Geothermics (i97o) - SPECIALISSUE 2
U. N. Symposium on the Development and Utilization o~ Geothermal Resources. Pisa I~7o. Vol. 2, Par~
Quantitative interpretation of Chemical Characteristics
of Hydrothermal Systems
A. I. ELLIS *
ABSTRACT
The paper gives a brief review of chemical reactions and
equilibria which occur in hydrothermal systems.
Experimental work, reacting rocks and water at high tern.
perature, has shown that it is not always necestau-y to postu-
late a magmatic fluid origin for chemicals in natural hot
waters. Only a few elements in watch, such as CI, B, Cs, are
not involved to any great extent in temperature and pressure
dependent chemical equilibria with rock minerals. T h e e ele-
ments are useful in identifying and following flows of partic-
ular waters within a field.
From knowledge of acid-base equilibria, the pH of hot
water at deep levels can be obtained, and also the variation
in pH with time during drillhol production. Combined with
metal ion concentrations, the pH enables an interpretation in
terms of water chemistry of mineral alteration a ~ m b l a g ~ ,
including the tendency for calcite formation. Phase diagrams,
using ratios a.Jau, a~a., aodaa., a~/a~-., etc., as parameters
show how mineral assemblages in hydrothermally altered rock
change as waters cool and lose carbon dioxide on approaching
the surface.
As equilibrium exists l~tween hot water and rock miner-
als at deep levels, the silica concentrations and Na/K ratios
in waters flowing rapidly to the surface give an ~'la-ate
measure of the deep temperature. Also, the pH of deep hot
water is a function of the water salinity, except in areas where
waters contact sulfur deposits. It is shown that calcium con-
centration in thermal waters, for a given temperature, is ap-
proximately proportional to the square of sodium ion con-
centrations.
Estimates of mco2 in underground waters can be made
through knowledge of any two of the variables, salinity, cal-
cium concentration, and bicarbonate concentration in surface
discharges. The concentration of carbon dioxide in deep hot
water is the factor determining whether or not waters will
deposit calcite in drillpipes. With increasing tacos, calcium
carbonate replaces minerals such as wairakite and epidote as
the equilibrium calcium phase in the rock.
An outline is given of isotope exchange equilibria which
can be used for determining temperatures at depth in a field.
Oxygen and sulfur isotope exchange, both between solutes,
and between solutes and minerals, are the most promising
in this .respect.
Base metal sulfide deposits are not limited to hydro-
thermal areas of highly saline waters. Minerals such as galena,
sphalerite, and chalcopyrite are found at deep levels in the
Broadlands geothermal field of dilute chloride waters, while
at the surface in the area precipitates of antimony and arsenic
sulfides rich in gold, silver, thallium, and mercury are formed
from spring and drillhole waters.
Introduction
In the last 6-8 years there has been an increasing
awareness that the composition of n a t u r a l high temper-
ature waters ( a p p r e c i a b l y over 100C) and steam in
* Chemistry Division, D.S.I.R., Petone, New Zealand.
516
geothermal areas results largely from the t e m p e r a t u r e ,
pressure, rock-compoSitional e n v i r o n m e n t in the fields.
G e o c h e m i s t r y has progressed to the stage w h e r e through
analysis and interpretation of surface discharges of
steam a n d w a t e r , m u c h can be d e d u c e d a b o u t tempera-
tures, hydrostatic pressures, gas pressures, rock types
a n d flow processes within the h y d r o t h e r m a l systems.
A correlation of w a t e r compositions with their condi-
tions of f o r m a t i o n and storage has obvious implications
as far as g e o t h e r m a l p o w e r d e v e l o p m e n t is concerned.
W h e r e a s at the time of the 1961 U.N. Conference on
N e w Sources of Energy, s e m i e m p i r i e a l relationships
b e t w e e n e n v i r o n m e n t and chemistry of fluids were exa-
mined, discussion is n o w on a m o r e quantitative basis.
This p a p e r sttmmariscs some i m p o r t a n t chemical
reactions a n d e q u i l i b r i a for which information has be-
come available. M a n y of the topics have already been
discussed in detail elsewhere so that only an outline is
given, w i t h reference to some relevant publications.
Some references s u m m a r i s i n g aspects of N e w Z e a l a n d
geothermal chemical w o r k are ELLIS and MAriON
(1964), ELLIS (1967, 1969), and ELLIS ET AL. (1970).
In the last reference the a p p l i c a t i o n of geochemistry
to geothermal systems is revised, with p a r t i c u l a r referen-
ce to the h o t - w a t e r type of geothermal field (e. g., as
at W a i r a k e i , Salton Sea, Mexicali, Otake).
C o m p o s i t i o n s of w a t e r a n d s t e a m
T h e compositions of w a t e r and steam are available
from m a n y geothermal areas. T a b l e I gives a compila-
tion of w a t e r compositions from h y d r o t h e r m a l areas in
several countries. W a t e r t e m p e r a t u r e s for the fields ta-
ken as examples range from 100 to 340C, while the
dissolved salts in the waters, expressed as chloride con-
centrations, range from about 30 to 155,000 p p m .
T h e compositions shown in the T a b l e show a
correlation between the w a t e r t e m p e r a t u r e and the sil-
ica concentrations (except for the Salton Sea area
w a t e r analysis) a n d an inverse relationship between
t e m p e r a t u r e and the ratios N a / K and N a / R b . The
calcium and magnesium concentrations are related to
the salinity of the water, but not in a linear manner.
Except for the basaltic Iceland geothermal areas, the
 waters contain unusually high concentrations of the
elements lithium, caesium, fluoride, boron and arsenic,
the elements which in the past often have been taken
to indicate the presence of magmatic fluids in geo-
thermal waters.
Table 2 gives the composition of steam from geo-
thermal drillholes in various parts of the world, includ-
ing both Larderello and The Geysers, where steam
is tapped by drillholes, and the more frequently occur-
ring hot water systems found in areas such as Japan,
Iceland, New Zealand, Mexico, and Central and South
America.
In the natural steam areas, the steam composition
is not dependent on the pressure of collection. Howe-
ver, in high temperature water areas, boiling occurs in
either the drill pipes or natural flow channels as wat-
ers rise to the surface. After only a few percent steam
separation from high temperature water, the steam
phase contains most of the less soluble gases (mainly
CO.~, H~.S, CH,, H.~ and N.~). In the hot water areas
the concentration of gases in the steam phase depends
on the percentage of steam and water present in the
flow at the pressure of collection. The amount of gas
in the steam varies widely between the different fields
and is one of the important factors in planning power
development. The Ahuachapan field in El Salvador,
with about 0.005 mole percent gas in the steam, has
the lowest gas so far observed, while drillholes in the
Ngawha area of New Zealand, and the Monte Amiata
field in Italy (CATALDI 1967), produced a mixture of
gas, steam, and water in comparable proportions. In
all cases carbon dioxide is the predominant gas pres-
ent, although hydrogen sulfide can reach major pro-
portions in areas where sulfur occurs at deep levels
(e. g., in the Tatun geothermal areas, Taiwan).
Origin of elements
Reasons may be sought for the composition of
waters and steam in particular geothermal areas. The
origin of the chemical constituents associated with
geothermal fluids is a controversial one. ELLIS and
MAriON (1964, 1967) discussed the composition of high
temperature waters in volcanic areas, while FACCA and
Tor~Ar~i (1964) examined the origin of constituents in
natural steam areas. FACCA and TONANX pointed out
that there was little evidence for a magmatic origin
of the gases carbon dioxide, hydrogen sulfide, hydro-
carbons and ammonia in the Larderello steam dischar-
ges, and simple decomposition reactions in the hot se-
dimentary rocks could account for the gaseous constit-
uents in the steam. The experiments of ELLIS and
MAHON, reacting various volcanic and sedimentary
rocks with high temperature water (100C to 600C)
under controlled conditions in pressure vessels gave
useful evidence on thermal water compositions. Firstly,
it was found that elements such as fluoride, chloride
and boron were readily dissolved from average rocks.
even before appreciable hydrothermal alteration occur-
red. Also, appreciable concentrations of rubidium and
caesium appeared in the hot water phase when rhyo-
litic volcanic rocks recrystallised to secondary minerals.
Secondly, the experiments emphasised that the concen-
trations of major rockforming constituents such as sil-
ica, alumina, sodium, potassium, calcium, magnesium,
iron and manganese were limited in solution by par-
ticular mineral-solution equilibria. Minor constituents
such as fluoride, carbonate and sulfate were limited
in natural hot waters and experimental solutions by
the solubility of particular sparingly-soluble minerals
such as fluorite, calcite and anhydrite. It became ap-
parent from the experiments that a natural hydrother-
real system with a rock/water ratio of the order of
10-20 could, under static conditions, produce through
the reaction of water and rock, solution compositions
typical of the New Zealand Wairakei-Broadlands-Ka-
werau type of system. Elements such as rubidium, li-
thium, caesium, boron, and fluoride, often hitherto re-
garded as magrnatic contributions to hydrothermal sys-
tems, could be explained simply through reaction of
water and rock at temperatures very much below those
of rock melting.
Isotopic ratios for both hydrogen and oxygen in
water from natural flows and from geothermal drillho-
les have revealed in many regions that the waters consist
almost entirely of local meteoric waters which have
been heated at deep levels, where they became char-
ged with chemicals. There is geological evidence that
particular hydrothermal systems may have been in exist-
ence for periods of 10~ years (WmTIZ 1957; GRINDLEY
1965). Many unsolved questions exist regarding the mech-
anism by which a supply of heat and chemicals could
be maintained to enable a flow-through hydrothermal
system to operate continuously for this period of time.
The experimental evidence of ELLIS and MAHON(1964,
1967), and water isotope evidence does not rule out
the possibility of magmatic solutions contributing to
the ehernical make-up of hydrothermal systems, but
points out that it would be almost impossible chemi-
cally, to distinguish natural hot waters which do or
do not have magmatic solution contributions. The iso-
topic make-up of particular elements in hydrothermal
solutions does, however, have the possibility of distin-
guishing origins.
From a chemical and heat balance of the Waira-
kei type of hydrothermal system ELLIS (1966) showed
that approximately equal volumes of rhyolitic rocks, or
rhyolitic magma, would be required to supply the che-
mical output, or heat output, respectively, of the Wai-
rakei system for a given period. The problems of ex-
tracting heat and chemicals from hot rock. at deep levels
are both associated with the difficultyof obtaining suf-
ficient contact between water and rock on a continuing
517
 TABLE 1. - - Composition o~ thermal

