Chemical Geology, 53 (1985) 000--000 Elsevier Science Publishers B.V.

, Amsterdam -- Printed in The Netherlands

303

THE ORIGIN OF THE FRACTIONATION OF PLATINUM-GROUP ELEMENTS IN TERRESTRIAL MAGMAS

SARAH-JANE BARNES*, A.J. NALDRETT a n d M.P. G O R T O N

Department of Geology, University of Toronto, Toronto, Ont. M5S 1A 1 (Canada) (Received January 10, 1985; accepted for publication June 18, 1985)

Abstract
Barnes, S.-J., Naldrett, A.J. and Gorton, M.P., 1985. The origin of the fractionation of platinum-group elements in terrestrial magmas. Chem. Geol., 53 : 303--323. The platinum-group elements (PGE's), when chondrite normalized, have been found to be fractionated in order of descending melting point (Os, Ir, Ru, Rh, Pt, Pd and Au). Mantle-derived material (garnet lherzolite and spinel lherzolite xenoliths and alpine peridotites) have essentially unfractionated PGE patterns. Periotitic komatiites have mildly fractionated patterns (Pd/Ir = 10), pyroxenitic komatiites are slightly more fractionated (Pd/Ir = 30). Both continental and ocean-floor basalts are highly fractionated (Pd/Ir = 100). Data from intrusive rocks show a large range in PGE fractionation from Pd-depleted chromitites of ophiolites (Pd/Ir = 0.1) to the extreme Pd enrichment in the JM Reef of the Stillwater Complex (Pd/Ir =

865).
Some possible mechanisms for the origin of this fractionation are: alteration, partial melting and crystal fractionation. Carbonate alteration affects Au and Pt and hydrothermal alteration mobilizes Pd. Solid substitution of Ir (and associated Os and Ru) into olivine and chromite, during crystal fractionation or partial melting is rejected as a mechanism of fractionating the PGE's. It is suggested; that the major factor in PGE fractionation is the differences in solubility of the PGE's in a silicate magma, that Pd, Pt and Rh are more soluble than Os and Ir, which form an alloy and Ru which forms laurite. These differences in PGE solubility could fractionate the PGE's during partial melting or crystal fractionation. During crystal fractionation prior to Fe--Ni--Cu sulphur saturation the low solubility of Os, Ir and Ru leads to the formation of Os-Ir alloys and RuS 2 in the magma. These may then be settled out of the magma by whatever phase is crystallizing and the remaining magma becomes fractionated in PGE's.

1. I n t r o d u c t i o n The platinum-group elements (PGE's) consist o f R u , R h , P d , Os, Ir, P t a n d A u . A u is s t r i c t l y s p e a k i n g n o t a p l a t i n u m - g r o u p ele m e n t b u t i t is a n o b l e m e t a l a n d w i l l b e included with the PGE's in this paper. In recent years the PGE's have attracted a great d e a l o f a t t e n t i o n . T h i s is b e c a u s e : ( 1 ) D e v e l o p m e n t s in t h e a n a l y t i c a l f i e l d *Present address: Geological Survey of Norway, P.O. Box 3006, N-7001 Trondheim, Norway. 0009-2541/85]$03.30

now allow the analysis of the entire group a t t h e levels a t w h i c h t h e s e e l e m e n t s o c c u r in c o m m o n c r u s t a l r o c k s ( C r o c k e t e t al., 1968; Gijbels and Hoste, 1971; Robert et al., 1 9 7 1 ; G r o s e t al., 1 9 7 6 ; H a f f t y e t al., 1 9 7 7 ; H o f f m a n e t al., 1 9 7 8 ; R a m m e n s e e and Palme, 1981). (2) The PGE's represent a coherent group of siderophile elements (Mason, 1965, table 3.10) from which it might be possible to ded u c e a s p e c t s o f t h e h i s t o r y o f a r o c k , s u c h as whether sulphur saturation has occurred, which are not indicated by lithophile elements.

1985 Elsevier Science Publishers B.V.

TABLE concentrations Ru Rh Pt Pd Au n Rock type Symbol in Fig. 1 ( a l l v a l u e s a r e in p p b ) i n i g n e o u s r o c k s Reference*

Platinum

group element

Os

Ir

(a) ---3.97 1.32 4 garnet lherzolite A

Mantle nodules
(Fig. la):

5.08

5.35

3.29 0.06

3.67 0.049 2.95

----

----

----

4.47 0.087 4.10

0.99 0.36 0.48

14 1 6

spinel lherzolite harzburgite spinel lherzolite

B C D

1 1 2

--6.74 (Fig. lb): --

4 9

4.02

7 18 4.15

----

----

5.1 3.7 4.49

1.8 6.9 0.79

garnet lherzolite garnet lherzolite estimate of mantle

E F G

2 3 4

(b)

Peridotites from Alpine Complexes and tectonites from ophiolites

-6.1 -----(Fig. lc): --2.1 0.29 7.63 0.27 1.39 4 3 --1.8 1.5 2.4 8.1 9.7 10 2.0 9.5 3.8 -5 13 7

5.4 4.59 7.29

----

----

10.7 4.99 9.1

5.55 2.04 5.25

1.47 0.33 1.38

4 4 8

lherzolite, Ronda harzburgite, Ronda harzburgite, Josephine dunite, Urals harzburgite, Mt. Alberta harzburgite, Thetford dunite, Thetford harzburgite, Troodos

A B C D E F G

5 5 5 6 7 8 8

4.7 6.7 --

4.1 2.2 3.2

-3.95

3.6 5.07

11

(c)

Chromitites from ophiolites

72 --(Fig. ld): 28 17 4.5 ------

35 50 100 177 39 30 ---

80 150 250 235 89

7.2 6 14 15

9.5 13.5 27 17 <28 1.5

2.7 8.4 5 3.2 <3.6 0.33

-----0.28

27 30 25 43 11 2

Kef Oman Josephine New Caledonia Greece Thetford

A B C D
E F

10 10 10 10
9 8

(d) -----------------

Differentiated rocks from ophiolites

---

2.4 0.24

21 29 3.0 0.9 13 3.1 2.72 0.47 ---

1.3 1.4 0.17 0.52 2.2 1.1

13 13 4 5 4 7 1 1

dunite, Thetford pyroxenite, Thetford gabbro, Thetford dunite, Troodos pyroxenite, Troodos gabbro, Troodos basalt, Troodos pillow lava, Troodos

A B C D E F G H

8 8 8 9 9 9 9 9

0.21 0.02

0.017 0.23 0.05

0.02 --

0.033 0.032

0.0006

0.023

(e) Ocean-floor material ( F i g . l e ) :

--w -

<0.001 0.086

0.0011 0.116

---

---

<0.10 6.29

0.01
---1.6

1.0
14

--

0.36

lower limit of MORB's upper limit of MORB's estimate of MORB's oceanic island

A B C D

12 12 13 14

(f) K o m a t i i t e s (Fig. l f ) :
- - -

- -

1 . 1

-- - - 9

0.38 -- - -

--10.6 --

--

14 10

8.3 11

11 11

- -

1 . 4 7

--

7.08

- -

1 . 3 6

2.02 6.7

? 4

s p i n i f e x , P y k e s Hill Fred's Flow spinifex, Western Australia dunite, Western Australia B-zone, Munro

A B C D E

15 15 16 16 15

(g) S u l p h i d e - b e a r i n g k o m a t i i t e s ( F i g . l g ) n o r m a l i z e d to 100% sulphides: 2,765 760 1,425 490

-983 4,938 1,168 1,674 646 1,436 367 720 --1,264 624 1,100 3,725 1,596 2,762 1,310 2,483 11,120 494 56 155 116 360

980 414 543 140

718 240 486 120

1,759 230 580 162

7,289 890 997 421

6,822 1,600 2,106 1,060

1,544 181 170 67

93 668 208 305

258 98 598 197 335

10 31 8 6 ? 20 14 28 46

Dundonald Langmuir, Abitibi McWatters, Abitibi Mt. Edward, Australia Ave, Western Australia Shangani, Zimbabwe Epoch, Zimbabwe Tronjan, Zimbabwe Ungava, northern Quebec

A B C D E F G H I

17 18 17 19 16 19 19 19 20

( h ) C o n t i n e n t a l tholeiites (Fig. l h ) -- - - - -

--15.4 11 147 15.3 39.1 80.2 15.5 367 1,330 333 1,477 708 1,113 8.6 70 ---

0.092

--

54

- -

0 . 1

A B
4.7 13 1 28

- -

1.8

0.36 2.4

8.3 12 9.5 185 139 397 147

C
29 15 22

14 13 5 21
Karroo and Deccan estimate W-1 sulphide-rich tholeiite, Trout Lake Great Lakes Insizwa, Karroo Duluth Complex

<5.6 56 6.6

4.9 88 6

D E F

19 19 19

(i) B u s h v e l d C o m p l e x ( F i g . l i )
- -

- -

0 . 6

--63 430

0.35 270 74

---

12 9.25 540 240

50 40 3,220 3,740

20 10 3,420 1,530

30 22 70 310

1 4

b a s a l - z o n e chill m i d d l e - z o n e chill UG-2 composite Merensky Reef (MR) composite

A B C D

22 22 23 24

c~ O 91

TABLE I (continued) Ru Rh Pt Pd Au n Rock type Symbol in Fig. 1 Reference*

O O

Os

Ir

(j) S t i l l w a t e r --9 640

(Fig. l j)
A B C 25 25 26

--

-22

0.25 66 19

6 230 50

5 160 150

12 535 5,000

55 960 17,300

basal z o n e chromitites JM R e e f

(k) K i m b e r l i t e s -6.5 -(Fig. 11) 4.4 82 32 -4 dunite, Urals --0.25 7.1 187 -----

(Fig. l k )
A B 14 27

-5

--

3.0 7.6 0.12

8.1 53 1.2

11 10 2

India and South Africa U.S.S.R. basanites

(1)

Alaskan

Zoned

Complexes

3.7

9.6

0.65?

