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Ann. Rev. Earth Planet. Sci. 1978. 6: 229-50 Quick links to online content
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HYDROTHERMAL =-=10093

ALTERATION IN ACTIVE
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GEOTHERMAL FIELDS
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P. R. L. Browne
New Zealand Geological Survey, Box 30368, Lower Hutt, New Zealand

INTRODUCTION

In the fall of 1929 the Carnegie Institution drilled a 124-m well in the Upper Geyser
Basin of Yellowstone National Park. Cores from this well and a subsequent well
at Norris Basin were studied by Fenner (1934, 19 36), who published the first
detailed accounts of subsurface hydrothermal alteration in an active geothermal
system. Of course, it had long been known from studies of hot springs and ore
deposits that thermal fluids can react with the rocks they contact so that both
change their compositions. Active geothermal systems, however, are places where
these reactions are ocCurring now and where it is often possible to make direct
physical and chemical measurements. Thus they may be regarded as large-scale,
uncontrolled, open-end natural experiments. But because there still usually remain
several unknown variables-such as the duration of thermal activity or the
composition of the fluid before it enters the system-studies of alteration in geo­
thermal samples complement, rather than replace, low-temperature mineral-stability
experiments.
This chapter is a survey .of hydrothermal alteration in several geothermal
systems recently explored by drilling. It is selective in that it usually mentions only
papers published since about 1968, and it excludes discussion of ore minerals since
these have been described elsewhere (White 1967, Weissberg et al 1978). Also
excluded are submarine thermal systems (e.g. Ridge 1973), geopressured sedimentary
basins (e.g. Carpenter et al 1974), and accounts of alteration at Steamboat Springs,
Nevada (Schoen & White 1965, 1968, Sigvaldason & White 1961, 1962, White
1968), Pauzhetsk, Kamchatka (Naboko 1970, 1976), Tahuangtsui, Taiwan (Chen
1966, 1967), Wairakei (Steiner 1953, 1955, 1968, 1970), and Waiotapu (Steiner
1963). Many aspects of geothermal systems are discussed in three massive volumes
forming the proceedings of a United Nations conference (1976), and an extensive
bibliography is also now available (ERDA 1976).

229
0084-6597/78/0515-0229$01.00
 230 BROWNE

HYDROTHERMAL MINERALS

A very wide range of hydrothermal minerals has been recognised in active geothermal
systems (Table 1). Many occur in low-grade metamorphic rocks and hydrothermal
ore deposits, but some are rare [e.g. buddingtonite (Erd et al 1964)] or perhaps
unexpected at low temperatures [e.g. aegirine and lepidolite (Honda & Muffler
1970, Bargar et al 1973)]. Wairakite, a calcium zeolite, is the best known mineral
first found in cores from an active geothermal field (Steiner 1955, Coombs 1955).
Several factors affect the formation of hydrothermal minerals and these vary in
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

Table 1 Some h ydrothermal minerals in selected geothermal fields·

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'" '"
QQ '" '" .,.
I': ·2 .>< <I) '"
... Q ...,
·s 0; <I)
"C
0 � .<:: I': .8.. oJ) I': "C
u '" 0. I': 0 I': I':
;;., � 0. '" '" >.
>; E '" N
� U '" ] Q)
�
� <I)-
I':
vi
'"
::.::
-.
�
I':
'" Il..
.0'
E
u
·2
�
:E
Q)
� ..:! �-
., 0. d' '" '" U ci.
>"0;
'i ·2 B
ell
� -i a:
oj
oj
-. oj
I':
� u
"0 15
ci.
E S .£
.- ... " .>< .<:: B "E
� 0 .<::N :; .s 0
QQ '" :> .� B <I)
8.� ..9 <I) :;
'" .><
'" Q �'" N E- � ..cQQ "C
...
Q) ..c '" 0; 0 0 '"
E '"
_u >- E- ll.. � (5 E- � ;i m � :E �

Allophane x
Quartz x x x x x x x x x x r? x x
Cristobalite x x x x x x x x

Kaol in gro up d x x x x x x x x x
Montmorillonite d x x x x x x x x x x

Interlayered i llite-mont. x x x x X X X X x
Illite x x x x x x x x x x
Biotite x x x
Chlorite x x x x x x x x x x ? x x
Celadonite x x x x
Alunite x x x x X x

Anhydrite x x x x x x x x x x
Sulfur x x x x x
Pyrophyllite x

Talc x x

Diaspore x x x
Calcite x x x x x x x X X X X X x
b b b
Aragonite x x x

Siderite x x x x x

Ankerite x x x

Dolomite d
Analcime x x x x X

Wairakite x x x x x x x x x

Gmelinite x
Gismondine x
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 231

Table 1 (continued)

'"
c
o
N
u
'a
os
u
'0
;>
N
i
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

Erionite x

Laumontite x x x x x x x x
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Phillipsite x

Scolecite X x

Chabazite X X

Thomsonite X x

Clinoptilolite x x

Heulandite x x x x x x x

Stilbite X X

M ordenite x x x x x

Prehnite x x x r? x

Amphibole x x x x

Garnet x ?
Epidote x x x x x x x x

Clinozoisite X
b
Pectolite x x

Sphene x x x x X

Adularia x x x x x x x X X x

Albite x x x x x X x

R utile x x x

Leucoxene x x x x x

Magnetite x

Hematite x x x x x x x x

Pyrite x x x x x x x x x x x x
Pyrrhotite x x x

Marcasite x x

Base-metal sulfides x x x

Fluorite x x

References: I mperia l V alley: Skinner et al 1967, Muffler & White 1969, Bird & Elders 1976,
Kendall 1976h, Reed 1976, Browne & Elders 1976. Yellowstone: Fenner 1936. Honda & Muffler 1970,
Bargar et al 1973, Keith & Muffler 1978, Keith et al 1978. The Geysers: Steiner 1958, McNitt 1964.
Pauzhetsk: Naboko 1970. Matsukawa: Sumi 1968. Otake: Hayashi 1973. Tongonan: C. P. Wood,
unpublished observations. Kawah Kamojang: Browne, u npub lis hed observations. N.Z. Vo lcani c
Zone: Steiner 1953, 1963, 1968, Browne & Ellis 1970, Browne, unpub lished observations. EI Tatio:
Browne, unpublish ed observations. Iceland: Sigvaldason 1963, Tomasson & Kristmannsd6ttir 1972,
1976, Kristmannsdottir & Tomasson 1976a, b, c, Kristmannsdottir 1976. Larderello: Marinelli 1969.
Note: d = detrital, r = relict.
, includes Cerro Prieto, Baja California, Mexico.
b d ep o sit e d in discharge pipes and channels.
 232 BROWNE

