209
GEOCHEMISTRY I N EXPLORATION AND PRODUCTION
Robert 0. Fournier
U .S. Geological Survey
Menlo Park, CA 94025
ABSTRACT
Geochemistry has many uses i n a geothermal
resources development program. It can provide
information about reservoir conditions before and
during production, t h e source o f recharge, and
directions o f f l u i d flow. It has important
applications i n regard t o corrosion, scaling, and
waste-disposal problems. When properly used,
chemical geothermometers and mixing models
applied t o hot- spring waters can give accurate
information about underground reservoir
temperatures and s a l i n i t i e s . However, when
i n t e r p r e t i n g chemical data, a t t e n t i o n should be
given t o geologic and hydrologic information.
Also, chemical models must be consistent w i t h
isotopic ta; p l o t s o f enthalpy versus chloride,
and are useful f o r determining t h a t
consistency . i n t e r e s t t o me a t t h i s time. I shall go i n t o
Equations expressing t h e sol o f quartz
i n water a t the vapor pressure o f the solution as
a function o f temperature and a function
of enthalpy permit c a l c u l a t i o n o f s i l i c a
geothermometer temperatures f o r solutions
up t o w i t h or without steam separation a t
any temperature. The s o l u b i l i t y o f quartz i n
NaCl solutions (expressed i n i s similar t o
t h a t i n pure water a t temperatures below about
A t higher temperatures quartz s o l u b i l i t y
i n s a l t solution i s g r e a t l y increased compared t o
pure water; t h i s has great importance f o r
determining conditions a t which scaling i s
l i k e l y t o occur.
INTRODUCTION
Compositions o f geothermal f l u i d s are
c o n t r o l l e d by a complex i n t e r p l a y o f hydrologic,
chemical, and physical processes. These include
leaching o f country rocks by migrating f l u i d s ,
b o i l i n g w i t h p a r t i t i o n i n g o f v o l a t i l e s between
l i q u i d and vapor phases, mixing o f waters o f
d i f f e r e n t sal i n i t i e s and temperatures, and
gas-water-rock reactions a t widely ranging
temperatures and pressures. I n t e r p r e t i n g t h e
chemical and i s o t o p i c compositions o f n a t u r a l l y
occurring l i q u i d s , gases, and s o l i d s i n r e l a t i o n
t o these processes i s what hydrothermal
geochemistry i s a l l about.
I n a sense hydrothermal geochemistry i s
s t r i k i n g out i n a l l d i r e c t i o n s a t once; i t i s a
v e r i t a b l e explosion o f hydrothermal information
and ideas. This burst o f a c t i v i t y has come about'
for many reasons: technological advances i n
nstrumentation and i n techniques f o r obtaining
chemical and i s o t o p i c data, exploration
d r i l l i n g and production o f new geothermal f i e l d s ,
and p u b l i c a t i o n o f downhole information obtained
from diverse geologic environments, greater
use o f computers and t h e development o f programs
t o model chemical and isotope systems, and t o
store, retrieve, and manipulate data, and the
need t o solve various chemical problems r e l a t e d
t o production and waste disposal.
To the many excellent and diverse
geochemical papers t h a t have been ished
recently would be impossible here. I shall
b r i e f l y touch upon some o f t h e ways t h a t
geochemistry can be used t o a i d i n geothermal
energy exploration and production and h i g h l i g h t a
few geochemical matters t h a t are o f p a r t i c u l a r
d e t a i l only i n regard t o two aspects o f
geochemistry w i t h which Ihave been d i r e c t l y
involved: development o f geochemical t o o l s
and techniques t o explore and evaluate geothermal
prospects, and determination o f the
sol i t y o f quartz i n hydrothermal solutions
and i t s p r a c t i c a l application.