(m) Chondrites 690 200 1,020 545 152 -C1 c h o n d r i t e s

28

514

540

*References: 1 = M o r g a n e t al. ( 1 9 8 1 ) ; 2 = M i t c h e l l a n d K e a y s ( 1 9 8 1 ) ; 3 = Paul et al. ( 1 9 7 9 ) ; 4 = S u n ( 1 9 8 2 ) ; 5 = S t o c k m a n ( 1 9 8 2 ) ; 6 = F o m i n y k h and Kvostova (1970); 7 = Crocket and Chyi (1972); 8 = Oshin and Crocket (1982); 9 = Becker and Agiorgitis (1978); 10 = Kef, O m a n a n d J o s e p h i n e f r o m v a r i o u s u n p u b l i s h e d s o u r c e s q u o t e d in Page et al. ( 1 9 8 2 ) ; 1 1 = A g i o r g i t i s a n d W o l f ( 1 9 7 7 , 1 9 7 8 ) ; 1 2 = H e r t o g e n et al. ( 1 9 8 0 ) ; 1 3 = R . R . K e a y s (pets. c o m m u n . , 1 9 7 9 ) ; 1 4 = C r o c k e t ( 1 9 8 1 ) ; 1 5 = M a c R a e ( 1 9 8 2 ) ; 1 6 = K e a y s ( 1 9 8 2 ) ; 17 = B a r n e s et al. ( 1 9 8 1 ) ; 1 8 = G r e e n a n d N a l d r e t t ( 1 9 8 1 ) ; 1 9 = N a l d r e t t ( 1 9 8 1 ) ; 2 0 = B a r n e s e t al. ( 1 9 8 2 ) ; 2 1 = B o r t h w i c k ( 1 9 8 4 ) ; 2 2 = S h a r p e ( 1 9 8 2 ) ; 2 3 = M c L a r e n a n d de Villers ( 1 9 8 2 ) ; 2 4 = H i e m s t r a ( 1 9 7 9 ) ; 2 5 = Page et al. ( 1 9 7 2 , 1 9 7 6 ) ; 2 6 = B a r n e s ( 1 9 8 3 b ) ; 2 7 = K a m i n s k i y et al. ( 1 9 7 5 ) ; 2 8 = v a r i o u s a u t h o r i t i e s q u o t e d in N a l d r e t t a n d D u k e ( 1 9 8 0 ) .

307 (3) The PGE's are an economically important group of elements. There are only three known major deposits, these occur in the Noril'sk--Talnakh area, U.S.S.R., the Stillwater Complex, U.S.A., and the Bushveld Complex, South Africa, and an understanding of the PGE geochemical cycle would be helpful in developing and locating new deposits. Naldrett et al. (1979) noted that if the PGE's are chondrite normalized (values listed in Table I), and plotted in order of descending melting point (Os, Ir, Ru, Rh, Pt, Pd, Au) smooth curves much like rare-earth element (REE) patterns are obtained. The analogue with the REE's breaks down, however, when the order of fractionation of the PGE's is considered. The REE's are lithophile and the order of fractionation of the REE's is related to their ability to substitute for major elements in c o m m o n minerals, which is controlled by their position in the periodic table. In contrast, the order of fractionation of the PGE's: Os<Ir< Ru<Rh<Pt<Pd analyses are shown in Fig. la--1. A determination of the entire group is not always presented because the most c o m m o n method of determining PGE's is neutron activation (NAA). The short half-life of Rh (4.4 min.) means that only laboratories that have counting facilities in the reactor building can analyse for Rh. Further, the sensitivity of the PGE's by instrumental neutron activation analysis (INAA) is: Ir>Au> Rh>> P d > P t > O s > Ru

is not the order in which they occur in the periodic table.On the basis of association the PGE's may be divided into two groups: the Ir group (IPGE's) consisting of Ru, Os and Ir, and the Pd group (PPGE's) consisting of Rh, Pt, Pd and Au. However, these groups are not analogous with light REE and heavy REE. Since Ru is a light PGE, it associates with the heavy PGE's Os and Ir; and Pt, a heavy PGE, associates with the light PGE's Rh and Pd. This paper will: (1) summarize what is presently known a b o u t the PGE's; (2) consider the origin of the fractionation of the PGE's. The influence of three processes will be considered: alteration, partial melting and crystal fractionation.
2. Data base

Therefore, in samples with low PGE concentrations, such as mid-ocean ridge basalts (MORB's), the analysis may be limited to Au, Pd and Ir. Fortunately these elements represent the two ends of the PGE pattern and hence the Pd/Ir ratio may be used to define the overall slope of the pattern, in much the same way that the La/Yb ratio is used in REE patterns (e.g., Hanson, 1980), although the details of the pattern may not be known. Au is not a very reliable indicator of the PGE slope because, as will be discussed later, it is frequently mobile. As this paper is concerned with the fractionation of the PGE's only those sources which included data for at least Ir and Pd would be considered.

2.1. Mantle xenoliths, alpine peridotites and ophiolitic tectonites

Three types of rocks are c o m m o n l y believed to represent mantle material, these are: mantle xenoliths, alpine peridotites and deformed ultramafic rocks from the base of ophiolites. The material above the tectonites in ophiolites is usually regarded as crustal (Coleman, 1977), this and the podiform chromitites found in ophiolitic rocks will be discussed separately. Fig. l a shows whole-rock PGE patterns for mantle xenoliths. Apart from the data of Paul et al. (1979) (Fig. la, curve F), the patterns for garnet lherzolites and spinel lherzolites from sites around the world are flat and cover the range 0.005--0.01 times chondrite. As has

Available data (this study and previous literature) on PGE's are listed in Table I and chondrite-normalized patterns of these

03 OO

0"1
,F

C)

E H "'E

0-1]
C

C)

u-u~
~C

~---

O.Ol
0-1 01

0.001001
I I I

I c 0001 ~ " "~ D~B

0.01

0.0001I i I I I J

0.0001-

Os Ir Ru Rh Pt P d A u

Os Ir Ru Rh Pt Pd Au

0 001

0-001

1.o
0-0001

@
0,0001

0.00001
B

0.00001

0.01
' "E
I I I

0 000001
I | | I I | I

0.000001
I I I ! I I I

Os Ir Ru Rh Pt Pd Au

Os Ir R u R h P t

Pd Au

0.001Os Ir RuRhPt PdAu

o.1B
A

Q)

loo

0.01
j '.

10

X"
"...
/

.,,//J

0-001
Bz
/

0.0001
I i i i i I I l I I i i

01
Os Ir Ru Rh Pt PdAu

Os Ir Ru Rh Pt Pd Au

~oo.o10'0

1000(9 lOO o-

(9
,/ / /, / / /. \

10 010.0 10

1"0-

1.0
J /

01

0.1
//'

B, /

/
/4'

#
C*__ z" / /~, ,/

0-1
~/// B

i
A
OIO1

0.01

// /, /',/

0.01
;//

0.001

0 001
B

0.001

/ A ~

0.0001 . . . . . . .

Os ]'r Ru Rh Pt Pd Au

0.0001

. . . . . . .

0.0001

Os IF Ru Rh Pt PdAu

Os Ir RuRh Pt PdAu

03 0

Fig. la--j. For caption see p. 310.

310

10 "1

/ ~'-.

//

/
/

,/

0.1/ !, /

/*
A

0.01

,B~'~.J'J

--"
/,
jJ

001 -

0.001.