relative importance from field to field. Some are so intimately related that it is
often impossible to separate one factor from another. The factors are: (a) temperature.
(b) pressure, (e) rock type, (d) permeability, (e) fluid composition, and if) duration
of activity. This list is similar to several suggested from work on ore deposits,
but geothermal studies have demonstrated that permeability and fluid composition
are usually at least as important as temperature.

Temperature
Most liquid-dominated systems explored so far have reservoir temperatures below
about 280°C, but several people have reported maxima above 300°C [including
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

the Salton Sea, California at 360°C (Palmer 1975), Cerro Prieto, Mexico at 388°C
(Mercado 1969) or 371°C (Mercado 1976), and Tongonan, Philippines at 324°C (C.
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P. Wood, personal communication)]. Vapor-dominated systems have maximum

temperatures after exploitation of 236°C (White et aI1971).
Except for epidote, ortho, ring, and chain silicates are uncommon alteration
minerals in active geothermal systems, but where present, usually occur at high
temperatures. Hydrothermal garnet and tremoJite are known from the Salton Sea
(Muffler & White 1969, Kendall 1976b), and tremolite also occurs at Tongonan
(C. P. Wood, personal communication). An unspecified amphibole is present at
one of the Icelandic fields (Kristmannsd6ttir 1976), and all its occurrences are
where well temperatures exceed 280°C, but garnet is present only above 320°C.
Epidote occurs at several fields (Table 1), usually above 240-260°C but in some
(Seki 1972), such as at Reykjavik (Sigvaldason 1963), it apparently occurs down
to 120°C. Possibly here, however, it is a relict formed when temperatures were
higher.
Pyrophyllite and talc also form at high temperatures, but the former is considered
to be relict at Kawah Kamojang, Indonesia and in several of the Japanese fields
(Sumi 1968). The distribution of clay minerals is also tcmperature dependent
(Browne & Ellis 1970, Muffler & White 1969, Steiner 1968). In the New Zealand
fields surface kaolinite, formed at low pH, does not persist above about 60°C,
although dickite is known in one well where measured temperatures are from 140
to 150aC. With increasing depth and temperature, the usually dominant clay, Ca­
montmorillonite, becomes increasingly interstratified with illite, to become inter­
layered illit�-montmorillonite, but above about 220°C, illite plus chlorite is the
typical clay-mineral assemblage. Of course, the apparent temperature dependence
of the clays is aided by the near-uniform composition of fluids throughout these
fields (Browne & Ellis 1970, Mahon & Finlayson 1972)-a condition not always
met elsewhere.
As expected, the distribution of zeolites is strongly temperature dependent, and
this is well illustrated by Icelandic and Japanese work (summarized later),
although the greatest range of zeolites is at Pauzhetsk (Naboko 1970). Typical
zonation in the New Zealand fields is mordenite-laumontite-wairakite, with
mordenite forming near SOT and wairakite usually above 21SoC, but occasionally
as low as 140°C (Browne & Ellis 1970, Steiner 1953, 1968). Cristobalite and
siderite frequently occur below !OO°C, but several minerals, including pyrite,
calcite, and chlorite, form readily at both low and high temperatures.
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 233

Pressure

Fluid pressures in geothermal areas are low and seldom exceed 200 bars. In
liquid-dominated fields they are usually close to, or slightly above, hot hydrostatic,
but occasionally, where self-sealing has occurred-for example at Yellowstone­
they must have exceeded Iithostatic pressure (Muffler et al 1971). In vapor­
dominated systems, fluid pressures are typically well below hydrostatic (White et
al 1971). Over the drilled depths pressure has little direct affect on hydrothermal
alteration, other than to influence the induration and lithification of sediments.
However, change of fluid pressure can affect fluid composition. This is most
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

obvious where boiling occurs and CO2 is lost; ·zones of subsurface boiling are often
characterized by hydrothermal quartz, K-feldspar and bladed calcite (Browne &
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Ellis 1970, Keith & Muffler 1978, Keith et al 1978). The effect of pressure on the
K-mica-K-feldspar equilibrium results in a given solution being more alkaline at
high pressure. Fluids released from high-pressure control, therefore, have a
tendency to deposit K-feldspar (Ellis & McFadden 1972).

Rock Type

The parent rock influences hydrothermal alteration mainly through the control
of permeability by texture and porosity. The initial mineralogy of the reservoir
rocks seems to have little affect on equilibrium alteration assemblages above about
280°C. For example, albite, K-feldspar, chlorite, Fe-epidote, calcite, quartz, illite,
and pyrite are the typical stable assemblage in basalts of Iceland, sandstones of
the Imperial Valley, rhyolites of New Zealand, and andesites of Indonesia. At
lower temperatures, however, the nature of the parent material clearly influences
the alteration product. High-silica zeolites, such as mordenite, are common in
rhyolitic fields at Yellowstone (Honda & Muffler 1970) and New Zealand (Browne
& Ellis 1970, Steiner 1968), whereas lower silica zeolites, e.g. chabazite, thomsonite,
scolecite, occur in the basalts of Iceland and andesites of Kamchatka
(Kristmannsdottir & Tomasson 1976c, Naboko 1970).

