Society of Economic Geologists
SpecialPublication 10, 2003, p. 1-18
Chapter 1
SEG Distinguished Lecture
Magma Degassing and Mineral Deposition in Hydrothermal Systems
along Convergent Plate Boundaries"
WERNER F. GIGGENBACH
lnstitute of Geological and Nuclear Sciences, Lower Hutt, New Zealand
lntroduction
To be honest, 1 am surprised to find myself address-
ing a meeting of the Society of Economic Geologists
-being neither a geologist nor economic. And look-
ing at the title of my paper, 1 wouldn't be offended if
people told me that I may be going to talk about some-
thing 1 know nothing about. After listening to sorne of
this afternoon's talks, however, it is clear to me that 1
wouldn't be the only one. With this 1 don't mean that
the previous speakers were inept but that there are
still quite a few basic problems which have to be
~olved ?efore we may safely say, we know what's go-
mg .ºn m hydrothermal systems. And by basic, 1 mean
bas1c.
The title of my talk links two processes: magma de-
gassing, something 1 have been studying now, from
the gases' point of view, for more than 20 years, and
mineral deposition, something 1 had my nose rubbed
in to by living in close vicinity to sorne of the biggest
gold freaks like Kevin Brown, Jeff Hedenquist, Dick
Henley, and Terry Seward. 1 myself had, quite early
on, declared gold a four letter word and had vowed
never to use it in any of my papers, together with
other uncouthities, such as zinc or lead. Now that the
above have dispersed, each into his corner of the
globe, 1 think myself free to reconsider my earlier
pledge.
When 1 joined the now defunct DSIR in 1968 I
think it was in the middle of the "neptunistic" peri~d
of interpreting processes in hydrothermal systems.
º Delivered befare the Society of Economic Geologists at their
meeting with the Geological Society of America, October 23,
1991, at San Diego.
1
Reprinted from Economic Geology,
Society of Economic Geologists Bulletin
1992,v 97, p. 1927-1944
On the basis of isotopic measurements, Craig (1963)
had suggested that by far the major proportions of
water in hydrothermal discharges are of local me-
teoric origin, Jim Ellis and Tony Mahon (1964) had
found that most of the chemical constituents of geo-
thermal waters could readilv be leached from
igneous and sedimentary rocks: In other words, peo-
ple put on a somewhat bemused look should one in-
voke a "magmatic" origin of sorne of the things one
found in one's samples.
Within a few years of arriving in New Zealand I
became involved with the chemical surveillance of
two of the most active volcanoes there: White Island
and Mount Ruapehu. N ow these were beyond doubt
systems closely associated with magmatic activity,
people had "seen and felt" it. The waters produced
there were, of course, quite different from those en-
countered at the geothermal systems and one was al-
lowed, at least tentatively, to consider a magmatic
origin of sorne of the constituents. After several years
of observation, it became apparent that White Island
went through cycles. Following a high-temperature
period in the early seventies, most of the fumaroles
cooled down and the earlier, typically volcanic dis-
charges, characterized by gases with S0 2 as the ma-
j?r S-containing species, with lots of HCl, and very
httle CH 4 , slowly reverted to "geothermal" dis-
charges with H 2 S as the major S species, very low
HCl, and much more CH 4 (Giggenbach, 1987). If
such a transition could take place in a bona fide mag-
matic system, why shouldn't it also happen at other,
less obviously "magmatic" systems? Anyway, White
Island started to convince me that magmatic contri-
butions to "geothermal" discharges may be much
2 WERNERF. GIGGENBACH
o have been taken from a vast inventory of earlier stud-
(km)
2 McNabb (1978), Bethke and Rye (1979), Burnham
4
Frc. 1. Schematic arrangement of alteration zones in a typical
"low sulfidation" porphyry-typc, hydrothermal mineral deposit.
more important than generally assumed. By compar-
ing the chemical and isotopic compositions of vol-
canic with geothermal discharges, soon "indicators"
emerged showing that even geothermal systems not
obviously associated with active volcanism might
contain a considerable proportion of magmatic con-
stituents.
In the meantime another bunch of people, called
geologists, approaching hydrothermal systems from
the opposite side, that of mineral or even ore deposi-
tion, found increasingly convincing evidence of a
magmatic connection. By the way, according to Noel
White (pers. commun.), a mineral deposit becomes
an ore deposit only if people are prepared to huy
shares in it. In order not to compromise themselves
too much, the commitment of the geological frater-
nity to the magmatic cause usually consisted of more
or less artistically executed magic arrows marked
"magmatic fluid" or even less specific "magmatic in-
put," pointing up from sorne nether regions where
anything could happen. Figures 1 and 2 represent
composite pictures of the two major types of these
allegedly magmatic hydrothermal systems, termed
for the time being, by geologists: "low sulfidation"
and "high sulfidation" (Bonham, 1986; Hedenquist,
1987; White and Hedenquist, 1990). Chemists may
have come up with a classification of these systems
into "near-neutral, reduced" and "highly acid, oxi-
dized" systems and associated fluids possibly into
mature and immature, or "benign" and "virulent"
(Reyes, 1990, 1991). I want to leave it to future gen-
erations to find the most suitable terms. Actually, I
am not sure what the term "low sulfidation" refers
to. Here I apply it to both epi- and mesothermal sys-
tems, including porphyry metal deposits.
Anyway, both Figures 1 and 2 have their
"mag(mat)ic" arrows in place. In this talk I will try to
put sorne meat onto them, by delineating the possible
origin of the "fluids" involved, their chemical evolu-
tion in hydrothermal systems, and the effects of
various modes of magma degassing on mineral deposi-
tion. Most of the bits and pieces I am presenting here
ies and models of these systems, su ch as those of Bun-
sen (1847), Krauskopf (1957), White (1957), Lowell
and Guilbert (1970), Holland (1972), Sillitoe (1973),
Whitney (1975), Cathles (1977), Henley and
(1979), Skinner (1979), Henley and Ellis (1983), Sil-
litoe and Bonham (1984), Eugster (1985), McKibben
and Elders (1985), Hayba et al. (1986), Stoffregen
(1987), Hedenquist (1987), White and Hedenquist
(1990), Candela (1991), and Hemley and Hunt
(1992), to name sorne. All I am trying to do is stick
them together with sorne glue extracted from chemi-
cal and isotopic analyses of quite a pile of geothermal
and volcanic water and gas samples. Having worked
now in New Zealand for more than 20 years, right
astride a convergent plate boundary and at the south-
western end of the horseshoe of fire around the Pa-
cific, my experience is somewhat tainted by this close
association with hydrothermal systems typical of this
kind of tectonic environment.
Nature and Origin of Magmatic Constituents
By far the most convincing evidence of a largely
nonmagmatic origin of geothermal waters was pro-
vided by the finding of Craig (1963) that all the
waters available to him then had the same deuterium
(D) contentas local ground water. If one or even sev-
era! "magmatic" waters existed, it would be too
much of a coincidence if all their D contents were to
agree with those of local ground waters. During an
earlier investigation into the isotopic composition of
steam discharged from high-temperature fumaroles
on White Island (Stewart and Hulston, 1975), D and
18
0 contents defined a trend suggesting formation
through equilibrium evaporation of a seawater de-
rived brine. 1 kept on collecting fumarolic conden-
sates and found a similar trend, but one which
pointed to the existence of a highly 18 0-enriched
end-member component with a D content in the vi-
HIGH "SULFIDATION" LOW
PROPYLITIC
ALTERATION
E
o
o
en
Frc. 2. Schematic arrangement of alteration zones in typical
"high" and "low sulfidation" hydrothermal mineral deposits. Ka-
olinite is taken to represent highly cation-depleted Al silicates.
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
cinity of -20 per mil. This D content was quite differ-
ent from that of the local meteoric waters. I didn't
take much notice and just thought, it' s one of those
things. But when in 1976, on the occasion of the re-
tirement of Athol Rafter, Hitoshi Sakai visited New
Zealand, he brought with him sorne preliminary data
on the isotopic composition of fumarolic vapor con-
densates from Japanese volcanoes (Sakai and Matsu-
baya, 1977), and there again was this end-member
water with óD = -20 per mil and ó18 0 > +5 per mil.
W e both agreed that there must be something to this
coincidence and that it possibly pointed to the exis-
tence of a common end-member component, sorne
kind of "andesitic water."
I only believed it half myself and kept on interpret-
ing so-called oxygen shifts purel y in terms of isotopic
exchange between local ground water and rock, even
if it didn't quite fit, as at Broadlands, now Ohaaki
(Giggenbach, 1971). As I got more and more in-
volved in geothermal exploration projects in Latín
America and other countries around the Pacific, it
became clear that "horizontal" 18 0 shifts were actu-
ally the exception rather than the rule. Except for El
Tatio (Giggenbach, 1978), oxygen shifts were usually
also accompanied by a positive deuterium shift. The
magnitude of the D shifts for these systems at low to
intermediate latitudes, however, were too small to
allow an unambiguous assignment to a common cause
or process.
More recently data became available for fumarole
condensates from volcanoes at very high latitudes, '
such as those from Saint Augustine volcano in Alaska
(Viglino et al., 1985) and volcanoes on the Kam-
chatka Península (Taran et al., 1989). By plotting
these data, together with those of discharges from
other geothermal and volcanic systems along conver-
gent plate boundaries, as shown in Figure 3, it be-
o
óD
(°loo)
-50
-100
-15 -10
Frc. 3. Deuterium versus 18 0 contents for geothermal waters and volcanic condensates, together with
associated local ground waters. Data from Giggenbach (in press).
3
carne apparent that they all followed similar trends
corresponding to mixing of local ground waters with
a surprisingly uniform end-member water with an
18
0 content corresponding to about + 1 O per mil, and
a D content of -20 per mil.
Now, if we accept that such a common end-
member water exists, its globally uniform composi-
tion can only be explained in terms of source waters
also with globally uniform isotopic compositions.