/. /

~-

00001

,0001

Os Ir Ru Rh Pt Pd Au

Os Ir R u R h Pt P d A u

Fig. 1. a - - c . C h o n d r i t e - n o r m a l i z e d P G E ' s : (a) m a n t l e n o d u l e s , A, E a n d F = g a r n e t l h e r z o l i t e , B a n d D = s p i n e l l h e r z o l i t e , C = h a r z b u r g i t e , G = e s t i m a t e ( f o r s o u r c e s a n d f u r t h e r d e t a i l s s e e T a b l e I); ( b ) a l p i n e c o m p l e x e s , A = l h e r z o l i t e , B, C, E, F a n d H = h a r z b u r g i t e , D a n d G = d u n i t e ; a n d (c) c h r o m i t i t e s f r o m o p h i o l i t e s . d a n d e. C h o n d r i t e - n o r m a l i z e d P G E ' s : ( d ) o p h i o l i i t e s , A a n d D = d u n i t e , B a n d E = p y r o x e n i t e , C a n d F = g a b b r o , G a n d H = b a s a l t ; a n d (e) o c e a n f l o o r , A = l o w e r - l i m i t M O R B ' s , B = u p p e r - l i m i t M O R B ' s , C = e s t i m a t e o f M O R B ' s , D = oceanic islands. f a n d g. C h o n d r i t e - n o r m a l i z e d P G E ' s : (f) k o m a t i i t e s A a n d C = A - z o n e s o f o l i v i n e s p i n i f e x f l o w s , B = c l i n o p y r o x e n e s p i n i f e x f l o w , D a n d E = B - z o n e o f o l i v i n e s p i n i f e x f l o w s ; a n d (g) s u l p h i d e s f r o m k o m a t i i t e s A = u p p e r limit, D = lower limit, I = Ungava. h. C h o n d r i t e - n o r m a l i z e d P G E c o n t i n e n t a l t h o l e i i t e s : A = K a r r o o , B = e s t i m a t e , C = A r c h e a n t h o l e i i t e , D = G r e a t Lakes, E = Insizwa, Karroo, F = Duluth. i a n d j. C h o n d r i t e - n o r m a l i z e d P G E ' s : (i) B u s h v e l d , A = l o w e r - z o n e m a r g i n a l r o c k , B = m a i n - a n d c r i t i c a l - z o n e m a r g i n a l r o c k , C = U G - 2 R e e f , D = M e r e n s k y R e e f ; a n d (j) S t i l l w a t e r , A = b a s a l z o n e , B = c h r o m i t i t e s , C = J M Reef. k. A l k a l i r o c k s , A a n d B = k i m b e r l i t e s , C = b a s a n i t e . I. A l a s k a n r o c k s , A = d u n i t e .

been p o in ted out by Kimura et al. (1974), Chou {1978), Jagoutz et al. (1979) and Morgan et al. (1981), these values are higher than would be e x p e c t e d if a metal core and a silicate mantle had reached equilibrium. These authors t h e r e f o r e pr opos e d t hat the excess noble metals were added to the mantle during m e t e o r i t e b o m b a r d m e n t of the Earth after core separation. Mitchell and Keays (1981) suggest t hat these authors did not

consider the effect of sulphides in the mantle on the partitioning of PGE's between the core and t he mantle and t h a t m e t e o r i t e addition to the mantle is n o t necessarily required. Further, t h e y state that the chondritic signature o f the xenoliths is a f u n c t i o n of multistage evolution, n o t single-stage core-mantle formation. It seems remarkable to the present authors that a multistage process would happen to p r o d u c e xenoliths with close

311 to chondritic ratios of PGE's. Chou et al. (1983) suggest 0.74% Cl-chondritic-like material has been added to the mantle to account for what they feel is the excess of siderophile elements in the upper mantle. Brett {1984) considers that siderophile element abundances in the upper mantle do not demand a late-stage meteoric addition, but of the PGE's he only considered Ir and calculated that there should be less than ~ 1 0 0 ppb Ix in the upper mantle. The single harzburgite nodule is severely depleted in all PGE's, except Au (Fig. la, curve C) and exhibits a slight PPGE enrichment. Mantle xenoliths are not necessarily a true representation of the mantle, due to their unique mode of emplacement and their size (usually < 15 cm); possibly more representive samples are those obtained from the larger ophiolite tectonites and alpine complexes. The material believed to represent primitive mantle (i.e. the average lherzolite, curve A in Fig. l b ) has a flat PGE pattern and is in the same range as mantle xenoliths, thus indicating that primitive mantle material may have unfractionated PGE patterns. The dunites (Fig. l b , curves D and G), which are cumulate and consist of olivine and chromite, are IPGE enriched, suggesting that during crystal fractionation either olivine or chromite has accepted IPGE's in preference to PPGE's. The ophiolitic harzburgites, also have unfractionated PGE patterns at 0.005--0.01 times chondrite (Fig. l b , curves E, F and H). In contrast the alpine R o n d a and Josephine harzburgites show slight Pd depletion or Ir enrichment (Fig. l b , curves B and C). Interpretation of the Pd depletion in these harzburgites depends on ones interpretation of the harzburgites. If the harzburgites are restites, then it is consistent with the removal of a partial melt enriched in Pd due to retention of Ir in the residuum. If the harzburgites are cumulates, then they contain cumulus chromites which are enriched in Ir over Pd the rock will be Ir enriched (see Section 3.3.2).

2.2. Ophiolite chromitites and differentiated portions of ophiolites

The origin of podiform chromites and dunite lenses in the tectonites of ophiolites has been the subject of much debate [see Lago et al. (1982) for a review]. Recently Lago et al. (1982) have suggested that these rocks represent mantle feeders to the overlying ophiolite, and that in irregularities in the feeders, a mini-convective system may develop which allows the formation of cumulate material within them. As pointed out by Page et al. {1979) PGE patterns from chromitites (Fig. l c ) are distinctly IPGE enriched. For chromitites the Os, Ir and Ru portion of the curve is relatively flat, while there is a steady decrease from Ru to Au. The variation in the PGE patterns within the Troodos and Thetford ophiolites, has led Agiorgitis and Wolf (1978, 1984) and Oshin and Crocket (1982) to suggest that the IPGE's are removed from the melt by fractionation of chromite, which produces the IPGE-enriched chromitites and dunites. The PPGE's are enriched in the melt and rocks that form from this liquid, gabbros and basalts (Fig. l d , curves C, F, G and H), are PPGE enriched. This hypothesis is supported by the observed PGE patterns, e.g. at Thetford the chromitites are markedly enriched in Ir [(Pd/Ir) ratio < 0.1], the dunites mildly Pd enriched [(Pd/Ir) ratio = 9], and the pyroxenites are Ir depleted [(Pd/Ir) = 120].

2.3. Ocean-floor basalts (OFB)

The ocean-floor basalts (OFB's) exhibit extremely steep patterns [{Pd/Ir) -~ 100, Fig. l e ] and show a wide range of values (0.000001--0.0001 chondrite normalized for It). The low concentrations of PGE's in MORB samples make it difficult to analyse these rocks for the full range of PGE's, and hence the shape of the pattern between Ir and Pd is not defined. The Os and Ir portion of the curve is flat. Hertogen et al.

312

(1980) have attributed the steep PGE patterns and low values found in MORB's to chromite fractionation. They argue that, as the magma rises from the mantle, chromite crystallizes, IPGE's enter the chromite and the chromite settles out. This hypothesis is consistent with the ophiolite data outlined above. But if MORB's represent 10--20% partial melting of the mantle, all the sulphide should melt and if they all dissolve in the melt, the bulk partition coefficient of Pd into the restite would be zero, and MORB's would contain 22--45 ppb Pd. This is a factor of 10--500 above the values obtained for MORB's. Three possible explanations for this depletion are: (1) Some sulphide does not dissolve in the melt and the Pd remains behind in the residuum. Morgan and Baedecker (1983) calculated that 25% partial melting is required to dissolve all the sulphide in the mantle. (2) The source was depleted in Pd prior to the formation of the MORB's. The mantle that MORB's forms from is frequently described as depleted. (3) Some sulphides have formed and settled out of the melt prior to its emplacement at surface.
2.4. Komatiites

The average olivine spinifex-textured komatiite from Canada and Australia has a (Pd/Ir) ratio of ~ 10 (Table I). Assuming t h a t random spinifex-textured samples represent a primary melt (Fig. l f , curves A and C), a bulk partition coefficient (D) of Pd into the restite of zero, and the concentration of Pd in the mantle as 4.26 ppb (average mantle nodule), then these samples would represent a 50% partial melt of the mantle, which is con'sistent with the high degrees of partial melting usually associated with komatiites. The B-zone or cumulate zone, of an olivine spinifex-textured flow from Western Australia has a (Pd/Ir) ratio of < 1 (Fig. l f , curve D), in contrast B-zones from olivine spinifex flows, of the Abitibi Belt, Canada have (Pd/Ir) ratios of 5.6 (Fig. l f , curve E), in-

dicating slight enrichment of Ir relative to the liquid but much less than in the Western Australian samples. As olivine is the only phase on the liquidus in olivine spinifextextured flows, Keays (1982) attributed the enrichment of Ir over Pd in the B-zone to olivine accepting Ir and rejecting Pd during crystal fractionation. The (Pd/Ir) ratio of flow-top breccia samples from Fred's Flow, a differentiated clinopyroxene spinifex-textured flow from the Abitibi Belt, is high (30) (Fig. lf, curve B). These samples are Ir depleted which is consistent with either Ir removal from the melt during crystal fractionation prior to emplacement or, if it is assumed that pyroxenitic komatiites form by lower degrees of partial melting than peridotitic komatiite, with Ir retention during partial melting. Komatiites frequently contain nickel sulphide deposits. The presence of the sulphides concentrates the PGE's, thus when sulphidebearing samples are analysed, the level of the PGE pattern is higher than for non-sulphidebearing rocks. This leads to the problem that the absolute concentrations of PGE's in the samples depend on the percentage of sulphide present and therefore the comparison of absolute PGE values from deposit to deposit is not necessarily valid. To circumvent this, Naldrett et al. (1979) and Keays et al. (1982) normalized the PGE analyses from Canada and Australia to 100% sulphide. This calculation assumes that all of the PGE's are in the sulphides and a normalizing factor is calculated for each rock on the basis of Cu, Ni, Co and S, assuming that the sulphides are pentlandite, chalcopyrite and pyrrhotite. Since all of the PGE's in an analysis are multiplied by the same constant, only the level of the pattern changes; the shape remains the same. The recalculated values are intended to represent the PGE concentration in the sulphide. In Fig. lg it can be seen that for komatiites from Canada, Western Australia and Zimbabwe, the Os and Ir portion of the curve is flat, then there is a step with Ru, Rh and Pt levels fairly coristant, although