Permeability

Studies on alteration in geothermal fields have clearly recognized the important

control of permeability on hydrothermal mineral deposition. Mineral reactions are
seldom isochemical and extensive alteration and hydration needs more than pore
water to proceed. In many cases, at least carbonate and sulfide species must
be added to rocks from solutions.
In rocks of low permeability, equilibrium between rocks and the reservoir fluid
is seldom achieved and primary minerals or glass can persist to high temperatures.
For example, dense welded tuffs at Broadlands, Wairakei, and Yellowstone have
locally remained little changed, even at high temperatures, because fluid access is
too difficult (Browne & Ellis 1970, Keith et al 1978). The marked zoning of
hydrothermal minerals about fluid channels in several Japanese geothermal fields
clearly shows structural control of alteration and demonstrates how intensity and
type of alteration reflect permeability (Sumi & Takashima 1976). Permeable
fissure channels at Wairakei, Broadlands, Waiotapu, Kawerau (all in New Zealand),
 234 BROWNE

and Tongonan, Philippines are characterized by vein adularia, usually together with
quartz and calcite (Steiner 1968, Browne 1970). Browne (1970) showed that at
Broadlands there is an approximate relationship between the nature of feldspars
in aquifer rocks and the measured well permeabilities; in order of increasing
permeability the feldspars are: primary andesine, albite, albite + adularia, adularia.
Thus rocks from highly permeable zones are often increased three- to fourfold in K20.
Isotopic analysis of hydrothermal minerals also gives information about
reservoir hydrology (Blattner 1975, Coplen et a11975, Clayton et a1 1968, Clayton &
Steiner 1975, Eslinger & Savin 1973, Kendall 1976a, b, Olson 1976). Kendall's
( 1976b) study, for example, shows that the carbon and oxygen isotopic composition
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

of minerals from the Salton Sea reflects variations in reservoir permeability, and
she was able to relate depletion of 018 in calcite with zones of high permeability
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as indicated by Saraband logs.

Fluid Composition

This was recognized by Fenner (1934) as a factor in hydrothermal alteration

at Yellowstone. However, only in the last few years has it been realized how close, in
fact, is the relationship between fluid chemistry and alteration mineralogy.
Successful use of the silica geothermometer to estimate deep temperatures depends
on silica in the fluids being in equilibrium with a silica mineral, usually quartz

Table 2 Concentration (mgjkg) in waters separated from discharge at atmosp heric pressure

SOU[(;t;
Drillhole Depth Temp pH Li Na K Rb Cs Mg Ca
No. (m) (' C) (15-25')

Salton Sea 1776 332 210 53,000 16,500 70 20 10 28,800

1 I D No. 2 *
Cerro Pri�to* 1300 305 5.43 10.9 4730 1180 0. 2 272
M.8
Yellowstone 1 57 194 8.1 3.5 270 11 0.Q2
1 26 .

Y-3
Matsukawa 162 100 2.8 2.1 12.0
Tl
Otake 550 220- 8.1 5.15 936 131 0.2 12.3
No. 9 240
Otake 720 240- 3.4 7.03 1186 228 0.47 15.0
H-2 270
Wairakei 695 260 8.4 14.2 1320 2 25 2.8 2.5 0.03 17
44
Broadlands 1092 260 8.6 9.5 910 143 1.1 1.4 0.05 1.1
10
Seltjarnarnes 2050 114 362 10 0.09 132
S-4
Hveragcrdi 650 216 9.6 0.3 212 27 0.04 <0.02 0.0 1.5
G-3
El Tatio 867 262 7.0 45.2 4840 830 0.6 17.4 0.16 211
7

a Helg eson 1968a C Bargar et al 1973 e Hayashi 1973

h Reed 1916 d Sumi 1968 'Ellis 1967
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 235

(Mahon 1966, 1976, Fournier & Rowe 1966, Fournier 1973, Arn6rsson 1975).
Similarly, the Na-K and Na-K-Ca geothermometers require that the solutions be
in equilibrium with albite and K-feldspar (Ellis & Mahon 1967, Fournier &
Truesdell 1973, Truesdell 1976).
Several significant papers on experimental and thermodynamic work have greatly
increased our understanding of hydrothermal alteration (Hemley et al 1969,
Hemley & Jones 1964, Helgeson 1967, 1968b, 1970, 1971, Helgeson et al 1969a, b).
For example, the experimentally derived activity diagram for equilibrium in the
system K20-Na20-AI20rSi02-HCI-H20 at 260°C (Figure 1), shows the
relationships between several mineral phases and water of Broadlands composition
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

(Browne & Ellis 1970); as expected from minerals in the cores, this water is in
near equilibrium with K-feldspar (adularia), albite, and K-mica (illite).
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By using petrographic studies of cores and analyses of well fluids and well
temperatures, diagrams for other element combinations can be constructed. For
example, the mineral stability diagram for calcium and potassium minerals
(Figure 2) shows that the deep 260°C water at Broadlands has a composition close
to equilibrium with K-mica, K-feldspar, wairakite, and calcite and emphasizes the
critical role of CO2 in determining the stability of calcium phases. Where CO2
concentrations are high, as at Broadlands (0. 15 moles), calcite tends to deposit
at the expense of epidote (zoisite) or wairakite during steam separation. A close

for selected geothermal fluids

F Cl Br so. SiO, B NH, CO, H,S Ref.

155.000 S � 30 400 390 500

9040 590 12 11.6 25�U 624

30 278 19.1 3.6 HCO,=

177
4.1 176 30 1.9 45.4

4.6 1474 3.4 0.3 136 665 32 40.7

1.5 1941 5.6 0.4 318 626 36 0.0

8.3 2260 6.0 0.3 36 690 29 0.15 19 1.0

6.2 -
1244 3.6 0.1 12 635 55 1.2 (CO, � -HCO,-)553

0.95 554 209 101 17 h

1.9 197 0.45 0.0 61 4�U 0.6 0.1 55 7.3

3.0 8790 30 766 203 2.3 5.4(HCO, =40)

II Rrowne & Ellis 1970 i Cusicanqui et al 1976

h Tomasson & Kristmannsd6ttir 1976 '" Corrected for steam loss
 236 BROWNE

relationship between fluid composition and alteration (Tables 1 and 2) is seen in

several Japanese fields including Otake. Here near-neutral pH waters form quartz,
K-mica, heulandite, wairakite, albite, and adularia, whereas deep low pH fluids
produce alunite (Hayashi 1973) in accord with the experimentally derived relations
of Hemley et al (1969).
Little has so far been published on alteration in vapor-dominated fields, but
the occurrence of wairakite at The Geysers (Steiner 1958) and epidote, adularia,
quartz, calcite, and zeolites at Larderello (Marinelli 1969) indicates that a liquid
was (or is) present in both fields. However, in rocks affected by steam, pyrrhotite
may form in preference to pyrite (Browne & Ellis 1970), and clays, especially
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

kaolinite or montmorillonite, may be more abundant under such conditions.

