Geochimica et Cosmochimica Acta, Vol. 60, No. 10, pp.

1739-1749, 1996
Copyright 0 1996 Else&x Science Ltd
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Constraints on the origin of the oxidation state of mantle overlying

subduction zones: An example from Simcoe, Washington, USA
ALAN D. BRANDON’ and DAVID S. DRAPER’
nent of Terrestrial Magnetism, Carnegie Institution of Washington, 5241 Broad Branch Road NW, Washington, DC 20015, USA
*School of Earth Sciences, Macquarie University, Sydney, NSW 2109, Australia

(Received October 2, 1995; accepted in revised form February 8, 1996)

Abstract-Type I spine1 peridotite xenoliths from Simcoe Volcano, southern Washington (USA), are
from lithospheric mantle approximately 65 km inboard from the axis of the subduction-related Cascade
Range. Oxygen fugacities calculated from contents of Fe’+/CFe in Simcoe spinels, determined by
Mossbauer spectroscopy, are up to 1.4 log units more oxidizing than the FMQ buffer. These are among
the most oxidized mantle xenoliths reported, with fugacities substantially higher than those calculated
for mantle beneath most of western North America. These results, together with those from amphibole-
bearing spine1 peridotites from Ichinomegata, Japan (Wood and Virgo, 1989), provide evidence that
the mantle above subduction zones is more oxidized than is oceanic or ancient cratonic mantle. We
suggest that oxidation was accomplished by an agent ranging in composition from solute-rich hydrous
fluid to water-bearing silicate melt. A qualitative model relating extent of oxidation, duration of the
oxidation process, and proportion of the available water (derived from subducting slabs) that oxidizes
Fe in subarc mantle peridotite, suggests that such an agent can easily produce the observed extents of
oxidation over timescales similar to the typical lifespans of subduction zones. For the Cascade arc with
a duration of 50 Ma, the observed oxidation in the Simcoe peridotites can be achieved by reacting about
6- 11% of the available water with the mantle. These results demonstrate that water can make an efficient
oxidizing agent, and because of the comparatively low ferric iron contents reported for mantle peridotites
from other tectonic settings, oxidation of the mantle by water is mostly restricted to subduction zones
where water is recycled from the surface and transferred into the mantle wedge.

1. INTRODUCTION
The origin of variation in the oxidation state of the Earth’s
mantle is under considerable debate (e.g., Ballhaus, 1993).
Oxidation is manifested in peridotite primarily by the ratio
of Fe?+ to Fe’+ in the mineral phases present. Ferric iron is
strongly partitioned into spinel, such that in spine1 facies
rocks, this mineral is (on a grain for grain basis) the primary
carrier of newly oxidized Fe (Wood and Virgo, 1989; Ball-
haus, 1993). Ferric iron also partitions into melt in equilib-
rium with peridotite (Menzies, 1990), and removal of melts
from more fertile mantle rocks should deplete them in ferric
iron, in turn resulting in a shift to lower calculated oxygen
fugacities (Arculus, 1994). The resultant melts can also
serve as oxidizing agents during magma-mantle interaction
(Menzies, 1990; Ballhaus, 1993).
Fluids may also serve as metasomatic and oxidizing-re-
ducing agents. Dehydration of subducted lithosphere is
thought to liberate hydrous fluid into the overlying mantle
(e.g., Peacock, 1990; Davies and Stevenson, 1992; Arculus,
1994; Ulmer and Trommsdorff, 1995). Convincing geo-
chemical evidence for the role of hydrous fluid in the source
regions of arc magmas includes, for example, the relatively
large contents of B, “Be (Tera et al., 1986; Morris et al.,
1990; You et al., 1994), H,O (Sisson and Layne, 1993;
Baker et al., 1994), and ferric iron (Arculus, 1994) in sub-
duction-related lavas. Slab-derived fluid interacting with arc
mantle should impart to it a distinctive chemical imprint.
One such signature could be a relatively high oxygen fugac-
ity (f0,) in arc mantle, which would result from upward
migration of slab-derived, water-rich fluid, either in isolation
or as part of a basaltic arc magma (Wood and Virgo, 1989;
Wood et al., 1990; Ionov and Wood, 1992; Davies and Ste-
venson, 1992; Stolper and Newman, 1994). Many perido-
tites from regions of past subduction in fact reflect some of
the highest fO,s estimated (Wood and Virgo, 1989; Ionov
and Wood, 1992). Of the many mantle peridotite suites that
have been studied, only the hydrous lherzolite xenoliths from
Ichinomegata, Japan, described by Wood and Virgo (1989),
are from a region of present-day subduction.
We have undertaken a study of Type I peridotite xenoliths
(i.e., Cr-diopside bearing, Frey and Prinz, 1978)) from Lo-
rena Butte, a monogenetic alkaline cinder cone on the flanks
of the Simcoe shield volcano, Washington (USA), located
65 km east of the axis of the modem Cascade arc (Fig. 1;
Draper, 1992). These xenoliths are samples of lithospheric
mantle that has been above an active arc for at least the
past 50 Ma. The xenoliths are primarily refractory spine1
harzburgite with minor websterite, but show evidence for
metasomatism such as the presence of phlogopite (Draper,
1992) and trace element enrichments in clinopyroxene
(Brandon et al., 1995). Because of the loss of ferric iron
during melting, these refractory peridotites could reflect
lower oxygen fugacities (e.g., Bryndzia and Wood, 1990;
Arculus 1994) relative to more fertile peridotites in western
North America, unless an oxidizing metasomatic agent af-
fected these rocks after melting. In order to address these
questions, we report Mossbauer spectroscopic data on spi-

1739
1740 A. D. Brandon and D. S. Draper

wt% Cr spine]), and one (Sim-8) is an olivine-spine1 websterite (68

wt% clinopyroxene, 24 wt% orthopyroxene, 4 wt% olivine, 4 wt%
Cr-poor spinel). One of the harzburgites (Sim-1 ) contains rare
phlogopite. Presumably, the harzburgites represent the mantle wall-
rock beneath Simcoe, whereas the websterites must have some other
origin, for example as cumulates from crystallization of a basaltic
magma, or as pods or veins that are not representative of the bulk
of the mantle in the region. The samples show little sign of alteration.
Textures are largely granular, with little evidence of brittle deforma-
tion, although olivine in most samples is mildly kink-banded. The
xenoliths range in overall size from 3 to > 10 cm in longest dimen-
sion. Additional details of different samples from the same locality
OREGON are given in Draper ( 1992).

