M11 Hydrothermal Alteration

Hydrothermal Alteration
Module 11
Contents i
Contents
1.
Introduction
2.
Alteration Intensity
3.
Alteration Rank
4.
Alteration Pervasiveness
5.
Alteration Assemblages
6.
Overprinting
6.1
6.2
6.3
7.
Prograde Overprinting
Retrograde Overprinting
Other Overprinting
Practical Exercise
12
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1.
Introduction
Hydrothermal fluids have various effects on the rocks they pass through: existing minerals
can be removed, new minerals can be deposited in fractures and pores in the rocks, or the
existing minerals can be replaced by other minerals in processes of hydrothermal
alteration. All of these processes may occur together. The new minerals that are formed,
whether by deposition in cavities or by replacement, are called secondary minerals. In this
module we are looking at secondary minerals which form by the alteration (replacement) of
other minerals. Mineral deposition (veining) is discussed in a separate module (Module
13), since although the mineralogy is similar, the textures are quite different.
Hydrothermal alteration is comparable to diagenesis, in which primary minerals are
replaced by diagenetic phases upon burial and the consequent increase in temperature and
pressure. Since the temperatures can be similar in both settings, the same minerals can
occur (e.g. clays, zeolites), and it can be difficult to distinguish hydrothermal alteration
from diagenesis in metasedimentary rocks.
The nature of the secondary minerals and the speed at which they form are controlled by
factors such as the temperature, fluid composition, rock composition, and water:rock ratio.
The last factor depends on the permeability of the rocks, the fluid flow rate and the length
of time available. Alteration will be most intense in permeable rocks, where there is a high
fluid flow, and in long-lived systems. Alteration can be described in terms of its intensity,
rank, and pervasiveness.
2.
Alteration Intensity
The intensity of alteration is an indication of how much a rock has been changed by the
fluids passing through. Alteration intensity can be determined quite accurately from the
proportion of secondary minerals relative to the proportion of primary minerals remaining,
and whether the original texture is preserved. The intensity will vary among different
lithologies according to the permeability of the rock and the reactivity of the primary
components. Thus a highly permeable limestone or glassy tuff will be very susceptible to
alteration, whereas a quartz sandstone will be very slow to react with hydrothermal fluids.
The general sequence among common minerals, going from most reactive to least reactive
is:
Carbonates
Volcanic glass
Mafic minerals
Plagioclase
K-feldspar
Apatite
Quartz
Zircon
There are exceptions; for example in some rocks the feldspars will be altered while the
mafic minerals are preserved, but this gives an idea of the susceptibility of common
minerals to alteration in the presence of hydrothermal fluids.
The alteration intensity may be reported as a percentage (e.g. 40% secondary minerals), or
using descriptive categories. Our procedure (as outlined in Appendix 2) is to describe
alteration as weak where secondary minerals make up less than 25% of the rock,
moderate where they comprise 25-75%, and strong if they total more than 75%. Rocks
with no secondary minerals are unaltered, whereas in rocks with few remaining primary
minerals (except for resistant phases such as quartz, apatite and zircon) alteration is
intense unless the primary textures are no longer visible, in which case it is total.
3.
Alteration Rank
The alteration rank is an indication of the conditions (especially temperature) responsible
for producing the secondary minerals within a rock. Thus, rocks which contain secondary
minerals that formed at low temperature are described as being of low rank, whereas those
with high temperature alteration minerals are high rank, and those between the two as
intermediate rank.
The intensity and rank of alteration caused by hydrothermal fluids are controlled by two
conflicting factors (Figure 1). On the one hand, most chemical reactions proceed more
rapidly at high temperatures, and the fluids are more mobile. So more rapid alteration is
expected at depth. In contrast, at near-magmatic temperatures the fluid, being basically of
magmatic origin, is close to being in equilibrium with rocks of igneous origin.
Furthermore, species such as HCl are much less dissociated at high temperatures, which
means that the effective acidity (H+ activity) is less than the molar concentration of HCl
would lead one to expect.
These effects were quantified for the reaction of carbonic acid with rhyolite by Bischoff
and Rosenbauer (1996). They found that the degree of reaction was greatest at 150
-200C. The extent of alteration at 200C was 27 times as great as at 350C. At lower
temperatures the rates of reaction were too slow to be effective (Table 1).
Table 1:
Rates of reaction for carbonic acid/rhyolite
Temperature
C
Time
300
200
100
50
Minutes
One day
4000 days (~ 11 years)
1000 years
The time given is that required for reaction to proceed to 50% of saturation (after Bischoff and
Rosenbauer 1996)
Surficial environment:
Reactions very slow, but fluids extremely
out of equilibrium with rocks. Supergene
alteration/ weathering ultimately texturally
destructive but very slow.
Original lithologies
may be recognisable
often unrecognisable
possibly recognisable
often recognisable
Possible downflowing
secondary hydrothermal
fluids
Upflowing primary
hydrothermal fluids
Shallow / cool hydrothermal:

Reactions slow - moderately fast, but fluids
well out of equilibrium with rocks. Strong
acids highly dissociated. Alteration low rank
but high intensity. May be totally texturally
destructive especially where secondary
fluids exist.
Deep / hot hydrothermal:

Reactions moderately fast, but fluids
somewhat in equilibrium with host rocks.
Strong acids partly dissociated. Alteration
moderate rank, moderate intensity.
Partially texturally destructive.
Near-pluton environment:
Reactions very rapid, but fluids not far out
of equilibrium with igneous host rocks.
Alteration high rank but only moderate
intensity: not texturally destructive.
k:geo\lect\min\98\mod1\4fig3a.ppt
Figure 1:
Variations in alteration style and intensity with depth/temperature
in volcanic terrane
There is therefore limited potential for alteration of the intrusive that forms the heat source
to a hydrothermal system, or igneous host rocks. Near-intrusive alteration is restricted to a
certain amount of hydration and potassium and silica metasomatism, giving K-feldspar and
biotite. (This is not of course the case if the host rocks have a different composition). As
the fluid cools, becomes diluted with more groundwater, and becomes modified through
reactions, it gets further and further out of equilibrium with the host rocks. So, while the
rate of reaction may be slower, it can have a greater effect on the mineralogy of the rocks.
In general, the process is one of removing ferromagnesian cations and replacing them with
alkalis, along with silica addition, hydration, and a variable amount of carbonation and
sulphidation. As the temperature drops, the Na/K ratio of the fluid rises, and that of the
rock correspondingly falls. This process leads to the systematic zonation of alteration that
we see in hydrothermal systems.
4.
Alteration Pervasiveness
Alteration may not be uniform in intensity throughout a rock sample, drill core or outcrop.
Instead, there may be parts that are intensely altered, and parts where alteration is weak or
moderate, or where a different alteration assemblage is present. In extreme examples,
alteration may be restricted to within a few millimetres of a vein, forming a visible halo
around it. The variation of alteration intensity is known as pervasiveness; where alteration
extends for many metres or kilometres it is pervasive, and where it is localised on a
millimetre to centimetre scale it is localised. In either case it might be of any intensity or
rank; here we are just describing how extensive it is. If alteration is localised, it might only
occur close to permeable zones (e.g. along bedding in tuffs or within fractures), or it may
have a more irregular distribution.
5.
Alteration Assemblages
From studying secondary minerals, geologists have learned that certain minerals often
occur together, forming distinctive mineral assemblages. Most assemblages are at
thermodynamic equilibrium, so comprise an equilibrium assemblage. Disequilibrium
assemblages may also occur; these contain minerals that should not occur together on
chemical or thermodynamic grounds, and are particularly common where there has been
rapid mineral deposition. This is especially common in assemblages formed from
aggressive acid solutions. Many of the reactions which work to produce an equilibrium
assemblage can be quite sluggish, and the original (primary or earlier-formed secondary)
minerals can persist metastably, thus forming a disequilibrium assemblage. In this way,
minerals from two or more different alteration assemblages may be preserved in a rock.
Although rank is a useful concept, in practice it is more common to refer to specific
alteration assemblages. Several alteration assemblages have been defined, although
slightly different definitions are used by different groups of workers. Others avoid all
reference to assemblages, and instead refer individually to all of the secondary minerals
that are present. We consider that the concept of alteration assemblages is a useful one,
provided each assemblage is clearly defined. It is of particular benefit for rapidly
describing groups of rocks, or comparing the alteration at different prospects, since the
conditions of formation of a particular assemblage should be similar anywhere. However,
as with any classification scheme, it is essential to first describe a rock and the minerals
and textures within it before assigning it to an alteration assemblage. The standard
definitions that we use are summarised below, and listed in Appendix 2.
Argillic:
Clay-rich assemblages dominated by low-temperature clays such as
kaolinite, smectite, and interlayered illite-smectite. These are formed by low
temperature (<230C), acid to neutral, low salinity hydrothermal fluids.
Phyllic:
Dominated by illite or sericite and quartz, together with pyrite and
possibly anhydrite. May also contain minor chlorite, calcite, titanite and rutile.
Formed in the presence of moderate to high temperature (approx. 230-400C), acid