This excludes straightaway any meteoric waters or
waters derived from them. The most obvious source
of globally uniform water is, of course, seawater. Its
óD value is by definition Oper mil. In order to reduce
it to -20 per mil, it would have to be mixed with
another water with a globally uniform, but lower, D
content. A possible candidate is "primary magmatic
water," or better, water dissolved in the mantle. Its
isotopic composition has been suggested to be in the
vicinity of -65 ± 15 per mil (Sheppard et al., 1969;
Taylor, 1986). Mixing it with a "shifted" seawater, as
shown in Figure 3, in the proportion 1 to 2 could
conceivably lead to the formation of a water with óD
= -20 per mil. Maintenance of such a precise mixing
ratio for waters from widely varying geologic and tec-
tonic environments, however, appears highly un-
likely. In a paper submitted more than a year ago
(Giggenbach, in press), and by now scrutinized by
more than a dozen reviewers, I propose these andes-
itic waters to represent essentially recycled seawater,
carried to the zones of are magma generation by the
subducted slab. The entire process is illustrated in
Figure 4.
Seawater may enter the subduction zones in essen-
tially three isotopically distinct forms: incorporated
into hydrous minerals forming within seawater-
driven hydrothermal systems along midocean ridges,
bound in pelagic clays, and as pore water (Peacock,
O local groundwaters
e geothermal discharges
• volcanic condensates
-5 o +5 o18Ó(%o)
4 WERNERF. GIGGENBACH

mid-oceon ridge
hydrothermol system

Frc. 4. Derivation of "andesitic water." Isotopic compositions are those of hydrogen in respective
waters.

1990). The first process involves quite high tempera- 1984), while pore water may be expected to retain its
tures and leads to the formation of amphiboles, zeo- isotopic composition. An "andesitic water" with a oD
lites, chlorite, and serpentinite with typical D frac- value of around -20 per mil could simply represent
tionations in the vicinity of 60 per mil, that is, the mixtures of these waters in albeit quite narrowly de-
minerals are isotopically depleted by this value with fined proportions. A more likely possibility is forma-
respect to seawater (Cole et al., 198 7). Incorporation tion of the andesitic water preferentially from the sed-
into sedimentary clays is accompanied by a smaller D imentary clay fraction (Giggenbach, in press). The
fractionation of about 30 per mil (Liu and Epstein, marine clays are carried on top of the subducting slab
and, depending on the angle of subduction, varying
proportions may be scraped off to form the accretion-
vesiculority Vv (%} 1D 10 50 90 ary wedges. A considerable fraction of subducted sed-
_10 earl vapor iments, however, may reach the mantle environ-
ment. There, they are early on exposed to conductive
heating from the mantle wedge leading to preferen-
-20 tial mobilization of sedimentary volatiles and their in-
corporation into rising andesitic magmas. The more
~ _
i)'j parent melt late vapor deeply buried water associated with the hydrated ba-
30
salt may reach deeper levels to replenish the reser-
closed-
system voir of mantle water with its lower D content.
-40 '\ degossing Exsolution of water from a magma is accompanied
\ (underground)
by minor but significant isotopic fractionation (Tay-
\
\ \ residual melt lor, 1986). Assuming a reasonable value of about 20
-50
\ \ per mil, the evolution of D contents during exsolu-
open- system \ ,.,,.,~
\ 1 tion corresponds to the trends depicted in Figure 5.
-60 degoss1ng __,,¿'.\\ \ Two degassing processes are distinguished: closed-
(surface 1 \ \
system degassing generally governing underground
\ \ vapor-liquid fractionation processes (Taylor, 1986),
and open-system degassing typical of surface degas-
.0001 .001 01 0.1 10 10
Rv
sing during eruptions. In both cases, the "early" va-
Frc. 5. Variations in oD values of water in coexisting melts and
por-that produced at small vapor/melt volume ra-
vapor as a function of vapor/melt ratios, Rv, for closed- and open- tios (RJ-is enriched in D by the value of the frac-
system degassing. tionation factor. From Rv values of 0.01 onward,
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
2ílillJ roe 100 000 He
FIG. 6. Relative H 2 0, C0 2 , and He contents for vapors asso-
ciated with andesític and basaltic magmatism. Data for andesític
volcanoes from Giggenbach et al. (1990).
significant amounts of water are transferred to the
vapor phase and hoth the D content of the vapor and
of the residual melt decrease. These decreases are
much more rapid in the case of open-system degas-
sing, and D contents for both vapor and residual melt
can reach very low values. The D contents of waters
in usually subaerially erupted andesitic lavas, there-
fore, are unlikely to be representative of those of the
original parent magmas. In the case of closed-system
degassing underground, the D content of the vapor
approaches that of the dissolved water at R values >
1.0, that is, when the volumes of coexisting vapor and
melt become about equal. The range of bD values
generated by this process agrees with that delineated
by the isotopic compositions of volcanic and geother-
mal waters as shown in Figure 3.
Water is not the only volatíle present in subducted
sediments. Another major source of volatiles is sedi-
mentary earbon (Peacock, 1990). Its remobilization
can be expected to give rise to increased C0 2 con-
tents of andesitic vapors. A comparison of relative
H 2 0 and C0 2 contents of volatiles uncontaminated
and contaminated by subducted sediments is carried
out by use of Figure 6. Uncontaminated vapors are
assumed to be represented by volatíles associated
with basaltic magmatism, as extracted from Mid-At-
lantic Ridge "popping rocks" (PR; Javoy and Pineau,
1991) and discharged from high-temperature fuma-
roles within the Sierra Negra caldera (SN) on the Ga-
lapagos hot spot (W. F. Giggenbach and R. J. Poreda,
in prep.). "Contaminated" vapors are represented by
gases collected from high-temperature fumaroles
(>300ºC) on the andesitic volcanoes Satsuma Iwo-
jima (SI) and Mount Usu (MU), Japan; White Island
(WI) and Ngauruhoe (NG), New Zealand; Pa-
5
pandayan (PP), Indonesia; and Vulcano Island (VU),
Italy (Giggenbach et al., 1990).
All the samples shown have 3 He/4He ratíos more
than five times those in air, indicating that the He is
essentially of mantle orígin. Helium may therefore be
used as a reference to measure other than mantle
contributíons to a magmatic gas. In spíte of their deri-
vation from two quite different tectonic envíron-
ments, a mídocean rídge and a hot spot, the composi-
tions of the two "basaltic" gases are quite similar,
with an average H 20/He ratio of 26,000 and a C0 2/
He ratio of 30,000. The averages for the six "andes-
itic" gases are about a hundred times higher for H 20/
He, at 2,720,000, and sorne five times higher for
C0 2/He, at 150,000. All these samples are from
high-temperature (>400ºC) fumaroles; dilution by
cooler crustal or ground waters, therefore, can only
be minor. The interna! consistency of the patterns
suggests that "andesitic vapors" have intrinsically
higher H 2 0 and C0 2 contents. The most likely
sources of this excess H 2 0 and C0 2 are again suh-
ducted marine sediments (Giggenbach, 1992).
Another ubiquitous constituent of volcanic and geo-
therrnal vapor discharges is N2 • Already in 1978,
Matsuo et al. ascribed highly increased N 2/Ar ratios
(>500) with respect to air (83) to the addition of N 2
from subducted sediments. By plotting relative N 2 ,
He, and Ar contents for hoth andesitic and basaltic
vapors (Fig. 7), the two groups can be shown to oc-
cupy distinct positions (Giggenbach, 1992). Again
N2 /He ratios for the andesitic vapors are consider-
ably higher (> 1,500) than those of the basaltic vapors
(<2.50). Accepting that all the excess amounts of
H,p, C0 2 , and N 2 are derived frorn subducted sedi-
rnents, only about 1 percent of the water and <20
percent of the C0 2 and N 2 in vapors associated with
andesitíc magmatism are of mantle origin. Because of
gases assoc1uted w1t h
• cm:Jesit1c
• tx::.salt1<.: rmgnahsm
50
20
Frc. 7. Relatíve N2 , He, and Ar contents of "andesitic" and
"basaltic" vapors. Data from Giggenbach (1992).
6 WERNERF. GIGGENBACH
the involvement of large proportions of subducted
marine constituents, a considerable part of the S and
Cl in vapor discharges from andesitic volcanoes is
likely to be of a similar origin.
Once entrained into the rising andesitic magma,
the volatiles will react with one another and the rock
in response to decreasing temperatures and pres-
sures to produce the variety of gases encountered at
the surface in volcanic and geothermal areas.
Chemical Evolution of Volatiles
The close association of geothermal systems with
volcanic systems has long been recognized (Bunsen,
184 7). In 19.57, White provided a classification of the
majar types of volcanogenic waters and suggested
processes that may account for their compositional
differences. The two majar chemical variables con-
trolling the composition of aqueous fluids and their
interaction with rock are redox potential and acidity.
I use the term "fluid" only reluctantly, as its indis-
criminate use is one of the indicators that someone
doesn't know what he/she is talking about, or can't
make up his/her mind whether it's a vapor or liquid.
If at all possible one should use the more specific
terms "liquid" or "vapor"; after all, they have quite
different properties and behave quite differently.
You may also notice that I use the somewhat vague
expressions "redox potential" and "acidity" when I
could have used, e.g., f 02 and pH, terms having a
much more distinct, if not distinguished ring about
them. . Use of these master variables is often only a cop-
When I accepted the invitation to give this lecture,
I asked SEG what they wanted me to talk about, and
they replied: anything you like, it is your chance to
get things off your chest, things you would never say
in a formal paper (also, of course, providing an excel-
lent chance to make a fool of myself). If they only had
known. I am conducting a number of minor pet cru-
sades. One of them is "fighting" the use of f 02 and
variables of a similar ilk, su ch as f 52 , Eh, in connection
with hydrothermal systems. You may ask, why
bother, after ali they are only convenient ordering
parameters, "master variables," very useful in the
depiction of the relative stability of mineral and other
phases.
