r,

._, :.-~. ,~ tim CHEMICAL

GEOLOGY INCLUDING
ISOTOPE GEOSCIENCE
ELSEVIER Chemical Geology 139 (1997) 185-205

Rhenium abundances and systematics in oceanic basalts

Erik H. Hauri ~'*, Stanley R. Hart b
a Department of Terrestrial Magnetism, Carnegie Institution of Washington, 5241 Broad Branch Rd. NW, Washington, DC 20015, USA
b Department of Geology and Geophysics, Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA

Received 21 October 1996; accepted 8 January 1997

Abstract

We have examined the systematics of Re abundances in concert with new and published data on major and trace
elements in oceanic basalts. Re abundances in MORB average 927 ppt (parts per trillion), a factor of 2.6 higher than the OIB
average (350 ppt). The variability of Re abundances in both MORB and OIB is only 45%, similar to moderately
incompatible major and trace elements such as Ca, A1, and the heavy rare earths. The inferred mantle/melt partitioning
behavior of Re is similar to Yb, and average Re/Yb ratios in MORB, OIB, and the continental crust are within 50% of each
other. The Re/Yb ratios of the depleted mantle and continental crust are both lower than the primitive mantle.
The R e / Y b systematics place constraints on core-mantle exchange. The incorporation of material from the outer core
into mantle plumes, and isolation of the upper mantle from the core, would result in Re/Yb ratios in OIB elevated by factors
of 5-24 over MORB. Although the scatter of the Ol13 Re/Yb data may allow core addition up to the 1.2% level, the lack of
a correlation between R e / Y b and Os isotopes in OIB, and the small difference in average Re/Yb ratios of MORB and OIB
suggests an upper limit of 0.2 wt% core material in mantle plumes.
A mass balance calculation between continental crust, depleted mantle, and primitive mantle indicates that the crustal
abundance of Re is too low (by a factor of ten) to balance the Re depletion of the depleted MORB mantle (DMM). Anoxic
sediments and black shales are an important crustal reservoir for Re, but the estimated abundance of these rocks in the
continental crust cannot be increased substantially without upsetting the crustal U budget and ratios of Th/U, Nb/U, and
U / P b in the depleted mantle. The Re missing from DMM must therefore reside in recycled oceanic crust stored in the deep
mantle.
We propose that elevated Os isotope ratios in OIB are a direct measure of a ubiquitous component of recycled MORB
crust in mantle plumes./'he Re-Os mass balance allows a simple estimate of the total size of the OIB reservoirs to be made.
A mass of recycled MORB equivalent to 4.4% of the mantle is required to balance the Re depletion of DMM. The total mass
of the OIB reservoirs is estimated at 4.4% to 22% of the mantle mass, depending on whether the low-lSTOs/18SOs
component(s) in OIB sources are external or intrinsic, respectively. Using an estimate of the present-day plume flux, the
average residence time of subducted slabs in the convecting mantle is estimated at 700-3500 Ma; however, the slab
residence time scales linearly with the size of the OIB reservoir (and thus the proportion of recycled crust in mantle plumes).

* Correspondingauthor. E-mail: hauri@dtm.ciw.edu

0009-2541/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.

PII S0009-2541 (97)00035-1
186 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
We prefer a model in which individual mantle plumes incorporate slabs with distinct ages. Consideration of Os and He
isotope covariations in OIB suggest a model in which subducted slabs are recycled through the whole mantle on timescales
of < 1.8 Ga. © 1997 Elsevier Science B.V.
Keywords: mantle; geochemistry; isotopes; osmium; rhenium; basalt
1. Introduction
The potential of the 187Re-187Osisotopic system
for studying a wide range of Earth science problems
has long been recognized (e.g. All~gre and Luck,
1980; Palmer and Turekian, 1986; Hart and Kinloch,
1989; Hauri and Hart, 1993). Recent progress in
analytical technique development (Volkening et al.,
1991; Creaser et al., 1991; Shirey and Walker, 1995)
now allows 187Os/188Os ratios to be measured with
a precision and reproducibility (typically 0.1-1%)
which is many orders of magnitude smaller than the
range observed in terrestrial rock samples ( >
1000%). As a result, interest has been renewed in the
systematics of Os isotopes in various Earth reser-
voirs, but the geochemical behavior of Re and Os
during many geologic processes is often not well
understood.
This paper will focus on the behavior of Re in
two major processes which result in the large-scale
differentiation of the Earth: genesis and recycling of
mid-ocean ridge basalt, and continental crust forma-
tion. During partial melting of mantle peridotite and
low-pressure fractionation of basalt, it is generally
accepted that Os behaves as a compatible element
like Ni or Cr (Morgan, 1986; Martin et al., 1994;
Hart and Ravizza, 1996; Hauri et al., 1996). The
behavior of Re, however, is less well understood.
Experimental studies of Re and Os partitioning would
be extremely useful, and such work is in progress
(Righter et al., 1995). However, such studies are
made difficult by the variety of stable oxidation
states accessible by both elements, and by the volatil-
ity of both Re and Os in their most oxidized form.
The purpose of this paper is to provide a first-order
observational understanding for the distribution and
mass balance of Re in various Earth reservoirs. This
will be done by examining the Re abundance sys-
tematics in oceanic basalts relative to other well-un-
derstood lithophile trace elements, and inferring the
geochemical properties and distribution of Re in the
Earth. Although the current Re-Os database for
abundances and isotopic compositions is somewhat
sparse, we hope to provide a framework which can
be improved and expanded upon with the addition of
more data.
2. Re abundances in peridotites and oceanic lavas
In order to study the behavior of Re during mantle
melting, our first impulse was to look at Re abun-
dances in mantle peridotites. Morgan (1986) pre-
sented a careful analysis of the Re and Os abundance
systematics in mantle peridotites, and first showed
that the parallel depletion of Re, S, and incompatible
major elements (Ca, A1, Fe) in these rocks reflected
the incompatible behavior of Re during partial melt-
ing. Subsequent Re-Os studies on orogenic lherzo-
lites are consistent with this observation (Reisberg
and Lorand, 1995); Re is generally well correlated
with S abundances, resulting in a R e / S ratio with
limited variability except in the most Re-poor peri-
dotites (Fig. 1).
In our re-examination of the geochemical behav-
ior of Re, we had hoped to take advantage of the
substantial expansion of the Re-Os peridotite
database since the work of Morgan (1986). However,
most subsequent Re-Os peridotite studies have ex-
amined xenoliths from kimberlites, and Re contami-
nation of xenoliths by kimbedite magma is a recog-
nized problem (Walker et al., 1989; Pearson et al.,
1991, 1995). Because of this problem, we have
chosen instead to focus on Re abundances in oceanic
mantle-derived lavas, with the understanding that our
imperfect knowledge of the host phases and precise
partitioning behavior of Re will allow only first-order
inferences about the Re abundances of mantle
sources.
Our database consists of published abundance
data for Re and other elements in oceanic island
basalts (OIB) and mid-ocean ridge basalts (OIB)
 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
(Hertogen et al., 1980; Hauri and Hart, 1993; Reis-
berg et al., 1993; Martin et al., 1994; Roy-Barman
and All~gre, 1994, ]995; Marcantonio et al., 1995).
We have excluded from our analysis lavas with
< 4.6% MgO in order to filter out differentiated
samples which may have fractionated trace phases.
The Re abundance database contains a respectable
number of OIB samples with associated major and
selected trace element data (48 samples). Included in
the OIB data are new major and trace element data
for our OIB sample~s from the south Pacific Ocean
(Tables 1 and 2) which were the subject of a previ-
ous Re-Os study (Hauri and Hart, 1993). Major and
trace elements were determined by XRF and ICP-MS
at Washington State University, using established
methods (Norrish and Hutton, 1969; Doherty, 1989).
Replicate analyses of individual samples are typi-
cally better than 7-10%. Agreement with previously
published isotope dilution (ID) data for Sr and Nd
(Hauri and Hart, 1993) is generally better than 10%,
but is no better than 20-30% for Th, U, and Pb.
These data were obtained in four separate groups
over 15 months; differences between ID and ICP-MS
data were usually consistent within a group of sam-
ples, but tended to v~u'y between groups. As a result,
we consider the XRF and ICP-MS data accurate to
within 10% for most elements, but we have more
confidence in previously published ID data for Th, U
and Pb in these samples (Hauri and Hart, 1993).
300-
oo
2OO
&
100
|•
0 a
i~o 2~o
s ppm
Fig. I. Re abundances (in ])artsper trillion,pp0 against(A) S (ppm) and (B) Yb (ppm) in peridotitcxcnolithsand orogenic lhcrzolites.Data
from BVSP (19gl), Morg~ (1986) and Reisbcrg and Lorand (1995).
187
2.1. Rhenium in OIB
Re abundances in OIB vary from 100 to 642 ppt
(parts per trillion), with one outlier at 1590 ppt
(RAR-B-9 from Hauri and Hart, 1993). Excluding
this sample, the average OIB Re abundance is 350
ppt (___45%, lcr). A calculation was made to correct
for low-pressure olivine fractionation to a constant
Mg # of 0.73 by adding back equilibrium olivine
(using a F e / M g K D of 0.3) and assuming that Re is
highly incompatible in olivine. After applying this
olivine correction, the OIB average Re abundance is
256 ppt (___48%, lcr), but the standard deviation of
the data is unchanged. This correction does not result
in any improved correlations of Re with SiO 2 or
FeO, and so in the subsequent discussion we will use
the raw data.
Although a weak positive correlation exists be-
tween Re and CaO, as a group, OIB Re abundances
do not show strong correlations with any of the
major elements. At most individual islands, Re abun-
dances are similarly uncorrelated with other ele-
ments. However, tholeiites from Mauna Loa and
Haleakala show good positive correlations of Re
with SiO 2, TiO 2, A120 3, CaO, Na20, and K 2 0 and
negative correlations with MgO (Fig. 2). In the
Hawaiian lavas, olivine is clearly the only fractionat-
ing phase; thus the correlations observed at Hawaii
are broadly consistent with olivine control, and the
3OO
A B
20O
e,
100
. 0
~o ~o o12 o14 06
Yb (ppm)
Table 1
XRF major and trace element data for oceanic island basalts from the south Pacific Ocean
SAV-B-5 SAV-B-7 SAV-B-8 SAV-B- 15 TAA-B-7 TAA-B-26 RAR-B-9 RRT-B-21 RRT-B-30 TBA-B-3 TBA-B- 15 TBA-B- 16 TBA-B- 19 TBA-B-22 TBA-B-23 MGA-B-47
SiO 2 47.90 45.93 45.99 48.08 48.68 48.95 43.31 45.45 44.37 43.60 45.65 45.77 48.34 44.66 43.02 44.50
A1203 12.43 12.65 12.72 13.60 12.31 12.77 8.49 11.51 12.66 11.98 12.31 11.58 15.35 8.07 11.99 7.99
TiO 2 2.73 2.77 3.41 2.89 2.90 3.22 3.01 2.35 3.55 2.91 2.53 2.40 2.70 1.96 2.68 1.74
FeO * 11.97 11.25 10.38 10.57 10.72 10.94 12.70 13.16 13.01 12.74 12.34 12.41 12.65 11.74 12.67 12.86
MnO 0.17 0.16 0.17 0.15 0.16 0.15 0.16 0.19 0.20 0.21 0.21 0.20 0.20 0.19 0.22 0.19
CaO 9.40 9.43 10.54 8.41 9.65 9.12 13.57 11.95 9.76 12.47 12.11 12.32 11.19 12.77 11.03 10.65
MgO 12.70 1 3 . 2 7 12.12 10.47 11.93 10.73 16.85 12.53 11.17 11.87 10.75 11.72 6.43 18.93 12.41 20.67
K20 0.94 1.49 1.92 1.89 2.20 1.09 0.58 0.30 1.09 0.89 0.74 0.75 0.75 0.49 1.16 0.48 :l
Na20 2.61 2.81 3.34 3.38 2.20 3.53 1.01 1.66 3.66 3.18 2.40 2.16 2.89 1.22 4.50 1.68
P205 0.32 0.51 0.71 0.54 0.45 0.55 0.24 0.29 0.65 0.53 0.38 0.36 0.37 0.24 0.80 0.23
Total 101.16 100.27 101.29 99.98 101.20 101.05 99.92 99.38 100.12 100.38 99.42 99.67 100.87 100.27 100.48 100.98

