Earth and Planetary Science Letters, 111 (1992) 59-68 59

Elsevier Science Publishers B.V., Amsterdam

[CL]

Osmium isotopic compositions from oceanic basalts

W i l l i a m J. P e g r a m a n d C l a u d e - J e a n All~gre
Laboratoire de Gdochimie et Cosmochimie, lnstitut de Physique du Globe de Paris, 4 Place Jussieu, 75252 Paris, France
Received July 8, 1991; revision accepted April 6, 1992

ABSTRACT

We report Os isotopic analyses of certain oceanic basalts as well as Re and Os concentrations of oceanic and continental
mafic igneous rocks. I87Os/186Os ratios of OIB from Loihi (1.10), Mauna Loa (1.13) and Reunion (1.11) are slightly more
radiogenic than estimates of the bulk silicate earth (~ 1.06) and the majority of published values for peridotites. An
ankaramite from Iceland has a 187Os/186Os of 1.07. These values preclude the possibility that these OIB are derived either
totally or largely by the fusion of ancient subducted oceanic crust, as such material would have extremely high 187Os/186Os
ratios. Mixing calculations show that a basalt with a lS7Os/186Os of 1.11 could have been generated from a source
containing ~ 8% of 3 Ga crust, assuming that the depleted mantle had chondritic Re-Os systematics. However, such an
interpretation of the more radiogenic OIB cannot be considered unique. The fact that the Iceland sample has a lower
187Os/186Os than samples from Reunion and Hawaii suggests that the age of the lithosphere through which the magmas
passed may be a factor. During ascent, OIB magmas could have been contaminated with either the oceanic crust itself,
which had evolved highly radiogenic 187Os/lS6Os ratios since its formation at the ridge, or with high-Re/Os components of
the lithospheric mantle. However, one cannot exclude the possibility that the difference in the Os isotopic compositions
between the more radiogenic OIB and those of continental and oceanic peridotites reflects the more depleted history of the
uppermost mantle (implying, in one interpretation, that the I87Os/186Os of the bulk silicate earth could be greater than
1.06).

I. Introduction
Osmium isotopic analyses of komatiites and
O s - e n r i c h e d p h a s e s in P r e c a m b r i a n l a y e r e d mafic
i n t r u s i o n s a n d p l a c e r d e p o s i t s have s u g g e s t e d t h a t
the O s i s o t o p i c c h a r a c t e r i s t i c s o f t h e m a n t l e have
g e n e r a l l y evolved a l o n g c h o n d r i t i c lines [e.g., 1-3].
In a d d i t i o n , 187Os/186Os r a t i o s a n d R e / O s ratios
f r o m p e r i d o t i t e s (the m a j o r i t y f r o m c o n t i n e n t a l
l i t h o s p h e r i c m a n t l e ) g e n e r a l l y fall n e a r o r slightly
b e l o w t h e c u r r e n t e s t i m a t e for t h e b u l k e a r t h as
d e t e r m i n e d f r o m t h e m a n t l e e v o l u t i o n line [4-7].
I n t h e past, t h e very low Os c o n c e n t r a t i o n s o f
m o d e r n basalts, which s a m p l e v o l u m e t r i c a l l y sig-
nificant p o r t i o n s o f t h e m a n t l e a n d w h o s e Sr, N d
a n d Pb isotopic c h a r a c t e r i s t i c s have b e e n u s e d in
Correspondence to: W.J. Pegram, Department of Geology
and Geophysics, Yale University, P.O. Box 6666, New Haven,
CT 06511, USA.
t h e p a s t to c o n s t r u c t m a n t l e m o d e l s , have p r e -
v e n t e d analysis o f t h e i r Os isotopic c o m p o s i t i o n .
R h e n i u m a n d o s m i u m d i s p l a y very d i f f e r e n t
s o l i d / l i q u i d p a r t i t i o n i n g d u r i n g m a n t l e melting.
R e b e h a v e s s o m e w h a t i n c o m p a t i b l y , b e i n g mildly
e n r i c h e d in b a s a l t s relative to m a n t l e p e r i d o t i t e s
[e.g., 8,9] (Fig. 1). F a r m o r e striking a n d i m p o r -
tant, however, is t h e d r a m a t i c d e p l e t i o n o f Os in
b a s a l t s relative to p e r i d o t i t e s (basalts having ~
0 . 1 - 1 0 % o f the Os c o n t e n t of p e r i d o t i t e s ) , re-
flecting a high to e x t r e m e l y high b u l k p a r t i t i o n
coefficient for Os d u r i n g m a n t l e m e l t i n g o r dur-
ing a s c e n t a n d e v o l u t i o n o f the m a g m a s [e.g:,
7-9]. C o n s i d e r i n g only t h e effects of p a r t i t i o n i n g
d u r i n g melting, o n e c a n n u m e r i c a l l y p r o d u c e
b a s a l t s falling in t h e h e a r t o f t h e b a s a l t field on
Fig. l b by using b u l k D ' s for R e o f 0.1 o r 0.2 a n d
b u l k D ' s for Os such as 50 o r 500. T o p r o d u c e
t h e total r a n g e o f Os c o n c e n t r a t i o n s in m o d e r n
b a s a l t s f r o m an a v e r a g e p e r i d o t i t e starting com-
p o s i t i o n w o u l d r e q u i r e a r a n g e o f "effective D °S''