Concentrations in mg/kg for water collected

Approx. Depth pH
Source and Reference temp. (m) (20 )
(0C) Li Na K Rb Cs Mg Ca

Drillhole, Reykjavik
Iceland (~) 100 600 8.6 < 0.1 95 1.5 < 0.02 .< 0.02 0.5
Hole G-3, Hveragerdi,
Iceland (:) 216 650 9.6 0.3 212 27 0.04 < 0.02 0.0 1.5

Pauzhetsk drillholes, 170. 195 300- 400 8.9 Na+K

940 7 119
Kamchatka, U.S.S.R. (-~)
Drillhole 1, Ngawha 230 585 7.4 12.2 950 80 0.8 0.4 Ca + Mg
New Zealand (3) 28
Drillhole 2, Broadlands
New Zealand (s) 260 1030 8.3 11.7 1050 210 2.2 1.7 0.1 2.2
Drillhole 24, Wairakei
New Zealand (s) 250 830 8.3 13.2 1250 210 2.9 2.5 0.04 12
Drillhole 2, Rotokaua
New Zealand (s) 220 880 7.8 10,2 1525 176 -- 50
Hole El03, Tahuangtsui
Tatun, Taiwan (4) 200 I000 3.2 282 54 -- 89 0
Hole I, Matsukawa,
Japan (5) ,,~ 300 945 4.9 264 144 ~ --- 8.7 22.9
Hole 5, Mexicali
Mexico (s) 340 1285 -- 19 5820 1570 ~ -- 8 280
Hole I, I.I.D. Salton Sea
California (r) * 340 1600 4.7 215 50400 17500 135 14 54 28OOO

* Concentrations and pH in deep aquifer.

Total C02; SiOz; etc., is the total COz + HCO3-- + CO3--= expressed as CO2; silica + silicate as SiO2; etc.

TABL~ 2. ~ Comlmaition

Steam "Iotal gas

Pressure
Source Temp. (arm) fraction in steam
Source depth (oC) in discharge at pressure
(m) abs. at pressure (mole %)

Average drillhole, Larderello 500 220 6 1.00 * 2.0

Average drillhole, The Geysers 150-350 200 7.8 1.00 * 0.3
Hole 3, Matsukawa 1207 300 4.5 0.75 0.5-06
Drillholes, Reykjavik 500 ~ I00 water only
Hole G-3, Hveragerdi 400 216 1 0.20 0.015
Average drillhole, Wairakei 650 26O 1 0.32 0.063
Hole II, Broadlands, N.Z. 760 260 1 l
0.355 0.61
Hole I, Ngawha, N l . 585 228 1 0.33 20
Hole E202, Matsao, Tatun 500 200 1 5.8
Hole 5, Mexicali 1285 340 1 0.44 0.54
Drillholes, Sahon Sea 1500-1800 300-350 16 0.18 0.1-1.0
Hole I, Ahuachapan 1195 230 I 0.23 0.005
Hole 7, Otake, Japan 350 230 3.o 0.215 0.10

* Area of steam discharge only.

Note: H C means total hydrocarbon gases.

518
waters /rom springs and drillholes

at a t m o s p h e r i c p r e s s u r e f r o m discharge M o l e c u l a r Ratios

Total Total Total Total

Mn Fe F CI Br I SO( As C02 SiO2 B NI-h C1/SO~ CUB C1/F Na/Li Na/K

-- -- -- 31 -- -- 16 -- 58 155 0.03 0.1 5.2 400 -- > 300 110

0.00 0.1 1.9 197 0.45 0.0 61 -- 55 480 0.6 0.1 8.7 100 55 200 13

-- ~ -- 1470 -- -- 164 -- 61 170 31,3 0.7 24 14.3 -- -- --

0.02 0.1 0.8 1625 -- 1.3 17 -- 61 460 1200 46 260 0.41 1100 23.5 20

0.009 0.25 7.3 1743 5,7 0.8 8 8.! 128 805 48.2 2.1 590 11.0 128 27 8.5

0.015 0.05 8.4 2210 5.5 0.3 28 4.5 17 670 28.8 0.2 210 23.5 140 28.5 10.1

-- -- 6.b 2675 -- 0.2 120 -- 55 430 102 3.2 60 8.0 217 45 14.7

-- 1363 -- 1223 -- -- 1462 -- -- 170 -- -- 2.7,6 . . . . 8.9

-- 508 -- 12.4 -- -- 1780 -- 26 635 61.1 ~ 0.019 0.062 -- -- 3.1

-- 0.2 -- 10420 l~t.1 3.1 0.0 -- 1653 740 12.4 -- -- 256 -- 92 6.3

1400 2290 15 155000 120 18 5 12 7100 400 390 386 80000 121 5500 705 4.9

Re/erences : (~) C h e m i s t r y D i v i s i o n , D . S J . R . , N.Z. a n d pers. c o m m . f r o m (7) y . C. L l u (pers. comm.).