Ni 335 328 252 273 317 250 343 271 271 220 186 198 51 500 272 574
Cr 537 502 481 359 567 451 761 556 375 409 574 731 54 1364 478 1499
Sc 26 21 23 22 26 21 42 45 27 32 35 41 26 39 17 38
V 248 228 287 244 237 230 297 337 277 265 297 291 286 273 213 211
Ba 204 372 473 404 439 541 182 117 290 328 244 223 186 247 489 108
Rb 24 35 48 51 44 - 11 5 20 19 18 22 18 14 30 11
Sr 382 572 706 562 583 717 472 361 764 670 482 429 422 444 1041 270
~o
Zr 161 214 261 260 281 346 142 135 238 242 176 165 171 123 257 112 t
t,o
Y 23 24 29 25 26 30 16 20 47 28 25 23 30 17 31 16
Nb 33.3 52 68 54 45 54 24.8 28.1 58 92 57 56 53 45 111 30
Ga 21 23 22 23 21 22 18 18 17 19 16 19 21 17 17 11
Cu 60 67 47 37 39 38 42 86 51 91 132 141 77 105 67 106
Zn 115 118 115 118 108 111 89 102 111 127 103 91 121 91 133 89
Table 2
ICP-MS trace element data for oceanic island basalts from the south Pacific Ocean
SAV-B-5 SAV-B-7 SAV-B-8 SAV-B- 15 TAA-B-7 TAA-B-26 RAR-B-9 RRT-B-21 RRT-B-30 TBA-B-3 TBA-B - 15 TBA-B- 16 TBA-B- 19 TBA-B-22 TBA-B-23 MGA-B-47
La 25.9 40.8 60.9 37.2 44.2 52.1 20.0 21.6 46.5 68.1 40.0 39.1 36.8 31.8 95.1 18.8 .rn
Ce 49.2 76.5 112 71.3 86.5 104 40.4 42.2 91.9 122 74.5 71.9 70.4 53.4 167 37.1
Pr 6.07 8.76 13.21 8.19 10.83 12.81 5.36 5.11 11.5 13.6 8.48 8.19 8.17 6.68 18.4 4.62
Nd 24.9 35.4 51.8 33.7 43.7 52.0 23.5 22.1 49.6 50.7 34.6 32.8 32.7 26.1 66.5 19.4
Sm 6.27 7.61 9.82 8.06 8.85 10.2 5.72 5.44 11.3 10.1 7.50 7.05 7.41 5.43 12.0 4.51
Eu 1.99 2.27 3.02 2.55 2.58 2.83 1.85 1.89 3.74 3.07 2.41 2.24 2.38 1.73 3.65 1.43
Gd 6.11 6.85 8.15 7.39 7.33 8.09 5.10 5.45 11.2 8.52 6.67 6.24 6.99 4.79 9.85 4.11
Tb 0.91 0.96 1.15 1.11 1.01 1.13 0.73 0.84 1.62 1.15 0.99 0.94 1.05 0.68 1.31 0.60
Dy 5.25 5.33 6.25 6.06 5.69 5.91 3.97 4.75 9.26 6.33 5.63 5.34 5.89 3.70 7.15 3.37
Ho 0.99 0.96 1.09 1.03 1.05 1.07 0.69 0.85 1.72 1.14 1.03 0.99 1.15 0.67 1.24 0.64
Er 2.48 2.34 2.50 2.40 2.51 2.61 1.57 2.09 4.32 2.71 2.52 2.48 2.98 1.64 2.94 1.61
Tm 0.31 0.29 0.31 0.29 0.32 0.33 0.18 0.25 0.52 0.34 0.32 0.32 0.38 0.21 0.36 0.20
Yb 1.71 1.66 1.84 1.66 1.81 1.89 1.03 1.49 2.92 1.88 1.93 1.84 2.32 1.20 2.03 1.21
Lu 0.24 0.24 0.25 0.22 0.27 0.28 0.15 0.21 0.44 0.27 0.28 0.27 0.34 0.17 0.27 0.17
Ba 251 399 504 406 500 556 223 118 264 375 238 216 214 278 506 131
Th 2.32 4.41 5.81 4.41 5.71 7.17 1.73 1.81 3.54 7.21 3.67 3.68 3.60 2.97 10.47 1.96
Nb 37.9 53.7 84.5 55.4 54.6 56.7 15.1 28.8 62.3 110 60.5 59.0 53.7 52.8 130 29.4
Y 25.7 25.7 31.7 25.9 27.8 28.6 18.1 20.9 50.8 29.5 25.5 24.0 29.9 18.5 34.7 16.3
I-If 4.22 5.11 6.42 6.54 7.78 8.87 2.71 3.52 5.85 6.35 4.70 4.31 4.32 3.17 5.89 2.85
Ta 2.21 3.22 4.31 3.70 2.95 3.31 0.96 1.72 3.65 5.68 3.57 3.44 3.04 2.59 6.04 1.64
U 0.44 1.21 1.09 1.13 1.21 1.59 0.39 0.58 1.00 1.66 1.01 0.92 0.87 0.64 2.27 0.52 b4

