Ores in ultramafic-mafic rocks B.

Mishra

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Generalized Classification Scheme for ores in ultramafic- mafic rocks










Crystal Fractionation Carbonatite association Liquid fractionation

i) Diamond in kimberlite REE, Nb, P, Sr, Ba i) Oxide liquid immsc. (Mt +
ii) Cr ores (Layered and Zr and sometimes apatite- Kiruna type)
Alpine types) Cu ii) Sulfide liquid Immiscibility
iii) Fe-Ti-Oxides in gabbro- Cu +Ni Co PGE ores
anorthosite association

Ores in the mainstream of ultramafic-mafic association include those formed by crystal and
liquid fractionations. Carbonatite association is included here because generation of
carbonatitic melt can be either due to (i) liquid immiscibility from phonolitic/ nephelinitic/
kimberlitic melt (Le Bas, 1987) or (ii) by direct melting fertile mantle peridotite at P >21
kbar (Wallace and Green, 1988). Additionally, some ultramafic-mafic rocks constitute
potential protore sources for Ni- and Au- bearing laterites.

There exist several commonalties that seem to be the unifying factors for the entire
spectrum of ore deposits in ultramafic-mafic settings. These include: (i) highly selective and
specific ore-rock assoc.; (ii) a very exclusive suit of elements, whose average crustal conc. in
the barren ultramafic-mafic rocks are order-of-magnitude higher than in any other barren
rock, typically forms their ore deposits in such rocks; (iii) ore bodies with rare exceptions
typically are physically confined within the hosts; and (iv) again barring exceptions (PGEs),
pervasive wall rock alteration is strikingly absent. The consanguinity of at least the metals
with the host rocks has never been questioned, excepting diamond in kimberlite. The problem
of ore genesis thus overlaps to a large extent with the problems of petrogenesis of the
ultramafic-mafic rocks




Ores in ultramafic-mafic Association

Ores in ultramafic-mafic rocks B. Mishra

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Essential differences between the stratiform and Alpine type chromites

LAYERED ALPINE

Age Pre-Camb to lower Paleozoic Paleozoic to Tertiary
Eg Bushveld Ign. Complex (SA) Urals, Philippines,
Skaergaard, Greenland Turkey, Cuba, India
Great dyke, Zimbabwe Pakistan
Muskox, NWT, Canada
Rock Comp. Peridotite at the base and Dunite to gabbro
Granite at the top Average: peridotitic
Average: gabbro
Morphology Saucer Shaped Elongated pod shaped
(inches to x100 thick) (inches to a foot thick)

Chromite MgO/FeO =0.6 -1.0 1.0 2.3
Composition Fe
2
O
3
low (<8 wt%) high (10 24 wt%)
(Fig. 1) Cr/ Fe =high (1.5- 4.5) low (0.75 1.75)
Al
2
O
3
- Cr
2
O
3
reciprocal relation Scattered
Assoc. of Ni as sulfides and arsenides Ni olivine
Po- pentlandite- gersdorfite etc




























Fig. 1 Schematic diagram showing solid solubility in natural
spinels.
Ores in ultramafic-mafic rocks B. Mishra

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Origin of essentially monomineralic chromite layers (Irvine, 1977)































The model is based on experimentally derived phase relations, related to contamination of a
fractionated (felsic) liquid with a more mafic liquid. The shape of the olivine-chromite
cotectic curve is such that crystallization along this leads to decrease in chromite/olivine ratio
(Fig. 2).
TWO POSSIBLE GEOLOGIC SITUATIONS:
(A) The common situation is when the intrusion contains liquids that has differentiated to
point f, where opx is on the liquidus and some new primitive (mafic) liquid (comp. a) is
introduced (Fig. 2). (1) Initially the primitive melt with high liquidus temperature crystallize
along the Ol-Chr cotectic (ab), producing peridotite. But with progressive mixing, instead
it will follow the path bf towards composition c. Because composition c extends across
the edge of the chromite field, continued crystallization should for some time produce only
CHROMITE and results in driving the melt composition back to the Opx field atd, leading
to formation of Opx (Fig. 2). The whole sequence is peridotite chromite orthopyroxenite
as seen in the Muskox intrusive, NWT, Canada.
Fig. 2 Phase diagram in part of the system (Mg, Fe)-Cr
2
O
3
-SiO
2
, showing the
olivine-chromite cotectic and theoretical mixing line with regard to chromite
crystallization.
Ores in ultramafic-mafic rocks B. Mishra