THE MANY USES OF GEOCHEMISTRY
Geochemistry can and should be used i n a l l
phases o f a geothermal resources development
program, from regional exploration through
s p e c i f i c s i t e evaluation t o production. When
properly used, chemical and isotopic
geothermometers ( E l l i s and Mahon, 1977; Fournier,
1977, 1981; Truesdell, Truesdell and
Hulston, 1980; D'Amore and Panichi, 1980) and
mixing models (Fournier, 1977, Truesdell
and Fournier, 1977) can provide excellent
information about underground reservoir
temperatures. Isotopic data may give an
i n d i c a t i o n o f t h e source, age, and amount o f
water t h a t has flowed through a geothermal
reservoir (Truesdell and Hulston, 1980; E l l i s and
Mahon, 1977). I n e r t gas concentrations may give
information about the i n i t i a l temperature o f the
recharge water and whether subsurface b o i l i n g
occurred before discharge a t the surface (Mazor,
1977). Variations i n composition o f s o i l gases
may give i n d i c a t i o n s o f subsurface b o i l i n g and
1ocations o f otherwise hidden f a u l t s (Tonani,
1970; Kahler, 1981; Roberts e t
and Tetsuro, 1976). Helium isotopes i n hot
., 1975; Koga
 21 0
Fourn ie r
springs can be used t o show mass transport from
subcrustal regions (Craig e t al., 1978).
Early chemical characterization o f reservoir
f l u i d s i s essential i f scaling, corrosion, and
environmental problems are t o be anticipated and
circumvented. Spatial v a r i a t i o n i n 1i q u i d and
gas compositons can give information about t h e
size, shape, and temperature o f the reservoirs,
and d i r e c t i o n s o f f l u i d flow. Relatively
c h l o r i d e - r i c h f l u i d s tend t o be found i n t h e
central upflowing zones o f 1iquid-dominated
hydrothermal systems, and a t i v e l y bicarbonate-
and s u l f a t e - r i c h waters i n t h e cooler margins and
tops o f both l i q u i d - and vapor-dominated
systems. An exception t o t h i s generalization
i n g r a n i t i c and metamorphic rocks, where even t h e
h o t t e s t upflowing waters i n liquid- dominated
systems may contain l i t t l e chloride.
F l u i d s produced s h o r t l y a f t e r completion o f a
well may give an early i n d i c a t i o n o f the
reservoir temperature long before t h e well
recovers thermally from the cooling e f f e c t s o f
c i r c u l a t i n g d r i l l i n g water (Fournier e t .,
1980). Changing compositions o f f l u i d s ( l i q u i d s
and gases) produced from wells can be used t o
monitor changing underground temperatures, v e r i f y
production from d i f f e r e n t aquifers, detect
b o i l i n g i n the aquifer, and monitor reservoir
drawdown and i n f l u x o f c o l d water long before
c o l d water i n f l u x i s detected by decreases i n
reservoir temperatures and enthal pies (Mahon,
1966; E l l i s , 1977; Glover, 1970; Truesdell,
press
Truesdell e t ., 1979; Grant e t ., in
a t i vely high concentrations o f some t r a c e
elements, such as Zn, Pb, and As, and the
presence o f c e r t a i n hydrothermal teration
products, such as K-feldspar, have been found t o
correspond t o zones where r e l a t i v e l y large
amounts o f f l u i d f l o w have occurred i n the past
(Browne, 1978; Christensen e t ., 1980). Zones
o f r e l a t i v e l y high permeability t h a t p e r s i s t i n
t h e rock up t o the present are l i k e l y t o be
located w i t h i n or near where f l u i d has flowed
most e a s i l y i n t h e past. Therefore, study o f
t r a c e elements and hydrothermal teration
products i n c u t t i n g s and core as d r i l l i n g
progresses may provide very useful information
about how t o complete a well.
Studies o f hydrothermal t e r a t i o n products
and f l u i d inclusions may provide information
about the thermal and chemical h i s t o r y o f a given
body o f rock and the water t h a t flowed through
it. I n studies o f ore deposits, primary f l u i d
inclusions are prized f o r the information they
provide about the conditions a t the t i m e o f
mineral growth, while secondary f l u i d inclusions
are generally considered a nuisance. I n studies
o f a c t i v e hydrothermal systems, however, I
suggest t h a t secondary f l u i d inclusions may
provide t h e k i n d o f information on reservoir
conditions t h a t we require, namely t h e range i n
hydrothermal temperatures and sal i n i t i e s t o which
a given body o f rock has been subjected. This
means t h a t quartz, feldspar, and other minerals
t h a t formed a t the time o f c r y s t a l l i z a t i o n o f an
igneous rock should be considered f o r studies o f
secondary f l u i d inclusions r e l a t e d t o superposed
hydrothermal a c t i v i t y .