to neutral fluids at a range of salinities, commonly in permeable zones and adjacent
to veins. Requires the addition of H2O, Si and K, and loss of Na, Ca and Mg from
the rock.
Propylitic: Characterised by chlorite, with some of illite/sericite, epidote, quartz,
albite, calcite, and anhydrite. Formed at moderate temperatures (mostly 200300C), in the presence of near-neutral pH fluids with a range of salinities,
commonly in low permeability areas. Require very little mass transfer, except for
the addition of volatiles: H2O, CO2 and sulphur.
High-temperature propylitic: Contains secondary actinolite and/or garnet in
addition to the above assemblage. Forms under similar conditions (i.e. low
permeability, little mass transfer), but higher temperatures (>290C) than propylitic
assemblages.
Potassic: Major secondary minerals are biotite, orthoclase, quartz, and
magnetite. Anhydrite is a common accessory, and minor albite and titanite or rutile
can also develop. Potassic alteration is caused by near-intrusive, hot fluids
(>300C) with a strong magmatic character and high salinity.
Advanced Argillic:
Contain alunite, diaspore, and/or pyrophyllite, together
with one or more of quartz, chalcedony, kaolinite, and dickite. Zunyite and
phosphorus-bearing phases such as woodhouseite may also occur. These
assemblages occur as tabular near-vertical zones formed from condensed acid
magmatic vapours in the porphyry environment, and as near-horizontal blankets at
shallow epithermal levels, where acid-sulphate fluids form from oxidised steam
condensates.
Skarn:
May contain garnet, clinopyroxene, vesuvianite, scapolite, wollastonite,
epidote, amphibole, magnetite and calcite as major components. Minor amounts of
biotite, K-feldspar, quartz and chlorite may also be present. Minerals present are
similar to those found in potassic, high temperature propylitic and propylitic
assemblages of porphyry systems, but with a wider range of cations. Developed in
the presence of calcium-rich, high salinity fluids over a wide temperature range, with
early anhydrous minerals forming in the range 300 - 700C. Occur near the contact
between calcareous lithologies and intrusives.
Some rocks lack any diagnostic minerals, and so can not be readily assigned to an
assemblage. This includes samples that consist largely or entirely of quartz, or calcite,
adularia, zeolites, or sulphide or sulphate minerals. Even so, we can often still infer
something about the fluid conditions (e.g. adularia = near neutral, zeolites = low CO 2). In
such cases, rather than trying to fit a rock into an assemblage, it may be best to refer to the
alteration as silicification, or calcite-, adularia-, zeolite-, sulphide- or sulphate-alteration,
as appropriate.
There can be extensive overlap among some of these assemblages, especially between
phyllic and propylitic, and phyllic and argillic alteration. In effect, these are useful endmembers, between which there may be a gradation. Some workers have attempted to
define additional assemblages which are variants or mixtures of those listed above. For
example, because of the overlap between phyllic, propylitic, and to a lesser extent argillic
assemblages, these are sometimes combined into a single category. However, the propylitic
assemblage differs from the other two in the extent of mass transfer (due to the degree of
water-rock interaction), rather than any differences in temperature or fluid chemistry. The
propylitic assemblage is in effect an intermediate step during formation of a phyllic
assemblage (or argillic, depending on the temperature), and so such overlap is to be
expected. We consider that there is benefit in distinguishing individual assemblages, and
where there is overlap it is worth noting the nature and proportions of secondary minerals
rather than simply allocating a sample to a single assemblage.
Some of the above terms have been used incorrectly. For example, the term potassic has