2.2. Preparation and Techniques

FIG. 1. Location map of Simcoe shield volcano relative to the Spinels analyzed by MGssbauer spectroscopy were taken from the
Cascade Range, including composite volcanoes Mt. Adams and Mt. interiors of the xenoliths (i.e., l-2 cm inward from the contacts
St. Helens. The present-day location of the Juan de Fuca trench is with the host lava shell). These grains are typically nearly pristine
also shown. (Fig. 2a), in contrast with spine1 near contacts with the host lava
(Fig. 2b). Many of the latter have symplectic rinds ranging in thick-
ness from 20-80 pm. The samples were crushed in a ceramic alu-
mina jaw crusher, and 50- to loo-mesh size spine1 grain fragments
nels (and some coexisting silicates) from these peridotites were concentrated using magnetic separation. The spine1 concentrate
and electron microprobe data on the spinels and coexisting was purified by handpicking under a microscope, resulting in 100-
150 milligrams of better than 99.9% pure spinel, with no visual
minerals. The Simcoe Type I peridotite samples are only the evidence of other mineral grains. The grains were leached in treat-
second from a region of modern subduction for which such ments of dilute HF and HCl to remove surficial alteration. The same
an approach has been taken. Using these data, we calculate techniques were used to prepare separates of silicate phases from
fO,s of the mantle beneath Simcoe. two samples.
Electron microprobe analyses were obtained with Macquarie Uni-
We also test whether water makes an efficient oxidizing versity’s 5 spectrometer Cameca SX-50 operating at 15 keV acceler-
agent in the mantle source for arc magmas, as earlier pro- ating voltage with a 40” takeoff angle. The instrument is calibrated
posed (e.g., Ballhaus, 1993; Arculus, 1994 and references using standards of natural and synthetic materials. Mineral phases
therein). To do this, we calculate the amount of water re- were analyzed with a 20 nA beam, and counts were collected for
quired to cause the observed oxidation shifts in the Simcoe 15 seconds on peak and 8 seconds on both background positions;
for minor elements, counts were collected for 30 seconds on peak
harzburgites, integrate over the volume of a model mantle and 15 seconds on each background position. At least five separate
wedge, and compare these values to published estimates of spots on each phase in each sample were analyzed. The count data
water flux into the mantle via subduction. Such modelling were reduced with PAP techniques. We calculated modal abun-
constrains the timescale for the observed oxidation shifts dances of phases in the samples by least-squares mass balance, with
analytical uncertainties propagated with the algorithm of AlbarCde
over a large volume of mantle that may be affected by fluid
and Provost (1977) (using M. B. Baker’s Simplex3 computer pro-
dehydration. Our model results show the general relationship gram) and using the linear algebra formulation described in Draper
between the extent of oxidation, the duration of the oxidation and Johnston ( 1992).
process, and, assuming water is the oxidizing agent, the pro- At present, reliable pressures cannot be calculated for spine1 facies
portion of the available water that interacts with and oxidizes peridotites. Accordingly, we chose a pressure of 1.5 GPa for the
calculations below because this pressure is roughly in the middle of
Fe in subarc peridotite. From these results, we suggest that the spine1 peridotite stability field, and facilitates comparison with
timescales on the order of 20-50 Ma are required to produce calculatedfOZs reported by other workers (Wood and Virgo, 1989;
the oxidation signatures recorded by the Simcoe peridotites Canil et al., 1990; and Ionov and Wood, 1992). If pressure differed
if the amount of water that reacts corresponds to only 6% by 20.5 GPa, calculatedfO,s would change by only 20.2 log units;
the effect of increasing pressure is to reducefO,s at a given tempera-
to 11% of the total amount subducted yearly. Given that the ture. The difference is, in any case, within uncertainty (see below),
typical longevity of subduction zones ranges from 20-100 and so would not obscure the oxidation signal.
Ma (Table 2.1 of Gill, 1981), we conclude that such a We calculate temperatures for the oxygen fugacity estimates be-
mechanism is a viable way to cause large-scale oxygen fu- low using four geothermometers (Table 2). The choice of thermom-
gacity heterogeneity in the mantle. eter is not critical because errors in temperature estimates as large
as 100°C result in errors info, of only 0.1-0.2 log units. With the
exception of the olivine-spine1 geothermometer (Sack and Ghiorso,
2. SAMPLES, PREPARATION, AND TECHNIQUES 1991) the temperatures are within ?5O”C, and range from -880 to
2.1. Samples 970°C for the sample suite (for the Brey and KGhler, 1990, pyroxene
thermometer). The effect of this variation on oxygen fugacity calcu-
Eight fresh xenoliths retrieved from the alkaline host lava erupted lations is within the errors cited below (Table 2). Temperatures
at Lorena Butte were selected for detailed study. These include Cr- calculated using the Sack and Ghiorso (1991) thermometer show a
diopside bearing spine1 harzburgites and websterites (Table 1) Six wide variation from -680-1100°C (with one near-host-lava rim
of the samples (Sim-1, -2, -3, -9c, 12, and -24) are spine1 harzburg- yielding lSOO”C), but are systematically lower by lOO-200°C using
ites (61-75 wt% olivine, 20-35 wt% orthopyroxene, 2.5-4 wt% the interior spine1 data, typical of olivine-spine1 thermometers in
clinopyroxene, 0.7- 1.5 wt% Cr-spine]; modes calculated from com- general compared with two-pyroxene formulations. Even such low
positional data by mass balance, see below). One sample (Sim- 10) is calculated temperatures do not shift calculated oxygen fugacities
a spine1 websterite (64 wt% clinopyroxene, 35 wt% orthopyroxene, 1 outside of the cited errors.
 Oxidation state of the mantle over subduction zones 1741

Table 1. Whole rock major element and weight percent mineral abundances
for Simcoe spine1 peridotites.

__...____...._______-....-- Hmurgi&y ..- _______._______...______ _-___ W&St&e ___..

Sample1 Sim-2 Sim-3 Sim-9c Sim-12 Sim-24 Sim-8 Sim-10
-- -.__--..-.
so2 44.3s 43.50 44.19 43.97 46.7 1 50.91 52.88
Ti@ 0.00 0.0 1 0.02 0.04 0.01 0.10 0.14
AL203 1.30 1 .os 1.45 1.27 1.32 6.36 4.93
FeO* 7.66 7.84 1.67 7.70 7.59 5.23 4.86
Eg 45.51
0.13 46.51
0.12 45.32
0.13 45.94
0.12 43.25
0.13 22.07
0.13 22.05
0.14

cao 1.02 0.89 1.10 0.90 0.91 14.78 14.65

NqO
Total 492494499EE%
99.99 99.96 99.97 2%
M& 91.4 91.4 91.3 91.4 91.0 88.3 89.0

mode in wt.% 3
011v1ne 68.62(2.23) 74.92(2.36) 71.51(1.40) 72.3K2.38) 6lSOQ..20) 4.13(2.12) ---
orthoovroxene 26.54f2.56) 20.98C2.571 23.0111.40) 23.O6C2.65) 35.4OC2.60) 23.7lC3.5 II 34.77C2.95)
clino&oxene 3.48(o.i2j 3.oo(O.12) 3.98(‘0.1 i j 3.06(b.llj 2.5(d.20j 68.Olil.43j 64.30(1.03)
spine1 1.35(0.19) l.CW(O.18) 1.50(0.12) 1.56(0.20) 0.7qo.20) 4.16(0.35) 0.93(0.36)

I. Major element analysis by XRF at Washington State University following

techniques reported by Brando” (1989) and references therein.
2. Mg# is the molar [Mgl(Mg + Fe)]*100 ratio.
3.. The modal abundance in weight percent is calculated using least squares
regression using whole rock major element abundances and mineral
compositions reported in this table and Table Z&3. Standard deviation at
the la uncertainty is reported in parentheses after each value.