0012-821X/92/$05.00 © 1992 - Elsevier Science Publishers B.V. All rights reserved

60 w.j. PEGRAM AND C.-J. ALLIEGRE

TABLE 1
Re and Os concentrations from selected oceanic and conti-
nental basalts
° Peridotites I

l
Sample Re (ppb) Os (ppb)
Komatiites
Basalts Iceland
Basalts-this study Tholeiite 0.460 _+0.033 0.0376 5:0.0004
Ankaramite 0.163_+0.005 0.111 :t:0.003
10
a) Hawaff
Mauna Loa tholeiite - 0.350 5:0.008
[]
Loihi tholeiite 0.6625:0.017 0.347 5:0.004
] x X~lWll° 0
.-. 1 [] [] • il ~ 0
Reunion oceanite
FAMOUS
0.239 5:0.007
0.86 _+0.10
0.107 5:0.002
0.0305 5:0.0004
• • iN (~o 0
Tubuaii alkali basalt 0.378 5:0.017 0.0041 _+0.0002
o°O~:j
.1
• •
• o ~_~I St. Helena alkali basalt 0.182 5:0.010

Mesozoic Appalachian tholeiites

0.0049 5:0.0006

%0 1 BRE - 0.294 _ 0.004

NC 114 0.689_+0.048 0.457 -t-0.006
............................ !o] Q-1 0.429_+0.016 0.496 5:0.005
.01 The samples from Loihi, Koolau and Reunion have accumu-
.001 .01 .1 1 lO
lated substantial olivine, so their Re and Os concentrations
Os (ppb) may not be indicative of the concentrations in magmas from
these locations that have not accumulated olivine. Similarly,
10 ~.\ . . . . . . . . . . . . . . . . . . . . . . . . . . Batch Melting the Iceland ankaramite contains abundant ( ~ 50 vol%) cumu-
U] late olivine and pyroxene. Analytical errors on concentrations
are based on run statistics and over- (or under-) spiking. The
BASALTS Re m 1~ following are documented sample numbers: Mauna Loa
./~. ID 0.2 0.1 (761228-8); Loihi (KK19-18); FAMOUS (CH31-DR081136.2);
~" P qk ~F1= II [ D TM 500 50 Tubuaii (033/150).

] Peridotite
Averago1t
•1OOl ....... ol ........ i ....... i " 'TTo
Os (ppb)
3000 1(300500 t00 10
: : : t
EFFECTIVE D Os
Fig. 1. (a) A comparison of Re and Os concentrations of
peridotites, komatiites and basalts that have been previously
published [2,4,5,6,9] and those of this study. (b) A comparison
between the field for basalts and numerically modelled melts.
Using standard batch partial melting equations [10] and a
typical peridotite starting material (being the averaged Re and
Os contents of the peridotite data appearing in part (a)), one
can produce model basalts falling in this field by using very
high bulk partition coefficients for Os and low ( < 1) partition
coefficients for Re. The effective D TM trajectory plots the
calculated D for melts assuming a starting composition of the
same average peridotite as above and 15% partial melting. To
cover the observed range in Os contents in basalt, the effec-
tive D TM during melting must vary from ~ 10 to ~ 3000.
of ~ 10 to > 3000. Clearly, one could not repro-
duce the two order of magnitude variation in Os
concentrations in basalts (Fig. 1 and Table 1)
merely by reasonably rearranging the mode of the
I residual major silicate mineralogy, even if one or
I more phases had a high partition coefficient for
I Os. More likely is the possibility that some man-
I tle melts were in equilibrium with Os metal or
platinum group element (PGE) alloys, with solid
PGE-rich sulfide phases or immiscible sulfide
melts, all with very high solid/liquid partition
coefficients for Os [e.g., 2,9,11-14].
Alternatively, high but more modest D values
existing during fractional crystallization of a
magma would produce rapid depletions in its Os
content. To illustrate, a hypothetical parental
magma with an Os content equivalent to the
highest yet measured in a basalt could produce a
melt with the lowest Os content measured in
basalt after 25% crystallization if the bulk D for
Os during crystallization were ~ 20. Again, solid
OSMIUM ISOTOPIC COMPOSITIONS FROM OCEANIC BASALTS 61