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Duration

Much has yet to be learnt about the age and evolution of geothermal systems, but
available evidence suggests they are long lived (Grindley 1965, Browne 1971,
White 1974, Sumi & Takashima 1976). Steamboat Springs, for example, has been
active, at least intermittently, for 1 million, and probably as long as 3 million years.
During such long periods geothermal activity changes in both intensity and
location, although many changes will be due to events not directly related to thermal

6
Albite

Na montmorillonite
4

'"I·
zI
OJ OJ
3
OJ
.2

2 Kaolin K-mica K-feldspar

o 2 3 4 5 6

Figure 1 Phase diagram for sodium and potassium in terms of ion activity ratios at 260°C
with quartz present. Solid circle plots Broadlands water composition and arrow shows
trend with steam loss; dotted lines indicate positions of phase boundaries at 230°C
(Browne & Ellis 1970).
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 237

actIvIty, such as erosion, earth movement, or volcanic activity. Self-sealing,

however, occurs at the tops and margins of fields where cooling waters deposit
quartz, or less commonly zeolites (Bird 1975, Elders & Bird 1976, Keith et al 1978).
Shifts in activity have long been recognized at Yellowstone from the migration of
thermal features, and surficial activity has been extinguished at Matsukawa (Sumi &
Takashima 1976) and, locally, Wairakei. Kristmannsdottir & Tomasson (1976a)
concluded that the Nesjavellir (Iceland) thermal field is shifting north and the
minerals have not yet adjusted to the new higher temperatures. By contrast, cooling
has been recognized at Kawah Kamojang and at Matsukawa (Sumi 1968), where
pyrophyllite and diaspore are thought to be relicts from temperatures above 310°C,
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

compared with 15Q-250°C at present.

Several proposed geothermometric methods have been tested on samples from
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geothermal areas. They include : aluminum-in-quartz (Hayashi 1973, Browne &

Wodzicki 1977), sphalerite compositions (Browne & Lovering 1973), sulfur isotope
fractionation between coexisting sulfide pairs (Browne et al 1975), oxygen isotope
fractionation between hydrothermal carbonates and silicates (Blattner 1975,
Eslinger & Savin 1973, Coplen et aI 1975), and fluid inclusions (Browne et al 1976,
Browne & Elders 1976, Hoagland 1976b). The last two methods appear to be the
most useful in their applications to geothermal systems.

10

- ------
Zoisite I Calcite mco2�0·01
--------

8 - - - ��+,...- - - - - - - -�·O
Wairakite =0,15

-c----------
Na-mont.

Kaolin K-mica K-feldspar

o ·2 4 6 8 10

Figure 2 Phase diagram for potassium and calcium minerals in terms of ion activity at
260°C with quartz present; m = moles. Circle plots Broadlands and cross Wairakei water
compositions; arrow shows trend with steam loss (Browne & Ellis 1970, Ellis & Mahon
1 977).
 238 BROWNE

The homogenization temperatures of 177 primary fluid inclusions in hydrothermal

quartz and sphalerite crystals from seven Broadlands wells varied between 2010
and 293°C; they ranged from BOC below to 37°C above well temperatures but
averaged 8°C above. One hundred and ninety-eight secondary or pseudosecondary
inclusions, which had a wider temperature spread than the primary ones, gave
filling temperatures that averaged 6°C below corresponding well temperatures.
This close agreement between filling and measured temperatures indicates either
that there has long been a stable thermal system at Broadlands or that the crystals
and their inclusions are modern.
By contrast, fluid inclusions in calcite from Holtz No. 1 well at Heber,
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

California appear to record two former thermal events; at 1525 m these were at
212 ± 9°C and 235 ± 5°C (Browne & Elders 1976), whereas present reservoir
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temperatures are probably about 190°C (Renner et al 1975). At well 6 - 1 East Mesa,
homogenization temperatures show that the fluid inclusions formed IS-20°C above
present well temperatures (Hoagland 1976b).
To date, there have been few measurements of the freezing temperatures of
inclusions to attempt estimates of past fluid salinities, but such studies are likely
to be extremely fruitful. In one study freezing temperatures were measured in 33
primary and 60 secondary (pseudosecondary) inclusions in eight hydrothermal
quartz and one sphalerite crystal (Browne et al 1976) from Broadlands. The
observed freezing point depressions (0.1 to 0.8°C) appear too large if only the
dissolved salts in the deep waters (3000 ppm) are considered, but are in agreement
with the present-day Broadlands water compositions when the range of downhole
CO2 compositions (0.1-0.3 moles) is included in the calculations.

HYDROTHERMAL ALTERAnON IN SELECTED AREAS

Examples of hydrothermal alteration in geothermal fields recently studied show, in

more detail, the variability of these usually interrelated factors.

