Dr.

Boddepalli Govindarao
 Sulfur immiscibility in magma (Silicate–sulfide immiscibility)

• Separation of a metal-rich sulfide liquid phase from silicate magma.

• Sulfide saturation: The point at which the magma can no longer dissolve sulfur and sulfide
liquid begins to form.

• Sulfur as sulfide is dissolved in magmas by displacing oxygen bonded to ferrous iron

FeO (melt) + 1/2S2⇔FeS (melt) + 1/2O2

• Sulfide solubility of melts is controlled by fO2, iron content, temperature, pressure

and the SiO2 concentration

• Sulfide solubility decreases with increasing oxygen content in a magma (fO2)

• Sulfide solubility increases as a function of increasing temperature, FeO content of

the magma; decreases with increasing pressure and SiO2 concentration.
 • Magma at A in Figure (left side), crystallizing
Fe-rich olivine (fayalite), would evolve along A–
A′ and eventually intersect the two-liquid
phase boundary where the residual melt would
comprise conjugate silicate and sulfide melts.

Phase equilibria established experimentally in the

system SiO2–FeO–FeS (after MacLean, 1969). The field
of two coexisting silicate and sulfide liquids is shown by
the stipple accentuated line. Oxidation of the magma
would shift the phase boundary in the direction shown
by the double arrow, and expand the field of two-
liquids. A magma represented by composition A and
crystallizing fayalite would evolve along the line A–A′.
Incorporation of sulfide and chalcophile elements into a silicate melt

▪ Chalcophile and siderophile elements will

be hosted to a large degree in the trace
sulfide minerals in mantle peridotite.

▪ The different partition coefficients of Ni,

Cu and PGEs between silicate melt and
sulfide melt and between silicate minerals
and melt mean that these elements reach
high concentrations in the melt at
different degrees of progressive melting
of mantle peridotite

Calculated concentrations of Ni, Cu and PGEs in different

percentage partial melts of mantle peridotite with 200 ppm S,
2500 ppm Ni, 40 ppm Cu and 5 ppb Pt and Pd (Naldrett, 2010).
At up to about 12% partial melting some of the sulfide remains
in minerals or in a separate sulfide melt. Sulfide is fully in
solution in the silicate melt at higher degrees of melting.
Sulfur saturation – formation of immiscible sulfide melt

• The sulfur content at sulfide saturation is seen

to decrease from a maximum of about 0.4 wt%
sulfide at the start of crystallization to below
0.1 wt% as olivine and orthopyroxene
crystallize

• A magma with an original sulfide content of

0.3 wt% would initially be undersaturated and
its position would plot below the curve.
An initial magma composition represented by A in
the Figure containing 0.3 wt% sulfide, would be
undersaturated relative to sulfide (i.e. sulfide
solubility at this stage is 0.4%). Extraction of
olivine from the magma (A–B in Figure) would
decrease its FeO content and result in sulfide
saturation with formation of an immiscible sulfide
fraction. With continued crystallization and
segregation of sulfides the magma would remain
saturated, following the solubility curve as shown
in Figure. If after some 20% crystallization (at
point C just prior to the appearance of plagioclase
as a cumulus phase) the chamber is replenished
with the injection of a new magma (similar to A)
and mixing occurs, then the composition of the
mixture would lie somewhere along the mixing line
between A and C. If the mixture is at AC it would
clearly be undersaturated again and any sulfide
globules present would be resorbed back into the
magma.
If, the chamber is replenished with the
injection of a new magma at point D (after 35%
crystallization, and after the introduction of
plagioclase as a cumulus phase), then a mixed
magma composition at, for example, AD would be
oversaturated with respect to sulfide. This
would result in the segregation of an immiscible
sulfide fraction, the mass of which exceeds the
expected cotectic proportion. A period of
enhanced sulfide production could be expected,
therefore, to accompany the injection of a new
magma at point D.
• Sulfide minerals like pyrrhotite,
pentlandite, cubanite and chalcopyrite
dominate magmatic sulfide deposit
mineralogy

• Host valuable metals such as nickel

(Ni), copper (Cu), and platinum-group
elements (PGEs).