D r G. B o v v ~ , s s o N , a n d D r G. E. S~VALVASON. (~) NAtoJ~tu'~, SUMI 1967
(=) A v e r y ~ r AL., 1961. (e) MmtC.A~ 1966.
(~) C h e m i s t r y D i v i s i o n , D . S J . R . , N.Z. (7) MUFFt.Zg, WHrr~ 1969.

o~ steam /rom drillholes

G a s c o m p o s i t i o n (mole %)

CO= H.~ H='=C H2 +N2A 02 NI'Ia I-hBO3 Ref.

92.8 2.5 2.0 0.55 1.70 0,45 (1)

69.3 3.0 11.8 12.7 1.6 1.6 (2)
85.3 ,1., R e m a i n d e r 3.5% (3)
100 (4)
73.7 7.3 0.4 5.7 12.9 (4)
91.7 4.4 0.9 0.8 1.5 0.6 0.05 (5)
94.8 2.1 1.2 0.2 1.5 0.2 (~)
93.9 0.7 4.1 0.5 0.8 0.04 (~)
49.3 41.7 Remainder 9.0% (s)
81.4 3.6 7.0 0.5 7.0 0.4 (7)
90 Remainder mainly H~S + m i n o r H C a n d H2 (s)
50-80 0 10-40 2-10 (4)
96.7 0.65 R e m a i n d e r 2.7% (o)

Re[erenees : (1) PI~cTA 1954. (4) SIGVALDASON (pers. comm.). (7) ALONSO 1966.
(2) M c N r r r 1963. (5) CHEMISTRY DIVISION, D.S.I.R., N.Z. (8) HFJ.~_SO~ 1968.
(a) AZUMA KAKO CO. LTD. 1966. 18) Y. C. LIU (pers. comm.). (g) NUGUcItI 1966.

519
basis. In areas of dense rock, continuous extraction of
chemicals by hot water for period of 104- 105 years
seems unlikely. In an area of this type (e. g., Steam-
boat Springs, Nevada), cycling of meteoric water
through the top of a magma chamber at deep levels
seems a likely model, if continuous long-term outflow
of the system is postulated.
In a permeable volcanic system such as at Waira-
kei, if the water output of 10 TM kg water/year was con-
stant for the suggested age of 500,000 years (GRINDLEY
1965), the water of the estimated cubic volume of the hy-
drothermal system (500 km ~) would have to be replaced
100 times, if the rock water ratio was ten. On a chem-
ical leaching explanation for the water compositions,
very dilute waters would be expected after I00 cycles
have been completed. There is, however, no certainty
that water flows have been continuous, or water com-
positions constant, over the lifetime of the system. It is
possible that over periods of approximately 105 years,
water is heated under almost static conditions at deep
levels, and convective inflow and outflow occurs only
during comparatively short periods of the order of l0 S
years, when new flow channels are created by major
tectonic activity. Cessation of flow may be caused
through the sealing of natural flow channels by quartz
and calcite.
Evidence from tritium and ~'C determinations on
water and steam flows in many geothermal areas (CP.AtG
1963; WILSOr~ 1965) indicates the turnover time of
the water heating cycle is well in excess of 50 years.
While the mechanism of deep heat and chemical trans-
ference is of great academic interest, from point of
view of power production over periods of a few tens
of years, hydrothermal systems at levels beneath l - 3
km can for many purposes be regarded essentially as
static bodies of hot water, giving rise to production of
dry steam, or hot water, at shallow levels, depending
on the temperature of the deep water and the character-
istics of the rock system (lAMES 1968).
Soluble ~ e l e m e n t c o n c e n t r a t i o n s
There are few elements present in natural hot
waters which are not controlled by temperature-and
pressure-dependent chemical equilibria involving rock
minerals. The main exceptions are the elements chlo-
rine, bromine, boron and caesium which act essen-
tially as soluble elements in most situations, and also
to a limited extent, fluoride, lithium, and arsenic in
springs of major outflow and waters at deep levels.
The <<~oluble )) type of element is most useful in iden-
tifying particular waters in a hydrothermal system, and
in predicting the type of rocks with which the waters
have had contact (ELLIS and MAHON 1964; ELLIS
1967). For example, low lithium and caesium is common
in basaltic areas. Low C1/B ratios, due to high bo-
ron concentrations, are common in hot waters of or-
ganic-rich sedimentary rocks (e. g., the Ngawha water
520
analysis, Table 1) where ammonia and carbon dioxide
are also commonly high in concentration.
The ratio C1/B is useful in identifying waters with-
in a hydrothermal area. Many areas have a constant
C1/B ratio in all hot waters, but occasionally more
than one group of values occurs in an area. or values
show a continuous trend across the field. More than
one aquifer may be indicated, or in the last situation
extraction of boron from a particular rock type may
occur in a sector of the field. Figure 1 gives the molec-
ular proportions of chloride, boron, and bicarbonate
in a range of waters in New Zealand hydrothermal
areas, both for hot spring and drillhole waters. The
homogeneity of waters in most of the areas is evident,
except for Waiotapu and Broadlands. In the Broad-
lands-Ohaki area, in the most eastern part of the field,
tow CI/B ratios occur through reaction of the hot wat-
er with a greywacke-argillite formation. There is a rap-
id trend in values across this part of the field.
The identity of waters can, in the same way, be
examined through the ratios Cl/Cs, C1/As a n d Cl/F.
MAnes (1970) gives greater detail on the use of these
ratios in surveying geothermal areas.
Solute equilibria
Within thermal systems of the hot-water type the-
re are numerous chemical equilibria, both between
solute species, and between solute and rock minerals.
Many acid/base equilibria exist in natural hot wat-
ers, e.g., carbonic acid-bicarbonate, hydrogen sulfide-
bisulfide, boric acid-borate, hydrogen fluoride-fluoride.
ammonium-ammonia, bisulfate-sulfate and silicic acid-
silicate. Within a geothermal field the pH of hot wat-
ers is a useful variable through which to examine va-
rious mineral solubilities and stabilities. Water pH val-
ues at the surface in New Zealand areas are common-
ly in the range 6.5 - 9.0, but this is after the waters
have boiled off steam and carbon dioxide into the at-
mosphere. As outlined by ELLIS (1967) the original pH
of the high temperature water at deep levels can be cal-
culated from analysis of drillhole steam+water dis-
charges. The original water composition at depth is
obtained by combining the constituents in the steam
and water discharged from a drillhole at a known
steam/water ratio. The combination of steam and wat-
er analyses gives a significant deep composition only
when drillholes discharge a steam/water mixture of
enthalpy equal to that of water at the measured under-
ground temperature, and where other characteristics of
the discharge indicate that it has been derived from
a single liquid phase underground.
Successive approximation calculations (ELLIS
1967), give the equilibrium concentrations of the va-
rious acids and bases in the deep waters.
Information is available on values of ionisation
constants of weak acid/base equilibria at high tempera-
tures (BARN,ES ET AL. 1966; ELLIS 1967; HELGESON
1967a). Calculated pH values for the waters supplying
deep drillholes in several New Zealand hydrothermal
areas are shown in Table 3.
A]ong with direct observations over the years of
changes in the chemistry of waters and steam from a
field (salt concentrations, ion ratios, gas concentra-
tions, gas ratios), changes in derived quantities such as
the underground pH of waters can give useful infor-
mation. Draw-down of hydrostatic pressures in the west-
ern Wairakei production zone has led to boiling of
waters at successively deeper levels, and gas concentra-