Imperial and Mexicali Valleys, Western North America

Several geothermal fields have been recognized in the Imperial Valley of Southern
California and its extension southward into the Mexicali Valley, Baja California.
Drilling has so far taken place at the Salton Sea, Brawley, Heber, The Dunes,
East Mesa, and Cerro Prieto. The main structural feature, the Salton Trough, is a
depression filled with up to 7000m of poorly sorted Colorado River detritus which
form sandstones, shales, siltstones, and minor conglomerates (Biehler et al 1964,
Muffler & Doe 1968). Five small young rhyolite domes occur at the Salton Sea,
rhyodacite reaches the surface at Cerro Prieto, and minor intrusive basalts have
been penetrated by wells at the Salton Sea (Robinson et a11976) and Heber (Browne
& Elders 1976).
The northernmost field, the Salton Sea, is the most famous, and here wells
encountered brines with over 250,000 ppm dissolved solids (Table 2) at temperatures
up to 360°C (Helgeson 1968a, Randall 1974, Palmer 1975). Salinities at the other
fields are much lower and are about 50,000 ppm at Brawley, 2000 to 30,000 ppm
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 239

at East Mesa, and about 17,000 ppm at Cerro Prieto. Copper- and silver-rich
scales deposited from brines (Skinner et al 1967) discharged from the Salton Sea
and their precipitation has been considered thermodynamically by Miller et al
(1977). Alteration in cores and (mainly) cuttings from several drill holes here have
been described by Muffler & White (1968, 1969), Keith et al (1968), Muffler & Doe
(1968), and Kendall (1976b); mineral isotope studies have been made by Clayton
et al (1968) and Kendall (l976a, b).
Muffler & White (1969) showed that the sediments, which contain detrital quartz,
calcite, K-feldspar, plagioclase, montmorillonite, illite, dolomite, and kaolinite,
gradually convert, in response to increasing temperatures, to an assemblage above
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

300°C of quartz, Fe-epidote, chlorite, K-feldspar, albite ± K-mica, pyrite, sphene,

sphalerite, and hematite. Detrital montmorillonite below lOO°C converts to illite­
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montmorillonite and then to K-mica below 210°C; ankerite can form as low as 120°C,
and chlorite, calcite, and CO2 are produced below 180°C in response to reaction
between dolomite, ankerite, and kaolinite plus Fe2+ added from the brine. Fe­
epidote and K-feldspar are abundant above 290°C, but calcite disappears at about
this temperature. Temperature is thought to be the main control on the formation
of this low-grade greenschist mineral assemblage, although lithostatic pressure
influences induration and lithification so that rock densities increase from below 2.0
at the surface to 3.0 at 15OOm. Muffler & White (1968, 1969) considered that
high CO2 activity relative to H20 precluded zeolite formation and favored
carbonate precipitation. An interesting aspect of this is that the CO2 at shallow
levels has probably been released from deeper reactions between dolomite and
kaolinite (ISO-200°C) and transformation of calcite into epidote (300-320°C).
Kendall (1976b) has given a detailed description of alteration in three wells
(Magmamax 2 and 3, Woolsey 1). As well as recognizing hydrothermal biotite,
tremolite, garnet, and a high-temperature expanding smectite, she showed that
there has been extensive oxygen and carbon isotope exchange between brines and
carbonates down to lOO- IS0°C; both detrital and authigenic quartz in sandstones
have exchanged oxygen at 290°C generally confirming the conclusions of Clayton
et al (1968). Kendall, however, attributes downwell variations in 018 to incomplete
isotope exchange between fluid and rock caused by differences in reservoir
permeability.
Hoagland (1976a, b) and Hoagland & Elders (1978) have described the
alteration and Coplcn (1976) measured the isotopic ratios of minerals from an
1830m deep well at East Mesa, which has a maximum temperature of 188°C.
The vertical extent of the reservoir can be defined by its alteration and, using
thermochemical evaluation of aqueous species and petrographic observations, two
distinct hydrothermal events were recognized. During the earlier event, quartz,
pyrite, illite, Fe-chlorite, and rare adularia deposited in sandstone, as less porous
siltstones and shales altcred to illite and chlorit e ; however, detrital kaolin,
montmorillonite, and interlayered clays persisted. Fluid inclusion measurements
show that this occurred IS-20°C above present temperatures. Fluids responsible
may have been similar to the sodium chloride brine with 26,900 ppm dissolved
solids that discharged from a deeper (2200-24S0 m) aquifer reached by a drill hol e
 240 BROWNE

400 m to the east. Later, cold water entered· the system laterally and, on heating,
partly dissolved the silicates and precipitated abundant calcite. Thermochemical
calculations show that this may have been of the same composition as sodium
bicarbonate-chloride fluid (2380 ppm dissolved solids) which discharges from the
well and derives from 1660-1800m. This fluid is in chemical, but apparently not
isotopic (Coplen 1976), equilibrium with kaolinite, calcite, and montmorillonite
rather than potassium silicates or dolomite.
A 612-m-deep well at the margin of the Dunes thermal area provides a good
example of self-sealing (Bird 1975, Bird & Elders 1976, Coplen et al 1975, Elders &
Bird 1976). In the upper 300 m, seven zones of dense quartzite have formed by
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

episodic reaction between permeable sandstones and laterally moving sodium

chloride fluids containing up to 3000 ppm dissolved solids. After the porosity of
by Lomonosov Moscow State University on 12/06/13. For personal use only.

the sandstones was reduced, water flowed by way of fractures where quartz,
adularia, pyrite, calcite, and hematite were deposited. Hydrothermal alteration has
increased both the bulk densities of aquifer rocks (from 2.2 to 2.6 gm cm - 3 ) and
their Si02 (35 -50% above initial content) and K20 (90-130%) relative to A1203.
The temperature profile shows maxima of 110°C at 110m and 104 °C at 285 m,
below which there is a reverse gradient. Further, the isotopic compositions of
quartz-water, alkali feldspar-water and calcite-water pairs (Coplen et al 1975)
show that temperatures here have never exceeded 130°C.
By contrast, temperatures as high as 388 °C have been recorded at Cerro Prieto
(Mercado 1969), although 370°C is more usual (Mercado 1976). More than 30
wells have been drilled to between 500 and 2630 m, but unlike the other very hot
field, Salton Sea, deep fluids (Table 2) have salinities of only about 17,000 ppm
(Mercado 1969). The two main factors affecting the formation and distribution
of hydrothermal minerals here are temperature and fluid composition (Reed 1976).
Kaolinite, montmorillonite, and illite-montmorillonite do not occur above 160°C,
nor dolomite above 210°C, but chlorite and illite-chlorite form above 14SOC,
wairakite above 240°C, and epidote above 255 °C. Authigenic orthoclase increases
in abundance above 300°C, in accordance with thermodynamic calculations
(Reed 1976) based on the composition of reservoir water, but is not easily
distinguished in the cuttings from detrital orthoclase or microcline.

