145 3.

2 Hydrothermal deposits formed around magmatic centres

SANTA EULALIA Ag, Pb, Zn

Chimenea
de Purisima

Santa Eulalia
plan projection of
western ore bodies N

stillos
Capping group (not shown on plan)

to de Bu
Ore bodies
Evaporite group

Man
Rhyolite & micro-granite
Dolerite & micro-diorite Chimenea
de Chorro
Grandodiorite
Limestone

1000 m

Santa Eulalia - Composite longitudinal projection of western ore bodies

2000 m

Chimenea
de Purisima

1500 m Chimenea
de Chorro

1000 m above sea level (No Data)

Figure 3.26 Maps and cross sections of the geometrically complex and irregular ore bodies with
mantos and chimneys (chimeneas) at the Santa Eulalia carbonate-replacement deposits, Mexico
(after Hewitt, 1968). There is a close resemblance between the ore-body geometry and karst
cave systems. The ores are mineralogically mainly either sulfide ores with pyrrhotite (or
pyrite)–galena–sphalerite, or oxide ores with a Pb and Zn carbonate and sulfate minerals and
Fe and Mn oxide minerals.

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146 Hydrothermal ore deposits I: magmatic and orogenic environments

for instance pyrite–galena–sphalerite, with up to 70% pyrite. One characteristic set of

non-sulfide ore minerals that is present in some carbonate-replacement ores include zinc
oxide (e.g. zincite, ZnO), zinc carbonate (smithsonite, ZnCO3) and lead carbonate
(cerrusite, PbCO3) minerals, for instance at Santa Eulalia. Zinc-rich ores with these
minerals form one type of so-called oxide ores of zinc.

Chemical and physical processes in the formation of skarn and carbonate replacement
The unique characteristics of these two deposit types result from the unique chemistry of
carbonate minerals and rocks. Carbonates are strongly soluble in high-temperature hydro-
thermal fluids that have low concentrations of dissolved CO2 and low ratios of Ca2þ/Hþ.
Importantly, carbonate minerals can dissolve orders of magnitude faster than silicate
minerals at similar temperatures. The characteristic sharp contacts between unaltered
and altered rocks are ‘reaction fronts’ and the bulbous shapes of the fronts are typical
of ‘reaction-infiltration instabilities’ that develop where there is positive feedback
between chemical reaction, in this case dissolution of carbonate minerals, and fluid
infiltration, hence focussing further reaction.
There are many instances in which there is a reaction front separating calcite marble
from skarn with an assemblage of diopside together with possibly garnet and magnetite.
Comparison of the mineral assemblages and textures across these reaction fronts shows
that the carbonate unit was effectively completely dissolved, and was replaced by the
skarn assemblage with little change in rock volume (isovolumetric replacement). The
chemical reactions to form prograde skarn assemblages are complex and can be inferred,
for instance in simplified and schematic form for a clinopyroxene skarn in limestone to
involve dissolution of calcite, addition of iron and silica from the hydrothermal solution,
precipitation of the calc-silicate minerals, and liberation of CO2, in schematic form:
calciteðCaCO3 Þ þ FeðaqÞ þ SiO2ðaqÞ ! clinopyroxeneðCaFeSi2 O6 Þ þ CaðaqÞ þ CO2 : ð3:6Þ
Some calcium will be released into solution if the reaction involves isovolumetric
replacement of calcite by clinopyroxene. Similarly complex reactions, for instance
involving replacement of calcite by pyrrhotite or pyrite, can be written for alteration at
carbonate-replacement deposits. The retrograde reactions in skarns are approximately
isochemical except for the addition of water.
There are multiple factors that control alteration mineralogy in a hydrothermal system
(see Section 3.1.3). Important controls on whether garnet, diopside or wollastonite is the
dominant mineral in a skarn include: the composition of the country rock (particularly
whether dolomite or limestone and whether a clay-rich carbonate unit); the fluid tempera-
ture, and hence distance from an associated intrusion or position within a magmatic
vapour plume; and the hydrothermal fluid composition.