What does it matter that there is only about one-
tenth of an 0 2 molecule in a km 3 of water in equilib-
rium with crustal rocks at 2.50ºC? What does it mat-
ter, we might as well use praseodymium (II/III) ra-
tios, thermodynamically they are all equivalent. The
thing is, of course, that we are doing geochemistry
and not thermodynamics and thermodynamics is only
a tool to be adapted to our needs and not the other
way round. We want to find out who does what to
whom and when, and 0 2 does nothing, to nobody,
never, in your average hydrothermal system. But peo-
ple argue we can measure it, we have, e.g., elec-
trodes which respond to it. Whom are they trying to
kid? These electrodes measure anything but f 02 . I
want to see the electrode capable of sensing one-
tenth of an 0 2 molecule in 1 km 3 of solution. What it
sees is perhaps f 82 , the Fe(II)/Fe(III) or Mn(II)/
Mn(III) activity ratio, but not f 02 . So why use some-
thing of no relevance? Are our brains so corroded by
thermodynamics or are we so blinded by the appar-
ent elegance, or rather arrogance of these concepts?
As with any other set of principies, belief systems, or
religions, thermodynamics, if pushed too far, can lose
its contact with reality and become meaningless.
Thermodynamics simply doesn't worry about atoms
and kinetics, real life is all atoms and kinetics.
And it does matter. Only yesterday, I went to a talk
where it was argued that the main advantage of using
f 02 , even in low-temperature diagenetic systems, is
its strong temperature dependence. I fully agree, f 02
would make a perfect geothermometer, if it could be
measured. Any lower temperature (<SOOºC) f 02 ,
however, is always obtained only indirectly, by use of
a conversion reaction such as
(1)
By expressing redox potentials in terms off 00 , we sim-
ply multiply in the steep temperature dependence of
a conversion reaction and nothing is gained. It is the
same as looking into your wallet with a magnifying
glass and thinking you have more money.
out and another good indicator that people don't
know what is really going on, in this case which vari-
ables actually control redox potential or acidity. It is
so easy to say: when the f 02 or pH goes up or clown,
such or such happens, but it doesn't tell one how, and
what, and when. To get these answers we have to
write our reactions in terms of actual reaction partici-
pants, which sometimes may not be easy. But by for-
getting about these cop-out variables, f 02 , Ís 2 , Eh,
and even pH, we are forced to look for the real reac-
tion participants. The use of nonexistent, practically
irrelevant reaction participants is probably justified
if we see chemical equations only as energy balances
and neglect the dualistic character of the law of mass
action, according to which a chemical equation is al-
ways also a mass balance. The reaction
(2)
may proceed on contact with air, but not deep within
a hydrothermal system;
2Fe 3 0 4 + H 20 = 3Fe 2 0 + H2 (3)
3
does.
After all this noise, it is probably up to me now to
show which variables to use and how to find them.
Nature only reveals her secrets if we ask the right
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
questions and listen, and listening in geochemistry
means sampling, analyzing, plotting. Before going
any further, I may be allowed to offer sorne more
recipes for successful listening. "Plotting" should be
based on data as measured, corrected for obvious
errors, but otherwise unencumbered by frequently
unjustified assumptions. Use of conversion reactions
to convert a measured variable to intellectually ever
so appealing "master variables" is always based on
the implied assumption that all reaction participants
were in equilibrium at sorne stage and that they are
still present in proportions representative of this hy-
pothetical equilibrium, which is not at all guaran-
teed. Measured variables and theory should be kept
strictly separate. This is most readily done by choos-
ing graphs with coordinates representing only mea-
sured, or at least measurable, values, such as concen-
trations and temperatures, and packing all theory
into the space outlined by the coordinates. Also, one
should try to preserve the identity of each measured
variable as much as possible by choosing combina-
tions involving at most two variables, such as a ratio.
Ratios also have the major advantage of being dimen-
sionless and therefore being independent of absolute
concentrations. In the case of geologic, frequently
quite dynamic, systems, combination of more than
two variables into complex concentration or activity
quotients greatly increases the uncertainty in the rele-
van ce of the values obtained. A typical example is the
Fischer-Tropsch reaction according to:
C0 2 may be controlled by formation of calcite at
deeper levels, H 2 by interaction with Fe(II)/Fe(III) of
the rock up to quite shallow levels, whereas CH 4 may
result from the decomposition of sediments in an en-
tirely different environment. Forming the complex
concentration quotient XcH 4 x~ 20/xc 02 x~ 2 presupposes
that all four components are present in our sample in
amounts representative of attainment of equilibrium
at sorne stage. As measured, they probably never are
and never were in equilibrium. There I have to con-
fess to sins of my younger, less enlightened years
(Giggenbach, 1980). So, what then is the use of a
"master variable"? With these minor details settled,
we can try to find out what's "really" going on.
T.ih~ thosP, TV cooks, I have all the ingredients al-
ready in little bowls, in this case diagrams, and we can
dispense with the preliminaries, such as sampling, an-
alyzing, and interpreting. To do the latter, it is
usually a good policy to look at the behavior of the
major species first. After all, they are most likely to
be part of major buffer systems or to dominate the
chemical environment. In the case of volcanic gases,
they are, after water, C0 2 , sulfur in its various oxida-
tion states, and HCI. In Figure 8, I plotted them in
7
•
0.8
••
•
0.6
502 8
~
ª
0.L
;;;
"~
0.2
• •
•
VOLCANIC VAPORS
•
• <300'C
• • >300ºC
0.L 0.8
0.2 0.6
100HCl
FIG. 8. Plot of xc 02 /(xco 2 + lOOxttci) vs. Xtt 2 s/(xtt 2 s + x802 ) for
vapors from andesitic volcanoes. Data from Giggenbach (1987)
and Giggenbach et al. (1990).
terms of relative H 2 0-HC1 versus relative S0 2 -H 2 S
values for volcanic vapor discharges from White Is-
land, N ew Zealand (Giggenbach, 198 7) and other vol-
canoes mentioned earlier (Giggenbach et al., 1990).
There are of course dozens of other ways to plot
these chemical compositions. The major advantage of
plots involving concentration or mole fractions, such
as Figure 8, over ratio plots is the possibility of plot-
ting pure components, as they treat all four variables
equally and none has to play denominator. Also, two-
component mixing is always represented by straight
lines.
Geothermal vapors are represented by only one
point in the upper right corner of the diagram, as
they usually don't contain S0 2 and HCI. High-temper-
ature (>300ºC) volcanic vapors occupy positions in
the lower left sector reflecting their highly oxidized
nature and high HCl contents. Lower temperature
discharges appear to fall into two groups: one reflect-
ing removal of HCl but remaining oxidized, the other
with most of the S reduced to H 2 S, at a minor loss of
HCI. It is obvious that the two major processes re-
sponsible for the conversion of volcanic-magmatic to
geothermal "fluids," removal of HCl by conversion
to a metal chloride, and reduction of S0 2 to H 2 S, may
operate quite independently, but in the end give the
same results: the formation of near-neutral, reduced
"geothermal" fluids.
HCl is a strong acid and the most likely process
leading to its removal is neutralization through inter-
action with oxidic components of the rock phase. As
pointed out above, geochemical processes are best
evaluated in terms of reactions involving actual reac-
8 WERNERF. GIGGENBACH
tion participants and on the basis of dimensionless
variables, such as concentration ratios. The variable
to be combined with mHcl to form a ratio should also
be a major component of the entire system. In the
present case, the most suitable is mKcl. A graphic rep-
resentation of possible reactions of HCl with minerals
of the rock phase to form KCl, as a function of temper-
ature, is given by Figure 9. It is based on data re-
ported by Sverjensky et al. (1991).
In an earlier investigation (Giggenbach, 1984), the
two limiting processes governing the interaction of
magmatic volatiles with crustal rock were suggested
to correspond to initial isochemical dissolutio~~of the
rock by the highly aggressive waters formed through
absorption of the volatiles into deeply circulating
ground water and to eventual equilibration of these
waters with a mineral assemblage resulting from iso-
chemical recrystallization of the original rock. In hy-
drothermal systems, the overall process consists es-
sentially of the conversion of framework silicates,
such as feldspars, to layer silicates, such as micas and
clays.
In Figure 9, trajectories are shown representing
these two end-member processes. Assuming the
gases, released at magmatic temperatures, to be ab-
sorbed directly into cooler ground water, without
any further interaction with rock, magmatic HCl/KCl
ratios are maintained and the cooling trajectory
corresponds to the horizontal path (a). On the other
hand, if the exsolved vapors rise more slowly in suffi-
cient contact and equilibrium with the rock, increas-
ing amounts of HCl are converted to alkali chlorides
through interaction with feldspars to form !ayer sili-
cates according to:
PYROPHYL
KAOLINITE
-2 -·-·-·-·-·-·-·
-3 ..._.
-4
100° 300°
F1c. 9. Stability of aluminum silicates as a function oftemperature and LHK = log (mHci/mKcJ) according
to Sverjensky et al. (1991). Dash-dotted lines represent solution paths as discussed in text.
1..5 feldspar + HCl <=± 0.5 mica+ 3 silica + KCl (5)
and the system may follow another path such as (b).
For solutions remaining in full equilibrium with the
rock, the ratio HCl/KCl drops from a value of about
0.1 at 600ºC, to 0.01 at .500°, and to 0.001at400º.
At lOOºC, >99.9 percent of the initial HCl is con-
verted to a metal chloride. The resulting waters are
neutral Cl waters typical of "mature" geothermal
systems, path (d).
In the case of the rapidly cooled waters, high initial
HCl/KCl ratios are preserved and the waters hecome
highly reactive with regard to alteration of primary
rock. Corresponding alteration products are highly
cation-depleted minerals such as pyrophyllite and
kaolinite. For acidities high enough, the process may
lead to complete cation leaching with only silica re-
maining. At sufficiently high sulfate concentrations,
alunite will form from even highly acid solutions. In
nature, actual interaction with rock may follow an in-
termediate path, such as (b) crossing the stability
fields of micas, as shown.