or liquid sulfide phases or PGE-rich metal alloys

could be involved.
Although the general incompatibility of Re is
30
acknowledged, the degree of its preference for
the liquid is unclear. Indeed, the degree of in-
compatibility of Re may vary from one system to
:: f/ / J
another as indicated by the observation that, con-
trary to what one would predict, Re contents in
MORB may be somewhat higher on average (or, - lOf//J
at least, not less) than OIB and continental mafic
igneous rocks despite the former's relative deple-
0 l 2 3 4
tion in classically incompatible trace elements A G E OF C R U S T (Ga)
(although the data base is still very small [e.g.,
Fig. 3. 187Os/186Os ratios of crustal segments of diverse ages
8,9]; Table 1).
and 187Re/186Os ratios. The x-axis is the mantle extraction
The powerful depletion of Os in mantle melts age of the crustal material. 187Re/186Os ratios in this case are
presents us with our greatest research opportuni- the ratios the materials had when first emplaced into the
ties (as well as our most severe analytical difficul- crust. The present-day 187Os/186Os ratios of materials with
ties) for it produces a tremendous fractionation 187Re/186Os ratios of 200, 600, 1000 and 4000 (values as high
in the R e / O s ratio between basalts and crustal as the latter are c o m m o n in M O R B [9]) would be ~ 7, ~ 20,
~ 33 and ~ 129, respectively.

a) rocks ( ~ 10-500) and the mantle ( ~ 0.1) (see Fig.