INTERPRETATION OF HOT-SPRING WATERS
One o f the most widespread uses of
geochemistry by geothermal workers i s t o estimate
reservoir temperatures from compositions of
hot- spring waters. The equations f o r chemical
are r e l a t i v e l y simple, and
seems t h a t everyone w i t h access t o water analyses
calculates geothermometer temperatures:
that the extent o f many
geochemical studies. This might be acceptable
p r a c t i c e i f only one spring were available f o r
sampling i n a given region or i f a l l the waters
were i d e n t i c a l i n composition. However, t h i s i s
generally not the case, and we can and should do
b e t t e r than t h a t w i t h our interpretations.
Good i n t e r p r e t a t i v e p r a c t i c e s t a r t s w i t h good
sampling procedures. This includes both t h e wise
selection o f water f o r analyses and the proper
preservation o f samples between the time o f
c o l l e c t i o n and analyses ( E l l i s and Mahon, 1977;
Shannon e t 1978). Where many hot springs
are available f o r sampling, a l l too frequently
only t h e b o i l i n g or h o t t e s t spring waters are
c o l l e c t e d while the cool and c o l d springs are
ignored. Collecting only t h e h o t t e s t waters
makes i t very d i f f i c u l t t o assess conductive and
adiabatic cooling processes and t o apply mixing
models, which a l l require knowledge o f cold,
non-thermal ground-water compositions. The best
sampling strategy i s t o c o l l e c t every available
ground-water, h o t and cold. I f f o r some reason
there i s a l i m i t a t i o n on t h e number o f samples
t h a t can be collected, one should t r y t o obtain a
s u i t e o f samples w i t h a great d i v e r s i t y i n
temperatures and compositions. A conductivity
meter or c h l o r i d e t e s t papers can be used t o
check r e l a t i v e s a l i n i t i e s o f various waters
before deciding which ones t o sample.
A t t h e t i m e o f sampling, temperatures and
measured o r estimated mass flow rates f o r each
spring and well should be recorded, whether
sampled o r not, and the t o t a l mass f l o w from t h e
area estimated. I n areas o f d i s t i n c t r a i n y and
dry seasons, springs shoul d be sampled a t
d i f f e r e n t times o f t h e year t o determine i f there
are seasonal changes i n temperature, composition,
and mass flow rates. I n areas o f few or no
f 1owing springs and no s t i n g water or
i r r i g a t i o n wells, one should consider d r i l l i n g a
few shallow wells s p e c i f i c a l l y t o obtain
ground-water samples f o r chemical analysis and t o
ne ogic gradients.
When a n a l y t i c a l data are available f o r
several water samples, i n t e r p r e t a t i o n should
s t a r t w i t h a general assessment o f how each o f
the samples r e l a t e s t o the others. Relations
i n v o l v i n g chloride are p a r t i c u l a r l y important
because c h l o r i d e i s more l i k e l y t o be
conservative i n a hydrothermal system than most
other dissolved components; t h a t is, the c h l o r i d e
concentration i n thermal water r i s i n g from a
reservoir i s not 1i k e l y t o change s i g n i f i c a n t l y
by i n t e r a c t i o n w i t h t h e surrounding rock, unless
the water traverses evaporites containing
i t e . Changes i n chloride concentration are
most l i k e l y t h e r e s u l t o f b o i l i n g (evaporation)
and mixing processes, while concentrations o f
most other components can also change as a r e s u l t
 21 1

Fournier
o f continued water-rock reactions. I
the f o l l o w i n g i n t e r p r e t i v e procedure:

1. Look for i n d i c a t i o n s of conductive cooling,

mixing, and adiabatic processes using graphs \ I
of vs. (measured mperature a t p o i n t \
, vs. I
f
o collection),
6 80 vs.
vs. and \
\ I
I
2. Look f o r i n d i c a t i o n s o f water-rock reactions \
a t intermediate temperatures using graphs o f \ I
vs. vs. c a t i o n (Na, K, L i , Ca, \ I
and and vs. (computed from \ I
t o t a l equivalents and \ I
3. Look f o r groups o f waters t h a t are \ I
compositionally s i m i l a r i n some respects but \
d i f f e r e n t from other waters. Possible ways
t o subdivide are by
and i n equivalents, and by
W
-
s a l i n i t y range.
