3 Review

Geochemistry
G
Volume 4, Number 5
Geophysics 3 May 2003
8905, doi:10.1029/2002GC000392
Geosystems
AN ELECTRONIC JOURNAL OF THE EARTH SCIENCES ISSN: 1525-2027
Published by AGU and the Geochemical Society

Subduction fluxes of water, carbon dioxide, chlorine, and

potassium
Richard D. Jarrard
Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah 84112, USA
( jarrard@mines.utah.edu)

[1] The alteration of upper oceanic crust entails growth of hydrous minerals and loss of macroporosity,
with associated large-scale fluxes of H2O, CO2, Cl
, and K2O between seawater and crust. This age-
dependent alteration can be quantified by combining a conceptual alteration model with observed age-
dependent changes in crustal geophysical properties at DSDP/ODP sites, permitting estimation of crustal
concentrations of H2O, CO2, Cl
, and K2O, given crustal age. Surprisingly, low-temperature alteration
causes no net change in total water; pore water loss is nearly identical to bound water gain. Net change in
total crustal K2O is also smaller than expected; the obvious low-temperature enrichment is partly offset by
earlier high-temperature depletion, and most crustal K2O is primary rather than secondary. I calculate
crustal concentrations of H2O, CO2, Cl
, and K2O for 41 modern subduction zones, thereby determining
their modern mass fluxes both for individual subduction zones and globally. This data set is complemented
by published flux determinations for subducting sediments at 26 of these subduction zones. Global mass
fluxes among oceans, oceanic crust, continental crust, and mantle are calculated for H2O, Cl
, and K2O.
Except for the present major imbalance between sedimentation and sediment subduction, most fluxes
appear to be at or near steady state. I estimate that half to two thirds of subducted crustal water is later
refluxed at the prism toe; most of the remaining water escapes at subarc depths, triggering partial melting.
The flux of subducted volatiles, however, does not appear to correlate with either rate of arc magma
generation or magnitude of interplate earthquakes.

Components: 28,530 words, 11 figures, 2 tables, 1 Auxiliary material.

Keywords: Subduction; flux; carbon dioxide; potassium; oceanic crust; Ocean Drilling Program.
Index Terms: 1030 Geochemistry: Geochemical cycles (0330); 1020 Geochemistry: Composition of the crust.
Received 18 June 2002; Revised 31 December 2002; Accepted 10 January 2003; Published 3 May 2003.

Jarrard, R. D., Subduction fluxes of water, carbon dioxide, chlorine, and potassium, Geochem. Geophys. Geosyst., 4(5),
8905, doi:10.1029/2002GC000392, 2003.

————————————
Theme: Oceanic Inputs to the Subduction Factory Guest Editors: Terry Plank and John Ludden

1. Introduction elements. Oceanic crustal alteration, associated

with axial and ridge-flank hydrothermal circula-
[2] Long-term average production of oceanic tion, modifies crustal abundances of several ele-
crust at spreading centers is balanced by subduc- ments. For upper crust, the largest changes occur
tion. The same is not true, however, for individual for structural water, carbon dioxide, and potas-

Copyright 2003 by the American Geophysical Union 1 of 50

 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
sium [Staudigel et al., 1996], all of which are
enriched by alteration.
[3] Subduction recycling of H2O, CO2, Cl
, and
K2O affects the geochemical evolution of the
mantle, oceans, and atmosphere, impacting our
understanding of a wide suite of global geochem-
ical cycles [Peacock, 1990]. Volatile outgassing
from MORB and arc magmas is probably the main
source of the water and chlorine for early growth of
the oceans [Rubey, 1951], but these fluxes are
currently nearly balanced by loss to subduction.
For no-growth continents, long-term sediment sub-
duction should approximately equal arc magma-
tism [Armstrong, 1968, 1991]. Slab dehydration
generates overpressures and reflux at shallow
depths [Moore and Vrolijk, 1992] and partial melt-
ing at 100 km responsible for arc magmatism
[Gill, 1981]. Subduction permanently removes
CO 2 that was temporarily isolated from the
ocean/atmosphere system by deposition of carbo-
nates and organic matter. Subduction recycling of
volatiles and potassium are also likely to generate
mantle heterogeneity and may affect compositions
of arc magmas [Plank and Langmuir, 1993; Stau-
digel et al., 1996], though these effects are yet to
be explored comprehensively.
[4] The subduction-related fluxes of this study
contribute to the Geochemical Earth Reference
Model (GERM), an interdisciplinary, long-term
initiative with the much wider aims of characteriz-
ing the Earth’s major chemical reservoirs and the
fluxes between them [Staudigel et al., 1998a].
Subduction fluxes for all major elements have been
estimated for both upper crustal extrusives [Stau-
digel et al., 1996] and overlying sediments [Plank
and Langmuir, 1998]. This study incorporates geo-
physical models for age-dependent crustal altera-
tion into calculations of fluxes for all subduction
zones.
2. Age Dependence of
Upper Crustal Properties
[5] The evolution of hydrothermal circulation is
well established qualitatively. At the ridge axis,
magmatic heat drives vigorous and deep axial
circulation [Humphris, 1995; Fisher, 1998]. Early
10.1029/2002GC000392
off-axis hydrothermal circulation may be largely
low-temperature (<30
C) with seafloor communi-
cation or higher-temperature (30–60
C) if sedi-
mentation isolates the circulation from seawater
[Fehn and Cathles, 1986; Davis et al., 1992;
Humphris, 1995]. Hydrothermal circulation con-
tinues within ridge flanks for at least tens of
millions of years (e.g., Anderson et al. [1977],
Fisher et al. [1990], and many others). Off-axis
waning of hydrothermal circulation is caused by
decrease in crustal heat, accumulation of a rela-
tively low-permeability sediment cover, and
decrease in crustal permeability caused by crustal
alteration [Anderson et al., 1977; Stein and Stein,
1994]. Of these three mechanisms, crustal alter-
ation has received the most attention, perhaps
because only it can account for the age-dependence
of upper crustal seismic velocities [Schreiber and
Fox, 1976, 1977]. My focus is on this crustal
alteration.
[6] According to this conceptual model, alteration
of oceanic crust begins as soon as crust is created.
The combination of axial heat and highly fractured,
permeable basalt promotes vigorous hydrothermal
circulation, which causes crustal alteration. Alter-
ation minerals eventually fill macroporosity (cracks
and interpillow voids), thereby reducing porosity
and permeability. Nevertheless, circulation on
flanks is responsible for 70% of the advective
heat loss from oceanic crust [Stein and Stein, 1994]
and substantial geochemical exchange with sea-
water [Mottl and Wheat, 1994; Elderfield and
Schultz, 1996].
[7] Low-temperature alteration patterns of upper
oceanic crust have been determined from petro-
graphic studies, core descriptions, and geochemis-
try; Honnorez [1981], Thompson [1991], Alt [1995,
1999], and Bach et al. [2003] provide comprehen-
sive reviews. Early formation of celadonite and
smectites (particularly saponite), often as inter-
growths, is followed by precipitation of carbonates
(mainly calcite). These three minerals are the
dominant alteration minerals in upper oceanic
crust; others include Fe-oxyhydroxides and zeo-
lites. Early low-temperature alteration is oxidative,
with high water-rock ratios and open seawater
circulation. Reducing conditions generally follow,
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 Geochemistry 3
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Figure 1. Locations of DSDP and ODP sites with significant penetrations into normal oceanic crust and with either
downhole logging or core physical properties. Also shown are locations of Holes 504B (Figure 3), Site 801 (Figure 4),
and gabbro Hole 735B.
associated with decreases in both flow rates and
exchange between seawater and pores.
[8] Basalt coring and logging by DSDP and ODP
provide abundant information on physical proper-
ties of upper oceanic crust, despite generally low
basement core recoveries and rare basement log-
ging [Goldberg, 1997]. Most of the analyses of
this section draw heavily from a synthesis of
DSDP/ODP petrophysical data on aging of upper
oceanic crust by Jarrard et al. [2003]. Of 1200
sites drilled by DSDP and ODP, 13 fulfill the
following two criteria: (1) basement composed of
normal oceanic crust formed in an open-ocean
environment, and (2) velocity logging of at least
40 m of basement (Figure 1). Jarrard et al.
[2003] confined their analyses to the top 300 m
of basement, because most sites have only 90–
200 m of velocity log and only four holes (395A,
418A, 504B, and 801C) penetrated more than
300 m of basement. A second search of the DSDP
and ODP databases and publications (Initial
Reports and Scientific Results) focused on index
properties of basalts. Only sites on normal oceanic
crust were considered, and data from multiple
holes at the same site were combined. Useful
index data are available for 25 sites (Figure 1).
10.1029/2002GC000392
These analyses of crustal alteration patterns
exclude data from ophiolites, for two reasons:
(1) most are formed in supra-subduction settings
that are nonrepresentative of normal, open-ocean
crust, and (2) ophiolitic alteration is generally
more intense, with much higher total fluid flux,
than normal crustal alteration [Alt and Teagle,
2000]. Sedimented ridges and back-arc spreading
are also excluded, because their hydrothermal
circulation histories probably differ from that of
open-ocean crust.
[9] Basalt physical properties at intergranular core-
plug scale may differ from those at the meter scale
measured by logs, because of differences in type of
porosity and in alteration history. At plug scale,
porosity consists mainly of vesicles and micro-
cracks, whereas log-scale porosity also includes
fractures and interpillow voids. At plug scale,
alteration converts glass, olivine, and plagioclase
mainly to clay minerals, thereby decreasing matrix
density and matrix velocity. Porosity may increase
due to this hydration, or decrease due to precip-
itation. At log scale and larger, porosity is thought
to decrease due to filling of cracks and interpillow
voids by alteration minerals. Consequently, a com-
parison of plug-scale and log-scale basalt physical
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 Geochemistry 3
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properties may yield insights concerning the scales
and varieties of alteration.
2.1. Permeability, Porosity, and Alteration
[10] Permeability is the architect of the crust’s
hydrothermal systems. Nearly all measurements
of the permeability of upper oceanic crust are
averages for portions of a borehole tens to hun-
dreds of meters in extent. Fisher [1998] provided
an excellent review and synthesis of these bulk
permeability measurements and their implications.
This large-scale crustal permeability is a critical
control on hydrothermal circulation patterns and
associated heat flux, because the volumetrically
dominant flux is channelized within the most
permeable zones, particularly large open fractures
[Fisher, 1998; Fisher and Becker, 2000] and brec-
cias [Bach et al., 2003]. Bulk permeabilities for the
top 1200 m of oceanic crust suggest two main
layers: the top 500 m has permeabilities of
10
14 –10
13 m2, and the next 700 m has per-
meabilities of 10
17 m2 [Fisher, 1998]. The
intense intergranular alteration of pillows and flow
margins, despite intergranular permeabilities that
are more than four orders of magnitude lower than
the fracture and interpillow permeabilities meas-
ured by packers, occurs via both microbial activity
[e.g., Furnes and Staudigel, 1999; Furnes et al.,
2001; Staudigel et al., 1998b] and diffusion. The
lower limit for sufficient diffusion to produce
significant alteration may be 10
19 m2, based
on the observation that lower intergranular perme-
abilities are encountered mostly in fresh, massive
basalts [Karato, 1983a, 1983b; Johnson, 1979a;
Hamano, 1979; Jarrard et al., 2003].
[11] ODP Hole 801C, which obtained the world’s
oldest section of in situ, normal oceanic crust,
provides the opportunity to examine relationships
among hydrologic properties (porosity, permeabil-
ity, fluid flow), crustal alteration, and geophysical
properties, at both core-plug and downhole-log
scales [Busch et al., 1992; Jarrard et al., 1995,
2003]. Within these upper crustal basalts, higher
porosity is responsible for higher permeability and
therefore higher fluid-flow rates. High fluid flux, in
turn, fosters alteration, particularly the hydration
reactions that generate clays. Consequently, poros-
10.1029/2002GC000392
ity is well correlated both with hydration intensity
determined by light-absorption spectroscopy
(LAS) (significant at 99% confidence level) and
with matrix density (significant at 99% c.l.).
Because hydration substantially reduces matrix
density, matrix density is correlated with LAS-
based hydration (significant at 99% c.l.) [Jarrard
et al., 2003].
2.2. Timing of Waning of Hydrothermal
Circulation: Previous Evidence
[12] Geophysical techniques disagree on the tem-
poral evolution of hydrothermal circulation and
resulting alteration in oceanic crust. Cementation
associated with ridge-flank hydrothermal circula-
tion appears to terminate as early as 5–10 Ma,
based on global data syntheses of upper crustal
seismic velocities [Grevemeyer and Weigel, 1996;
Carlson, 1998]. Similarly, crustal permeabilities
decrease exponentially from 1 Ma to 8 Ma; sub-
sequent changes (if any) are undetermined [Fisher
and Becker, 2000].
[13] In contrast, the global heat flow synthesis of
Stein and Stein [1994] indicated that the heat flow
deficit (theoretical minus observed) gradually
decreases with age, disappearing at about 65 Ma.
The deficit indicates advection via open circulation
between seawater and the crust; beyond 65 Ma,
heat flow is dominantly conductive, with an age-
dependent decrease in heat flow variance that
suggests continued fluid flow [Stein and Stein,
1994]. Von Herzen [2003] reanalyzed 58 detailed
heat flow surveys from old crust and concluded
that ongoing hydrothermal circulation is common
in Mesozoic crust; it is likely in half of the surveys
on crust 65–95 Ma, and in a third of those on >95-
Ma crust. Heat flow data cannot unambiguously
determine whether hydrothermal circulation in old
crust is closed-cell (no interchange with seawater)
or slow open-cell [Fisher, 1998], yet the two differ
crucially in geochemical mass balance. For closed-
cell fluid flow, precipitation equals solution, and
crustal geophysical properties may be unchanged
by ongoing alteration.
[14] These conflicting indications of when off-axis
hydrothermal circulation wanes have been partly
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 Geochemistry 3
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reconciled. Fisher and Becker [2000] suggested

that the rapid initial increase in velocity and
decrease in permeability are not necessarily incom-
patible with heat flow evidence for persistence of
open-cell convection. They hypothesized that
hydrothermal circulation continues to 65 Ma, in
localized channels within the crust that are too
small a percentage of total upper crust for signifi-
cant effects on average crustal velocity. Crustal
alteration beyond 5–10 Ma is too subtle for most
geophysical methods to resolve, but the next three
sections examine continuing geophysical changes
that are detectable.

2.3. Core Alteration and

Matrix Density Versus Age
[15] Johnson and Semyan [1994] examined the
possibility of age-dependent changes in velocity,
porosity, density, oxidation state, and hydration,
based on a compilation of core-plug measurements
from DSDP and ODP basalts. The increase of
crustal alteration with increasing age is most evi-
dent among parameters sensitive to hydration.
Age-dependent oxidation is clearest for 0.1–5 Ma
and is not resolved beyond 10–30 Ma [Johnson
and Semyan, 1994; Zhou et al., 2001b]. Analyses
of bound water, or H2O+, provide a semiquantita-
tive measure of the extent of alteration-induced
hydration [Alt et al., 1992]. The H2O+ compilation
of Johnson and Semyan [1994] confirmed earlier
indications [Hart, 1970, 1973; Donnelly et al.,
1979a; Muehlenbachs, 1979] that hydration
increases with increasing age (R = 0.35; significant
Figure 2. Age-dependent geophysical properties of
at 95% confidence level), but dispersion is too high upper oceanic crust. Each point represents one DSDP or
to identify when most of this hydration occurs. ODP site. Regression lines are used to predict crustal
properties at subduction zones, based on crustal age. A–
[16] Matrix density is the average density of the C are modified from Jarrard et al. [2003].
minerals forming the solid part of the rock, includ-
ing any alteration minerals. Matrix densities provide
the strongest demonstration of systematic increase density continues to decrease, at a rate proportional
in alteration versus time (Figure 2b) (R =
0.70; to logarithm of age, throughout the period 0–167
significant at 99.9% confidence level), indicating Ma. However, data dispersion in the time period
that approximately half of all intergranular-scale 10–70 Ma is high, and the hypothesis of no change
crustal alteration occurs after the first 10–15 Ma. beyond about 40–60 Ma cannot be rejected.
Site 597, where sampling concentrated on a massive
flow [Shipboard Scientific Party, 1985] and matrix 2.4. Velocity Versus Age
density is anomalously high, is excluded. The [17] Compilations of published seismic experi-
simplest interpretation of this pattern is that matrix ments from throughout the world ocean demon-
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 Geochemistry 3
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strated that seismic velocities of the upper oceanic
crust increase rapidly for the first 5–8 Ma, from an
average of 2.3 km/s at the spreading center to 4.3–
4.4 km/s at 5–10 Ma (Figure 2a) [Grevemeyer and
Weigel, 1996; Carlson, 1998]. The amount of
associated crustal alteration is undetermined.
Velocity modeling suggests that the large near-
ridge velocity increases may be accomplished by
changing the shape of pore spaces via secondary
mineralization with relatively small overall poros-
ity reduction [Wilkens et al., 1991; Shaw, 1994;
Moos and Marion, 1994]. Beyond 10 Ma, no
significant change in upper crustal velocity is
resolvable with seismic velocity data [Carlson,
1998]; data dispersion is too high to resolve
systematic changes of <1 km/s. DSDP and ODP
velocity logs, with an age range of 6–167 Ma that
is beyond any seismically resolvable age depend-
ence, indicate that crustal velocity increase con-
tinues (Figure 2a, significant at 95% c.l.), rising
from 4.2–4.7 km/s at 6 Ma to 5.0–5.1 km/s for
>100 Ma. This gradual increase in large-scale
velocity occurs despite systematic velocity
decrease at the intergranular scale, as indicated
by core-plug velocities for 0–100 Ma [Christensen
and Salisbury, 1973; Johnson and Semyan, 1994;
Jarrard et al., 2003]. Precipitation in cracks and
interpillow voids must be dominant over intergra-
nular-scale alteration in controlling the evolution
of large-scale crustal velocity.
2.5. Macroporosity Versus Age
[18] Plugs reveal intergranular patterns, but they
tend to miss cracks and crack-filling that poten-
tially are major controls on large-scale velocity
[Hyndman and Drury, 1976; Anderson and
Zoback, 1982]. Evaluation of crack porosity based
on incomplete core recovery is difficult [Johnson,
1979b]. If much of basalt porosity is in the form of
large-scale voids and fractures that are not
sampled by 10-cm3 core plugs, then comparison
of core and log measurements of porosity has the
potential of detecting this macroporosity. I use
core and log velocity for macroporosity determi-
nation, because velocity logs provide the most
robust, unbiased measure of in situ porosities of
oceanic basalts.
10.1029/2002GC000392
[19] Before comparing atmospheric-pressure core-
plug velocities to in situ log velocities, pressure
effects must be considered. Rebound, the core
expansion that accompanies change from in situ
to laboratory pressure, can reduce plug velocities
[e.g., Nur, 1971; Bourbié et al., 1987]. Rebound is
generally minor in oceanic extrusive basalts,
because burial depths are much too small to induce
microcracks. The extensive suite of core velocity
measurements for Hole 504B [Wilkens et al., 1983;
Christensen and Salisbury, 1985; Christensen et
al., 1989; Iturrino et al., 1995; Salisbury et al.,
1996] shows that the average pressure-induced
percentage difference between atmospheric and in
situ velocities for the upper 600 m of basement is
only
0.3% based on differential pressures,

0.6% based on lithostatic pressures, and
2.0%
based on confining pressures. In contrast, the two
diverge at greater depths: at about 1100 m subbase-
ment, 300 m into the dikes, the unmistakable
signature of microcracks appears and atmospheric-
pressure measurements are no longer a useful
indicator of in situ velocities (Figure 3). Conse-
quently, I assume that atmospheric-pressure veloc-
ities can be used for macroporosity calculations
within this and other extrusive sections, whereas
high-pressure measurements would be required for
dikes and gabbros.
[20] Figure 2c compares core-plug and log veloc-
ities for the 13 sites with significant basement
penetration. Because a systematic difference
between the two is thought to result primarily from
the influence of macroporosity on logs but not on
cores, I used the Wyllie et al. [1956] time-average
equation to express the difference between each
core/log velocity pair as an apparent macroporos-
ity. Matrix velocity may also decrease with age
[Jarrard et al., 2003] but no macroporosity bias
results, because both core-plug and log velocities
are similarly affected. Total macroporosities exhibit
a decrease with increasing age (R =
0.87) that is
significant at the 99.9% confidence level, and this
decrease appears to continue throughout the avail-
able age range (Figure 2c). Initial macroporosities
of 8–10% eventually are reduced to near zero. This
systematic macroporosity decrease contrasts with
the absence of significant age-dependent porosity
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Figure 3. Downhole K2O variations, seismic layers, lithologic units, and P wave velocity rebound at Hole 504B.
Sources in text. K2O variations are shown with red dots for core XRF analyses, black lines for well log, and vertical
green line for assumed pre-alteration K2O concentration. Velocity rebound is shown as percentage ratio of velocity at
atmospheric pressure compared to that at in situ (lithostatic) pressure.