3. RESULTS the websteritic rocks is Fo~~-~~, orthopyroxene is Ens*, and

3.1. Mineral Compositions
Table 2 lists average major element compositions of cores
and rims of spinels in the Simcoe samples. Table 3 lists
averaged compositions of Simcoe olivines and pyroxenes.
3.1.1. Harzburgites
In the harzburgites, Cr numbers (defined as molar (Cr/
(Cr + Al) * 100)) of spine1 in the xenolith interiors (Fig.
2a) range from 32-37, typical of so-called depleted perido-
tites. These spinels have core-to-rim variations in Cr number
always 51, and this zoning has virtually no effect on the
oxygen fugacities calculated below. At xenolith margins,
within 1 cm of contact with the host lava, symplectic rinds
(outer -50 pm) of spine1 (Fig. 2b) have compositions very
different from those of the interior spinels, with an increase
in Cr number and lower Mg# (Table 2). Olivines and ortho-
pyroxenes have a narrow range in composition from
Fo90-93 and En90, respectively. Clinopyroxenes also have
fairly uniform compositions of Wo47En49Fs4 and have 0.8-
0.9 wt% Cr203 (Table 3). With the exception of the rims
of spine1 near the contacts with the host lava, zoning in
harzburgite minerals is very slight. Amongst the silicate
phases, only clinopyroxene has measurable core-to-rim vari-
ations, with slightly less magnesian cores than rims (50.5
mol% En component).
3.1.2. Websterites
Spine1 Cr number is - 13 in Sim-8, the olivine websterite,
and 30 for Sim-10, the olivine-free websterite. The rims of
spinels near contacts with the host lavas show increases in
Cr number, in similar fashion to the harzburgites. Olivine in
clinopyroxene is Woq7Em7Fs6, with 1.3 wt% Cr203 in clino-
pyroxene in Sim-10.
We used these data to calculate the mass-balance wt%
modes given in Section 2.1. Propagated analytical uncertain-
ties (Albarede and Provost, 1977) are listed in Table 1. We
initially performed these calculations including a vector for
the spine1 rim compositions as separate phases and found
that insignificantly small amounts are required to satisfy the
mass balance (many of these calculations in fact failed,
yielding noninvertible phase composition matrices). In addi-
tion, without exception the rims of analyzed spinels are very
thin. Compositional differences arise only in the outermost
few percent of the grains’ cross sectional areas. Accordingly,
we are confident that the composition of pristine, xenolith-
interior spine1 cores accurately reflect the major processes
to which the samples were subjected.
Table 2 also gives Fe3+/CFe in spinels and pyroxenes
(from two samples) as determined by Mossbauer spectros-
copy using the procedures of Wood and Virgo ( 1989)) where
complete details of analysis procedures can be found. There
is only a weak correlation between spine1 Cr number and
Fe3+/XFe. Harzburgite spinels having Cr numbers of 32-
34 have Fe3+/CFe ranging from 0.25-0.35, and those with
Cr numbers of 34-37 have Fe3+/ZFe from 0.33-0.45. Spi-
nels in the websterites have the highest Fe3+/CFe, with val-
ues of 0.72 and 0.84. Olivines from two Simcoe samples
from which silicate phases were analyzed by Mossbauer
yielded measurable ferric iron contents (Fe3+/CFe = 0.02
and 0.04). However, in light of the care taken by Canil et
al. ( 1994) to measure ferric iron in mantle olivine, and their
conclusion that olivine could not accommodate Fe3+ in quan-
tities measurable by Mbssbauer, we conclude that these re-
sults are spurious and likely arise from microinclusions in
I142 A. D. Brandon and D. S. Draper
FIG. 2. Backscattered SEM photomicrographs showing textural
features of Simcoe spinels. (a) Typical pristine spine1 grain from
xenolith interior. Other grains are orthopyroxene. Sim-24; long di-
mension of photograph is approximately 1120 pm. (b) Spine1 grain
in contact with host lava. Note pronounced symplectic rind; finer-
grained material surrounding spine1 grains is host lava. Sim- 1; long
dimension of photograph approximately 320 pm.
the olivines. Accordingly we do not incorporate the olivine
results in subsequent modelling and discussion. Additional
microprobe and MGssbauer data for the minerals are avail-
able from the authors upon request.
3.2. Calculation of Oxygen Fugacity
Oxygen barometry for spine1 peridotites is based on the
equilibrium
2Fe304 + 3Fe2SiZ06 = 6Fe2Si204 + OZ. (1)
Spl”d orthopyroxene “llVl”t.
Because the magnetite component in spine1 is very small,
large errors can result for oxygen fugacities calculated from
electron microprobe analyses. Fe’+/CFe ratios can be mea-
sured in spine1 with uncertainties of <lo% by Miissbauer
spectroscopy (Wood and Virgo, 1989) and we felt it was
important to use this technique on the Simcoe samples. Com-
bining these data with standard electron microprobe analyses
allows calculation of oxygen fugacities for the bulk rocks
with uncertainties of 20.4-0.5 log units, using reasonable
estimates of the activities of Fe3+ and oxygen (see Wood
and Virgo, 1989; Wood, 1991; Ionov and Wood, 1992 for
details). Resulting fO,s (Table 2) are reported relative to
f0, for the fayalite-magnetite-quartz (FMQ) buffer (using
the buffer equation of O’Neill, 1987) at the temperature and
pressure in question and are denoted AFMQ. All AFMQ
calculations used compositions of cores of spinels from the
xenolith interiors.
The calculated AFMQs for the Simcoe samples range
from +0.3 to + 1.4 (from here on we cite AFMQs calculated
using the Brey and KGhler ( 1990) temperatures unless other-
wise specified). We summarize these calculations in Fig. 3,
which plots oxygen fugacity against temperature, using the
Brey and Kiihler (1990) thermometer. Although not shown,
plots using the other three thermometers also display similar
trends above FMQ. These systematic oxygen fugacity rela-
tionships suggest that a common process (or combination of
processes) has acted to produce them.
4. DISCUSSION
4.1. Are Simcoe AFMQs Primary or Secondary
Features?
It is unlikely that the Simcoe host lava imparted the oxi-
dized signature on the xenoliths (with the exception of rims
of some spine1 in Sim-9c), although ferric iron contents of
lavas at Simcoe (data from Draper, 1992) reflect AFMQs
ranging from 1.6-5.0 (calculated with the oxybarometer of
Kilinc et al., 1983; T = 1175°C). Peridotite xenoliths can
survive in their hosts for no longer than a few tens of hours
before being dismembered and consumed (Scarfe and Brear-
ley, 1987)) and this is too short a time for the mineral phases
in the peridotite to reequilibrate or react, at least in the interi-
ors of the xenoliths where our analyzed spinels were located.
If, instead, Simcoe harzburgite is closely related to the source
material for the host lava, then the host flow may have inher-
ited its oxidized signature from its source (e.g., Carmichael,
1991) via a process like that outlined by Ballhaus ( 1993).
Accordingly, we conclude that the calculated AFMQs accu-
rately reflect the oxidation state of the mantle beneath
Simcoe. This may, of course, be due to the passage of oxi-
dized magmas through the mantle, which should result in a
shift towards higher f0, (see below).
The AFMQs for the Simcoe samples are among the high-
est reported and differ markedly from those for Type I spine1
peridotites from other localities in western North America
(Fig. 4). The latter have average AFMQs that are slightly
negative ( -0.22 to -0.39), about 1.2-1.4 log units less
oxidized than those for the Simcoe samples, and are not from
regions of present-day subduction. The only other peridotite
samples so far reported from a modem arc on which M&s-
bauer spectroscopy has been used to measure Fe3+/ZFe ra-
tios in spine1 (Ichinomegata, Japan, Wood and Virgo, 1989)
also have calculated AFMQs that plot towards the high-fOz
end of the mantle spectrum (Fig. 4), and similar results are
found in other studies currently underway (Parkinson, pers.
commun., 1995). Abyssal peridotites, which most likely rep-
resent upper-mantle source regions for depleted MORB mag-
 Oxidation state of the mantle over subduction zones 1743