been wrongly applied to phyllic or even argillic altered rocks. Although these rocks may
have elevated potassium contents, they are quite different from the potassic alteration as
defined above, in which there is biotite rather than illite or illite-smectite, and orthoclase
rather than adularia.
6.
Overprinting
Overprinting is the partial or complete replacement of one secondary mineral assemblage
by a different assemblage, and must occur due to changes in physical and/or chemical
conditions. In a stable hydrothermal system, provided there is sufficient permeability,
reactions between fluids and rocks will eventually produce a secondary mineral assemblage
that is in equilibrium both internally, and with the fluid, at the prevailing conditions. Yet
hydrothermal systems are seldom stable for long (in the geological sense), and when
conditions change, then a new set of reactions works to produce a new equilibrium
assemblage. Such changes generally affect the fluid temperature, pH, or chemistry, or
possibly all three, and may be associated with mineralisation.
Overprinting may be prograde (producing assemblages of higher rank), retrograde
(producing lower rank assemblages) or neither (due to differences in fluid chemistry or
state, rather than temperature or pressure). If overprinting reactions are sufficiently
complete, there may be no remnants of the prior assemblage left. However, usually some
minerals are preserved because they are resistant to alteration or they are enclosed in a
resistant mineral, while others may be recognisable from crystal pseudomorphs. Prior
generations of veining or fluid inclusion data might also indicate that overprinting has
occurred; for example, there may be two populations of fluid inclusions (as distinct from
mixed populations due to phase separation).
6.1
Prograde Overprinting
In hydrothermal systems, prograde overprinting commonly results from a rise in
temperature. A rise in temperature may be due to heating in response to renewed
magmatism (e.g. emplacement of a shallow intrusive body). If a system is already at or
near a boiling point for depth profile, it will not sustain higher temperatures unless the
pressures increase. This can occur if the water level is raised or permeability is sufficiently
low for lithostatic pressures to be contained, even temporarily. If the water level is already
near the surface, more rock must be added before the water level can be raised. This may
occur by the gradual accumulation of material, as in submarine hydrothermal systems and
VHMS deposits, or by sudden accumulation of material, as in caldera basins.
Renewed magmatism:
With renewed magmatism, the boiling point for depth profile is commonly exceeded, so
catastrophic phreatic eruptions occur at the surface, with hydrothermal brecciation and
boiling at depth (Browne and Lawless, in prep). The sudden boiling and loss of gas result
in destabilisation of bisulphide complexes, and deposition of gold and other metals at
depth. Overprinting may follow such an event, but usually takes longer to achieve,
occurring after the hydrothermal system has returned to a stable temperature profile at or
below that of boiling point for depth conditions. This may require elevation of the water
table and/or a decline in the heat flux into the system.
Magmatic activity has been documented in historical times at several active geothermal
systems, including Rotomahana in New Zealand (1886), Suoh in Indonesia (1933), and
Pinatubo in the Philippines (1991). The effects on the hydrothermal system are commonly
overshadowed by the volcanic effects (e.g. Pinatubo), since the phreatic/ phreatomagmatic
eruptions are generally smaller and less spectacular than volcanic eruptions (although at
Rotomahana the reverse was true). Phreatomagmatic eruptions were observed at Suoh in
1933, and the system there still maintains a boiling point for depth profile today. Possible