Figure 9 also provides a good illustration for the
need to select the most relevant variables. Using HCl
and KCl, species actually consumed and produced,
an immediate quantitative assessment of the process
can be made. Another popular variable in the con-
struction of thermodynamic stability diagrams is the
activity ratio aw/aK+. Corresponding stability bound-
aries, according to Sverjenski et al. (1991) are also
shown in Figure 9 by dashed lines. The change in
aw/aK+ is much smaller for full equilibrium interac-
tion along the feldspar-mica boundary than that in
mHc1/mKcl. It could wrongly be interpreted to mean
01
.01
.001
K-FELDSPAR
.0001
400° 500' ('C) 600°
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES 9

that interaction of acid volcanic waters with rock is

accompanied by only small amounts of alteration be-
cause the activitv ratio of the "reactants" remains al- (FeO) rock buffer
most constant. Át temperatures > 300ºC, acids are
increasingly associated and H+ becomes a very "un-
important" species, unsuitable to be used as a quanti-
tatively relevant, "actual" reaction participant.
Purely on the basis of Figure 9, interaetion of origí-
nally magmatic volatiles wíth rock at lower tempera- -4
tures is able to generate a wide range of geochemical
environments depending on temperature and dura-
tion of interaction wíth rock contacted.
According to Figure 8, the other major process ac-
companying conversion of magmatic volatiles to geo-
-5
thermal fluids, is reduction of S0 2 , and other oxi-
dized S species, to H 2S. Again, by definíng a variable,
involving actual and measurable reaction partici-
pants, H 2 and H 20, the limiting processes governing
redox reactions in volcanic systems were found to be
equilibration with the major redox pair of the vapor -6

phase H 2 S-S0 2 , and with Fe(II)-Fe(III), the rnajor re-

dox system of the rock phase (Giggenbach, 1987). In
lower temperature hydrothermal systems, S0 2 can
be expected to disproportionate into H 2S and a sul-
fate speeies and redox buffering is likely to be dueto -7

these species, as shown in Figure 1O. It was drawn by

use of thermodynamic data for minerals provided by
Bowers et al. (1984) and for solute speeies by Murray
and Cubicciottí (1983).
Depending on the degree of neutralization of the
solutions, the H 2S-sulfate buffer lines move with de-
creasing acidity to higher val u es of Rn = log Un 2/fn 20)
~ log (xn 2 /xn 20), where Í¡ and X¡ are the fugacities or
vapor phase concentrations of the species i. Opti-
mum efficiencv of a buffer is achieved when both
components ar'e present in comparable amounts, not
activities. Nevertheless, the lines shown in Figure 1O
are based on more "easilv" estirnated activitv ratios.
Accepting these lines to ~eflect buffer trends: a num-
ber of likely paths, taken by fluid mixtures during
their rise from a magmatic environment to the sur-
face, can be drawn (Giggenbach, 1991).
Again, assuming the vapor released from the
magma to be cooled rapidly, without signifícant in-
teractíon with the rock, the redox potential is deter-
mined by interna! equilibration among the fluid
phase components and the systern moves clown the
"gas buffer" line. At lower temperatures, H 2S03 will
disproportionate into H 2 S and a sulfate species. The
positions of the H 2 S-sulfate isoactívity lines depend
on the degree of neutralization of the solutions. Their
general directions, however, remain similar and the
path of a rising fluid will change from the trend
marked by the gas buffer to one parallel to an H 2 S-
sulfate isoactivity con tour, paths (b) or (c).
Figure 1 O also contains stability boundaries for a
number of minerals. Alunite is likely to form only at
Hsoz
100·
FIG. 1 O. Potential buffer systerns controlling redox potentíal,
RH = log (fi1,/fH 20), as a function ofternperature. Dash~dotted lines
represent solution paths as discussed in text.
very low values of RH and therefore only from solu-
tíons cooled rapidly, such as those generated by ab-
sorption of volcanic vapors into shallow ground
waters or crater lakes, path (a). The coexistence of
pyrite and alunite ín the Summitville "high sulfida-
tion" ore deposit at temperatures of 250ºC (Stoffre-
gen, 198 7) fixes its position in Figure 1 O. In the case
of more slowly rising waters, acidities may be re-
duced sufficiently to allow anhydrite to form (path
b). Even more slowly rising waters soon leave an
early zone of formation of a sulfate mineral and most
of the Sis deposited as pyrite (path c). At RH values >
-4, the buffer capacity of the H 2 S-S04 system is
heavily impaired as by far most of the S0 4 is con-
verted to H 2S, and solutions should have no problems
to attain full equilibrium with the Fe(II)-Fe(III)
"rock buffer." The presence of both pyrite and pyr-
rhotite at 300ºC places the point for the Ohaaki geo-
thermal system right on the rock buffer line. It may
have reached this position by following path (d).
Assigning comparatively well-defined positions to
these systems, however, is highly misleading. Within
each of these systems, microenvironments are likely
10 WERNERF. GIGGENBACH
to exist spanning the entire range of R8 values, from
highly oxidizing to full equilibrium with the rock
buffer. The entire set of processes occurring may be
compared to a tennis game with the two players rep-
resented by the two major buffers. A given subsys-
tem may represent the hall moving between the two,
with thermodynamics providing the rules and mass
balances the lines on the ground. Any thin section of
a rock sample taken from anywhere within the sys-
tem then may contain a series of "snapshots" of the
position of the hall in either court. A veinlet may at
sorne stage be exposed to a good flow of fluid, thus
recording "fluid-dominated" alteration processes.
Once it becomes blocked, the trapped solutions may
have time to react and the same subsystem converts
to a "rock-dominated" alteration system. The rapid
changes in equilibration conditions among minerals
and solutions are well documented by drastic zoning,
for instance, in the isotopic composition of sulfide
minerals as detected by SHRIMP (McKibben and El-
dridge, 1990). Rather than being due to global
changes affecting the entire system, they may simply
be due to local changes in fluid flow. In the case of
the S isotopes, the drastic changes may reflect vary-
ing degrees of reduction of the initially oxidized mag-
matic sulfur. At low degrees of reduction, close to
path (a), the small amounts of sulfide formed are very
depleted in 34 S, with increasing reduction, the com-
position of any sulfides formed approaches that of the
original magmatic sulfur. The isotopic compositions
of the sulfides then may simply record oscillations
between these two end-member situations. No exter-
na! input, such as inflow of oxygenated ground water,
or major changes in steady-state physical and chemi-
cal conditions, such as boiling, as frequently invoked,
would be required.
The above discussion covers the possible origin of
fluid phase constituents associated with andesitic
magmatism and chemical pathways traveled by the
fluid mixtures from a degassing magma body through
the crust. Not much has actually been said yet about
the actual mode or modes of magma degassing, the
true nature of the "mag(mat)ic arrows" of Figures 1
and 2.
Modes of Magma Degassing
According to Figures 9 and 1 O one might conclude
that the evolution of magmatic to hydrothermal, or
geothermal, fluids is a continuous process. In this
case we should observe an entire spectrum of epither-
mal mineral deposits, from highest to lowest sulfida-
tion, so to speak, and also transitional systems where,
e.g., a high sulfidation deposit evolves into something
resembling a porphyry copper deposit or vice versa.
At a meeting organized by the Geological Survey of
Japan on "High Temperature Fluids and Associated
Alteration and Mineralisation" (Matsuhisa et al.,
1991), it was the general Iack of such intermediate
and transitional systems which alerted us to the possi-
bility that the formation of these two types of epither-
mal mineral deposits must be controlled by addi-
tional factors, not just the temperature and degree of
magma degassing but possibly also the mode of
magma degassing itself.
The most obvious and rapid mode of degassing of
andesitic magmas is that accompanying volcanic erup-
tions such as those recently from Mount Saint Helens,
Nevado del Ruiz, and Mount Pinatubo. In these
cases, the volatiles are released directly into the atmo-
sphere and any interaction with cooler rock and
ground water is very limited. During periods of less
violent, fumarolic activity, high-temperature vola-
tiles may still be released from deeper lying, but
freely degassing, "boiling" magma bodies. Depend-
ing on the depth to the degassing magma body, the
configuration and permeability of the gas conduits,
and hydrological conditions, sorne of the gases may
be prevented from escaping directly and may start to
interact with local ground water to form a crater Iake
such as at Mount Ruapehu, New Zealand (Giggen-
bach, 197 5), El Chichón, Mexico (Casadeval et al.,
1984), Sirung, Indonesia (Poorter et al., 1989), and
Poás, Costa Rica (Oppenheimer, 1992), or secondary
volcanic waters as discharged from highly acid and
mineralized Cl-S0 4 springs within the crater (Gig-
genbach, 1987; Poorter et al., 1989) or the outer
slopes of a volcanic structure (Giggenbach et al.,
1990). The minerals forming from these waters in-
clude gypsum or anhydrite, alunite, pyrite, and a sil-
ica polymorph. At El Ruiz, a thick deposit of an amor-
phous As-Sb sulfide was observed along a spring
channel (Giggenbach et al., 1990).
In these volcanic systems, formation of mineralized
waters may consist of direct absorption of magmatic
volatiles, possibly released from such subterranean
"lava lakes" (Giggenbach, 198 7; LeCloarec et al.,
1992) into local ground water at comparatively shal-
low levels. Their acidity and redox potential corre-
spond to those indicated by paths (a) in Figures 9 and
1 O. With increasing depth to the degassing magma
body, maintenance of a freely degassing lava surface
and associated open conduits becomes increasingly
difficult and at sorne stage the degassing magma body
will become sealed by the formation of a shell of solid-
ifying rock. Over its inner parts, this shell remains
plastic and therefore impermeable to volatíles (Carri=
gan, 1986; Goldfarb and Delaney, 1988). Under
these circumstances, direct transfer of magmatic vola-
tiles to circulating ground water is impeded and a
different degassing mechanism is required.
As the encased magma body cools, volatiles are
likely to accumulate on top of the still liquid interior
(Candela, 1991) to be incorporated into a volatile-sat-
urated carapace as discussed in detail by Burnham
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
(1979). On further cooling the boundary of solidify-
ing magma retreats to lower levels and the trapped
volatiles become incorporated into increasingly
cooler and rigid layers of volcanic rock. If the volatile
contents of the cooling magma were high enough,
part of the volatiles may exsolve to accumulate in vesi-
cles.