change among core plugs [Johnson and Semyan,
1994; Jarrard et al., 2003]. In contrast to the
precipitation in cracks and interpillow voids that
causes macroporosity decrease, intergranular alter-
ation can either fill small cracks and vesicles or
generate porosity by breakdown of individual min-
erals such as olivine.
2.6. CO2 Versus Age
[21] Ridge volcanism releases CO2 at axial hydro-
thermal vents, mainly via degassing at magma
chambers rather than via crustal alteration [Ger-
lach, 1989]. Residual CO2 concentrations within
the basalts are minor, only 0.045 wt.% [Gerlach,
1989]. Subsequent low-temperature alteration adds
CO2 to the upper crust, primarily in the form of
CaCO3, using CO2 from seawater and CaO mostly
from the basalts [Staudigel et al., 1989, 1996].
This carbon sink has been demonstrated to be an
important term in global carbon budgets [Staudi-
gel et al., 1989; Peacock, 1990; Alt and Teagle,
1999].
[22] Progressive CO2 enrichment of oceanic crust
can be quantified by analysis of DSDP and ODP
sites, but avoidance of sampling bias is non-trivial.
Most whole-rock CO2 analyses target the least
weathered samples and avoid carbonate-filled
cracks. Core recovery is also biased, losing some
of the larger-scale crack filling. Two studies of
crustal CO2 have succeeded in minimizing these
biases: Staudigel et al. [1996] and Alt and Teagle
[1999].
[23] Adjacent Holes 417A, 417D, and 418A in the
west-central Atlantic provide an unusually good
record of the alteration of old oceanic crust, due to
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
penetration of almost the entire extrusive section,
relatively high core recovery (70%), and sam-
pling of both hydrothermal downflow and upflow
zones. Staudigel et al. [1996] took several steps to
obtain representative samples of downhole geo-
chemical variations within these holes: they
sampled a range of alteration states for all extrusive
styles (flows, pillows, and volcaniclastics), includ-
ing vein materials, and then they blended the
results using best estimates of the in situ propor-
tions of alteration states and extrusive styles. These
composite CO2 concentrations provide an excellent
demonstration of the difference between average
geochemical analyses and representative samples;
the former are almost all 0–2 wt.% CO2, whereas
the latter exhibit a systematic decrease downhole:
5.6% for 0–100 m subbasement, 5.0% for 130–
290 m, and 1.0% for 455–540 m. The resulting
weighted average for the upper extrusive section
(0–300 m subbasement) is 5.2%, similar to an
earlier 5.0% value by Staudigel et al. [1989], and
the overall average CO2 concentration of the
extrusives at these three holes is 2.95% [Staudigel
et al., 1996].
[24] Alt and Teagle [1999] combined best estimates
of bulk-rock and vein CO2 to obtain representative
samples of the average CO2 contents of upper
oceanic crust at Sites 504, 896, 843, and 801.
Bulk-rock CO2 measurements were averaged for
different alteration types, then these results were
weighted based on observed proportions of the
alteration types, producing an average bulk-rock
CO2 for each crustal section. The amount of vein
carbonate was calculated from detailed core
descriptions of carbonate vein abundances and
thicknesses plus breccia carbonate abundance.
These results demonstrated that carbonate precip-
itation in veins continues beyond the 6 Ma age of
Sites 504 and 896, resulting in enrichment of total
CO2 content of the upper extrusive section.
[25] Figure 2d combines the upper crustal CO2
determinations of Alt and Teagle [1999] with that
of Staudigel et al. [1996]. The pattern of progres-
sive CO2 enrichment extends far beyond 10 Ma,
once hypothesized to be the conclusion of calcite
precipitation [Staudigel et al., 1981]. Alt and
Teagle [1999] emphasized that these data establish
10.1029/2002GC000392
an increase in CO2 between 6 Ma and 110 Ma but
not the specific timing of this increase. Given the
evidence of continuing upper-crustal alteration
based on velocity (Figure 2a), macroporosity (Fig-
ure 2c), matrix density (Figure 2b), and variance of
global heat flow [Stein and Stein, 1994], however,
the simplest explanation of age-dependent CO2 is
that CO2 enrichment is ongoing but waning, with a
logarithm of time dependence (Figure 2d; R =
0.88).
[26] Cretaceous atmospheric CO2 levels were an
order of magnitude higher than Neogene levels
[Ekart et al., 1999; Pearson and Palmer, 2000;
Berner and Kothavala, 2001], possibly explaining
the pattern of Figure 2d without requiring contin-
ued off-axis carbonate precipitation. Within-site
correlations of highest whole-rock and vein CO2
with highest present-day porosity and presumably
permeability are consistent with – but cannot
prove – ongoing, progressive fluid flow and asso-
ciated carbonate enrichment. Petrographic studies
indicate that carbonate precipitation generally post-
dates smectite alteration [Alt and Teagle, 1999].
This observation is consistent with the regressions
of Figure 2, which suggest that half of all matrix
density lowering (smectite/celadonite alteration)
occurs after the first 15 m.y., whereas half of all
CO2 addition occurs after the first 25–30 m.y. The
calculated modern CO2 subduction fluxes of this
study depend only on the pattern of Figure 2D, not
its mechanism, whereas modern precipitation flux
is sensitive to both.
2.7. Potassium Versus Age
[27] Low-temperature crustal alteration processes
include oxidation, hydration, and alkali fixation.
The latter two generate clay minerals, the most
abundant alteration products [e.g., Donnelly et al.,
1979a; Andrews, 1980; Gillis and Robinson, 1988;
Alt and Honnorez, 1984; Alt et al., 1986]. Saponite
(a smectite clay) and celadonite (a mica) are
commonly formed during low-temperature diagen-
esis [e.g., Donnelly et al., 1979b; Alt and Hon-
norez, 1984], usually incorporating potassium
extracted from seawater [Hart, 1969; Andrews,
1980]; an exception is saponite formed by alter-
ation of interstitial glass [Zhou et al., 2001a].
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 Geochemistry 3
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Figure 4. Comparison of velocity and potassium logs
for Hole 801C tholeiites. The strong inverse correlation
between these logs indicates that precipitation of
potassium-rich clays and celadonite occurs mainly in
the most porous (lowest-velocity) zones. Modified from
Jarrard et al. [2003].
Consequently, altered basalts are generally higher
in potassium than unaltered basalts [Hart, 1969;
Hart et al., 1974]. Deep penetration of old oceanic
crust at Holes 417A/417D/418A provided the first
compelling evidence of widespread alteration-
induced K2O enrichment in the upper crust [Don-
nelly et al., 1979a, 1979b].
[28] Potassium enrichment is greatest in the most
porous, permeable zones. Figure 4, which overlays
K2O and velocity logs versus depth for the Hole
801C tholeiites, demonstrates that potassium var-
iations are closely linked to porosity changes
(velocity is used here as a porosity indicator).
The spectral gamma-ray log of potassium is here
converted to K2O weight percent by multiplying by
1.2. The lowest observed K2O contents, 0.07–
0.12%, are comparable to values typical of unal-
tered MORB tholeiites, suggesting that the most
massive, low-porosity units are minimally altered.
K2O maxima of 1% result from a high proportion
of potassium-bearing alteration minerals and occa-
sional sediment interlayers. This strong inverse
correlation between velocity and potassium-bear-
ing alteration minerals is not inconsistent with the
earlier observation that log velocity increases with
time and crustal alteration (Figure 2a): the highest-
porosity zones experience the most alteration and
associated porosity reduction, yet they remain
more porous than fresher, more massive intervals.
10.1029/2002GC000392
[29] Only seven of the thirteen logged basement
sites in normal oceanic crust have potassium logs.
These logs show no consistent pattern of potassium
increase or decrease with depth. Among these
seven sites, average log-based potassium content
is strongly correlated with average core-based
matrix density (R =
0.86; significant at 99%
confidence level) (Figure 5). This correlation, like
the Hole 801C correlation between potassium and
velocity logs (Figure 4), demonstrates that alter-
ation entails potassium enrichment. Also shown on
Figure 5 are results for Site 768, which may be the
most altered thick sequence of oceanic crust yet
sampled by DSDP or ODP [Shipboard Scientific
Party, 1990a]. This crust was formed by back-arc
spreading and is consequently excluded from these
analyses of normal crustal alteration, but it illus-
trates extreme alteration and associated potassium
enrichment.
[30] Despite the excellent correlation of Figure 5,
the temporal evolution of potasium enrichment is
an outstanding problem. Potassium-rich celadonite
is generally one of the earliest-formed alteration
minerals [Alt, 1999], and the few sites with potas-
Figure 5. Black dots: average core-based matrix
density versus average log-based K2O concentration,
for upper oceanic crust at all DSDP/ODP sites with both
data types; regression line is also shown. Dashed lines
and associated labels identify 3-component (fresh basalt,
saponite, celadonite) mixing models. For prediction of
K2O and structural water at subduction zones, the best
fit alteration mineral assemblage of 80% saponite and
20% celadonite is assumed.
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 Geochemistry 3
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sium logs show only a fair correlation (R = 0.47) of
potassium with logarithm of crustal age [Jarrard et
al., 2003].
2.8. Alteration Mineralogy Model
[31] Geochemical changes associated with the pro-
gressive alteration of oceanic crust can be modeled
as an age-dependent mix of fresh basalt and alter-
ation minerals. I assume that the dominant alter-
ation minerals in the upper extrusives are saponite
and celadonite, though this is only a first-order
approximation. Given the matrix densities and K2O
contents of smectite, celadonite, and fresh basalt,
one can compute the proportions of these three
components from the relationship between matrix
density and K2O (Figure 5).
[32] The average matrix density of fresh basalt is
3.01 g/cc, based on applying the regression of
matrix density on age (Figure 2b) to ages <1 Ma.
The local value depends on concentration of dense
phenocrysts such as olivine and pyroxene. I
assume a K2O content of 0.085 weight percent,
based on analyses of fresh basalts from Holes
417A/417D/418A [Spivack and Staudigel, 1994;
Staudigel et al., 1996] and 801C [Shipboard Sci-
entific Party, 2000a]. Average unaltered N-MORB
[Hart et al., 1999] and fresh glasses from dredged
basalts [Jochum et al., 1983] are slightly higher:
0.106% and 0.12%, respectively. The freshest
basalts from Holes 504B and 896A have an aver-
age K2O of 0.04% [Shipboard Scientific Party,
1992], much lower than typical MORB. This
depletion may slightly affect the lowest two points
on Figure 5, but the overall influence of magmatic
K2O variations is clearly minor in comparison to
alteration-induced variations.
[33] The matrix density of celadonite is assumed to
be 2.56 g/cc, the same as that of glauconite [Serra,
1986], based on compositional similarity of the two
minerals [Buckley et al., 1978]. Celadonite has an
average K2O content of about 9.07%, based on 13
analyses by Buckley et al. [1978]. Saponite has an
average K2O content of about 0.21%, based on 35
analyses of Honnorez et al. [1983].
[34] The structural interlayer water of smectites can
vary from 10% to 25% by weight or higher
[Ransom and Helgeson, 1995]. Furthermore, sam-
ple drying, required for either matrix-density meas-
urement or chemical analysis, drives off not only
pore water but also some of the loosely held
structural interlayer water. Consequently, measured
matrix densities are biased upward [Brown and
Ransom, 1996] and H2O+ analyses are too low.
Measured structural-water content of saponite aver-
ages 12 wt.%, based on 35 analyses by Honnorez
et al. [1983], but I assume that the true value is
20 wt.%. Brown and Ransom [1996] estimated that
the true water content of largely authigenic smec-
tites offshore Barbados is 20 wt.%, and Schlum-
berger used neutron and density log analysis to
propose that montmorillonites have a water content
of 41% by volume [Serra, 1986], or 20 wt.%.
Applying this estimate to basalt saponites, how-
ever, could be inaccurate by as much as 5 wt.%.
The assumed bound-water content of 5% for cela-
donite is based on only one measurement by
Buckley et al. [1978], because most analyzed
oceanic crustal celadonites are a mix of celadonite
and smectite [Andrews, 1980] (e.g., water contents
of 9.5–11% for mixed celadonite/smectite analyses
of Buckley et al. [1978]).
[35] For calculation of alteration mineral percen-
tages using Figure 5, it is appropriate to use
measured rather than true saponite matrix density,
based on measurements with similar sample drying
procedure to those applied to basalts: 24 hours
heating at 110
C. Smectite sediments from Site
1222 have an average measured matrix density of
2.51 g/cc (std. dev. 0.05, N = 17) [Shipboard
Scientific Party, 2002]. I assume that smectites
within basalts are similar in water content to these
and have an apparent matrix density of 2.50 g/cc.
[36] The dashed lines on Figure 5 show expected
positions on a K2O versus matrix density plot of
mixtures of fresh basalt, saponite, and celadonite.
Observed data points, including Site 768, lie along
a line for a mixture of fresh basalt and an alter-
ation-mineral assemblage of 80% saponite and
20% celadonite; the data regression line lies vir-
tually on top of that mixture line. Consequently, I
assume that the alteration minerals in extrusive
basalts are – to a first approximation
80%
saponite and 20% celadonite. Other alteration min-
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
erals are present, but I assume that they either are
similar in properties to these minerals or have a
minor effect on total K2O and matrix density. For
example, smectite is dominant in both early oxi-
dizing and later reducing alteration, but early
celadonite can be followed by zeolites with similar
K2O and matrix density. This model composition
for alteration minerals, along with their K2O con-
tents and matrix densities, permits estimation of the
K2O content of an extrusive sequence, based on the
age-dependent function for matrix density (Figure
2b). The direct regression of K2O on matrix density
(Figure 5) yields an almost identical result for
predicted K2O and total global K2O flux. I use
the mineralogic model instead because of its geo-
logic grounding and because it predicts both K2O
and structural water from matrix density (Table 1).
[37] Both matrix density functions – versus age
and versus K2O – are based on core-plug matrix
density rather than log matrix density. However,
large-scale matrix density may differ from inter-
granular matrix density because the amount or kind
of fracture-fill minerals differs from intergranular
alteration minerals. This difference does not bias
the K2O value, which is log-based and therefore
representative, but it does mean that computation
of structural water is accurate only for intergranular
alteration minerals. When macroporosity of old
basalts has been filled by alteration minerals,
large-scale matrix density is modified slightly from
intergranular matrix density. Fortunately, the per-
centage of filled macroporosity is so small that its
influence on total matrix density and structural-
water estimates is minor; nevertheless, I employ a
correction for this effect (Table 1).
3. Data Set: Global Subduction
3.1. Subduction Zones
[38] Nearly all of the world’s currently active
subduction zones are included in this analysis
(Table 2), regardless of whether the subducting
oceanic crust formed in an open-ocean or back-
arc environment. Continent/continent collisions
(e.g., India/Asia) and portions of a subduction zone
undergoing continental collision (e.g., Aegean, E.
Sunda) are excluded. With few exceptions, the
10.1029/2002GC000392
subduction zones are those tabulated and analyzed
by Jarrard [1986] and von Huene and Scholl
[1991], though some names have been updated.
The total length of active subduction zones in this
study is 44,450 km, close to the 43,250 km total of
von Huene and Scholl [1991]. Total ridge length is
49,000 km [Kominz, 1984]. The total length of
convergent plate boundaries, including 10% con-
tinent-continent collisions, is also 49,000 km, so
global average convergence and divergence rates
are nearly equal.
[39] Convergence rates for the major plates are
based on the NUVEL-1A global motion model
[DeMets et al., 1990, 1994], supplemented by
GPS data [Bevis et al., 1995; Tregoning et al.,
1998] and the Philippine plate motion of Seno et
al. [1993]; some Philippine plate GPS data are too
recent to be included [Miyazaki and Heki, 2001;
Kato and Kotake, 2002]. Only the component of
convergence perpendicular to each trench is consid-
ered. When applicable, back-arc spreading rates are
added to the major-plate motions, using back-arc
rates summarized by Jarrard [1986]. A few con-
vergence rates for short trenches in Southeast Asia
(Manila, Cotabato, Negros, Sulu, and Trobriand) are
poorly known but slow, and crustal age at San
Cristobal is ill-determined; subsequent calculations
of global fluxes are insensitive to these local uncer-
tainties. For most of the longest subduction zones,
McCaffrey [1997] has computed perpendicular-con-
vergence rates and average subducting-plate ages
pointwise along each trench, obtaining a more
accurate average for each than is obtainable by
subjectively selecting a representative crustal age,
trench azimuth, and convergence rate for an entire
subduction zone. In general, I use McCaffrey’s
[1997] averages when available (Table 2), but I
have not undertaken a similar pointwise approach
for the other subduction zones.
[40] Total consumption of oceanic crust on the
subduction zones of Table 2 is 2.42 km2/yr, much
less than the 3 km2/yr (3.3 km2/yr including back-
arc spreading) of crustal generation calculated from
early global motion solutions [Minster and Jordan,
1978; Parsons, 1981] and usually used for estima-
tion of subduction fluxes [Ito et al., 1983; Peacock,
1990; Bebout, 1995; Staudigel et al., 1996]. Part of
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Table 1. Parameters for Flux Calculations

Variable Units Symbol Zone Value

Trench length km L meas.

Converg. rate, perp. mm/yr V? meas.
Crustal age Ma A meas.
Fluid density g/cm3 rf 1.02
Zone thickness m Ts sed. meas.
Tu upper ext. 300
Tl lower ext. 300
Td dikes 1400
Tg gabbros 5000
Microporosity % fm,u upper ext. 7.8
fm,l lower ext. 5.1
fm,d dikes 2.2
fm,g gabbros 0.7
Macroporosity % fm,u upper ext. fm,u = 13.01
5.625*log(A)
fm,l lower ext. fm,l = fm,u/2
fm,d dikes 0.84
fm,g gabbros 0
Total porosity % ftot,u upper ext. ftot,u = fm,u + fm,u
ftot,l lower ext. ftot,l = fm,l + fm,l
ftot,d dikes ftot,d = fm,d + fm,d
ftot,g gabbros ftot,g = fm,g + fm,g
Matrix density g/cm3 rma,u upper ext. rma,u = 3.01
0.0631*log(A)
rma,l lower ext. rma,l = 3.01
0.5*0.0631*log(A)
rma,d dikes 2.98
rma,g gabbros 2.99
Bulk density g/cm3 rb,s sed. meas.
rb,u upper ext. rb,u = (0.01*ftot,u)*rf + (1
0.01*ftot,u)*rma,u
rb,l lower ext. rb,l = (0.01*ftot,l)*rf + (1
0.01*ftot,l)*rma,l
rb,d dikes rb,d = (0.01*ftot,d)*rf + (1
0.01*ftot,d)*rma,d
rb,g gabbros rb,g = (0.01*ftot,g)*rf + (1
0.01*ftot,g)*rma,g
K2O wt. % K2Os sed. meas.
K2Ou upper ext. K2Ou = 11.58
3.823*rma,u
K2Ol lower ext. K2Ol = 11.58
3.823*rma,l
K2Od dikes 0.014
K2Og gabbros 0.06
CO2 wt. % CO2s sed. meas.
CO2u upper ext. CO2u =
1.55 + 2.493*log(A)
CO2l lower ext. CO2l = CO2u/2
CO2d dikes 0.14
CO2g gabbros 0.02
Structural H2O wt. % H2OSs sed. meas.
H2OSu upper ext. H2OSu = (103.1
34.27*rma,u) + (0.17*(13.01
fm,u))
H2OSl lower ext. H2OSl = (103.1
34.27*rma,l) + (0.17*(13.01
fm,l))
H2OSd dikes 1.76
H2OSg gabbros 0.79
pore H2O wt. % H2OPs sed. meas.
H2OPu upper ext. H2OPu = ftot,u*rf/rb,u
H2OPl lower ext. H2OPl = ftot,l*rf/rb,l
H2OPd dikes H2OPd = ftot,d*rf/rb,d
H2OPg gabbros H2OPg = ftot,g*rf/rb,g
chloride wt. % Cl each Cl = 0.019*H2OP
K2O flux g/yr FK2O each FK2O = K2O*(1
0.01*H2OP)*T*rb*L*V?*104
CO2 flux g/yr FCO2 each FCO2 = CO2*(1
0.01*H2OP) *T*rb*L*V?*104
structural H2O flux g/yr FH2OS each FH2OS = H2OS*(1
0.01*H2OP)*T*rb*L*V?*104
pore H2O flux g/yr FH2OP each FH2OP = H2OP*T*rb*L*V?*104
chloride flux g/yr FCl each FCl = 0.019*FH2OP

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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
this difference is due to substantial reductions (10–
25% in the Pacific) of many seafloor spreading
rates by NUVEL-1, 2% of which is attributable to
time-scale revisions [DeMets et al., 1990], with a
further 4.4% time-scale-induced reduction by
NUVEL-1A [DeMets et al., 1994]. I am not aware
of a recalculation of global crustal generation based
on NUVEL-1 or NUVEL-1A. In addition, total
consumption of oceanic crust is less than total
generation because of continent-continent conver-
gence, such as the 0.2 km2/yr convergence
between India and Asia.
3.2. Sediment Subduction
[41] Some previous analyses of global subduction
fluxes have excluded sediment subduction [Stau-
digel et al., 1996; Alt and Teagle, 1999], and some
have included it by assuming a ‘‘typical’’ package
of incoming sediments [Ito et al., 1983; Peacock,
1990; Bebout, 1995]. The partitioning of incoming
sediments into accreted and subducted components
has presented a challenge to quantitative analyses.
Hilde [1983] emphasized the role of flexural gra-
bens as sediment traps fostering sediment subduc-
tion, and he documented the circum-Pacific
occurrences of these grabens. More recent multi-
channel seismic profiling across accretionary mar-
gins has permitted identification of the décollement
separating accreting from underthrusting sedi-
ments. Three analyses dealt with the extreme
regional heterogeneity of sediment subduction by
undertaking global syntheses.
[42] Von Huene and Scholl [1991] compiled trench
length, pre-NUVEL-1 orthogonal convergence
rate, and trench sediment thickness for virtually
all modern subduction zones. They used these data,
along with reference porosity/depth curves and
identification of accretionary versus nonaccretion-
ary margins, to calculate total fluxes of both sub-
ducting sediment (1.5 km3/yr, or 4.0  1015 g/yr)
and pore water (0.9 km3/yr or 9  1014 g/yr).
Incoming sediment was partitioned between sub-
duction and accretion by assuming 100% subduc-
tion for subduction zones lacking prisms, 80% for
those with small to medium-sized prisms, and 70%
for those with large prisms. von Huene and Scholl’s
[1991] analysis is the only one that has evaluated
10.1029/2002GC000392
trench-fill sediments and subduction erosion. They
estimated that the global volume of subduction
erosion is comparable to that of deeply subducted
incoming sediment, and that the combined total is
1.3–1.8 km3/yr.
[43] Rea and Ruff [1996] used a quite different set
of assumptions to assess global sediment subduc-
tion. Rather than consider trench-fill, their sedi-
ment thicknesses were based on DSDP and ODP
reference sites seaward of trenches. This approach
allowed them to calculate the amount of incoming
sediment for three lithologies (terrigenous, calcite,
and opal) and to accurately separate mass fluxes of
minerals and pore water. Uneven distribution of
reference sites necessitated grouping of many
adjacent subduction zones into ‘‘trench systems’’.
Accretion was assumed to be zero for the incom-
ing sedimentary blanket sampled at the reference
sites and 100% for the unconsidered trench fill.
Rea and Ruff [1996] estimated that the global
sedimentary flux of solids is 1.43  1015 g/yr
and of pore fluids is 9.1  1014 g/yr. This fluid
flux is virtually identical to that of von Huene and
Scholl [1991], whereas the solid flux is only 35%
of theirs. The analysis of Rea and Ruff [1996] did
not consider fluxes of structural water, K2O, or
CO2, but their calcite flux of 2.2  1014 g/yr
suggests a sediment-hosted CO2 flux of 1.0 
1014 g/yr.
[44] The most comprehensive analysis of sediment
subduction is that of Plank and Langmuir [1998],
who calculated subduction fluxes for major and
trace elements at 26 subduction zones. Like Rea
and Ruff [1996], they computed sedimentary com-
ponents based on analysis of DSDP and ODP
reference sites on the incoming plate, but their
more detailed lithologic analysis was calibrated
with geochemical measurements, permitting calcu-
lation of bulk compositions and therefore elemental
fluxes. By comparing sediment-hosted elemental
fluxes for individual subduction zones to the com-
position of arc volcanics, they were able to eval-
uate the effects of sediment subduction on arc
volcanism.
[45] The analysis of Plank and Langmuir [1998]
quantitatively assessed the sediment-hosted sub-
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 Table 2. Subduction Zones Analyzed and Their Calculated Fluxesa
Geophysics
Geosystems
Geochemistry