Cl

k+ 4
j
_ x /
'" "

4 ~ i 9 -~,lJBr lt, 4 =

o=,
X / Deep drillholes
/ F,/ Shallowdrillholes
X Springs 1
/X Ngawha
--X , xeNg I
/ v v v v v v V v v
10 HCO3 10 B
FIG. 1 -- Molecular proportions o/chloride, boron, and bicarbonate in waters of various hydrothermal areas o/ New Zealand.

T~LE 3.
pH values (--log all) for deep waters supplying drillholes in six areas of New Zealand.
Trends with time at Wairakei over 8 years are given.
Area W. Broadlands Kawerau Waintapu Rotokaua
pH 6.3 6.2 6.1 5.9
Area Te Kopia Wairakei Wairakei Wairakei Wairakei
(1958) (1962) (1964) (1966)
pH 7.1 6.3 6.6 6.9 7.0

521
tions in water tapped by drillholes at a particular level 7I

6J_
have consequently decreased with time (GLovER 1970). i I i
Water pH values underground have risen and Table 3
gives the changes in average deep water pH from 1958
to 1966.
Allaite J
Over the years the Wairakei waters have also
changed from being slightly under-saturated with cal-
"~Wcairctke; 7 i
cite (see Figure 7) to a level of saturation with respect Nca-montmoriltonit e
i
to this mineral. Whereas in 1958 there was a differ- 4i
A
ence in pH of about 0.5 units between that for calcite
precipitation and the estimated water pH, the differ-
ence is now zero.
Kaolinite I K-micra K-Fet~spar I
Mineral soluteequilibria
MAHON (1966) and FOURNIER and Rowe (1966) t
observed independently that high temperature waters i
within hydrothermal areas are saturated with silica in
equilibrium with quartz. This has made possible a sim-
ple chemical method for determining temperatures of i I
waters supplying either drillholes or hot springs of 1 2 w,~ ( % / caM) 5 6 7
high discharge. By assuming that waters reach the sur-
face by an adiabatic isoenthalpic expansion of the orig- Fm. 3. - - Phase diagram of sodium and potassium minerals
commonly found in hydrothermal alteration, relating miner-
inal high temperature water to a steam-water mixtu- al stabilities to the ion activity ratios a~.~/am and aK/a~.
re, Figure 2 gives the silica concentrations in boiling The Wairakei composition point is calc,tlated from ana-
lyses o/ drillhole discharges. (Published from ELLIS 1969
surface waters which correspond to particular under- with permission o/ the Institution o/ Mining and Metal-
ground water temperatures. Use of this method has lurgy: the log (aK/a,) scale has been revised slightly /or
pressure e[]ects).
enabled measurement of temperatures in New Zealand
geothermal areas to within about 4- 2C (MAriON 1966).
Moreover, the measurement is made while driUholes It was shown by ELLIS (1969) that in undisturb-
discharge, and the estimate is for waters which supply ed hydrothermal systems it is common for the pH of
the discharge. Physical measurements made downhole the underground waters to be controlled by an equilib-
during static conditions are often affected by convec- rium between the solution and alumino-silicates in the
tion within the hole. secondary alteration mineral assemblages. HEMLEY
and loses (1964) determined equilibrium constants for
the following type of reactions:

3/2 K - f e l d s p a r + H + = 1 / 2 K - m i c a + 3 Q u a r t z + K + (1)
1000 - - 7 albite 4- 6 H + 4- 3H~O = 3 N a - M o n t m o r i l l o n i t e
+ 10 Q u a r t z 4- 6 N a + (2)

Certain activity ratios of ions aK/aH arid aN,/a H

800 respectively, exist at a particular temperature and pres-
sure, during the coexistence of the minerals taking
part in the reaction. Equilibrium constants are availa-
ble over a range of temperatures for individual potas-
sium/hydrogen and sodium/hydrogen exchange reac-
O5 tions of this type (HEMLEY and IONES 1964).
HELGESON (1967b), produced a combined phase
diagram for sodium and potassium minerals at 300 , in
terms of the ion ratios aN./a, and aK/a.. Figure 3 is
a diagram of this type for 250.
In the Wairakei system, albite, potassium feldspar
I
200 Aquifer Tom!~erature(*C) 3P and potassium mica exist in equilibrium in the deep
Fie. 2. - - The relationship between silica concentrations in alteration mineral assemblage. The deep water compo-
100C waters at the surface and the original under- sition obtained by calculation from drillhole dischar-
ground temperature el water which was saturated with ge analytical data. is shown to coincide within pos-
quartz. Cocling o] water is by adiabatic isoenthalpic ex-
pansion into steam and water on route to the surface. sible errors with the point A for the co-existence of the

522
 three minerals derived from HEMLEY and IONES' (1964)
experimental data. In several other areas the waters 16
have also been found to have sodium/hydrogen and po-
tassium/hydrogen ratios equivalent to that for equilib-
rium with albite, potassium feldspar, and potassium
mica.
The discussion of chemical equilibria which fol-
lows will apply quantitatively only at temperatures
above about 175-200C, as the alumino-silicate equilib- 13
ria at lower temperatures are not certain. The existen-
Atomic
ce of an equilibrium between alteration minerals and ratio
deep hot solution has several implications. For co-exi- Na/K
stence of sodium and potassium feldspars, a certain
Na/K ratio exists in solution at a given temperature 11
and pressure (the pressure effect is minor and is not
considered further in this discussion). ELLIS and 10
MAHON (1967) showed that the reaction of hot water
with volcanic rocks produced temperature-dependent
Na/K ratios in solution which were in agreement with
the ratios in high temperature thermal waters of known
temperature. The Na/K ratio in waters has been cali-
brated by field and experimental work as a means of
.i I ] I I
\ |
measuring temperatures of water supplying drillholes 200 Water Temperature"C 300
and hot springs. Examples of its use are found in the FIG. 4. - -The variation with temperature ot the ratio Na/K
paper by CUSlCANOUI and ELLIS (1970). Figure 4 gives in waters in equilibrium with albite and K-]eldspar.
the relationship between water Na/K ratio and tem-
perature.
With cooling of water, e.g., through boiling on I
rising towards the surface, the Na/K exchange reaction
I I
is slower to readjust than the silica equilibrium. A
memory of deep temperatures is carded upwards, but Oj~8T~Kopio~N.Z.
the temperatures indicated by the silica and the Na/K
method may disagree, the latter showing a higher tem- 7
perature. The Na/K ratio can for example indicate
whether or not higher temperatures exist beneath the
depth of drilling (MAno~ 1970).
The Na/K method is a more reliable method for \o.o. \
estimating deep temperatures from spring flows, but
for drillhole discharges, the silica method is capable of 6
~iving more accurate temperatures at the production
levels.
The constant relationships aNa/a.; and aN,/at at
a temperature for ecmilibrium rock alteration mineral-
og~, requires that the water pH vary with salinity 5
(ms, + inK) in the manner shown in Figure 5. This
aptHies beneath the level of boiling. Waters of highest
salinity and highest temperature will have the lowest
DH. The high pH of the very. dilute and lower teml~er-
ature Iceland geothermal waters is, for example, ex-
r~lained. The pH points calculated from acid/base equi- 4
200 300 Temperature, C 400
libria for several hydrothermal areas are shown on the
diagram as circles and are in good agreement with FIG. 5~ ~ The pH ( ~ log all) values predicted ]or waters
those predicted for mineral/solution equilibrium (shown at various temperatures in equilibrium with albite, K-mica
and K-[eldspar. Lines for (m,, + inK) o] 0.01, o.1, and 1.0
as arrowheads). are given. Points show pH values calculated trom acid-
The solubility, of calcite in solutions containing base equilibria Jor deep waters in various hydrothermal
areas, while arrowheads show the position expected from
sodium chloride and carbon dioxide was discussed by the mineral equilibrium prediction.