4. Within groups o f s i m i l a r waters determine t h e
best samples or best chemical data t o use for
c a l c u l a t i n g geothermometer temperatures.
5. Determine i f t h e s i l i c a mixing model i s GF28
applicable using c r i t e r i a discussed by
Fournier and Truesdell Truesdell and
Fournier and Fournier 1981).
6. Display t h e i n t e r p r e t e d subsurface conditions -90 -80 -70 -60 - 50
on an enthalpy vs. c h l o r i d e p l o t .
7. Check t o see ift r i t i u m and stable- isotope Fig. 1. Graph o f enthalpy versus showing t h e
data are consistent w i t h t h e r e l a t i o n s shown ranges i n possible i n i t i a l reservoir
i n the enthalpy vs. c h l o r i d e p l o t . I do t h i s conditions and separated steam f o r d i f f e r e n t
w i t h graphs of enthalpy vs. isotopes and cooling mechanisms t h a t r e s u l t i n a h o t
c h l o r i d e vs. isotopes. spring water represented by p o i n t See
t e x t f o r discussions.
When steam has separated from a water before
t h a t water was c o l l e c t e d b o i l i n g spring or
flashed well water), t h e i s o t o p i c composition o f water indicates an i n i t i a l reservoir temperature
t h a t water must be corrected f o r the p a r t i t i o n i n g o f about 260°C 1134 i f t h e water cooled
o f isotopes between t h e l i q u i d and gas phases. e n t i r e l y by conduction, o r 230°C (990 i f it
Truesdell e t al. showed t h a t t h e f i n a l cooled nearly a d i a b a t i c a l l y . Point A shows the
i s o t o p i c composition o f a water t h a t flashed from i n i t i a l c o n d i t i o n o f t h e reservoir water i f
a given i n i t i a l temperature and pressure t o a cooled conductively, p o i n t the i n i t i a l
f i n a l temperature w i l l depend upon whether t h e c o n d i t i o n i f t h e water cooled a d i a b a t i c a l l y w i t h
steam remained w i t h the b o i l i n g water u n t i l i t single- stage steam separation a t atmospheric
separated a l l a t once a t a given pressure pressure, and p o i n t t h e i n i t i a l condition i f
(single- stage steam separation), or whether t h e t h e water cooled by b o i l i n g owing t o
steam underwent e i t h e r continuous or -stage decompression w i t h continuous separation o f
removal from t h e residual l i q u i d a t a succession steam. Because spring GF28 had only a moderate
o f s p e c i f i c decreasing pressures and f l o w r a t e o f 15 t o 25 a t t h e time o f
temperatures. Truesdell e t (1977) give c o l l e c t i o n and was not vigorously b o i l i n g , t h e
equations and graphs f o r determining t h e i s o t o p i c water most 1i k e l y cooled p a r t l y by conduction and
compositions o f waters t h a t r e s u l t from p a r t l y by b o i l i n g . The s t i p p l e d area i n Fig. 1
single- stage and continuous steam separation. I shows t h e range o f i n i t i a l r e s e r v o i r conditions
f i n d i t i n s t r u c t i v t o construct enthalpy vs. f o r a l l combinations o f conductive and adiabatic
and enthalpy vs. 80 diagrams using cooling. Point gives t h e i s o t o p i c
f r a c t i o n a t i o n f a c t o r s l i s t e d i n t h a t paper. For compositions o f a l l o f t h e steam t h a t would
example i n Fig. 1, p o i n t shows t h e enthalpy separate i n a single- stage process, and p o i n t
and values o f water i n a b o i l i n g spring (410 shows t h e i s o t o p i c composition o f the f i r s t steam
a f t e r an unknown amount o f steam t h a t separates a t w i t h continuous steam
separation. The s i 1 concentration i n t h a t separation. The l i n e shows how the
i s o t o p i c composition o f t h e evolved steam would
change as t h e water temperature decreased ng
t h e curve A p l o t o f enthalpy vs. 6
f o r sample GF28 would be s i m i l a r t o Fig. 1.
A consistent p i c t u r e should emerge when t h e
same waters t h a t have been p l o t t e d on an enthalpy
vs. c h l o r i d e diagram e p l o t t e d on enthalpy vs.
and enthalpy vs. diagrams. I f not,
d e f i c i e n c i e s are present i n the model or i n t h e
data.