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(2) Alternatively, if the volume of the fractionated liquid (f) >>>volume of new addition
(a) no peridotite will form and the sequence will be orthopyroxenite chromite as
observed in the Bushveld Ign. Complex, SA.
(3) Alternatively, if addition of fresh liquid (a) is quite large hybrid liquid formation and
the bulk composition will return to the Ol-Chr cotectic after chromite crystallization leading
to a sequence of peridotite chromite peridotite orthopyroxenite as observed in the
cyclic units of Stillwater, Montana, US.
(B) The differentiated liquid is still on the Ol-Chr cotectic at a point just above the chromite
control line (Fig. 2). The mutual solution (and mixing) of this liquid with a primitive liquid
(a) yield liquid compositions in the chromite field leading to formation of peridotite
chromite as observed in Great dyke, Zimbabwe.

Sulfide Liquid Immiscibility: Generalized phase diagram to illustrate
diverse genetic types of Ni ores

(A) Crystallization from a melt composition represented by pt.1 (92% silicate + 5%
magnetite +3% pyrrhotite) moves the liquid composition to pt.2 and sulfide liquid of
TWO POSSIBLE CRYSTALLIZATION SEQUENCES













Fig. 3 Ternary phase relation in the system Fe-silicates (gabbro)Fe-
oxide (magnetite)Fe-sulfide (pyrrhotite), showing the course of
crystallization from melts of two compositions represented by 1
and 8.
Ores in ultramafic-mafic rocks B. Mishra

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composition 3 separates out with continued crystallization of silicates. Similar sequence can
be seen for pt.4 and pt.5. Continued crystallization of silicates leads to movement of residual
liquid composition moving from pt. 5 to pt.6 and leads to crystallization of magnetite and
silicate (Fig. 3). Finally, liquid composition reaches pt.7, the ternary eutectic ( 90%
pyrrhotite +8% magnetite +<5% silicate). If some trace amount (400 ppm) of Ni was
present in the initial melt (pt.1), then that would be greatly enriched in the final crystallization
product at pt.7, thus giving a magmatic Ni- sulfide deposit, formed due to liquid
immiscibility.
(B) On the other hand, crystallization of a liquid of composition 8, which has higher Fe
3+
/
Fe
2+
ratio (because of relatively high fO
2
compared to that at pt.1), the path will be towards
pt.9, without any liquid immiscibility. Magnetite and silicate crystallize together along the
cotectic and although crystallization stops at pt.7 and a sulfide deposit of essentially
pyrrhotite- magnetite mineralogy will form, it would be devoid of Ni, due its early strong
partitioning into crystallizing olivine and other early formed silicates along the cotectic.
These Ni-olivines serve as protore which on weathering forms Ni- laterites.

Sulfur Solubility in silicate melts
Knowledge of S-solubility in mafic and ultramafic silicate melts is important in
understanding how magmatic sulfide deposits form and also in evaluating the potential
igneous bodies as host for ore deposits of this type. At low fO
2
(< 10
-6
atm.) and at
temperature 14001500C, sulfur dissolves primarily as sulfide and the function can be
termed as S-capacity of the silicate melt (C
s
), which is constant for melts of same
composition.

The entry of sulfur into silicate melts is governed by the simple exchange eqn.

[O]
melt
+1/2S
2
=[S]
melt
+1/2O
2


As the amount of oxygen displaced by the above reaction is very low and constant, it can be
written as C
s
=S
m
[fO
2
/fS
2
]
1/2
, where S
m
is the sulfur content of the melt. C
s
increases with
temperature and composition of the melt generally increasing with increasing FeO and
MgO contents and decreasing with SiO
2
and Al
2
O
3
contents But as seen from Fig. 4, C
s
is
Ores in ultramafic-mafic rocks B. Mishra

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very high for FeO-SiO
2
system at any X
SiO2
value compared to MgO-SiO
2
and CaO-SiO
2

system; thus implying that sulfur can displace the oxygens bonded to Fe
2+
at ease.

