Table 2. Compositional data of Simcoe spinels, calculated temperatures, and oxygen fugacities.

SlOZ 0.07(02) O.ZO(2.5) O.OS(Ol) 0.07(02) 0.01X03) O.lO(OO) 0.07(01) 0.13(05) 0.05(02) O.OG(O2) 0.09 O.OY(Ol) 0.85(63) 0.05(02) O.OG(Ol)
Ti02 0.39(07) 0.59(13) O.Ol(Ol) 0.04(01) 0.05(02) 0.42(04) O.lC+J) 1.71(18) 0.16(02) 0.07(02) 0.10 0.04(02) 0.26(13) 0.191031 0.49(02)
AL203 41.52(27) 31.72(214) 38.24(28) 26.09(87) 38.19(31) 31.23(14) 40.24(30) 25.34(289) 35.52(84) 38.14(70) 38.45 55.05(42) 45.89(292)40.23(1101 35.04(591
FeO* 12.45(22) 13.16(74) 14.63(51) 14.52(46) 14.24(08) 14.17(10) 12.87(05) 20.21(169) 15.24(61) 13.21(81) 9.96 14.05(20) 8.27(323) 15.56(69) 12.85(1261
M&’ 18.33(16) 16.65(42) 17.50(15) 15.79(34) 17.77(26) 16.73(03) 18.50(12) 13.72(171) 17.10(27) 18.19(60) 20.66 18.33(57) 22.53(157) 15.99(57) 17.56(66)
NIO 0.24(05) 0X(08) 0.27(02) 0.14(01) 0.31(01) 0.17(03) 0.29(00) 0.19(02) 0,24(04) 0.29(05) 0.27 0.45(02) O.ZO(lO) 0.33(021 0.17(05)
Cr203 2!iu3a36.5911601~~z994L16137.58120)28.09112)37.66(254)39.60145)~ 3QLs liiJ.wamw32.80178)
Total 99.32(231 99.071691 99.37(291 98.85(71) 100.56(50)100.39(45)100.21(251 98.97(99) 98.91(27) 99.47(60) 100.16 100.20(68) 99.30(931 98.5X401 98.96(791

(Cr/Cr+Al) 33.5 43.6 33.5 66.1 34.5 44.7 31.9 49.9 36.6 34.2 34.8 12.9 23.8 30.4 38.6
Fe3+/EFe2 0.35 0.44 0.38 0.27 0.33 0.39 0.84 0.72

TOCW3 753 807 759 881 792 835 831 7 40 774 835 1500 686 680 752 1084
AFMQ4 0.89 1.47 0.87 0.44 1.19 1.00 1.32 1.52
T oCwens 968 949 953 995 937 1009 97s 968
AFMQ 0.69 1.32 0.74 0.31 1.08 0.87 0.82 1.32
T ‘CKreQ 935 932 921 962 918 972 902 874
aFMQ 0.72 1.33 0.76 0.33 1.09 0.90 0.92 1.40
T ‘CBKN 928 900 897 956 888 969 915 909
AFMQ 0.72 1.35 0.78 0.33 1.11 0.90 0.91 1.37

1. Interior- spin& from the interiors of the xenollth which were selected for Mossbauer spectroscopy. MargIn - symplectlc rims of splnels from the
margins of the xenollths In contact with the host lava.

2. Fe3+/ZFe ratios for spinels were obtalned by M&,sbauer spectroscopy at University of Bristol (B.J. Wood analyst) following the methods of Wood and
Virgo (1989). Uncertaintles in these ratios are about ~.OOS.

3. T 1s the temperature calculated using ollvlne-spine1 (Ts&G, Sack and Ghlorso, 1991) and pyroxenes (Tw~]]s. Wells, 1977: T&en. Kretz, 1983; and TBKN,
Brey and KOhler, 1990), wlth P - 1.5 GPa. The uncertainties are typically 20 to 50%.

4. AFMQls calculated using the Nell-Wood oxybarometer, following Ionov and Wood (1991) and references therein, defined as log R& (sample) - m2 (FMQ
buffer at P, TL using the buffer equadon of O’Nelll(1987). Uncertalntles in relative fD2 are about a.4 to 0.5 log units.

Table 3. Averaged major element abundances for Simcoe olivine,

orthopyroxene, and clinopyroxene.