 212

er
I n some s i t u a t i o n s t r i t i u m analyses can be water comes from a high-temperature environment
very h e l p f u l i n a geothermal exploration and picks up on t h e way t o t h e surface,
program. When applying geochemical the c o r r e c t i o n w i l l lead t o estimated
geothermometers, waters t h a t have been temperatures t h a t are t o o low. A t t h i s time
underground f o r a long time, as shown by low t h e r e i s no easy way t o de ermine when t o apply
t r i t i u m values, are more l i k e l y t o have a t t a i n e d and when t o ignore t h e orrection.
water-rock chemical e q u i l i b r i u m than those t h a t Agreement between t h e
have been underground only a short t i m e (high isotope geothermometer and
t r i t i u m ) . When assessing t h e hydrologic other geothermometers suggests t h a t t h e water had
significance of mixing o f high- and a comparatively long residence t i m e i n an
low-temperature waters it i s o f value t o know i f underground r e s e r v o i r a t about the indicated
t h e low-temperature component i s from a shallow, temperature. I n some places, such as Yellowstone
l o c a l source, or a deeper, c o l d aquifer. Where National Park, Wyoming (McKenzie and Truesdell,
hot springs ( o r well waters) contain d i f f e r e n t and Long C a l i f o r n i a (Fournier
amounts of c h l o r i d e and t r i t i u m as a r e s u l t o f e t al., the
d i f f e r e n t amounts o f mixing o f hot and c o l d geothermometer gives temperatures much higher
waters, extrapolation t o zero t r i t i u m gives t h e than those indicated by t h e s i l i c a and c a t i o n
maximum c h l o r i d e i n the deep component. Repeat methods, but i s i n agreement w i t h
analyses of t r i t i u m and c h l o r i d e over a mixing model temperatures. When t h e
protracted p e r i o d o f t i m e can be used t o confirm temperature i s higher than other
t h a t t h e deep component has zero t r i t i u m . geothermometer temperatures, i t suggests t h a t
Information about t h e c h l o r i d e concentration i n intermediate temperature reservoirs are present
t h e deep, high-temperature component can, i n t u r n and t h a t water moves through them w i t h residence
be used i n an enthalpy- chloride mixing model t o times o f a few weeks t o a few months.
estimate t h e temperature o f t h a t hot-water
AN UPDATE ON THE SOLUBILITY OF QUARTZ AND
When i n t e r p r e t i n g chemical geothermometers,
keep i n mind the e f f e c t s t h a t d i f f e r e n t
ogic conditions may have upon hot- spring Over the past several years there has been an
compositions. The r e l i a b i l i t y or f a i t h t h a t one a t i o n of experimental r e s u l t s by various
places upon p a r t i c u l a r geothermometer r e s u l t s workers f o r t h e s o l u b i l i t y of quartz i n water a t
should depend upon t h e number o f thermal waters and near t h e vapor pressure o f t h e s o l u t i o n
t h a t were analyzed and t h e mass flow r a t e s and (Fournier and Potter, 1982). The data suggest
measured temperatures o f those waters. t h a t t h e s o l u b i l i t y o f quartz a t 250°C i s
If the silica, and s l i g h t l y l e s s than t h a t given by Fournier and
geothermometers 11 give temperatures i n excess Rowe A revised equation f o r t h e
of 150°C and concentrations are r e l a t i v e l y s o l u b i l i t y o f quartz i n water along t h e
low, chances are good t h a t a deep r e s e r v o i r vapor-pressure curve f o r t h e temperature range
temperature w i l l be as great or greater than t h a t 25" t o i s given by Fournier and Potter ( i n
i n d i c a t e d by t h e geothermometers. I f t h e s i l i c a press) as
temperature i s much l e s s than t h e
and temperatures, then + + + +
e i t h e r s i l i c a may have p r e c i p i t a t e d from s o l u t i o n
a f t e r leaving t h e reservoir or t h e water i s a where t i s temperature i n degrees Celsius, S
mixed water t h a t d i d not r e - e q u i l i b r a t e a f t e r s i l i c a concentration i n and through
mixing. I f t h e s i l i c a (chalcedony) and are constants given i n Table 1.