Pb 2.14 3.97 4.83 4.33 4.93 6.27 1.55 1.45 2.09 3.79 2.38 2.43 1.59 1.49 5.83 1.82
Rb 24.7 37.9 52.6 51.0 45.9 - 11.2 6.0 19.0 20.8 18.8 21.5 19.2 16.4 32.0 12.1
Cs 0.29 0.37 0.64 0.62 0.43 1.32 0.13 0.08 0.29 0.35 0.17 0.23 0.15 0.25 0.20 0.12
Sr 390 566 726 568 594 739 480 369 784 705 501 444 434 477 1046 281
190 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997) 185-205

trend of increasing Re with decreasing MgO sug- been affected by crustal contamination, Martin et al.,
gests that Re is highly incompatible in olivine. This 1994).
observation is consistent with the limited experimen-
tal Re partitioning data that exist (Righter et al., 2.2. Rhenium in MORB
1995). However deviations from the olivine control
lines may reflect variations in the Re abundances of The number of MORB samples with Re and
primitive Hawaiian magmas. Interestingly, the large major element data is quite small (twelve samples
differences in Re concentrations between tholeiites from Hertogen et al., 1980 and Roy-Barman and
from Mauna Loa and Haleakala (Fig. 2) probably All~gre, 1994), and only seven of these have any
indicate distinct Re abundances in primitive magmas associated trace element data (Hertogen et al., 1980),
from these two volcanoes. At a given MgO, the This group of MORBs has a fairly restricted range in
higher Re abundances in Mauna Loa tholeiites com- MgO (7.3-9.2%) with the exception of samples ARP
pared with Haleakala tholeiites are consistent with 73-10-3 (24.2% MgO), Midlante (15.6% MgO), and
the higher 187Os/188Os ratios of Manna Loa lavas CYP 74-31-35 (10.4% MgO) from Roy-Barman and
(Hauri et al., 1996) compared to those from Haleakala All~gre (1994). In order to compare these three
(excluding low-Os Haleakala samples which have samples in a reasonable manner to the remainder of

r~OO

[]
A

400 ¸

1OO - • . . . . . . . Itoo
10 12 14 16 8 9 10 11

A1203 (wt%) CaO(wt%)

t3
C

400'

t~

2OO'

tOO
18 20 t .0
~
,
1.2
.
1.4
,
1.6
- ,
1.8
- .
2.0
,
2.2
.
'2~1

2.4
11111

MsO (wt%) Yb (ppm)

Fig. 2. Re abundances in tholeiites from Manna Loa and Haleakala against (A) A1203, (B) CaO (wt%), (C) MgO (wt%), and (D) Yb (ppm).
Thin lines are olivine control lines; deviations from olivine control lines probably represent distinct mixing between parental magmas with
distinct Re abundances. Parental magmas from Mauna Loa appear to have more Re than those from Haleakala, consistent with higher Os
isotope ratios in Mauna Loa lavas (Hauri et al., 1996).
 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997) 185-205 191

the MORB data, we have corrected their composi-
tions to 8 wt% MgO by subtracting Foss olivine,
again with the assmnption that Re is perfectly in-
compatible in olivine. The fractionation-corrected Re
abundances for these three samples are within the
range of the other MORBs. The ranges of SiO 2,
A1203, FeO, CaO and Na20 abundances in these
MORBs cover about 60-70% of the global variabil-
ity of these elements in MORB (Klein and Lang-
muir, 1987). Because our 'Re-bearing' MORB data
set has an average MgO of 8.1 wt%, and the individ-
ual MORB compositions are already at or near sam-

Mid-Ocean Ridge Basalts

1600 • 16oo

1400
o• A B • 14oo

1200 @

, , . . , .
48 49 50 51 52 t4 15 1; 6
SiO2 (wt%) AI203 (wt%)
1600 1600

C D
1400

1200

1~ fi ~[ " 1] 6 1~ 14
FeO* (we/.) CaO (wt%)

E
100o

o.125 0.6o o.1~ ~1~ 0.145

lSTOs/lSSOs(leached)
Fig. 3. Correlations of Re in MORB with (A) SiO 2 (wt%), ({3) AI203 (wt%), (C) FeO * (wt%, all iron a s F e 2 + ) , (D) CaO (wt%), and (E)
Os isotope ratios. Based on the behavior of major elements during MORB genesis, the correlations of Re with SiO 2 and FeO suggest a
possible pressure effect on Re partitioning. The negative correlation of Re abundance with Os isotopes (E) is inconsistent with partial
melting of marie componems in the MORB source suggested by Roy-Barman and All~gre (1994).
192 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205

ration of olivine only (as estimated using the MELTS of the trends shown in Fig. 3. However, the correla-
program of Ghiorso and Sack, 1995), it is unlikely tion of Re abundance with Os isotopes in the MORB
that the major dement variability present in this data studied by Roy-Barman and All~gre (1994) would
set is a result of low-pressure crystal fractionation. paradoxically require the high-187Os/188Os pyroxen-
Rather, the major element variability is probably a ite component to yield magmas with low Re abun-
reflection of similar variability in primitive MORB dances (Fig. 3E). Although the origin of the trends in
magmas as discussed by Klein and Langrnuir (1987). Fig. 3 remains speculative, and the trends may not
Re abundances in these MORB range from 330 to hold up with more MORB data, these trends would
1470 ppt, and average 928 ppt ( + 37%, ltr), a factor seem to be most consistent with Re abundances
of 2.6 higher than the OIB average. There is little being influenced by a combination of source hetero-
overlap between the abundances of Re in MORB and geneity and variations in the mean pressure of partial
OIB, even if the two data sets are corrected to the melting within the spinel lherzolite stability field.
same MgO content or Mg #. This difference in the
Re abundances of MORB and OIB is clearly a
feature which is characteristic of primitive MORB 3. Distribution of rhenium during partial melting
and OIB magmas. Despite the small number of
MORB Re analyses, Re abundances are well corre- The approach that we take is to infer the geo-
lated with abundances of S i O 2 , A l 2 0 3 , FeO* and chemical behavior of Re by comparing Re abun-
CaO (Fig. 3). As discussed above, these trends can- dances to more well-understood lithophile trace ele-
not represent variable amounts of low-pressure frac- ments. The methods are identical to those of Hof-
tionation operating on a single parental magma com-
position. 100"
Inferences on the behavior of Re during MORB Abundances in Ocean Island Basalts h
genesis may be made in the context of the major
"~
o 8 0 "
element model of Klein and Langmuir (1987). The
lack of correlation between Re and Na20 would
seem to argue against control of Re abundances by
variable degrees of partial melting of a homogeneous
source. However, the positive trends of Re with CaO
20
and Al203 demonstrate that Re is incompatible dur-
ing MORB genesis, and that the Re abundance in
0 , • .... , -, -, -, -,-, -, -,., -, -,., , . , -. -, ..,
MORB is determined in part by the extent of partial N b Ba La K Ce Sr N d Zr SmNa Ti Y Yb Sc V C a Al Zn Fe Si

melting. However, the Re correlations with SiO 2 and

1000
FeO* would also seem to suggest a pressure effect, Re/X Ratios in Oceanic Island Basalts B
with low-Re samples apparently generated at lower
mean pressures (approx. 10 kbar from FeO-SiO 2
systematics) than high-Re samples (approx. 20 kbar).
This apparent increase of MORB Re abundances
with pressure is at odds with the low Re abundances
of OIB, which are generated at higher pressures than -d
MORB.
The MORB trends cannot be explained by mixing
of MORB magmas with OIB-type magmas having 10 . . - . - .
N b L a Ba C e K
. , - , , • , - . • , - . - . . . . , . , . , . . . , . ,
N d Z r S m S r T i Y N a ~tb 2 h S c .4.1 V S i F e C a