FeO
(melt)
+1/2S
2
=FeS
(melt)
+1/2O
2

K =[a
Fes
(fO
2
)
1/2
]/[a
FeO
(fS
2
)
1/2
]
a
Fes
=
FeS
X
FeS
=K x a
FeO
x [fS
2
/ fO
2
]
1/2

logX
FeS
=1/2 logfS
2
+[logK +log a
FeO
- 1/2 log fO
2
- log
FeS
] (1)

If for small changes in X
FeS
,
FeS
is assumed to remain constant and also if the amount of FeS
formed by the above reaction is sufficiently small then FeS formation has no appreciable
effect on a
FeS
, then it follows from eqn.(1) that X
FeS
vs logfS2 relation should produce a
straight line with slope = (Fig. 5) , at constant fO
2
. This is reasonable since the amount of
The sulfur capacity is somewhat misleading. It
does not represent the overall capacity of a melt to
dissolve sulfur, but it is somewhat akin to the
equilibrium constant of the above reaction. C
s

merely relates to the amount of sulfur that will
dissolve in a given melt in response to imposed fS
2

and fO
2
.
Maclean (1969), from his studies in the
system Fe- S- O- SiO
2
found that the S- content of
a silicate melt in equilibrium with the S-rich liquid
decreases with increasing O-content. This S-
content is henceforth referred to as the sulfur
content at sulfide saturation (SCSS). Maclean
attributed this to the fact that sulfur dissolves in
silicate melt by displacing oxygens bonded to Fe
2+

and that increasing oxygen results in an increase in
Fe
3+
at the expense of Fe
2+
in the melt.
Shima and Naldrett (1975) studied a komatiitic
melt and obtained strong evidence supporting the
observations of Maclean. Considering the reaction

Fig. 4 The effect of melt composition
on sulfur capacity of a silicate melts.
Also note the variation of SiO
2
content
of the magma

Ores in ultramafic-mafic rocks B. Mishra

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Fe interacting with sulfur amounts to 0.2 0.6% in most melts containing about 8 12 wt%
FeO. Buchanon and Nolan (1979) performed a series of experiments with varying fO
2
and
FeO (+TiO
2
) contents; their results are shown in Figure 6.



















Effect of temperature

Buchanan et al (1983) determined the solubility of sulfur as a function of fS
2
in a
basaltic melt containing 17 wt% FeO at temperature range of 10001400C. At constant fO
2

and fS
2
, the dissolved sulfur content increases by a factor of 8.5 times/ 100C at 1000C but
this factor falls to 3 times/ 100C at 1400C. Wendlandt (1982) observed that the increase in
temperature of a basaltic melt (FeO 8 wt%) at 13001400C (20 kbar) and fO
2
close to the
C/CO
2
/CO buffer (about one log unit above the FMQ buffer) caused an increase in SCSS
from 0.09 to 0.16 wt%. Possibly an increase in SCSS of 3 to 5 times from 1200 to 1450C is
of the order expected in nature.

Effect of pressure

(1) Huang and Williams (1980) from their experiments in the Fe-Si-S-O system at 30 kbar
pointed out that the miscibility gap (between silicate and sulfide liquids) expands with
increasing pressure.
Fig. 6 Sulfur solubility as a function
of FeO (+TiO2) contents of the melt
and fO
2
.
Fig. 5 X
FeS
f
S2
relations in a given silicate melt at
two values of fO
2
(10
10.4
and 10
9.2
).

Ores in ultramafic-mafic rocks B. Mishra

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(2) Wendlandt (1982) studied the SCSS- variation in two in two basalts and an andesite at P=
12.5 kbar and 30 kbar. The observation was SCSS increases with temp. and decreases
with press. This implicates that when magma rises to the surface, its ability to dissolve
sulfur increases, hence it is unlikely to approach saturation with sulfides.
(3) Wendlandts data have been shown as variation in FeO content (in magma) as a function
of pressure and S-solubility (Fig. 7), as modified by Naldrett (1988). The relationship
shows the variation to be expected in a basaltic melt from a depth corresponding to a
press 30 kbar, which looses heat and stays at its liquidus temps. (1500C/ 30 kbar to
1330C/ 12.5 kbar). The reduction in SCSS due to cooling would presumably to a large
extent counterbalance the effect of pressure.




