Yellowstone, U.S.A.
Because of environmental constraints, no deep drilling is normally allowed within
Yellowstone National Park-one of the world's most famous and spectacular
thermal areas. However, in 1967- 1968 13 shallow diamond-core wells were drilled
as part of a comprehensive scientific project by the U.S. Geological Survey. A
major strength of this work, following the example of Fenner (1934 , 1936) and
Allen & Day (1935), is the close integration of geological, petrologic, and geochemical
methods. Although the deepest well (Y-12) is only 329.6 m deep and most are
near 150m deep, both the drilling and the wells were closely monitored, so that
an excellent physical record was obtained (White et al 1975). In addition, the
near completeness of core recovery (usually above 90%) has made possible the
most detailed work so far on hydrothermal alteration in an active geothermal
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 241

system. Alteration studies have now been completed for wells Y-l (Honda &
Muffler 1970), Y-5 (Keith & Muffler 1978), Y-7, and Y-8 (Keith et al 1978). Less
detailed information from Y-3 (Bargar et al 1973) and Y-ll (White et al 1971) is
also available.
Wells in the Upper Geyser Basin (Y-l, Y-7, Y-S, and Fenner's C-l) penetrated
sandstone, siltstone, and conglomerate mainly composed of rhyolitic detritus over­
lying rhyolite; Y-S, in Midway Geyser Basin, was drilled, for the most part, into
densely welded rhyolitic ash flow tuff. Maximum well temperatures are: 171°C in
Y-1, 170°C in Y-S, 143°C in Y-7, and 170°C in Y -S.
Several minerals not previously known in geothermal systems have been
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recognized. For example, aegirine occurs in Y -1 where the well temperature is

160°C and in Y-3 it also coexists, in the core from 23.8 to 28.5 m at temperatures of
by Lomonosov Moscow State University on 12/06/13. For personal use only.

130�140°C, with quartz, pectolite, montmorillonite, analcime, ?albite, and lepidolite

(with 7.5% LhO). Fluids depositing these minerals (Table 2), although dilute, have
high LijK ratios (1.8) and low Cl/F ratios (about 5).
Factors affecting hydrothermal alteration at Yellowstone vary in importance
from well to well and are not easily separated. The nature of the starting material is
important in Y-1, Y-7, and Y-S where detrital obsidian alters readily, but coexisting
lithoidal rhyolite of essentially the same composition remains unchanged. The
dense, welded ash-flow tuff in Y-S shows only incipient alteration (to mont­
morillonite) as its devitrification products, quartz and sanidine, are more stable
than glass so that hydrothermal minerals are here more abundant than in Y-S.
Obsidian clasts in Y-7 and Y-8 alter, first nearly isochemically, to ?metastable
potassic clinoptilolite (K20 up to 5.7%) and then to analcime plus K-feldspar.
Temperature is important but its effect is often equivocal and difficult to
distinguish from fluid composition or variations in permeability. Obsidian in Y-l is
completely replaced above 85°C, but persists to 170°C in Y-8 because of lower
permeability in the vitrophyric flow breccia, which indicates that through-going
solutions are needed here for even devitrification to occur. Opal occurs only below
43°C in Y-5 and near t04°C in Y- t, whereas in this welt /1-cristobalite is not
present above 115°C. Erionite is present in cores from several wells where
temperatures are below 110°C. Differences in fluid composition, especially Si02
activity, rather than temperature, evidently account for the observed distribution of
clinoptilolite, mordenite, and cx-cristobalite and the quartz-analcime association in
Y-l. Subsurface boiling caused changes in fluid pH through loss of CO2, thereby
resulting in deposition of adularia in wells C-l and Y-13 and bladed calcite in Y-8
and Y-S. The Yellowstone work, however, confirms the important effect of
permeability in determining the extent and type of hydrothermal alteration in
geothermal systems. For example, K-feldspar, quartz, mordenite, and celadonite
have formed in permeable zones of Y-8, but in deeper impermeable parts of this
well glass persists. Further, mineral deposition in pore spaces of a correlated unit
in the 130 m between the sites of Y-7 and Y-8, the latter of which is thought to be
closer to the upflow zone, has caused self sealing, so that there is now a pressure
differential of .015 bar m I between the two wells.
-

These two wells also provide a good record of relationships among silica
 242 BROWNE

minerals in a geothermal field. X-ray-amorphous opal dominates in superficial

sinter and also forms near-surface cement, whereas IX- and ,B-cristobalite have
irregular distributions at greater depth. In Y-7, ,B-cristobalite occurs mainly in
vein lets and the IX-form is in the groundmass, but cores from Y-8, the hotter well,
contain quartz and chalcedony. This suggests that the distribution of silica minerals
is controlled primarily by temperature. From a study of veinlets, Keith et al (1978)
found that the silica forms, deposited from oldest to youngest, were quartz,
chalcedony, IX-cristobalite, ,B-cristobalite and opal; this is also the order of decreasing
stability and increasing solubility with respect to water of constant temperature
(Fournier 1973, Arnorsson 1975). Keith et al (1978) concluded that water from the
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

wclls is strongly supersaturated with respect to quartz, chalcedony, and IX­

cristobalite; is slightly undersaturated relative to p-cristobalite; and is under­
by Lomonosov Moscow State University on 12/06/13. For personal use only.

saturated above 80°C with respect to opal. However, fluids in the reservoir itself
are just saturated with quartz. Their suggested model is one in which ascending
silica-rich water penetrates aquifers which, through self-sealing, become partially
closed systems; the trapped pore water then becomes progressively lower in SiOz as
more stable silica minerals are successively reconstituted from the earlier deposited
phases.

