspar solid solution effects on activities are small ip,
these equations. If this approximation is not nearly correct, then the geo-
t h e r m o m e t e r would not yield reasonable temperature estimates and would
require additional input data. Further work on the magnitude and variability
of the activity coefficient pr oduc t ratio term is in progress. Theref(>rc. crude-
ly, eq. 7(: can be simplified 1o:

AS
2.24 . . . . AS -- 42.9 J.~'-~(K~)-~"K -~ (7d)
2.303R

With these assumptions, the calculated t h e r m o d y n a m i c parameters and the

stoichiometry constraint are solid phase independent.
The graphically determined values used in the F & T g e o t h e r m o m e t e r
equation, provide little insight into the actual t h e r m o d y n a m i c s of the equilib-
rium reactions. Least-squares (LS) calculations using the data tabulated in
Fournier and Truesdell (1973) provide a comparison with the values used by
Fournier and Truesdell and a rigorous mathematical determination of the
t h e r m o d y n a m i c and stoichiometric parameters of the pertinent equilibria.
The form o f the g e o t h e r m o m e t e r equation used in the LS fit calculation,
given in eq. 8, minimized the LS residual with respect to lIT. Other forms
could be used; however, this form is best suited to the experimental, con-
trolled temperature, data:

1 _

2.303R log (Na+/K÷) _~2'303R

........ log (x/-(~a~/Na ÷) + -AS
-- (8)
T AH AH AH

Unfortunately, in this form, the calculations of the stoichiometry parameter,

~, and e n t r o p y parameter, AS, are d e p e n d e n t on the enthalpy parameter, AH,
and the corresponding calculated LS error in enthalpy is propagated through
to the errors in the other parameters. The results are summarized in Table I.
The LS calculation incorporates the data over the t em perat ure intervals sug-
gested by Fournier and Truesdell as being distinct equilibria regimes. Also
given in Table I are the root-mean-square (RNS) t em perat ure deviations
between the nominal water-source temperature given in Fournier and
Truesdell and the temperatures calculated from bot h the F & T and LS
parameters. Note that although the T < 100°C LS parameters have large
errors, the calculated temperatures are closer to the measured temperatures
than are F & T-calculated temperatures. The range of calculated t em perat ure
 171

TABLE I

Comparison of parameters given by Fournier and Truesdell (1973) and parameters

calculated by least-squares using the data of Fournier and Truesdell

Enthalpy Stoiehiometry Entropy RMS T

[ J . M '(K÷)] coefficient(~) [J.M ~(K÷).°K -~] deviation

T =< 100°C
F&T 31530
- 4/3 -42.9 31 °
LS + 425,000 ± 860,000 - 6 . 3 ± 14.1 +1230 - 2410 13 °
Calc. error range
14°-31 °

T > IO0°C
F&T 31530
- 1/3 -42.9 28 °
LS - 27100 +- 1100 0.055 + 0.053 32.4 ± 2.1 24 ~
Calc. error range
10~--25 °

e r r o r s a r e also g i v e n in T a b l e I. T h e s e e r r o r c a l c u l a t i o n s u s e t h e L S p a r a m e t e r s ,
e r r o r s , a n d c o r r e l a t i o n c o e f f i c i e n t s a n d a 10~c e r r o r o n e a c h c a t i o n a n a l y s i s .
E a c h c a t i o n a n a l y s i s is a s s u m e d t o b e i n d e p e n d e n t o f t h e o t h e r c a t i o n s .
T h e n e w c o n s t a n t s in T a b l e I c a n b e r e c a s t t o y i e l d r e v i s e d f o r m u l a t i o n s o f
t h e N a - K - C a g e o t h e r m o m e t e r f o r t h e t w o d i s t i n c t t e m p e r a t u r e r e g i m e s sug-
gest by Fournier and Truesdell:

l o g ( N a + / K +) - 6 . 3 l o g (x/C~r~/Na +) = - 2 2 2 0 0 / T + 64.2 for T ~ 100°C

l o g ( N a ÷ / K ÷) + 0 . 0 5 5 l o g ( ~ / N a ÷) = 1 4 1 6 / T - 1 . 6 9 for T > 100°C

Further calculations using natural water data published since 1973, including
individual error estimates, should elucidate the origins of the errors and further
delineate the number of distinct temperature regimes requiring calibration.
T h e L S c a l c u l a t i o n w a s also p e r f o r m e d o n t h e a q u e o u s p h a s e ( T a b l e I V ) o f
t h e e x p e r i m e n t s d e s c r i b e d b e l o w . T h e r e s u l t s ( T a b l e s V I a n d V I I ) w i l l b e dis-
c u s s e d l a t e r in c o n t e x t w i t h t h e e x p e r i m e n t a l l y d e t e r m i n e d m i n e r a l o g y .