low Re, low S i O 2 , low Al203 and high FeO* (Fig.
3). Roy-Barman and All~gre (1994) have proposed
that high Os isotope ratios in MORB are due to
melting of a marie component (pyroxenite) in the
upper mantle, and this may be responsible for some
Denominator Element (e.g. Re/X)
Fig. 4. Standard deviations of OIB data for (A) trace element
abundances, and (B) trace element ratios involving Re. Ratios of
Re against slightly incompatible elements show the least variabil-
ity.
 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997) 185-205 193

mann and co-workers (1983, 1988), in which the
slope of the data trend on a plot of Re/X vs. X is
used to infer the partitioning of Re relative to
lithophile element X. All twelve MORB samples
with Re data have corresponding major element data,
and can be compared directly with the OIB data.
However, due to the limited amount of correspond-
ing trace element and Re data for MORB, our analy-
sis involving other trace elements will focus mainly
on the OIB data.
Following the approach of Hofmann (1988), Fig.
4A shows the standard deviations of the OIB abun-
dance data, including Re. Re shows a rather limited
variability in OIB (45%), similar to slightly incom-
patible elements such as the heavy-rare-earth ele-
ments (HREE), Y, A1, Fe, and Ca. Fig. 4B shows the
standard deviation of various trace element ratios
with Re in the numerator (e.g. Re/Yb, Re/CaO,
etc.). Re/CaO ratios show the least variability in
OIB, consistent with the weak positive correlation
between CaO and Re noted above. The limited vari-
ability in ratios of Re against the moderately incom-
patible major elements (A1, Ca, Fe) simply reflects
the generally limited variability of all of these ele-
ments in OIB. Re/Y, Re/TiO 2, and Re/Yb ratios
are only somewhat more variable than the
Re/major-element ratios.
Importantly, the absence of any systematic varia-
tion in ratios involving Re, major elements, Y, and
Yb (e.g. Re/Yb vs. Yb, Fig. 5) demonstrates that Re

I(]~00' 1000
A B
• oo U
,. o q~
I00~0' • oo
0 o 0 °
0 o
~o • b °°o° •
• oO 0
Re/K20 tom. v.e/~o
(pptlw~) noo (ppt/ppm)

100'

10 I0
,01 .'~ 1 10

K20 (wt~) qDpm)