Subducting Sediment Fluxes Igneous Crust Fluxes

G

Length, Conv. Rate, Age, Mw Chloride, Chloride,

3

K2O, CO2, H2O+, Pore H2O, K2O, CO2, H2O+, Pore H2O,
Trench km Ref mm/yr Ref Ma Ref Thrust g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr

Aegean 850 l 5 b 90 l 7.00E + 10 2.05E + 11 1.11E + 12 5.43E + 11 1.03E + 10

Alaska 1490 a 56 a 49 a 9.2 1.46E + 12 0 5.00E + 12 3.80E + 13 7.21E + 11 1.31E + 12 3.35E + 12 2.11E + 13 1.12E + 13 2.13E + 11
Aleutian, E. 1246 a 59 a 56 a 9.1 5.21E + 11 0 1.98E + 12 1.75E + 13 3.33E + 11 1.16E + 12 3.09E + 12 1.87E + 13 9.79E + 12 1.86E + 11
Aleutian, W. 1102 a 18 a 72 a 7.1 3.21E + 11 8.99E + 11 5.13E + 12 2.59E + 12 4.91E + 10
Andaman 1089 a 23 a,d 83 a 5.7 2.93E + 12 7.17E + 10 1.24E + 13 3.62E + 13 6.89E + 11 4.10E + 11 1.18E + 12 6.54E + 12 3.22E + 12 6.13E + 10
Antilles, N. 400 e 24 e 87 a 6.1 4.25E + 10 1.39E + 10 2.98E + 11 1.40E + 12 2.65E + 10 1.58E + 11 4.60E + 11 2.51E + 12 1.23E + 12 2.34E + 10
Antilles, S. 400 e 24 e 87 a 6.1 6.19E + 11 1.77E + 10 2.05E + 12 9.48E + 12 1.80E + 11 1.58E + 11 4.60E + 11 2.51E + 12 1.23E + 12 2.34E + 10
C. America 1506 a 72 a 16 a 7.8 2.60E + 11 1.02E + 13 1.76E + 12 3.63E + 13 6.91E + 11 1.54E + 12 2.77E + 12 2.54E + 13 1.60E + 13 3.03E + 11
Cascadia 990 a 36 a 5 a 7.2 1.69E + 12 0 6.46E + 12 3.02E + 13 5.73E + 11 4.53E + 11 3.86E + 11 7.73E + 12 5.71E + 12 1.09E + 11
Chile, C. 1306 a 71 a 23 a 9.5 1.36E + 12 2.80E + 12 2.23E + 13 1.33E + 13 2.52E + 11
Chile, N. 1579 a 74 a 41 a 8.5 1.80E + 12 4.42E + 12 2.92E + 13 1.60E + 13 3.03E + 11
Chile, S. 1218 a 16 a 16 a 5.7 2.76E + 11 4.98E + 11 4.57E + 12 2.87E + 12 5.45E + 10
Colombia 1355 a 65 a 21 a 8.8 2.96E + 10 5.08E + 12 1.58E + 12 1.62E + 13 3.08E + 11 1.28E + 12 2.56E + 12 2.10E + 13 1.27E + 13 2.41E + 11
Cotabato 500 k 20 f 42 n,i 1.54E + 11 3.81E + 11 2.50E + 12 1.36E + 12 2.59E + 10
Hikurangi 794 a 21 a 100 a 7.7 2.77E + 11 8.30E + 11 4.40E + 12 2.11E + 12 4.01E + 10
Izu-Bonin 1167 a 50 g 145 a 6.6 4.06E + 11 1.89E + 12 2.45E + 12 1.50E + 13 2.85E + 11 9.99E + 11 3.20E + 12 1.58E + 13 7.15E + 12 1.36E + 11
Japan, NE 1061 a 76 a 132 a 8.2 4.79E + 11 0 2.84E + 12 1.81E + 13 3.44E + 11 1.37E + 12 4.32E + 12 2.17E + 13 9.96E + 12 1.89E + 11
Java 1200 f 71 b 100 f 7.8 6.29E + 11 2.69E + 11 2.06E + 12 1.70E + 13 3.23E + 11 1.42E + 12 4.24E + 12 2.25E + 13 1.08E + 13 2.05E + 11
jarrard: subduction fluxes of water

Kamchatka 900 a 74 a 115 a 9.0 1.84E + 11 0 2.90E + 12 1.56E + 13 2.96E + 11 1.12E + 12 3.44E + 12 1.77E + 13 8.33E + 12 1.58E + 11
Kermadec 1422 a 52 a 100 a 8.0 2.00E + 11 0 7.74E + 11 1.20E + 13 2.28E + 11 1.23E + 12 3.68E + 12 1.95E + 13 9.37E + 12 1.78E + 11
Kurile 1243 a 75 a 128 a 8.5 5.54E + 11 0 3.29E + 12 2.09E + 13 3.98E + 11 1.58E + 12 4.95E + 12 2.50E + 13 1.16E + 13 2.19E + 11
Makran 950 c 37 b 97 d 6.79E + 12 1.23E + 13 1.28E + 13 6.10E + 13 1.16E + 12 5.82E + 11 1.73E + 12 9.26E + 12 4.46E + 12 8.48E + 10
Manila 1050 c 10 c 30 h 1.58E + 11 3.54E + 11 2.57E + 12 1.47E + 12 2.80E + 10
Mariana 1812 a 47 e 134 a 7.8 7.90E + 11 1.52E + 12 3.94E + 12 1.73E + 13 3.30E + 11 1.45E + 12 4.58E + 12 2.29E + 13 1.05E + 13 2.00E + 11
10.1029/2002GC000392

14 of 50
 Geophysics
Geosystems
Geochemistry

Table 2. (continued)
G
3

Subducting Sediment Fluxes Igneous Crust Fluxes

+
Length, Conv. Rate, Age, Mw K2O, CO2, H2O , Pore H2O, Chloride, K2O, CO2, H2O+, Pore H2O, Chloride,
Trench km Ref mm/yr Ref Ma Ref Thrust g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr g/yr

Mexico 1383 a 49 a 9 a 8.0 7.96E + 10 0 6.47E + 11 9.31E + 12 1.77E + 11 9.11E + 11 1.23E + 12 1.53E + 13 1.04E + 13 1.98E + 11
Nankai 824 a 38 g 23 a 8.1 6.25E + 11 0 1.21E + 12 4.82E + 12 9.16E + 10 4.59E + 11 9.47E + 11 7.53E + 12 4.48E + 12 8.52E + 10
Negros 400 k 20 c 16 m 1.13E + 11 2.04E + 11 1.88E + 12 1.18E + 12 2.24E + 10
New Britain 600 f 110 c,o 50 d 1.03E + 12 2.67E + 12 1.67E + 13 8.87E + 12 1.69E + 11
Peru 1599 a 65 a 37 a 8.1 7.00E + 10 1.35E + 12 5.09E + 11 1.05E + 13 2.00E + 11 1.59E + 12 3.79E + 12 2.58E + 13 1.43E + 13 2.72E + 11
Philippine 1509 a 64 g 43 a 8.0 8.64E + 10 4.90E + 11 3.72E + 11 9.50E + 12 1.80E + 11 1.49E + 12 3.71E + 12 2.42E + 13 1.31E + 13 2.50E + 11
Ryukyu 1153 a 57 g 46 a 6.3 2.28E + 11 0 6.08E + 11 8.54E + 12 1.62E + 11 1.02E + 12 2.59E + 12 1.65E + 13 8.90E + 12 1.69E + 11
San Cristobal 1050 c 49 p 50 d 8.07E + 11 2.08E + 12 1.30E + 13 6.92E + 12 1.31E + 11
Scotia 1005 a 44 a 57 a 7.0 1.30E + 11 0 4.70E + 11 6.59E + 12 1.25E + 11 7.01E + 11 1.87E + 12 1.13E + 13 5.88E + 12 1.12E + 11
Sulawesi, N. 600 c 30 d 42 n,i 2.78E + 11 6.87E + 11 4.50E + 12 2.46E + 12 4.66E + 10
Sulu 500 k 20 f 16 m 1.42E + 11 2.55E + 11 2.35E + 12 1.47E + 12 2.80E + 10
Sumatra 2462 a 50 a 61 a 7.1 6.22E + 12 3.55E + 11 1.83E + 13 8.23E + 13 1.56E + 12 1.96E + 12 5.31E + 12 3.15E + 13 1.63E + 13 3.09E + 11
Sunda, E. 950 f 71 b 145 j 7.10E + 11 2.64E + 12 3.20E + 12 2.01E + 13 3.82E + 11 1.15E + 12 3.70E + 12 1.82E + 13 8.26E + 12 1.57E + 11
Tonga 1460 a 148 a 100 a 8.5 1.56E + 11 0 6.22E + 11 1.24E + 13 2.36E + 11 3.59E + 12 1.08E + 13 5.70E + 13 2.74E + 13 5.20E + 11
Trobriand 590 f 20 c 50 d 1.85E + 11 4.77E + 11 2.98E + 12 1.59E + 12 3.01E + 10
Vanuatu 1189 a 111 a 40 a 7.5 1.29E + 12 3.33E + 12 4.20E + 12 5.26E + 13 1.00E + 12 2.03E + 12 4.95E + 12 3.29E + 13 1.81E + 13 3.43E + 11
jarrard: subduction fluxes of water

Yap-Palau 550 c 3 g 32 d 2.49E + 10 5.70E + 10 4.05E + 11 2.30E + 11 4.37E + 09

Total (26 zones) 2.72E + 13 3.95E + 13 9.27E + 13 5.79E + 14 1.10E + 13
Global total 44454 3.62E + 13 5.26E + 13 1.24E + 14 7.72E + 14 1.47E + 13 3.81E + 13 1.00E + 14 6.14E + 14 3.23E + 14 6.14E + 12
a
Fluxes for subducting sediments are modified from Plank and Langmuir [1998]. Thrust references in McCaffrey [1997]. References are as follows: (a) McCaffrey [1997]; (b) DeMets et al. [1990, 1994];
(c) von Huene and Scholl [1991]; (d) Jarrard [1986]; (e) Plank and Langmuir [1998]; (f) this study; (g) Seno et al. [1993]; (h) Brias et al. [1993]; (i) Beirsdorf et al. [1997]; (j) Sager [1992]; (k) Rangin and
Silver [1990]; (l) Robertson et al. [1996]; (m) Shipboard Scientific Party [1990a]; (n) Shipboard Scientific Party [1990b]; (o) Honza et al. [1987]; (p) Tregoning et al. [1998].
10.1029/2002GC000392

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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
duction fluxes of four components focused on in
this study: structural water (H2O+), pore water,
CO2, and K2O. Chloride, the fifth component, is
readily calculated from pore water. Their tabula-
tions confirmed that H2O+ and K2O are ubiquitous
in subducting sediments: H2O+ occurs mainly in
clays but also in opal, and K2O is present in the
nonbiogenic, terrigenous component. In contrast,
CO2 is often virtually absent from subducting
sediments; it is, of course, highest in calcareous
units, but it is also moderately abundant in clays
and volcaniclastics.
[46] Plank and Langmuir [1998] used more accu-
rate, trench-specific measurements of partitioning
between sediment subduction and accretion than
any other study. Many of their rates and trench
lengths were from von Huene and Scholl [1991]
and are now superceded. Applying the revised
rates (mostly NUVEL-1A) and trench lengths of
this study (Table 2) to Plank and Langmuir’s
[1998] concentrations of structural water, pore
water, CO2, and K2O changes fluxes at most
individual subduction zones substantially. Their
global fluxes of these four components are quite
robust, however, and are revised by only
1.5% to
+3%.
[47] A limitation of the Plank and Langmuir
[1998] study is that its reliance on reference drill
sites precludes analysis of 14 of the subduction
zones of this study. The most volumetrically sig-
nificant omissions are probably the Aegean and the
three segments of Chilean subduction zones. Their
analysis includes two thirds of the global trench
length represented in Table 2, but a more useful
correction factor would be percentage of globally
subducted sediment included in their analysis.
Based on the virtually complete suite of global
subduction zones analyzed by von Huene and
Scholl [1991], the subset analyzed by Plank and
Langmuir [1998] accounts for 75% of total glob-
ally subducted sediments. Consequently, I assume
that the global sediment-hosted fluxes of structural
water, pore water, CO2, and K2O are one-third
higher than those calculated by Plank and Lang-
muir [1998] and slightly refined above. It should
be noted, however, that the heterogeneity of sedi-
ment CO2 contents makes that one-third adjust-
10.1029/2002GC000392
ment less accurate for CO2 than for the other three
components.
3.3. Oceanic Crustal Layers
[48] Oceanic crustal layering was first determined
based on seismic refraction. The Raitt-Hill layer-
ing [Hill, 1957; Raitt, 1963] consists of the fol-
lowing: Layer 2, the ‘‘volcanic layer’’, which is
1.71 ± 0.75 km thick; underlain by Layer 3, the
‘‘oceanic layer’’, which is 4.86 ± 1.42 km thick;
separated by Moho from Layer 4, the upper
mantle. Many subsequent seismic experiments
have refined the seismic structure of Layer 2, its
sublayers 2a, 2b, and 2c, and Layer 3. The syn-
thesis of White et al. [1992] concluded that normal
Layer 2 is 2.1 ± 0.6 km thick and Layer 3 is 5.0 ±
0.9 km thick, for a total crustal thickness of 7.1 ±
0.8 km.
[49] Attempts to correlate this layering with petro-
logical variations have met with limited success.
Moho is a distinctive boundary, but seismic Moho
may not correspond exactly with petrological
Moho. The deepest drilling into in situ oceanic
crust is at Hole 504B. The top layer here is a 572
m extrusive volcanic section, underlain by a 208-
m thick transition zone (572–780 m sub-base-
ment), underlain by sheeted dikes that continue to
the 1836 m sub-basement bottom of the hole. The
top 100 m is low-velocity Layer 2A, but the
main petrological change within the extrusives is a
change from more open to more restricted low-
temperature alteration near the middle of the
extrusives [Alt et al., 1996b]. The layer 2B/2C
boundary, generally considered to mark the
change from extrusive basalts to dikes, occurs
within the transition zone. The Layer 2C/3 boun-
dary has been commonly considered to be the
change from dikes to gabbros [Fox and Stroup,
1981], but at Hole 504B it is probably a meta-
morphic front within the sheeted dikes [Salisbury
et al., 1996].
[50] I follow the example of Hole 504B in
assuming that the upper extrusive layer is 600 m
thick, divided into two 300-m thick layers that
may have significantly different porosity struc-
tures and associated alteration states (Table 1). I
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
include the transition zone with the sheeted dikes,
because its alteration history is generally similar to
that of the upper dikes [Alt et al., 1996b], but its
velocity and porosity structure are more like the
lower extrusives than the sheeted dikes. I follow
many previous investigators in assuming that the
base of the dikes is at 2 km sub-basement, while
recognizing that this assumption is largely based
on the outdated interpretation of Layer 2C/3 at 2.1
km as this petrological boundary. The seismic
Moho at 7 km is taken as the base of oceanic crust
and the lower boundary of these analyses. These
layers are generally much thinner in ophiolites
[Coleman, 1977]. An exception is the Semail
ophiolite, with crust that is 7 km thick. The seismic
structure of this ophiolite is generally comparable
to that of normal oceanic crust, but the extrusive
section is twice as thick as at Hole 504B, the
sheeted dikes extend to 3.3 km, and some perido-
tites occur above seismic Moho [Christensen and
Smewing, 1981].
[51] Crustal accretion at slow spreading rates
involves more episodic volcanism, a deeper melt
lens [Purdy et al., 1992] and more abundant fault-
ing than that at intermediate-to-high rates, resulting
in disrupted igneous stratigraphy and more com-
plex, heterogeneous structure [e.g., Cannat, 1996;
Karson, 1998]. Despite these differences, seismic
crustal thickness is only weakly correlated with
spreading rate [White et al., 1992; Small, 1998],
except for rare occurrences of rates <6 mm/yr
[Dick et al., 2002].
3.4. Properties of Upper Extrusives
[52] Values for the top 300 m of the extrusive
section (Table 1) are based on the core and log
analyses of section 2.
3.4.1. Microporosity
[53] Microporosity is a routine shipboard core
measurement. The primary control on microporos-
ity of extrusives is volcanic style: pillows have
microporosities that are several percent higher
than more massive flows. I assume an age-inde-
pendent microporosity of 7.8% for the upper
crust, based on averaging 839 measurements from
10.1029/2002GC000392
the normal crustal sites tabulated by Jarrard et al.
[2003].
3.4.2. Macroporosity
[54] Macroporosity, consisting mainly of cracks
and interpillow voids, decreases systematically
with increasing age, as described by the linear
regression of Figure 2c. The secondary minerals
responsible for this macroporosity reduction are
assumed to be an 80:20 mix of saponite and
celadonite (section 2.8), the same as at an inter-
granular scale. Calcite is undoubtedly present as
well at a relatively small percentage, which is
already accounted for in the analysis of Alt and
Teagle [1999] and section 3.4.5 below.
3.4.3. Total Porosity
[55] Total porosity is simply the sum of micro-
porosity and macroporosity.
3.4.4. Matrix Density
[56] Matrix density is assumed to decrease system-
atically with increasing age, as described in the
linear regression of Figure 2b, due to gradual
replacement of primary minerals by secondary
minerals.
3.4.5. Carbon Dioxide
[57] Carbon dioxide is assumed to increase system-
atically with increasing age, as described in the
linear regression of Figure 2d.
3.4.6. Potassium and Bound Water
[58] Potassium and intergranular bound water are
calculated from age-dependent matrix density (Fig-
ure 2b), attributing reduction in matrix density to
an 80:20 mixture of saponite and celadonite (Fig-
ure 5). Bound water is also present within alter-
ation minerals filling fractures and interpillow
voids (section 3.4.2); these alteration minerals are
also assumed to be a saponite/celadonite mix.
3.5. Properties of Lower Extrusives
[59] Significant sections of the lower extrusives
(300–600 m sub-basement) have been penetrated
at only four sites: Holes 395A, 418A, 504B, and
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
801C. Consequently, generalizations concerning
the properties of this zone are based primarily on
comparisons of these four sections to their over-
lying extrusive zones. Tectonic windows provide
another perspective on this zone [e.g., Karson,
2002], if they are representative [Francheteau et
al., 1975].
[60] The upper and lower extrusives are expected to
be broadly similar in geophysical characteristics,
volcanically and hydrologically. Volcanic style may
exhibit recurrent patterns of flows, pillows, and
hyaloclastics [Robinson et al., 1979; Schmincke
and Bednarz, 1990; Pezard, 1990; Pezard et al.,
2000], but resulting stratigraphic architecture has a
wavelength of tens of meters, not several hundreds
of meters. Large-scale permeability measurements
of upper oceanic crust are too sparse for quantitative
comparison of upper versus lower extrusives, but
the first-order generalization of these studies is that
the entire extrusive interval acts as a hydrologic unit
during off-axis hydrothermal circulation [Fisher,
1998; Fisher and Becker, 2000]. Seismic studies
(e.g., ESP, OBS, OBH) indicate strong velocity
gradients within the top few hundred meters of
oceanic crust [Vera and Mutter, 1988; White et
al., 1992], whereas no systematic pattern of down-
hole velocity increase is detected within the upper
300 m of basement for DSDP and ODP sites
[Jarrard et al., 2003].
3.5.1. Core-Based Alteration
[61] Core descriptions of the four deep-crustal sites
provide ground-truth comparisons of variations in
alteration with depth. In all four extrusive sections,
smectite is the most abundant alteration mineral. At
Hole 395A, depth-dependent alteration was noted
principally as downhole increases in non-carbonate
veins [Shipboard Scientific Party, 1978] and tem-
perature of mineral formation [Lawrence et al.,
1978], though nearly all diagenesis is low-temper-
ature. At Hole 418A, alteration is consistently
higher in the top 200 m than in the underlying
250 m [e.g., Broglia and Ellis, 1990]. At Hole
504B, the upper and lower extrusives are generally
similar in alteration mineralogy, but the lower
extrusives are less altered [Alt et al., 1996b] and
have more chlorite and mixed chlorite-smectite [Alt
10.1029/2002GC000392
et al., 1985, 1986]. The tholeiitic section at Hole
801C penetrates only 100 m of the lower extru-
sives, and depth-dependent changes in alteration
are difficult to isolate from flow/pillow-induced
heterogeneity (Figure 4).
[62] Chemical analyses generally underestimate
alteration because of sampling bias and underre-
covery of both altered basalts and macroporosity-
filling alteration minerals. For example, despite the
observed difference in alteration between upper
and lower extrusives at Hole 504B [Alt et al.,
1996b], H2O+ analyses are similar: 0.86% (std.
dev. 0.32%, N = 51) and 0.83% (std. dev. 0.66%,
N = 77), respectively. The short interval of lower
extrusives at Hole 801C continues an overall
pattern of downhole decrease in alteration, partic-
ularly decrease in CO2 and possibly also H2O+ but
not K2O [Shipboard Scientific Party, 2000a]. Stau-
digel et al. [1996] quantitatively distinguished
recovered and unrecovered materials for Site 417/
418, by carefully weighting their samples to
achieve representative sampling. Like some core/
log comparisons, their analysis demonstrated that
total abundance of alteration minerals is much
higher than most XRF measurements detect. In
the lower extrusives, average K2O is 14%, struc-
tural H2O is 64%, and CO2 is 19% of that in the
upper extrusives [Staudigel et al., 1996].
3.5.2. Log-Based Alteration
and Total Porosity
[63] Potassium data from cores indicate that most
K-rich alteration minerals are in the uppermost
crust, and they suggest a near-exponential decrease
to 600 m sub-basement [Booij and Staudigel,
1997]. Potassium logs provide unbiased, integrated
comparisons of total potassium enrichment for
upper versus lower extrusives at Holes 395A,
418A, and 504B. The four potassium logs for Hole
395A indicate that the lower extrusives have 110%,
101%, 120%, and 128% of the K2O content of the
overlying extrusives. In contrast, the potassium log
for the lower extrusives at Hole 418A averages
only 57% of the K2O in the upper extrusives. At
Hole 504B, the corresponding proportion is only
35% based on the potassium log and 46% based on
458 XRD measurements (Figure 3).
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
[64] All three sites have both multichannel sonic
and reprocessed Schlumberger sonic logs that yield
similar large-scale velocities; in conjunction with
core-based velocities, these provide macroporosity
estimates. In general, the deeper extrusives have
macroporosities that are about half those of the
shallower extrusives: 0–3.7% versus 6.0–8.2% at
Hole 395A, 1.8–2.1% versus 3.4–4.2% at Hole
418A, and 2.5–5.0% versus 8.0–8.1% at Hole
504B. Similarly, core-based microporosities for
Holes 395A, 418A, 504B, and 801C are signifi-
cantly lower for the lower extrusives than upper
ones, averaging 5.1% (std. dev. 3.8%, N = 154) and
7.8% (std. dev. 5.9%, N = 839), respectively
(medians 4.0% and 5.8%). Matrix densities are
different as well: 2.97 g/cc for lower extrusives
versus 2.93 g/cc for upper ones, corresponding to
8% and 16% alteration, respectively, based on the
mineral alteration model of section 2.8.
[65] In summary, the bulk of the available evidence
indicates that the lower half of the extrusive layer has
about half as much macroporosity as the upper half.
This difference is apparently not alteration induced;
indeed, matrix densities and potassium logs suggest
about half as much hydration and potassium enrich-
ment for the lower extrusives as for the upper ones.
The weight of the volcanic pile may cause a few
percent more macroporosity reduction of the lower
extrusives compared to upper ones, thereby reduc-
ing permeability and associated fluid flow and gen-
erating a seismically detectable vertical velocity
gradient. Seawater that does eventually penetrate
the lower extrusives generates reducing conditions,
lacking the celadonite of the upper extrusives but
retaining the strong smectite dominance.
[66] The flux estimates of this paper assume that
the lower extrusives exhibit age-dependent macro-
porosity and alteration that are half those of the
overlying extrusives. Age-dependent changes in
matrix density, structural water, carbon dioxide,
and potassium are calculated from this assumption
of proportional alteration (Table 1).
3.6. Properties of Dikes
[67] Hole 504B could be the type section for
Layer 2 of oceanic crust. Seven DSDP and ODP
10.1029/2002GC000392
legs at this site have cored and logged through a
572-m thick extrusive layer, a 208-m transition
zone, and 1056 m of sheeted dikes, thought to
represent virtually the entire dike layer. No other
DSDP or ODP site has sampled the dike layer
(Layer 2C and upper Layer 3), though isolated
dikes have been encountered within the extrusive
layer. The only other stratigraphic sections of this
portion of oceanic crust are from ophiolites [e.g.,
Coleman, 1977; Christensen and Smewing, 1981],
whose geophysical properties may have been
affected by emplacement and post-emplacement
processes. Consequently, this study bases its char-
acterization of the dike layer on Hole 504B,
combining the transition zone and sheeted dikes
into a nominally uniform layer.
[68] Alt et al. [1996b] provided a synthesis of
alteration mineralogy and the multistage alteration
history of the Hole 504B dikes. Olivine alters to
chlorite, clay, and talc, plagioclase to albite, zeo-
lites, chlorite, or clay, and augite rarely alters to
actinolite [Alt et al., 1996b]. Alteration of the upper
dikes and transition zone began with greenschist-
facies metamorphism at 350–380
C during axial
hydrothermal alteration, followed by mixing of
upwelling hydrothermal fluids with cooler sea-
water circulating through the extrusives. Alteration
of the lower dikes began with exposure to very
high-temperature (>400
C) hydrothermal vent flu-
ids, followed by 300–400
C greenschist metamor-
phism, and concluding with rare off-axis (<250
C)
veins [Alt et al., 1996b].
[69] Index measurements on 91 samples from the
transition zone and sheeted dikes of Hole 504B
establish a mean matrix density of 2.98 g/cc (stand-
ard deviation 0.04 g/cc) and mean microporosity of
2.25% (standard deviation 2.10). Macroporosity
calculation based on comparison of lab and log
velocities must use lab measurements at elevated
pressure rather than at atmospheric pressure,
because microcrack opening becomes significant
at depths >300 m into the dikes. With this
approach, Salisbury et al. [1996] estimated dike
macroporosities as 0–1.4%. Average macroporosity
of the dikes is 0.8%, based on lithostatic-pressure
core measurements. Most of this macroporosity is
concentrated in the transition zone, where macro-
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
porosity is 5.6%, in contrast to near-zero (mean

