Chapter 4

Hydrothermal Alteration

4.1 Introduction

Hydrothermal alteration is a very complex process involving mineralogical,

chemical and textural changes, resulting from the interaction of hot aqueous fluids
with the rocks through which they pass, under evolving physico-chemical condi-
tions. Alteration can take place under magmatic subsolidus conditions by the action
and infiltration of supercritical fluids into a rock mass. At lower temperature and
pressure, exsolution of gas and aqueous phases constitute hydrothermal solutions
which act on the surrounding rocks, producing changes as the result of disequilibri-
um, largely due to H+ and OH- and other volatile constituents (e.g. B, CO 2, F).
In essence, hydrothermal fluids chemically attack the mineral constituents of the
wall rocks, which tend to re-equilibrate by forming new mineral assemblages that
are in equilibrium with the new conditions. The process is a form of metasomatism,
i.e. exchange of chemical components between the fluids and the wall rocks.
Therefore, it is also possible that the fluids themselves may change their
composition as a result of their interaction with the wall rocks. The main factors
controlling alteration processes are: (1) the nature of wall rocks; (2) composition of
the fluids; (3) concentration, activity and chemical potential of the fluid compo-
nents, such as H+, CO2, O2, K+, S2 etc. the so-called operators of Rose and Burt
(1979). Henley and Ellis (1983) believe that alteration products in epithermal
systems do not depend so much on wall rock composition as on permeability,
temperature and fluid composition. They cite, for example, that in the temperature
range of 250-280°C, similar mineral assemblages (e.g. quartz-albite-K-feldspar-
epidote-illite-calcite-pyrite) are formed in basalts, sandstone, rhyolite and andesite.
Other workers, however, emphasise the fundamental role played by the nature and
composition of wall rocks in hydrothermal alteration processes, particularly in
porphyry systems.
The action of hydrothermal fluids on wall rocks is by infiltration and/or
diffusion of chemical species (Rose and Burt 1979). Hydrothermal circulation and
the related alteration generally involve large quantities of fluids that pass through a
given volume of rocks, which therefore must have considerable permeability in the
form of fractures, or connected pore spaces. Small quantities of fluids have lesser, or
even negligible effects, as exemplified by metamorphic hydrothermal systems in
which the amount of fluids in relation to the rock, i.e. the water/rock ratio (w/r), is
small, and the resulting mineral deposits have small or negligible wall rock
alteration (Chap. 15). Thus the interaction between H 20 and rocks, and the
F. Pirajno, Hydrothermal Mineral Deposits
© Springer-Verlag Berlin Heidelberg 1992
102 Hydrotermal Alteration

intensity of alteration is, inter alia, a function of the water/rock ratio (w/r). This
ratio is an important parameter because it affects the degree of exchange with the
wall rocks. In hydrothermal systems, w/r ratios may range from 0.1 to 4, with a
lower limit obtained when all free water is absorbed as hydrous minerals (Henley
and Ellis 1983). Exchange of oxygen isotopes during water/rock interaction permits
one to calculate the w/r ratios (see Chap. 2), as discussed by Taylor (1974) for
various granitic rocks, in which meteoric waters circulated through a very large
volume of rocks. Within this volume the w/r ratio is calculated at between 0.1 to 3.0.
Henley and Ellis (1983) report values of 0.7 to 2.0 w/r for the New Zealand
geothermal fields.

4.2 Hydrogen Ion Metasomatism and Base Exchange

Hydrolysis and hydration were introduced in Chapter 1. Here, these terms are
defined in the context of hydrothermal alteration processes. Hydrolysis, or
hydrogen ion metasomatism, is a very important phenomenon involving the ionic
decomposition of H 20 into H+ and OH-. In hydrothermal alteration, H+ (or OH-)
is consumed during reaction with the silicate minerals, so that the ratio H+ /OH-
changes. The source of H+ ions can be subsolidus reactions during alkali
metasomatism (see later), water, or acids in the hydrothermal solution. The
conversion of anhydrous silicates to hydrous ones (e.g. micas or clays) is a reaction
which consumes H+ and releases metal ions into the solution. This in turn affects the
pH of the solution and its power to dissolve or to keep cations in solution. This is
related to the dissociation of complexes containing H+, the degree of association of
compounds such as NaCl, and consequently the formation of chloride complexes
and the solubility of metallic elements (Guilbert and Park 1986). A typical example
of hydrogen ion metasomatism, or hydrolytic decomposition of feldspar, is given
by:

K-feldspar K-mica quartz

H+ + OH- = H 20.

The sum of the first and second reactions gives:

It can be seen from this reaction that K+ is released and H+ is consumed. Hydration,
the transfer of molecular water from the solution to a mineral, often accompanies
hydrolysis. A typical example is the conversion of olivine to serpentine, according
to:

olivine serpentine