I00 I0

C D
oo

0 0 0

O0
• o0 RelCr
Re/Sc io $ Q I (ppt/ppm)
(ppt/ppm) ,ee
• 0 O0 •oo
~o • o
$ •

O •

1 .I
1o ~ ~ ~ so isoo 2ooo
sc ~ m ) Cr (ppm)
Fig. 5. Ratios of Re (ppt) against (A) K20 (wt%), (B) Yb (ppm), (C) Sc (ppm), and (D) Cr (ppm) in MORB (open symbols) and OIB (solid
symbols). The negadve co~rrelations in (A) and (D) indicate that Re is clearly more compatible than K and more incompatible than Cr.
194 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
behaves as a moderately incompatible element dur-
ing the melting and differentiation processes that
produce OIB. For example, following the approach
of Hofmann and White (1983), the ratios Re/CaO,
Re/FeO, Re/AI203, and Re/Yb display no sys-
tematic behavior when plotted against a proxy for
the degree of melting (e.g. highly incompatible ele-
ments such as Rb or Nb). However, when Re is
ratioed against elements more incompatible than Sm
(e.g. R e / K 2 0 , Fig. 5A), clear trends emerge with
apparent degree of melting, the sense of which indi-
cate that Re is invariably more compatible than the
denominator element. As an additional constraint, we
note that the negative trend in the plot of R e / C r vs.
Cr in OIB (Fig. 5D) indicates that Re is more
incompatible than the moderately compatible Cr. A
more precise estimate of the relative partitioning
behavior of Re would require high-precision (e.g.
isotope dilution) data for the moderately incompati-
ble elements, which inherently show limited variabil-
ity. The result of this analysis is that Re appears to
behave as a moderately incompatible to slightly
compatible element in OIB, similar to such elements
as Ca, AI, and the HREE.
Although the data are much more limited, the
behavior of Re during MORB genesis appears to be
similar. The Re/Yb ratios of the MORB samples
studied by Hertogen et al. (1980) are also quite
limited (Fig. 5), as for OIB. For the MORB samples
studied by Roy-Barman and All~gre (1994), Re/Yb
ratios have been calculated by estimating Yb abun-
dances from the general correlation between Yb and
MgO observed in MORB; these estimated Re/Yb
ratios are within the range reported by Hertogen et
al. (1980). The average MORB R e / Y b (ppt/ppm) is
280; this value agrees well with the average Re/Yb
(275) for composite mid-ocean ridge gabbro samples
from ODP Hole 735B (J. Blusztajn and S.R. Hart,
unpublished data). The incompatible behavior of Re
in MORB noted above is consistent with the absolute
abundances of Re in MORB (avg. 927 ppt) com-
pared to fertile upper mantle peridotite (260 ppt,
Morgan, 1986). This last observation leads us to
conclude (albeit on the basis of limited MORB data)
that Re is also moderately incompatible during
MORB genesis.
From these observations in MORB and OIB, we
chose Yb as a reference incompatible lithophile trace
element which has a similar behavior to Re during
melting and differentiation of basalt. This choice is
dictated primarily by the abundance of Yb data for
the samples in our database and the generally good
precision of Yb analyses afforded by ICP-MS and
NAA techniques, rather than by the superiority of
correlations of Re with other HREE. In addition, the
use of major elements (e.g. Ca, AI, Fe) as reference
elements for Re is complicated by phase equilibrium
controls, rather than by simple partitioning relation-
ships. In short, the comparison of Re abundances
with other lithophile trace elements indicates that Re
behaves as a moderately incompatible element, simi-
lar to the HREE.
4. Which phases control rhenium partitioning?
4.1. The role of sulfide
Based on its high concentrations in magmatic
sulfide deposits, rhenium is generally considered to
be a chalcophile element. However, because the Re
contents of coexisting sulfide and silicate melts have
never been measured in natural samples, rhenium
partition coefficients between sulfide and silicate
melts must be inferred from experiments. Experi-
mental rhenium partitioning data in sulfur-bearing
systems have been reported by Jones and Drake
(1986), Agee (1993), and Jana and Walker (1995);
data for sulfur-free systems is presented by O'Neill
et al. (1995), Ohtani and Yurimoto (1996), and
Righter and Drake (1996). All of these studies have
been conducted outside the range of pressure, tem-
perature, and sulfur content relevant to basalt petro-
genesis, the only possible exception being the experi-
ment of Jones and Drake (1986) on metal-silicate
partitioning at sulfur-undersaturated conditions. In a
relative sense, the Re content of sulfide ores gener-
ally tends to be lower than the concentrations of the
platinum-group elements (PGEs). As an example,
Foster et al. (1996) report Re/Os ratios for mag-
matic sulfide ores which are systematically lower
than associated komatiites. By inference, Re is in-
ferred to be less chalcophilic than the PGEs, and this
inference is consistent with existing experimental
studies. However, a more precise estimate of the
partitioning of Re between sulfide and silicate melts
 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
is hampered by a lack of experimental data at the
P - T - X conditions pertaining to mantle melting and
melt differentiation.
Righter and Drake (1996) discuss a parameteriza-
tion of the existing iRe partitioning data which pre-
dicts Re partition coefficients between Fe-Ni-S liq-
uid and silicate mek, as a function of P (kbar), T
(Kelvin), fo2, sulfur content of the metal phase
(mole fraction), anti melt structure (nbo/t, non-
bridging oxygens di:vided by tetrahedrally coordi-
nated cations):
In D = 0.441(1n fo2) - 19300/T+ 8 1 . 6 P / T
-2.03(nbo/t) + 1 3 . 9 [ l n ( 1 - X s ) ] + 15.1
(1)
This parameterizafion shows that decreasing pres-
sure and increasing S and fo~ work to reduce the
partitioning of Re into a sulfur-bearing liquid metal
phase. However, the usefulness of Eq. 1 in describ-
ing Re partitioning between sulfide and silicate melts
is limited by the lack of moderate-pressure (e.g.
10-30 kbar) sulfur-hearing experimental data, and
by the validity of the expression under sulfur-
saturated conditions. Reasonable conditions relevant
to genesis of MORB and OIB are P - - 2 0 kbar,
T = 1623 K, nbo/t = 0.9, ln(fo ~) -- - 1 2 (log(fo2)
= -5.22, equivalen! to QFM buffer at this P and
T), and X s = 0.48 (equivalent to Fe-Ni sulfide melt
with 34 wt% S). Using these parameters, Eq. 1
predicts a surprisingly low sulfide-melt/silicate-melt
partition coefficient for Re of 0.34. Clearly, such a
low partition coeffic:ient for Re would indicate a
minor role for residual sulfide during partial melting.
Such a low partition coefficient for Re in sulfide
seemingly goes against conventional wisdom, espe-
cially considering the parallel depletions of Re and S
in peridotites with increasing degree of major ele-
ment depletion (Fig. 1). Clearly, low-pressure sul-
fide/silicate partitioning studies for Re would be
useful to confirm the validity of Eq. 1 under sulfur-
saturated conditions at pressures relevant to basalt
genesis, and thereby further illuminate the role of
sulfide in determining the Re concentrations of
basaltic magmas.
Some interesting observations can be made from
the positive correlation of Re and S in spinel peri-
dotites shown in Fig:. 1A. This trend indicates an
195
average R e / S of 0.99 (ppt/ppm); the standard devi-
ation of this ratio in peridotites is only 47%, the
lowest of any ratio involving Re and another trace
element. This strongly suggests that Re abundances
in peridotites are controlled by sulfide. If this trend is
extrapolated to a sulfur concentration of 34 wt%
(typical of monosulfide solid solution in peridotites),
a Re concentration of 0.4 ppm is inferred for sulfide
in peridotite. If we assume equilibrium between this
sulfide and a MORB melt with 927 ppt Re, a value
of 430 is inferred for the sulfide-melt/silicate-melt
partition coefficient for Re. If this value is multiplied
by the abundance of sulfide in fertile peridotite
(8.8)< 10 -4, assuming 300 ppm S in peridotite and
34 wt% S in sulfide), a value of 0.38 is calculated
for the bulk peridotite/melt partition coefficient for
Re. This value is similar to the bulk peridotite/melt
partition coefficient for Yb in spinel peridotite, an
observation which is in agreement with the limited
variability of Re/Yb in MORB.
4.2. The role of silicate phases
It is important to also infer the role of silicate
phases in determining Re partitioning. There exist
some notable similarities in the behavior of Re and
the HREE in MORB and OIB. For the peridotites
plotted in Fig. 1, the R e / S ratio shows the lowest
standard deviation (47%); the ratios with the next-
lowest standard deviations are Re/Sc (55%), R e / A l
(59%), and Re/Yb (61%). In oceanic basalts, Re
appears to be moderately incompatible or slightly
compatible during genesis of MORB and OIB, re-
spectively, similar to the HREE. Also like the HREE,
average Re abundances are higher in MORB than
OIB by a factor of 2.6; this is approximately the ratio
of average Yb abundances in MORB compared to
OIB, an effect which is readily attributed to the
presence of residual garnet during OIB genesis and
the reduced role of garnet during MORB genesis
(Hofmann et al., 1984; Salters and Hart, 1989).
On the basis of these observations, it is possible
that Re may be compatible in garnet, and that garnet
may play an important role in mantle/melt partition-
ing of Re, akin to its role in partitioning of the
HREE. Circumstantial evidence in support of this
suggestion is provided by the Re measurements of
196 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997)185-205
Roy-Barman et al. (1996) on a mafic layer from the
Lherz peridotite; these workers measured a Re abun-
dance in a garnet separate (12 ppb) which is much
higher than the whole rock (1.15 pb). The moder-
ately incompatible partitioning of Re between mantle
peridotite and basaltic melts, as illuminated by the
Re abundance systematics in MORB and OIB, may
be controlled entirely by garnet, or entirely by sul-
fide, or by some combination of the two. Unfortu-
nately, the observational and experimental data on
Re partitioning are sufficiently sparse as to allow all
of these possibilities.
5. Constraints on core-mantle exchange
Recently, Walker et al. (1996) have proposed that
entrainment of material from the outer core into