2). Thus, due to the beta decay of 187Re to 187Os
O~D (X) 03:30 t3( (half-life = 42.3 Ga [15]), crustal rocks evolve
187Os/186Os ratios that are much more radio-
[Carb. Chondrites [ genic than either their initial values or the values
for contemporaneous mantle. The rate of growth
of these differences is graphically portrayed on
[Peddotites I Fig. 3, which plots the present-day 187Os/186Os
ratio of crustal material with typical 187Re/186Os
.01 .1 1 10 100 1000 ratios of 200, 600 and 1000 versus the ages (man-
Re/Os tle-extraction ages) of these materials. Given the
highly radiogenic nature of the crust and the
b) great isotopic differences between crust and man-
tle, the R e / O s system will be particularly valu-
0 ~ 0 able as either a sensitive chronometer for the
evolution of the crust or as an indicator of the
[Carb. Chondrites [ + +2+2 2 3+ +
involvement of old crustal material during the
generation or evolution of mantle-derived mag-
mas.
[Peridotites J 0 0 0 000 01~0 0 0 Cl 0
Some investigators have suggested that crustal
material, either subducted oceanic crust +
0.90 0.95 1.00 1.05 1.10 1.15 1.20 sediments or a mixture of such material with
oceanic lithospheric mantle, is a significant
187 OS / 186 OS
(sometimes dominant) component of OIB sources
Fig. 2. (a) A comparison of R e / O s ratios for peridotites, [16-20]. Such models often call for long-term
carbonaceous chondrites and basalts. Data from [4,5,6,9,27]
storage of such material at Some level in the
and this study. (b) A comparison of 187Os//186Os ratios for
basalts, carbonaceous chondrites and peridotites. Data from
mantle (mesosphere boundary [16,17], the base of
[4,6,27] and this study; 2 and 3 indicate the n u m b e r of the mantle [18], or throughout the upper mantle
analyses with that particular 187Os/lS6Os ratio. in marble-cake banding [20]). Magmas produced
62
by the fusion of such hybrid mantle segments,
particularly if the old crustal material preferen-
tially contributed to the melt, could have lS7Os/
lS6Os ratios in excess of those for "normal" man-
tle peridotite. With such possibilities in mind, we
have determined the Os isotopic composition of
basalts from Loihi, Mauna Loa, Reunion, Iceland
and the Seychelles. Preliminary versions of these
results were presented by [37] and [38]. Simulta-
neously with this study, Candace Martin at Yale
also analyzed oceanic basalts for osmium isotopic
composition, finding results similar to ours and
arriving at many of the same conclusions [36].
2. Analytical procedures
Prior to the chemical extraction and purifica-
tion of Os according to the procedures outlined
by Luck and All~gre [21], the samples were ini-
tially processed by either a direct dissolution
technique or by preconcentration of Os by nickel
sulfide fire assay. Analyses of samples from Loihi,
Mauna Loa, Reunion and the Seychelles were by
fire assay. By this technique, following the proce-
dure of Robert et al. [22], sample powder was
fused in the presence of a sodium carbonate/
sodium tetraborate flux (carbonate to borate ratio
= 1:1; flux to sample r a t i o = 1:1) and nickel
sulfide. Prior to sample fusion, the flux was itself
melted for ~ 2 hours to cleanse it of Os, an
element which is volatile under such conditions.
We prepared the nickel sulfide beginning with
ultrapure Ni metal which had previously been
fused in a reducing, and then an oxidizing atmo-
sphere. During the sample fusion (charge was
maintained in a molten state at 1000°C for ~ 1
h), Os is scavenged by the immiscible nickel sul-
fide melt which settles to the base of the charge.
After freezing and smashing the crucible, the
nickel sulfide bead was easily separated from the
glass and placed in 10N HC1 for dissolution. The
insoluble residue remaining from this step con-
tains the sample Os, probably in noble metal
sulfides that are insoluble in HCI. In the final
step before distillation, this residue was placed
along with n 2 s o 4 in a sealed digestion vessel
overnight at ll0°C. Blanks for this procedure
varied with sample size, but the ratio of sample
Os to blank Os was always greater than 200:1.
Re and Os concentrations for samples processed
W.J. PEGRAM AND C.-J. ALL~'GRE
by fusion were determined on separate sample
splits processed by the dissolution technique de-
scribed below.
The Icelandic ankaramite, a split of the Loihi
sample processed by fusion, and all of the sam-
ples analyzed for concentration by isotope dilu-
tion were processed by a dissolution technique
that followed closely that of Walker [23]. Up to
10 g of sample plus a quantity of 185Re-19°Os
spike were weighed into 120 ml Savillex ® dissolu-
tion vessels. To this was added the dissolution
mixture of ~ 10 ml concentrated HF, ~ 10 ml
10N HCI, and ~ 8 ml ethanol (the reducing
medium created by the HC1 and ethanol prevents
the loss of Os as OsO 4 during dissolution and
drydown). The samples were sealed and placed
overnight in a 110°C oven for digestion. The
following day, the solution was dried, mixed again
with an identical dissolution cocktail, heated
overnight, and dried. After the fifth such diges-
tion step but before the final drydown, an aliquot
was removed for Re analysis. Following drydown,
the residue was mixed with concentrated H2SO 4