0.1%) in the sheeted dikes.
[70] Concentrations of structural water are rela-
tively uniform within the dikes of Hole 504B,
except for significantly higher values within the
transition zone (mean 2.37%, std. dev. 0.78%, N =
140) than in the sheeted dikes (mean 1.67%, std.
dev. 0.67%, N = 274). I assume that the overall
average of 1.76% (std. dev. 0.72%, N = 314) is
representative of Layer 2C globally. Unlike the
situation for the extrusives, this value is probably
not significantly biased by loss of structural water
during sample preparation, because pure smectites
are absent and expandable clays are not abundant
[Alt et al., 1985, 1996b]. Although core recovery in
the dikes is generally low, the core-based determi-
nation of structural water may not be significantly
biased by preferential coring loss of crack-fill
alteration minerals, because H2O+ measurements
suggest relatively uniform hydration. Broglia and
Ellis [1990] analyzed a neutron log of upper dikes
(875 – 1250 m sub-basement) of Hole 504B,
accounting for borehole effects, porosity, and struc-
tural water contributions. They concluded that
volume percentage of total water is 7–8% within
the upper dikes; of this, porosity is <2% and is
probably entirely microporosity, whereas hydrous
mineral content of about 10–30% contributes 6%
H2O.
[71] Considering both whole-rock CO2 and vein
carbonate, average CO2 at Hole 504B is 0.58 wt.%
for the transition zone and 0.07% for the sheeted
dikes [Alt and Teagle, 1999]. The thickness-
weighted average is 0.14%.
[72] K2O content of the dikes of Hole 504B has
been measured via XRF analyses of cores and
downhole logging (Figure 3). K2O leaching [Alt
et al., 1996b] has so depleted this interval, how-
ever, that it is near or at the resolution of both
methods. Based on 343 XRF measurements, aver-
age K2O is 0.014% (std. dev. 0.013), with values
that decrease gradually downhole (Figure 3) from a
level of 0.023% (std. dev. 0.011) in the transition
zone to 0.011% (std. dev. 0.012) in the underlying
sheeted dikes. Spectral gamma ray logging indi-
cates significantly higher K2O: 0.034% for ACT
10.1029/2002GC000392
logging of 1075– 1823 mbsf on Leg 148, and
0.057% for logging of 1349–1871 mbsf on Leg
140. The difference between core and log K2O
could be caused by either non-representative core
recovery (as observed within the extrusives) or
measurement bias. I attribute the difference to
biased log measurements, resulting from K2O
levels that are much lower than those anticipated
during tool design. For example, minimum K2O
detectability and minimum K2O readings are both
sensitive to trace amounts of K2O in the detector
crystal. Different detector crystals may account for
the 65% difference in average K2O for logs
obtained on different legs. I assume that K2O is
sufficiently uniform within the dikes (Figure 3) for
the mean XRF-based K2O of 0.014% to provide a
representative estimate of the K2O content of
Layer 3. This low value results from leaching of
an already K2O-depleted magmatic composition
[Alt et al., 1996a, 1996b]. More typical MORB
compositions may or may not have higher final
K2O contents; K2O availability for leaching may
determine final K2O content (J. Alt, personal
communication, 2002).
[73] With only one dike section available, it is
impossible to examine the possibility of age-
dependent dike alteration directly. Because the
alteration mineral assemblage within the Hole
504B dikes is mainly high-temperature [Alt et al.,
1996b], it is largely attributable to near-ridge
alteration. Consequently, I assume that dike alter-
ation is age-independent, at least for the 5–145 Ma
average ages of subducting crust in modern sub-
duction zones (Table 2). The heat flow pattern at
Hole 504B suggests present-day hydrothermal cir-
culation within the dikes [Wang and Davis, 2002],
and late-stage dike alteration may be occurring [Alt
et al., 1996b], so the assumption of age-independ-
ent alteration could be only a first-order approx-
imation. I apply the Hole 504B values for dike
microporosity, macroporosity, structural water,
K2O, CO2, and matrix density to the dike layers
at all subduction zones.
3.7. Properties of Gabbros
[74] The processes that bring the gabbro layer
within sampling reach also assure that the samples
20 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
will be nonrepresentative of normal in situ con-
ditions. DSDP and ODP have encountered short
gabbro intervals at various sites, often where only
basalts were anticipated. Significant penetrations of
Layer 3 gabbros were obtained at two localities:
Hole 735B on Atlantis Bank of Southwest Indian
Ocean Ridge [Shipboard Scientific Party, 1989,
1999] and Site 894 at Hess Deep [Shipboard
Scientific Party, 1993]. At both localities, faulting
has unroofed the gabbroic section and exposed it at
the seafloor, resulting in stratigraphic sections that
are enhanced in fracturing, microcracks, and low-
temperature alteration, compared to what is likely
for normal in situ Layer 3 [Shipboard Scientific
Party, 1989, 1993, 1999; Bach et al., 2001]. Never-
theless, I assume that these two sites provide the
most representative sample of Layer 3 currently
available.
[75] Hole 735B was cored to 501 mbsf on Leg 118
and deepened to 1508 mbsf on Leg 176. Core
recovery was exceptionally good, but loss of the
bottomhole assembly during Leg 176 prevented
downhole logging of much of the newly drilled
interval. The entire drilled interval consists of
Layer 3 gabbros. Index measurements on 346
samples establish a mean matrix density of 2.99
g/cc (standard deviation 0.12 g/cc) and mean
microporosity of 0.74% (standard deviation 2.76).
Ildefonse and Pezard [2001] measured 63 addi-
tional samples, which have a mean matrix density
of 2.98 g/cc and microporosity of 1.11%. The
microporosity distribution is, however, non-normal,
skewed positively by a few high-porosity samples;
median microporosity of the 346 samples is only
0.2%. This microporosity is partly microcracks,
based on resistivity measurements [Ildefonse and
Pezard, 2001] and on velocity measurements that
average 5.6% higher at 200 MPa than at atmos-
pheric pressure [Stephen, 2001]. Microcracks may
not be present in unexhumed gabbros of normal
oceanic crust.
[76] Amphibolite-facies alteration of upper Hole
735B is extensive, averaging 20–30% and with
veins comprising 2.4% of total volume [Dick et al.,
1991; Robinson et al., 1991]. By comparison,
alteration of the Semail ophiolite is characterized
by rare conversion of clinopyroxene to actinolite in
10.1029/2002GC000392
the layered plutonics [Lippard et al., 1986] and by
actinolite and Fe-Ti oxides plus cavity fillings in
more isotropic plutonics [Ernewein et al., 1988].
[77] Measurements of structural water at Hole
735B are most abundant for the interval drilled
during Leg 118: 0.79% average of 94 samples
[Shipboard Scientific Party, 1989]. I assume that
this value is representative of gabbros in general,
but high-temperature alteration of gabbros may
generally be limited to the upper few hundred
meters by available fracture permeability [Alt,
1995]. At Hole 735B, high-temperature alteration
extends to about 600 mbsf, and unroofing-induced
low-temperature alteration is locally common
below 500 mbsf [Bach et al., 2001]. Consequently,
the 1.97% average structural water concentration
for 20 altered samples from below 500 mbsf is less
representative than the 0.79% average for 18 fresh
samples [Bach et al., 2001]. The gabbros cored at
Hess Deep Site 894 average 1.26% for 22 samples
(1.39% including one extremely hydrated sample).
Carlson [2001] cited an average bound water
content of only 0.04% for the gabbros of Holes
735B, 894G, and 923A.
[78] CO2 content of gabbros is assumed to be 0.02
wt.%, the average of whole-rock analyses from
upper Hole 735B, Hess Deep, and MARK sites
[Alt and Teagle, 1999]. Fresh gabbros from the
deeper portion of Hole 735B, however, have a
much higher median CO2 of 0.09% [Bach et al.,
2001].
[79] K2O content of the gabbros of Hole 735B has
been measured via XRF core analyses and down-
hole logging. Based on 280 XRF measurements
from Legs 118 and 176 [Shipboard Scientific
Party, 1989, 1999], average K 2 O is 0.065%
(0.061% excluding a single extreme value of
3.97%). Leg 176 samples affected by low-temper-
ature alteration average twice as much K2O as
fresh samples [Bach et al., 2001]. Three spectral
gamma ray logs of the upper portion of this interval
give reasonably consistent average K2O contents
(0.124%, 0.138%, and 0.146%) that are twice as
high as XRF results. The good log replicability and
mean K2O readings that are apparently well above
measurement threshold argue against log measure-
21 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
ment bias as an explanation. The logs may provide
a more representative sample than cores of the K2O
contents of gabbros at Hole 735B, yet be less
appropriate for evaluating the K2O of gabbros in
general. The logs are more sensitive to occasional
K2O spikes caused by low-temperature alteration
minerals, present at Hole 735B because of its
unroofing history but not expected to be present
in deep gabbros.
[80] I assume that Layer 3 gabbros have an average
K2O of 0.061%, based on the Hole 735B XRF
results; this value is close to the weighted average
of 0.05% determined by Dick et al. [2002]. This
value is significantly less than the 0.11% average
for the upper third of this hole based on strip
samples [Hart et al., 1999]. It is consistent with
the XRF-based average of 0.08% for the much
shorter interval of gabbros sampled at Hess Deep
Site 894. It should be noted, however, that uncer-
tainty in gabbro K2O has a huge impact on sub-
sequent calculations of total K 2 O flux into
subduction zones: using the log-based value,
instead, would increase computed total K2O flux
by 71%.
4. Subduction Fluxes
4.1. Water Flux
[81] The annual global flux of subducted water is
1.83  1015 g/yr. This flux includes four major
sources (Figure 6): sediment pore water (42%),
sediment structural water (7%), igneous crustal
pore water (18%), and igneous crustal structural
water (33%). The global contributions from sub-
ducting sediments and crust are nearly equal.
Regionally, in contrast, combined structural and
pore water of incoming igneous crust is nearly
uniform, whereas the quantity of sediment pore
water subduction per meter of trench length varies
by more than an order of magnitude. Variations in
total-water fluxes among individual subduction
zones (Figure 6) are most sensitive to convergence
rate, trench length, and thickness of the subducting
sedimentary section.
[82] The computed water contents for crust of
various ages are remarkably uniform: their total
10.1029/2002GC000392
range is only 5.5–5.7%, a variation of only 3%
among incoming crust at modern subduction
zones. This similarity arises from two factors. First,
all age-dependent changes in macroporosity and
alteration within dikes and gabbros are assumed to
occur near-ridge, so that the structural and pore
water contents of these portions of the crust are the
same throughout the 5–145 Ma average ages at
modern subduction zones. Age-dependent changes
in macroporosity and alteration are confined to the
extrusives, which account for only 16–31% of
total crustal structural water and 35–51% of total
crustal pore water. Second and more important,
age-dependent decreases in upper crustal macro-
porosity are nearly balanced by increases in struc-
tural water. Most of this structural water is within
the mineral matrix, mainly replacement of feldspar
and olivine by saponite; only 17% of macroporos-
ity fill is structural water. Although the average
structural water content of the extrusive section
varies by a factor of 2.3 (2.2–5.1%) among sub-
duction zones, and average pore water content
varies by a factor of 1.9 (2.6%–5.0%), leading to
an 18% regional variation in total bound water and
24% variation in total pore water, total water varies
by only 3%.
[83] The mass balance for water addition and
removal within oceanic crust appears to permit
off-axis crustal alteration to be confined to the
oceanic crust, without significant interchange with
seawater, such as might be expected when a
relatively impermeable sediment blanket inter-
venes. Similarly, much of late-stage intergranular
alteration is accomplished by local redistribution of
elements without substantial bulk-rock geochemi-
cal change [Alt, 1999; Zhou et al., 2001a]. How-
ever, interchange with seawater to at least 65 Ma
is indicated by both heat flow data and by the other
elemental mass fluxes of this study. The structural
water enrichment at the expense of pore water
implies either chlorine outflow or increase in pore
water chlorinity, and ongoing additions of both
potassium and CO2 have been documented earlier.
4.1.1. Comparison to Prior Flux Estimates
[84] My calculated global fluxes of 1.24  1014
g/yr for structural water and 7.72  1014 g/yr for
22 of 50
 Geochemistry 3
Geophysics
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Figure 6. Water fluxes at global subduction zones, from Table 2. H2O+ is bound water in minerals; for crustal
H2O+, loosely bound water is distinguished from water in stabler, more temperature-resistant minerals.

pore water in subducting sediments are based on
minor revisions of the comprehensive evaluation
of Plank and Langmuir [1998]. An earlier value
of 0.7  1014 g/yr for structural water by Peacock
[1990] was based on a single hypothetical sub-
ducting sediment column, in contrast to the eval-
uations for individual subduction zones by Plank
and Langmuir [1998]. Most prior estimates for
sediment pore water flux are slightly higher than
my 7.7  1014 g/yr: 1  1015 g/yr [COSOD-II,
1987], 1  1015 g/yr [von Huene and Scholl,
1991], 1.8  1015 g/yr [Moore and Vrolijk, 1992],
and 9  1014 g/yr [Rea and Ruff, 1996]. The
good agreement of Rea and Ruff’s [1996] value
with Plank and Langmuir’s [1998] result is partly
attributable to methodological similarities in the
two analyses, including use of many of the same
reference sites.
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
[85] Most previous analyses of water budgets for
oceanic crust do not quantify pore water; they
focus instead on structural water. Estimates for the
latter are higher than the 6.14  1014 g/yr of this
study: 8.8 ± 2.9  1014 [Ito et al., 1983] and 8 
1014 [Peacock, 1990]. Ito et al. [1983] used
assumed abundances and associated water con-
tents for hydrous alteration minerals in an oceanic
crust consisting of alteration-based layers: halmyr-
olysis, greenstone, amphibolite, and unaltered gab-
bro. Their structural-H2O values are similar to
ours for the extrusives, higher for the dikes, and
much lower for the gabbros. Peacock [1990]
assumed 2% structural H2O for basalts and 1%
for gabbros, based on consideration of whole-rock
analyses from three upper-crustal sites and the
gabbros of Hole 735B and Oman. Peacock
[1996] noted that dredged rocks indicate much
higher structural water: 1.7–4.9% (avg. 3.5%) for
basalts and 1.6–5.8% (avg. 2.5%) for gabbros,
based on the data of Anderson et al. [1976].
Bebout [1995, 1996] suggested that total water
flux may be 18  1014 g/yr, about double the
structural-H2O values of Ito et al. [1983] and
Peacock [1990], to account for the high H2O+
contents of outcropping metamorphosed subduc-
tion-zone rocks such as the Catalina Schist. He
noted, however, that this additional water may
come from sedimentary or basaltic pore fluids.
My structural-H2O flux for the extrusives, 1.58 
1014 g/yr, is significantly higher than the 1.01 
1014 of Staudigel et al. [1996], due to a combi-
nation of higher structural H2O, thicker extrusive
section (600 m versus 500 m), and lower porosity
(7–13% versus 18.5%).
[86] Moore and Vrolijk [1992] calculated global
water fluxes for both subducting sediments and
oceanic crust, using trench lengths and conver-
gence rates from von Huene and Scholl [1991],
upper crustal porosity and hydrous minerals for
Hole 504B [Becker et al., 1990], and hydrous
minerals in sediments of Kastner et al. [1991].
They estimated fluxes (typo-corrected) of 1.8 
1015 g/yr for sediment pores (versus my 7.7  1014
g/yr), 4.3  1014 g/yr for H2O+ in sediments
(versus my 1.2  1014 g/yr), and 3.5  1014 g/yr
for pore and structural water in the top 1 km of
10.1029/2002GC000392
oceanic crust (versus my 3.7  1014 g/yr for the
same portion).
[87] Nearly all of the water that enters subduction
zones comes from seawater or – in the case of
bound water in sediments – terrestrial hydrous
minerals. Seven studies of fresh MORB glasses
indicate about 0.15–0.25% H2O+ [Ito et al., 1983].
Sobolev and Chaussidon [1996] argued that fluid
inclusions in olivine phenocrysts provide a more
reliable measure of initial MORB H2O+ (0.12
wt.%) than glass does. This value, in conjunction
with a crustal consumption rate of 2.4 km2/yr,
basaltic layer thickness of 2 km, and weighted
average density of 2.76 g/cc, indicates that 1.6 
1013 g/yr of subducted water, or 0.9% of the total
subducted water, is primary water from crustal
generation.
4.1.2. Slab Fluid Expulsion Pattern
[88] Subducting fluids control first-order structural
and petrologic problems: structural style and evo-
lution of accretionary prisms [Davis et al., 1983]
and generation of arc magmas [Gill, 1981] and
consequently long-term growth of continents [e.g.,
Reymer and Schubert, 1984]. Unfortunately, even
rough fluid budgets demonstrate that our knowl-
edge of slab fluid expulsion patterns still faces
first-order uncertainties: present-day fluid expul-
sion rates from some subduction zones are an
order of magnitude higher than fluid sources [Le
Pichon et al., 1991; Kastner et al., 1991], and an
order of magnitude more fluid enters subduction
zones than is eventually released within arc mag-
mas [Ito et al., 1983]. Yet, the 1.83  1014 g/yr
loss of water to subduction zones must be nearly
balanced by gains elsewhere, because even a
sustained 20% imbalance implies a long-term sea
level change of 1 m/Ma, which is unlikely on the
time scale of >100 Ma.
[89] Figure 7 summarizes slab fluid expulsion
patterns, based on the incoming global water
budgets of Table 2 and dehydration evidence
discussed in this section. A useful starting point
is to stipulate that there are five types of sub-
ducting water, each of which might be released
at a different point in the subduction process:
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water 10.1029/2002GC000392

Figure 7. Hypothesized water expulsion pattern in a generalized subduction zone. Bottom: cross-section of a
subduction zone, with solid arrows showing escape paths of subducting water, and dashed lines showing mantle flow
paths. Dehydration mechanisms are shown above the cross-section, with solid bars above the portion of slab
undergoing each dehydration reaction. The plot of total global subducted water semiquantitatively illustrates
expulsion magnitudes; starting values are from Table 2, but expulsion rates are only approximate, as discussed in text.