geothermometers give temperatures bel ow 100°C and Other vapor-pressure quartz- sol i t y curves
gives a temperature g r e a t l y above the have been suggested (Walther and Helgeson, 1977;
temperature probably i s i n error. I f a Fleming and Crerar, 1982) t h a t are s i g n i f i c a n t l y
water contains l i t t l e Mg and the below t h e Fournier and Potter ( i n press) curve.
temperature i s several degrees above t h e I believe t h a t the calculated values o f Walther
temperature, the temperature may be too and Helgeson are low because they assumed
high because p r e c i p i t a t e d from s o l u t i o n t h a t s o l u b i l i t i e s of quartz a t 1013 bars reported
before the water was c o l l e c t e d (or a f t e r by et were correct. It now
c o l l e c t i o n ift h e sample was not a c i d i f i e d ) . The appears t h a t a t 1013 bars and temperatures below
p r e c i p i t a t i o n of i s l i k e l y t o have 200°C Morey e t measured t h e s o l u b i l i t y
influenced the calculated temperature i f o f chalcedony rather than quartz. The p o s i t i o n
t h e s o l u t i o n was saturated i n respect t o c a l c i t e o f t h e Fleming and Crerar curve i s
a t t h e t i m e and place o f sampling. However, even strongly influenced by r e s u l t s o f experiments by
though t h e s o l u t i o n may be unsaturated w i t h Crerar and Anderson (1971). Fournier and
respect t o c a l c i t e a t t h e time and place o f Fournier and Potter (1982) concluded t h a t the
collection, may have p r e c i p i t a t e d from a experimental technique employed by Crerar and
b o i l i n g s o l u t i o n underground, w i t h t h e s o l u t i o n Anderson was l i k e l y t o have produced
subsequently becoming unsaturated w i t h q u a r t z - s o l u b i l i t y values t h a t were too low. I f
during subsequent cool ing. the Fournier and Potter ( i n press)
The a p p l i c a t i o n of an correction t o i t y curve i s correct, then t h e
the geothermometer may be essential i f a e x c e l l e n t discussion Fleming and Crerar
water r e a l l y comes from a low-temperature of e f f e c t s on quartz s o l u b i l i t y and
underground environment. However, i f a

appl i c a t i o n s t o geothermal f l u i d processing
should be modified, using
+ + + +
where i s t h e neutral molal s o l u b i l i t y o f
quartz, T i s absolute temperature, and
are constants given i n Table 1.
I n the
Fournier and Rowe
geothermometer description by
two reference curves
were drawn; one showed dissolved s i l i c a w i t h
conductive cooling and the other dissolved s i l i c a
a f t e r adiabatic cooling t o 100°C a t constant
enthalpy. However, where b o i l i n g springs occur
a t high elevations, adiabatic cooling continues
t o temperatures s i g n i f i c a n t l y 1ower than 100°C.
Also, w e l l waters are comnonly sampled a f t e r
steam separation a t temperatures above 100°C.
Fournier and Potter ( i n press) use a p l o t o f
dissolved s i l i c a vs enthalpy (Fig. as a simple
method o f c o r r e c t i n g f o r steam separation a t any
temperature. The enthalpy o f l i q u i d water a t t h e
I t h e basis o f a small amount o f data Fournier and
400
200
0
0 1000 1500 2000
Enthalpy ,
Fig. Dissolved s i l i c a versus enthalpy f o r
quartz dissolved i n pure water a t t h e vapor
pressure o f t h e solutions. See t e x t f o r
discussion.
c o l l e c t i o n temperature (or c o l l e c t i o n pressure)
can be determined from steam t a b l e s (Keenan
e t al., 1969). Points C and E i n Fig. 2
represent two samples c o l l e c t e d a f t e r steam 1oss
a t d i f f e r e n t temperatures, and t h e l i n e AB shows
t h e s o l u b i l i t y o f quartz a t t h e vapor pressure o f
t h e s o l u t i o n .as a f u n c t i o n o f enthalpy. Points
and show t h e enthalpy o f steam i n
e q u i l i b r i u m w i t h p o i n t s C and E respectively.
The i n t e r s e c t i o n s of t h e l i n e s drawn from to
C and t o E w i t h curve AB (points F and D
respectively) g i v e t h e i n i t i a l enthalpies of t h e
r e s e r v o i r f l u i d s before adiabatic cooling.