Sample ~&,.J~&g&~sim;24f&.&J~

SiO2 40.87(38) 41.02(26) 41.13(20) 41.04(13) 41.01(41) 40.94(30) 40.46(30) 40.22(10)

FeO* 8.95(23) Q.tHl(l4) Q.lq20) 9.12(17) 8.88(20) 8.78(18) 12.68(48) 11.61(15)
MnO 0.15(M) 0.13(04) 0.14(M) 0.13(02) 0.13(04) 0.12@4) 0.21(04) 0.18(04)
MsO 49.89(46j 5O.l7(3Oj 50.01(24) 49.73(24) 50.23(36) 49.78(60) 47 OP(44) 47.99(27)
NiO 9.4001L4aLa61~~~0.390~0.240
Total 100.26(84)100.72(47) 100.85(42)100.43(39) 100.68(72)100.01(86)100.83(63) 100.24(29)
Fa 0.091 0.091 0.093 0.093 0.090 0.090 0.131 0.119

OrlhoDIlorene
S107 56.10(19) 56.34134) 56.42(20\ 56.21(241 56.23(30) 56.15(19) 54.88167) 54.69(23)
TiO; o.i7ii7j o.olYol) 0.03ti2j o.o3&2j o.o6(03j o.o3(03j 0.04(02) 0.06(03)
AI203 2.88(11) 2.61(05) 2.62@6) 2.97(1 I) 2.63(09) 2.77(1 I) 4.01(23) 4.19(14)
FeO’ 5.77(20) 5X2(13) 5.87(16) 5.88(12) 5.82(14) 5.61(11) 8.00(23) 8.07(16)
MnO 0.12iO2j 0.12(03) 0.12(03) 0.13(04) 0.13(03) 0.1 l(O4) O.lB(OZ) 0.17(04)
MS0 34.12(21~ 34.07131) 34.37(211 33.93(201 34.36(26) 34.22(17) 32.0%42) 32.01(14)
CF2O3 0.45io9j 0.44io3j 0.47iosj 0.43io6j 0.47io4j 0.48(07j 0.37iosj 0.78~1 I)
cao 0.72om0.7W08)-m9.79(13)mD.70(06)
Total 100.33(58)100.09(62) 100.60(36)100.28(38) 100.34(51)100.16(29)100.29(49) 100.67(31)
FS 0.085 0.086 0.086 0.087 0.086 0.083 0.121 0.122
Eli 0.902 0.901 0.901 0.899 0.902 0.902 0.864 0.864
Fe’+/EFe’ 0.14 0.13

Clinonvroxene
SiO2 52.89(37) 53.44(28) 53.37(34) 53.00(28) 53.16(40) 53.40(38) 51.89(38) 51.47(25)
Ti02 0.48(08) 0.02(01) 0.04(02) O.lO(O3) 0.14(02) 0.04(02) 0. I3(03) 0.22(03)
Al701 3.49(13) 3.00113) 2.82(08) 3.33123) 3.04(071 2.92(1 I) 4.43(33) 4.60(14)
Fe& - 2.52iI3j 2.60;]0; 2.52&; 2.68;15; 2.64;l I; 2.54;20) 3.55(12) 3.51(1 I)
MIIO 0.07(03) 0.07(03) 0.06(14) 0.06(03) 0.07(05) 0.07(04) 0.1 l(O3) O.OP(O4)
w 16.83(32) 16.85(20) 17.09(17) 16.91(14) 16.80(14) 17.45(36) 16.12(35) 15.73(23)
Cr203 0.76(11) 0.79(14) 0.82(10) 0.77(11) O.Pl(O8) O.Sl(lS) 0.62(12) 1.31(13)
cao 22.40(54) 22.50(21) 22.93(16) 22.14(55) 22.47(18) 22.55(47) 22.55(32) 22.42(23)
Na20 9.67(14)_az2Lau9.48(02)~~~~0.52(031
Total 100.11(23)99.99(38) 100.13(42)99.62(37) 99.90(25) 100.19(50)99.85(37) 99.87(35)
FS 0.041 0.042 0.040 0.044 0.042 0.041 0.058 0.058
En 0.490 0.489 0.488 0.493 0.486 0.497 0.470 0.465
Fe’+/ZF e 0.28 0.27