sediment pore water (7.7  1014 g/yr), sediment
structural water (1.2  1014 g/yr), igneous-crust
pore water (3.2  1014 g/yr), igneous-crust
loosely bound structural water (1.6  1014
g/yr), and igneous-crust firmly bound structural
water (4.6  1014 g/yr). A likely sixth source,
structural water in serpentinites, is ignored here
because its magnitude is unknown. Structural
water within the extrusive portion of oceanic
crust is mostly in smectites, whereas that in
the dikes and gabbros is in more temperature-
resistant minerals such as actinolite and horn-
blende, so release of the former may be more
closely related to smectite breakdown within
sediments than it is to breakdown of lower
crustal hydrous minerals. Structural water within
the sediments is primarily in clays (particularly
smectite) and secondarily in opal, and most
smectite interlayer water is released at temper-
atures below 150
C.
[90] Subduction at margins containing accretionary
prisms expels water due to compaction within the
accreting and underthrust sediments [Bray and
Karig, 1985] and transformation of smectite to illite.
Kastner et al. [1991] and Le Pichon et al. [1991]
simultaneously demonstrated the discrepancy
between present rates of water expulsion at Barba-
dos, Nankai, and Peru prisms and the amount of
water that can be accounted for by generation within
the prism. Kastner et al. [1991] calculated average
water expulsion of 7 m3/yr per m of trench (global
mass of 3  1014 g/yr) from internal fluid sources
(compaction and dehydration), much less than the
100 m3/yr per m of trench presently being vented at
the three margins. The difference was initially
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
thought to be provided mainly by meteoric water
[Kastner et al., 1991] and shallow seawater con-
vection [Le Pichon et al., 1991].
[91] Isotopic studies and identification of low-
chlorinity and high-methane anomalies demon-
strated the significant contribution from deeper
diagenetic processes, particularly smectite dehy-
dration and hydrocarbon generation [Kastner et
al., 1991, 1993]. In addition, the assumption of
steady state compaction may be invalid [Moore
and Vrolijk, 1992; Le Pichon et al., 1993]. Recent
modeling of flow and solute transport at Nankai
accretionary prism incorporated transient flow,
caused by a hydrofracture-induced temporary
increase in permeability along the décollement
[Saffer and Bekins, 1998].
[92] Subducted sediments are initially overpres-
sured and underconsolidated [Davis et al., 1983;
Moore and Vrolijk, 1992]; rate of fluid expulsion
depends on a combination of loading, convergence
rate, and permeability [Saffer and Bekins, 2002].
Normal consolidation is achieved and most smec-
tite dehydrates after perhaps 30–40 km of sub-
duction (5 km burial) [Saffer and Bekins, 1998;
Moore and Saffer, 2001]; near-complete loss of
pore and structural waters is presumed to occur
within a few additional kilometers of burial. It
appears doubtful, however, that any significant
net escape of fluids from oceanic crust occurs at
these shallow depths, because the framework
strength of basalts prevents compaction. This does
not preclude fluid flow within the basalts, possibly
including flushing of water whose chlorinity has
been lowered by saponite breakdown, driven by
the buoyancy force of warmer waters flowing
updip from deeper sources. Vein and fabric studies
of outcropping forearc sedimentary rocks indicate
an evolution of fluid flow style during subduction:
initial mud-filled veins, then cracks with calcite fill,
then scaly fabric [Fisher, 1996]. Updip migration
of fluids may occur mainly within the high-perme-
ability scaly fabric of the upper portion of under-
thrust sediments, at least for burial depths of
<15 km [Fisher, 1996].
[93] Studies of the Catalina Schist showed a slab-
parallel melange fabric, suggesting that most fluid
10.1029/2002GC000392
loss at depths of 15–45 km is similarly updip,
toward the toe of the prism [Bebout, 1991]. At
these depths, fluid loss from subducted sediments
is nearly completed and slab devolatilization
begins, driven by metamorphism rather than com-
paction. Bebout [1995] documented this process
for the metasedimentary and metamafic rocks of
the Catalina Schist, including loss of both water
and CO2 and associated homogenization of oxygen
and hydrogen isotopic signatures. Bebout [1996]
extended these observations to other eclogite-facies
subduction complexes. For both metasedimentary
and metamafic rocks of the Catalina Schist, volatile
loss progresses with increasing metamorphic grade,
from H2O+ concentrations of 5–6% for lawsonite-
albite to 1–2% for amphibolite-facies metamor-
phism [Bebout, 1995]. Bebout [1995] noted that
H2O+ contents of up to 10% for the low-grade
metabasalts are higher and more homogeneous
than those of DSDP/ODP basalts and ophiolites.
He suggested that low-grade metamorphism trans-
forms both original hydrous minerals and pore
water into new hydrous minerals.
[94] Although the Catalina Schist is unlikely to be
representative of all subducted sediments and
basalts, its pattern of progressive water loss pro-
vides a first-order indication of devolatilization at
moderate depths. By 15 km depth, a water
content of 5% by weight for sediments, for a global
sediment subduction of 1.7  1015 g/yr, implies
8.4  1013 g/yr of water subduction, only 9% of
the pore and structural water within initially sub-
ducted sediments. By 40 km depth, reduction of
this water content to 1.3% expels all but 2% of
the initial water. Assuming that the Catalina Schist
metabasalts are representative of the extrusive
portion of oceanic crust, 5% water content at
15 km depth implies 2.1  1014 g/yr of water,
or 72% of the originally subducted upper crustal
waters, and 1.3% at 40 km depth implies a
residual water content there of 5.6  1013 g/yr,
or 19% of original subduction volumes (Figure 7).
By 15 km depth, 50% of the water that entered
the subduction zone has been expelled, mainly
updip toward the prism toe. By 40 km, 60%
has been expelled. Inclusion of water expulsion by
metamorphic reactions within the dikes and gab-
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
bros presumably would raise this total substan-
tially. For example, similar amphibolite-grade
metamorphism of the dikes, reducing their water
content from 2.8 to 1.3%, would expel 1.5  1014
g/yr, or an additional 8% of originally subducted
water.
[95] Magnetotelluric surveys have detected high-
conductivity zones attributed to free water in or
near the top of the subducting slab at several
subduction zones: at 25–50 km depth in Juan de
Fuca [Wannamaker et al., 1989], at roughly 20–
60 km beneath the Okinawa Trough forearc and
somewhere within the interval 60–130 km depth
beneath the arc [Shimakawa and Honkura, 1991],
extending to >60 km depth in Izu-Bonin [Toh,
1993], and from 13 km to 30 km depth in Mexico
[Arzate et al., 1995]. The excellent resolution of
the Juan de Fuca resistivity model detected an
order-of-magnitude conductivity decrease from
the trench to 60 km inland, due to pore water
loss, followed by a sudden increase in conductiv-
ity at 25 km depth, interpreted as dehydration of
greenschist-facies minerals [Wannamaker et al.,
1989].
[96] Updip reflux persists at least to 15 km and
possibly to 45 km, based on the Catalina Schist
melange fabric [Bebout, 1991, 1995]. The Juan de
Fuca conductivity increase at 25 km [Wannamaker
et al., 1989], however, does not suggest reflux.
Whether subducting crust below 45 km depth
retains sufficient fracture permeability for volatile
escape is unknown. Dehydration may generate its
own permeability, by inducing hydrofracture [Fyfe,
1997]. A magnetotelluric survey of the Vancouver
Island portion of Cascadia subduction zone
detected porosities of 0.5–4.0% (assuming sea-
water salinity) well above the slab, attributed to
fluid rise from the slab to an impermeable barrier
[Hyndman, 1988].
[97] When the slab reaches 80 –120 km depth,
large-scale release of volatiles into the overlying
mantle wedge generates the partial melting that
results in arc volcanism [Gill, 1981]. Except per-
haps for very young slabs, the crust undergoes little
partial melting [Defant and Drummond, 1990;
Peacock, 1990; Peacock et al., 1994].
10.1029/2002GC000392
[98] Based on a variety of H2O+ studies of arc
magmas, Ito et al. [1983] calculated that the water
flux at arcs is 1  1014 g/yr; major uncertainties
in magma volumes result in a possible range of
0.95–2.0  1014 g/yr. Peacock [1990] provided a
similar estimate, 1.4  1014 g/yr, without mention-
ing data sources. A more appropriate measure of
the volatile content of magmas may be fluid
inclusions in olivine phenocrysts, which average
2.5% [Sobolev and Chaussidon, 1996]; in conjunc-
tion with an arc magmatism rate of 2.9–8.6 km3/yr
[Crisp, 1984], resulting water flux is 2–6 times
that of Ito et al. [1983] or Peacock [1990]: 2–6 
1014 g/yr. Of the 6  1014 g/yr of subducting
water that appears to reach 45 km depth, at least a
third and perhaps all is later released to the mantle
wedge and reaches the arc. The remainder may be
released into other parts of the mantle wedge, enter
arc magmas but degas during volcanism, or be
retained into the deep mantle. I emphasize, how-
ever, that the cumulative errors in this mass balance
are huge and impossible to quantify. For example,
Reymer and Schubert [1984] calculated an arc
magmatism rate of 1.1 km3/yr (1.3 km3/yr with a
more accurate total trench length) from seismic
profiles across arcs that is only 13–38% of Crisp’s
[1984] rate from active arc volcanism; I use the
latter. The unknown amount of water loss to the
deeper mantle makes estimation of the mantle
water budget problematic [Bell and Rossman,
1992; Thompson, 1992; Williams and Henley,
2001].
[99] Many authors have interpreted phase diagrams
based on experimental petrology to infer the cause
of the fluid release responsible for arc magmatism
[e.g., Peacock, 1990, 1991, 1993, 1996; Pawley
and Holloway, 1993; Pawley, 1994; Poli and
Schmidt, 1995; Liu et al., 1996; Iwamori, 1998,
2001; Ono, 1998; Ernst, 1999]. A single volatile-
expulsion event is not expected. A suite of hydrous
minerals (lawsonite, chlorite, amphibole, epidote/
zoisite, chloritoid, and others) is expected to break
down in a series of overlapping depth zones
[Schmidt and Poli, 1998; Kerrick and Connolly,
2001]. Systematic lateral variations in water-solu-
ble elements in magmas from forearc to arc suggest
a progressive decrease in water input from the slab
27 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
[Ryan et al., 1996], possibly a change from
amphibole breakdown near the trench to phlogo-
pite decomposition in the backarc [Tatsumi and
Kogiso, 1997].
[100] Even if a single volatile-release event were
likely within each slab, it should not occur at
similar depths in subduction zones with widely
varying slab ages and subduction rates, based on
pressure-temperature phase diagrams. Slab temper-
ature at any depth is very sensitive to both sub-
duction rate and slab age, as confirmed by thermal
models. For example, for a constant subduction
rate, the temperature of the top of upper crust at
100 km depth varies from 540
C for 145-Ma crust
to 1180
C for 5-Ma crust [Peacock, 1990].
Accordingly, the same dehydration reaction that
is expected to release water beneath the arc for
intermediate geotherms releases that water beneath
the forearc for high-temperature geotherms (slow
subduction and/or very young crust) and retains
that water to the deep mantle for low-temperature
geotherms (rapid subduction and/or old crust)
[Kerrick and Connolly, 2001]. Early release of
volatiles from young, hot slabs may affect compo-
sitions of later, deeper arc magmas, based on a
possible association between slab age and magma
composition in only two subduction zones [Green
and Harry, 1999; Harry and Green, 1999]. In
contrast, ultrafast subduction, such as occurs today
in Tonga, favors retention of some water to the
deep mantle, possibly generating chemical anoma-
lies in the mantle [Staudigel and King, 1992].
[101] Volatile release within the subducted slab
may occur earlier within the extrusives than in
the dikes and gabbros, not only because of more
loosely held water in less stable minerals, but also
because of larger-scale metamorphic phenomena.
Hacker [1996] concluded that conversion of the
extrusives to eclogite is complete by 250
C,
whereas eclogite conversion of the gabbros usually
is complete by 550
C and may continue to
>800
C.
[102] In contrast to the wide variability of depths
for volatile release, both within and among slabs,
volatile escape culminating in generation of arc
magma is generally confined to 100 km depth.
10.1029/2002GC000392
Sub-arc slab depths are readily computed from slab
intermediate dip (0–100 km) and arc-trench gap,
both tabulated by Jarrard [1986] for 26 of the
subduction zones of Table 2. All but two sub-arc
depths are between 80 and 120 km. In modern
subduction zones, subduction rates vary by a factor
of 30, and average ages of the slab vary from 5 Ma
to 145 Ma, yet no correlation is found between
sub-arc depth and subduction rate, slab age, or their
product, strongly implying that melting within the
mantle wedge is insensitive to temperature of the
adjacent oceanic crust. This observation is consis-
tent with thermal models incorporating convection
of the mantle wedge, whereas models lacking
convection exhibit strong slab-induced cooling of
the mantle wedge [Anderson et al., 1980]. Nor
does fluid availability affect the depth of melting:
sub-arc depth is not correlated with CO2 or any of
the four types of water flux, nor with these fluxes
per meter of trench length.
[103] Predictions of multiple volatile expulsions and
thermally dependent expulsion imply large-scale
transport prior to release beneath the arc. Even with
available water to lower melting temperature, par-
tial melting of the mantle wedge cannot occur until
a temperature of at least 1000
C is reached. Water
released between 50 km and 100 km may remain
within the slab or migrate into the adjacent mantle
that is dragged downward (Figure 7). In either case,
the upper part of the slab and mantle wedge have
insufficient permeability to permit large-scale
escape of volatiles, until partial melting of the
mantle wedge occurs, with associated volatile
advection. Of the volatiles that are released after
much deeper subduction, some may trigger slab or
adjacent mantle melting and reflux along the slab
top to the arc-magma generation zone, and some
may be lost to the deep mantle.
[104] Because partial melting in the mantle wedge
is triggered by volatile release, a correlation
between rate of arc volcanism and amount of
deeply subducted water may exist. Early explora-
tions of this hypothesis, using convergence rate as
a proxy for subducted water, found no correlation
between convergence rate and either arc eruption
rate [Gill, 1981] or seismic-based arc growth rate
[Reymer and Schubert, 1984]. Subducted water per
28 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
unit arc length (Table 2) is well correlated (R =
0.72) with arc growth rate if arc ages of Jarrard
[1986] are used to calculate the latter, but inversely
correlated (R =
0.57) if arc ages from Reymer
and Schubert [1984] are used; in both cases, 1–2
extreme points dominate the correlation. A com-
prehensive analysis of these hypotheses, using
water fluxes from Table 2, may be warranted but
is beyond the scope of this paper.
4.1.3. Slab Devolatilization
and Benioff Zone Seismicity
[105] Devolatilization within the slab has been
suggested as a mechanism for several aspects of
Benioff zone seismicity. Metamorphic reactions
and associated fluid release could control the updip
and downdip limits of the large earthquakes gen-
erated at the contact between underthrusting and
overriding plates [Hyndman et al., 1997; Kasahara
et al., 2001]. Alternatively, the updip edge of
interplate seismicity may be attributable to a suite
of diagenetic changes that increase rock strength
[Moore and Saffer, 2001], and the downdip edge
may be compositionally determined, occurring at
the overriding plate’s Moho [Ruff and Tichelaar,
1996]. Dehydration is likely to elevate pore pres-
sures and lower effective stress, thereby inducing
earthquakes via hydrofracture. This dehydration
embrittlement may be responsible for intermedi-
ate-depth earthquakes in subducting crust during
transformation to eclogite [Kirby et al., 1996] and
in the lower plane of double seismic zones during
breakdown of serpentine to forsterite and enstatite
[Peacock, 2001; Omori et al., 2001]. Serpentine
dehydration may also be the cause of deep-focus
earthquakes [Raleigh and Paterson, 1965; Meade
and Jeanloz, 1991]. In all three cases, the wide
depth distribution without a localized seismicity
maximum is surprising.
[106] Slab devolatilization might also affect mag-
nitude of interplate earthquakes: increased fluid
pressure might decrease coupling between the
plates, leading to smaller earthquakes. Rea and
Ruff [1996] tested this hypothesis by comparing
maximum earthquake magnitude to incoming
sedimentary pore water for their 12 trench groups,
and they found no correlation. They suggested,
10.1029/2002GC000392
however, that a more diagnostic test would con-
sider individual subduction zones rather than
trench groups. For 23 subduction zones, incoming
contents of bound and pore water of Table 2 can
be compared to maximum earthquake magnitudes
tabulated by McCaffrey [1997]. Water content is
used rather than water flux, to remove the effects
of trench length and convergence rate. This com-
parison confirms Rea and Ruff’s [1996] conclu-
sion that pore water content does not affect
earthquake magnitude, and it extends this conclu-
sion to include sediment bound water and total
water from sediments and basalts. A weak corre-
lation (R2 = 0.28
0.30) is found, but it is almost
entirely attributable to a single subduction zone,
Andaman, which has the highest content of
incoming water and lowest earthquake magnitude.
Convergence rate, rather than fluids, is the dom-
inant control on earthquake magnitude, either
because of coupling [Ruff and Kanamori, 1980;
Jarrard, 1986] or recurrence time [McCaffrey,
1997]. Slab age may [Ruff and Kanamori, 1980;
Jarrard, 1986] or may not [McCaffrey, 1997] be a
secondary influence. Subducting fluids are not
even a second-order influence, based on compar-
isons to earthquake magnitude residuals (observed
minus predicted based on regression on conver-
gence rate).
4.2. Chlorine Flux
[107] Assuming a typical seawater chlorinity of
19% (34.3% salinity) for subducted pore waters,
2.08  1013 g/yr of chlorine enters the world’s
subduction zones via pores in sediments and crust.
Amounts of chlorine in subducting minerals are
less reliably known but certainly much smaller. Ito
et al. [1983] calculated that 2.9 ± 1.5  1012 g/yr
of chlorine is subducted as oceanic crustal miner-
als, based on measured chlorine contents of the
hydrous minerals and approximate mineral abun-
dances; updated subduction rates would change
this value to 2.5 ± 1.3  1012 g/yr. For chlorine
within subducted sedimentary minerals, the geo-
synclinal average of 1200 ppm chlorine [Ronov
and Yaroshevskiy, 1976] for a sedimentary subduc-
tion rate of 1.68  1015 g/yr provides a very rough
estimate of 2  1012 g/yr. Total chlorine entering
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Figure 8. Flowchart of global chloride fluxes. See text for sources. All arc volcanism is shown as occurring on
continents, but some occurs on oceanic crust that may later become continental crust.
global subduction zones is therefore 2.5  1013
g/yr.
[108] Figure 8 presents a flowchart of global chlor-
ide fluxes. Although mantle degassing has trans-
ferred about 40% of Earth’s chlorine to oceans and
crust [Magenheim et al., 1995], the global chloride
budget is probably near long-term mass balance,
because salinity of the ocean has been relatively
stable throughout at least the last 1.5 b.y. The
oceanic chloride reservoir is so huge (2.7 
1022 g), however, that even massive temporary
imbalances have a negligible impact. The ocean
loses chloride to cyclic sea salt and pores, and this
loss is likely to be balanced by dissolved river influx
and water reflux from the shallow subducted slab.
[109] Chloride fluxes between the ocean and con-
tinents are 1–2 orders of magnitude larger than
other chloride fluxes. Livingstone [1963] con-
cluded that river influx of dissolved materials to
the sea is 2.5–4  1015 g/yr, of which 6.5% is
chloride, so the chloride influx is 1.6–2.6  1014
g/yr. Meybeck [1979] noted that pollution is often a
major source of chloride in rivers, and he evaluated
the natural river flux of chloride as 2.2  1014 g/yr.
Much of this chloride, however, is ‘‘cyclic salt’’,
sea salt captured by the atmosphere and carried
inland, where it is either deposited or washed out
of the atmosphere by rain or snow [Clarke, 1924].
10.1029/2002GC000392
Direct measurement of the cyclic salt flux is not
possible. Between 28% [Meybeck, 1983] and 82%
[Berner and Berner, 1987] of the pollution-cor-
rected chloride flux in rivers is attributable to
dissolution of evaporites, and the rest is from cyclic
salt. Consequently, cyclic sea salt transport of
chloride from sea to land is 4–16  1013 g/yr.
[110] The mantle loses chloride to MORB and arc
volcanism [Schilling et al., 1978] and to reflux, and
it gains chloride from subduction. Using an aver-
age chlorine content of 48 ppm for MORB glasses,
Ito et al. [1983] calculated a chloride supply rate of
2.7  1012 g/yr at spreading centers. Their estima-
tion of chloride flux at arc volcanoes is subject to a
factor of 20 uncertainty associated with magma
generation rates [Ito et al., 1983]. Using an average
chlorine content for arc magmas of 900 ± 500 ppm
and the upper range of magma generation estimates
(5–10  1015 g/yr), Ito et al. [1983] computed a
chloride supply rate of 4.3–9.5  1012 g/yr. The
MORB Cl
flux is not changed by newer geo-
chemical data [Jambon et al., 1995], nor by revised
seafloor spreading rates and crustal thicknesses of
this study. Revised arc magma generation (2.9–8.6
km3/yr) [Crisp, 1984] changes the arc Cl
flux to
7–22  1012 g/yr.
[111] Reflux at and near the toes of accretionary
prisms expels half of total subducted water prior to
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
slab subduction to 15 km, and reflux may expel the
two thirds of total subducted water released by 45
km (section 4.1.2). Associated chloride flux for the
latter consists of 1.4  1013 g/yr from sediment
pores and may include up to 0.6  1013 g/yr from
basalts. The average chlorinity of reflux water is
therefore 11–16%, much less than the normal
chlorinity of 19% for seawater and pore fluids.
Chlorinity anomalies appear to be a common
feature of décollements [Kastner et al., 1991].
For example, chlorinity of the Nankai décollement
is 15%, less than can be accounted for by
smectite dehydration of subducting sediments and
therefore implying an additional, deeper source of
low-chlorinity water [Kastner et al., 1993; Under-
wood et al., 1993]. The Nankai chlorinity anomaly
has been reproduced with a coupled flow and
solute-transport model that incorporates transient
flow within the sediments [Saffer and Bekins,
1998]. The water fluxes of Table 2 suggest that
inclusion of smectite breakdown in the oceanic
crust may be appropriate for reproducing the Nan-
kai chlorinity anomaly; structural water in the
Nankai upper crust is 50% higher than that in the
subducted sediments.
[112] If the interpreted patterns of slab dewatering
and associated reflux (Figure 7) are valid, then
fluid inclusion studies of eclogites are predicted to
exhibit the following chlorinities: 19% (sea-
water) for metasediments with possible smectite/
illite transformation followed by compaction flush-
ing, 6–13% (depending on crustal age) for meta-
basalts with partial expulsion of pore and structural
water, and near-zero for metabasalts with extensive
flushing from downdip portions of the slab. Meta-
morphic rocks from subduction zones (but not
continental collisions) are consistently low-chlor-
inity [Bebout, 1996], generally 9–12% [Philippot
et al., 1998].
[113] The mantle chloride budget may be close to
mass balance currently (Figure 8), but uncertainties
are large: total loss to arc and MORB volcanism
and reflux is 2.4–4.5  1013 g/yr, and total gain
from subduction is 2.5  1013 g/yr. In the near
future, chlorine isotopic studies may be able to
refine our understanding of chloride fluxes associ-
10.1029/2002GC000392
ated with both crustal alteration and subduction
recycling [Magenheim et al., 1995].
4.3. CO2 Flux
[114] Global CO2 subduction totals 1.53  1014 g/
yr. Two thirds of this amount is within the oceanic
crust, particularly the upper portion of the extru-
sives, and the remainder is in accreted sediments
(Figure 9). Nearly all of this CO2 is in the form of
carbonate, primarily calcium carbonate. CO2 con-
tent of most subducting igneous crust varies within
about a factor of two. In contrast, CO2 contents of
subducting sediments are much more variable, with
negligible carbonate and CO2 in half of the sub-
ducting sediment sections (Table 2). Variations in
CO2 subduction fluxes among individual subduc-
tion zones (Figure 9) are most sensitive to con-
vergence rate, trench length, and amount of
subducting sedimentary carbonate.
4.3.1. Comparison to Prior Flux Estimates
[115] My 5.26  1013 g/yr for CO2 in subducting
sediments is based on very minor revisions of the
comprehensive evaluation of Plank and Langmuir
[1998]. These results supercede that of Peacock
[1990], whose 1.6  1014 g/cc was based on a
single hypothetical subducting sediment column
that lacked hemipelagics and turbidites and was
72% carbonate; in contrast, Plank and Langmuir
[1998] found that average subducting sediment is
only 7% carbonate.
[116] Crustal CO2 subduction is calculated to be
1.00  1014 g/yr, within the wide range of previous
estimates: 1.63  1014 [Staudigel et al., 1989],
0.6  1014 [Peacock, 1990], 1.8  1014 [Bebout,
1995, 1996], 1.18  1014 [Staudigel et al., 1996],
and 1.48  1014 [Alt and Teagle, 1999]. These
previous studies are based on estimating the CO2
content of typical old subducting crust. In contrast,
flux calculations for the extrusives based on very
young 6-Ma crust [Alt et al., 1996a] and 3.5 Ma
hydrothermal fluids [Sansone et al., 1998] were an
order of magnitude lower – 0.7–1.6  1013 and
0.4–1.1  1013, respectively.
[117] Peacock [1990] assumed 0.1% CO2 for
both basalts and gabbros, based on consideration
31 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water 10.1029/2002GC000392

