Magmatic-Hydrothermal Ore Deposits

Porphyry Deposits

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 - SnO
2
), tungsten (wolframite) and molybdenum (molybdenite - MnS
2
).
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.
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).

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 and Subduction zones
- 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 contents
(H
2
O, CO
2
, Cl, etc).
I-magma
intrusion
-in the second stage, the sub-volcanic magma chills
against the country rocks, thus crystallizing magma close
to the country rock
magma
crystallization
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.
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.
pressure
build-up
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.
fracturing and
formation of
stock work
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 (H
2
O, CO
2
,
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 propylitic alteration further out.
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 CO
2
, boron, and fluorine (topaz and tourmaline are common minerals in
granitic pegmatites).
The Albite-H
2
O 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 ~1100
o
C 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:




H
2
O 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
+
):
3KAlSi
3
O
8
+ 2H
+
> KAl
3
Si
3
O
10
(OH)
2
+ 6SiO
2
+ 2K
+

Sericite to kaolin (H-metasomatism, hydrogenating):
2KAl
3
Si
3
O
10
(OH)
2
+ 2H
+
+ 3H
2
0 > 3Al
2
Si
2
O
5
(OH)
4
+ 2K
+

Hydrogen comes from the ore-forming reaction:
CuCl
2
+ FeCl
2
+ H
2
S +
1
/
4
O
2
> CuFeS
2
+
1
/
2
H
2
O + 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 Sn
4+
out of the magma easily. An example of a mineral Sn
4+
is compatible in
is sphene - CaTiSiO
5
. Ti generally has a valency of 4+, so tin substitutes readily
into the mineral to make molailite - CaSnSiO
5
. D
Sn4+
sphene/melt
= 70; D
Sn2+
xals/melt
< 1,
so while Sn
4+
is more compatible in a mineral, Sn
2+
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% H
2
O, X
w
m
~ 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 fO
2


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 fO
2


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
Quadrilateral
Neogene magmatism