mantle plumes can explain two major features of Os
in OIB compared with MORB: their higher concen-
trations and higher isotopic compositions. Since crys-
tallization of the inner core has been claimed to
increase the R e / O s ratio of the outer core (Walker et
al., 1996), in theory the outer core could have a
radiogenic Os isotope signature which, when added
to typical mantle, results in elevated Os concentra-
tions and 18708//1880S ratios in plumes originating
from the core-mantle boundary.
In order to test further the possibility of core-
mantle interaction, we have made a simple calcula-
tion to estimate the composition of the bulk core, the
outer core, and mantle-outer core mixtures assuming
that the solid inner core formed by crystallization
from the bulk core early in Earth's history. The
elements Re, Os (along with the other PGEs), W,
Mo, Fe and Ni are likely the most sensitive tracers of
Table 3
Geochemical signatures of core-mantle mixing
Bulk C1 core Dsm/Im a Outer core (OC) b
Re (ppb) 291 15 164
Os (ppb) 3250 19 1629
Mo (ppb) 6180 2.7 5655
W (ppb) 618 36 200
Fe (wt%) 60 1 60
Ni (wt%) 20 1 20
a Partition coefficient between solid metal and sulfur-bearing liquid metal.
b Outer core after 5.5 wt% crystallization of solid metal to form the inner core.
this process, based on their measured and inferred
partitioning between silicates, solid metal, and sul-
fur-bearing liquid metal (Fleet et al., 1981; Brett,
1984; Schmitt et al., 1989; Jones and Walker, 1991;
Jones et al., 1993; Walker et al., 1996; Righter and
Drake, 1996).
A maximum concentration of highly siderophile
elements in the Earth's core can be estimated from
the calculation of Hart and Zindler (1986), which
involves (1) devolatilization of C1 chondrite (1.7 X
enrichment factor), and (2) concentration of the en-
tire chondritic budget of highly siderophile elements
into the Earth's core (3.1 × enrichment factor). This
results in a maximum enrichment factor of 5.27 for
highly siderophile elements in the Earth's core (the
mantle abundances having been established by the
'late veneer'). The resulting core composition is
given in Table 3, assuming a core composition of
60% Fe, 20% Ni, and 20% S. The abundances of Re
and Os and the R e / O s ratio in this model core are
very similar to those estimated by Walker et al.
(1996), who used the metal phase in chondrites as a
core analogue. To the extent that the Earth has been
constructed dominantly from chondrites (e.g. as op-
posed to iron meteorites), the estimates in Table 3
can be considered maximum estimates for the con-
centrations of Re, Os, Mo and W in the bulk core of
the Earth.
The composition of the outer core is then calcu-
lated after 5.5% fractional crystallization of solid
metal from the bulk C1 core using the partition
coefficients listed in Table 3. Finally, this outer core
composition is allowed to evolve its Os isotopic
composition for 4.55 Ga, after which it has
187Os/lS8Os = 0.1325. This outer core is then mixed
in various proportions with a primitive mantle com-
Primitive mantle (PM) PM + 0.1% OI2 PM + 0.6% OC PM + 4% OC
0.26 0.45 1.28 6.49
3.1 4.9 13.1 65
55 61 89 265
9.74 10 11 17
7.5 7.6 8.2 11.7
0.2 0.24 0.46 1.8
 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997)185-205
position estimated fi:om Hofmann (1988). We have
calculated three different mixing models which could
potentially account for three observations in plume-
derived basalts: (Model 1) the difference in Os iso-
topic compositions between the primitive upper man-
fie (187Os/188Os = 0.1268 (Luck and All~gre, 1992)
and the lower bound of mantle plumes (187Os/188Os
--0.1300); (Model 2) the composition of HIMU
basalts (Hauri and Hart, 1993), assuming an arbitrary
187Os/188Os = 0.150 for the outer core; and (Model
3) the difference in Os abundances between primi-
five plume basalts (600 ppt) and the highest Os
concentrations measured in MORB (30 ppt) (Roy-
Barman and All~gre, 1994).
The results of this calculation are shown in Table
3. Model 1 (PM + 0.12% OC) requires the addition
of 0.12 wt% core to the mantle to account for the Os
isotopic gap between DMM and plumes: This small
amount of core wouM result in significant changes in
the abundances of other siderophile elements com-
pared with normal mantle (e.g. Re ( + 73%) and Os
(+58%)). The 73% elevation in the mantle Re/Yb
ratio implied by this model would not be obscured in
derivative basalts due to partial melting effects.
Model 2 (PM + 0.65% OC) requires the addition of
0.65 wt% core to make the elevated Os isotope ratios
of the HIMU source, resulting in abundances of Re
and Os elevated by factors of 4-5 compared with
normal mantle, and substantially higher abundances
of Mo ( + 62%). A factor-of-5 increase in R e / Y b in
OIB over MORB would be clearly observed in this
case. Model 3 (PM-~ 4% OC) requires the addition
of 4 wt% outer core l:o account for the differences in
Os abundance betwe,en primitive OIB and MORB
magmas, which would result in extremely high abun-
dances of Re (+2500%), Mo (+480%) and W
(+175%) which would be clearly observed in
derivative lavas. Fe and Ni abundances are changed
by factors of 2-9 in core-mantle mixing Models 2
and 3 (Table 3).
The test of these models of core-mantle interac-
tion comes in comparing the abundances of W, Mo
and Re with lithophile elements of similar compati-
bility in the peridotite/silicate melt system (Newsom
et al., 1986; Sims et al., 1990; this study), since the
abundances of lithophile elements will be unaffected
by addition of core material. If this process is impor-
tant, ratios of W / B a , M o / C e and R e / Y b should be
197
1000
i ~..l 12% N
o 00%
(ppt/ppm) O~%J • ~i~6,,~e00.
0.~- I • ~ •
• o
I~ o~]. .'Tee~
Yb (ppm)
Fig. 6. Re/Yb (ppt/ppm) versus Yb (ppm) in MORB and OIB;
symbols as in Fig. 5. The Re/Yb ratio of both the depleted
MORB mantle (DMM) and continental crust (CC) are less than
the primitive mantle (PM); the budget of missing Re is likely
present as recycled crust in the mantle. Scale with tick marks
shows the effect on Re/Yb ratios of mixing metal from the
Earth's outer core into mantle plumes. The spread in Re/Yb in
OIB can be explained by < 1.2% core contribution; however,
there is no correlation of Re/Yb with Os isotopes which would be
expected from such a process (Walker et al., 1996). The similarity
of Re/Yb in MORB and OIB is consistent with isolation of both
the upper mantle and OIB source from the Earth's core.
systematically higher in plume-derived basalts than
MORB. W / B a is not particularly sensitive to core-
mantle interaction, becoming elevated outside the
observed range only for Model 3 (4 wt% core).
However, M o / C e and especially Re/Yb are quite
sensitive to this process. Addition of 0.65 wt% core
as in Model 2 would result in M o / C e and Re/Yb
ratios in plume basalts to be higher than MORB by
60% and 490%, respectively. Even as little as 0.1%
core material in mantle plumes would result in
Re/Yb ratios 73% higher in OIB than in MORB.
Such differences are outside of the observed data
(Newsom et al., 1986; Sims et al., 1990) (Fig. 6).
Although the magnitude of the scatter in the OIB
data could allow for up to 1.2% core material to
explain the highest OIB Re/Yb ratios (Fig. 6), there
is no correlation between R e / Y b and Os isotopes in
any subset of the OIB data; such a correlation is
predicted by the core interaction model of Walker et
al. (1996). Since MORB actually have somewhat
higher Re abundances and higher Re/Yb ratios than
198 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
OIB, the small difference between the average
Re/Yb ratio of MORB (sources presumably isolated
from the core) and the highest Re/Yb ratio in OIB
suggests an upper limit of 0.2 wt% core material in
mantle plumes; this estimate is in excellent agree-
ment with similar arguments based on T i / P d ratios
in peridotites and volcanic rocks (McDonough,
1997). The abundance systematics of Re in MORB
and OIB argue against significant exchange of mass
between the mantle and core. Thus addition of core
material is an unlikely explanation for the elevated
187Os//188Os ratios which are nearly ubiquitous in
OIB (Hauri and Hart, 1993; Reisberg et al., 1993;
Marcantonio et al., 1995; Roy-Barman and Allbgre,
1995).
6. Estimating the Re abundance of mantle sources
Mention should be made here of the effects of
partial melting on the Re/Yb ratio. For ratios of
highly incompatible elements such as Th/U, N b / U
and Ce/Pb in basalts, such ratios can be used reli-
ably as source indicators; this is because the degree
of melting is usually larger than the bulk partition
coefficients of these elements and they are largely
partitioned into the melt (Hofmann and White, 1982;
Newsom et al., 1986; Hofmann et al., 1986). How-
ever, such a magma-source relationship is much
more difficult to apply to the ratio of two moderately
incompatible elements such as Re and Yb. This is
partly due to the limited degree of variability of
moderately incompatible elements; precise data are
required to distinguish the relative incompatibility of
such elements. Another uncertainty is in identifying
the phases which control partitioning during melting.
If the partitioning of Re and Yb are controlled by
different phases (e.g. sulfide for Re and garnet + cpx
for Yb), Re and Yb may be fractionated from each
other even if their bulk partition coefficients (at the
onset of melting) are identical, due to the non-modal
contribution of different phases to the melt and
consequent changes in bulk partition coefficients with
increasing extents of melting. Given the uncertainty
in the partitioning behavior of rhenium, any melting
calculation would be speculative at best. It should be
repeated that our choice of Yb as a lithophile ana-
logue for Re is dictated partly by the availability of
published data for MORB and OIB, and it is possible
that more high-quality data for other HREE might
illuminate a better choice than Yb. However, it is
clear that the variations of Re in oceanic basalts
mimic those of the HREE, and thus it is possible to
make some first-order observations about the Re
abundances of MORB and OIB mantle sources using
the Re/Yb ratio and Re-Os isotope systematics.
It is well established that OIB have systematically
higher 187Os//188Os ratios than the abyssal peri-
dotites which are the end product of MORB genera-