EXPERIMENTALPROCEDURE

Two kinds of experimental hydrothermal systems were used to generate

solution and overgrowth data. Both are systems which circulate fluid at high
temperatures and pressures over machined rock disks or prisms. In the first
system (Fig. I) eight rock disks were heated to the same run temperature.
Fluid temperature was then allowed to drop to room temperature and
recirculated. A rock disk was removed at 1 mo., 2 too., 4 mo., etc. for
examination. In the second system (Fig. 2) six rock prisms were placed along
the axis of a long pressure vessel in a temperature gradient. Flow was from
relatively cooler to hotter portions of the vessel. Prisms were placed at 72,
 172

Gauge
'\ " x
Dripper
Safety Valve ~ Ball Check Valve ~
~ ~ 'I

Furnace /~"P Reservoir

I TO Hot Sampler /T
Pressure Circulation
Vessel Pump
Heat
Tapes

Line Filter
Gauge Protector /'~"
Gauqe

Fig. 1. F i x e d - t e m p e r a t u r e circulation system. Note : T I 8 are t h e r m o c o u p l e s .

Circulator

/Furnac 7 Heat
Tapes
/ I

I I Thermocouples
- Ballast
Tank Cooling Coil L
Pressure
Vessel I[
I TO HOt
Sampler
To Cold
Sampler Circulation Pump.~ y/Lioo
Filter

/ w 4

Gauge
Protector
/ Haskell
Pump

Dripper /
Safety Valve Bleed
/ Gauge
/
Reservoir

Fig. 2. The controlled-temperature gradient circulation system. F l o w is c l o c k w i s e

 173

119, 1 6 1 , 2 0 9 , 2 7 0 , and 310°C. All prisms were removed at the conclusion

of the experiment.
In most cases, for both systems, fluid was sampled as it exited from the
reaction vessel at run temperature (Hot) and pressure and at a second down-
stream point at r o o m temperature (Cold) and run pressure. Samples were
extracted in constant pressure and temperature samplers of our design
(Charles et al., 1979). The samplers were pressurized with argon, heated to
the desired temperature, and opened to the circulation system pressure line.
The argon was bled off slowly through a water trap, thus drawing in fluid
from the circulation system with practically no throttling, pressure, or
temperature effects. The Haskel pump introduced fluid into the circulation
system to replace the fluid withdrawn. Experiments 1 and 2 (see Table II) did
not use the constant pressure and temperature sampler for the h o t samples.

TABLE II

Experimental conditions

Rock Circulation system Temperature Pressure Duration

(°C) (kbar) (h)

1. 9519" Fixed temperature 200 1/3 6579

2. 9522* Fixed temperature 300 1/3 5816
3. 9519" Temperature gradient 72,119,161,209, 270,310 1/3 1440
4. Basalt Fixed temperature 300 1/3 3600
5. Basalt Temperature gradient 72,119,161,209,270, 310 1/3 1440
*Biotite granodiorite

These two sets of data reveal fractionation with respect to SiC2 between the
hot and cold samples. The fluid in all cases started out as distilled water
which was allowed to reach a steady state in the system through recirculation.
Rock specimens were examined by means of a scanning electron micro-
scope and electron microprobe. Solutions were analyzed by plasma emission
spectrometry and atomic absorption.
Two granodiorites and a basalt were reacted in separate experiments. 1Vodal
analyses and experimental conditions are shown in Table III. The two grano-
diorites, which were very similar in composition, were prepared from cores
from the reservoir rock of the F e n t o n Hill H o t Dry Rock (HDR) system.
The basalt was a sample from one of the Sentinel Bluff flows of the Grand
Ronde Basalt of the Yakima subgroup of the Columbia River Basin group.
The basalt contains a significant a m o u n t of micropegmatite with a rhyolite
normative composition in addition to the more basaltic minerals. In all rock
types the two-feldspar plus quartz assemblage was present even though the
total bulk compositions were quite varied.
TABLE IIIA

Biotite granodiorite modal analysis: 9522

Mineral Wt. c; Mineral Wt. ~:; Mineral Wt. ~

Potassium feldspar 15 Magnetite i Sphene

Plagioelase 40 Muscovite tr. Zircon E~
Quartz 30 Calcite 2 Sulphide
Blot ite 7 Epido~e l Prehnite
Chlorite tr~ A patite 2

Major and minor phase composition

Microcline Ko.93,0.01 Nao.05.0.01 Si2.98.0.01 All.03:0.01 ()8

Plagioclase, core Ko.ol _0.01 Nao.75.0.01 Ca0.26~0.01 Si2.68~0.02 All .32-0.02 ()8
Plagioclase, rim Ko.02 : o.o 2 Nao (~0+0.ol Cao. lo_0.05 Si2.87.0.05 -\]l.l 2t0.05 O~
Biotite K0.78.0 02 \'ao.o1.0.01 Cao.ol : 0.01 .\~g1.40~ 0 0 t |' e1.16+0.01
M11-(1.04 : o.i) 1 'Fio.O}~ = 0 . 0 2 AIo.27-0 02 SJ2.82 0.02 ,'\ 11.18:0.02
()1 o( OH )2
• 3+
Epidote Ko.ol 0.01 (:al.99 ~0.02 F e:).85to.() 5 Mn0.02:0.01 Si3.09+0.02
Pd2.20 0.0:~ O12(OH)
Sphene Cal o7 0.02 t~'eo.o5+0.01 Ti0.82 =o.01 Sil.01 -o,oi
Alo 12 O.Ol 05