Melt- Melt Equilibrium - partitioning of chalcophile elements between sulfide
and silicate melts: implication on composition of magmatic Ni- Cu sulfide ores
The partitioning coefficient of a minor or trace metal between the silicate and sulfide melts
could be expressed by the Nernst partitioning coefficient, defined as
D
i
(SL/SM)
=wt% i in SL / wt% i in SM (2)
SL: sulfide liquid and SM: silicate melt
Fig. 7 Solubility of sulfur in basaltic melts of varying FeO
contents estimated as function of pressure (after Wendlandt,
1982).
Ores in ultramafic-mafic rocks B. Mishra

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If Fe, Ni, Co, Cu etc are bonded to oxygen and sulfur in SM and SL respectively then we can
consider their partitioning behavior by equilibrium (A)

NiO
(SM)
+1/2 S
2
=NiS
(SL)
+1/2 O
2
(A)
K
A
=(a
NiS
)
SL
/ (a
NiO
)
SM
x [fO
2
/ fS
2
]
1/2

=(
NiS
/
NiO
) x (N
NiS
/ N
NiO
) x [fO
2
/ fS
2
]
1/2
(3)

From eqns. (2) and (3), we see that D
i
=f (fO
2
, fS
2
, T, P and compositions of the two liquids).
However, reaction (A) can be combined with FeO-FeS equilibrium and we can write

NiO
SM
+FeS
SL
=NiS
SL
+FeO
SM
(B)

K
B
=(a
NiS
) / (a
NiO
) x (a
FeO
/ a
NiO
)
=(
NiS
/
NiO
) x (
FeO
/
FeS
) x (N
NiS
/ N
NiO
) x (N
FeO
/ N
FeS
) (4)

K
B
f(fS
2
, fO
2
), although fS
2
and fO
2
may affect. For example, fS
2
will affect
NiS
and
FeS
.

However,
(i) Scott et al (1974) pointed out that in liquids of same composition as mss (Fe
1-x
S - Ni
1-
x
S),
NiS
and
FeS
will have similar values (
NiS
/
FeS
=1), although both the
i
terms
decrease with increasing fS
2

(ii) Variation in fO
2
can affect N
FeO
by changing the Fe
3+
/ Fe
2+
ratio in the magma, but if
fO
2
10
8
bar, the effect in basaltic magma is small.
(iii) Doyle and Naldrett (1986) emphasized that fO
2
variation also affects the O-contents
of sulfide-oxide liquids and therefore the a-X relations within them. But provided that
the fO
2
/fS
2
ratio (and hence the O/O+S ratio in the sulfide- oxide liquids) remains
approximately constant leading to negligible effect in metal partitioning.




Ores in ultramafic-mafic rocks B. Mishra

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Application to natural ores
Ni and Ni-Cu sulfide deposits are spatially associated with ultramafic and mafic igneous
rocks respectively. Relationship between compositions of the ores and the rocks reveal
Cu/(Cu+Ni) ratios in natural sulfide deposits show a general increasing trend with decreasing
basicity of host igneous rocks, i.e., an observed negative correlation between wt% MgO and
Cu/(Cu+Ni) ratios (Fig. 8).
























Ni-Cu ores formed are formed by segregation of sulfide droplets from the host silicate
melts and their concentration by gravitational settling. The factors that govern composition of
these ores are (i) the composition of host magma at the timing of liquid immiscibility, and (ii)
partitioning behavior governing distribution coefficients of Fe, Ni, Cu and Co between the
sulfide and silicate melts. Much of the compositional changes in silicate liquid are due to
crystallization and removal of olivine, causing depletion of Ni in the residual liquid, since Ni
has a strong preference to olivine relative to silicate liquid. Cu on the other hand, tends to get
enriched in the residual magma, because it lacks any preference to early formed Fe-Mg
silicates (Fig. 9). Such contrasting behavior of Ni and Cu, results in rapid decrease in Ni/Cu
ratio during fractional crystallization of ultramafic and mafic magmas. The Nernst
distribution coefficient of an ore forming metal between sulfide liquid (SL) and silicate melt
(SM), during liquid immiscibility is given by
Fig. 8 Relationship between the Cu/(Cu +
Ni) ratio of sulfide ores and the nature of
its host magma or rock.
Fig. 9 Variation of Ni and Cu with
wt % MgO in the successive
liquids of fractionally crystallized
komatiitic magma.
Ores in ultramafic-mafic rocks B. Mishra

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SM
SL
metal wt
metal wt
D

=
%
%
(5)


While D
i
values for metals such as Pb, Zn, Sn, W, Mo <1.0, those for metals like Cu, Ni, Co,
PGE >1.0.
Table 1 Average experimentally determined partioning coefficients (Di) values (from
Rajamani and Naldrett, 1978).