523
ELLIS (1963) and HOLLAND (1967). The calcite solu-
bility equilibrium can be expressed as follows:
CaCO~ + H,:CO~ = Ca +2 + 2HCO~-
KCHC = ac~" a:Hcoa/aco2
2 2
= ac..aco._K,,,/a,
and '
a c a a c o 2 ----- a . KcHc/K~,
Ka, is the first ionisation constant of carbonic acid
(RYZHENKO 1963). In addition, for the feldspar, mica
equilibrium
a~./art = Kf,,,
2 .I2
K c , c . ms. ,..
so that inca" tacos. = K2 ~ ,,2
al " K fm " ~ Cl
In these equations the activities, a, and molalities,
m, of the ions and of carbon dioxide are shown, and
Kfm is the equilibrium constant for the mica, two-feld-
spar equilibrium. The activity of carbon dioxide is
taken as being equal to the molality. :, is the stoichio-
metric ion activity coefficient. If natural hot waters
are in equilibrium with calcite, mica, and feldspars,
then at a temperature the product of calcium and car-
bon dioxide concentrations will be approximately pro-
portional to m ,t . , or m~<. Figure 6 shows lines for
estimated values of inc,. tacos, versus ms, for a range
of temperatures. Points are added from analyses of geo-
termal drillhole discharges from several fields. (Several
waters have such low calcium concentrations that large
analytical errors are possible). With a few exceptions.
calcium concentrations in the waters are found to be
close to those for equilibrium with calcite. Taking this
to be a common situation, providing that the water
temperature is known (the silica and N a / K methods)
Figure 6 can be used to estimate approximate carbon
dioxide concentrations in underground waters from
analyses of sodium and calcium concentrations in sur-
face water discharges.
The value of the first ionisation constant for
(< carbonic acid ,.
Kal - - ar~ aHcos/aco:
is known over a wide range of temperatures ( R Y z H E N K O
1963). From a knowledge of the bicarbonate concen-
tration in waters of boiling springs with a good flow.
and the appropriate activity coefficients, a second esti-
mate of the carbon dioxide concentration in the deep
water of an area can be made, as an approximate aH
is available from the sodium concentration (Figure 5).
From use of equation 3, a knowledge of calcium and
bicarbonate ion concentrations also can ~ve a measure
of mee~2 in deeo water saturated with calcite.
HELGESON (1967) showed for the Salton Sea area
how from a combination of experimental data and
field observations on mineralogy and ion concentrations
524
(3)
(4)
(5)
(6)
(7)
0.1 mNo 1.0
F13. 6. - - The estimated variation in the products me. moo:
with sodium ion concentrations, ms., in waters of various
temperatures in equilibrium with albite, K-mica, K-]eld-
spar, and calcite.
in water, a series of equilibrium phase diagrams for
hydrothermal alteration minerals could be developed
in terms of as,/a~, av,/aH, ac,/a~, and aMJa~(e.g.,
Figure 3). This type of diagram was developed further
by ELLIS (1969) and ELLIS and BROWNE (1970) tO
explain the relationship between water chemistry and
mineralogy in the hydrothermal areas at Broadlands and
at Wairakei, New Zealand, where the rock/water
system contains as the main chemical components,
Na~O, K.O, CaO, MgO, Al.,Os, SiO:, H~O, and CO~..
At constant temperature and pressure, at least 7 miner-
al phases (plus sulfide and iron phases) can be ex-
pected to coexist with water. A common hydrothermal
alteration mineral assemblage includes albite, K-feld-
spar, K-mica, (wairakite or epidote), chlorite, calcite,
and quartz. The equilibrium phase diagram for sodium
and potassium minerals was described (Figure 3). A
comparable phase diagram for potassium and calcium
minerals at 2600 (Figure 7) correlates the hydrothermal
alteration mineral assemblages at Wairakei and Broad-
lands with the deep water compositions. The solid lines
show phase equilibria in the absence of carbon dioxide.
When carbon dioxide is added to the system, bicarbo-
nate and carbonate ions are formed until an equilib-
rium pH is attained. For a particular concentration
of carbon dioxide, a dashed horizontal line represents
the value of log (ac,/a~) at which calcite precipitates.
Values above this line do not occur. Lines are drawn
for mco: equal to 0.01, 0.15, and 1.0. At 0.01 mco,.
 * I ' I
Zoislte
/ tendency for the water to impose a new composition
//~
~
7/
Wairakei" ' l " qD/
II ~ 1
Wairakit. --~" 4~--
/ II
J~ ~ - - - - -'~roo,4ton,~?
-
Kaolinite K- mice:
I a I change of phase boundaries with temperature, the
2 tog a~ "~ 4
F]o. 7. Phase diagram /or calcium and potassium minerals
- -
at 200o, in terms o~ ac./a. - and az'a.. Water compositions
/or Wairakei and W. Broadlands are shown, and dashed
lines show values o/ ac./au"- /or calcite precipitation at
mcca values o/ 0.01, 0.15 and 1.0.
(Published lrom Eu.IS (1969) with permission of the In-
stitution of Mining and Metallurgy. The log (aca.) scale
is revised slightly /or pressure e/leers, and the present
ac./a. 2 scale is correct. In the earlier diagram me. values
.,ere in error used as ac, values).
all of the minerals have areas of stability. With in-
creasing carbon dioxide concentration, first the field of
zoisite (epidote) disappears, and at about mco2 = 1.0 m
the wairakite field also disappears. For particular
solution conditions at a given temperature, the presence
or absence of wairakite or epidote in the mineral alter-
ation assemblages can be related to carbon dioxide
concentrations in the water. Phase diagrams of this
type can give useful comments on trends in hydrother-
real alteration throughout an area (ELus and BROWNE
1970). Brief examples are given.
At deep levels at Wairakei and Broadlands before
steam loss through boiling, the water compositions
marked as solid points fall, respectively, close to co-
existence of epidote, wairakite and K-feldspar; and
wairakite, calcite, K-mica and K-feldspar. Calcite is a
common alteration mineral at Broadlands and less com-
mon at Wairakei, while the reverse situation applies
to the occurrence of wairakite and epidote.
If waters boil, the loss of CO2 from solution causes
a rise in pH and the water becomes out of equilibrium
with the mineral assemblage with which it was in
contact. The effect this water has as it continues to rise
through the country depends on whether it flows in a
homogeneous manner or is channelled in fissures with
~ 1 I more limited contact with rock. There is a general
on the rocks at levels above the point of first boiling.
For slow homogeneous movement of water through
Cclclte, m = 0.0tin rock, with increasing pH, the water would tend to im-
~ .... .. _ _ C O 2 ~
(Wairakei) pose the following sequence of alteration minerals.
~t (Broc~Ion~$) Quartz would be precipitated throughout. Taking the
| Calcite, m C O = 0 15 Broadlands area as an example, the following sequence
2 "7 in mineralogy would, in theory, be noted:
I cateite, me0 ~-0 l
a) 2600 water in equilibrium with albite, K-mica, K-