"FABLE IIIB

Biotite granodimite modal analysis: 9519-2

Mineral Wt. 7; Mineral Wt. 7~ Mineral ~t.%

Potassium feldspar 15 Chlorite tr. Calcite tr

Plagioelase 38 Opaques 1 Apatite 1
Quartz 25 Epidote 2, Zircon tr
Biotite 13 Sphene 2 Sericite I

Major and minor phase composition

Potassium feldspar Nao.07:0.01 Ko.93zo,o 1 A11.02zo.o 1 Si 2.98±0.01 08

(microcline)
Plagioelase, core Na0.74:0.01 K0.01 ~0.01 Ca0.26±0.01 A11.28±0.01 Si2.72z0.01 O8
Plagioelase, rim Na0.89¢0.01 Ko.02±o.o I Ca0.09±o.o 1 AI 1.13±0.01 Si2.87 ±0.01 08
Biotite K0.88= 0.02 Mgt.37±o.02 Fe 2+
1.2120.01 Mn0.04±O.Ol Tio.09+-O.Ol
Al 1.41 ~0.01 Si2.81~0.01 O 10(OH)2
Chlorite Mg2.50±o.02 A12.49±0.02 Fe 2.*18±0.01 Mno.o8~o.01 Si2.73±0.01
O]o(OH)8
Epidote Cal,99±0.02 Fe03+77±0.05 A1~.24±0.04 Si3.11±o.o 1 O12(OH )
Sphene Ca 1.00=0.02 Alo.09±o.o I 2+
Feo.06±o.o 1 Ti0.87±0 01 Sil.03±o.o 1 05
Sericite Nao.o3to-01 K0.89±0.01 Mgo.13±o.03 ~ e 30.24-*0.04
~ + • A12.60±0.07
Si3.17±0.02 Olo(OH)2
Prehnite Cal.92 +_0.01 A11.99±0.01 Si3.02±0.01 Olo(OH)2
 175

TABLE IIIC

Sentinel Bluff basalt modal analysis

Mineral Wt. % Mineral Wt. % Mineral Wt. %

Plagioclase 44 Pigeonite 7 Pyrite tr.

Groundmass 24 Ti-magnetite 3 Apatite tr.
Augite 21 Nontronite 1

Phase composition

Augite Mg0.88±0.02 Feo.46to.03 Ca0.70±0.02 Ti0.02_+0.01 A10.07_+0.01

Sil.90+0.01 06 0.03
Pigeonite Mg0.82±0.10 Feo.9s±o.07 Ca0.26±0.02 Mno.02±0.01 A10.03_+0.01
Sil.92±0.01 06
Plagioclase,
average : Na0.47 Ca 0.51 K0.03 All.47 Si2.49 08
range : rim-Abs7 An40Or 3 to core - Ab40An58Or 2
Ti magnetite Mt551145
Nontronite 3+
Ca0.32_+0.01 Mgl.49_+0.03 Fe3.40_+0.03 Si7.31_+0.03 All .70_+0.01
O20(OH)4
Groundmass 0r29.o_+1.4 Ab29.4±4.9 An 3.1+o.6 Qtz38.5±4.4
as alkali feldspar (sanidine) + quartz

EXPERIMENTAL RESULTS

The solution analyses are shown in Table IV. The data show irregularities
in solution composition early in the runs because of hydrolysis and surface
damage during preparation of the rock (cutting and polishing). In general,
the solution concentrations reached a steady state, within the limits of
error, after about 2 to 4 weeks. The equilibrium cation ratios were attained
in a matter of days. These two temporally distinct equilibration regimes may
be manifestations of two kinetically controlled mechanisms: solid phase
dissolution and cation exchange.
A variety of overgrowths were detected on the reacted rock. These are
tabulated in Table V and shown in Figs. 3- 11. The electron microprobe
analyses are subject to about a 10% error due to analytical scatter resulting
from the overgrowths uneven texture.
While the interior of the rock is out of equilibrium with the circulating
fluid, the secondary phases are in local equilibrium with the fluid as indi-
cated by the relatively constant solution compositions. Presumably these
are the equilibria that regulate any chemical geothermometer.
Figure 3 shows the overgrowth which grew on the #9519 granodiorite
after 9 months of reaction at 200°C. Stumpy crystals of a Ca, K, Na phase,
presumably a zeolite, grow exclusively upon a template of plagioclase feld-
spar. An unreacted biotite grain appears in the upper left hand corner.
176

Figures 4 and 5 exhibit overgrowths grown on the #9522 granodiorite at

300°C after 8 months of reaction. The spongy vermiculite (Fig. 4) grows on
chloritized biotite seen also to the left. The herringbone structure to the
right of the vermiculite is a l t e r e d plagioclase. Albite is p r e f e r e n t i a l l y removed.