and heated in the sealed digestion vessel
overnight. Total chemistry blanks by this tech-
nique were ~ 4 pg for Os and ~ 30 pg for Re.
Os was then separated by a two-step distilla-
tion process. First, the samples in concentrated
HzSO 4 from the last stages of the fire assay and
direct dissolution steps were diluted to 4N HzSO 4
in the distillation vessel itself. To this was added
CrO 3 as an oxidizing agent (50 m g / g of sample
processed by dissolution, 500 mg for the fire assay
samples). The sulfuric solution was then heated
to boiling and the distillate containing Os col-
lected in a l % H z O 2 - 1 % H z S O 4 solution. After
the first distillation step was finished, this solu-
tion was itself boiled and the distillate collected
in 9N HBr. The condensation and collection
apparatus for this second step was built entirely
of teflon. (Note that although the same teflon
distillation apparatus was used during the course
of the investigation, no significant memory effects
caused by the absorption of OsO 4 into the mate-
rial were observed.) The product of the second
distillation, now diluted to ~ 3N HBr by the
addition of the distillate, was sealed and heated
overnight at 110°C to reduce the Os to the non-
volatile bromide form. To remove organics and
other undesirable molecular debris, the sample
OSMIUM ISOTOPIC COMPOSITIONS FROM OCEANIC BASALTS
single grain of Chelex 100 resin (Os is retained by
the resin in < 1N H B r and eluted in 9 N HBr).
Afterwards, the sample was loaded onto a silicon
chip for analysis. The Re aliquot from the final
dissolution step was dried, taken up in concen-
trated H N O 3 and dried again (these last two
steps were repeated twice more). The sample was
taken up in 0.8N H N O 3 and loaded onto a 100
ml column of AG1 X4 anion resin. By this stick-no
stick chemistry, Re was eluted in 8 N H N O 3. This
column step was repeated. Finally, the sample in
a 0.8N H N O 3 solution was loaded onto a single
grain of A G I X8 resin from which the Re was
eluted by 8 N H N O 3.
A Cameca IMS 3f ion probe was the instru-
ment of choice for Os isotopic analysis. To cor-
rect the measured ratios for isotopic fractiona-
tion, we assumed a linear law and a 192Os/188Os
ratio of 3.08271 [21,24]. 187Os/186Os ratios were
determined from the measured 187Os/188Os ratio
and an assumed m6Os/mSOs ratio of 0.12035
[21]. Subsequent isotope dilution calculations used
the 190Os/192Os ratio. From the 191 peak
(19°OsH), we determined the quantity of hydride
interference from which we applied a correction
factor to all masses. Similarly, the 185 mass was
monitored for the presence of Re. For all sam-
ples, we used a high voltage offset of - 1 5 V to
remove isobaric molecular interferences (energy
filtering).
3. Results and discussion
3.1 Re and Os concentrations
Re and Os concentrations for a number of
oceanic and continental basalts a p p e a r in Table
1. Re contents vary from 0.16 to 0.86 ppb while
Os, in accordance with previous analyses, is much
more variable, ranging from 0.004 to 0.496 ppb.
Many of the samples were chosen for this study
because they contained accumulated olivine phe-
nocrysts (in the hope that this would artificially
increase the Os content of the sample above
magmatic values and thereby ease analysis). Thus,
some of the samples at the low-Re, high-Os range
display somewhat artificially high Os and low Re.
However, the aphyric Tubuaii alkali basalt shows
that low Re ( < 0.5 ppb) values may obtain in
certain magmas. Further, the lack of reported Os
63
(or Ir) contents greater than ~ 0.160 ppb in
M O R B [e.g., 9,14] and the existence of phe-
nocryst-poor O I B with substantial Os contents
indicate that some O I B Os contents and some
continental tholeiite (Mesozoic A p p a l a c h i a n
tholeiites) Os contents are indeed higher than
typical M O R B . (Curiously, only the samples from
the two H I M U localities of St. Helena and
Tubuaii have Os contents similar to most M O R B .
However, one should probably resist the tempta-
tion to use this as evidence that H I M U are, in
fact, derived from subducted oceanic crus.t [e.g.,
18,19] as high distribution coefficients for Os
during melting or crystallization would obscure
any relationship between the Os contents of mag-
mas and their sources.)
3 . 2 0 s isotopic compositions
We determined the Os isotopic composition of
the following oceanic basalts: (1) a tholeiite from
Loihi (most likely < 1000 yrs old [25]), (2) a
M a u n a Loa tholeiite from the Ninole Series (his-
torical), (3) an oceanite from Reunion (Piton de
la Fournaise, 1977 eruption), (4) an ankaramite
from Hvammsmuli, Eyjafj611, southern Iceland
(maximum of 700 ka [26]), and (5) a 500 Ma old
diabase from the Seychelles archipelago.
Os isotopic ratios for the O I B a p p e a r in Table
2. The Loihi sample (Os = 347 ppt) was analyzed
by fusion and by direct dissolution; the analyses
agree within error to yield a 187Os/186Os ratio of
~ 1.10. The Mauna Loa tholeiite (Os = 350 ppt)
exhibits a somewhat more radiogenic 187Os/186Os
TABLE 2
Os isotopic compositions of oceanic basalts
Sample 187Os/186Os Method
Iceland ankaramite 1.069+0.010 Dissolution
Reunion oceanite 1.110+_0.012 Fusion
Loihi tholeiite 1.109 _ 0.025 Fusion
1.094+0.017 Dissolution