Japan

Japan has about one hundred geothermal systems, excluding fumaroles on the
craters of active volcanoes (Sumi & Takashima 1976). Several fields have been
investigated by exploratory drilling and numerous accounts of their alteration
have been published recently'; space, however, permits mention of only a few.
Most Japanese geothermal systems, and indeed, many in the west Pacific, are
associated with late Cenozoic andesite-dacite volcanic centers where there is usually
a strong structural control on hydrology. A characteristic feature of their alteration
is marked surface zonation; typically, between 3 and 10 alteration zones can be
clearly recognized (Sumi & Takashima 1976). This, and the rarity of zone overlaps,
shows that thermal episodes were commonly single events in contrast with many
systems where mineral zoning, even when recognizable, is irregular. However,
cross sections of alteration in several Japanese fields, such as Matsukawa (Sumi
1968), show more complicated zoning in the subsurface than is evident at the
surface. Sulfates (particularly alunite) and kaolin are common, and pyrophyllite
and zeolites occur in several fields (Hayashi & Fujino 1976, Hayashi & Yamasaki
1976, Sumi & Takashima 1976, Takashima 1971, Yamada 1976, Yoshida 1974,
Yoshida et al 1976). An example of calcium zeolite formation is at Katayama,
Onikobe where the zonation, with increasing depth and temperature, is mordenite­
laumontite (± yugawaralite, analcime)-wairakite (Seki et a11969, Seki & Okumuru
1968). However, the transition temperatures between laumontite and wairakite
(75°C to 175"C in four wells) seem to be below the usual formation temperatures of
wairakite (about 220°C), possibly because water pressures at Katayama are low.
However, it is not clear that the measured well temperatures are the same as
those that prevailed before drilling. Yamada (1976) suggests that IX-cristobalite
occurs in the vapor zone at shallow depths, but zeolite alteration results from
 HYDROTHERMAL ALTERA nON IN GEOTHERMAL FIELDS 243

reaction between andesite and mildly alkaline solutions. Near the bottom of one
1200-m well (GO-lD), however, quartz and kaolin have deposited from acid
chloride solutions.
Another field where alteration shows a close dependence on fluid composition is
at Otake, north-central Kyushu (Hayashi et al 1968, Hayashi 1973, Hayashi
& Fujino 1976, Hayashi & Yamasaki 1976, Yamasaki & Hayashi 1976), where
two chemically distinct fluids (Table 2) have deposited minerals zoned about
fractures. In the Otake area itself deep waters are neutral to alkaline but wells at
Hatchobaru, 3 km south, encountered fluids with a pH between 3.4 and 4.6. Hayashi
(1973) classifies the alteration into five types (Table 3), based on the composition of
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

the altering fluids, and subdivides further depending on measured well temperatures
and fluid pressures. However, the temperatures in many wells were measured only
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a few days, or even hours, after drilling, so that they are unlikely to be quite
the same as the temperatures of mineral deposition. Where acid fluids prevail,
Type B alteration is conspicuous and Type D either occurs at shallow levels or
where reaction is incomplete. By contrast, at Otake itself, mildly alkaline fluids
have restricted Type B alteration but Types D and E are widespread. Major
element analysis (Hayashi 1973) shows that massive amounts of Si02 were addcd to
rocks with alteration of Type A, but during formation of Types B and C, Si02,

Table 3 Classification of hydrothermal alteration in the Otake geothermal area (after

Hayashi 1973)

Temperature
Type Minerals' Fluid (0C) P fluid (bars)

A crist strong acid < 100 < 15

quart7. acid 100 to 230 30 to 50
B alunite+ crist strong acid < 100 < 15
alunite+ quartz strong acid 100 to 230 15 to 50
C kaol+ crist acid < 100 < 15
kaol + quartz acid 100 to 200 < 30
dickite+py acid 1 50 to 250 < 60
+quartz
py+ quartz acid > 230 > 50
D mont+ crist weak acid < 100 < IS
mont S/M + quartz weak acid 100 to 200 < 30
ch+S/M+ quartz weak acid 1 50 to 250 < 60
S+quartz neutral > 230 > 50
E he ul+crist n eutral < 100 < IS
laum+wair+ neutral 100 to 200 < 30
qu artz
albite+ quartz weak alkaline 1 50 to 250 < 60
adularia+ quartz weak alkaline > 230 > 50

a Abbreviations are as follows: crist, cristobalite; kaol, kaolinite; py, pyrophyllite; mont, mont-
morillonite; ch, chlorite; S/M sericite-montmorillonite; S, sericite; heul, heulandite; laum, laumontite;
waif, wairakite.
 244 BROWNE

Alz03, and TiOz are nearly immobile, as are Fez03, CaO, and Mgo during
formation of Types D and E; however, NazO and KzO are the most mobile
constituents.
The Matsukawa field, northern Honshu, also has zoned surface alteration (Sumi
1968, 1969, Sumi & Takashima 1976) that extends over an area of 7 by 1.5 km.
It is elongated about fissures so that structural control of fluid flow and alteration
is obvious. From the margin inward four alteration zones are characterized by
saponite plus chlorite, montmorillonite, kaolin, and alunite, but other hydrothermal
minerals present include laumontite, calcite, and anhydrite in the chlorite zone,
calcite, anhydrite, and quartz in the montmorillonite zone, and quartz in both the
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

kaolin and alunite zones. A far smaller zone of pyrophyllite, usually with diaspore,
zunyite, andalusite, quartz and anhydrite, which is overlapped by three other zones,
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is thought to be relict alteration formed above about 3 10°C, whereas present well
temperature maxima are near 230 to 250°C; (Sumi 1968, Truesdell 1976). When
first opened, the wells typically discharged wet steam of low pH (about 5) and
high sulfate contents (Table 2). Zoning from alunite-quartz at the center to outer
kaolin is consistent with acid (at 200°C pH below 4) solutions moving outwards
from channels and becoming more alkaline by reaction with reservoir rocks.