1. F&+/ZFe ratios obtained by Mijssbauer spectroscopy.

 A. D. Brandon and D. S. Draper

Thermometer

o”n”“‘n’a’d~
-1.2 -0.8 -0.4 0.0 0.4 0.8 1.2
n .’2.0
1.6
AFMQ
700 750 800 850 900 950 1000 1050 1100
FIG. 5. AFMQ variation (uncertainty 0.6 log units) with Cr num-
TOC ber in spinels from Simcoe, southwestern USA, and British Colum-
bia, with data sources as in Fig. 4. These results are consistent with
FIG. 3. Calculated logfOZ vs. temperature for the Simcoe perido-
an interpretation that oxygen fugacity is independent of melting
tites using the Brey and KShler ( 1990) geothermometer. Also shown processes that affect silicate phases.
are the magnetite-hematite (M-H), fayalite-magnetite-quartz (FMQ),
and carbon-carbon monoxide (CCO) buffers. Note that all of the
data plot above FMQ, indicating the oxidized nature of the mantle
represented by these samples.
Wood, 1992) and suggest a distinctive high-f0, association
with mantle at subduction zones.
Melting processes do not appear to be the primary control
mas (Ballhaus, 1993), have maximum AFMQs of +OS. In onf02 of the Simcoe peridotites. Chromium number in spi-
addition, back-arc basalts and arc lavas record higher oxygen nel increases with increasing degree of melting (Dick and
fugacities than do lavas found in other tectonic settings (Fig. Bullen, 1984). For Simcoe peridotites, as well as those from
4; Ballhaus, 1993). These correlations support the notion elsewhere in western North America, no strict correlation
that high oxygen fugacity is imparted on the overlying man- between the Cr number in spine1 and f0, is observed (Fig.
tle during subduction (e.g., Wood et al., 1990; Ionov and 5). This conclusion was also reached by Ionov and Wood
(1992) for samples from central Asia. However, Ballhaus
( 1993) reasoned that oxidation state of asthenospheric melts
is in fact fundamentally dependent on the depth of magma
generation and degree of melting. These effects may not be
apparent owing to overprinting by post-melting processes,
IBack-arc Basalts including metasomatism, which appears to be the case for
Arc Lavas 7 1 western North American samples. If, as suggested by Arcu-
Archean-Cratoni C lus ( 1994)) the generation of comparatively ferric-rich mag-
Mantle mas results in local reduction of the source regions, then the
I observation that the Simcoe samples are in fact quite oxi-
2.5 -2 -1.5 -1 -0.5 0 0.5 1 1.5 2 2.
dized would seem to require that a metasomatic process
W. N. America and Arc Mantle
Simcoe, Avg. = 0.98 f 0.30
subsequent to melting acted to produce the observed oxida-
Southwest USA, Avg. = -0.39 f 0.36 tion.
0 British Columbia, Avg. = -0.22 f 0.40
q Ichmomegata, Japan, Avg. = 0.76 f 0.33
s- 4.2. Role of Fluids and Melts in Subarc Mantle
%‘ou, Oxygen Fugacity
$10
52 4.2.1. Free $uid phase
$2 5
z The most obvious reason for highfO* in modem subarc
0 -1
-2.5 -2 -1.5 -1 -0.5 0 0.5 1 1.5 2 2. 5 peridotites is recycling of water-rich fluid through subduc-
AFMQ tion zones (Wood et al., 1990; Arculus, 1994). In contrast,
it would seem that water-poor fluids may have played a role
FIG. 4. Histogram of AFMQ for peridotites in the western North
America and Ichinomegata, Japan (Wood and Virgo, 1989; Canil et in less oxidized peridotites (with negative AFMQ) from
al., 1990). Also shown are ranges for abyssal peridotites, back-arc other localities in western North America. For example, at
basalts, arc lavas, and Archean cratonic mantle (Wood and Virgo, 1.5 GPa within the spine1 facies in the mantle, oxygen buff-
1989; Ionov and Wood, 1992; Ballhaus, 1993; and references ering by a water-poor, COz-rich fluid results in AFMQ at
therein). The modem arc peridotites, Simcoe and Ichinomegata,
record the highest oxygen fugacities. Simcoe has both higher average or below the CC0 buffer, i.e., graphite saturation is required
and maximum AFMQ than does mantle beneath either southwestern (Ballhaus, 1993; Canil et al., 1994). Such a fluid cannot
North America or British Columbia. produce the observed oxidation in the Simcoe suite, which
 Oxidation state of the mantle over subduction zones
recordsfOls at least two orders of magnitude more oxidizing
than CCO.
It is a commonly-held view that slab-liberated volatiles
infiltrate the mantle wedge. Some workers maintain that this
material will migrate as a free fluid phase as a reaction front,
and such a fluid could be an effective oxidizing agent. Fluids
derived from subducting slabs appear to be dominated by
H20 over CO* by about a factor of 10 (Peacock, 1990).
Stolper and Newman (1994) calculated similar proportions
of HZ0 and COZ in their water-rich component in basaltic
magmas from the Mariana trough. They proposed that this
water-rich component was derived by dehydration of a sub-
ducting slab and subsequently equilibrated with peridotite.
Recent experimental results (Schmidt and Poli, 1994;
Pawley and Holloway, 1993; J. Holloway and K. Domenik,
pers. commun. 1993) suggest that such hydrous phases as
lawsonite and/or zoisite are stable to much greater depth
than previously thought. In a typical subducted slab assem-
blage, lawsonite ( lo- 11 wt% H20) could easily accommo-
date all the HZ0 produced from dehydration of amphibole
(2 wt% HzO), even if the assemblage contained up to 50%
amphibole but as little as 10% lawsonite. Water could be
transported to depths such that its ultimate release would be
beneath the arc front, or even beneath the backarc (Pawley
and Holloway, 1993; Pawley, 1994). Further, dehydration
of serpentine residing in the ultramafic layer of subducted
crust occurs at 150-200 kilometer depths (Ulmer and
Trommsdorff, 1995). The breakdown of antigorite to pro-
duce forsterite plus enstatite results in 13 wt% liberated H,O,
which can then migrate upwards into the overlying mantle
wedge. Liberated water from the dehydration of serpentine
and amphibole-lawsonite should be available to cause partial
melting and/or oxidation in the overlying mantle wedge.
4.22. Silicate melts
Many workers argue that slab-liberated water will induce
partial melting, producing mafic melts with OS- 1 wt% H,O
(e.g., Stolper and Newman, 1994; and references therein),
and in some cases up to 6 wt% HZ0 (Baker et al., 1994).
The relatively oxidizing conditions reflected by mafic arc
and back-arc lavas (Fig. 4) suggests a connection between
relatively highfO*, magmatic water contents, and ferric iron
( Arculus, 1994). Passage of these oxidized magmas through
subarc mantle should produce an oxidation signature similar
to that observed in the Simcoe suite. For example, the Ball-
haus (1993) model suggests that basaltic lavas are on the
order of two log units more oxidized than their mantle
sources. This situation is similar to that for Simcoe; the host
basaltic lavas and xenoliths reflect fO,s that are different by
about two log units (see above).
Another possible silicate-melt oxidizing agent is that rep-
resented by more silicic, alkaline, aluminous glass, very poor
in MgO and FeO, found in many of the Simcoe samples in
small amounts (<l-2 wt%; Draper, 1992). The composi-
tions of these glasses are similar to those reported from other
xenolith localities worldwide, and Draper ( 1992) argued that
the most likely interpretation for their origin was that they
represented a metasomatic silicate liquid. Recently, Schiano
1745
and coworkers (Schiano and Clocchiatti, 1994; Schiano et
al., 1994, 1995) have identified virtually identical composi-
tions in glasses found as melt inclusions in minerals in a
wide range of mantle xenoliths including those from volcanic
arcs. Although the Simcoe glasses yield microprobe totals
between 97- lOO%, the presence of volatiles is strongly indi-
cated by the presence, in some glass-bearing veinlets, of
voids that clearly were once vapor bubbles. Thus the glasses
appear to have lost any dissolved volatiles during degassing
upon eruption of the xenolith-bearing host lava. In addition,
two semiquantitative determinations of La content in the
glasses (by electron microprobe with 100 nA beam current
and 30 min. counting times) show that there is at least 100
ppm La in the glass (sample WSX-8 of Draper, 1992). Thus,
they have many features that have been proposed for subarc
metasomatic silicate liquids with large light rare earth ele-
ment contents (e.g., Schiano et al., 1995). Further, clinopy-
roxenes from the Simcoe harzburgites have very low Sm/
Nd ratios consistent with enrichment via such silicate liquids
(Brandon et al., 1995). At present, however, we lack the
information to assess whether this liquid could act as an
oxidizing as well as metasomatizing agent. Full details of
experiments designed to constrain their origins will be given
elsewhere (D. S. Draper and T. H. Green, unpubl. data),
but preliminary results indicate that such liquids can (under
anhydrous conditions) coexist with typical mantle minerals
despite their unusual compositions (Draper and Green,
1994).
4.2.3. Carbonate-rich melts
Carbonate breaks down rapidly via decarbonation reac-
tions such as do1 + opx = 01 + cpx + CO*. Thus, carbonate
minerals present at depth are only rarely preserved in mantle
xenoliths (e.g., Canil, 1990; Luth, 1993). ThefO,s recorded
by the Simcoe xenoliths are higher than those at which Wal-
lace and Green (1988) found carbonate liquid coexisting
with carbonated peridotite, and the Simcoe temperatures are
too high to maintain carbonate stability, although CO2 vapor
would be stable. We thus conclude that any role played by
carbonate liquids in metasomatizing Simcoe peridotites was
very minor. This view is supported by the following evi-
dence. First, apatite is not observed in any of our samples,
as in, for example, other samples described as the products
of carbonate metasomatism (Yaxley et al., 1991; Hauri et
al., 1993). Apatite is also predicted from experiments to
be the consequence of carbonatite interaction with mantle
lithosphere (Meen et al., 1989). Second, light rare earth
element abundances in Simcoe samples (Brandon et al.,
1995) are l-2 orders of magnitude too small to be in equilib-
rium with carbonated melts. For example, Hauri et al. ( 1993)
reported 58-125 ppm Nd and 8.4-25 ppm Sm in clinopy-
roxenes they considered to have been metasomatized by car-
bonate-rich melts. Neodymium and samarium abundances in
clinopyroxenes from Simcoe harzburgites range from 1.2-
13.9 and 0.4-2.6 ppm, respectively, too low to be in equilib-
rium with carbonate liquids. Carbonate liquids also strongly
partition Sr, and coexisting clinopyroxene would be expected
to have negative Sr anomalies (Hauri et al., 1993). Negative
1146 A. D. Brandon and D. S. Draper