Metal Andesitic Basaltic Olivine basaltic
1255C 1255C 1305C 1325C
Ni 460 274 (34) 257 231
Cu 243 245(33) 180 333
Co n.d. 80 (15) 61 n.d.


























Since Fe
2+
is the principal cation for the magmatic sulfide deposits, the equilibrium
relation between the SL and SM can be written as the exchange reaction

(FeS)
SL
+(MeO)
SM
=(MeS)
SL
+(FeO)
SM
(C)

a
b
Fig. 10 Ni (wt %) in the sulfide liquids a function of Ni (ppm) in the coexisting basaltic melt
at 1255C.The error bars represent 1 from the plotted mean values. The slope defines the
Nernst partition coefficient (a). Cu (wt. %) in the sulfide liquid as a function of Cu (ppm) in
the coexisting basaltic melt at 1255C (b).
Ores in ultramafic-mafic rocks B. Mishra

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The equilibrium constant (K) for the above reaction can be expressed in terms of the K
D

values
D
SM
MeO
FeO
SL
FeS
MeS
K K

(7)

Where K is the equilibrium constant of the above melt-melt exchange reaction and is
independent on the melt compositions (SL and SM) at a given temperature; Me stands
for chalcophile elements such as Ni, Cu, Co etc.

Table 2 Average distribution coefficients (K
D
) values.
Metal Andesitic Basaltic Olivine basaltic
1255C 1255C 1305C 1325C
Ni 59 42 (7) 38 231
Cu 34 35(6) 24 333
Co n.d. 15 9 n.d.

The experimentally determined K
D
values involving basaltic melts (Table 2) can be
theoretically extrapolated to melts of more mafic composition, for example peridotitic
melts. The procedure is briefly outlined below.

(FeS)
BMS
+(NiO)
BM
=(NiS)
BMS
+(FeO)
BM
(D)

(FeS)
PMS
+(NiO)
PM
=(NiS)
PMS
+(FeO)
PM
(E)

where BM and BMS stand for basaltic melt and the sulfide liquid segregating from the
basaltic melt respectively. Same is the case with PM and PMS. Now from reactions (D) and
(E), we can write







Ores in ultramafic-mafic rocks B. Mishra

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(6)

As mentioned before, from the theoretical study Scott et al. (1974),
NiS
and
FeS
will have
similar values (
NiS
/
FeS
=1). Hence, the first term in eqn. (6) is reduced to unity and we can
write
(7)

Because the contents of Na
2
O, K
2
O and Al
2
O
3
generally decrease as the silicate melt
composition varies from basalt to peridotite,
FeO
will decrease with the increasing basicity of
silicate magma. Using Roeder's equation (
FeO
=0.048 wt % A1
2
O
3
+0.084 wt % Na
2
O +
0.12 wt % K
2
O +0.19) and considering average compositions of basalt and peridotite, the
first term in eqn. (7) turns out to be 2.14. By similar theoretical considerations, the second
term is equal to 0.2. Hence, we can write
(8)
Considering similar theoretical rationale for Cu, we can obtain

(9)













Fig. 11Variation in Ni and Cu contents in the
sulfide liquid that segregated from successive
liquids of fractionally crystallizing komatiitic
magma with wt% MgO of these liquids.
Fig.12 Calculated (open circle) relationship
between the Cu/(Cu+Ni) ratios of sulfide
liquids and wt% MgO of a komatiitic
magma, superimposed on Figure 8.
Ores in ultramafic-mafic rocks B. Mishra

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Eqns. (8) and (9) demonstrates theoretical predictions of k
D
values of Ni/Cu to a sulfide liquid
separated from a peridotitic melt, from the experimental k
D
values for basaltic melt. Similar
thermodynamic calculations have been performed for intermediate silicate melt compositions
and the results are shown Fig. 12, with open circles and by the curve drawn through them,
which relates the compositions of silicate liquid and magmatic sulfide ore.

Conclusions

The Ni-Cu sulfide deposits in mafic-ultramafic rocks are primary and formed by
liquid immiscibility.
The ore composition depends on the silicate magma composition and timing of liquid
immiscibility.