• Other minerals include gold (Au),

tellurides.
• Magmatic sulfide deposits form from the segregation of
a sulfide liquid from a silicate liquid

• If sulfide saturation of the mafic-ultramafic magma

occurs there is a partitioning of elements between the
silicate magma and the segregating sulfide liquid.

In particular, the chalcophile elements, such as Ni, Cu, and

the PGE, are scavenged from the silicate liquid and partition
into the sulfide liquid, thereby creating a sulfide liquid
enriched in chalcophile elements and a silicate liquid
depleted in chalcophile elements

• The final concentration of the chalcophile metals in the

sulfide liquid is dependent on a number of factors
including the initial concentration of chalcophile metals
in the parental silicate liquid, how readily the element
partitions into the sulfide liquid (i.e., the partition
coefficient), and the mass of silicate liquid to sulfide
liquid (R factor)
Schematic of pathways to formation of
economic magmatic massive sulfide deposits
in mafic intrusions and in komatiites. The
stipple density represents the
concentration of chalcophile and siderophile
elements (Cu, Ni, PGEs). Sulfide saturation
is reached by assimilation of either felsic
wall-rock or S-bearing wall-rock. The ore
elements are fractionated into the sulfide
melt droplets after sulfide saturation.
Droplets segregate due to settling to the
base of the magma and/or due to irregular
magma flow.

• The most common sulfide minerals in

magmatic sulfide ore deposits:
pyrrhotite, pentlandite , chalcopyrite,
cobaltite
 When and how base metal sulfides form?

Fe-Cu-S system
from 900 to 500 °C

• MSS is the first phase to form above

950 °C, it persists to 550 °C before it
decomposes to pentlandite and Ni-rich
Fe-Ni-S system from 1100 to 550 °C pyrrhotite at 450 °C.
Magmatic nickel-
sulfide deposits
 PGE deposits

The platinum group metals (PGMs) comprise 6

elements, which are platinum, palladium, rhodium,
ruthenium, iridium, and osmium.

• high melting points,

• high heat resistance,
• high corrosion resistances,
• unique catalytic properties

Platinum group minerals:

• braggite [(Pt,Pd,Ni)S],
• laurite[RuS2],
• malanite [CuPt2S4 ]
• moncheite[Pt(Te,Bi)2],
• cooperate [PtS])
• alloys.
 • Mafic and ultramafic igneous rocks and magmatic Ni-Cu sulfide
deposits host PGEs

• Economically viable concentrations of PGEs may not be found in some

layered mafic complexes and magmatic Ni-Cu sulfide deposits as

(1)original concentrations of PGE in magmatic reservoirs

are very low

(2) Lack of effective communication of sulfide magma

with the entire magma reservoir.
PGE enrichment C1 = [CoDi(R+1)]/(R+Di)

C1: final concentration in the sulfide melt

• Only a sulfide melt interacting with an 𝐶o: initial concentration in the silicate melt
infinite reservoir of magma is likely to get Di: metal's partition coefficient between sulfide and silicate
the fullest possible PGE concentration. So R: mass ratio of silicate: sulfide (the R-factor)
along with original abundance and D
(distribution coefficient) the “R” factor
(silicate/sulfide liquid mass ratio) is
important.

• The partition coefficients of PGEs are

very high, and their abundances in the
parental magma is very low, thus only the
very first formed sulfide fraction will be
enriched in the PGEs.

• The R-factor represents the mass of

silicate magma that a segregated sulfide
liquid has equilibrated with
Schematic models illustrating the segregation of an immiscible sulfide liquid (a), crystallization and
exsolution (b to e), and late magmatic/ hydrothermal alteration (f) of base-metal sulfides in a magmatic
sulfide deposit. MSS, monosulfide solid solution; ISS, intermediate solid solution; PGM, platinum-group
minerals; Po, pyrrhotite; Pn, pentlandite; Ccp, chalcopyrite; Py, pyrite; Mag, magnetite; Sil, silicates. The
R-factor is the ratio of silicate liquid to sulfide liquid
Po: pyrrhotite, Pn:
pentlandite , Ccp:
chalcopyrite,
CGSS: cobaltite–
gersdoffite solid
solution.