Ore genesis at skarn and carbonate-replacement deposits

The assemblages of prograde gangue minerals in skarns form at approximately 450–
600  C, which is the upper end of the range of fluid temperatures that are implied by fluid
inclusions in these deposits. The complex paragenetic histories of many skarn deposits
with prograde and retrograde stages reflect heating and cooling of the rock volume around
high-level intrusions. Temperatures of formation of carbonate-replacement deposits have
been estimated to be around 300  C to locally about 400  C (for instance in the Cu–Ag

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147 3.2 Hydrothermal deposits formed around magmatic centres

chimney at Gilman, Figure 3.25) based on fluid-inclusion data and on isotope fraction-
ation between coexisting minerals. These deposits thus formed at significantly lower
temperatures than skarn deposits and the differences in the gangue minerals are related
dominantly to which minerals are stable at each range of temperature.
The common metal content of skarn and carbonate-replacement ores and associated
porphyry and greisen ores implies a common magmatic-hydrothermal source of the metals.
The gangue minerals that are paragenetically associated with ore are thus also likely formed
as the result of infiltration of magmatic-hydrothermal fluids. In contrast to the prograde
reactions, the retrograde reactions are approximately isochemical except for the addition of
water, and may thus be the result of convection of groundwaters during cooling of the
intrusion.
The relatively high grades and polymetallic nature of both skarns and carbonate-
replacement deposits can be explained as results of the unique chemical nature of carbonate
rocks. As described in the section on porphyry deposits, magmatic-hydrothermal
fluids become acidic on cooling as a result of disassociation of acid aqueous species such
as HCl in solution. Dissolution of carbonate minerals, however, buffers fluid pH, through
reactions such as:
CaCO3 þ 2Hþ ! Ca2þ þ CO2 þ H2 O: ð3:7Þ
Most ore minerals are more soluble in acidic than neutral solutions. The solubility, for
instance, of sphalerite in a fluid in which Zn is transported as a chloride complex can be
expressed as:
ZnCl4 2 þ H2 S ! ZnS þ 2Hþ þ 4Cl : ð3:8Þ
Neutralisation of an acidic fluid by dissolution of carbonates thus induces a decrease in
ore mineral solubility. The relatively high ore grades of skarn and carbonate-replacement
ores compared to adjacent and related porphyry or greisen deposits are the result of
efficient chemical precipitation of ore minerals as acid is neutralised.

Patterns of fluid flow and sources of hydrothermal fluids at skarn and

carbonate-replacement deposits
The settings and distributions of skarn and carbonate-replacement deposits around mag-
matic centres and their forms are variable.
The Bingham Cu–Au–Mo porphyry deposit is surrounded by a partial halo of Cu skarn
deposits and by Pb–Zn–Ag carbonate-replacement deposits (Figure 3.23). The Cu skarn
deposits lie within the low-grade Cu halo of the porphyry deposit. For instance, the Carr Fork
deposits, which had grades of about 2–3% Cu, are hosted in carbonate units that are
interbedded between quartzite units and are adjacent to one flank of the Bingham Stock
and within the low-grade halo to the lower levels of the shell of the major porphyry ore body
(Figure 3.24). Both the interbedded quartzite and adjacent stock have sub-economic Cu
grades of between 0.1 and 0.3%. Temperatures of skarn ore formation are within the range of
those estimated for the potassic alteration zone in the enveloping low-grade halo of the
porphyry deposit and the paragenetic timing of ore mineral precipitation is the same as that
of potassic alteration. The skarn deposits can thus be interpreted to have formed in the
peripheral parts of the magmatic vapour plume from which the porphyry deposit was formed
(cf. Figure 3.15). The metals and sulfur are thus most likely derived from the pluton that fed

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