effects on the geothermal system are illustrated in Figure 2.
At Kelian (Indonesia), mineralisation coincided with prograde overprinting due to renewed
magmatic activity at a waning hydrothermal system. There was little in the way of
mineralogical change, because this event was short-lived. Evidence remains in the form of
late stage, hot, saline fluid inclusions, a large phreatomagmatic breccia body, and a large
gold deposit (Van Leeuwen et al. 1990). The same mechanism has probably occurred in
many other mineralised systems, but the temperature transient may often be too temporary
to cause significant recognisable overprinting.
Accumulation of material:
Prograde overprinting may also arise from more gradual changes (Figure 2), such as where
the land surface is subsiding, with accumulation of material during the course of
hydrothermal activity, or where there is a rising water table (due to climatic change,
tectonic activity, etc.). Examples are submarine hydrothermal systems, and systems
located within structural basins or calderas in which epiclastic and/or pyroclastic deposits
are accumulating. Although these changes may seem rapid from a human perspective, the
consequent temperature increase is gradual, and will not in itself cause mineralisation.
Temperature (C)
100
150
200
250
300
350
0
200
Depth (m)
400
600
Renewed
magmatism
Accumulation
of material
800
10% NaCl
(1.7 m)
1000
Pure
Water
1200
1400
4.4% CO2
(I.0 m)
1600
BPD.xls
BPD.xls
k:geo\lec\min\98min\mod1\figbpd.ppt
Figure 2
Temperature - depth diagram, showing the likely effects of
renewed magmatism and accumulation of material on a fixed
point in a hydrothermal system. Also shown are hydrostatic
boiling point for depth curves for pure water, and 10%NaCl and
4.4%CO2 solutions (from Henley 1985).
6.2
Retrograde Overprinting
Retrograde overprinting (also known as telescoping) generally results from a temperature
decline. A drop in temperature may be due to gradual cooling of a hydrothermal system at
it wanes. It is thus almost inevitable in fossil hydrothermal systems, and for this reason is
more common than prograde overprinting. However, cooling at a given point can also
occur following lowering of the water level. This may be due to climatic change, or the
removal of a thickness of rock from the surface; either a gradual loss of material by
erosion, or sudden loss due to volcanic eruption or sector collapse. Volcanic eruptions also
have other effects on hydrothermal systems (including heating), but sector collapses can
occur in the absence of recent volcanic activity.
Sector collapse:
Major sector collapses have been recognised at many active geothermal fields, including
Papandayan in West Java, Indonesia (1772), Muria in Central Java, Indonesia (undated)
and Lihir in Papua New Guinea. Sector collapse structures are often mistakenly identified
as calderas. There are important differences between the two, both in terms of their
origins, and their effects on a hydrothermal system.
A caldera is a large volcanic depression formed by the downward collapse of the
ground surface above a magma chamber during an eruption. Calderas are typically
kilometres to tens of kilometres across. Caldera-forming eruptions produce
pyroclastic deposits, which are generally fine grained and distributed more or less
evenly around the caldera (depending on wind direction and strength at the time of
eruption). The caldera basin itself will be partially to completely infilled with
eruption deposits and slumped material from the caldera walls, so that a point on the
original land surface will be buried. Up to 50% of the erupted pyroclastic material
may fall back into the caldera basin, especially in the largest calderas, where it can
be as much as 5 km thick (Lipman 1984). As an example, the 1883 eruption of
Krakatau (Indonesia) ejected some 18km3 of dacitic pyroclastics and produced a
caldera measuring 6 km by 7 km.
Cross sections through sector collapse