Figure 9. Carbon dioxide fluxes at global subduction zones, from Table 2.

of whole-rock analyses from three upper-crustal
sites and the gabbros of Hole 735B and Oman,
whereas Bebout [1995, 1996] used 0.3% for the
entire oceanic crust, based on data of Staudigel
et al. [1989]. Staudigel et al. [1989, 1996]
analyzed Holes 417A/417D/418A, and Alt and
Teagle [1999] analyzed Sites 843 and 801. Both
studies were carefully weighted to obtain a rep-
resentative sample (see section 2.6 above) for the
extrusives. Alt and Teagle [1999] extended this
approach to encompass the dikes of Hole 504B
and gabbros at three ODP localities. In contrast,
Staudigel et al. [1989] interpolated between their
value for the extrusive section and near-zero at
1100 m subbasement, and Staudigel et al. [1996]
confined their flux assessment to the extrusive
section.
[118] My CO2 flux calculation for oceanic crust is
based largely on the excellent and comprehensive
analysis of Alt and Teagle [1999]. Indeed, I adopt
their CO2 values for the dikes and gabbros and for
4 of the 5 upper extrusive sections of Figure 2d.
Rather than assume a uniform CO2 content for all
altered crust, however, I use the tentative age-
dependent CO2 enrichment pattern of Figure 2d
32 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
to compute upper crustal CO2 for each subduction
zone. The resulting total flux is only 70% of that of
Alt and Teagle [1999], mainly because I use a total
subduction rate that is only 71% of theirs (see
section 3.1 discussion of revised subduction rates).
4.3.2. CO2 Flux Budget
[119] Consideration of the complete global CO2
flux budget (including mantle, continental crust,
oceanic crust, oceans, and atmosphere) is beyond
the scope of this paper. Berner et al. [1983] and
François and Walker [1992], among others, pre-
sented CO2 flux budgets and models. My focus, in
contrast, is on mantle and oceanic crust CO2
budgets.
[120] The dominant CO2 additions to the ocean/
atmosphere system from crust and mantle sources
are magma degassing at spreading centers and arc
volcanoes, organic carbon breakdown, and possi-
bly metamorphic breakdown of calcite to silicate.
The dominant removal mechanisms are subaerial
silicate weathering, which generates bicarbonate
and culminates in calcite precipitation, carbonate
uptake by oceanic crust, and organic carbon
burial.
[121] Degassing at spreading centers contributes
2.8–5.5  1013 g/yr [Gerlach, 1989] or 5.7–
13.6  1013 g/yr [Marty and Tolstikhin, 1998] of
CO2; these values should probably be reduced
10% to account for lower spreading rates for
NUVEL-1A than for earlier plate motion models.
Degassing of arc volcanoes contributes another
11 ± 3  1013 g/yr [Zhang and Zindler, 1993;
Marty and Tolstikhin, 1998] or 8–11  1013 g/yr
[Kerrick, 2001], and plumes may add a compara-
ble amount [Marty and Tolstikhin, 1998]. Subaerial
weathering removes 2  1014 g/yr of CO2 from
the atmosphere [Berner, 1990]. Burial of organic
carbon removes 2.2 ± 0.9  1014 g/yr, but 9 ± 4 
10 13 g/yr is released by thermal breakdown
[Berner, 1990]. Carbonate uptake by oceanic crust
may approximately equal its current subduction
rate, 1.0  1014 g/yr, or it may be much less (see
sections 2.6 and 4.5). The ocean/atmosphere sys-
tem must be close to steady state balance with
crust and mantle, but that is not apparent from
10.1029/2002GC000392
comparing these total CO2 atmosphere/ocean sour-
ces (3.5 ± 1.2  1014 g/yr) to sinks (5.6 ± 1.2 
1014 g/yr). Additional possible sources, such as
abiogenic methane and non-volcanic CO2 degass-
ing, are discussed by Kerrick [2001]. The close
coupling between CO2, climate, and silicate weath-
ering may prevent major long-term imbalance
between atmospheric CO2 sources and sinks
[Berner and Caldeira, 2002].
[122] Subduction of sediments and oceanic crust
removes 1.53  1014 g/yr of CO2 from the
ocean/atmosphere system. In contrast to the initial
subduction fluxes of water and chloride, most of
which are lost to reflux, a negligible portion of
subducted CO2 is lost to reflux. The CO2 content
of reflux waters is likely to be close to saturation,
or 0.02% for seawater at 0
C, so a water reflux of
two-thirds initial subduction volume entrains 2.9
 1011 g/yr of dissolved CO2, or only about 0.2%
of subducting CO2.
[123] From the perspective of CO2 mass balance
for the mantle, the subducting flux of CO2 exceeds
the individual supplies from ridge volcanism and
arc volcanism, but it is much less than the total
degassing rate of 2.6  1014 g/yr (range 1.8–4.4
 1014) [Marty and Tolstikhin, 1998]. Some
crustal CO2 reaches the deep mantle, based on
the excess of CO2 subduction over arc magma-
tism, the observation that CO2 appears to be
mostly retained during metamorphism at depths
of 15–45 km [Bebout, 1995], and the relatively
large amount of CO2 still present in the mantle
[Zhang and Zindler, 1993]. Phase equilibria sug-
gest only minor decarbonation at and above subarc
depths [Kerrick and Connolly, 2001], but dehy-
dration enhances decarbonation and vice versa
[Peacock, 1990; Kerrick and Connolly, 2001].
Kerrick and Connolly [1998] suggested that the
CO2 in arc magmas is derived mainly from sub-
ducted sediments and extrusives, whereas CO2
within subducting mantle serpentinites (not con-
sidered in my flux calculations) is released in the
deep mantle.
[124] The modern rate of crustal CO2 subduction is
more significant than that of sedimentary CO2 for
several reasons. First, total crustal CO2 subduction
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water 10.1029/2002GC000392

Figure 10. Potassium fluxes at global subduction zones, from Table 2.

is double that from sediments. Second, all subduct-
ing crust contains significant CO2 whose ultimate
release affects melting in the mantle wedge,
whereas most sedimentary CO2 is in a few sub-
duction zones. Third, the modern rate of crustal
CO2 consumption is a robust indicator of long-term
removal from the ocean/atmosphere system. In
contrast, present-day sediment subduction is less
relevant to ocean/atmosphere CO2 change than is
carbon removal as deposition of calcium carbonate
and organic matter. A significant portion of carbo-
nate deposition [Hay, 1994] and most organic
carbon deposition [Dymond and Lyle, 1994] are
on continental shelves and are therefore isolated
from mantle recycling for tens to hundreds of
millions of years.
4.4. K2O Flux
[125] Sediments and igneous crust contribute about
equal amounts to total subduction flux of K2O
(Figure 10): 3.62  1013 g/yr and 3.81  1013
g/yr, respectively. Variations in K2O fluxes among
individual subduction zones (Figure 10) are most
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water 10.1029/2002GC000392

K2O fluxes (x 10 12 g/yr)

air transfer
1-4
dissolved
continents in rivers 60 oceans
suspended
in rivers
sed.
370 diagenesis
arc low-T 5-7
volcanism 52 alteration high-T
400-1200 12 alteration
sediments
36 subduction

MORB 37 oceanic
mantle volcanism
subduction crust
38

Figure 11. Flowchart of global potassium fluxes. All arc volcanism is shown as occurring on continents, but some
occurs on oceanic crust that may later become continental crust. Most suspended sediments transported to oceans are
deposited on oceanic crust as shown, but some are deposited on continental margins.