T A B L E IV

S o l u t i o n a n a l y s i s in p p m . All d u r a t i o n s are in h o u r s

A. 9 5 1 9 G r a n o d i o r i t e at 2 0 0 ° C (Charles, 1 9 7 9 )

Duration K Na Ca

Hot sample
29 3.2 ± 0.2 6.3 ± 0.3 1.1 ± 0.1
53 1.6 ± 0.1 3.8 ± 0.2 1.1 -* 0.1
213 4.8 ± 0.3 11.0 ± 0.6 2.3 -+ 0.1
817 4.9 ± 0.3 12.2 ± 0.6 2.5 ± 0.2
1372 4.6 ± 0.3 11.4 + 0.6 1.7 ± 0.1
3147 4.7 + 0.3 20.7 ± 1.0 1.6 ± 0.1
6579 3.2 + 0.2 18.1 ± 0.8 1.6 ± 0.1

Cold sample
29 5.8 ± 0.3 8.6 ± 0.4 3.4 + 0.2
53 4.5 ± 0.2 7.9 ± 0.4 3.2 ± 0.2
213 5.0 ± 0.3 8.8 ~: 0.4 4.2 ± 0.2
817 4.1 ± 0.2 9.5 ~ 0.5 2.4 ± 0.1
3147 5.0 ± 0.3 16.2 ± 0.8 2.4 ± 0.1
6579 3.5 ± 0.2 17.1 ~ 0.8 1.4 ± 0.1

B. 9 5 2 2 G r a n o d i o r i t e at 3 0 0 ° C (Charles, 1 9 7 8 )

Duration K Na Ca

Hot sample
32 53.0 ± 1.1 23.2 ± 0.6 0.3 ± 0.1
56 8.9 ± 0.8 27.7 ± 0.7 0.1 ± 0.1
176 6.1 ± 1.0 23.1 ± 0.6 0 ± 0.1
368 7.3 ± 1.3 21.3 ± 0.6 0.2 ± 0.1
752 6.6 ± 0.1 27.2 ± 0.1 0.2 ± 0.1
1544 5.7 ± 0.1 18.8 + 0.1 0.2 ± 0.1
3104 8.4 ± 0.2 22.5 * 1.1 0.1 + 0.1
5816 6.4 ± 0.9 25.9 ± 0.1 0 ± 0.1

Cold sample
32 9.6 ± 0.9 26.6 ± 0.7 0.4 ± 0.1
56 8.0 ± 0.8 25.3 + 0.7 0.3 ± 0.1
176 8.0 ± 0.9 24.3 ± 0.7 0.4 ± 0.1
368 7.9 ± 0.9 25.3 ± 0.7 1.4 ± 1.4
752 6.9 ±1 26.8 ± 0.4 0.1 ± 0.1
1544 5.7 ±1 19.9 ± 0.4 0.2 ± 0.1
3104 8.2 ± 0.2 22.6 ± 0.4 0.2 ± 0.02
5816 6.7 ± 0.5 23.4 ± 0.9 0.6 ± 0.1
 177

C. 9519 G r a n o d i o r i t e r e a c t e d in a t e m p e r a t u r e gradient ( 7 2 - - 3 1 0 ° C ) (Charles a n d

Bayhurst, 1981 )

Duration K Na Ca

Hotsample
24 14.2±0.7 8.2±0.4 0.20 ± 0.1
48 13.8±0.7 11.7±0.6 0.20 ± 0.1
96 7.2±0.4 7.7±0.4 0.20 ± 0.1
168 7.2±0.4 7.4±0.4 0.60 ± 0.1
336 7.7±0.4 6.8±0.4 0.40 ± 0.1
720 8.0±0.4 13.5±0.7 0.17 ± 0.1
1440 7.9±0.4 15.5±0.7 0.24 ± 0.1

Coldsample
24 2.6±0.2 2.2±0.1 0.10±0.1
48 10.0±0.5 6.9±0.3 0.20±0.1
96 6.5±0.3 7.3±0.4 0.10±0.1
168 6.2±0.3 9.2±0.5 0.20±0.1
336 5.7±0.3 5.7±0.3 0.30±0.1
720 6.7±0.3 12.1±0.6 0.08±0.08
1440 6.9±0.3 12.8±0.6 0.14±0.1

D. S e n t i n e l Bluff basalt at 300°C, Hot s a m p l e

Duration K Na Ca

24 3.1±0.2 2.3±0.2 2.6±0.2

48 13.0±0.5 13.0±0.5 1.0±0.2
96 8.1±0.5 12.6±0.5 0.2±0.1
168 10.5±0.5 17.4±0.5 0.2±0.1
336 11.2±0.5 13.7±0.5 0.1±0.1
720 6.9±0.5 15.0±0.5 0.2±0.1
1440 8.8±0.5 21.4±0.5 0.5±0.1
3600 7.8±0.5 15.2±0.5 0.7±0.2