cones and collapse calderas
A
B
Normally faulted
down-dropped block
Bezymianny
Trapdoor caldera
St. Helens
Collapse along
outward-dipping faults
Bandai
Caldera subsidence
on vertical faults
Iriga
Collapse into a small

vent during eruption
Simple downsag or
flexure without faulting
Galunggung
Figure 3:
A: Cross sections of composite cones that have undergone
sector collapse (from Siebert 1984), and B: Schematic cross
sections through different types of calderas (from Wohletz and
Heiken 1992, after Walker 1984).
k:geo\lect\min\99\mod02\Afig2.ppt
A sector collapse is the lateral (outward) collapse of part of a volcano to form a

large debris flow (Figure 3), and may or may not be associated with an eruption.
Sector collapses may be up to several kilometres across. They produce coarse
epiclastic sector collapse deposits that extend out as a fan on one side of a volcano.
10
Following sector collapse and lateral removal of the collapsed material, a point
originally at depth will be exposed at the surface. For example, in 1980 a sector
collapse removed 2.3 km3 of material during the eruption of Mt. St. Helens, leaving
a large amphitheatre with a steep back slope (Voight et al. 1981).
A sector collapse above a hydrothermal system will suddenly reduce the confining
pressure, which may result in hydrothermal brecciation, boiling and mineralisation. The
effects are similar to those of renewed magmatism, but with a different mechanism;
decreased confining pressure, rather than increased temperature (Figure 4). A sudden
pressure decrease can have the same effect on a hydrothermal system as sudden heating,
pushing the system beyond boiling point for depth conditions. However, in this case the
temperature will decrease rather than increase (though more slowly than the pressure
decreased), causing retrograde overprinting. In contrast, caldera collapse is likely to result
in prograde overprinting.
Temperature (C)
100
150
200
250
0
200
Depth (m)
400
600
300
350
Sector collapse
Erosion,
cooling,
tectonics
Gradual
cooling
Caldera
collapse
800
Renewed
magmatism
Accumulation
of material
10% NaCl
(1.7 m)
1000
Pure
Water
1200
1400
4.4% CO2
(I.0 m)
1600
BPD.xls
BPD.xls
k:geo\lec\min\98min\mod1\figbpd.ppt
Figure 4
Temperature - depth diagram, showing the likely effects on a
hydrothermal system of sector collapse, caldera collapse, gradual
cooling and erosion/cooling/tectonic activity.
An example of mineralisation that has been attributed to the effects of sector collapse and
retrograde overprinting is the giant Ladolam gold deposit on Lihir Island (PNG). Here
there was a porphyry system, with potassic alteration and incipient Au-Cu mineralisation
forming at depth beneath a clay-altered volcanic pile. A massive sector collapse of the
11
weak clay-altered material exposed the top of the porphyry system. The sudden large
pressure drop that occurred during this collapse resulted in massive brecciation and
boiling, so that epithermal mineralisation was superimposed on the porphyry system
(Moyle et al. 1990). Several features indicate that Lihir is a sector collapse, rather than a
caldera, including exposed monzonitic intrusives and high temperature overprinted by low
temperature alteration within the caldera.
Furthermore, rather than producing
pyroclastic deposits, coarse epiclastic debris flow deposits extend tens of kilometres
offshore to the northeast (Herzig et al. 1994).
Erosion, cooling or tectonic activity:
Many hydrothermal systems are located in areas of active uplift and tectonism, and it is
possible for a system to be uplifted and eroded to considerable depth over its lifetime.
Gradual changes due to slow uplift or declining temperatures in a waning hydrothermal
system will produce retrograde overprinting, or telescoping, as discussed by Sillitoe
(1994a) and described in further detail in Module 5. Such telescoping due to gradual uplift
will generally not cause mineralisation, but sudden pressure changes accompanying
tectonic activity might. Mineralisation and retrograde overprinting at Porgera (PNG) could
result from repeated sudden pressure fluctuations associated with tectonic activity during
uplift and erosion of a mesothermal system.
6.3
Other Overprinting
Overprinting may reflect changes in fluid chemistry, or changes from liquid-dominated to
vapour-dominated conditions. However, these changes in themselves are not likely to
cause mineralisation, except where they are associated with processes such as boiling or
mixing of different fluids. Mineralisation in such systems is generally related to one or
other state of the system, rather than to the process of overprinting. For example, at
Masupa Ria (Indonesia), high and low-sulphidation epithermal systems are superimposed,
but mineralisation is principally associated with the low-sulphidation event (Thompson et
al. 1994).
12
7.
Practical Exercise
How would you describe the alteration in the following samples? You should note the
pervasiveness, intensity, alteration assemblage(s), and comment on overprinting
relationships, if present.
A
Dark green porphyritic rock with abundant chlorite, cut by a 1 mm quartz vein that
is surrounded by a 5 mm thick whitish clay-rich zone.
.............................................................................................................
Whitish illite-rich rock with disseminated pyrite and a faint porphyritic texture, cut
by 2 to 5 mm wide quartz-K-feldspar-magnetite-chalcopyrite veins, which in turn
are cut by 1 to 2 mm quartz-zeolite veins.
..................................
...

M11 Hydrothermal Alteration

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Hydrothermal Alteration

Rates of reaction for carbonic acid/rhyolite

Shallow / cool hydrothermal:

Deep / hot hydrothermal:

Formed in the presence of moderate to high temperature (approx. 230-400C), acid

Cross sections through sector collapse

Collapse into a small

A sector collapse is the lateral (outward) collapse of part of a volcano to form a

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