From a given temperature downward, the mechan-
ical strength of the still hot rock increases sufficiently
to give rise to brittle fracturing allowing sorne of the
stored fluids to escape or external fluids, ground
water, to penetrate as evaluated in detail by Lister
(197 4). Other models of the processes governing the
distribution of temperatures and fluids around cool-
ing magma bodies have been presented by Whitney
(1975), Cathles (1977), Burnham (1979), Hardee
(1982), and Carrigan (1986). Fournier (1992) puts
the temperature of transition from plastic to brittle
behavior in silicic rocks as low as 400º to 375ºC.
According to the above evaluation, there exist two
distinct thermal regimes governing the release of
magmatic volatiles: that associated with freely degas-
sing surfaces of liquid magma at temperatures >
l,OOOºC, the other with brittle fracturing in solidify-
ing rock at temperatures < 400ºC. In the latter case,
volatiles stored in vesicles or along grain boundaries
may be released in two ways: at shallow levels where
hydrostatic pressures are low, they may escape partly
in vapor form, to be absorbed later into shallow
ground water; at greater depths, "degassing" resem-
bles more a leaching process of originally magmatic
volatiles, or their reaction products with the rock, by
more highly pressured, deeply circulating ground
water. The assumption of release of originally mag-
matic volatiles by the latter process also bridges the
gap between two major theories advanced to explain
the origin of hydrothermal sol u te species: rock leach-
ing as proposed by Ellis and Mahon (1964) and
magma degassing by Krauskopf (1957), Holland
(1972), Burnham (1979), and Eugster (1985). Re-
lease of the originally magmatic volatiles, partly
stored in vesicles, into minor amounts of invading
ground water may lead to the formation of highly sa-
line solutions and gassy vapors and corresponding
fluid inclusions, as frequently observed over the cen-
tral parts of hydrothermal systems or ore deposits
(Roedder, 1971; Reynolds and Beane, 1985; Reyes,
1990; Bodnar, 1992).
In addition to the marked differences in the temper-
ature of volatile "exsolution," the composition of the
volatiles associated with the two major types of
magma degassing may also be quite different. Basal-
tic magmas were shown to become saturated with re-
spect to dissolved gases at a depth of around 50 km
(Bottinga and Javoy, 1990). Andesitic magmas, with
their probably much higher volatile contents, can be
expected to start to "boíl" at even greater depth. By
11
the time the magmas are erupted at the surface, by
far the largest proportions of the original volatiles
have left the melt phase; any volatiles subsequently
extracted from accessible samples of solid material,
such as volcanic glass, melt inclusions, or crystals,
therefore, are likely to represent only a very minor
residual fraction of the original "andesitic volatiles."
Both isotopic and chemical compositions will be
heavily modified by fractionation processes accom-
panying such extensive vapor exsolution. Even vol-
canic gases collected from high-temperature fuma-
roles are unlikely to be fully representative of the
volatile contents of the original andesitic magmas but
may give an indication of the composition of vapors in
equilibrium with andesitic magmas at comparatively
shallow levels, levels similar to those of emplacement
of the magma bodies driving hydrothermal systems.
By "calculating back," the compositions of potential
melts coexisting with fumarolic gases may be evalu-
ated as shown in Figure 11.
The composition of vapors released from andesitic
volcanoes is represented by six data points taken
from the same compilation as those shown in Figure
8. Their average composition corresponds to mole ra-
tios of C0 2 /St/HC1 = 10:3:1. They are all produced
from probably very shallow bodies of magma, at low
pressures, and the vapor/melt volume ratios accom-
panying vapor exsolution can be assumed to be very
high, > 1O. In this case most of the e ven more soluble
components, S and HCl, should have partitioned into
the vapor phase and the composition of fumarolic
gases becomes very similar to that of the volatiles
originally dissolved in the deep magma. Accepting
that the composition of volcanic gases, as sampled,
FIG. 11. Relative C0 2 , total S, and HCI contents of vapors from
andesitic volcanoes. Lines are given representing the composition
of vapor and residual melt forming from an average andesitic vapor
as a function of the vapor/melt ratio, Rv.
12 WERNERF. GIGGENBACH
may resemble closely that of the volatiles originally
dissolved, the compositions of volatiles in the resid-
ual magma, coexisting with these vapors, were calcu-
lated, as a function of Rv, the vapor/melt volume ra-
tio, by techniques described in detail by W. F. Gig-
genbach and R. J. Poreda (in prep.). Even far low
values of Rv of <0.1 (vesicularity < 11 %), relative
C0 2 contents of the residual magma drop rapidly at
constant S/Cl ratios. When values of Rv exceed 1 (ve-
sicularity > 50% ), increasing proportions of S parti-
tion into the vapor phase and the residual magma be-
comes very C0 2 and S poor, and relatively Cl rich.
The compositions of vapors released from an andesi-
tic magma are given by the curve marked "vapor."
Recently a number of investigations involving H 2 0
and Cl have been carried out; they allow a much
more comprehensive and detailed evaluation of va-
por-melt distribution processes accompanying magma
degassing (Shinohara et al., 1989; Metrich and Ruth-
erfard, 1992; Webster, 1992).
The point marked "degassed melt" represents the
volatile mixture remaining dissolved in the residual
rock after extensive closed-system degassing. The
major parts of the volatiles released from a magma at
depth reside in the vesicles; their composition is
likely to resemble closely that released from fuma-
roles. This distinction is important when it comes to
comparing the isotopic and chemical composition of
"free volatiles" and those extracted from andesitic
solids, such as glasses or melt inclusions. They can in
no way be compared directly. Following incursion of
deeply circulating ground waters, the volatiles dis-
solved in the rock matrix and stored in vesicles are
released to farm highly saline solutions and gas-rich
vapors to be trapped in "hypersaline" and COrrich
fluid inclusions (Bodnar, 1992), partly reflecting the
composition of the originally magmatic vapors.
Summing up, farmation of an impermeable shell
around cooling magma bodies leaves only two "win-
dows" far the exsolution of magmatic volatiles. The
high-temperature window is only able to remain
open far magma bodies emplaced at shallow levels
and gases are released directly to the atmosphere or
into shallow ground water. The other window opens
once the temperature has become low enough far
brittle fractures to farm, allowing sorne of the
trapped volatiles to escape or to be "leached" by in-
vading ground water. The existence of these two dis-
tinct modes of degassing may give rise to two distinct
modes of mineral deposition.
Modes of Mineral Deposition
One of the most obvious differences in the two ma-
jar modes of magma degassing is the temperature of
volatile release: > l,OOOºC in the case of free release
from a "boiling" magma surface, <400ºC in the case
of subsolidus degassing. Based on isotopic and fluid
inclusion evidence, however, the temperatures of
mineral deposition are with 250º to 350ºC, very simi-
lar far both high and low sulfidation, epithermal ore
systems (Stoffregen, 198 7; White and Hedenquist,
1990). The marked differences in the mineralogies of
high and low sulfidation ore deposits therefare are
likely to be due to differences in the modes rather
than the temperatures of mineral deposition. Again,
the chemical processes are probably best discussed
separately in terms of those controlling acidity and
redox potential.
The likely path of solutions resulting from direct
degassing of a magma at high temperatures and ab-
sorption into cooler ground water is marked (a) in
Figure 9. At magmatic temperatures, the fluid is in
equilibrium with its mineralogical environment and
any alteration of primary rock by circulating fluids is
likely to be restricted to isochemical recrystallization
or to minor K metasomatism of the rocks contacted
(Giggenbach, 1984). Depending on the extent of
these early reaction zones, the system may fallow an-
other path (b) with initially high magmatic mttc1/mKCI
ratios lowered to varying degrees. Generally, the ris-
ing solutions become, with decreasing temperature,
increasingly reactive with respect to rock alteration
or more specifically H metasomatism. lnitially the al-
teration products will be those typical of phyllic alter-
ation, such as micas. At lower temperatures, the min-
erals farming in the now highly acid systems are
highly cation-depleted phases such as pyrophyllite,
kaolinite, or at the usually very high S0 4 contents,
alunite. At sufficiently low temperatures, the solu-
tions may become aggressive enough to give rise to
complete rock destruction and removal of ali cationic
components including Al and Fe, leaving only a resi-
due of "vuggy" silica typical of high sulfidation ore
deposits (Stoffregen, 1987; Izawa, 1991). The para-
genetic relationships implied by paths (a) and (b) in
Figure 9, correspond exactly to those observed at
most of these systems with decreasing depth (White
and Hedenquist, 1990; lzawa, 1991). Examples of
the aggressive solutions farmed in these volcanic sys-
tems are the highly acid and mineralized waters dis-
charged from springs on White Island (Giggenbach
and Glasby, 1977) and Nevado del Ruiz (Giggenbach
et al., 1990) or present in volcanic crater lakes (Gig-
genbach, 1975; Oppenheimer, 1992; Casadeval et
al., 1984).
For the volatiles trnpped in the solidifying shell
surrounding a cooling magma body, prolonged and
persistent contact with rock at decreasing tempera-
ture should favor maintenance of, or at least clase
approach to, fluid-rock equilibrium and the system
may fallow path (d), including the stretch marked
"fluids trapped in solidifying magma.'' They are only
released once the system reaches the point marked
"brittle fracturing." By this time >95 percent of any
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
magmatic HCl may have been converted to an alkali
chloride. Any free vapor released, therefore, will be
much less aggressive with respect to rock dissolution
than those released under magmatic conditions. Any
liquid phase remaining in the rock will be highly sa-
line and very similar to the hypersaline fluid inclu-
sions as frequently observed in drill cores from wells
into volcanic hydrothermal systems (Reyes, 1990;
Reyes and Giggenbach, 1992) or in samples from hy-
drothermal ore deposits (Roedder, 1971; Reynolds
and Beane, 1985).