tion (Martin, 1991; Hauri and Hart, 1993; Reisberg
et al., 1993; Snow and Reisberg, 1995). In light of
this observation, it is perhaps surprising that MORB
and OIB have very similar R e / Y b ratios (Fig. 6);
one might expect OIB to have higher R e / Y b than
MORB. However, because Re is only moderately
incompatible, melt generation and metasomatic pro-
cesses are largely incapable of producing selective
enrichment of Re over other incompatible trace ele-
ments. In fact, most highly alkaline lavas such as
lamproites and kimberlites have Re abundances and
Re/Yb ratios which are broadly similar to OIB and
MORB, while Re abundances and 187Os//188Os ra-
tios are uniformly low in peridotite xenoliths which
are highly metasomatized and demonstrably ancient
(Walker et al., 1989; Carlson and Irving, 1989;
Pearson et al., 1995; R.W. Carlson, pers. commun.,
1996).
The above observations demonstrate the difficulty
of producing large enrichments of Re over other
moderately incompatible elements during melting and
melt generation. Yet mantle reservoirs with high
187Os/188Os ratios do exist, requiring the existence
in the convecting mantle of regions with elevated
Re/Os ratios. Preferential depletion of Os (or en-
richment in 187Os) in these regions (e.g by core-
mantle interaction) is considered unlikely, because
such a process would not produce the correlated
variations of 187Os//188Os with other isotopes which
are common in OIB (Hauri and Hart, 1993; Marcan-
tonio et al., 1995; Hauri et al., 1996; Widom and
Shirey, 1996). Furthermore, these regions of the
mantle have 187Os/lSaOs ratios which are higher
than chondritic meteorites; thus the high-
187Os/188Os OIB reservoirs must be enriched in Re.
Magmas which produce oceanic and continental
crusts are the only widespread rock types which have
 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997) 185-205
the required high Re/Os ratios, and so the most
straightforward way of creating the high-
lS7Os/lSSOs OIB reservoirs is to mix these materials
(as partial melts or recycled crust) into the peridotitic
mantle.
There are two important aspects of this process
which should be highlighted. First, oceanic and con-
tinental crusts have high Re/Os due to low concen-
trations of the compatible Os; furthermore, because
Re is only moderately incompatible, the Re concen-
trations of crustal materials do not vary widely. As a
result, the R e / O s ratio of any crust-peridotite mix-
ture is a first-order measure of the crust/peridotite
ratio, since crust has little Os and peridotite has little
Re. Second, because Re is only moderately incom-
patible, Re is only mildly enriched in magmas com-
pared to their mantle sources. The important implica-
tion of these two observations is that the creation of
a high-187Os//188Os reservoir in the peridotitic man-
tie requires an admixture of partial melt or recycled
crust in substantial amounts, at least 10% (Hauri and
Hart, 1993; Reisberg et al., 1993; Hauri et al., 1996).
We stress that because Re is only moderately
incompatible, the resulting limited variations in ra-
tios of Re to HREE ~md major elements requires that
the addition of Re to a mantle source (in the form of
partial melt or recycled crust) must be accompanied
by a substantial mass of other elements, particularly
major elements. Correlated variations in lS7Os/18SOs
and major elements provide strong support for the
incorporation of recycled crustal material into OIB
sources (Hauri, 1996). In this context, it is not
surprising that OIB and MORB have very similar
R e / Y b ratios despite large variations in
187Os/mOs, particularly if the high lSTOs/188Os
ratios of OIB are due to the presence of large
amounts of recycled MORB in their mantle sources.
7. Mass balance of rhenium in the earth
With this first-order examination of Re abun-
dances in hand, it is instructive to calculate a mass
balance for Re in vmious Earth reservoirs. The mass
balance calculation is constrained mainly by the
Re-Os isotope systematics of Earth's reservoirs, but
independent estimates for the Yb abundances in these
same reservoirs provide a basis for calculating the
199
R e / Y b ratios of these reservoirs and comparing
them to R e / Y b ratios measured in derivative lavas.
The lSYOs/lSSOs ratio of the primitive upper
mantle (PUM) has been estimated at 0.1268 by Luck
and All~gre (1992), a result which is consistent with
the PUM Re and Os abundances of 260 ppt and 3100
ppt, respectively, as estimated by Morgan (1986).
Hart and Zindler (1986) estimate the PUM Yb abun-
dance at 0.414 ppm, resulting in a Re/Yb ratio of
627 (ppt/ppm) for PUM. Assuming a mean age for
the depleted MORB mantle (DMM) of 1.8 Ga, the
Re abundance of DMM can be estimated from the
average and most-depleted 187Os/lSSOs ratios for
abyssal peridotites (0.1246 and 0.1221, respectively)
(Martin, 1991; Roy-Barman and All~gre, 1994; Snow
and Reisberg, 1995). The resulting DMM Re abun-
dances are 177 ppt (average abyssal peridotite) and
122 ppt (most-depleted abyssal peridotite). Assuming
that DMM is 10% depleted in Yb (DMM-Yb = 0.373
ppm), the Re/Yb ratio of DMM is estimated to be in
the range of 327-475 (ppt/ppm). The DMM Re/Yb
estimate is consistent with the peridotite data (BVSP,
1981; Morgan, 1986), but is higher than the average
MORB value (280, ppt/ppm), suggesting some frac-
tionation of MORB Re/Yb from the source value
during partial melting. The Re/Yb of the continental
crust is similarly estimated at 200 (ppt/ppm) from
the crustal estimates of Esser (1991) (CC-Re = 400
ppt) and Rudnick and Fountain (1995) (CC-Yb = 2.0
ppm).
A feature of the data which is immediately appar-
ent is that the Re/Yb estimates for DMM and the
continental crust are not complementary; both would
appear to be lower than the primitive mantle value
(Fig. 6). This feature of the Re data was also noted
by Martin et al. (1991). Assuming that DMM makes
up 40-82% of the mass of the mantle (Hart and
Zindler, 1986), and if indeed DMM is depleted in Re
to the extent estimated from abyssal peridotites
(122-177 ppt), the amount of Re removed from
DMM is calculated to be 1.36 - 4.62 × 1017 g, which
amounts to 12-42% of the PUM inventory of Re.
This is surprisingly high given the moderately in-
compatible nature of Re.
As a preferred estimate, we use the Re abundance
of DMM implied by average abyssal peridotite (177
ppt) and a mass for DMM of 50% of the mantle to
calculate a DMM Re depletion of 1.7 × 1017 g.
200 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
Using Esser's (1991) crustal estimate of 400 ppt Re,
at first glance the continental crust would appear to
contain only 1.04 X 1016 g of Re, or less than 10%
of the PUM inventory. Thus, Esser's Re inventory of
continental crust appears to be insufficient (by at
least a factor of ten) to balance the Re depletion of
the upper mantle inferred from abyssal peridotites.
If the bulk silicate Earth formed with a homoge-
neous R e / O s distribution, and the Re depletion of
DMM is accurately represented by abyssal peri-
dotites, then it would appear that a reservoir with
high R e / Y b has not been accounted for. There are
two possibilities to account for this 'missing Re'.
Martin et al. (1991) attributed the missing Re to
subducted oceanic crust stored in the deep mantle.
This is an appealing possibility considering the ele-
vated Os isotope ratios of many mantle plumes (e.g.
Hauri and Hart, 1993). A second possibility is that
the crustal abundance of Re has been underesti-
mated.
8. Where is the missing rhenium?
8. I. Re and U in the continental crust
Let us first examine the Re systematics of the
continental crust. The analyses of Re in river sedi-
ments and glacial loess deposits reported by Esser
(1991) probably give an accurate estimate for the Re
abundance in the felsic portion of the upper conti-
nental crust. To the extent that the lower continental
crust is approximately basaltic (Rudnick and Foun-
tain, 1995), then its Re abundance is probably within
the factor-of-two range in the average Re abun-
dances of MORB, OIB, and upper continental crust.
However, an additional important crustal reservoir
has not been incorporated into the crustal Re esti-
mate, namely anoxic marine sediments and their
metamorphic equivalents, black shales. These rocks
are extremely enriched in Re (and also U); measured
Re abundances are in the range of 10-1000 ppb
(Vine and Tourtelot, 1970; Poplavko et al., 1978;
Ravizza and Turekian, 1989, 1992; Ravizza et al.,
1991), a factor of 10-2000 higher than oceanic
basalts and felsic continental crust.
It is instructive to consider more explicitly the
role of black shales in controlling the continental
crustal abundance of Re. Black shales and anoxic
sediments have a median Re abundance of 100 ppb,
and assuming a DMM mass of 40-82% of the
mantle, then 1.36 - 4.62 × 1024 g of these rocks are
required to balance the DMM Re depletion. This
would translate into a crustal abundance for anoxic
sediments and black shales of 5-18% by weight, and
a crustal Re abundance of 5.2-17.8 ppm. However,
black shales and anoxic sediments are also notable
for their very high concentrations of U; with a
median black shale/anoxic sediment value of 30
ppm for U (Vine and Tourtelot, 1970), a crustal
abundance of 6.5 wt% (1.69 X 1024 g) of these rocks
would contain 5.07 X 1019 g of U, or 62% of the
PUM inventory of U. The crustal U abundance
estimated in this way (3.27 ppm) is more than a
factor of two higher than previous estimates, and as
such it is probably wrong. Such a high crustal abun-
dance of U would violate many geochemical and
heat flow constraints. For example, the K / U , N b / U ,
and U / P b ratios of the depleted mantle would need
to be shifted by more than a factor of two, in clear
violation of the trace element and isotope data for
MORB. In addition, such a crustal U estimate would
suggest that very little U remains in the mantle to
drive convection, and that crustal heat flow estimates
are low by approximately a factor of two. As a
result, it is likely that the 'missing Re' is located not
in the continental crust, but is stored in the Earth's
mantle.
8.2. Recycled oceanic crust and the mass of the OIB
reservoirs
The location of the budget of rhenium missing
from the upper mantle has potentially important im-