E. S e n t i n e l Bluff basalt r e a c t e d in a t e m p e r a t u r e gradient ( 7 2 - - 3 1 0 ° C )

Duration K Na Ca

Hotsolution
48 13.0±0.5 9.7±0.5 0.2±0.1
144 12.4±0.5 9.2±0.5 0.1±0.1
336 13.4±0.5 11.9±0.5 0.1±0.1
720 12.3±0.5 12.5±0.5 0.2±0.1

Cold solution
24 9.6 ± 0.5 8.1 ± 0.5 0.2 ± 0.1
48 8.9 ± 0.5 6.4 ± 0.5 0.1 ± 0.1
144 9.5 ± 0.5 6.8 ± 0.5 0.1 ± 0.1
336 10.4 ± 0.5 10.6 ± 0.5 0.1 ± 0.1
720 9.9 ± 0.5 11.4 ± 0.5 0.2 ± 0.1
Fig. 3. 9519 biotite granodiorite reacted at 200°C for 6579 hr in the fixed~temperature
circulation system. Stumpy zeolite on plagioclase feldspar. Biotite is at Northwest.

Fig. 4. 9522 reacted at 300°C for 5816 hr. Overgrowth is vermiculite surrounded by
epidote, eroded plagioclase (east), sphene (north), and chloritized biotite {west).
 179

Fig. 5. 9 5 2 2 biotite granodiorite reacted at 300°C for 5816 hr. Overgrowth is sugary
zeolite on original plagioclase.

TABLE V

Overgrowths ; water c o n t e n t is n o t directly measured

Rock Temperature Phase

biotite 200°C zeolite Cas. s Nao. ~Ks.o FeSo.*sSi,, .o A19.o O,o" 15H :O
granodiorite
(9519)
biotite 300°C zeolite: Cas.o Nao.s Sis.s Al,.s O 2o. 6 H 2 0
granodiorite clay : K o., Nao., Cao .s Fe~*.7Mgo.s Si s.s AI 2.30 so(OH),
(9522)
biotite t e m p e r a t u r e gradient
granodiorite (1) 72°C--119°C clay: Ko., Cao., Nao.l A13., Feo3+.sSiT.o A1, .oO2o(OH), •
(9519) nH~O
(2) > 119°C--<209°C zeolite : Cao.s Nao. 5Ko. 5SiT. o AI 2. o O 2o" 6---7 H 20
(3) 209°C--310°C zeolite : Nao. ~Ko.~ Ca4.o Si~ ~.o Alg.o O,o" 12Hs O
basalt 300°C clay: K o .6 Cao.~Mg3.s Fe~:2 Sig.s A19.o O,o(OH)8
basalt t e m p e r a t u r e gradient
(1) 72°C--209°C clay : Cao .4 Mg3. s Fe9 .o A l , o Tio. 5 Sig.s A16.4 O,o (OH) 8
(2) > 209°C--310°C clay: Nao. ~Cao. 9 K o .3 Mg2.9 Fe~.3 SiTAl O2o(OH),
180

A resistant sphene is shown at the top. The sugary overgrowth tFig. 5) of a

Ca, Na phase, another zeolite, grows almost exclusively on plagioclase feld-
spar. Altered plagioclase and sericite surround the hysteresis loop-shaped
overgrowth.
Figures 6, 7, and 8 illustrate the different overgrowths found on grano-
diorite reacted in a temperature gradient. The prisms reacted at 72°C and
119°C (Fig.6) have overgrowths of poorly crystallized botryoidal material
of clay composition. The prism reacted at 161°C has an entirely different
overgrowth of mossy textured zeolite {Fig. 7). At 2 0 9 , 2 7 0 , and 310°C,
a different zeolite with sugary texture grows almost exclusively on the
plagioclase feldspar (Fig. 8). Eroded microcline is seen at the top right.
Basalt reacted at 300°C yielded clay (Fig. 9) growing primarily on the
pyroxenes, while basalt reacted in the temperature gradient shows a low
silica, low alkali clay growing at 7 2 , 1 1 9 , 1 6 1 , and 209°C on pyroxenes
and nontronite (Fig. 10). A high-Ca, alkali, and silica clay grows at 270°C
and 310 ° C with similar morphology ( F i g . l l ) . The unreacted feldspar matrix
also appears in Fig. 11. These clays are distinct from the natural alteration
to nontronite.

Fig. 6. 9519 biotite granodiorite reacted in the temperature gradient system. The botryoidal
coating is clay in composition and entirely covers the rock. It appears at 72°C and 119°C.