As stated above, the relative proportions of the
fluids released in the form of vapor or leached by
circulating ground water will depend on the depth to
the degassing magma body. At shallow levels, or high
within a volcanic structure, hydrostatic pressures are
comparatively low and volatiles are likely to be re-
leased as vapors followed by absorption into cool
ground water. This process was assumed to lead to
the formation of the comparatively acid, high sulfate
waters discharged over the outer slopes of the El
Ruiz (W. F. Giggenbach and R. J. Corrales, in prep.)
and Miravalles volcanic structures (Giggenbach,
1992). The path taken by these fluids, in Figure 9, is
likely to approach that of a horizontal line extending
away from the point marked "brittle fracturing" to
lower temperatures, path (c).
At greater depths, increasing hydrostatic pressures
will aid penetration of ground water, facilitating hy-
drothermal alteration and "leaching" of the trapped,
originally magmatic volatiles. The resulting solutions
have a good chance to remain in equilibrium with the
(g)
100
FELDSPAR+ CaA1 2 -SILICATE +
~ C0 2 = CALCITE +MICA ~
ro
(.')
z
::J
§ 10
15
~
a:
fi'.
6
~ 1.0
10g
b
200º
FIG. 12. Equilibrium amounts of K mica formed (in g) through alteration of feldspars, as a function of
initial HCI and C0 2 contents of hydrothermal solutions for a drop in temperature by 1OºC.
13
rock matrix to end upas neutral chloride waters typi-
cal of "mature" geothermal systems.
The above evaluation is based on the behavior of
only one of the acid constituents of an originally mag-
matic vapor phase, HCl. Another important compo-
nent is C0 2 . The relative efficiency of these two,
with respect to rock alteration, may be evaluated as a
function of temperature and in terms of the amounts
of feldspar converted to layer silicates. The interac-
tion of HCI with feldspar may be represented by the
reaction:
feldspar + 2HC1 = mica+ 2KC1 (6)
and that of C0 2 by
alkali feldspar + Ca feldspar + C0 2
= mica + calcite. (7)
The amounts, in g, of mica formed, for a drop in
temperature of 1 OºC, as a function of initial contents
of HCl and C0 2 , in g/kg of solution, and according to
the above two reactions, are shown in Figure 12. At
temperatures above 600ºC, the solutions are inert
with respect to rock alteration by either HCI or C0 2
and no mica is formed. The onset of attack by HCI is
quite sudden and by far most of the HCl reacts ac-
cording to reaction (6) at temperatures above 400ºC.
The temperature range of 400º to 600ºC, of course,
is within that where volatiles remain trapped within
the cooling magma, facilitating neutralization of most
of the acidity due to HCl before the trapped fluids
are able to escape. C0 2 becomes reactive with re-
FELDSPAR+ 2 HCI =MICA+ 2KCI
100g co,1kg solulion 100gCI 10gCl 1gCl/kg
little alterotion
400° (ºCJ 600°
14
(FeO)
rock buffer
-3
(Feü1_5l /'
ft o
§ o
g
RH
/ likely paths of solutions rising from degassing magma
-- -
-4
/'
/ moto, 1991). Instead of H 2 S-S0 4 contours, Figure 13
-5 pyrite
-6
alunite
-7
(ºC)
FrG. 13. The solubility of gold, in µg/kg, as HAu(SH) 2 as a func-
tion of temperature and RH. Dash-dotted lines represent solution
paths as defined in Figure 10. Sulfate minerals are represented by
either anhydrite or alunite.
spect to rock alteration only at temperatures <
330ºC. Again the onset of feldspar alteration is quite
sharp and peters out at temperatures below 150ºC.
In addition to the two alteration regimes imposed
by the mechanical strength of a cooling magma, we
have two distinct regimes defined by the nature of
the major acidity-controlling species: HCl at high
temperatures 400° to 600ºC or in solutions affected
by direct absorption of magmatic vapors; C0 2 in
lower temperature (<350ºC) hydrothermal systems.
The acidity caused by C0 2 is insufficient to give rise
to the intense alteration observed in high sulfidation
ore deposits. These high acidities can only be gener-
ated from magmatic fluids released at high tempera-
tures in a way preventing strong acids from becoming
neutralized at intermediate levels and temperatures.
Conditions allowing strong acids to survive neutral-
ization by interaction with rock are restricted to sys-
tems with very steep temperature gradients and
therefore to comparatively shallow levels within or
beneath a volcanic structure. Preliminary assess-
ments for White Island show that the amounts of min-
eral components involved in these processes are suf-
WERNERF. GIGGENBACH
ficient to generate sizable ore deposits (Giggenbach
and Glasby, 1977; Hedenquist et al., 1992).
The actual modes of mineral deposition are illus-
trated in Figure 13 for gold in terms of the other ma-
jor variable controlling fluid-rock interaction, the re-
dox potential. Again, the dashed lines represent
bodies. In neutral to alkaline waters, Au is likely to be
transported as the Au(SH)2 species (Seward, 1973);
in the generally more acid solutions discussed here,
the most likely species is HAu(SH) 2 (Hayashi and Oh-
shows contours representing dissolved Au in the
form of HAu(SH) 2 , the thio-gold complex predomi-
nating at pH values of <5. The Au solubility contours
were calculated by use of the reactions:
0.1
0.01 2Au + 2 pyrite + 3 water
0.001
O.OOll = 2HAu(SH) 2 + hematite, (8)
Au (~g/kg)
2Au + 2 alunite + l.5H 2
= 2HAu(SH) 2 + 2 mica+ 19 water, (9)
and
2Au + 4 anhydrite + 4 kaolinite + l.5H 2
= 2HAu(SH)z + 4CaAl 2 silicate + 7 water, (10)
400°
where hematite represents the thermodynamic
proxy of Fe(III) of the rock phase. Calcium in an Al
silicate is represented by CaA1 2 silicate, laumontite at
low, wairakite at intermediate, and anorthite at high
temperatures.
Reaction (8) is independent of the redox potential,
therefore contours in Figure 13, over the pyrite
stability field, are vertical and only a function of tem-
perature. In contrast, contours based on the two reac-
tions involving sulfate minerals, are highly depen-
dent on RH and virtually independent of tempera-
ture. The behavior of Au with respect to
transportation and deposition can therefore be ex-
pected to be quite different in these two environ-
ments. In an environment dominated by the forma-
tion or presence of sulfate minerals, simple cooling
would actually increase the solubility of Au and any
Au acquired at deeper levels would remain in solu-
tion. On the other hand, in a more reduced environ-
ment, dominated by the formation of pyrite, a drop in
temperature by 30ºC would be accompanied by the
deposition of 90 percent of the Au from any saturated
solution. In nature, mineral-depositing processes
rarely involve only one variable and the overall pro-
cess is probably more realistically modeled in terms
of the various fluid paths as derived in Figure 10.
Following path (a), the one most closely reflecting
redox control by the "fluid buffer," concordant
changes in both temperature and RH would lead to
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES 15

rapid deposition of dissolved Au. For solutions follow-

ing more reduced paths, such as (b) and (c), the rate
of deposition of Au depends on the nature of the pre-
dominant S mineral, pyrite or anhydrite. If the latter
predominates and if solution mineral equilibrium is
maintained, initially saturated solutions can be ex-
pected to traverse considerable ranges of tempera-
ture where they become undersaturated again. On
crossing into the pyrite stability field, however, all
these solutions will lose most of their Au on further
cooling, conductively or by dilution with cooler
ground water. Diagrams such as Figure 13 can be con-
structed for any other mineral-depositing system. As
1 have already overdrawn my allocated time consider-
ably, 1 better start summing up.
Summary and Conclusions
One of the major purposes of my talk was to throw
sorne light, or to put sorne meat, onto the possible
nature of the "magic arrows" generally employed to
signify injection of magmatic fluids into hydrother-
mal systems. In the case of such systems associated
with volcanic activity along convergent plate bound- Frc. 1.5. Schematic model ofhydrothermal systems responsible
for the formation of a "low sulfidation," porphyry-type mineral
aries, isotopic and chemical evidence suggest that the
deposit.

major fluid components H 2 0, C0 2 , and probably Cl,

FIG. 14. Schematic models of hydrothermal systcms responsi-
ble for the formation of "high sulfidation" (paths a and b) and "low
su!fidation" (path e) epithermal mineral deposits. The low sulfida-
tion system, on the right, is assumed to be situated on the flanks of
a volcanic structure. The dotted line represents the path of gas-
charged vapors, the dashed lines that of downward-percolating air-
oxidized, acid sulfate waters.
may largely be derived from subducted marine sedi-
ments and seawater. Depending on the leve! reached
by the rising, generally andesitic magmas, volatiles
are degassed in two distinct modes: at magmatic tem-
peratures from an effectively freely boiling magma
either at the surface, during eruptions, or from sub-
terranean "lava lakes"; and from the solidified shell
surrounding a more deeply buried magma body in
response to thermal fracturing.
The active systems likely to give rise to the forma-
tion of the mineral deposits represented by Figures 1
and 2 are shown again schematically in Figures 14
and 15. In the case of "high sulfidation" systems, part
or ali of the vapors degassing from a subterranean
lava surface may be absorbed at shallow levels into
cool ground waters leading to the formation of ini-
tially only little reactive solutions capable of phyllic
to argillic alteration of primary, usually igneous rock.
With decreasing temperature, the solutions become
increasingly acid and oxidizing, thus promoting
wholesale rock destruction and the deposition of sec-
ondary minerals such as alunite, anhydrite, pyrite,
and silica. At sufficiently low temperatures, <250ºC,
acidities may become high enough to cause complete
rock destruction with only "vuggy" silica remaining.
Part of the ore-forming constituents are likely to be
derived from the dissolved rock; a considerable pro-
portion may be introduced directly with the mag-
matic vapor. Gold is deposited from the resulting so-
16 WERNERF. GIGGENBACH
lutions, once saturated, largely in response to de-
creasing temperature ata rate of about 90 percent for
everv 30°C.