2 -- -- "~
feldspar, calcite, wairakite and chlorite.
K- fe~(~s;)(tr
t b) Slight steam loss and pH rise would move the water
composition point so that K-feldspar and wairakite
remain stable, but not K-mica. Chlorite would re-
main stable. Calcite would be precipitated, as the
horizontal calcite line on the diagram rises propor-
tionally to pH change while the composition point
rises proportionally to twice the pH change. Due to
6 8 water composition trends into the K-feldspar stabil-
ity field, and growth of K-feldspar is required to
bring water back on to the two feldspar equilib-
rium line.
c) With further steam loss the same trends would be
followed, except that epidote would be favoured
rather than wairakite. Calcite and K-feldspar would
continue to form.
The rock mineral system has a buffering action
towards the changes which the rising water attempts
to bring about. While the trends in mineralogy can be
pointed out, the extent to which the changes are
brought about at a particular level depends on the rel-
ative volumes of water and rock in contact. In contrast
to slow upflow through homogeneous rock, water rising
and boiling in a fissure will produce about the flow
zone, secondary minerals which are dominated by ef-
fects of the trends in water pH. The buffering effect
from the rock is at a minimum. In the Broadlands
example, the main minerals formed about the flow fis-
sure would be K-feldspar, calcite and quartz. Formation
of wairakitc in the fissure at the level of first boiling,
followed by epidote at higher levels could also be
consistent with phase diagrams. A lowered p H is pro-
duced in water heated by steam and carbon dioxide
condensing into it, and mineral assemblages such as
albite, K-mica, wairakite or montmorillonite, !(-mica
and wairakite, are favoured. Kaolinite and halloysite
are stable at 260 o in waters of the Broadlands compo-
sition only under low p H conditions.
A reason why some hydrothermal areas precipitate
calcite in drillholes and flow fissures, while other areas
do not, is seen from diagrams such as Figure 7. For
Wairakei, separation of steam from the deep water
raises the pH and brings its composition up to the
525
epidote, K-feldspar stability line. An appreciable" steam
separation is required before the composition point
catches up with the rising, calcite precipitate line. At
Broadlands, however, the deep water composition is
close to both the K-mica, K-feldspar boundary and to
those for wairakite and calcite. With steam separation,
calcite would be the preferred calcium phase precipi-
tated, and although the composition point would sub-
sequently follow the wairakite, K-feldspar boundary,
it is unlikely that wairakite would nucleate and grow
with any efficiency while calcite is forming.
For a particular temperature, there is a particular
carbon dioxide concentration above which, calcite
would precipitate as the first calcium mineral phase
with first steam separation from water, and below
which, a calcium silicate phase would form or remain
stable with steam separation. At 260* this critical car-
bon dioxide concentration is about 0.1 m. (The Broad-
lands drillholes are slightly affected by calcite sealing).
Hydrothermal areas with high carbon dioxide concen-
trations are most likely to be affected by calcite scaling
problems in discharge pipes.
The concentration of magnesium in high tempera-
ture waters is usually maintained at low levels (Table
I) through mineral equilibria involving chlorite. The
concentration changes markedly with temperature. Ther-
mal areas which have dilute neutral pH waters con-
taining appreciable magnesium concentrations (above
few ppm) in springs of good flow, would be regarded
with suspicion for geothermal developments. It could
indicate that the waters do not have temperatures at
depth much greater than at the surface. However the
possibility of surface dilution with magnesium-con-
taining cold waters should be kept in mind.
Phase boundaries between common mineral pairs
such as chlorite-walrakite are marked by a particular
value of the ratio am/a~. With increasing salinity,
(lower pH), the equilibrium magnesium concentrations
in waters increase in the same manner as for calcium
concentrations. The increase in iron and manganese
concentrations in waters of high salinity (ELLXS 1969)
could also be explained in this way.
Sulphur containing equilibria
As indicated by ELLIS and BROWNE (1970), the
occurrence of pyrite or pyrrhotite in hydrothermally
altered rocks, depends on the ratio log (pH~s/pn2) in
the environment. As hydrogen is less soluble in water
than hydrogen sulfide, water which has lost steam
would favour pyrite formation in the rocks which it
contacts, while rock exposed to a separated steam
phase may produce pyrrhotite because of the lower
pH~s/pH2 ratio in the steam.
The occurrence of sulfur in country rock in con-
tact with hot water causes considerable corrosion prob-
lems during the development of a hydrothermal area,
526
as in the Tatun area of Taiwan. Hot water reacts with
sulfur following the equation below.
4H~_O + 4S -- 3H2S -+- H,.SO,
Acidic waters high in H.oS are produced. A laboratory
study of this hydrolysis reaction showed, for example,
at 150 , 2000 and 250 , concentrations of H.~S in water
in contact with sulfur of approximately 0.001m,
0.005m and 0.02m respectively, pH values in cooled
waters of 3 or much lower were produced. In the Ro-
tokaua, New Zealand hydrothermal area, sulfur occur-
red in rocks at shallow levels, and waters were of the
acid chloride, sulphate type, but deep drillholes passed
through to high temperature neutral pH water beneath.
Unfortunately, in the Tatun area deep drillholes still
encountered sulfur-bearing strata and extremely corro-
sive conditions persisted. In this situation the acidity
developed from sulfur hydrolysis overrides the alumino-
silicate pH buffering systems which occur during the
simple recrystallisation of a volcanic rock.
It was shown by ELLIS ~T AL. (1970), that in many
deep hydrothermal systems partial pressures of hydro-
gen of approximately 0.I atm occur. At this hydrogen
pressure, the redox equilibrium in solution between
sulfide and sulfate strongly favours sulfide. Except
where sulfur or sulfur dioxide hydrolysis occurs, sulfate
should not occur at high concentrations in deep high
temperature waters. In neutral pH waters sulfate is also
restricted in concentration at high temperatures by
anhydrite solubility.
Gas equilibria
HULSTON ( 1961 ) showed that if a chemical equilib-
rium is assumed to exist between the co-existing gases
carbon dioxide, hydrogen and methane present in natu-
ral steam it is possible to estimate the temperature of
equilibrium at depth from known thermodynamic data
for the following reaction:
CH, + 2H,O = CO~ + 4H.,
Equilibrium constants are available for this reaction,