313

occasionally negative Pt anomalies develop. Pd exhibits a distinct enrichment. Proterozoic komatiite-related deposits from Ungava (curve I) exhibit a very similar trend to the Archean komatiite-related deposits, except that the steps from Ir to Ru and from the Rh to Pd are both larger. Three possible explanations for this increase in fractionation are that the host magmas: (1) form from lower degrees of partial melting than Archean komatiites; (2) came from a more fertile source than the Archean komatiites; (3) they underwent more fractionation prior to emplacement than Archean komatiites.

2.5. Continental tholeiites

Data from non-sulphide-bearing continental tholeiites is limited to Pd and Ir so that the details of the curve are not k n o w n but the (Pd/Ir) ratio is high, ~ 100 (Fig. l h , curves A and B). Continental tholeiites are t h o u g h t to represent 5--10% melts of fertile mantle that have undergone some crustal contamination or some fractionation in magma chambers at the crust--mantle boundary (e.g., Cox, 1980). Accepting this premise, if the mantle contains 4.46 ppb Pd (Table I) and D Pd = 0, then at these degrees of partial melting the rocks should contain 43--86 ppb Pd. They actually contain 10 ppb, thus as in the MORB case either Pd is not incompatible at 5--10% partial melting or Pd has been removed from the melt during magma ascent, possibly by sulphides. The PGE patterns for sulphide ores associated with continental tholeiites are also plotted (Fig. l h , curves C--F). The Os, Ir and Ru portion of the curve is fairly flat and there is a steady increase from Ru to Pd. But the (Pd/Ir) ratio varies considerably (8-3OO).

2.6. Layered intrusions

Economic deposits of PGE's are associated with layered complexes, in particular with Stillwater and Bushveld Complexes. There-

fore, an examination of these two occurrences could help in explaining the origin of PGE fractionation. The proposed initial liquids for the Bushveld Complex have (Pd/Ir) ratios of ~ 30 (Sharpe, 1982) (Fig. li, curves A and B), much lower than either continental tholeiites or ocean-floor material. The Pd content is similar to that of continental tholeiites but the Ir content is three times higher. The shape of the PGE curve does not resemble that of other rock groups; in that Rh is enriched relative to Pt and Pd. In the ore-bearing horizons UG-2 (Upper Group 2) and MR (Merensky Reef) the (Pd/Ir) ratios are 14 and 20, respectively (Fig. l k , curves C and D, respec.). This drop in Pd/Ir ratio is achieved by an increase in Ir by a factor of 450 over the initial liquid while Pd only increased by 170, i.e. the UG-2 layer concentrated 2.6 times more Ir than Pd. Similarly, in the MR Ir increased 211 times over the second-cycle initial liquids while Pd increased by a factor of 153. Since both of these reefs contain chromite it could be argued that the Ir was concentrated by the chromite. Cousins and Vermaak (1976), however, discount this on the grounds that there is no correlation between the PGE's and Cr. The overall shape of the PGE patterns for both ore horizons is similar; a steady increase from Ir to Pd. The Stillwater initial liquid PGE pattern (Fig. lj, curve A) closely resembles nonsulphide-bearing continental tholeiites, except for the low-level Pt anomaly. However, Pd is enriched by a factor of 5 and Ir by a factor of 2.5 over continental tholeiites. The chromite seams of the lower portion of the Stillwater exhibit an overall enrichment over the initial liquid (Fig. lj, curve B) but unlike chromitites from ophiolites (Fig. lc) their PGE patterns do not show a steep negative slope. However, the (Pd/Ir) ratio of the Stillwater chromitites is much lower (14) than t h a t of the initial liquid (220), indicating that the chromite may have concentrated It. The PGE pattern obtained for a chromite layer is dependent on the Pd/Ir ratio of the

314

liquid from which the chromite crystallized so that it is not surprising that ophiolite chromitites with an initial liquid (Pd/Ir) ratio of < 20 [(Pd/Ir) ratio of the pillow lavas at Toodos] should have (Pd/Ir) ratios of 0.1 while chromitites formed from Stillwater magma with an initial liquid (Pd/Ir) ratio of 220 should have (Pd/Ir) ratios of 14.
2.7. Alkaline rocks

3.1. Alteration

It might be argued that all igneous rocks initially have steep positive PGE patterns and that the variations in PGE patterns presently observed in the rocks are a result of the variations in the tendency of the PGE to be dissolved in deuteric, metamorphic or other types of fluids. Cousins (1973) found that the solubility of the PGE in aqua regia increases in the order: Ir<Os<Ru<Rh<Pd<Pt If aqua regia is any guide to the reactivity of a natural oxidizing solution an unaltered rock might be expected to have a positive PGE pattern and as interaction with fluids increased Pt and Pd might be expected to be removed and PGE patterns flattened out. Some support for this order of reactivity with neutral-pH surface waters is provided by placer deposits (Cousins and Vermaak, 1976). It has been shown (McCallum et al., 1976; Keays et al., 1981, 1982) that vein ore is enriched in Au, Cu and Pd, suggesting that under certain conditions Au, Cu and Pd may be more easily transported than the other PGE's, giving rise to the modified PGE patterns. If the PGE fractionation is due to this kind of interaction, the slope of the patterns

The increase in Pd/Ir from mantle xenoliths to Archean komatiites to Proterozoic komatiites to tholeiites, correlates with the increase in La/Yb ratio. Thus it might be expected that kimberlites and basanites should have steep PGE patterns. However, as can be seen in Fig. l k the Pd/Ir ratio for these rocks is 10. The kimberlite pattern is flat from Os to Ru, but from Ru to Pt the PGE concentrations increase steadily and then flatten out at Pd. 3. Possible causes of the PGE f r a c t i o n a t i o n Since the rocks considered here are all igneous, three processes for the origin of the PGE fractionation may be considered: alteration, partial melting and crystal fractionation. Each of these will now be discussed.
"D O N O 5
/ t

Dundonald

lo

E L-O ,/~ @1.0. 4--"

I--

.\\ ~ .-"./, "" .... '~.\ / / , ~..*'~

/..:F, ";, ~ ~', '/I , / \ .'k", / \\ "..F Langmuir NacWatters Shangani Troian Mr. E d w a r d Epoch

.............. -

.
.....

"0 <-0.5 O r

-.

..... . . . . . ;:/ />",'/_ /

-.. :..'." . / / .........." ~"
,/

-~

'. ,'" / ,, / /

"<\ ', E ,,,.

~ D

'O

............

0"1

Os

I'r

R'u

R'h

Pt

Pd

Au

Fig. 2. C h o n d r i t e - n o r m a l i z e d P G E ' s in a l t e r e d k o m a t i i t e s , d a t a in T a b l e I.