"Dry" degassing of a solidifying magma at shallow
levels leads to the release of less aggressive but still
acid and oxidizing vapors which, on contact with
ground water, may give rise to the fonnation of acid
Cl-S0 4 waters, typical of active volcanic systems, in-
tensive rock alteration, and the deposition of elemen-
tal sulfur. Part of the "dryly" degassed vapors may
accumulate within the volcanic structure (Gíggen-
bach et al., 1990), to be released duríng eruptions,
thus contributing to the large excess of volatiles fre-
quently observed (Williams et al., 1990). Because of
the limited spatial extent of these systems and the
absence of metal-rich, high-temperature magmatic
vapors, their potential for forming mineral deposits,
except of elemental S, is probably only minor. The
comparative rarity of typical volcanic hydrothermal
discharges (Reyes and Giggenbach, 1992) also sug-
gests that both their spatial and temporal extents are
verv limited. Nevertheless, the incursion of even
mi~or amounts of these acid Cl-S0 4 waters into geo-
thermal wells drilled too close to volcanic systems
may generate majar problems.
Both the time and amount of source material avail-
able for the fonnatíon of significant mineral deposíts
can be expected to increase as zones of water-rock
interactíon progress to deeper and deeper levels. Fig-
ure 14 also presents the distribution of fluids in a hy-
drothermal system thought to be responsible for the
formation of a volcano-hosted, epithermal, now low
sulfidation mineral deposít. The system is assumed to
be situated on the flanks of a volcanic structure and,
therefore, to be supplied by "magrnatic" vapors
through "dry" degassing, too. Absorption of these
vapors into ground water at ínterrnediate depths is
likely to lead again to the formation of acid Cl-S0 4
waters, whích, on further interaction with rock are
converted to neutral Cl watcrs. Simple gravity separa-
tion within the system causes vapors and liquid to be
discharged at separate areas. Oxidation of H 2 S
carried by the vapors gives rise to the production of
dilute, acid SO 4 waters, percolating downward to con-
siderable depth, up to .500 m, and the establishment
of extensive zones of argillic alteratíon (Reyes,
1991). The neutral Cl waters may be discharged at
lower altitudes considerable distances (10-20 km)
away (Giggenbach et al., 1990; Giggenbach an<l
Corrales, 1992). Because of the limited depth, areal
extent, and duration of water-rock interaction in
these systems, resulting mineral bodies are only of a
limited size.
A much more extensive and lasting envíronment
for the extraction of originally magmatic volatiles and
metals is provided by the hydrothermal systems asso-
ciated with formation of "low sulfidation" mineral de-
posits of the porphyry type, as shown in Figure 15.
There the penetration of ground water into the cool-
ing rock, a process favored by high hydrostatic pres-
sures and therefore, greater depth, may go on for
very long periods, and integrated rock volurnes possi-
bly involved in this process may be very large, thus
providing a large source of ore-forming components.
The cylindrical shape and position of the ore shell at
the boundary of potassic to phyllic alteration sug-
gests that the major process giving rise to ore deposi-
tion in porphyry metal deposits is coolíng and possi-
bly dilution by the incursion of cooler ground water
at intermediate depths. Boiling may be more impor-
tant in low sulfidation, epithermal deposits.
Anyway, if nothing else, my lecture may have pro-
vided you with two important criteria to evaluate the
geochemical literature on hydrothermal systems: if a
paper indiscriminately uses lots of "fluids" beware, if
also «f02 ' s" and "fs 2 ' s," re ad the newspaper instead.
Acknowledgments
I want to thank A. J. Ellis for introducing me to the
intricacies of hydrothermal fluid-rock interaction,
the former DSIR to allow me to follow the twists and
turns of the evolutíon of fluids in these svsterns, and
my former colleagues, especially J. W. Íledenquist,
R. W. Henley, and T. M. Seward, for rescuing me
from a number of geological dead alleys.
REFERENCES
Bethke, P.M., and Rye, R. O,, 1979, Environment of ore deposi-
tion in the Creede mining district, San Jnan Mountains, Colo-
rado: IV. Souree of fluids from oxygen, hydrogen, and carbon
isotope studies: ECON. GEOL., v. 74, p. 1832-18.51.
Bodnar, R. J., 1992, Can we reeognize magmatic fluid inclusions in
fossil systems based on room temperature phase relations and
micro-thermometric behavior, in Magmatic contributions to hy-
drothermal systems: Japan Geol. Survey Rept. 279, p. 26-30.
Bonham, H. R., 1986, Models for volcanic-hosted epithermal
precious metal deposits: A review: Jnternat. Volcanology Cong.,
5th, Auckland, New Zealand, Proc., p. 13-17.
Bottínga, Y., ami Javoy, M .. 1990, MORB degassing: Bubble
growth and ascent: Chem. Geology, v. 81, p. 255-270.
Bowers, T. S., Jackson, K. l., and Helgeson, H. C., 1984, Equilib-
ríum activity diagrams: Berlin-New York, Springer-Verlag,
397 p.
Bunsen, R., 1847, Über den inneren Zusarnrnenhang der pseudo-
vulkanischen Erscheinungen Islands: Liebigs Annalen Chemie
Pharmaeologie, v. 62, p. 1-.59.
Burnham, C. W., 1979, Magmas and hydrothermal fluids, in
Barnes, H. L., ed., Geoehemistry ofhydrothermal ore deposits:
New York, Wiley lntersci., p. 71-136.
Caudela, P. A., 1991, Physics ofaqueous phase evolutíon in plu
tonie environments: Arn. Mineralogist, v. 76, p. 1081-1091.
Carrigan, C. R., 1986, A two-phase hydrothermal cooling mo<lel
for shallow intrusions: Jour. Volc:anology Geotherrn. Research,
V. 28, p. 17.')~192.
Casadeval, T. J., de la Cruz-Reyna, S., Rose, W. l., Bagley, S.,
Mena, M., Finnegan, D. L., and Zoller, W. H., 1984: Crater
Lake and post-eruptíon hydrothermal activity, El Chichón vol-
cano, Mexico: Jour. Volcanology Geotherm. Research, v. 23, p.
169-191.
Cathlcs, L. M., 1977. An analysís of the cooling of intrusives by
 MAGMA DEGASSING AND MINERAL DEPOSITION IN HYDROTHERMAL SYSTEMS ALONG CONVERGENT PLATE BOUNDARIES
ground-water convection which íncludes boiling: EcON. GEOL.,
v. 72, p. 804-826.
Cole, D. R., Mottle, M. J., and Ohmoto, H., 1987, Isotopic ex-
change in mineral-flnid systcms. Il. Oxygen and hydrogen isoto-
pic investigations of the experimental basalt-water system: Geo-
chim. et Cosmochim. Acta, v . .51, p. 1523-1538.
Craig, H., 1963, The isotopic geochemístry of water and carbon in
geothermal areas, in Tongiorgi, E., ed., Nuclear geology on geo-
thermal areas, Spoleto: Pisa, Consiglio Nazíonale delle Ri-
cherche, p. 17-.53.
Ellis, A. J., and Mahon, W. A. J., 1964, Natural hydrothermal sys-
tems ami experimental hot water/rock interactions: Geochim. et
Cosmochim. Acta, v. 28, p. 132.3-13.57.
Eugster, H. P., 198.5, Granites and hydrothermal ore deposits: A
geochemical framework: Mineralog. Mag., v. 49, p. 7-23.
Fournier, R. O., 1992. The influence of depth of burial and the
brittle-plastic transition on the evolution of magmatic fluids, in
Magmatic contributions to hydrothermal systems: Japan Ceo!.
Survey Rept. 279, p ..57-59.
Giggenbach. W. F., 1971, Isotopíc composition of waters of the
Broadlands geothermal fleld, New Zealand: New Zealand Jour.
Sci., v. 14, p. 959-970.
- - 1975, The chemistry of Crater Lake, Mt Ruapehu (New Zea·
land) during and aftfü the 1971 active period: New Zealand
Jour. Sci., v. 17, p. 33-·15.
1978, The isotopic composition of waters from the El Tatio
geothermal field, northern Chile: Geochim. et Cosmochim.
Acta, v. 42, p. 979-988.
- - 1980, Geothermal gas equilibria: Geochim. et Cosmochim.
Acta. v. 44, p. 2021-2032.
1984, Mass transfer in hydrothermal alteration systems: Geo-
chim. et Cosmochim. Acta, v. 84. p. 2693-2711.
1987. Redox processes governing the chemistry of fumarolic
gas discharges from White Island, New Zealand: Appl. Geoehem-
istry, v. 2, 14.3-161.
- - 1991, Redox processes aceompanying the deposition of min-
erals ín volcanic-magmatic-hydrothermal systems: Japan Geol.
Survey Rept. 277, p. 91-96.
1992, The composition of gases in geothermal and volcanic
systems as a function of tectonic setting: Interna!. Symposium
Water-Rock Interaction, 7th, Park City, Proc., p. 873-878.
·-- in press, Isotopic shifts in waters from geotherrnal and vol-
canic systems along convergent plate boundaries and their ori-
gin: Earth Phmet. Sci. Letters.
Giggenbach, W. F., and Corrales, R., 1992, The isotopic and chem-
ical composition of water aud steam discharges from volcanic-
magmatie-hydrothermal systems of the Gnanacaste geothermal
province, Costa Rica: Appl. Geochemístry. v. 7, p. 309-332.
Giggenbach, W. F., and Glasby, G.P., l 977, Thc influence of ther·
mal activity 011 the trace metal distribution in marine scdiments
around White Island, New Zealand: ;\;ew Zealand Dept. Sci.
Indus. Research Bull., v. 218, p. 121-126.
Giggenbac:h, W. F., García, P. N., Londoüo, C. A.. Rodríguez,
V. L., Rojas, G. N., and Calvache, V.M. L., 1990, The chemistry
of fumarolic vapor and thermal spring diseharges from the Ne-
vado del Ruiz volcanic-magmatic-hydrothermal system: Jour.
Voleanology Geotherm. Researeh, v. 42, p. 13-39.
Goklfarb, M. S., and Delaney, J. R., 1988, Response of two-phase
íluids to fracture configurations within submarinc hydrothermal
systems: Jour. Geophys. Research, v. 93, p. 4.585-4.594.
Hardec, H. C., l 982. Permeable convection above magma bodies:
Tectonophysics, v. 84, p. 179-19.5.