either as a gas phase equilibria or in liquid water. For
a natural steam system only the mole fractions of the
various gases and the total pressure are required to
estimate the temperature of equilibrium at depth. For
a deep high temperature water system it is necessary to
know in addition the relationship between the steam
analysed and the parent water, i.e., the percentage
steam flash. When analysing fumarole steam the possi-
bility of a contaminating addition of methane at shallow
depths from decomposing organic material should be
kept in mind.
The method is best used in association with iso-
topic temperature measuring techniques to provide a
mutual crosscheck of values. In a hydrothermal area
in which the natural activity is entirely fumarolic it is
one of the few ways to obtain estimates of underground
temperatures.
Isotope equilibria
Several isotope exchange reactions offer the pos-
sibility of deep temperature estimation from surface
measurements on water or steam flows. Equilibrium
costants for many isotope exchange equilibria are now
becoming available, and some important examples are
summarised below. In all the isotopic equilibria it is
assumed that the equilibrium achieved at deep levels
is ~ frozen in ,, between the time, and the deep point
of equilibrium until the analysis of material at the sur-
face. Many isotopic equilibria have a slower rate of
adjustment with changing temperature than chemical
equilibria (e.g. Na/K ratio, silica concentrations). In
the future the isotope techniques are likely to play an
increasingly important role in measuring temperatures
at deep levels within hydrothermal systems.
SOLUTE EOUILIBRIA
The relative ratios of l~C/~-~C in co-existing carbon
dioxide and methane varies with temperature, and
ratios determined for the two gases in geothermal
discharges have been interprete.d to give underground
temperatures. As reviewed by ELLIS ET AL. (1970), tem-
peratures of 215-315cC were obtained for Larderello
steam, and 245-250cC for deel~ Wairakei water.
The isotopic distribution a'S/a~S between hydrogen
sulfide and metal sulfides in altered rock, and between
co-existing metal sulfides shows promise of being useful
in estimating the temperature of rock alteration under-
ground. The Institute of Nuclear Sciences, DSIR, New
Zealand, is at present investigating systems of this type.
Two exchange equilibria between solute specie~
which are potentially useful for estimating deep level
water temperatures, are the following:
H2160 + SlgO,2- = H2~O + S160,2-
H2nS + ~SO, ~- = ~S + ~SO, 2-
RAFTER and MITSUTANI (1969) determined exper-
imentally the oxygen isotope equilibrium distribution
for the first reaction at various temperatures, and from
isotopic analysis of water and suifate from Wairakei
waters calculated underground water temperatures of
250 o . 300C.
The sulfur isotope exchange between sulfide and
sulfate was considered by RAFTER ET AL. (1958) for the
Wairakei system. However, only theoretical equilibrium
constants were available, and deep water temperatures
estimated from these in conjunction with analysis of
Wairakei drillhole discharge samples were in the vicin-
ity of 370C, i.e., much higher than measured. With
experimental calibration of the isotope equilibrium, im-
proved results may be obtained.
MINERAL-SOLUTE EQUILIBRIA
Isotopic equilibria between solution species and
a mineral enable estimates to be made of temperatures
which existed in the field before drilling, through ana-
lysis of drillcores and drillhole discharges. Equilibrium
constants for the isotopic distribution of oxygen bet-
ween water and the minerals calcite, quartz, alkali
feldspars, and muscovite, were reported by TAYLORET
AL. (1967). A good example of the use of this isotope
technique was given by CLAYTON ~T AL. (1968) who
showed that calcite in rocks intersected by a Salton
Sea area drillhole was in isotopic equilibrium with the
co-existing water, from temperatures of over 3000 down
to at least 1500. Oxygen isotopic equilibrium between
quartz and water was not achieved in this situation.
Heavy metal concentrations
Appreciable concentrations of arsenic and antimo-
ny are commonly found in natural thermal waters, but
it is only the more saline, high temperature, waters that
contain noteworthy concentrations of iron, manganese,
copper, zinc, lead and silver. The Salton Sea area
hydrothermal system is the most spectacular in this
respect (SKINNER ET AL. 1967). Discharges from Salton
Sea area drillholes produced siliceous scale rich in
copper, iron, sulfur, silver, antimohy and arsenic. EL-
LIS (1968) showed that during the experimental reac-
tion of common rocks with salt solutions at elevated
temperatures, high proportions of the lead and copper
in the rock were liberated into solution. There was
a relationship between salinity and the concentration of
metals such as manganese, iron, lead and copper, found
in solution at a temperature. The reason for the va-
riation in concentration of these metals is mainly to be
sought in terms of pH variation with salinity, as discus-
sed above, although chloride complexes may also play
a part.
Although concentrations of heavy metals such as
copper, zinc, silver, and lead are only at the parts per
billion level in the dilute waters of the Broadlands
New Zealand field, drillholes at depths from 2500 to
6000 ft have intersected extensive mineralised bands
containing sphalerite, galena and chalcopyrite (BRowNE
1969). Although the more saline thermal waters are
capable of carrying higher concentrations of heavy
metals in solution it is apparent that even dilute waters
such as are found in the New Zealand areas are capable
of producing extensive mineralisation within present-
day hydrothermal fields, because of the large through-
put of water which occurs.
WEISSBERG (1969) studied the mineralogy and
chemistry of antimony-arsenic-sulfide precipitates form-
ed at the surface from both springs and drillhole
discharges in several areas of the Taupo Volcanic Zone
of New Zealand. He showed that selective co-precipi-
tation, adsorption, processes produced high concentra-
tions of elements such as silver, gold, thallium and
mercury in the precipitates. At Broadlands the precipi-
tates c~ntained up to 85 ppm Au, I000 pFrn Tl, 2000
ppm Hg, 200 ppm Zn, 50 ppm Pb, and 500 ppm Ag.
527
At Broadlands the conditions which caused precipitation
of lead, zinc, and copper at deep levels in the field al-
lowed transport of antimony, arsenic, mercury, gold and
thallium to the surface. Transport of the latter group of
elements is apparently controlled by sulfide complexes.
The association of heavy metal sulfide mineralisa-
tion with present-day hydrothermal systems is not only
of academic interest. It is possible that both hot wa-
ter/steam, and metal ore, may in the future be produced
from particular depths or positions in a hydrothermal