sensitive to convergence rate, trench length, and
thickness of subducting terrigenous sediments.
4.4.1. Comparison to Prior Flux Estimates
[126] Subduction recycling of K2O was first quan-
tified roughly by Sleep and Wolery [1979], who
suggested that crustal alteration absorbs 1–2 
1013 g/yr of K2O and that subducting red clays
raise the total to 3  1013 g/yr. These values are
less than half of mine. The estimated K2O flux of
3.62  1013 g/yr for subducting sediments is
based on minor revisions to the comprehensive
evaluation of Plank and Langmuir [1998]. Based
on geochemical comparison of Holes 417A/417D/
418A to unaltered crust, global K2O flux into the
extrusives was estimated as 2.2  1013 g/yr
[Spivack and Staudigel, 1994] and 1.95  1013
g/yr [Staudigel et al., 1996], similar to my 1.58 
1013 g/yr for this zone. K2O fluxes have also
been calculated for ophiolites [Lecuyer et al.,
1990].
4.4.2. K2O Flux Budget
[127] The oceanic potassium budget (Figure 11)
consists of supply from rivers (both dissolved and
suspended load), sediment loss by deposition,
diagenesis of seafloor sediments, K2O gain from
oceanic crust during high-temperature alteration,
and K2O loss to oceanic crust during low-temper-
ature alteration. The mantle potassium budget,
which is related to mantle thermal regime and
40
Ar [Sleep, 1979; Sleep and Wolery, 1979; Joc-
hum et al., 1983; Azbel and Tolstikhin, 1990],
consists of loss to magmas during MORB, arc,
and hot spot volcanism and plutonism, and gain
during subduction of sediments and igneous oce-
anic crust. Neither budget need be in short-term
or long-term balance. In particular, erosion
roughly balances sediment subduction only on a
time scale of tens to hundreds of millions of
years.
[128] The oceanic K2O budget (Figure 11) is domi-
nated by eroded K2O that is transported by rivers to
the oceans as suspended sediment load and bed-
load, which total 3.7  1014 g/yr of K2O [Milliman
and Meade, 1983]. Nearly all of this sediment is
delivered to oceanic crust; only a few percent of
Quaternary terrigenous marine sediments are
deposited on continental shelves [Hay, 1994].
Annual river influx of dissolved K+ is also signifi-
cant: based on a total dissolved load of 2.5–4 
1015 g/yr, of which 1.9% is K+ [Livingstone, 1963],
potassium transport (expressed as K2O) is 6–9 
1013 g/yr; Meybeck [1979] estimated this influx as
6  1013 g/yr. Residence time of K2O in seawater
(1.4  1024 g @ 0.38% K+) is therefore 8–13 m.y.
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
A small portion of this dissolved potassium comes
from airborne cyclic sea salt: 1–4  1012 g/yr
(expressed as K2O) based on air transfer of chlor-
ide and the relative proportions of chloride and
potassium in seawater. Potassium is absorbed from
seawater by early diagenesis of aluminosilicates
(zeolites and clays) at and very near the seafloor.
Pore water K+ profiles indicate a global K+ flux of
1.1  1018 mEq/yr (5.2  1013 g K2O/yr) [Martin
and Sayles, 1994]. Compared to most other oce-
anic potassium fluxes, the net removal of 5–7 
1012 g/yr from high- and low-temperature crustal
alteration is comparatively small. For example, I
conclude that only 20% of the river input of
potassium is absorbed during low-temperature
alteration of oceanic crust (Figure 11), in contrast
to an earlier 50% estimate [Spivack and Staudigel,
1994]. Calculated total input of dissolved K2O into
the ocean (6.7  1013 g/yr; Figure 11) is surpris-
ingly close to total output (6.6  1013 g/yr),
considering the 10% errors in both.
[129] The subduction flux of crustal K2O includes
both inherited magmatic K2 O and alteration-
induced changes. Earlier discussions of crustal
K2O fluxes concentrated on addition of K2O to
the extrusive section during off-axis low-temper-
ature alteration. This process was recognized long
ago to be one of the dominant geochemical sig-
natures of low-temperature alteration [Hart et al.,
1974; Donnelly et al., 1979b]. In contrast, high-
temperature alteration of the dikes at and near the
ridge axis removes K2O and is more deeply pen-
etrating [Hart and Staudigel, 1982; Elderfield and
Schultz, 1996].
[130] If the initial K2O content of basalts is 0.085%
(section 2.8 and Figure 3), then only 22% of the
1.58  1013 g/yr extrusive K2O flux to subduction
zones is primary. Both primary and alteration K2O
fluxes for dikes are poorly known. Near-ridge
high-temperature leaching apparently reduces the
primary K2O dike flux (8.3  1012 g/yr) by 65–
80%, to 1.4–2.9  1012 g/yr. The higher estimate
assumes reduction from a typical MORB magmatic
content of 0.085% K2O to the present Hole 504B
content of 0.014%. The lower estimate assumes
that the 65% K2O leaching of Hole 504B dikes,
from an initial K2O of 0.04% [Shipboard Scientific
10.1029/2002GC000392
Party, 1992], is representative of dikes in general,
but leaching is even less if initial K2O is less. The
2.15  1013 g/yr K2O in subducting gabbros
appears to be almost entirely primary; average
K2O at Hole 735B is 0.05% for fresh rocks [Bach
et al., 2001] and 0.06% for all rocks (section 3.7).
Thus, only 13% of subducted crustal K2O is
attributable to addition from seawater; the rest
(3.31  1013 g/yr) is inherited from MORB mag-
mas. Because more than half of the total crustal
K2O subducted is in the gabbros, any alteration-
induced change in gabbro K2O could easily surpass
those from the extrusives and dikes.
[131] The K2O budget for igneous oceanic crust
(excluding sediments) almost balances, with 4.9 
1013 g/yr input and 4.3–4.5  1013 g/yr output
(Figure 11). The slight imbalance is because the
rate of crustal generation is 10% higher than that
of subduction: 10% of convergence is continent/
continent collision, so total K2O flux from mantle
to oceanic crust at spreading centers is 3.64  1013
g/yr (= 1.1  3.31  1013 g/yr).
[132] The largest uncertainty in global K2O fluxes
is in the dominant component, K2O flux from the
mantle to arc magmatism, mainly because of
uncertainties in the ratio of observed arc volcanism
to hidden arc plutonism. Based on 0.4–0.6 km3/yr
of arc volcanism and 2.5–8 km3/yr of arc pluton-
ism [Crisp, 1984], a density of 2.7 g/cm3, and
average K2O of 3.8% for silicic igneous rock and
5.5% for calc-alkalic granite [Nockolds, 1954], the
total K2O flux due to arc magmatism is 4–12 
1014 g/yr. This flux to continents is comparable to
the total K2O flux from continents to oceans of
4.3–4.7  1014 g/yr, but it is more than an order of
magnitude higher than the MORB crustal K2O flux
and about an order of magnitude higher than the
combined subduction flux of 7.4  1013 g/yr from
sediments and oceanic crust.
[133] K2O fluxes from subduction and arc magma-
tism need not balance: most of the latter is thought
to come from low-degree partial melting of the
mantle wedge rather than the slab [e.g., Ionov et
al., 1997], as required by the flux imbalance of
Figure 11. Arc K2O is accompanied by long-term
mantle 40Ar, and helium similarity of arc and
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
MORB volcanism suggests similar source regions
[Sleep and Wolery, 1979]. In contrast, the system-
atic increase in arc magma K2O with increasing
slab depth [Dickinson and Hatherton, 1967; Dick-
inson, 1975] suggests a slab contribution. K2O is
scoured from the slab and released through solu-
tion in fluids, and amount of K2O release may
depend more on dehydration history than on initial
concentrations of K2O or hydrous minerals [Lee-
man, 1996]. Metabasalts from <45 km burial depth
retain their pre-subduction K2O concentrations
[Bebout, 1995]. Most of the hydrous phases that
break down within the slab at depths of <110 km
are potassium-free. In contrast, phengite (a K-rich
mica) could be the dominant K-rich hydrous phase
to break down at depths of >100 km and enrich arc
magmas [Schmidt, 1996].
[134] Subducted water has been suggested to affect
arc magma chemistry, based on comparison of arc
K2O contents to convergence rates [Sugisaki,
1976], but confounding variables such as continen-
tal contamination and degree of partial melting
were not considered. Plank and Langmuir [1993]
minimized these confounding effects by consider-
ing only primitive arc basalts and normalizing arc
potassium contents to sodium. For eight analyzed
subduction zones, they found a very good correla-
tion (R2 = 0.739) between arc potassium content
and the amount of potassium subducted in sedi-
ments. This correlation is just as good with the
parameters of Table 2 (R2 = 0.763), but it is
significantly degraded if crustal K2O sources are
included: R2 = 0.624 including upper extrusives,
and R2 = 0.044 for total subducted K2O. This
pattern suggests that K2O recycling to arc magmas
is largely confined to subducted sediments.
[135] The present-day imbalance between K2O
subduction (7.5  1013 g/yr) and arc magmatism
(4–12  1014 g/yr) is expected, based on the
overall imbalance between 1.60  1015 g/yr of
terrigenous sediment subduction [Plank and Lang-
muir, 1998] and 10–20  1015 g/yr of terrigenous
sediment deposition [Holland, 1981; Milliman and
Syvitski, 1994]. Rea and Ruff [1996] explored the
implications of the terrigenous imbalance and con-
cluded that mass balance is likely to prevail only
over the hundreds-of-million-years time scale of
10.1029/2002GC000392
Wilson cycles. Alternatively, long-term growth of
continents may result; Reymer and Schubert [1984]
used volumes and ages of arcs to estimate that this
growth averages 4  1015 g/yr.
4.5. Are Present Fluxes Representative
of Prior Ones?
[136] Modern subduction fluxes of H2O, CO2,
K2O, and Cl
are probably quite different from
those that characterized early earth history. Differ-
ent modeling approaches agree that most volatile
release from the mantle occurred quite early
[McGovern and Schubert, 1989; Franck and Bou-
nama, 1997; Harrison, 1999]. Continental growth
was probably also mainly Archean [e.g., Harrison,
1999], but rate of Phanerozoic growth is debated
[Reymer and Schubert, 1984]. Thermal modeling
suggests that Precambrian spreading rates were no
more than twice modern ones [Sleep, 1979]. Rapid
Archean spreading implies generally younger
slabs, which may have dehydrated at a shallower
depth than modern ones [McCulloch, 1993], but
rapid subduction also implies retarded slab heating,
which leads to deeper devolatilization [Staudigel
and King, 1992; Kerrick and Connolly, 2001]; the
latter is likely to dominate. Archean ophiolites of
South Africa and Australia appear to have under-
gone hydrothermal histories quite similar to mod-
ern oceanic crust [DeWit and Hart, 1993].
Phanerozoic variations in seafloor spreading rate
[Gaffin, 1987] have associated changes in MORB
degassing, subduction fluxes, and possibly arc
degassing [François and Walker, 1992].
[137] Modern subduction fluxes of H2O, CO2,
K2O, and Cl
are sensitive to the volume of
subducting sediments, which changes dramatically
as plate geometries evolve. Rea and Ruff [1996]
discussed this problem in the context of the order-
of-magnitude discrepancy between current terrige-
nous sedimentation and subduction. von Huene
and Scholl [1991] appraised the long-term rate of
sediment subduction as only about two thirds of the
current rate, because sedimentation rates have been
unusually rapid during the last 15–30 m.y. [Rea,
1993]. These rates have been even more rapid
during the Quaternary, associated with increased
glacial activity [Hay, 1994]; this factor affects
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
sediment subduction calculations incorporating
trench fill [von Huene and Scholl, 1991] much
more than those based on distal reference sites [Rea
and Ruff, 1996; Plank and Langmuir, 1998; this
study].
[138] Comparisons of subduction fluxes to the
dissolved and suspended loads of rivers (e.g.,
Figures 8 and 11) are severely limited by tempo-
ral changes in the latter: river fluxes for the
Recent are nonrepresentative of earlier fluxes
[Hay, 1994; Meybeck, 1994], and both dissolved
and suspended loads have varied by one order of
magnitude in the past [Meybeck, 1994]. For
example, the suspended-sediment estimate of
Milliman and Meade [1983], which we used for
K2O, has been revised upward by 50% [Milliman
and Syvitski, 1994], but the flux prior to wide-
spread farming was less than half of this value
[Milliman and Syvitski, 1994].
[139] Late Mesozoic and Cenozoic variations in
atmospheric CO2 have probably affected the
observed pattern of age-dependent upper crustal
CO2 (section 2.6). More rapid seafloor spreading
rates during the Cretaceous [Kominz, 1984; Lar-
son, 1991] have been causally linked not only to
higher sea levels [Hays and Pitman, 1973], but
also to higher atmospheric CO2 levels and con-
sequently warmer temperatures [Berner et al.,
1983; François and Walker, 1992]. Rate of ridge-
axis CO2 degassing is proportional to spreading
rate, but this effect is counteracted by increased
subduction of CO2-rich sediments and crust; the
net effect is flux to the atmosphere/ocean system if
generally younger, less altered crust with thinner
sediments is subducted. Faster subduction may
foster increased arc CO2 degassing, but this
assumption is hazardous [Kerrick, 2001]. Further-
more, calcareous phytoplankton deposition has
fluctuated widely [Nakamori, 2001]. Numerical
modeling of the Phanerozoic carbon cycle,
attempting to consider most of these variables
and their feedbacks, suggests that the dominant
temporal change is either seafloor alteration [Fran-
çois and Walker, 1992] or–more likely–terrestrial
silicate weathering [Caldeira, 1995]. Alternatively,
individual CO2 enrichment events may have differ-
ent sources [Kerrick, 2001].
10.1029/2002GC000392
[140] The ‘‘modern’’ subduction fluxes of this
study are actually time-averaged fluxes, represen-
tative of several million years. As mentioned
previously (section 4.1.2), present-day fluid fluxes
from accretionary prisms, observed at the seafloor
via submersibles or inferred from heat flow, are
much higher than long-term averages [e.g., Le
Pichon et al., 1991; Kastner et al., 1991]. This
discrepancy is significantly reduced by considering
not just shallow sediment sources but also deeper
reflux water from both crust and sediments. For
Nankai, Peru, and Barbados, whose long-term fluid
fluxes were estimated as 7 m3/yr per m along
trench [Kastner et al., 1991], revised fluxes are
17, 24, and 35 m3/yr per m (not including com-
paction within each prism), based on Table 2 and
the conclusion that two thirds of subducted water is
refluxed. Transient flow can account for the orig-
inal discrepancies [Moore and Vrolijk, 1992; Le
Pichon et al., 1993], with a flux cycle on an
individual trench lasting perhaps 2.5 – 5 Ma
[Saffer and Bekins, 1998]. If most of a several-
million-year budget of subducted water and CO2 of
a high-flux subduction zone like Makran were
refluxed within a few-thousand-year period, it
would raise sea level by 1 m and double atmos-
pheric CO2. However, the sea level effect is minor
in comparison to ice-induced sea level change, and
CO2 reflux is unlikely to exceed saturation levels.
4.6. Uncertainties
[141] A weakness of the preceding flux analyses is
the inability to attach confidence limits to com-
puted fluxes. Calculation of confidence limits from
regression relations such as Figure 2 is straightfor-
ward, as is formal uncertainty analysis for means
given standard deviation and number of points.
The problem, however, is that systematic errors are
likely to overwhelm random errors in most cases.
For example, mean microporosity for gabbros of
Hole 735B is 0.74%, with 95% confidence limits
of ±0.29%, but this value is probably strongly
biased by unroofing-induced fracturing; in situ
microporosities of most gabbros might be much
lower. This section focuses on some of the domi-
nant uncertainties - particularly biases - that affect
these flux estimates. An Excel spreadsheet com-
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
bining the calculations of Tables 1 and 2 is
included as an auxiliary material file, to encourage
readers to supercede my calculations by revising
parameters or assumptions.
4.6.1. Unquantified Variables Affecting
Upper Crustal Alteration
[142] The assumed alteration mineralogy for upper
oceanic crust–saponite, celadonite, and calcite (sec-
tion 2.8)–is only a first-order approximation. Actual
alteration mineralogy is invariably more complex,
but this alteration model probably provides a rea-
sonable indication of the age-dependent enrichment
of K2O and H2O+ within the upper extrusives.
[143] The time-dependent alteration of upper oce-
anic crust, as well as associated changes in geo-
physical properties, can be locally overwhelmed by
four other sources of variance.
[144] 1. Initial permeability is sensitive to porosity
and therefore also to volcanic style. Flows are
generally much more massive and impermeable
than pillows, so they are less subject to alteration.
Consequently, systematic age-dependent changes
in log-scale velocity, core-plug velocity, and mac-
roporosity are much stronger for pillows (signifi-
cant at 95%, 95%, and 99% c.l., respectively) than
for flows (none is significant) [Jarrard et al.,
2003]. Volcanic style is the dominant variable
controlling within-site alteration variations, but
the ubiquitous preponderance of pillows over flows
prevents volcanic style from obscuring the age-
dependent relationships.
[145] 2. Local basement topography often controls
the geometry of hydrothermal circulation, concen-
trating outflow at topographic highs [Fisher et al.,
1990, 1994]. This pattern is evident for paired
holes on adjacent topographic highs and saddles,
at 417A/417D/418A and at 504B/896A.
[146] 3. Spreading rate affects crustal structure (see
section 3.3) and therefore 3-D permeability struc-
ture. A relationship between spreading rate and
crustal alteration is likely, but none has been
detected yet.
[147] 4. Sedimentation restricts access of seawater
to crustal porosity. Crustal age is more globally
10.1029/2002GC000392
important than sedimentation in determining the
transition from convective to conductive heat
loss [Stein and Stein, 1994], but sedimentation
can locally control hydrothermal circulation and
resulting alteration. These analyses exclude areas
such as the Juan de Fuca sedimented ridge
where sedimentation undoubtedly dominates, yet
they include Hole 504B which has sufficient
sediment blanket for more conductive than con-
vective heat flow [Fisher et al., 1990] despite its
young age.
[148] These four sources of local variation in
alteration are probably the main causes of disper-
sion among sites in Figure 2, but they do not
introduce systematic bias into these patterns. For-
tunately, statistically significant age-dependent
crustal alteration patterns are evident despite this
variance: macroporosity reduction and consequent
chloride expulsion (99.9% confidence level), CO2
enrichment (97.5% c.l.), matrix density reduction
and consequent hydration (99.9% c.l.), and K2O
enrichment (based on age versus matrix density
@99.9% c.l. and matrix density versus K2 O
@99% c.l.).
[149] Calculated global fluxes are relatively insen-
sitive to the assumed patterns of age-dependent
upper crustal alteration. If age-dependence is
ignored and the upper crustal alteration state of
all subduction zones is assumed to be that of 77-
Ma crust, the global average age [Sprague and
Pollack, 1980], global fluxes change by 12% for
CO2, 3% for K2O, 2% for bound water, and
3%
for pore water and chloride. The impact on calcu-
lated fluxes for individual subduction zones is
much higher, ranging from
19% to +28% for
most fluxes and >80% for CO2 in young subduct-
ing crust.
4.6.2. Rejuvenation of Hydrothermal
Circulation
[150] The geochemical signature of age-dependent
crustal alteration, though only roughly known, can
provide an essential starting point for geochemical
mass balances associated with subduction. Implicit
to such calculations, however, is the assumption
that normal oceanic crust is not modified by the
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 Geochemistry 3
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Geosystems G jarrard: subduction fluxes of water
subduction process itself. This assumption may be
invalid.
[151] The flexure of lithosphere prior to subduction
generates an outer rise, with associated normal
faulting that might rejuvenate hydrothermal circu-
lation. The two lowest matrix densities on Figure 2b
are Holes 1149B and 1149D, the only holes that
have sampled basaltic basement from an outer rise
[Shipboard Scientific Party, 2000b]. If this correla-
tion is not coincidental, analyses of geochemical
fluxes at subduction zones should incorporate the
effects of hydrothermal rejuvenation within oceanic
crust immediately seaward of the trench axis. The
effects of extensional cracking extend to depths of
at least 25 km [Christensen and Ruff, 1988], much
deeper than the crust. These cracks are likely to
permit fluid percolation into the mantle and induce
serpentinization [Peacock, 2001].
4.6.3. Properties of Gabbros
[152] The properties assumed for gabbros (section
3.7 and Table 1) are based on Hole 735B, with
supporting evidence from Site 894, but both sites
have been affected by the unroofing that made
gabbro drilling possible. For example, I introduced
section 4.6 with the example of gabbro micro-
porosity bias. Furthermore, Hole 735B appears to
be nonrepresentative of the geochemically hetero-
geneous lower crust [Dick et al., 2000]. Gabbro
uncertainties have a disproportionate impact on
mass flux calculations, because 70% of oceanic
crust is gabbro. The impact is greatest for K2O
fluxes: section 3.7 noted that determining gabbro
K2O based on the K2O log rather than XRF would
raise the global subduction flux for crustal K2O by
71%. The high-temperature K2O fluxes between
gabbros and seawater, if any, are undetermined.
4.6.4. Peridotite Subduction Fluxes
[153] This study considers only those subduction
fluxes associated with oceanic crust and its over-
lying sediments. Mantle peridotites are excluded,
although they comprise the majority of subducting
lithosphere, because their in situ alteration state is
virtually unknown [e.g., Peacock, 1996]; obtain-
able samples are unlikely to be representative of
normal lower lithosphere. Peacock and Hyndman
10.1029/2002GC000392
[2001] noted that typical upper mantle velocities of
8.2 km/s are consistent with anhydrous peridotite.
Dehydration of serpentinites, which contain 13%
H2O+, could be a major source of the H2O in arc
magmas [Ulmer and Trommsdorff, 1995; Kerrick
and Connolly, 1998], and subducting ophicarbon-
ates (calcite-rich serpentinites) may transport CO2
to the deep mantle [Kerrick and Connolly, 1998].
Even 5% serpentinization of the upper mantle
would constitute about one third of the subducting
water flux [Peacock and Hyndman, 2001].
4.6.5. Subduction Erosion
and Underplating
[154] The comparisons of subduction fluxes to arc
fluxes in this paper neglect the possibility that the
slab may exchange material with the overriding
plate through subduction erosion or underplating.
The inverse correlation between shallow slab dip
and arc age (duration of subduction) [Jarrard,
1986] implies substantial subduction erosion, and
von Huene and Scholl [1991] estimated that this
erosional flux may be comparable to the flux of
sediment subduction. Both subduction erosion and
underplating are poorly known [Dewey and Wind-
ley, 1981]; neglecting them, however, biases com-
parisons of subduction fluxes to arc fluxes.
5. Conclusions
[155] High-temperature alteration of the oceanic
crust occurs at and very near the spreading center;
reference Holes 504B and 735B offer perspectives
on this alteration for the dikes and gabbros, respec-
tively. In contrast, a dozen logged DSDP and ODP
sites document the progressive, age-dependent
low-temperature alteration of extrusives. Two main
variables control alteration of the extrusives: (1)
extrusive type (flows, pillows, hyaloclastites),
which affects permeability and therefore water/
rock ratio, and (2) time. Intersite variations in
proportions of flows versus pillows are a principal
source of local variance: pillows are much more
porous, permeable, and altered than more massive
flows. Regionally, however, this variance is aver-
aged, and the waning impact of off-axis hydro-
thermal circulation on geophysical properties is
evident. Seismic velocity and permeability detect
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
only the large changes during the first 10 Ma after
crustal formation [Carlson, 1998; Fisher and
Becker, 2000], but some properties have the resolv-
ing power to detect subtler off-axis changes. I
identified the following systematic changes in
properties of the upper extrusives, each of which
appears to wane with a log(age) dependence,
throughout the lifetime of oceanic crust: (1) macro-
porosity reduction, (2) intergranular alteration to
smectite, celadonite, and calcite, with the calcite
cementation occurring generally later than the
others, and (3) increase in large-scale velocity
due to macroporosity reduction, mainly in pillows.
These changes involve progressive uptake of
H2O+, CO2, and K2O, with attendant expulsion
of pore water and its Cl
. Given crustal age, one
can calculate the average concentrations of pore
H2O, H2O+, CO2, Cl
, and K2O in the extrusives.
[ 156 ] Surprisingly, low-temperature alteration
causes no net change in total water. Macroporosity
is replaced with alteration minerals containing
some structural water, and intergranular alteration
forms hydrous minerals, but pore water loss is
nearly identical to H2O+ gain. Chloride is presum-
ably expelled by these transformations, but reliable
pore water samples have not been obtained from
the extrusives. The overall alteration effect on total
crustal content of K 2 O is also smaller than
expected. Enrichment by low-temperature altera-
tion of the upper extrusives is obvious at abundant
DSDP and ODP crustal sites, but substantial K2O
depletion occurs within the dikes during high-
temperature alteration. The majority of crustal
K2O for all crustal ages is primary rather than
secondary, and most is in the gabbros. The largest
net geochemical flux from crustal alteration, by an
order of magnitude, is the CO2 enrichment that
occurs at both intergranular scale and via fracture
filling. Its pattern of age-dependence is yet to be
documented in detail, but existing data are com-
patible with the log(age) dependence seen for
crustal geophysical properties (Figure 2).
[157] By applying these predictions to 41 modern
subduction zones, one can determine modern mass
fluxes of pore H2O, H2O+, CO2, Cl
, and K2O,
both for individual subduction zones and globally.
This data set is complemented by flux determina-
10.1029/2002GC000392
tions for the same components within subducting
sediments at 26 of these subduction zones by Plank
and Langmuir [1998].
[ 158] Subducted crustal water is released and