Mauna Loa tholeiite 1.130+0.023 Fusion
Seychelles diabase 26_+ 1 Fusion
"Fusion" is the Ni sulfide nickel assay technique as modified
from Robert et al. [20]. "Dissolution" is the direct dissolution
technique of Walker [21]. Error on the measured ratios is
twice the normalized standard deviation of 10-ratio block
averages. The following are documented samples: Mauna Loa
(761228-8); Loihi (KK19-18).
64
ratio of 1.13. The oceanite (Os = 107 ppt) from
Reunion, an island whose Pb-Sr-Nd isotopic traits
suggest the possibility of recycled crustal compo-
nents in its source (i.e., relative to MORB, higher
2°7pb/2°4pb at a given 2°6pb/2°4pb, lower 143Nd/
144Nd, higher 87Sr/86Sr), yielded a 187Os/186Os
ratio of 1.11. The Iceland ankaramite (Os = 111
ppt) has a 187Os/186Os value of ~ 1.07. Finally,
the measured 187Os/186Os ratio of the Seychelles
sample was 26 +_ 1, which we include merely to
show the explosive evolution of the 187Os/186Os
ratio in some segments of the crust (time-in-
tegrated 187Re/186Os ~ 3000). The rough similar-
ity of the measured isotopic compositions of the
modern basalts with those of chondrites (Fig. 2b)
is clearly not compatible with the derivation of
OIB largely from ancient subducted crustal mate-
rial (Fig. 3). However, of these analyses, the
Mauna Loa, Loihi and Reunion values are slightly
but significantly above what is considered to be
the present-day value of the bulk silicate earth
and the average value of carbonaceous chondrites
( ~ 1.06 [27]) (Fig. 2b). Only the value for the
Iceland ankaramite falls close to this value.
As none of the OIB (with the obvious excep-
tion of the Seychelles sample) is of sufficient age
that age-corrected values would be significantly
different from the measured value, we can dis-
miss the possibility that the elevated 187Os/186Os
ratios of the OIB are due to the rapid evolution
of this ratio between eruption and analysis. [The
Iceland ankaramite, which is perhaps as old as
700 ka, could have had an appreciable age correc-
tion if its R e / O s ratio were higher than 100 (i.e.,
as high as values reported for certain M O R B [9]).
This sample, however, has an unusually low
R e / O s for a crustal rock (1.46), which is a result
of the combined effects of an increase and a
decrease in the Os and Re contents, respectively,
by the accumulation of olivine and pyroxene and
an apparently low (relative to the M O R B of [9])
Re content in the original magma itself ( ~ 0.35-
0.4 ppb)].
The possibility that radiogenic ingrowth of
lS7Os during the lifetime of the magma (from
removal from its source to eruption) produced
the relatively elevated OIB 187Os/186Os ratios is
slightly less easily dismissed. If we assume that
the R e / O s ratio of an OIB magma were 10
(conservatively estimating a Re content of 1 ppb
W.J. PEGRAM AND C.-J. A L L E G R E
(the scarce available data suggest that average Re
contents of OIB may be less than the ~ 1 ppb
average for MORB) and an Os content of 100 ppt
(assuming that the higher values reported for our
samples were products of accumulation)), the
lifetime of the magma would have to be ~ 6 Ma
to generate a difference of 0.04 between it and its
source. Based on calculations in Zindler and Hart
[28], a nonconvecting spherical magma chamber
with, for example, a diameter of ~ 4 km, could
exist for 6 Ma if the temperature difference be-
tween the magma and the wallrock were as low as
~ 10°C. However, whether magma chambers
could exist for such long periods of time as closed
systems in areas such as Reunion and the Hawai-
ian Islands where t h e magma flux is high is very
doubtful. The time factor becomes less of a prob-
lem if one assumes that OIB melt might freeze in
the mantle only to be reactivated or incorporated
in an ascending magma at a later time. However,
it seems unlikely that this could be a realistic
model to explain how the enormous volumes of
Reunion and Hawaiian magmas could have ele-
vated 187Os/186Os ratios (if it were to be demon-
strated that our Reunion and Hawaiian values
are characteristic of these islands).
The similarity of the 187Os//186Os of the Ice-
land sample with the estimate of the bulk silicate
earth versus the slightly more radiogenic values
for the Hawaiian and Reunion lavas suggests that
the OIB Os isotopic compositions could be re-
lated to the age of the oceanic lithosphere through
which the magmas passed. The ~ 100 Ma crust
on which the Hawaiian volcanoes sit would have
a 187Os/186Os ratio as high as 7.7 if its R e / O s
ratio were a MORB-like 100 (e.g., Re = 1 ppb,
Os = 0.01 ppb). Assuming a parental magma with
a 187Os//186Os of 1.06 and a concentration of 0.1
ppb, the isotopic compositions of the Loihi and
Mauna Loa magmas could be reproduced if they
had assimilated ~ 6% and ~ 10%, respectively,
of oceanic crust ( ~ 18% and ~ 28% respectively
if the parental magma had a concentration as
high as the 350 ppt concentration of the Loihi
and Mauna Loa samples themselves). Contamina-
tion of a parental Reunion magma (Os content =
100 ppt) with ~ 9% of younger ( ~ 65 Ma), less
lS7Os-rich oceanic crust would reproduce the Os
isotopic composition of this sample. These con-
servatively calculated crustal proportions, based
OSMIUM ISOTOPIC COMPOSITIONS FROM OCEANIC BASALTS 65