Fig.8. 9519 biotite granodiorite reacted at 161°C in the temperature gradient system. The
mossy overgrowth is a zeolite.
 181

Fig.7. 9519 biotite gmnodiorite reacted at 310°C in the temperature gradient system.
The sugary overgrowth is a zeolite on plagioclase. Eroded K-feldspar is at east and north.
The same overgrowth appears at 209°C and 270°C.
182

Fig. 9. Basalt r e a c t e d at 30ff'C in t h e f i x e d - t e m p e r a t u r e circulation s y s t e m for 3600 hour~

The clay grows on the p y r o x e n e s while t h e plagioclase and m a t r i x are e r o d e d
 183

Fig. 11. Basalt reacted in the controlled temperature gradient system. Clays grow between
resistant feldspars at 270°C and 310°C.

CALCULATION OF CONSTANTS FROM THE EXPERIMENTAL DATA

The experimental water--rock equilibrium data presented above have the

advantages of a well-controlled thermal and compositional environment. The
solution composition and changes in the solid phase assemblage can be deter-
mined as functions of temperature, time, initial solution composition, and
initial rock type and mineralogy. Although the experiments were not
initially designed for the calculation of LS geothermometer parameters, the
data produced a good fit for both biotite-granodiorite and basalt rock types
resulting in the parameters listed in Table VI. It is important to note that
the solution compositions from the temperature gradient systems reflect the
highest experimental temperature, even for the cold-drawn samples. Addi-
tionally the rate of equilibration appears to increase with the decrease in
mean grain size, based on data for just two rock types.

EXAMINATION OF THERMODYNAMIC PARAMETERS

Assuming feldspar end--members, the stoichiometry coefficients in Table I

Fig. 10. Basalt reacted in the controlled temperature gradient system. This clay is grown
on the prisms at 72, 119, 161, and 209°C.
184

TABLE VI

Experimental data: parameters and equilibria

T > 200°C (mean 540°K)

Enthalpy [J.M-~(K÷)] Stoiehiometry coefficient (~) Entropy [J.M-~(K ÷) -°K ~ ]

LS 43000 +- 4500 0.98 ± 0.10 -55.5 ± 7.3

K ÷ + 0.02 NaA1Si30~ + 0.49 CaAI:Si:O 8 + 1.96 SiO 2 = 0.02 Na ÷ + 0.49 Ca 2+ + KA1Si30~

AGr (Robie et al., 1979) = 26.5 kJ
~Gr (LS) = 1 3 . 0 k J

TABLE VII

Equilibrium reactions derived from the parameters given in Table I, assuming feldspar
end -members

T <_ 100°C (mean 320°K)

F&T: K ÷ + l / 3 N a ÷+2/3CaA12Si~O ~+8/3SiO2 = 2 / 3 C a 2÷+KA1Si308 + l / 3 N a A I S i ~ O ~
AGr (Robie et al., 1979) = - 6.5 kJ, AGr (F&T) = 17.8 kJ
LS: K ÷ + 3.15 Ca 2÷ + 7.30 NaA1Si3Os = 7.30 Na + + KA1Si~O~ + 3.15 CaA12Si~O ~ +
12.6 SiO 2
AG r (Robie et al., 1979) = 2.8 kJ, AGr (LS) = 33 kJ

T > 100°C (mean 500°K)

F&T: K ÷+2/3NaAlSi~Os + l / 6 C a A I : S i 2 0 ~ + 2 / 3 S i O : = 2 / 3 N a ÷ + 1 / 6 C a ~÷+KAISi30~
AGr (Robie et al., 1979) = 9.8 kJ, ~Gr (F&T) = 10.1 kJ
LS: K + + 0 . 9 4 5 N a A 1 S i 3 0 ~ +0.0275CaAI2Si20 ~ + 0 . 1 1 0 S i O : = 0 . 9 4 5 N a + +
0.0275 Ca 2÷ + KA1Si30 ~
AGr (Robie et al., 1979) = 5.3 kJ, AGr (LS) = -10.9 kJ

c a n b e u s e d t o d e f i n e t h e e x c h a n g e r e a c t i o n s p r e s e n t e d i n T a b l e VII. T h e
free e n e r g y o f e a c h r e a c t i o n is c a l c u l a t e d f r o m t h e d a t a o f R o b i e et al. ( 1 9 7 9 )
at t h e m e a n t e m p e r a t u r e o f t h e F o u r n i e r a n d T r u e s d e l l d a t a u s e d f o r t h e LS
calculations. These free-energy values can be c o m p a r e d from those o b t a i n e d
f r o m t h e solid phase i n d e p e n d e n t LS a n d F & T e m p i r i c a l p a r a m e t e r s , as
l i s t e d in T a b l e I.
F r o m T a b l e V I I it a p p e a r s t h a t t h e F & T a n d LS r e a c t i o n s are s i g n i f i c a n t l y
d i f f e r e n t a n d , m o r e i m p o r t a n t ~ , it a p p e a r s t h a t , f r o m c o m p a r i n g t h e free-
e n e r g y v a l u e s , t h e f e l d s p a r e n d - m e m b e r s are n o t t h e s o l i d p h a s e s w h i c h
c o n t r o l t h e s o l u t i o n c o m p o s i t i o n . F e l d s p a r solid s o l u t i o n e f f e c t s are u n l i k e l y
t o b e large e n o u g h t o r e s o l v e t h e d i f f e r e n c e s b e t w e e n t h e A G r v a l u e s in
T a b l e s V I a n d V I I . U n f o r t u n a t e l y , n o t h e r m o d y n a m i c d a t a exists f o r t h e
observed a l t e r a t i o n clays and zeolites.
As i n f e r r e d f r o m t h e c a l c u l a t e d r e a c t i o n free e n e r g i e s i n T a b l e s V I a n d V I I ,
feldspars do n o t c o n t r o l the s o l u t i o n - - r o c k equilibria even t h o u g h the rock
c o n t a i n a b u n d a n t feldspars. Reversed e q u i l i b r i u m stability diagrams (Liou,
 185