Iceland
Work on hydrothermal alteration in geothermal fields of Iceland has several
important aspects: (a) it provides the best examples of reactions between thermal
fluids and basalts, (b) there is extensive zeolitisation, especially in the low
temperature « 150°C) fields, (c) in the Reykjanes area the thermal fluid is modified
sea water (Kristmannsd6ttir 1975, 1976, Kristmannsd6ttir & T6masson 1976a, b,
c, Sigvaldason 1963, T6masson & Kristmannsd6ttir 1972, 1976).
Reservoir rocks are basalt, basaltic hyaloclastites and minor dolerite. Glass
readily alters first to opal, smectite, calcite, or a zeolite, and then to mixed-layer
clays, although where permeability is low it persists to 200°e. Olivine is the most
unstable mineral and it and pyroxene are often partly replaced by smectite-illite
or chlorite. Complete replacement of plagioclase by epidote or albite is also rare,
indicating that disequilibrium between fluids and rocks is usual. Factors controlling
alteration are rock type, water composition, permeability, temperature, and the age
of the system-although the first two are less important.
The high-temperature (up to 298±4°C) fields occur in areas of active volcanism
and, except for potash enrichment in some permeable zones at Reykjanes,
alteration is near isochemical involving hydration and oxidation. Clays are
abundant but poorly crystalline; iron-rich saponite, present below 200°C, is replaced
by mixed-layer chlorite-smectite in the range 200° to 230°C and chlorite above
230°e. Zeolites are common below 230°C, but thermal gradients are so steep
that a distinct temperature zoning cannot be readily detected. Epidote is abundant
above 260°C and an amphibole (of unspecified composition) occurs locally where
temperatures exceed 280°e. In the Nesjavellir field, prehnite is present above 250°C
and calcite alternates in abundance with the zeolites. Well fluids are rich in
carbonate ( 1355 ppm COz equivalent) and sulfide (3 1 1 ppm), and consequently
 HYDROTHERMAL ALTERATION IN GEOTHERMAL FIELDS 245

carbonate and sulfide minerals dominate the deep alteration. However, the observed
hydrothermal minerals were not formed at the measured well temperatures
because activity is shifting north and there has not been time for minerals to
adjust to the higher temperature regime.
A high-temperature system in the Reykjanes area, southwest Iceland, is only
one of several fields (Truesdell 1976) in which modified sea water is the thermal
fluid, but it has the best record of alteration minerals formed from its reaction
with reservoir rocks. Hydrothermal minerals are crudely zoned according to
temperature (which reaches 300°C) : (a) montmorillonite-zeolite-calcite zone;
(b) mixed-layer clay-prehnite zone; (c) chlorite--epidote zone. These minerals occur
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

in many fields in Iceland and elsewhere, although fluid compositions vary greatly,
leading Tomasson & Kristmannsdottir ( 1972) to conclude that permeability,
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porosity, and especially temperature are the main controls of hydrothermal

alteration. Anhydrite, deposited when sea water heated, has an irregular distribution
that may be due to about 20 to 30 sea water invasions which occurred when the
usually impermeable boundaries of the field were ruptured by tectonic events.
Alteration in low-temperature (below 150°C at IOOOm) fields expands the
smectite-zeolite zone of the hotter areas and confirms the control of temperature
on zeolite distribution. Kristmannsdottir ( 1976) distinguishes four zones character­
ised by: (a) chabazite, opal, calcite ± levyne and stable to about 80°C; (b) mesolite­
scolecite present from 80 to 90°C; (c) stilbite occurring between 100 and 120°C;
and (d) laumontite above 120°e. Smectites occur at shallow depths typically
coexisting with chlorite from about 180°C, although both "swelling" chlorite and
random mixed-layered clays are also present. However, prehnite, epidote,
quartz, and possibly chlorite in at least two low temperature fields are thought
to be relicts from an earlier hotter regime.

THE FUTURE

No simple enumeration of factors affecting hydrothermal alteration can yet account

for all the observed complications. With new or greatly expanded drilling programs
in many parts of the world, however, much more will be learnt (and, hopefully
published) so that it may soon be possible to isolate more confidently the effects of
a single factor without distorting the general pattern.
Observations made so far confirm the important effect of temperature in the
formation of hydrothermal mineral assemblages, but also demonstrate the critical
role of permeability. Geochemical studies of thermal fluids have made a major
contribution to knowledge of the intimate relationship between fluid composition
and mineral deposition. However, few attempts have yet been made to interrelate
the distribution of minor and trace elements in rocks, minerals, and fluids. Reasons
why so many hydrothermal minerals occur in geothermal fields are still sought :
possibly some phases are metastable, or stabilized by the substitution of minor or
trace elements. Fluid inclusion measurements have great promise in helping unravel
the evolution of geothermal systems, particularly when used in conjunction with a
thermodynamic model for mineral deposition, such as that suggested by Helgeson
 246 BROWNE

(1970). Experimental mineral syntheses and thermodynamic calculations of mineral

equilibria should help clarify low-temperature phase relations, especially if the
effects of solid solution are also considered.
Ot her rewa rdi ng approaches for some fields would be to evaluate quantitively
mass transfer between fluid and solid phases ; such studies, however, need careful,
detailed petrologic and geochemical analysis of altered and unaltered rock samples.
Although an understanding of hydrothermal alteration in active geothermal
systems will add greatly to our knowledge of low-grade metamorphism and hydro­
thermal ore deposition, much already known about these subjects could also be
usefully applied to predict the evolution, and conditions, in geothermal reservoirs
Annu. Rev. Earth Planet. Sci. 1978.6:229-248. Downloaded from www.annualreviews.org

below drilling depth.

by Lomonosov Moscow State University on 12/06/13. For personal use only.

ACKNOWLEDGMENTS

I am grateful for the helpful comments of W. A. Elders, A. J. Ellis, J. H. Lowery,

W. A. Watters, B. G. Weissberg, D. E. White and C. P. Wood, and I also thank
Mrs. M. Ruthven for typing and Mrs. P. Williams for drawing the two figures.

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