area. For example, our work in Chile has suggested
that it is possible that in a shallow aquifer in the
Tatio field, partial oxidation of sulfide, causing de-
struction of metal sulfide complexes, may have led
to the deposition of a quantity of precipitates of the
type described by WmSSSERO (1969). Drilling will
check on this possibility.
REFERENCES
ALONSO H. 1966 ~ La zona geotermica de Cerro Prieto, Baja
California. Bol. Soc. geol. mex., 29, 17.
Avezr~v V. V., N^Dogo S. I., PnP B. 1. 1961 - - Contemporary
hydrothermal metamorphism in regions of active volcanism.
Dokl. Akad. Nauk S.S.S.R., 137, 407.
AZiJMA Kxgo Co. Ltd. 1966 ~ Matsukawa electric power
station by utilizing geothermal energy. News Sheet.
B~es H. L., H E W N H. C., ELLIs A. I. 1966 ~ In:
Handbook of Physical Constants ~, S. P. Clark ]r. ed.,
Geol. Soc. Am. Mere., 97, 401.
BaowNs P. R. L. 1969 ~ Sulfide mineralization in a Broad-
lands geothermal drillhole, Taupe Volcanic Zone, New
Zealand. Econ. Geol., 64, 156.
C^TALnl R. 1967 ~ Remarks on the geothermal research in the
region of Monte Amiata, Tuscany, Italy. Bull. voican., 30,
243.
CLAY'tON R. N., MravFt,~ L. P. l., Wrlm~ D. E. 1968 ~ Oxygen
isotope study of calcite and silicates of the River Ranch
No. I well. Sahon Sea geothermal field, California. Amer.
/. Sci., 266, 968.
Ca^tc H. 1963 ~ The isotopic geochemistry of water and car-
bon in geothermal areas. In: Nuclear Geology on Geo-
thermal Areas ~, E. Tongiorgi ed., Pisa, Consiglio Nazio-
nale delle Ricerche, 71.
Ct~stc,~Qu~ H., ELLis A. I. 1970 ~ Geochemistry of the Tatio
geothermal area, Chile. In press.
ELLIS A. [. 1963 ~ The solubility of calcite in sodium chloride
solutions at high temperatures. Amer. ]. Sci., 261, 259.
ELLIS A. I. 1966 ~ Volcanic hydrothermal areas and the in.
terpretation of thermal water compositions. Bull. volcan.,
29, 575.
ELLtS A. l- 1967 m The chemistry of some explored geothermal
systems. In.: Geochemistry of hydrothermal ore depo-
sits ~, H. L. Barnes ed.. Holt, Rinehart and Winston. New
York. 465.
ELL1S A. ~, 1968 ~ Natural hydrothermal systems and expe-
rimental hot-water/rock interaction: Reactions with NaC1
solutions and trace metal extraction. Geochim. cosmochim.
Acta, 32, 1~56.
ELLm A. 1. 1969 - - Present day hydrothermal systems and
mineral deposition. Prec. 9th Commonwealth Mining Me-
tallurgical Congr., London.
Et.L~S A. l., Baowi~ P. R. L. 1970 - - The Ohaki-Broadlands
hydrothermal area: Mineralogy and related geochemistry.
Amer. ]. Sci., in press.
ELLIS A. 1., MAnO~ W. A. I. 1964 ~ Natural hydrothermal
systems and experimental hot.water/rock interactions. Geo-
chim. cosmochim. Acre, 28, 1323.
ELLIS A. |.. MAnO~ W. A. I. 1967 - - Natural hydrothermal
systems and experimental hot-water/rock interactions, Part.
11. Geochim. cosmochim. Acta, 31, 519.
ELLm A. l., Ht~^LV 1., Hocgs'm~s M. P., lAMES C. R. 1970
528
Geothermal Exploration ,. Plenum Press. New York, in
press.
F^cc^ G., TON,~t F. 1964 - - Theory and technology of a geo-
thermal field. Bull. volcan., 27, 1.
Fotntsml~ R. O., Row~ I. I. 1966 m Estimation of underground
temperatures from the silica content of water from hot
springs and wet-steam wells. Amer. ]. Sci., 264, 685.
Gt.ov~.a R. B. 1970 - - Interpretation of gas compositions from
the Wairakei f i d d over 10 years. U. N. Syrup. on Develop-
ment and Utilization o~ Geothermal Resources, Pisa.
G~ur,nat~v G. W. 1965 w The geology, structure and exploita-
tion of the Wairakei geothermal field, Taupe, New Zea-
land. Bull. geol. surv. N. Z., 75.
H~t~aso~ H. C. 1967a ~ Thermodynamics of complex disso-
ciation in acqueous solution at elevated temperatures. /.
Phys. Chem., 71, 3121.
Hm,o~oN H. C. 1967b m Solution chemistry and meta-
morphism. In: t Researches in Geochemistry ~, Vol. 2.
P. H. Abelson, ed., Wiley, N e w York.
H g ~ H. C. 1968 - - Geologic and thermodynamic cha-
racteristics of the Salton Sea geothermal system. Amer. ].
Sci., 266, 129.
HeML~y I. l., l o ~ s W. R. 1964 - - Chemical aspects of hydro-
thermal alteration with emphasis on hydrogen motasoma-
tlsm. Econ. Geol., 59, 538.
H O L E D H. D. 1967 - - Gangue minerals in hydrothermal de-
posits. In: Geochemistry of Hydrothermal Ore Depo-
sits ~, H. L. Barnes ed., Holt, Rinehart and Winston, New
York, 382.
HULSrON 1. R. 1961 m Isotope geology in the hydrothermal
areas of New Zealand. U. N. Conl. New Sources ~.nergy,
Rome 1961, Pap. 35/G/31.
l ~ a s C. R. 1968 - - Wairakei and Larderello: geothermal
power systems compared. N. Z. ]. Sci., 11, 706.
M c N r r r I. R. 1963 ~ Exploration and development of geo-
thermal power in California. Spec. Rep. Cat~/. Div. Mines
Geol., 75.
MAHON W. A. I. 1966 - - Silica in hot water discharged from
drillholes at Wa/rakei, New Zealand, N. Z. I. Sci., 9, 135.
MArteN W. A. I. 1970 ~ Chemistry in the exploration and ex-
ploitation of hydrothermal systems. U. N. Syrup. on Deve-
lopment and Utilization of Geothermal Resources. Pisa.
Me'LCADO S. 1966 ~ Aspeatos quimicos del approvechamiento
de la energia geotermica. Campo geot~rmico Cerro Prieto,
B. C. Mexico, D. F., Comisi6n Federal de Electricidad.
Murt~t,La L. P. l., W e r m D. E. 1969 - - Active metamorphism
of Upper Cenozoic sediments in the Salton Sea geothermal
field and the Salton trough, south-eastern California. Geol.
Soc. Amer. Bull., 80, 157.
NAKAMURA H., SUMI K. 1967 - - Geological study of Matsukr.-,va
geothermal area, northeast lapan. Bull. geol. Sur. lapan,
18, 58.
No.qucrll T. 1966 - - Exploration of the Otake steam field.
Bull. volcan., 29, 529.
Prrzcr^ F. 1954 - - Ricerche e studi sui fenomeni esalativo-idro-
termati ed iI problema delle Forze endogene ). Ann.
Gee~is., 7, 317.
RAr'rEa T. A., WmSON S. H., SmLTON W. B. 1958 ~ Sulphur
isotope variations in nature, Pt. 5, Sulphur isotope varia-
tions in New Zealand bore waters. N. Z. ]. Sci., 1, 103 .
Rvzg,,Ngo B. N. 1963 - - Determination of dissociation con-
stants of carbonic acid and the degree of hydrolysis of the
CCh-- and HCO~-- ions in solutions of alkali carbonates
and bicarbonates at elevated temperatures. Geochimiia. No.
2, M7; Geochem. Int., 151.
T^VLOa H. P. 1967 ~ Oxygen isotope studies of hydrothermal
mineral deposits. In: Geochemistry of Hydrothermal Ore
Deposits ~, H. L. Barnes vd., Holt, Rinehart and Winston.
New York, 109.
SKIr,'r~g B. 1., WrlrrE D. E., Rose H. l., MArs R. E. 1967 - -
Sulfides associated with the Salton Sea geothermal brine.
Econ. Geol., 62, 316.
W E x s s ~ c ; B. G. 1969 - - Gold-silver ore-grade precipitates
from New Zealand thermal waters. Econ. Geol.. 64. 95.
WurrE D. E. 1957 ~ Thermal waters of volcanic origin. Geol.
Soc. Amer. Bull., 68, 1637.
WILSON S. H. 1963 - - Tritium determinations on bore waters
in the light of chloride-enthalpy relations. In: ~ Nuclear
Geology on Geothermal Areas ,, E. Tongiorgi ed., Con-
siglio Nazionale delle Ricerche, Pisa, 173.