Magmatic-Hydrothermal Ore Deposits

Porphyry Deposits
Porphyry: large, low grade metal deposit associated with granite.
Epigenetic: ore mineralisation added to a previously existing rock
(e.g. porphyry deposit).
Syngenetic: host rock and ore mineralisation formed at the same
time (e.g. banded iron formations).

Porphyry deposits are a type of magmatic-hydrothermal deposit and are subduction zone
related. They normally host copper (chalcopyrite, bornite), gold (in Cu phases), tin
(cassiterite - SnO2), tungsten (wolframite) and molybdenum (molybdenite - MnS2).

All porphyries are associated with granites / granitic rocks, in particular, porphyritic
granite, from which the deposit gets its name. Porphyritic granites contain large
phenocrysts (crystals formed in the magma chamber) and fine groundmass indicating rapid
cooling after phenocryst formation.
Most porphyry deposits have very large tonnage but low grade. Significant amounts of
metal and other elements (Cu, Au, Cl, S) come out of volcanoes in gases. Cl and S are the
most popular ligands - elements that make metals soluble, for example AuHS.

They are very wet, unlike mafic rocks

Associated with island arcs Subduction zones
and
 I-magma
intrusion

- the first stage in the formation of

Porphyry copper deposit is the intrusion of
a sub-volcanic magma to a depth ~ 4 km.
The magma type is I-type (e.g. granite I-
type magma) and thus has high volatile
 magma
crystallizatio
n

-in the second stage, the sub-volcanic magma

chills against the country rocks, thus
crystallizing magma close to the country rock
 separation
of magmatic
fluid

- in stage three, magmatic fluids

(hydrothermal fluid or water volatile
content) separate during the
crystallization. This process is known
as the second boiling.
 pressure
build-up

In this stage, pressure starts to

build-up as the magmatic fluid
boils to form steam, producing
increase in volume. This process is
known as the first boiling.
 fracturing
and
formation of
stock work

In stage 5, the pressure generated by first

boiling results to the fracturing of the
crystallized magma and country rocks as
the pressure build-up is greater than
pressure of the country rocks.
In stage 6, the fracture of the crystallized magma
and country rocks results to rapid fluid escape into
the fracture network known as stock work;
deposition of ore mineral in the stock work, as the
magmatic fluid contains copper mineral. This stage is
also part of second boiling.
Requirements for the formation of
porphyry Cu
1.I-type (e.g. granite / granadiorite I-type magma)
and thus has high volatile contents (H2O, CO2, Cl,
etc).
2.crystallization at low pressures to form anhydrous
phases (~4 km); intermediate depth
3.Exsolvation of fluids at a certain pressure
4.first boiling and second boiling
5. they wont sulfur-saturate (because Cu will stay
with sulfur)
In the last stage, the magmatic fluid may undergo
phase separation into low density vapour and
brine phases. The dense brine will tend to pond at
the top of the intrusion. The potassic alteration
develops close to the core of the system and
 Porphyries and water

Water is the crucial factor in forming porphyry deposits

Wet magmas can travel higher in the crust than dry magmas, however, as soon as they
reach a pressure low enough to exsolve water, they stop and crystallise in place, whereas
dry magmas move incrementally, fractionating (crystallising) on the way up.

The addition of water to granitic systems causes melting to occur at a much lower
temperature than it otherwise would, that is, the liquidus moves to a lower temperature. A
substance that causes melting to occur at a lower temperature than normal is a flux. Other
examples are CO2, boron, and fluorine (topaz and tourmaline are common minerals in
granitic pegmatites).
The Albite-H2O system is a good example of this as it is simple and
reflects the behaviour of all rock-water systems.

The maximum melting temperature of albite is ~1100oC at 1 atmosphere

(rising with increasing pressure). As more water is added to the system
(5%, then 10%) (red lines) the liquidus moves to a lower temperature (blue
lines).
Granites in porphyry systems are fractured due to the release of water. This water then
carries away all ore-forming elements, and deposits them some distance above / away. This
is why a dry granite is worthless when it comes to forming porphyries. Chlorine, which
dissolves in the melt, is also carried away when the water exsolves and forms compounds
with metals such as copper and tin.

If you start crystallising at low pressure, hydrous phases are formed. These phases
take water out of the magma, so that at the end you are only crystallising
anhydrous phases. The result is that the magma doesn't become saturated in
water, and a porphyry is unable to form.

If you crystallise the magma at high pressure, however, anhydrous phases form,
so the magma becomes water saturated! The term used to describe the depth at
which porphyry deposits form is hypabyssal, which means intermediate depth
 Another important concept with respect to porphyry ore
formation is boiling. Boiling is what concentrates the ore
metals in the fluid and causes them to be deposited. First
boiling is decompression saturating the magma in water
which then exsolves (just take P down ). Second boiling is
saturation of magma by water caused by the crystallisation
of anhydrous phases . Usually a combination of both
occurs, and the whole process can be summed up as:

H2O in granite > saturate > exsolve fluid >boil (concentrate) >
deposit
 Alteration

Wall rock alteration is always present around porphyry deposits. When water exsolves from
the granitic magma, it causes the surrounding rocks to crack and a water saturated
carapace (a shell around the magma) is formed. The released water is extremely hot and is
able to alter the rocks around the granite
Hot fluid passing through the rock not only changes the composition of the rock (alteration)
but this in turn changes the composition of the ore-bearing fluid. The changes in rock and
fluid compositions causes several alteration zones to form around the igneous rock. These
are described in order from innermost to outermost alteration:

Potassic (K-metasomatism): Very high temperature fluid. K-feldspar

replaces most other minerals. Other secondary minerals include
sericite and biotite. This type of alteration is particularly indicative
of porphyry deposits.
Phyllic (acidic): Characterised by quartz-sericite-pyrite assemblage.
Argillic: Characterised by kaolinite (clay).
Propylitic: As the fluid has cooled significantly by this stage, this
type of alteration can be found all over the world and so is not very
indicative of any particular deposit. It is characterised by chlorite-
epidote-carbonate.
The following alteration reactions occur (in order):

K-feldspar to sericite (consuming H+):

3KAlSi3O8 + 2H+ > KAl3Si3O10(OH)2 + 6SiO2 + 2K+
Sericite to kaolin (H-metasomatism, hydrogenating):
2KAl3Si3O10(OH)2 + 2H+ + 3H20 > 3Al2Si2O5(OH)4 + 2K+
Hydrogen comes from the ore-forming reaction:
CuCl2 + FeCl2 + H2S + 1/4O2 > CuFeS2 + 1/2H2O + 3H+ + 4Cl-
Ore is found in the potassic and phyllic zones, where boiling occurs.
Aluminium is not a very mobile element, and normally the only way to increase its
abundance is to take everything else away from it. As you remove potassium and iron, you
increase alumina.

Alkalis (K, Na, etc) are easily remobilised and deposited near the core, hence potassic
alteration. The next rocks out are affected by fluid that has lost its potassium but is rich in
hydrogen (H+), and is therefore acidic. This rock is more aluminium rich, and muscovite is
produced. Finally chlorite and epidote are produced in the outer rocks. Hydrous phases are
not made initially because the water is too hot.
 Different types of porphyries

All porphyries are formed in the same way. So how do you make different metal
deposits?

It turns out that it is not so much the type of melt but the melt's history that forms
different deposits, specifically, the magma's oxidation state.

It is also important to remember Goldschmidt's rule - an element must have the

same valency and size to replace another element.
Magnetite is found in oxidised magmas while ilmenite is found in reduced
magmas.

Copper deposits form from oxidised granites and are not fractionated

Tin deposits, on the other hand, form from reduced granites and are highly
fractionated, meaning that the magma spent a lot of time crystallising during its
ascent and as a result altered the melt composition.
 Why don't oxidised magmas make tin deposits?

In an oxidised magma the valency of tin is 4+. So there must be something that
takes Sn4+ out of the magma easily. An example of a mineral Sn 4+ is compatible in
is sphene - CaTiSiO5. Ti generally has a valency of 4+, so tin substitutes readily
into the mineral to make molailite - CaSnSiO5 . DSn4+sphene/melt = 70; DSn2+xals/melt < 1, so
while Sn4+ is more compatible in a mineral, Sn2+ prefers to stay in the melt and so
forms tin deposits.
 How to make a porphyry (Cu, Mo, Sn, W, Au...):

1. need a wet granite (~6.4 wt% H2O, Xwm ~ 0.5)

2. must crystallise at low enough pressure to form anhydrous ph
ases, but high enough to prevent explosion
3. exsolve fluid at the right pressure
4. don't sulfur-saturate (Cu will stay with sulfur)
5. appropriate fO2
 How not to make a porphyry:

1.have a dry granite (anorogenic, found at centres of continents)

2.crystallise deep (at high P)
3.crystallise at very low P (let it erupt)
4.sulfur-saturate
5.wrong fO2
 EXPLORING FOR COPPER

The concentration of a metal in an ore is called its grade. Grade is usually

expressed as a weight percentage of the total rock. For example, 1000 kilograms
(kg) of iron (Fe) ore that contains 300 kg of iron metal has a grade of 30%:
Grade = (kg metal / kg rock ) x 100

Most of the world's copper comes from porphyry cooper deposits located
primarily in South America, New Guinea, Indonesia, the United States, and
Canada.
Vertical cross section showing a porphyry copper deposit as it occurs deep within
the earth. (Modified from Evans, 1980)
In addition to forming ore deposits, this circulating water can form large bodies of
altered rocks surrounding the stocks known as alteration zones. Minor copper
mineralization can be formed away from the stocks within thin planar bodies
known as veins. However, this mineralization does not usually contain enough
copper to be considered ore.
Exploration Techniques

One important technique is geologic mapping. A geologic map shows the

distribution of the various rocks at the surface of the earth. In the case of
porphyry copper deposits, geologists know that such deposits usually form on the
outer edges of the igneous stocks and within alteration zones. Once a map is
constructed, the geologists can focus their exploration activity in these areas.

Another common exploration technique is called geochemical exploration

Another commonly used geochemical exploration technique is soil geochemistry.

Geologists establish a sampling grid over an area of interest
One difficulty in using sediment and soil
geochemistry to explore for ore deposits is
the occurrence of anomalies related to
human activities. Construction of bridges
often produces high concentrations of
metals in sediments. Pollution from
industry or landfills can impart high
metal content to soils, streams, or the
atmosphere. Such geochemical anomalies
produced by human activities can be
confused with anomalies that might
indicate the presence of ore deposits.

Paleogene Magmatism
 Golden
Quadrilate
ral

Neogene magmatism