on minimum Os concentrations for these OIB,

seem unrealistically high. If for no other reason,
the incorporation of such quantities of oceanic
MIXTURES OF PERIDOTITE WITH SUBDUCTED
crust, much of which would be altered, would OCEANIC CRUSTOF DIVERSEAGES
produce shifts to more radiogenic 87Sr/86Sr ra- 1.20
tios at given 1 4 3 N d / l n n N d ratios~characteristics .... ~~ Ga 4 .... /
not associated with Hawaiian lavas [e.g., 29].
However, if Reunion and Hawaiian magmas are
1.16
in fact more radiogenic than both depleted man- ©
tle and OIB that have risen through near-zero-age
oo
lithosphere, contamination with some litho-
spheric component cannot be excluded. \ 1.12
Alternatively, the OIB 187Os/186Os ratios could
directly reflect those of their sublithospheric
oo
source regions. Clearly, again, that the measured 1.08
187Os/186Os ratios are not those of aged crustal I
material but are close to bulk silicate earth elimi- I I I
I I I
nates the end-member possibility that the OIB 1 , ~ I I
I I
I *1 I i , , ,
I
I I , , , I * , I I I I

were derived from the melting of ancient sub-
ducted oceanic crust with little or no equilibra-
tion or mixture with "normal" mantle material.
However, could the fact that the Reunion and
Hawaiian ratios are consistently higher than esti-
mates of bulk silicate earth and the mean of
carbonaceous chondrites (and the possibility that
the t87Os/186Os of the Iceland sample may be
higher than depleted asthenospheric mantle) re-
flect the hybridization of their source regions
with some significant proportion of old high
R e / O s material such as subducted crust?
Figure 4 is an attempt to model the quantity of
old oceanic crust needed in the OIB sources to
produce the isotopic differences between bulk
earth and the OIB. The curves on this figure
assume that the Os isotopic characteristics are
the result of mixtures between mantle peridotite
with a 187Os/lS6Os of 1.06 and subducted oceanic
crust with ages of 1 Ga, 2 Ga, 3 Ga and 4 Ga (the
ages representing, in effect, the time elapsed
since the material was created at the ridge crest).
According to these mixing curves, the ! 8 7 O s / / 1 8 6 O s
value of Reunion (1.11) could be explained if
~ 21% of its source were 1 Ga crust, ~ 12% of
its source were 2 Ga crust, ~ 8% were 3 Ga crust
or ~ 6% were 4 Ga crust. (Assuming preferential
melting of subducted crust, the real density of
crustal segments in the sub-Reunion mantle
would be something less than these figures.) The
fifth curve in Fig. 4 ("Cake") is within the context
of a marble-cake mantle model [20]. Assuming
0 0.10 0.20 0.30 0:40
WEIGHT FRACTION RECYCLED COMPONENT
Fig. 4. Os isotopic compositions of mixtures of mantle peri-
dotite and subducted oceanic crust of various ages. In all
cases, mantle peridotite was assumed to have an Os concen-
tration of 3500 ppt and a chondritic tS7Os/lS6Os ratio of 1.06.
The oceanic crust was given a Re concentration of 1 ppb,
being a rough average of eight published MORB [9,33]. Speci-
fying Os concentrations in the crust is more problematic.
Most MORB (again the data are very sparse) show concentra-
tions of < 0.01 ppb [9]. However, based on analyses of two
Indian Ocean samples reported in [9], Morgan [7] proposed
that MORB parental magmas have concentrations as high as
0.09 ppb and that the more common much lower concentra-
tions represent the loss of Os during evolution of the magma
during ascent. If true, and if the depletion of the Os occurred
at crustal levels, the bulk Os content of the crust could be
quite high, being a mixture of Os-poor basalt and Os-rich
sulfide and silicate cumulates. For the calculations, the crust
was allotted an Os concentration of 0.01 ppb. However, the
uncertainty in the Os concentration of the crust has little
bearing on the mixing calculations for, after specifying the Re
content, any loss of sensitivity in the mixture caused by a
lowering of the Os content of the crust is very nearly compen-
sated by the increased sensitivity caused by the more radio-
genic nature of that crust after storage in the mantle. Thus,
the curve for 1 Ga applies not only for the specified Re and
Os contents of the crust but, roughly speaking, for any such
crust with 1 ppb Re. According to this model, the source for
Reunion could have contained ~ 21% of 1 Ga crust, ~ 12%
of 2 G a crust, ~ 8 % of 3 Ga crust, or ~ 6 % of 4 Ga crust.
The "Cake" curve, within the context of a marble-cake model
[20], is a mixture of the same peridotite as above and the
mafic layer from Ronda with the lowest Os concentration (10
ppt) and the highest I87Os/186Os ratio (50) [6]. According to
this scheme, ~ 39% of the Reunion mantle source could
consist of such a component.
66
that orogenic lherzolite mafic layers are in fact
the thinned bands of oceanic lithosphere pre-
dicted by the model to exist in the mantle and
using the Ronda mafic layer with the lowest Os
concentration (10 ppt) and the most radiogenic
187Os/186Os (50) [6], this curve suggests that the
Reunion sources could have contained ~ 39% of
such a recycled component.
However, certain difficulties exist for such sim-
ple mixing schemes. Such calculated proportions
of recycled material, even for 3 Ga crust, seem
too great to reconcile with observed incompatible
element concentrations and isotopic characteris-
tics of these OIB (barring some propitious chemi-
cal processing of the subducted crust after entry
into the mantle either in the subarc environment
or later). However, the uncertainty of the R e / O s
systematics of the materials involved in this mix-
ing model are such that the calculated crustal