315

should depend on the degree of interaction experienced by the sample. Some evidence of the modification of the patterns by solutions causing talc--carbonate alteration is observed in the case of Au and Pt in the komatiites of Western Australia and of the Abitibi Belt, Canada. Fig. 2 presents PGE patterns from komatiites which have experienced varying degrees and types of alteration. The PGE pattern from rocks which have experienced only pumpellyite-facies metamorphism (Fig. 2, curve A) show a regular increase in PGE concentration from Os to Au. Patterns B and C are from rocks from the mid-greenschist facies, while patterns E and D are from rocks which have experienced lower and mid-amphibolite-facies metamorphism, respectively. All four patterns exhibit mild negative Au and Pt anomalies and have experienced mild talc--carbonate alteration. Patterns F and G are from Epoch and Shangani; both have experienced amphibolite-facies metamorphism and extensive talc--carbonate alteration and serpentinitization. Both exhibit large negative Au and Pt anomalies. During talc--carbonate alteration neutral pH and oxidizing Eh conditions should occur (Eckstrand, 1975). If chlorine (possibly derived from seawater) was present during alteration, conditions suitable for the mobility of Au would arise (Westland, 1981). Thus Au is probably mobile. The correlation between Au and Pt anomalies suggests that Pt may also be mobile under the right conditions. For alteration to be the controlling factor in PGE fractionation the solubility of the PGE should be in the order of the PGE on the chondrite-normalized diagram. But on the basis of the Eh--pH diagrams presented by Westland (1981), the solubility of the PGE's would increase in the order: Os<Ru< Rh<Ir<Pd<Pt

which is hard to attribute to alteration. Thus we conclude that while in vein ores Pt'and Au may have been modified by alteration it is not the dominant process in PGE fractionation. 3.2. Partial melting If partial melting or crystal fractionation is the mechanism of fractionation of the PGE's some mineral or minerals must accept the PGE's in the order: Os>Ir>Ru>Rh>Pt>Pd olivine, chromite, monosulphide solid solution (MSS) and platinum-group minerals PGM's have all been suggested. 3.2.1. Olivine Ross and Keays (1979) found that Ir was present at 5.6 ppb and Pd at 0.21 ppb in Kambalda olivines. This led Naldrett et al. (1979) and Crocket (1979) to propose that PGE fractionation is caused b y different degrees of partial melting. In this model the IPGE's are held in a refractory phase such as olivine or spinel while the PPGE's are held in a phase that enters into the melt at an early stage, such as sulphides. The model proposes at low degrees of partial melting, more of the PPGE-bearing phase dissolves into the melt than the IPGE-bearing phase, resulting in a melt enriched in PPGE's over IPGE's and a restite enriched in IPGE's and depleted in PPGE's. Mitchell and Keays {1981) analysed mantle xenoliths for Pd and Ir and then analysed all the phases in the xenoliths, including olivine, spinels and garnet. They found that none of these were enriched in Ir relative to Pd. They suggest that 70% of the Pd was present in the sulphide while only 30% of the Ir was present as sulphide. They were unable to locate the remaining Ir and concluded that it was present as minute refractory metal particles. The lack of Ir enrichment in olivine, spinel or other silicates suggests that these phases cannot control PGE

which is not the order on the PGE diagram. As can be seen in Fig. la--1 and Table I the degree of fractionation of the PGE's increases with the fractionation of the rocks,

316

fractionation during partial melting. Since PGE's were f o u n d to be present in sulphides and a hypothetical refractory metal, the effect of the presence of either sulphides or refractory metals during partial melting is considered below.

/ ~ su,phides

//05%

// J

3.2.2. Sulphides
Iron and nickel sulphides (the most comm o n sulphides) melt at temperatures that would be achieved during partial melting; however, the sulphide liquid need not necessarily dissolve in the silicate magma. If a sulphide liquid is present b u t does not dissolve it will have the same effect as a restite phase. Many factors influence what concentration of sulphur may dissolve in a silicate melt; temperature, composition of the melt, fo2, fs2 and pressure. Wendlandt (1982) showed experimentally that for a variety of rock compositions the a m o u n t of S that can be dissolved varies from 0.05% to 0.26%. Sun (1982) gives a lower limit of 350 ppm and an upper limit of 1000 ppm for sulphur concentrations in the mantle, i.e. between 0.1% and 0.3% sulphides. Assuming the maximum sulphur solubility listed b y Wendlandt (0.26%), Sun's lower and upper sulphur limits imply that 13% and 38% partial melting, respectively, would be required to dissolve all of the sulphide liquid. This agrees with J.W. Morgan's (pers. commun., 1983) estimate that 25% partial melting is required to dissolve all of the sulphides. Most alkali rocks and continental tholeiites are believed to have formed from degrees of partial melting less than 13% and hence sulphide melt in the restite could affect their PGE patterns. The effect of the sulphide in the restite on the silicate melt is illustrated in Fig. 3; a plot of Pd/Ir in the melt vs. degree of partial melting using the batch melting equation (Shaw, 1970) and DPsu = 10 2 d and DsIrul= I 0 3

/:,,
Iphdes 0

10

08

06
F

04

02

Fig. 3. Plot of P d / I r ratio in a melt of fertile mantle vs. degree of partial melting illustrating three cases: (a) 1% sulphides in the mantle; (b) 0.5%; and (c) 0.1%. The solubility of the sulphur in the melt is assumed to be 2600 p p m (see text).

even if higher partition coefficients are chosen, the argument remains the same. (It might be thought that if higher partition coefficients are chosen the PGE values in the model melt would fall below those observed in rocks. Surprisingly this is not true, e.g. for:
Ir Dsul/si 1 = 10 s and Pd D s u l / s i 1 = 103

at 10% partial melting the concentration of Ir and Pd in the melt would be 0.02--0.177 and 1.98--12 ppb, respectively. These value not dissimilar to those observed in continental tholeiites.) For the presence of the sulphide liquid to affect the PGE fractionation there must be a difference in partition coefficients of the PGE between silicate and sulphide liquid and if this is the mechanism of PGE fractionation then:
Os Ir Ru Rh D s u l / s i l > Dsul/si 1 > D s u l / s i l > D s u l / s i 1 Pt Pd > Dsul/si 1 > Dsul/si 1

The authors do not wish to imply that these are real partition coefficients. One author (A.J.N.) feels that they are far t o o low, b u t

Partition coefficients for PGE's between silicate and sulphide liquid are unknown,

317 estimates in the literature vary from 102 (Ross and Keays, 1979) to 10 s {Campbell and Barnes, 1984) the partition coefficients chosen here are simply to illustrate the point that the PGE's could be fractionated by sulphides during partial melting if it can be shown that the partition coefficient for Ir into sulphide is much greater than that for Pd. Another w a y in which sulphides could fractionate the PGE's during partial melting is by incongruent melting (F.A. Frey, pers. commun., 1983) of the sulphides. If it is assumed that the PGE's are present in the mantle in sulphides and during partial melting the PPGE's released from the sulphide dissolved in the silicate magma, b u t the IPGE's did not and instead formed restite minerals, perhaps an Os--Ir alloy and RuS2. and other Western Australian komatiites, indicates that the high Ir values observed by Ross and Keays (1979) are unusual. These observations and the siderophile nature of the IPGE's suggest that they do not enter the olivine b y solid substitution (Barnes, 1983a). The mechanism that results in IPGE's being preferentially included in olivine in some komatiites cannot be random inclusion of PGE's in crystal defects in the olivine since then both PPGE's and IPGE's would be present.

3.2.3. Refractory metals The refractory metals' hypothesis suggests that the IPGE's might be thought of as being present in the mantle as refractory metals such as Os--Ir alloys while the PPGE's are present in sulphides. Thus during partial melting the sulphides dissolve and release the accompanying PPGE's which may then enter the melt. The Os--Ir alloy dissolves much less and very little IPGE's enter the melt. 3.3. Crystal fractionation
A crystal fractionation model suggests that PGE fractionation is brought a b o u t by removal of IPGE's from the magma in olivine, chromite, sulphides or PGM's. Each of these possibilities is examined below.

3.3.1. Olivine The inclusion of IPGE's in olivine could explain the enrichment of IPGE's in the Bzones of some komatiites. However, as pointed o u t above mantle olivines do n o t contain Ir and an examination of olivines formed by crystal fractionation, from other localities, e.g. R h u m (Gijbels et al., 1976)

3.3.2. Chromite Preferential inclusion of IPGE's in chromites appears to be a possibility because chromitites from ophiolites and layered complexes are IPGE enriched (see Section 2.2). The data from the Thetford and Troodos ophiolites are particularly suggestive. It would be hard to deny that the (Pd/Ir) ratio of the initial liquids have been modified by the removal of chromite. Oshin and Crockett (1982) argue that Os and Ir are included in the chromite by solid substitution during crystal fractionation and that the alloys found in ophiolitic chromites are the result of exsolution of the PGE's during cooling. Agiorgitis and Wolf {1978) noted a positive correlation between Os, Ir, Ru and Cr in Greek chromites which they t o o k to suggest solid-solution substitution between Cr 3 ions and the PGE's. Cousins and Vermaak (1976) noted that in the Bushveld chromites the PGE content correlates with sulphur rather than Cr, suggesting that the PGE's are present as sulphide inclusions in the chromite. Careful examination of the chromites from ophiolites and alpine complexes (Prichard et al., 1981; Stockman and Hlava, 1984) reveal that they contain sulphides and Os, Ir and Ru metal alloys. Stockman (1982) studied chromites from the Josephine peridotite, where he found two types of PGM inclusions; t y p e 1 or primary inclusions which in order of abundance were, laurite (RuS2), Os--Ir alloy, Pt alloy, erlichmanite ((Os,Ir)S2), Ir--Cu--Ni-

318

sulphide, PtS and PtAs and t y p e 2 or altered inclusions, Ru alloys, Fe--Pt alloys and base metals. Stockman (1982, p.173) felt on the basis of textural evidence that type-/ inclusions represent
" s o l i d s w h i c h were e n g u l f e d in growing c h r o m i t e crystals".

chromite. The weight of the evidence points to inclusions in the chromite rather than solid-solution substitution.