Hayashi. K.-1.. and Ohmoto, H., 1991, Solubility of gold in NaCl-
and H 2S-bearing aqueous solution at 2.59-3.50ºC: Geoehim. et
Cosrnochim. Acta, v. 5.5, p. 211-216.
Hayba, D. O, Bethke, P. M., Hcald, P., and Foley, N. K., l 986.
Geologie. mineralogic and geochcmical characteristics of vol-
canie·hostcd epithermal precíous.meta! deposits: Rev. Econ. Ge-
~ogy, v. 2,p. 129-162.
17
Hedenquist, J. W., 1987. Mineralisation associated with volcanic-
related hydrothcrmal systems in the Circum-Pacific basin: Cir-
cum-Pacific Energy Mineral Resources Conf., 4th, Singapore,
Trans., p. 513-524.
Hemley, J. J., and Hunt, J. P., 1992, Hydrothermal ore-forming
processes in the light of studies in rock-bulfered systems: II.
Some general geologic applications: ECON. GEOL., v. 87, p. 23-
43.
Henley, R. W., and Ellis, A. J., 1983, Gcothermal systems, ancíent
and modern: A geochemieal review: Earth-Sci. Rev., v. 19, p.
1-50.
Henley, R. W., and McNabb, A., 1978, Magmatic vapor plurnes
and groundwater interaction in porphyry copper emplacement:
EcoN. GEoL, v. 73, p. 1-20.
Holland, H. D., 1972, Granites, solutíons, and base metal deposits:
ECON. GEOL., v. 67, p. 281-:301.
Izawa, E., 1991, Hydrothermal alteration associated with Nan·
satsu·type gold mineralisation in the Kasua area, Kagoshima Pre·
fecture, Japan: Japan Geol. Survey Repl. 277, p. 49-52.
Javoy, M., and Pineau, F., 1991, The volatile record of a "pop-
ping" rock from the Mid-Atlantíc Ridge at 14º N: Chemical and
isotopic composition of gas trapped in the vesides: Earth Planet.
Sci. Letters, v. 107, p. 598-611.
Krauskopf, K. B., 1957, The heavy metal content of magmatic va-
por at 600ºC: ECON. GEOL., v. 52, p. 736-807.
Le Cloarec, M. F., Allard, P., Ardouin. B., Giggenbach, W. F., and
Sheppard, D. S., 1992, Radioactive isotopes and trace elements
in gaseous emissions from White Island, New Zealand: Earth
Planet. Sci. Letters, v. 108, p. lfl-28.
Líster. C. R. B., 197 4, On lhe penetration of water into hot rock:
Royal Astron. Soc. Geophys. Jour., v. 39, p. 465-.509.
Liu, K., and Epstein, S., 1984. The hydrogen isotope fractionation
between kaolinite ami water: Isotope Geoscí., v. 9.5, p. 335-
350.
Lowell, J. D., and Guilbert, J. M., 1970, Lateral and vertical alter-
ation-mincralization zoníng in porphyry ore deposits: EcoN.
GEOL., v. 65, p ..373-408.
McKibben, M. A., and Elders. W. A., 1985, Fe-Zn-Cu-Pb mineral-
ization in the Salton Sea geothermal system, Imperial Valley.
California: ECON. GEOL., v. 80, p ..539-5.59.
McKibben, M. A., and Eldridge, C. S., Hl90, Radical sulfur isotope
zonation of pyrite accompanying boiling and epithermal gold
deposition: A SHRIMP study ofthe Valles Caldera, New Mexico:
ECON. GEOL., v. 8.5, p. 1917-1925.
Matsuhisa, Y., Aoki, M., and Hedenquist, J. W., 1991, High-tem·
perature acid fluids and associated alteration and mineralisation:
Japan Geol. Survey Rept. 277, 112 p.
t-.fatsuo, S., Suzuki, M., and Mizutani, Y.. 1978. Nitrogen to argon
ratio in volcanic gases: Advances Earth Planet. Sci., v. 3, p. 17-
2.5.
Metrich, N., ancl Rutherford, M. J., 1992, Experimental study of
chlorine behavior in hydrous silicic: melts: Geoehim. et Cosmo-
chim. Acta, v. 56, p. 607-616.
Murray, C., and Cubicciotti, D., 1983, Thermodynamics of
aqueous sulfur species to .300°C and potential-pH diagrams:
ElectrochE'm. Soc. Jour., v. 130, p. 863-869.
Oppcnheirner, C., 1992, Sulphur eruptions at Volean Poas, Costa
Rica: Jour. Volcanology Geotherm. Research, v. 49, p. l-21
Peacock, S. M., 1990, Fluid processes in subcluctíon zoncs:
Seíenee, v. 218, p. '.329-337.
Poorter, R. P. E., Varekamp, C., van Bergen, M. J., Kreulen, R..
Siriwana, T., Vroon. P. Z., and Wiraknsumah, A. D., 1989, The
Sirung volcanic boiling spring: An extreme chloride-rich, acid
bri11e on Pantar (lesser Sunda Islands, Indonesia): Cht'm. Geol-
ogy, v. 76, p. 215-228.
Reyes, A. G., 1990, Petrology of Philippine geothermal systems
ami the applieation of alteration mineralogy to their assessment:
Jour. Volcanology Ceotherm. Research, v. 43, p. 279-309.
l 991, Mineralogy, distribution and origin of acid alteration in
18 WERNERF. GIGGENBACH
Philippine geothermal systems: Japan Geol. Survey Rept. 277,
p. 59-6.5.
Reyes, A. G., and Giggenbach, W. F., 1992, Petrology and fluid
chemistry of magmatic-hydrothermal systems in the Philíppines:
Intemat. Symposium on Water-Rock lnteraction, 7th, Park City,
Utah, Proc., p. 1341-1344.
Reynolds, T. J., and Beane, R. E., 1985, Evolution ofhydrothermal
fluid characteristics at the Santa Rila, New Mexico, porphyry
copper deposit: ECON. GEOL., v. 80, p. 1328-1347.
Roedder, E., 1971, Fluid inclusion studies of the porphyry-type
ore deposils at Bingham, Utah, Butte, Montana, and Clímax, Col-
orado: ECON. GEOL., v. 66, p. 98-120.
Sakai, H., and Matsubaya, O., 1977, Stable isotope studies ofJapa-
nese geotherrnal systems: Geothermics, v ..5, p. 97-124.
Seward, T. M., 1973, Thio complelles gf gg]¡l i:m<l the tnmsport of
gold in hydrothermal ore solutions: Geochim. et Cosmochim.
Acta, v. 37, p. 370-399.
Sheppard, S.M., Nielsen, R. L., and Taylor, H. P., 1969, Hydrogen
and oxygen isotope ratios in minerals from porphyry copper de-
posíts: ECON. GEOL., v. 66, p. 515-542.
Shínohara, H., Iiyama. J. R., and Matsou, S., 1989. Partitioning of
chlorine compounds between silicate melt and hydrothermal so-
lutions. l: Partition ofNaCl-KCI: Geochim. et Cosmochim. Acta,
v.53,p. 2617-2630.
Sillitoe, R. H., 1973, The tops and bottoms of porphyry copper
deposits: EcoN. GEOL., v. 68, p. 799-815.
Sillitoe, R. H., and Bonham, H. F., 1984, Volcanic landforms and
ore deposits: EcoN. GEOL., v. 79, p. 1286-1298.
Skinner, B. J., 1979, The many origins of hydrothermal mineral
deposits, in Barnes, H. L., ed., The geocbemistry ofhydrother-
mal ore deposits: New York, Wíley Intersci., p. 1-21.
Stewart, :\1. K., and Hulston, J. R., 1975, Stable isotope ratios of
volcanic steam from White Island, New Zealand: BulL Volcanol-
ogy, v. 24, p. 28-46.
Stoffregen, R, 1987, Genesis of acid sulfate alteration and Au-Cu
mineralization at Summitvílle, Colorado: ECON. GEOL., v. 82, p.
1575-1591.
Sverjensky, D. A., Hemley, J. J., andD'Angelo, W. M., 1991, Ther-
modynamic assessment of hydrothermal alkali feldspar-mica-
aluminosílícate equilibria: Geochim. et Cosmochim. Acta, v. 55,
p. 989-1004.
Taran, Y., Pokrovsky, B. G., and Esikov, A. D., 1989, Deuterium
and oxygen-18 in fumarolíc steam and amphiboles from sorne
Kamchatka volcanoes: "Andesitic waters": Akad. Nauk SSSR
Dokl., v. 304, p. 440-443.
Taylor, B. E., 1986, Magmatic volatiles: Isotopic variations of C, H,
ami S: Rev. Mineralogy, v. 16, p. 185-225.
Viglino, R. S., Harmon, R. S., Borthwich, J., Nehriug, N. L., Mtyka,
R. J., Whíte, L. D., and Johnston, D. A., 1985, Stable isotope
evidence for a magmatic component in fumarole condensates
from Augustine volcano, Cook Inlet, Alaska, USA: Chem. Geol-
ogy, v. 49, p. 141-157.
Webster, J. D., 1992, Fluid-melt interactions involving Cl-rich
granites: Experimental study frorn 2 to 8 kbar: Geochim. et Cos-
mochim. Acta, v. .56, p. 659-678.
White, D. E .. 19.57, Thermal waters of volcanic orígin: Geol. Soc.
AmericaBull., v. 68, p. 1637-1658.
White, N. C., and Hedenquist, J. W., Hl90, Epithermal environ-
ments and styles of mineralization: Variations and their causes,
and guidelines for exploration: Jour. Geochem. Explor., v ..36, p.
445-474.
Whitney, J. A., 197.5, Vapor generation in a quartz monzonite
magma: A synthetic model with application to porphyry copper
deposits: EcoN. GEOL., v. 70, p. 346-358.
Williams, S. N., Sturchio, N. C., Calvache, V.M. L., Mendez, F. R..
Londono. C. A., and García, P. N., 1990, Sulfur dioxide from
Nevado del Ruiz, Colombia: Total flux and isotopic constraints
on its origin: Jour. VolcanoL Research, v. 42, p ..53-68.