1 9 7 1 a , b) i n d i c a t e t h e f e l d s p a r e n d - m e m b e r s are n o t t h e r m o d y n a m i c a l l y
stable u n d e r m o s t o f t h e e x p e r i m e n t a l c o n d i t i o n s used in this study. T h e
o b s e r v e d a l t e r a t i o n phases b u f f e r t h e s o l u t i o n c o m p o s i t i o n a n d are t h e
i m p o r t a n t phases in N a - K - C a g e o t h e r m o m e t r y . F u r t h e r e x p e r i m e n t s are
u n d e r w a y at t e m p e r a t u r e s i n t e r m e d i a t e t o t h o s e p r e v i o u s l y used. T h e
d i f f e r e n c e b e t w e e n t h e LS p a r a m e t e r s , f o r t h e T > 100°C F & T d a t a and the
e x p e r i m e n t a l T =~ 200°C d a t a is n o t p r e s e n t l y u n d e r s t o o d , h o w e v e r ; the
v a r i a t i o n s of t h e LS p a r a m e t e r s c a l c u l a t e d f r o m t h e F o u r n i e r and Truesdell
( 1 9 7 3 ) w a t e r d a t a using 50 ° intervals (Table V I I I ) suggests t h a t : (1) several
d i f f e r e n t equilibria are involved as a f u n c t i o n o f t e m p e r a t u r e ; (2) the geo-
t h e r m o m e t e r m o d e l o f F o u r n i e r and Truesdell ( 1 9 7 3 ) is insufficient; a n d / o r
(3) t h e n a t u r a l w a t e r s d a t a are in error, m o s t likely t h e m e a s u r e d t e m p e r a -
tures are n o t t h e ( m a x i m u m ) t e m p e r a t u r e s o f equilibration. E x p e r i m e n t a t i o n
is t h e best a p p r o a c h to u n d e r s t a n d i n g t h e t h e r m o d y n a m i c s and kinetics of
the g e o t h e r m o m e t e r and its r e l a t i o n s h i p to n a t u r a l w a t e r s c o m p o s i t i o n
and m e a s u r e d t e m p e r a t u r e .

TABLE VIII

LS parameters using natural water data (Fournier and Truesdell, 1973) over 50 ° tempera-
ture intervals

T (°C) No. of AH [kJ.M-~(K+)] ~ (Stoichiometry) AS [J.M-~(K+).°K -~]

samples

0--50 19 98 ± 35 -0.02 ± 0.33 360 _+110

51--100 17 189 ± 145 2.0 ± 1.1 -490 ± 400
101--150 11 58 + 22 0.44 ± 0.21 114 ± 56
151--200 15 -103 ± 39 0.09 ± 0.30 199 ± 84
201--250 13 230 ± 510 -3.8 ± 6.4 600 ± 1000
251--300 20 -81 ± 30 0.25 ± 0.16 -133 ± 56
301--375 14 -180 ± 130 0.63 ± 0.60 -270 + 200

A l t h o u g h t h e LS m e t h o d yields an i m p r o v e d set o f c o n s t a n t s for Na-K-Ca

g e o t h e r m o m e t r y a n d an e s t i m a t e o f t h e r m o d y n a m i c a l l y significant p a r a m e t e r s
f o r t h e w a t e r - - r o c k equilibria, f u r t h e r utilization o f these t h e r m o d y n a m i c
c o n s t r a i n t s is d e p e n d e n t on o b t a i n i n g t h e r m o d y n a m i c d a t a for t h e o b s e r v e d
a l t e r a t i o n phases.
T h e s u b s t i t u t i o n o f p o t a s s i u m m i c a f o r p o t a s s i u m feldspar, as suggested b y
Ellis ( 1 9 7 0 ) , c a n n o t be a d d r e s s e d at p r e s e n t b e c a u s e p H was n o t t a b u l a t e d
with t h e n a t u r a l or e x p e r i m e n t a l Na-K-Ca data. A d d i t i o n a l l y , m e a s u r e d p H
values o f s u r f a c e - s a m p l e d w a t e r s m a y h a v e little m e a n i n g ( F o u r n i e r and
Truesdell, 1973). F u t u r e c a l c u l a t i o n s will include H ÷ as a f o u r t h c a t i o n
c o m p o n e n t w h i c h will be solved f o r b y d i f f e r e n c e (to o b t a i n charge balance)
f r o m t h e c a l c u l a t e d Na-K-Ca c a t i o n s t o i c h i o m e t r y . This H ÷ d e t e r m i n a t i o n ,
a l t h o u g h o n l y an e s t i m a t e , will p e r t a i n to the c o n d i t i o n s o f Na-K-Ca
equilibration and is i n d e p e n d e n t o f the solid phases, and, in fact, m a y
c o n s t r a i n the possible solid p h a s e assemblages.
186