Sr anomalies are not observed in clinopyroxene from Simcoe

samples (Brandon et al., 1995). These features in Simcoe
clinopyroxenes are inconsistent with enrichment by carbon-
ate-rich melts, and hence oxidation was most likely the result
of another process.
In summary, we believe that the weight of the evidence
supports a water-rich fluid or a hydrous silicate melt as the
oxidizing agent for the Simcoe xenoliths. If the compara-
tively oxidizing conditions recorded by mantle xenoliths
from subduction settings are directly correlated with the sub-
duction process, it would seem reasonable to propose that t....,....,,.,.,,,,,,.,,,i
O.95 30 35 40 45- 50
this link involves water-rich fluids liberated from the down- WC
going slab as outlined above. Our data can be used to test
such a link more explicitly.

4.3. Assessing the Role of Water in Oxidation of the

Mantle Wedge
In order to evaluate the role of water in oxidizing subarc
mantle, we have calculated the amounts of water required
to increase AFMQ by approximately l-2 log units. That is,
we choose a reasonable representation of as-yet-unoxidized
mantle, and compute the changes necessary to bring it to
conditions reflected by the Simcoe xenoliths. A reaction by
which conversion of Fe3+ to Fe’+ in peridotite silicates and
oxides might take place is (Canil et al., 1994)
2FeO + HZ0 = FezO, + HZ, (2)
provided H2 can efficiently escape the system.
To estimate the amount of water necessary to produce a
given amount of ferric iron per kilogram of mantle by this
reaction, we require the following assumptions and condi-
tions. First, as did Canil et al. ( 1994)) we calculate the bulk
rock Fe”/CFe ratios for Sim-3 and Sim-9 using Mossbauer
results for spinel, clinopyroxene, and orthopyroxene, and
their wt% modes (Table 1). These values are 0.0419 and
0.0447, respectively. These two samples span the range in
harzburgite major element compositions in the Simcoe suite
(Table 1) and thus the likely range in ferric iron contents.
These ratios are at least 22 times those for spine1 peridotites
from other tectonic settings (see Canil et al., 1994 and refer-
ences therein). The amounts of Fe?O? are thus 0.253 and
0.257 wt%, respectively, for these two harzburgites.
Second, an amount of newly produced Fez03 from oxida-
tion by reaction (2) can be estimated if the initial amount
of Fe20i is known. We have estimated the initial Fe203
contents using comparisons with mantle peridotites having
calculatedfOZs 1-2 log units lower than those we calculate
for the Simcoe rocks. In plots of Fe203 vs. MgO and A1203
(Fig. 6)) cratonic mantle peridotite xenoliths, and in particu-
lar spine1 bearing xenoliths, form arrays which generally
trend from primitive upper mantle (Canil et al., 1994; McDo-
nough, 1990) to lower Fe,O, and AlZ03, and higher MgO.
For spine1 peridotites similar in MgO and AlaO, contents
(and also CaO and Cr203, not shown) to the Simcoe xeno-
liths, Fe203 abundances range from about 0.075-o. 15 wt%
(Fig. 6). According to Canil et al. ( 1994)) depleted abyssal
peridotites have ~0.1 wt% Fe?O,, and continental peridotites
with 40-45 wt% MgO have ~0.2 wt% Fe,03. From these
0 1 2 3 4 5
A1203
FIG. 6. Major oxide plots of mantle peridotites where bulk rock
FeZOi has been calculated using Fe’+/EFe ratios from MBssbauer
spectroscopy (data from Canil et al., 1994, and this study). The two
Simcoe samples are Sim-3 and -9, and these have ferric iron contents
higher than spine1 peridotites with similar major element composi-
tions from other tectonic settings (i.e., MgO, Al,O-i. CaO, and
Cr,O?). Linear regressions of the spine1 peridotite data (Simcoe
not included) in these plots intersect the primitive upper mantle
composition (PUM, McDonough, 1990; Canil et al., 1994).
comparisons of Fez03 contents of the Simcoe samples with
mantle samples reflecting lower fO,s (Fig. 4), we suggest
that the excess FeaO-, in the Simcoe peridotites ranges from
0.105-0.180 wt% and results from the oxidation process.
Finally, the amount of water per kilogram of mantle repre-
sented by these Simcoe xenoliths can be calculated using
reaction (2) and the estimated amount of excess FezOl.
These results require 0.1184-0.2030 grams of water to pro-
duce the additional Fe203 in 1 kilogram of Simcoe mantle.
The amount of water should result in oxidation shifts of
about l-2 log units higher, when comparing AFMQ’s of
subarc-mantle xenoliths with cratonic peridotite xenoliths
and abyssal peridotites (Fig. 4).
It is conceivable that oxidation could take place via a
reaction in which CO2 is the oxygen source. However, bal-
anced reactions with CO* and iron oxides produce elemental
C as well as ferric iron (Canil et al., 1994). Such reactions
cannot, as noted above, proceed for the Simcoe samples,
because their calculated fO,s are all well above the CC0
buffer (Fig. 3), where carbon is not stable, so we restrict
our attention to the case for water alone.
4.4. Comparison With Subduction Zone Water Flux
Given the calculated amounts of water needed to produce
oxidized iron in the Simcoe samples, is there enough water
 Oxidation state of the mantle over subduction zones
passing through the mantle wedge above subduction zones
to produce the ferric iron observed in these xenoliths and thus
the oxidation shifts? To help answer this question, consider a
model subduction zone in which oceanic crust subducts at
an angle of 45” beneath crust 30 km thick; the back-arc
region extends to 300 km from the trench. This hypothetical
subduction zone approximates the major features of the Cas-
cade-Simcoe setting (Bostock and VanDecar, 1994)) includ-
ing evidence for subduction-related magma generation in the
back-arc (e.g., Brandon, 1989). In this geometry, a 1 km
thick slice (i.e., 1 km of strike length) of the mantle wedge
occupies approximately 36200 km3. Assuming a density of
3.4 g-cm-‘, this slice contains 1.23 X lOI kg of peridotite.
Peacock (1990) estimated that, in present-day subduction
zones, a total of 1.4 x 10” kg H20 is subducted each year.
The aggregate strike length of all present-day ocean crust
subduction zones has been estimated at 30,000 km (Silver
et al., 1988; P. G. Silver, pers. commun., 1995). Thus, one
can estimate that the mass of water subducted per year per
km of subduction zone strike length is 4.67 X lo6 kg. Not
all of the water subducted actually passes through the mantle
wedge, however. The discussion of Arculus (1994) implies
that 55-58% of the water subducted is in fact released into
the mantle wedge. To be conservative, we assume a value
of SO%, so that the amount of water infiltrating the mantle
wedge is 2.33 X lo6 kg per year per km of subduction zone
strike length, and we denote this quantity the available water.
We assume for modelling purposes that this water is uni-
formly distributed over the whole volume of the model man-
tle wedge. It is likely that water is not distributed in this
way during dehydration and migration in a reaction front or
after incorporation into silicate melt, but using this assump-
tion will predict whether enough water is available to oxidize
a volume of a mantle wedge over the course of a typical
lifespan of a subduction zone and hence assess the signifi-
cance of oxidation by this process. Finally, not all the water
that is available will actually oxidize the peridotite, but there
are few data available to estimate the proportion of the avail-
able water that will do so. This will in part depend on the
composition of the C-H-O fluid and how other species in
this fluid affect the reactivity of H20. As discussed above,
C-H-O fluids derived from subducting slabs are most likely
at least 90 wt% H20, and, therefore, such an approximation
is likely reasonable.
Armed with this information, we can model the general
relationships between the extent of oxidation of the mantle
wedge, the time required for this oxidation, and the propor-
tion of the available water that will react with Fe in subarc
peridotite. We scale our model to a unit km of subduction
zone strike length and characterize the conditions necessary
to achieve the minimum and maximum oxidation recorded
by the Simcoe samples as represented by newly produced
ferric iron; that is, we cover the range encompassed by them.
We combine (a) the amounts of water per kg of mantle
required to oxidize Fe in the peridotite from initial to mea-
sured conditions; (b) the amount of water available per km
strike length per year; and (c) the volume and mass of the
model slice of mantle wedge to produce the relationships
summarized in Figs. 7 and 8.
1147
3 ypical Lifespan of
3 ubduction Zones -
s
‘r’
2 Minimum Duration
100
I3
Cascade Arc -
5
‘i;m
4
6
IO
0 5 10 15 20 25 30 35 40 45 50
% of Available Hz0 Reacted
FIG. 7. Oxidation duration in millions of years (Ma) vs. the %
reacted of water being fluxed through subduction zones. The shaded
area represents the intersection of the typical lifespan of subduction
zones and the curves for minimum and maximum amounts of oxida-
tion of Fe in the Simcoe samples. At worst, where the lifespan is
20 Ma, only 50% of the water passing through needs to react to
produce the maximum amount of newly produced ferric iron esti-
mated in the Simcoe peridotites over a whole volume of mantle
wedge. See text for additional details and model assumptions and
requirements.
In Fig. 7, the amount of time required to produce the
minimum and maximum extents of oxidation is shown as a
function of the proportion of the available water that actually
oxidizes Fe in Simcoe peridotite. Because we are assuming
that the amount of available water represents 50% of the
total water subducted, the values on the abscissa can be
halved to read the percentage of the total amount of water
subducted. Figure 7 shows, for example, that the minimum
newly produced Fe203 in the Simcoe samples integrated over
the entire volume of the model mantle wedge can be
achieved in approximately 35 Ma if only 22% of the avail-
able water ( 11% of the total subducted per year) oxidizes
Fe. About 45 Ma would be required to attain the maximum
newly produced Fe,O? with this percentage of water reaction.
The shaded area on this plot is that spanned by the minimum
and maximum curves and the durations 20 and 100 Ma, the
range of typical lifespans of subduction zones (from Table
2.1 of Gill, 1981). The mechanism and reaction proposed
here can produce the range of observed oxidation under
conditions represented by this shaded region.
The estimated results can be viewed in another way (Fig.
8). Here, the volume of mantle (again scaled per km of
subduction zone strike length) that can be oxidized is plotted
as a function of the time over which the oxidizing process
is active. The lines on this diagram are labeled with the
percentage of available water that actually oxidizes Fe. For
example, to produce the minimum extent of oxidized Fe over
a volume mantle wedge of 50000 km3 (steeper dipping slab
or distribution of water > 300 km from then trench), about
22% of the available water is needed for a subduction zone
lifespan of 40 Ma, and about 11% of the water is needed
for a subduction zone lifespan of 80 Ma. Likewise, a smaller
1748 A. D. Brandon and D. S. Draper