plications for the style of convection in the Earth's
interior, and the residence time of recycled litho-
spheric slabs in the convecting mantle. Our intention
here is to propose a basic model for the total size of
the OIB reservoirs and a corresponding average slab
residence time, with the hope that future investiga-
tions will result in further constraints on these issues.
The storage of Re in the deep mantle, in the form
of recycled oceanic crust, was first proposed by
Martin et al. (1991). This scenario is appealing, as it
 E.H. Hauri, S.R. Hart~ChemicalGeology139 (1997) 185-205
is consistent with the high 187Os//188Os ratiOS of
OIB. Extrapolating the present mean rate of subduc-
tion, the total mass of oceanic crust subducted over
4.5 Ga is approximately ten times the mass of the
continental crust, or 2,6 × 10 26 g. If this mass of
crust were to remain stored in the deep mantle and
not mixed back into DMM, then it would need a
mean Re concentration of 650 ppt to balance the Re
depletion of DMM. This is well within the range of
typical MORB.
We agree with the assessment of Martin et al.
(1991) that the Re depletion of DMM is balanced by
subducted oceanic crust. Furthermore, we propose
that the high lS7Os/18SOs ratios of OIB are a ubiqui-
tous feature of mantle plumes, and that Os isotopes
are a direct reflection of the presence of recycled
oceanic crust in plumes (see also Hauri and Hart,
1993). With the exception of lavas which carry
lithospheric mantle xenoliths (Widom and Shirey,
1996), there are very few OIB which have
187Os/laSOs as low as DMM (0.1247) or PUM
(0.1268). Thus, the most straightforward mechanism
for creating elevated 187Os//188Os in the convecting
mantle is by addition of recycled oceanic crust. Such
a mechanism suggests separation of the oceanic crust
from its residual lithospheric mantle, lithologic
preservation of the crustal portion of the lithospheric
slab (Hauri, 1996), o:r a preferential incorporation of
recycled MORB crust in mantle plumes. In addition
to Os isotope constraints, the recycled oceanic crust
model has substantial support from the systematics
of Pb isotopes and major elements in OIB (Hofmann
and White, 1982; Hauri and Hart, 1993; Hauri, 1996).
The combination of the Os isotope signatures of
OIB, the depletion of Re in DMM, and the storage of
this Re in recycled oc,eanic crust allow us to estimate
the size of the OIB reservoir in a simple manner.
First, let us assume that the recycled crustal compo-
nents of the OIB reservoirs have a Re abundance
identical to the MORB average (927 ppt). The Re
depletion of DMM (:l.7 X 1017 g of Re) indicates a
total mass of 1.8 X 10 26 g for the recycled crustal
components. The recycled crustal component thus
calculated amounts to 4.4% of the mantle mass, and
implies that at least: 22-44% of the mantle has
melted to produce this crust (assuming 10-20% par-
tial melting); the mass of the depleted mantle (40-
82%) estimated by Zindler and Hart (1986) is more
201
than sufficient to account for the required mass of
recycled oceanic crust.
With a recycled oceanic crust mass estimate in
hand, there are two ways to estimate the total size of
the OIB reservoirs, which differ depending on the
nature of the low-187Os/188Os component(s) in
mantle plumes. If the low-187Os/188Os component(s)
in OIB are attributed to the upper mantle (Roy-Bar-
man and All~gre, 1994) a n d / o r the lower mantle
(Hauri et al., 1996), then the total mass of the OIB
reservoirs is simply the mass of recycled oceanic
crust estimated above (1.8 × 10 26 g, 4.4% of mantle).
The 'external' choice for the IOW-187Os//188Os com-
ponent(s) requires a physical separation of the recy-
cled oceanic crust from its residual mantle litho-
sphere during convection.
If the low-187Os/188Os component(s) in OIB are
assumed to be intrinsic to OIB sources (e.g. if the
oceanic crust and mantle lithosphere remain physi-
cally coherent), then another estimate emerges as
follows. The highest 187Os//188Os ratios recorded
from individual hotspots (excluding crustally con-
taminated samples) average around 0.145; according
to the mixing model of Hauri et al. (1996), this
amount of radiogenic 187Os requires a minimum of
20% crust with a Re abundance of 927 ppt. Thus, if
mantle plumes contain on average 20% recycled
oceanic crust, the mass of the OIB reservoir is
estimated at 9 X 1026 g (22% of the mantle). Thus
we obtain estimates of the total size of the OIB
sources ranging from 1.8 to 9 × 1026 g (4.4% to
22% of the mantle mass).
8.3. Residence time of slabs in the convecting mantle
By taking the OIB source mass estimates and
dividing by the present plume mass flux of 2.56 X
1017 g / y r (Sleep, 1990), the average residence time
of recycled crust in the mantle is estimated at 700-
3500 million years. If the average plume flux over
the age of the Earth is higher than at present, as
seems likely, then the slab residence time is reduced
by a corresponding amount. The slab residence times
thus estimated can be compared to the 0.6-1.4 Ga
residence times estimated for plume material in the
upper mantle (Galer and O'Nions, 1985; Kellogg and
Wasserburg, 1990; White, 1993; O'Nions and Tol-
stikhin, 1994; Porcelli and Wasserburg, 1995). To
202 E.H. Hauri, S.R. Hart/Chemical Geology 139 (1997) 185-205
the extent that residence time is a measure of the
vigor of convection, the 700-Ma estimate implies a
convective regime similar to that estimated for the
upper mantle, while the 3500-Ma estimate might
reflect a more sluggish convective regime, perhaps in
the lower mantle.
The choice of a short (700 Ma) or long (3500 Ma)
average residence time for slabs depends fundamen-
tally on the origin of the IOW-187Os//188Os compo-
nent(s) in plumes (external or intrinsic, respectively),
and does not depend at all on the choice of upper or
lower mantle for the low-187Os/188Os component in
OIB. Conversely, the choice of layered or whole-
mantle convection depends strongly on whether the
low-187Os/188Os component in OIB is upper mantle
or lower mantle material. In our view, it is likely that
a range of slab residence times is reflected in the
Re-Os systematics of individual mantle plumes. As
an example, the Pb-Pb age of the recycled crustal
component in lavas from the HIMU islands of Tubuai
and Mangala was estimated at 1800 Ma by Hauri
and Hart (1993), which would correspond directly to
the residence time of this particular slab in the
convecting mantle. Although we have proposed that
such recycled crustal material is present in all plumes
which exhibit high 187Os/188Os, we would expect
slab residence times to be different for different
mantle plumes. In this context, the tendency of the
low-187Os/188Os component(s) in plumes to exhibit
high 3 H e / 4 H e ratios (Hauri et al., 1994, 1996; the
FOZO component of Hart et al., 1992), in our opin-
ion, favors an 'external' origin for the low-
187Os/188Os component(s) in plumes, namely the
lower mantle. This choice favors a whole-mantle
convective regime which allows transport of slabs
into the lower mantle, and their subsequent entrain-
ment in mantle plumes, on timescales of 700-1800
million years.
9. Conclusions
Rhenium abundances in oceanic basalts show lim-
ited variability, and indicate that Re behaves as a
slightly incompatible element during partial melting
and low-pressure differentiation. Based on a limited
data set, Re appears to show a mantle/melt parti-
tioning behavior similar to HREE such as Yb. Aver-
age R e / Y b ratios in MORB, OIB, and the continen-
tal crust are within 50% of each other. However, the
moderately incompatible nature of Re and Yb make
the R e / Y b ratio strongly susceptible to fractionation
during partial melting, and thus the R e / Y b ratios of
mantle-derived magmas are a poor measure of their
source ratio.
A Re mass balance calculation between the conti-
nental crust, depleted mantle, and primitive mantle
indicates that the estimated Re abundance of the
continental crust (Esser, 1991) is too low by a factor
of ten to balance the Re depletion of DMM. In the
continental crust, Re is strongly concentrated into
anoxic marine sediments and black shales, but the
abundance of these rocks in the crust cannot be
increased without seriously disturbing the crustal U
abundance. Thus, this 'missing Re' is likely present
in recycled ocean crust which is stored in the Earth's
deep interior. Based on the depletion of Re in the
depleted mantle, the mass of currently stored recy-
cled oceanic crust is estimated at 4.4% of the mantle
mass.
We propose that elevated Os isotope ratios in OIB
are a direct measure of the presence of a ubiquitous
component of recycled MORB crust in mantle
plumes. The OIB sources are estimated to make up
4.4-22% of the mantle mass, depending on whether
the low-187Os/188Os component(s) in OIB sources
are external or intrinsic, respectively. Assuming a
reasonable plume flux (Sleep, 1990), the average
residence time of lithospheric slabs in the OIB reser-
voirs is thus estimated at 700-3500 Ma. We propose
that the average slab residence time is within the
shorter half of this range, with the upper bound
constrained by the oldest apparent Pb-Pb ages in
mantle plumes (1800 Ma for HIMU plumes).
The abundance systematics of Re in oceanic
basalts suggests minimal exchange of mass between
the mantle and core. Incorporation of metallic core
material into mantle plumes would result in R e / Y b
ratios in OIB enhanced by a factor of 5-24 over
those in MORB. The similarity in R e / Y b ratios in
MORB and OIB is inconsistent with the incorpora-
tion of core metal into mantle plumes and isolation
of the upper mantle from the core. The amount of
core material in mantle plumes must be less than 0.2
wt% in order to be consistent with the Re data in
oceanic basalts.
 E.H. Hauri, S.R. Hart~Chemical Geology 139 (1997) 185-205
Acknowledgements,
This paper has t,een inspired by the originality,
creativeness, wit, and good nature of the 1997 Gold-
schmidt medalist, AI Hofmann. Thanks to Kevin
Righter, Alberto Saul, and Jurek Blusztajn for dis-
cussions on unpublished partitioning and abundance
data on rhenium. "[he paper was improved by re-
views from Laurie Reisberg and two anonymous
reviewers. This work was supported by NSF grants
EAR 9315698 to EHH and EAR 9219958 to SRH.
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