Fournier and Potter ( i n press) give t h e equation
of l i n e A6 as
S + + + + Fig. 3. Quartz dissolved i n water and 4 m NaCl
where S i s s i l i c a concentration i n
21 3
Fournier
enthalpy o f l i q u i d water i n and through
are constants given i n Table 1. They a l s o
g i v e a computer program i n BASIC t o c a l c u l a t e
(2) (quartz) geothermometer temperatures w i t h
adiabatic cooling t o any temperature, w i t h
i n i t i a l r e s e r v o i r temperatures up t o and a
computer program t o c a l c u l a t e mixing model
temperatures w i t h or without steam loss before
.
m i x i ng
Fournier and Potter (1982) found that, i n
logarithmic p l o t s o f dissolved s i l i c a vs.
s p e c i f i c volume o f water, t h e experimental data
l i e along smooth, nearly p a r a l l e l isothermal
curves, and they devised an equation t h a t f i t s
most o f the data q u i t e well. The Fournier and
Potter (1982) equation allows t h e
geothermometer, derived vapor f o r pressure
conditions, t o be corrected f o r pressure e f f e c t s
i n deep reservoirs.
Up t o t h i s p o i n t s i l i c a geothermometry has
been discussed f o r d i l u t e solutions, but what i s
t h e e f f e c t of dissolved s a l t ? This i s o f great
i n t e r e s t from the p o i n t o f view o f scaling. On
Rowe concluded t h a t t h e a d d i t i o n o f 2 m
NaCl generally does not s i g n i f i c a n t l y influence
t h e s o l u b i l i t y o f quartz. That conclusion now
appears v a l i d a t the vapor pressure o f t h e
s o l u t i o n only a t temperatures below about 260°C
and a t high pressures bars) below about
and when are expressed i n
units o f Figure 3 shows the s o l u b i l i t y of
quartz i n pure water and i n 4 m NaCl a t as
a function o f pressure. I n Fig. 3, note the
6 I500
500
400
300
a
200
a t 350°C.
 214

Four n e r
difference i n r e l a t i v e p o s i t i o n s o f t h e pure REFERENCES
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potentials, f a r i n excess of p o t e n t i a l s expected enthalpy- chloride diagrams i n t h e p r e d i c t i o n
from t h e pure water data. o f underground conditions i n hot spring
F i n a l l y , I would l i k e t o speculate b r i e f l y systems: Journal o f Volcanology and
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d i l u t e water t h a t i s heated t o temperatures above polymorphs o f high pressures and
about 350" t o 400°C w i l l p r e c i p i t a t e quartz as a temperatures: American Journal Science, v.
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brine. I f a brine f i l l s t h e open space on t h e L. and L. J. P. Muffler, editors, p.
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gradient across t h a t b a r r i e r might be very l a r g e Fournier, R. O., i n press, A method o f
and t h e f l u i d pressure i n t h e pore spaces on t h e c a l c u l a t i n g quartz s o l u b i l i t i e s i n aqueous
high-temperature side equal t o 1i t h o s t a t i c sodium c h l o r i d e solutions: Geochemica e t
pressure. Those who d r i l l toward very high im i ca Acta.
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temperatures and f l u i d pressures might suddenly Calculation o f amorphous s i l i c a s o l u b i l i t i e s
increase f a r more r a p i d l y than anticipated. a t 25" t o 300°C and apparent c a t i o n hydration
numbers i n aqueous s a l t solutions using t h e
concept of e f f e c t i v e density o f water:
Geochimica e t Cosmochimica Acta.
 21 5

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C. F., 1980, I n t e r p r e t a t i o n o f chemical
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geothermal w e l l s a t Coso, C a l i f o r n i a :
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Journal o f Research, v. no. 3, p.
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Table 1--Constants f o r equations 1, 2, and 3

Equation 1 Equation 2 Equation 3
-4.2198 x = 1.3290 x El = -3.5532 x
C2 2.8831 x = -9.4573 x E2 = 1.4600 x
x D3 -7.5578 x E3 = x
C4 3.1665 x D4 = 1.2488 x E4 = 1.2305 x
7.7034 x = -8.2181 x E5 = -4.9421 x