, oceanic mantle, ancient cratonic mantle, or other localities

in western North America not associated with present-day
subduction. The average and range of Simcoe fLFMQs are
similar to those for Ichinomegata, Japan, which is also lo-
cated in a region of modem arc magmatism. We conclude
that the most likely oxidizing agent for the Simcoe samples
is either a hydrous fluid, a water-bearing silicate melt, or
some hybrid between them (i.e., solute-rich fluid). Metaso-
b matism in regions unrelated to subduction is often attributed
"E 20000 to a similar agent, but we suggest that it is the addition of
Y an oxidized signature that is distinctive in arc settings. Our
10000 I calculations show that this signature can be accounted for
0 IO 20 30 40 50 60 70 80 90 100 via the involvement of H20. A volume equaling the present-
Duration of Oxidation Process (Ma) day mantle wedge could be oxidized by 2 logfOZ units in
a time similar to that over which subduction has taken place
FIG. 8. Volume in mantle oxidized (in kilometers3 ) vs. oxidation
duration in millions of years (Ma) for the minimum and maximum in the Cascades arc, using conservative estimates of the
amount of newly oxidized Fe observed in the Simcoe samples. The amount of water fluxed through subduction zones, and for
model mantle wedge has a volume of 36200 km’ and the Cascade the amount of water that will react with the mantle. Our
arc has been active for about 50 Ma. For this volume and duration, measurements give the strongest confirmation to date for the
the minimum and maximum oxidized indicated by the Simcoe sam-
ples can be produced by about 12-21%, respectively, of the available commonly-held view that the mantle in subduction zones is
subducted water (see text). more oxidized than elsewhere, and that water must play a
central role.

volume of mantle wedge can be oxidized with lesser volumes Acknowledgments-We are grateful to Dr. B. J. Wood, who provided
of water in longer-lived subduction zones. MGssbauer spectroscopic analyses for this study. We thank Drs. John
We conclude from these considerations that it is quite rea- Adam, Fred Frey, Jim Meen, Bill McDonough, Trevor Green, Dmitri
Ionov, Gordon Gales, and Norman Pearson for helpful discussions
sonable to propose that oxidation of the mantle wedge above and reviews. Journal reviews by Dante Canil, Ian Parkinson, and
subduction zones is accomplished by slab-derived water. For Alan Woodland were very helpful. This work was supported by an
the specific case of the Cascades-Simcoe setting, where sub- NSF Post-doctoral Fellowship in Earth Sciences (EAR 9200972)
duction has been active for at least 50 Ma, 21% of the avail- and a Carnegie Post-doctoral Fellowship to ADB, and by a Mac-
quarie University Research Fellowship to DSD.
able water (10.5% of the total subducted) must oxidize Fe in
peridotite to produce the maximum oxidation observed over
the whole mantle wedge. We acknowledge that it is difficult Editorial hnndling: M. Menzies
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