CONCLUSION

O r i g i n a l l y t h e a u t h o r s felt t h a t i d e n t i f i c a t i o n of t h e i n d i v i d u a l o v e r g r o w t h s
was c r i t i c a l t o t h e a p p l i c a t i o n o f t h e g e o t h e r m o m e t e r . T h e v a r i a t i o n in c o m -
p o s i t i o n a n d s t r u c t u r e o b s e r v e d f o r t h e s e o v e r g r o w t h s , h o w e v e r , suggests
t h a t m a n y d i f f e r e n t r o c k - - f l u i d r e a c t i o n s m a y g e n e r a t e s o l u t i o n s o f suffi-
c i e n t l y similar c a t i o n r a t i o s f o r a single c h e m i c a l g e o t h e r m o m e t e r e x p r e s s i o n
to a p p l y t o a f a i r l y b r o a d r a n g e o f b u l k c o m p o s i t i o n a l e n v i r o n m e n t s . [n
other words, the t h e r m o d y n a m i c parameters for the reactions of certain clays
a n d z e o l i t e s o b s e r v e d h e r e i n are s i m i l a r a n d d o n o t s i g n i f i c a n t l y a f f e c t t h e
c o n s t a n t s u s e d in t h e g e o t h e r m o m e t e r . F u r t h e r e x p e r i m e n t a l s t u d i e s are
needed to define the best constants for the geothermometer expressions,
t h e i r t e m p e r a t u r e ( a n d p r e s s u r e ) ranges, a n d t h e a p p r o p r i a t e r o c k t y p e s a n d
bulk compositions.

REFERENCES

Charles, R.W., 1978. Experimental geothermal loop: I, 295°C study. Los Alamos Sci. Lab.
Rep., LA-7334-MS, 44 pp.
Charles, R.W., 1979. Experimental geothermal loop: II, 200°C study. Los Alamos Sci.
Lab. Rep., LA-7735-MS, 40 pp.
Charles, R.W. and Bayhurst, G.K., 1983. Rock-fluid interactions in a temperature gradient:
biotite granodiorite + H20 (water). In: G. Heiken and F. Goff (Editors), Geothermal
Energy from Hot Dry Rock. J. Volcanol. Geotherm. Res., 15: 137--166.
Charles, R.W., Bayhurst, G.K. and Vidale, R.J., 1979. Two dynamic hydrothermal systems
and fluid samples for studying rock-fluid interactions. Los Alamos Sci. Lab. Rep.,
LA-7766-MS, 12 pp.
Ellis, A.J., 1970. Quantitative interpretation of chemical characteristics of hydrothermal
systems. Geothermics, Spec. Iss. 2, 2 ( 1 ): 516--528.
Fournier, R.O., 1977. Exchange of Na ÷ and K + between water vapor and feldspar phases
at high temperature and low vapor pressure. Geochim. Cosmochim. Acta, 40: 1553--
1561.
Fournier, R.O., 1981. Application of water chemistry to geothermal exploration. In:
L. Rybach and L.J.P. Muffler (Editors), Geothermal Systems: Principles and Case
Histories. Wiley, New York, N.Y., pp. 109--143.
Fournier, R.O. and Potter, R.W., 1979. Magnesium correction to the Na-K-Ca chemical
geothermometer. Geochim. Cosmochim. Acta, 43: 1543--1550.
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. and Truesdell, A.H., 1974. Geochemical indicators of subsurface tempera-
ture-Part 2, Estimation of temperature and fraction of hot water mixed with cold
water. U.S. Geol. Surv. J. Res., 2: 263--270.
Liou, J.G., 1971a. Analcime equilibria. Lithos, 4: 389--402.
Liou, J.G., 1971b. P-T Stabilities of Laumontite, Wairakite, Lawsonite, and related
minerals in the System CaAl~Si20~-SiO2-H20. J. Petrol., 12: 379--411.
Michard, G. and Fouillac, C., 1976. Remarques sur le g~othermom~tre Na-K-Ca.
J. Volcanol. Geotherm. Res., 1: 297--304.
Robie, R.A., Hemingway, B.S. and Fisher, J.R., 1979. Thermodynamic properties of
minerals and related substances at 298.15 K and 1 bar (10 s pascals) pressure and
at higher temperatures. U.S. Geol. Surv., Bull. 1452, 456 pp.