proportions should be taken with a grain of salt.
Another consideration for these calculations is
that any equilibration of high-187Os/186Os OIB
melts with Os-rich, relatively lower-187Os/186Os
mantle material would produce precipitous de-
clines in the 187Os/186Os ratio of the melt, even
for OIB melts that are as high in Os content as
Loihi and Mauna Loa. For example, if a magma
with a 187Os//186Os ratio of 1.11 and an Os con-
tent of 100 ppt equilibrated with four times its
own mass of mantle peridotite (thus being chemi-
cally similar to a 20% partial melt) with a 187Os/
186Os ratio of 1.06 and an Os concentration of
3500 ppt, the new 187Os//186Os ratio of the melt
would be < 1.061. Thus, whether more radio-
genic magmas passing through "normal" mantle
peridotite could retain their distinct Os isotopic
compositions is uncertain-such factors as depth of
removal of the magmas from their sources and
time that elapsed between removal from their
sources and eruption or emplacement would be
critical. Speaking qualitatively, however, and de-
spite the above reservations, the existence of some
quantity of recycled material in the source re-
gions of certain OIB is compatible with the Os
isotopic data.
On the other hand, perhaps the discrepancy in
the Os isotopic compositions of these OIB with
those of the majority of peridotites and the esti-
mate of the bulk silicate earth reflects a real
difference between the mantle sources of OIB
W.J. PEGRAM AND C.-J. ALLIEGRE
and the uppermost mantle. The conventional in-
terpretation of the differences in the incompati-
ble element isotopic characteristics of the upper-
most mantle (as sampled by MORB) and the OIB
sources is that the former is more depleted. As-
suming the general incompatibility of Re, the
lower time-integrated R e / O s ratios of mantle
peridotites could merely reflect this greater de-
pletion. In such a case, the higher OIB ~SVOs/
186Os ratios would more closely approximate bulk
silicate earth than measured mantle materials.
Support for this idea comes from the fact that
Mauna Loa, Loihi, Reunion and Iceland all have
higher-than-MORB 3He/4He ratios, indicating
the involvement of less-degassed material in their
sources (i.e., more primitive mantle components,
closer to bulk silicate earth in composition) [e.g.,
30,31]. Accordingly, the bulk silicate earth 187Os/
186Os would then be at least as great as the upper
range of carbonaceous chondrite values as re-
ported by Walker and Morgan [27], and not that
of the average value.
Alternatively, the equilibration of the mantle
with the newly formed core could have produced
R e / O s ratios in the mantle that were in excess of
the chondritic ratio if Os had a higher core/man-
tle partition coefficient than Re (based on Re
and Ir partitioning between silicate and Fe-sulfide
melts referenced in [32]). Conceivably, the lower-
most mantle could have maintained higher-than-
chondritic R e / O s due to early and ongoing equi-
librium with the core while the uppermost mantle
acquired relatively lower R e / O s ratios due to
extraction of the continental crust and, possibly,
to infall of siderophile element-rich planetary de-
bris, soon after the earth's formation [e.g., 7,33-
34]. Derivation of the OIB source materials from
great depths in the mantle could then produce
magmas whose 187Os//186Os ratios reflect time-in-
tegrated R e / O s ratios in excess of average car-
bonaceous chondritic values. However, the previ-
ous equilibrium of oceanic basalt magma sources
with the core is not readily compatible with the
relative abundances of chalcophile and sidero-
phile elements in MORB and OIB [35]. In addi-
tion, Re and Os partitioning between core and
mantle remains uncertain. Clearly, more Os iso-
topic data for MORB and OIB are necessary to
explore this possibility and those presented above.
OSMIUM ISOTOPIC COMPOSITIONS FROM OCEANIC BASALTS
4. Conclusions
187Os/186Os ratios of the OIB analyzed for this
study are close to (Iceland ankaramite) or slightly
higher than (samples from Loihi, Mauna Loa and
Reunion) the average value of carbonaceous
chondrites and are more radiogenic than most
peridotite values. These characteristics disallow
the end-member possibility that OIB sources are
dominated by ancient subducted oceanic crust.
The more radiogenic OIB may have contained
some quantity of high-Re/Os material in their
sources or may have been contaminated with
radiogenic material during ascent through the
oceanic lithosphere. However, the possibility re-
mains that the OIB sources, perhaps from the
lower mantle, have time-integrated R e / O s ratios
greater than average carbonaceous chondrites due
to a relatively high bulk silicate earth R e / O s or
due to early or ongoing equilibration of OIB
source mantle with the core.
Acknowledgements
Jean-Marc Luck introduced W.J.P. to the pro-
cedures for chemical separation and analysis of
osmium. Laurie Reisberg was all that one could
hope for in a friend and coworker with whom to
share the analytical, interpretational, and spiri-
tual difficulties of osmium in those pre-NTIMS
days. Many conversations with the always-inter-
ested David Graham about mantle and basalt
geochemistry were much appreciated. David, and
Vala Ragnarsdottir, also provided samples for the
study. Thanks to Alan Zindler and two other
EPSL reviewers for comments on the manuscript.
An N S F / C N R S postdoctoral exchange award to
W.J.P. partially supported the work. Finally, we
acknowledge the research and technical staff at
the IPGP for their abundant support and kind-
ness. Thanks for the memories.
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