3.3.3. Sulphides
The presence of PGE's in sulphides has been reported by numerous authors (Wagner, 1929; Hawley, 1962; Chyi and Crocket, 1976; Keays and Crocket, 1970; Hakli et al., 1976; Ross and Keays, 1979; Naldrett, 1981). The effect of the presence of sulphides on PGE patterns is discussed by Naldrett et al. (1982). The question of whether the PGE actually substitute for base metals in sulphides is difficult to assess. In theory the +2 PGE ions are of suitable charge and size to substitute for base metals (Table II) and the bonds in sulphides tend to be more covalent than those in silicates and oxides (this is due to the fact that S has a higher electronegativity than oxygen) thus taking account of the high electronegativity of the PGE's. Some substitution does take place; Skinner et al.

Prichard et al. (1981) came to a similar conclusion, concerning the genesis of the inclusions in the Unst chromites. A model for PGE fractionation involving chromite and crystal fractionation and using the above information might suggest that laurite and Os--Ir alloys have crystallized in the magma and that chromite nucleated on them. The chromite might then settle o u t of the magma leaving a melt depleted in Ir--Os and Ru and a chromite cumulate rich in these elements. In summary while the mechanism of how chromite affects PGE fractionation is debatable, it is clear that during crystal fractionation the PGE's are fractionated by
T A B L E II Physical p a r a m e t e r s o f the P G E ' s Element Z Charge Size *~ (A)

Pauling's OFSE electronegativity* 2 2.2 12/5 10/5 8/5 9/5 12/5 10/5 6/5 9/5 12/5 12/5 8/5 9/5 12/5 6/5 12/5

m.p. .3 (C)

b.p. .3 (C)

Ru

44

+2 +3 +4 +2 +3 +4 +2 +3 +4 +2 +4 +2 +3 +2 +4

0.74 0.68 0.62 0.72 0.66 0.60 0.86 0.76 0.615 0.74 0.63 0.74 0.68 0.80 0.625

2,310

3,900

Rh

45

2.2

1,966

3,727

Pd

46

2.2

1,552

3,140

Os Ir Pt

76 77 78

2.2 2.2 2.2

3,045 2,410 1,722

5,027 4,130 3,822

O F S E = o c t a h e d r a l field s t a b i l i z a t i o n energy. ,1 S h a n n o n ( 1 9 7 6 ) ; ,2 Evans ( 1 9 6 6 ) ; ,3 Weast ( 1 9 7 5 ) .

319

(1976) found that at 1000C pyrrhotite contains up to 1.5 at.% Pd b u t less than 0.5 at.% Pt. Ross and Keays (1979) noted a positive correlation between Ir and Pd and Ni, in Western Australian komatiites, from which they deduced that these elements are present in the nickel sulphides. Chyi and Crocket (1976) showed that Pd is concentrated in pentlandite, while Ir is evenly distributed among pentlandite, pyrrhotite and chalcopyrite. Keays et al. (1981) found that at Kambalda the (Pd/Ir) ratio varied from 3.2 in the massive sulphide at the base of the flow to 14 in the overlying disseminated sulphides. They suggest that when the sulphide originally separated from the silicate it had a uniform (Pd/Ir) ratio (that of the silicate liquid) and that Ir migrated to the base of the sulphides, due to the thermal gradient and that Pd migrated into veins. Two alternative suggestions for this zonation could be proposed: (1) The observed zonation is a kinetic effect. If the sulphides cool rapidly, then, as crystallization advances through the sulphide pile from the base up, the concentration of a particular PGE is partly dependent on the rate of exchange of PGE's between the crystallizing solid sulphide surface and the sulphide liquid. Thus one explanation for the zonation in the sulphides is that Ir is trapped on the crystallizing surface of the sulphide solid more effectively than Pd. (2) Distler et al. (1977) and Malevskiy et al. (1977) found that in the crystallization of a MSS from a sulphide melt, the MSS accepts Ru and Rh over Pd and by extension Os and Ir over Pt. Thus during crystal fractionation of a sulphide melt, early forming MSS's could crystallize and settle o u t to the base of the sulphide pile, thereby depleting the remaining sulphide melt in IPGE's and Fe, Ni and enriching the remaining melt in PPGE's and Cu. Naldrett et al. {1982) have used the possible fractionation of the PGE's by MSS in explaining the observed ore zonation at Sudbury. In this case there is a

complementary Cu zonation which supports fractionation of the PGE's by MSS's. If the PGE's are fractionated by the formation of a sulphide liquid during magma ascent, the amount of fractionation experienced by the PGE's will depend on the difference in the partition coefficients and on the percentage of sulphide to segregate [the R-factor of Campbell and Naldrett (1979)] Pd . l__ Ir Thus if the (Dsu I tq/sil liCJ ) is 10 of (Dsu 1 lq/sil liq) and the sulphide liquid settled o u t of the silicate magma, the (Pd/Ir) ratio of the magma would be disturbed. Fig. 4 illustrates what would happen in both the magma and the solid during Rayleigh fractionation, assuming Pd = (D~I liq/sil liq) ;% 1000 and (Dsu 1 liq/sil liq 100) for 0.--_ sulphide fractionation. If equilibrium crystallization rather than Rayleigh fractionation is assumed a similar set of curves can be produced (Fig. 4, dashed

cJO 80 70
6,3

i su{phides 05%

su % 0 Iphees

C 5o
"~ "0 L.O

30 2O 10

/ ~-.-_-_-:~_---~

t . 0=0,. ;:: o ~ O / o
. Ol.~

1%

o 9 [ '09I ' ~ ~ s
08 .--'"'"

,I "1

IF.

07

.--'"

..

"'"

0,6
05
o~.

--""
.... 1%
o.5o/o

/ " ...'o

,/,,,"

"

/O 1%

I'

03
0.2 C11 .--"

..--"

~o~o I

Fig. 4. P l o t o f P d / I r ratio in b o t h t h e liquid a n d c u m u l a t e vs. degree o f c r y s t a l l i z a t i o n d u r i n g c r y s t a l f r a c t i o n a t i o n . T h r e e cases are i l l u s t r a t e d : (a) 1% s u l p h i d e s in t h e c u m u l a t e ; (b) 0.5%; a n d (c) 0.1%. S o l i d lines = R a y l e i g h f r a c t i o n a t i o n ; d a s h e d lines = equilibrium fractionation Note Rayleigh fractionation has a greater effect than equilibrium fractionation.

320 lines), but in this case the effect of the sulphide to magma ratio is not as dramatic. This hypothesis assumes that Ds~ul >> DsPu d. solutions with silicates or oxides. Their concentrations in the silicate liquid will increase until the solubility of either the PGE metal or PGE sulphide phase is exceeded. If the magma does not become saturated with an Fe--Ni--Cu-sulphide, it could become saturated with Os--Ir metal and RuS2, resulting in the nucleation o f extremely fine PGM's. These may form nuclei for silicate crystallization, by which means the PGM's are settled from the magma. Rh, Pt and Pd do not exceed their saturation levels and continue to build up in the magma. Once Fe--Ni--Cu sulphur saturation occurs all the PGE's enter the sulphide liquid and which will have the Pd/Ir ratio of the silicate liquid just prior to saturation. An important aspect of this model concerns the effect of variations in the timing of sulphur saturation. If sulphur saturation is delayed for any reason there will be more o p p o r t u n i t y for the separation of PGM's, leading to increased fractionation of the PGE's. 4. Conclusions (1) Alteration may disturb Au and Pt, and hydrothermal fluids may mobilize Pd. (2) If it can be shown that the partition coefficients of the PGE between sulphide liquid and silicate liquid vary, the PGE could be fractionated separation of a sulphide liquid during either partial melting or crystal fractionation. (3) Differences in the solubility of the PGE's in a silicate magma may cause large changes in (Pd/Ir) ratio during partial melting and crystal fractionation. (4) Olivine and chromite are not suitable minerals for solid substitution of PGE's, although they may have a role in mechanical settling o u t of refractory metals.

3.3.4. Platinum-group minerals (PGM) Hiemstra (1979) pointed o u t t h a t the PGM's that occur in the Merensky Reef of the Bushveld Complex are too small to have settled out of the magma by crystal settling. He suggested that the PGM's crystallized as small grains and that chromite then nucleated on these grains. The chromite then settled out of the magma to form the Merensky Reef. Keays and Campbell (1981) and Keays et al. (1982) suggest a similar model for PGE fractionation based on the high Ir contents of the Kambalda olivines. They propose based on a fs~ vs. temperature diagram that ]r is in the metal state while Pd is in the sulphide state and that Ir metal may be settled out of the magma by olivine, thus producing an Ir-depleted melt. If the order of PGE fractionation were based on the order in which the PGE's are sulphuridized, then the order would be (Westland, 1981):
Ru<Pt< Ir<Os

There are no data for Rh and conflicting data for Pd. If Keays and Crocket's (1970) calculation is used Pd is sulphidized first, however, these authors were unaware of Niwa et al. (1962) data which indicate that Pd would be sulphidized after Ru and Pt. Neither of the data sets predict the observed order of PGE fractionation. The sulphidation arguments do not get to the heart of the problem. During crystallization of magma the PGE's will partition strongly into an Fe--Ni--Cusulphide liquid if one forms. If a sulphide liquid is not present, they will remain in the silicate magma, increasing in concentration as the silicate magma crystallizes, so long as they are not removed in solid solution in early forming silicates or spinel. It has already been argued that removal of noble metals in solid solution in olivine or spinel is unlikely. For the purpose of developing a model, assume that none of the metals form solid

Acknowledgements
The authors would like to thank Dr. H.W. Stockman for allowing us access to his unpublished thesis data and for a constructive

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critism of an earlier draft, Dr. E.W. Sawyer for drafting the diagrams. References
Agiorgitis, G. and Wolf, R., 1977. The distribution of platinum, palladium and gold in Greek chromites. Chem. Erde, 36: 349--351. Agiorgitis, G. and Wolf, R., 1978. Aspects of osmium, ruthenium and iridium contents in some Greek chromites. Chem. Geol., 23: 267--272. Agiorgitis, G. and Wolf, R., 1984. Variations of the Os/Ir ratio in terrestrial rocks and minerals. Chem. Geol., 42: 277--286. Barnes, S.J., 1983a. The fractionation of platinum group elements in Archean komatiites of the Abitibi Greenstone Belt, northern Ontario, Canada. Ph.D. Thesis, Univ. Toronto, Toronto, Ont. (unpublished). Barnes, S.J., 1983b. Petrology and geochemistry of a portion of the Howland (J-M) reef of the Stillwater complex, Montana. Ph.D. Thesis, University of Toronto, Toronto, Ont. (unpublished). Barnes, S.J., Gorton, M.P. and Naldrett, A.J., 1981. Platinum group elements in Abitibi komatiites associated with nickel sulphide deposits. Ont. Geol. Surv., Misc. Pap., 98: 1--11. Barnes, S.J., Coats, C.A.J. and Naldrett, A.J., 1982. Petrogenesis of Proterozoic nickel sulphide-komatiite association: the Katiniq Sill, Ungava, Quebec. Econ. Geol., 77: 413--429. Becker, R. and Agiorgitis, D., 1978. Iridium, osmium and palladium distribution in rocks of the Troodos Complex, Cyprus. Chem. Erde, 37: 302--306. Bird, J.M. and Basset, W.A., 1980. Terrestrial osm i u m - i r i d i u m - r u t h e n i u m alloys: evidence for a deep mantle history. Abstr. Am. Geophys. Union, Spring, EOS, 61: 375. Blander, M., Fuchs, L.H., Horowitz, C. and Land, R., 1980. Primoridal refractory metal particles in the Allende meteorite. Geochim. Cosmochim. Acta, 44: 217--224. Borthwick, A., 1984. The geology of the Big Trout Lake intrusion. M.Sc. Thesis, University of Toronto, Toronto, Ont. (unpublished). Brett, R., 1984. Chemical equilibrium of the earth's core and upper mantle. Geochim. Cosmochim. Acta, 12: 1183--1189. Campbell, I.H. and Barnes, S.J., 1984. A model for the geochemistry of the platinum group elements in magmatic sulfide deposits. Can. Mineral., 22: 151--160. Campbell, I.H. and Naldrett, A.J., 1979. The influence of silicate:sulfide ratio on the geochemistry of the magmatic sulfides. Econ. Geol., 74: 1503--1505. Campbell, I.H., Naldrett, A.J. and Barnes, S.J., 1983.

A model for the origin of the platinum-rich sulfide horizons in the Bushveld and Stillwater complexes. J. Petrol., 24: 133--165. Chou, C.L., 1978. Fractionation of siderophile elements in the earth's upper mantle. Proc. 9th Lunar Planet. Sci. Conf., pp. 219--230. Chou, C.L., Shaw, D.M. and Crocket, J.H., 1983. Siderophile trace elements in the earth's oceanic crust and upper mantle. J. Geophys. Res., 88: A507--A518. Chyi, L.L. and Crocket, J.H., 1976. Partition of platinum, palladium, iridium and gold among coexisting minerals from the deep ore zone Srathcona Mine, Sudbury, Ontario. Econ. Geol., 71: 1196--1205. Coleman, R.G., 1977. Ophiolites. Springer, Berlin, 230 pp. Cousins, C.A., 1973. Notes on the geochemistry of the platinum group elements. Trans. Geol. Soc. S. Afr., 76: 77--81. Cousins, C.A. and Vermaak, C.F., 1976. The contribution of Southern African ore deposits to the geochemistry of the platinum group metals. Econ. Geol., 71: 287--305. Cox, K., 1980. A model for flood basalt volcanism. J. Petrol., 21: 629--650. Crocket, J.H., 1979. Platinum-group elements in mafic and ultramafic rocks: a survey. Can. Mineral., 17: 391--402. Crocket, J.H., 1981. Geochemistry of the platinumgroup elements. Can. Inst. Min. Metall., Spec. Iss., 23: 47--64. Crocket, J.H. and Chyi, L.L., 1972. Abundances of Pd, Ir, Os and Au in an alpine ultramafic pluton. 24th Int. Geol. Congr., Sect., 10: 202--209. Crocket, J.H., Keays, R.R. and Hsieh, S., 1968. Determination of some precious metals by neutron activation analysis. J. Radioanal. Chem., 1: 487-507. Distler, V.V., Malevskiy, A.Yu. and Laputina, I.P., 1977. Distribution of platinoids between pyrrohotite and pentlandite in crystallization of a sulphide melt. Geochem. Int., 14: 30--40. Eckstrand, O.R., 1975. The Dumont Serpentinite: A model for control of nickeliferous opaque mineral assemblages by alteration reactions in ultramafic rocks. Econ. Geol., 70: 183--201. Evans, R.C.~ 1966. Crystal Chemistry. Cambridge University Press, Cambridge, 2nd ed., 410 pp. Fominykh, V.G. and Kvostova, V.P., 1970. Platinum content of Ural dunites. Dokl. Akad. Nauk S.S.S.R., 191: 443--445. Gijbels, R. and Hoste, J., 1971. Nuclear analytical methods in the production and industrial use of noble metals. Eur. Comm. Eurisotope Off., Rep. ITE-66-E, 108 pp. Gijbels, R., Millard, H.T., Desborough, G.A. and Bartel, A.J., 1974. Osmium, ruthenium, iridium

322

and chromite from the eastern Bushveld Complex, South Africa. Geochim. Cosmochim. Acta, 38: 319--337. Gijbels, R., Henderson, P. and Zels, J., 1976. Geochemistry of some trace elements in mineral separates from Rhum, Inner Hebrides, with special emphasis on iridium. Econ. Geol., 71: 1364-1370. Green, A.H. and Naldrett, A.J., 1981. The Langmuir volcanic peridotite associated nickel deposits: Canadian equivalents of the Western Australian occurrences. Econ. Geol., 76: 1503--1523. Gros, J., Takahashi, H., Hertogen, J., Morgan, J.W. and Anders, E., 1976. Composition of the projectiles that bombarded the lunar highlands. Proc. 7th Lunar Sci. Conf., pp. 2403--2425. Groves, D.I. and Keays, R.R., 1979. Mobilization of ore-forming elements during alteration of dunites, Mt. Keith--Betheno, Western Australia. Can. Mineral., 17: 373--389. Haffty, J., Riley, L.B. and Goss, W.D., 1977. A manual on fire assaying and determinations of the noble metals in geological material. U.S. Geol. Surv., Bull. 1445, 58 pp. Hakti, T.A., Hanninen, E., Vuorelainen, Y. and Papunen, H., 1976. Platinum-group minerals in the Hitura nickel deposit, Finland. Econ. Geol., 71: 1206--1213. Hanson, G.H., 1980. Rare earth elements in petrogenetic studies of igneous systems. Annu. Rev. Earth Planet. Sci. Lett., 40: 203--219. Hawley, J.E., 1962. The Sudbury ores: their mineralogy and origin. Can. Mineral., 7: 1--207. Hertogen, J., Janssen, M.J. and Palme, H., 1980. Trace elements in ocean ridge basalt glasses: implications for fractionation during mantle evolution and petrogenesis. Geochim. Cosmochim. Acta, 44: 2125--2143. Hiemstra, S.A., 1979. The role of collectors in the formation of platinum deposits in the Bushveld Complex. Can. Mineral., 17: 469--482. Hoffman, E.L., Naldrett, A.J., van Loon, J.C., Hancock, R.G.V. and Mason, A., 1978. The determination of all the platinum group elements and gold in rocks and ores by neutron activation analysis after preconcentration by a nickel sulphide fire assay technique on large samples. Anal. Chim. Acta, 102: 157--166. Jagoutz, E., Palme, H., Baddenhausen, H., Blum, K., Dreibus, G., Spettel, B., Lorenz, V. and Wanke, H., 1979. The abundance of major, minor and trace elements in the earth's mantle as derived from primitive ultramafic nodules. Proc. 10th Lunar Planet. Sci. Conf., pp. 2031--2050. Kaminskiy, F.V., Frantsesson, Ye.V. and Khvostova, P., 1975. First information on platinum metals (Pt, Pd, Rh, It, Ru, Os) in kimberlitic rocks. Dokt. Akad. Nauk S.S.S.R., 219: 190--193.

Keays, R.R., 1982. Palladium and irridium in komatiites and associated rocks, application to petrogenetic problems. In: N.T. Arndt and E.G. Nisbet (Editors), Komatiites. Allen, London, pp. 435--458. Keays, R.R. and Campbell, I.H., 1981. Precious metals in the Jimberlana Intrusion, Western Australia. Implications for genesis of platiniferous ores in layered intrusions. Econ. Geol., 76: 1118-1141. Keays, R.R. and Crockett, J.H., 1970. A study of precious metals in the Sudbury nickel irruptive ores. Econ. Geol., 65: 438--450. Keays, R.R., Ross, J.R. and Woolrich, P., 1981. Precious metals in volcanic peridotite-associated nickel sulphide deposits in Western Australia, II. Distribution within the ores and host rocks at Kambalda. Econ. Geol., 76: 1645--1674. Keays, R.R., Nickel, E.H., Groves, D.I. and McGoldrick, P.J., 1982. Iridium and palladium as discriminants of volcanic-exhalative hydrothermal and magmatic nickel sulfide mineralization. Econ. Geol., 77: 1535--1547. Kimura, K., Lewis, R.S. and Anders, E., 1974. Distribution of gold and rhenium between nickel-iron and silicate melts; implications for abundance of siderophile elements on the earth and moon. Geochim. Cosmochim. Acta, 38: 683--701. Lago, B.L., Rabinowicz, M. and Nicolas, A., 1982. Podiform chromite ore bodies -- A genetic model. J. Petrol., 23: 103--125. MacRae, W.E., 1982. Noble metal concentrations in selected komatiitic and tholeiitic Archean volcanic rocks from Munro Township. M.Sc. Thesis, McMaster University, Hamilton, Ont. (unpublished). Malevskiy, A.Yu., Laputina, I.P. and Distler, V.V., 1977. Behavior of the platinum-group metals during crystallization of pyrrhotite from a sulphide melt. Geochem. Int., 14: 177--184. Mason, B., 1965. Principles of Geochemistry. Wiley, New York, N.Y., 329 pp. McCallum, M.E., Lovacks, R.R., Carlson, R.R., Cooley, E.F. and Docrye, T.A., 1976. Platinum metals associated with hydrothermal copper ores of the New Rambler mine, Medicine Bow Mountains, Wyoming. Econ. Geol., 71: 1429--1450. McLaren, C.H. and de Villers, J.P.R., 1982. The platinum-group chemistry and mineralogy of the UG-2 chromite layer of the Bushveld Complex. Econ. Geol., 77: 1348--1366. Mitchell, R.H. and Keays, R.R., 1981. Abundance and distribution of gold, palladium and iridium in some spinel and garnet lherzolites -- Implications for the nature and origin of precious metalrich intergranular components in the upper mantle. Geochim. Cosmochim. Acta, 45: 2425--2442. Morgan, J.W., Wanderless, G.A., Petrie, R.K. and Irving, A.J., 1981. Composition of the earth's upper mantle, I. Siderophile trace elements in

323

ultramafic nodules. Tectonophysics, 75: 47--67. Naldrett, A.J., 1981. Nickel sulfide deposits: classification, composition and genesis. Econ. Geol., 75: 628--655. Naldrett, A.J. and Duke, J.M., 1980. Pt metals in magmatic sulfide ores; the occurrence of these metals is discussed in relation to the formation and importance of these ores. Science, 208: 1417--1424. Naldrett, A.J., Hoffman, E.L., Green, A.H., Chen-Lin Chou and Naldrett, S.R., 1979. The composition of Ni-sulfide ores, with particular reference to their content of PGE and Au. Can. Mineral., 17: 403--415. Naldrett, A.J., Innes, D., Gorton, M.P. and Sowa, J., 1982. Compositional variations within and between five Sudbury ore deposits. Econ. Geol., 77: 1519--1534. Niwa, K., Yokokawa, T. and Isoya, T., 1962. Equilibria in the PdS--H2--Pd,S--H~S and Pd,S--H~-Pd--H~S systems. Chem. Soe. Jpn., Bull., 35(9): 1543--1545. Oshin, I.O. and Croeket, J.H., 1982. Noble metals in the Thetford mines ophiolite Quebec, Canada, Part I. Distribution of gold, iridium, platinum and palladium in the ultramafic and gabbroic rocks. Eeon. Geol., 77: 1556--1570. Page, N.J., Rowe, J.J. and Haffty, J., 1972. Platinum metals lateral variations of platinum, palladium and rhodium in the Stillwater Complex, Montana. Econ. Geol., 67: 915--923. Page, N.J., Rowe, J.J. and Haffty, J., 1976. Platinum metals in the Stillwater Complex, Montana. Econ. Geol., 71: 1352--1363. Page, N.J., Pallister, J.S. and Brown, M.A., 1979. Platinum-group metals in chromite-rich rocks from two traverses through the Semail ophiolite, Oman. EOS (Trans. Am. Geophys. Union), 60: 963 (abstract). Page, N.J., Cassard, D. and Haffty, J., 1982. Palladium, platinum, rhodium, ruthenium and iridium in chromitites from the Massif du Sud and Tiebaghi Massif, New Caledonia. Econ. Geol., 77: 1571-1577. Palme, H. and Wlotzka, F., 1976. A metal particle from a Ca, Al-rich inelusions from the meteorite Allende and the condensation of refractory siderophile elements. Earth Planet. Sei., Lett., 33: 45--60. Paul, D., Crocket, J.H. and Nixon, P.H., 1979. Abundances of palladium, iridium and gold in kimberlites and associated nodules. Proc. 2nd Int. Kimberlite Conf., Vol. 1. Am. Geophys. Union, Washington, D.C., pp. 272--279. Prichard, H.M., Potts, P.J. and Neary, C.R., 1981. Platinum group element minerals in the Unst

chromite, Shetland Isles. Inst. Min. Metall., 90: B186--B188. Rammensee, W. and Palme, H., 1981. Meta-silicate extraction technique for the analysis of geological and meteorite samples. Abstr. on Modern Trends in Activation Analysis. Univ. of Toronto, Toronto, Ont. Robert, R.V.D., Van Wyk, E. and Palmer, R., 1971. Concentration of the noble metals by a fire assay technique using nickel sulphide as the collector. Natl. Inst. Metall. Repub. S. Afr., Rep., 1371: 14 pp. Ross, J.R. and Keays, R.R., 1979. Precious metals in volcanic-type nickel sulphide deposits in Western Australia, I. Relationship with the composition of the ores and their host rocks. Can. Mineral., 17: 417--435. Shannon, R.D., 1976. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr., 32: 751--767. Sharpe, M., 1982. Noble metals in the margin rocks of the Bushveld Complex. Econ. Geol., 77: 1286-1295. Shaw, D.M., 1970. Trace element fractionation during anatexis. Geochim. Cosmochim. Acta, 34: 237--243. Skinner, B.J., Luce, F.D., Dill, J.A., Ellis, P.E., Hagan, H.A., Lewis, D.M., Odell, D.A., Sverjensky, D.A. and Williams, N., 1976. Phase relationships in ternary portions of the system Pt--Pd--Fe--As-S. Econ. Geol., 71: 1469--1475. Stockman, H.W., 1982. Noble metals in the Ronda and Josephine peridotites. Ph.D. Thesis, Massachusetts Institute of Technology, Cambridge, Mass. (unpublished). Stockman, H.W. and Hlava, P.F., 1984. Platinumgroup minerals in alpine chromitites from southwestern Oregon. Econ. Geol., 79: 491--508. Sun, Shen-Su, 1982. Chemical composition and origin of the earth's primitive mantle. Geochim. Cosmochim. Acta, 46: 179--192. Wagner, P., 1929. Platinum deposits and mines of South Africa. Oliver and Boyd, London, 326 pp. Wark, D.A. and Lovering, J.F., 1976. Refractory Platinum Metal Grains in Allende Ca--Al-rich Clasts. In: Lunar Science, VII. Lunar Sci. Inst., Houston, Texas, 912 pp. Weast, R.C., 1975. Handbook of Chemistry and Physics. Chemical Rubber Company, Cleveland, Ohio, 56th ed., 2894 pp. Wendlandt, R.F., 1982. Sulphur saturation of basalt and andesite melts at high pressures and temperatures. Am. Mineral., 67: 877--885. Westland, A.D., 1981. Inorganic chemistry of the platinum-group elements. Can. Inst. Metall., Spec. Iss., 23: 5--18.