expelled at various slab depths by several mecha-
nisms, depending on how the water is held–in
sediment pores, in sedimentary smectites, in basalt
pores, in loosely bound hydrous minerals in the
extrusives, and in relatively stable hydrous miner-
als within the dikes and gabbros (Figure 7). At
burial depths of <10 km, sediment compaction
dominates, with additional water coming from
smectite/illite conversion in both sediments and
extrusive basalts. At greater depths, metamorphic
reactions convert pore water to structural and
expelled waters. I estimate that half to two thirds
of subducted water is later refluxed at or near the
toe of the prism, rising along the slab from at least
15 km and possibly as deep as 45 km. This long-
distance transport is inferred from patterns of
dehydration along slab-parallel permeability at
15–45 km in the Catalina Schist [Bebout, 1995,
1996] and from magnetotelluric evidence of free
water in slabs at 15–60 km depth. Crustal dehy-
dration may be as important as transformation of
sedimentary smectite to illite in generating the low-
chlorinity anomalies seen in some décollements.
[159] The remaining water is more deeply sub-
ducted as stable hydrous minerals. Much or most
of this water is released by a series of dehydration
reactions at depths of 45–100 km. It is carried along
with the slab until it escapes by triggering the partial
melting that permits it to reach Earth’s surface at the
arc. Surprisingly, there is little evidence that amount
of subducted volatiles affects either amount of
magma generation or earthquake magnitude on
the interplate boundary, despite indications that
reflux water traverses the entire boundary.
[160] Global flux balances for H2O, CO2, Cl
, and
K2O are constrained partly by the ocean/crust
interchanges documented above, partly by the
subduction fluxes above, and additionally by other
published data. In general, fluxes among oceans,
oceanic crust, continental crust, and mantle bal-
ance, within the uncertainties. A major exception is
the present order-of-magnitude excess of marine
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 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
sedimentation over sediment subduction, most
obvious in the K2O and CO2 budgets but also
affecting porosity and therefore H2O and Cl
.
Presumably, a closer balance is achieved on a time
scale of hundreds of millions of years, though
some imbalance may persist in the form of long-
term growth of continents. Temporal variation in
dissolution and precipitation of evaporites can
unbalance the global chloride budget dramatically,
without significantly affecting ocean salinity.
[161] A brief overview of CO2 mass fluxes con-
firms that carbonate precipitation in the oceanic
crust is a major CO2 sink, but it provides an
unsatisfactory balance of mantle and crust input
versus output. Subducted CO2 reaches subarc
depths with minimal loss to reflux, supplying the
CO2 erupted in arc magmas and replenishing
deeper-mantle CO2.
[162] The oceanic potassium budget is well bal-
anced, with almost as much loss to seafloor dia-
genesis as gain from dissolved river input. Some
signature of subducted sediment K2O on arc
magma K2O has been demonstrated [Plank and
Langmuir, 1993]. The major excess of arc magma
K2O over slab K2O, however, requires that most of
the former comes from the mantle wedge and
crustal enrichment.
Acknowledgments
[163] I am grateful to J. C. Alt and an anonymous reviewer
for their constructive reviews. This project was made possible
by the data acquisition efforts of shipboard scientific parties,
operations managers, and particularly the logging scientists of
two dozen DSDP and ODP legs. Just as important to the
success of this project was the availability of log and core data,
on CD-ROM and at the Web sites of ODP Logging Services
and JANUS. This research used samples and data provided by
DSDP and ODP. ODP is sponsored by the U.S. National
Science Foundation and participating countries under manage-
ment of Joint Oceanographic Institutions, Inc.
References
Alt, J. C., Subseafloor processes in mid-ocean ridge hydrother-
mal systems, in Seafloor Hydrothermal Systems, Physical,
Chemical, Biological, and Geological Interactions, Geo-
phys. Monogr. Ser., vol. 91, edited by S. E. Humphris et
al., pp. 85 – 114, AGU, Washington, D.C., 1995.
10.1029/2002GC000392
Alt, J. C., Very low-grade hydrothermal metamorphism of
basic igneous rocks, in Low-Grade Metamorphism, edited
by M. Frey and D. Robinson, pp. 85 – 114, Blackwell Sci.,
Malden, Mass., 1999.
Alt, J. C., and J. Honnorez, Alteration of the upper oceanic
crust, Deep Sea Drilling Project Site 417: Mineralogy and
chemistry, Contrib. Mineral. Petrol., 87, 149 – 169, 1984.
Alt, J. C., and D. A. H. Teagle, The uptake of carbon during
alteration of ocean crust, Geochim. Cosmochim. Acta, 63,
1527 – 1535, 1999.
Alt, J. C., and D. A. H. Teagle, Hydrothermal alteration and
fluid fluxes in ophiolites and ocean crust, in Ophiolites and
Oceanic Crust: New Insights from Field Studies and the
Ocean Drilling Program, edited by Y. Dilek et al., Geol.
Soc. Am. Spec. Pap., 349, 273 – 282, 2000.
Alt, J. C., C. Laverne, and K. Muehlenbachs, Alteration of the
upper oceanic crust: Mineralogy and processes in DSDP
Hole 504B, Leg 83, Initial Rep. Deep Sea Drill. Proj., 83,
217 – 247, 1985.
Alt, J. C., J. Honnorez, C. Laverne, and R. Emmermann, Hy-
drothermal alteration of a 1-km section through the upper
oceanic crust, Deep Sea Drilling Project Hole 504B: Miner-
alogy, chemistry and evolution of seawater-basalt interac-
tions, J. Geophys. Res., 91, 10,309 – 10,335, 1986.
Alt, J. C., C. France-Lanord, P. A. Floyd, P. Castillo, and
A. Galy, Low-temperature hydrothermal alteration of Juras-
sic ocean crust, Site 801, Proc. Ocean Drill. Program Sci.
Results, 129, 415 – 427, 1992.
Alt, J. C., D. A. H. Teagle, C. Laverne, D. Vanko, W. Bach,
J. Honnorez, K. Becker, M. Ayadi, and P. A. Pezard, Ridge
flank alteration of upper ocean crust in the eastern Pacific:
A synthesis of results for volcanic rocks of Holes 504B and
896A, Proc. Ocean Drill. Program Sci. Results, 148, 435 –
452, 1996a.
Alt, J. C., et al., Hydrothermal alteration of a section of upper
oceanic crust in the eastern equatorial Pacific: a synthesis of
results from Site 504 (DSDP Legs 69, 70, and 83, and ODP
Legs 111, 137, 140, and 148), Proc. Ocean Drill. Program
Sci. Results, 148, 417 – 434, 1996b.
Anderson, R. N., and M. D. Zoback, Permeability, underpres-
sures and convection in the oceanic crust near the Costa Rica
Rift, eastern equatorial Pacific, J. Geophys. Res., 87, 2860 –
2868, 1982.
Anderson, R. N., S. Uyeda, and A. Miyashiro, Geophysical
and geochemical constraints at converging plate boundaries;
Part I. dehydration in the downgoing slab, Geophys. J. R.
Astron. Soc., 44, 333 – 357, 1976.
Anderson, R. N., M. G. Langseth, and J. G. Sclater, The me-
chanisms of heat transfer through the floor of the Indian
Ocean, J. Geophys. Res., 82, 3391 – 3409, 1977.
Anderson, R. N., S. E. DeLong, and W. M. Schwarz, Dehy-
dration, asthenospheric convection, and seismicity in sub-
duction zones, J. Geol., 88, 445 – 451, 1980.
Andrews, A. J., Saponite and celadonite in layer 2 basalts,
DSDP Leg 37, Contrib. Mineral. Petrol., 73, 323 – 340, 1980.
Armstrong, R. L., A model for the evolution of strontium and
lead isotopes in a dynamic Earth, Rev. Geophys., 6, 175 –
199, 1968.
42 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Armstrong, R. L., The persistent myth of crustal growth, Aust.
J. Earth Sci., 38, 613 – 630, 1991.
Arzate, A. J., M. Mareschal, and D. Livelybrooks, Electrical
image of the subducting Cocos Plate from magnetotelluric
observations, Geology, 23, 703 – 706, 1995.
Azbel, I. Y., and I. N. Tolstikhin, Geodynamics, magmatism,
and degassing of the Earth, Geochim. Cosmochim. Acta, 54,
139 – 154, 1990.
Bach, W., J. C. Alt, Y. Niu, S. E. Humphris, J. Erzinger, and
H. J. B. Dick, The geochemical consequences of late-stage
low-grade alteration of lower ocean crust at the SW Indian
Ridge: Results from ODP Hole 735B (Leg 176), Geochim.
Cosmochim. Acta, 65, 3267 – 3287, 2001.
Bach, W., S. E. Humphris, and A. T. Fisher, Fluid flow and
fluid-rock interaction within ocean crust: reconciling geo-
chemical, geological, and geophysical observations, in Sub-
surface Biosphere at Mid-Ocean Ridges, Geophys. Monogr.
Ser., edited by W. Wilcock et al., AGU, Washington, D.C., in
press, 2003.
Bebout, G. E., Geometry and mechanisms of fluid flow at 15
to 45 kilometer depths in an Early Cretaceous accretionary
complex, Geophys. Res. Lett., 18, 923 – 926, 1991.
Bebout, G. E., The impact of subduction-zone metamorphism
on mantle-ocean chemical cycling, Chem. Geol., 126, 191 –
218, 1995.
Bebout, G. E., Volatile transfer and recycling at convergent
margins: Mass-balance and insights from high-P/T meta-
morphic rocks, in Subduction Top to Bottom, Geophys.
Mon., vol. 96, edited by G. E. Bebout et al., pp. 179 – 193,
AGU, Washington, D.C., 1996.
Becker, K., et al., Drilling deep into young oceanic crust, Hole
504B, Costa Rica Rift, Rev. Geophys., 27, 79 – 102, 1990.
Beiersdorf, H., et al., Age and possible modes of formation of
the Celebes Sea basement, and thermal regimes within the
accretionary complexes off SW Mindanao and N Sulawesi,
paper presented at International Conference on Stratigraphy
and Tectonic Evolution of Southeast Asia and the South
Pacific, GEOTHAI’97 conference, Int. Union of Geol. Sci.,
Bangkok, Thailand, 1997.
Bell, D. R., and G. R. Rossman, Water in Earth’s mantle: The
role of nominally anhydrous minerals, Science, 255, 1391 –
1397, 1992.
Berner, E. K., and R. A. Berner, The Global Water Cycle:
Geochemistry and Environment, 397 pp., Prentice-Hall,
Old Tappan, N.J., 1987.
Berner, R. A., Global CO2 degassing and the carbon cycle:
Comment on ‘‘Cretaceous ocean crust at DSDP sites 417 and
418: Carbon uptake from weathering versus loss by mag-
matic outgassing,’’ Geochim. Cosmochim. Acta, 54, 2889 –
2890, 1990.
Berner, R. A., and K. Caldeira, The geologic carbon cycle and
the evolution of atmospheric carbon dioxide, Eos Trans.
AGU, 83(47), Fall Meet. Suppl., F383, 2002.
Berner, R. A., and Z. Kothavala, GEOCARB III: A revised
model of atmospheric CO2 over Phanerozoic time, Am. J.
Sci., 301, 182 – 204, 2001.
Berner, R. A., A. C. Lasaga, and R. M. Garrels, The carbonate-
silicate geochemical cycle and its effect on atmospheric car-
10.1029/2002GC000392
bon dioxide over the past 100 million years, Am. J. Sci., 283,
641 – 683, 1983.
Bevis, M., et al., Geodetic observations of very rapid conver-
gence and back-arc extension at the Tonga arc, Nature, 374,
249 – 251, 1995.
Booij, E., and H. Staudigel, Controls and diversity of altered
oceanic crust composition, Eos Trans. AGU, 78(46), AGU
Fall Meet. Suppl., F806, 1997.
Bourbié, T., O. Coussy, and B. Zinszner, Acoustics of Porous
Media, 334 pp., Educ. Technol., Paris, 1987.
Bray, C. J., and D. E. Karig, Porosity of sediments in accre-
tionary prisms and some implications for dewatering pro-
cesses, J. Geophys. Res., 90, 768 – 778, 1985.
Brias, A., P. Patriat, and P. Tapponnier, Updated interpretation
of magnetic anomalies and seafloor spreading stages in the
South China Sea: Implications for the Tertiary tectonics of
Southeast Asia, J. Geophys. Res., 98, 6299 – 6328, 1993.
Broglia, C., and D. Ellis, Effect of alteration, formation absorp-
tion, and standoff on the response of the thermal neutron
porosity log in gabbros and basalts: Examples from Deep
Sea Drilling Project-Ocean Drilling Program sites, J. Geo-
phys. Res., 95, 9171 – 9188, 1990.
Brown, K. M., and B. Ransom, Porosity corrections for smec-
tite-rich sediments: Impact on studies of compaction, fluid
generation, and tectonic history, Geology, 24, 843 – 846,
1996.
Buckley, H. A., J. C. Bevan, K. M. Brown, J. R. Johnson, and
V. C. Farmer, Glauconite and celadonite: two separate miner-
al species, Mineral. Mag., 42, 373 – 382, 1978.
Busch, W. H., P. R. Castillo, P. A. Floyd, and G. Cameron,
Effects of alteration on physical properties of basalts from
the Pigafetta and East Mariana Basins, Proc. Ocean Drill.
Program Sci. Results, 129, 485 – 499, 1992.
Caldeira, K., Long-term control of atmospheric carbon diox-
ide: Low-temperature seafloor alteration or terrestrial sili-
cate-rock weathering?, Am. J. Sci., 295, 1077 – 1114, 1995.
Cannat, M., How thick is the magmatic crust at slow-spreading
oceanic ridges?, J. Geophys. Res., 101, 2847 – 2857, 1996.
Carlson, R. L., Seismic velocities in the uppermost oceanic
crust: Age dependence and the fate of layer 2A, J. Geophys.
Res., 103, 7069 – 7077, 1998.
Carlson, R. L., Lower crustal water contents, P-wave velo-
cities, and modal mineralogy of oceanic diabase and gab-
bro, Eos Trans. AGU, 82(47), Fall. Meet. Suppl., F1154,
2001.
Christensen, D. H., and L. J. Ruff, Seismic coupling and outer
rise earthquakes, J. Geophys. Res., 93, 13,421 – 13,444,
1988.
Christensen, N. I., and M. H. Salisbury, Velocities, elastic
moduli and weathering-age relations for Pacific Layer 2 ba-
salts, Earth Planet. Sci. Lett., 19, 461 – 470, 1973.
Christensen, N. I., and M. H. Salisbury, Seismic velocities,
densities and porosities of Layer 2B and Layer 2C basalts
from Hole 504B, Initial Rep. Deep Sea Drill. Proj., 83, 367 –
370, 1985.
Christensen, N. I., and J. D. Smewing, Geology and seismic
structure of the northern section of the Oman Ophiolite,
J. Geophys. Res., 86, 2545 – 2555, 1981.
43 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Christensen, N. I., W. W. Wepfer, and R. D. Baud, Seismic
properties of sheeted dikes from Hole 504B, ODP Leg 111,
Proc. Ocean Drill. Program Sci. Results, 111, 171 – 176,
1989.
Clarke, W. M., The Data of Geochemistry, U. S. Geol. Surv.
Bull., 770, 841 pp., 1924.
Coleman, R. C., Ophiolites: Ancient Oceanic Lithosphere?,
229 pp., Springer-Verlag, New York, 1977.
COSOD-II, Report of the Second Conference on Scientific
Ocean Drilling, Strasbourg, 6 – 8 July, 1987, 142 pp.,
JOIDES, Washington, DC, 1987.
Crisp, J. A., Rates of magma emplacement and volcanic out-
put, J. Volcanol. Geotherm. Res., 20, 177 – 211, 1984.
Davis, D. M., J. Suppe, and F. A. Dahlen, Mechanics of fold-
and-thrust belts and accretionary wedges, J. Geophys. Res.,
88, 1153 – 1172, 1983.
Davis, E. E., et al., FlankFlux: An experiment to study the
nature of hydrothermal circulation in young oceanic crust,
Can. J. Earth Sci., 29, 925 – 952, 1992.
Defant, M. J., and M. S. Drummond, Derivation of some mod-
ern arc magmas by melting of young subducted lithosphere,
Nature, 347, 662 – 665, 1990.
DeMets, C., R. G. Gordon, D. F. Argus, and S. Stein, Current
plate motions, Geophys. J. Int., 101, 425 – 478, 1990.
DeMets, C., R. G. Gordon, D. F. Argus, and S. Stein, Effect of
recent revisions to the geomagnetic reversal time scale on
estimates of current plate motions, Geophys. Res. Lett., 21,
2191 – 2194, 1994.
Dewey, J. F., and B. F. Windley, Growth and differentiation of
the continental crust, Philos. Trans. R. Soc. London Ser. A,
301, 189 – 206, 1981.
DeWit, M. J., and R. A. Hart, Earth’s earliest continental litho-
sphere, hydrothermal flux and crustal recycling, Lithos, 30,
309 – 335, 1993.
Dick, H. J. B., P. S. Meyer, S. H. Bloomer, S. H. Kirby, D. S.
Stakes, and C. Mawer, Lithostratigraphic evolution of an in-
situ section of oceanic layer 3, Proc. Ocean Drill. Program
Sci. Results, 118, 439 – 538, 1991.
Dick, H. J. B., et al., A long in situ section of the lower ocean
crust: Results of ODP Leg 176 drilling at the Southwest
Indian Ridge, Earth Planet. Sci. Lett., 179, 31 – 51, 2000.
Dick, H. J., J. Lin, P. J. Michael, H. Schouten, and J. E. Snow,
Ultra-slow spreading - a new class of ocean ridge, Eos Trans.
AGU, 83(47), Fall Meet. Suppl., F1267, 2002.
Dickinson, W. R., Potash-depth (K-h) relations in continental
margin and intra-oceanic magmatic arcs, Geology, 3, 53 – 56,
1975.
Dickinson, W. R., and T. Hatherton, Andesitic volcanism and
seismicity around the Pacific, Science, 157, 801 – 803, 1967.
Donnelly, T. W., R. A. Pritchard, R. Emmermann, and
H. Puchelt, The aging of oceanic crust: synthesis of the
mineralogical and chemical results of Deep Sea Drilling
Project, Legs 51 through 53, Initial Rep. Deep Sea Drill.
Proj., 51 – 53, 1563 – 1577, 1979a.
Donnelly, T. W., G. Thompson, and P. T. Robinson, Very-low-
temperature hydrothermal alteration of the oceanic crust and
the problem of fluxes of potassium and magnesium, in Deep
Drilling Results in the Atlantic Ocean: Ocean Crust, Maur-
10.1029/2002GC000392
ice Ewing Ser., vol. 2, edited by M. Talwani, C. G. A. Har-
rison, and D. E. Hayes, pp. 369 – 382, AGU, Washington,
D.C., 1979b.
Dymond, J., and M. Lyle, Particle fluxes in the ocean and
implications for sources and preservation of ocean sedi-
ments, in Material Fluxes on the Surface of the Earth, edited
by W. W. Hay et al., pp. 125 – 142, Natl. Acad. Press, Wa-
shington, D.C., 1994.
Ekart, D., T. E. Cerling, I. P. Montanez, and N. J. Tabor, A 400
million year carbon isotope record of pedogenic carbonate:
Implications for paleoatmospheric carbon dioxide, Am. J.
Sci., 299, 805 – 827, 1999.
Elderfield, H., and A. Schultz, Mid-ocean ridge hydrothermal
fluxes and the chemical composition of the ocean, Annu.
Rev. Earth Planet. Sci., 24, 191 – 224, 1996.
Ernewein, M., C. Pflumino, and H. Whitechurch, The death of
an accretion zone as evidenced by the magmatic history of
the Samail ophiolite (Oman), Tectonophysics, 151, 247 – 274,
1988.
Ernst, W. G., Hornblende, the continent maker: Evolution of
H2O during circum-Pacific subduction versus continental
collision, Geology, 27, 675 – 678, 1999.
Fehn, U., and L. M. Cathles, The influence of plate movement
on the evolution of hydrothermal convection cells in the
oceanic crust, Tectonophysics, 125, 289 – 312, 1986.
Fisher, A. T., Permeability within basaltic oceanic crust, Rev.
Geophys., 36, 143 – 182, 1998.
Fisher, A. T., and K. Becker, Channelized fluid flow in oceanic
crust reconciles heat-flow and permeability data, Nature,
403, 71 – 74, 2000.
Fisher, A., K. Becker, T. N. Narasimhan, M. Langseth, and
M. Mottl, Passive, off-axis convection on the southern flank
of the Costa Rica Rift, J. Geophys. Res., 95, 9343 – 9370, 1990.
Fisher, A. T., K. Becker, and T. N. Narasimhan, Off-axis hy-
drothermal circulation: Parametric tests of a refined model of
processes at Deep Sea Drilling Project/Ocean Drilling Pro-
gram Site 504, J. Geophys. Res., 99, 3097 – 3121, 1994.
Fisher, D. M., Fabrics and veins in the forearc: A record of
cyclic fluid flow at depths of <15 km, in Subduction Top to
Bottom, Geophys. Monogr. Ser., vol. 96, edited by G. E.
Bebout et al., pp. 75 – 89, AGU, Washington, D.C., 1996.
Fox, P. J., and J. Stroup, The plutonic foundation of the ocea-
nic crust, in The Sea, vol. 7, The Oceanic Lithosphere, edited
by C. Emiliani, pp. 119 – 218, John Wiley, New York, 1981.
Francheteau, J., P. Choukroune, R. Hekinian, X. Le Pichon,
and H. D. Needham, Oceanic fracture zones do not provide
deep sections in the crust, Can. J. Earth Sci., 13, 1223 –
1235, 1975.
Franck, S., and C. Bounama, Continental growth and volatile
exchange during Earth’s evolution, Phys. Earth Planet. Int.,
100, 189 – 196, 1997.
François, L. M., and J. C. G. Walker, Modelling the Phaner-
ozoic carbon cycle and climate: Constraints from the
87
Sr/86Sr isotopic ratio of seawater, Am. J. Sci., 292, 81 –
135, 1992.
Furnes, H., and H. Staudigel, Biological mediation in ocean
crust alteration: How deep is the deep biosphere?, Earth
Planet. Sci. Lett., 166, 97 – 103, 1999.
44 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Furnes, H., H. Staudigel, I. H. Thorseth, T. Torsvik, K. Mueh-
lenbachs, and O. Tumyr, Bioalteration of basaltic glass in the
oceanic crust, Geochem. Geophys. Geosys., 2, Paper number
2000GC000150, 2001.
Fyfe, W. S., Deep fluids and volatile recycling; crust to mantle,
Tectonophysics, 275, 243 – 251, 1997.
Gaffin, S., Ridge volume dependence on seafloor generation
rate and inversion using long term sealevel change, Am. J.
Sci., 287, 596 – 611, 1987.
Gerlach, T. M., Degassing of carbon dioxide from basaltic
magma at spreading centers: 2. mid-oceanic ridge basalts,
J. Volcanol. Geotherm. Res., 39, 221 – 232, 1989.
Gill, J., Orogenic Andesites and Plate Tectonics, 390 pp.,
Springer-Verlag, New York, 1981.
Gillis, K., and P. T. Robinson, Distribution of alteration zones
in the upper oceanic crust, Geology, 16, 262 – 266, 1988.
Goldberg, D., The role of downhole measurements in marine
geology and geophysics, Rev. Geophys., 35, 315 – 342, 1997.
Green, N. L., and D. L. Harry, On the relationship between
subducted slab age and arc basalt petrogenesis, Cascadia
subduction system, North America, Earth Planet. Sci. Lett.,
171, 367 – 381, 1999.
Grevemeyer, I., and W. Weigel, Seismic velocities of the
uppermost igneous crust versus age, Geophys. J. Int., 124,
631 – 635, 1996.
Hacker, B. R., Eclogite formation and the rheology, buoyancy,
seismicity, and H2O content of oceanic crust, in Subduction
Top to Bottom, Geophys. Monogr. Ser., vol. 96, edited by
G. E. Bebout et al., pp. 337 – 346, AGU, Washington, D.C.,
1996.
Hamano, Y., Physical properties of basalts from Holes 417D
and 418A, Initial Rep. Deep Sea Drill. Proj., 51 – 53, 1457 –
1466, 1979.
Harrison, C. G. A., Constraints on ocean volume change since
the Archean, Geophys. Res. Lett., 26, 1913 – 1916, 1999.
Harry, D. L., and N. L. Green, Slab dehydration and basalt
petrogenesis in subduction systems involving very young
oceanic lithosphere, Chem. Geol., 160, 309 – 333, 1999.
Hart, R. A., Chemical exchange between sea water and deep
ocean basalts, Earth Planet. Sci. Lett., 9, 269 – 279, 1970.
Hart, R. A., A model for chemical exchange in the basalt-
seawater system of oceanic Layer II, Can. J. Earth Sci.,
10, 799 – 816, 1973.
Hart, S. R., K, Rb, Cs contents, and K/Rb, K/Cs ratios of fresh
and altered submarine basalts, Earth Planet. Sci. Lett., 6,
295 – 303, 1969.
Hart, S. R., and H. Staudigel, The control of alkalis and ura-
nium in seawater by ocean crust alteration, Earth Planet. Sci.
Lett., 58, 202 – 212, 1982.
Hart, S. R., A. J. Erlank, and E. J. D. Kable, Sea floor basalt
alteration: some chemical and Sr isotopic effects, Contrib.
Mineral. Petrol., 44, 219 – 230, 1974.
Hart, S. R., J. Blusztajn, H. J. B. Dick, P. S. Meyer, and
K. Muehlenbachs, The fingerprint of seawater circulation
in a 500-meter section of ocean crust gabbros, Geochim.
Cosmochim. Acta, 63, 4059 – 4080, 1999.
Hay, W. W., Pleistocene-Holocene fluxes are not the Earth’s
norm, in Material Fluxes on the Surface of the Earth, edited
10.1029/2002GC000392
by W. W. Hay et al., pp. 15 – 27, Natl. Acad. Press, Washing-
ton, D.C., 1994.
Hays, J. D., and W. C. Pitman, III, Lithospheric plate motion,
sea-level changes, and climatic and ecological consequences,
Nature, 246, 18 – 22, 1973.
Hilde, T. W. C., Sediment subduction versus accretion around
the Pacific, Tectonophysics, 99, 381 – 397, 1983.
Hill, M. N., Recent geophysical exploration of the ocean floor,
Phys. Chem. Earth, 2, 129 – 163, 1957.
Holland, H. D., River transport to the oceans, in The Sea, vol.
7, The Oceanic Lithosphere, edited by C. Emiliani, pp. 763 –
800, John Wiley, New York, 1981.
Honnorez, J., The aging of the oceanic crust at low tempera-
ture, in The Sea, vol. 7, The Oceanic Lithosphere edited by
C. Emiliani, pp. 525 – 587, John Wiley, New York, 1981.
Honnorez, J., C. Laverne, H.-W. Hubberten, R. Emmermann,
and K. Muehlenbachs, Alteration processes in layer 2 basalts
from Deep Sea Drilling Project Hole 504B, Costa Rica Rift,
Initial Rep. Deep Sea Drill. Proj., 69, 509 – 546, 1983.
Honza, E., H. L. Davies, J. B. Keene, and D. L. Tiffin, Plate
boundaries and evolution of the Solomon Sea region, Geo.
Mar. Lett., 7, 161 – 168, 1987.
Humphris, S. E., Hydrothermal processes at mid-ocean ridges,
U. S. Natl. Rep. Int. Union Geod. Geophys., 1991 – 1994,
Rev. Geophys., 33, 71 – 80, 1995.
Hyndman, R. D., Dipping seismic reflectors, electrically con-
ductive zones and trapped water in the crust over a subduct-
ing plate, J. Geophys. Res., 93, 13,391 – 13,405, 1988.
Hyndman, R. D., and M. J. Drury, The physical properties of
oceanic basement rocks from deep drilling on the Mid-Atlan-
tic Ridge, J. Geophys. Res., 81, 4042 – 4052, 1976.
Hyndman, R. D., M. Yamano, and D. A. Oleskevich, The
seismogenic zone of subduction thrust faults, Island Arc, 6,
244 – 260, 1997.
Ildefonse, B., and P. Pezard, Electrical properties of slow-
spreading ridge gabbros from ODP Site 735, Southwest In-
dian Ridge, Tectonophysics, 330, 69 – 92, 2001.
Ionov, D. A., W. L. Griffin, and S. Y. Oreilly, Volatile-bearing
minerals and lithophile trace elements in the upper mantle,
Chem. Geol., 141, 153 – 184, 1997.
Ito, E. D., M. Harris, and A. T. Anderson Jr., Alteration of
oceanic crust and geologic cycling of chlorine and water,
Geochim. Cosmochim. Acta, 47, 1613 – 1624, 1983.
Itturrino, G. J., N. I. Christensen, K. Becker, L. O. Boldreel,
P. K. H. Harvey, and P. Pezard, Physical properties and
elastic constants of upper crustal rocks from core-log mea-
surements in Hole 504B, Proc. Ocean Drill. Program Sci.
Results, 137/140, 273 – 292, 1995.
Iwamori, H., Transportation of H2O and melting in subduction
zones, Earth Planet. Sci. Lett., 160, 65 – 80, 1998.
Iwamori, H., Transportation of H2O and melting beneath the
Japan arcs, Bull. Earthquake Res. Inst. Univ. Tokyo, 76,
377 – 389, 2001.
Jambon, A., B. Deruelle, G. Dreibus, and F. Pineau, Chlorine
and bromine abundance in MORB; The contrasting beha-
viour of the Mid-Atlantic Ridge and East Pacific Rise and
implications for chlorine geodynamic cycle, Chem. Geol.,
126, 101 – 117, 1995.
45 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Jarrard, R. D., Relations among subduction parameters, Rev.
Geophys., 24, 217 – 284, 1986.
Jarrard, R. D., R. L. Larson, A. T. Fisher, and L. J. Abrams,
Geophysical aging of oceanic crust: Evidence from Hole
801C, Proc. Ocean Drill. Program Sci. Results, 144, 649 –
663, 1995.
Jarrard, R. D., L. J. Abrams, R. Pockalny, R. L. Larson, and
T. Hirono, Physical properties of upper oceanic crust: ODP
Hole 801C and the waning of hydrothermal circulation, J. Geo-
phys. Res, 108(D7), 2188, doi:10.1029/2001JB001727,
2003.
Jochum, K. P., A. W. Hofmann, E. Ito, H. M. Seufert, and
W. M. White, K, U and Th in mid-ocean ridge basalt glasses
and heat production, K/U and K/Rb in the mantle, Nature,
306, 431 – 436, 1983.
Johnson, D. M., Fluid permeability of oceanic basalts, Initial
Rep. Deep Sea Drill. Proj., 51 – 53, 1473 – 1477, 1979a.
Johnson, D. M., Crack distribution in the upper oceanic crust
and its effects upon seismic velocity, seismic structure, for-
mation permeability, and fluid circulation, Initial Rep. Deep
Sea Drill. Proj., 51 – 53, 1479 – 1490, 1979b.
Johnson, H. P., and S. W. Semyan, Age variation in the physical
properties of oceanic basalts: implications for crustal forma-
tion and evolution, J. Geophys. Res., 99, 3123 – 3134, 1994.
Karato, S., Physical properties of basalts from Deep Sea Dril-
ling Project Hole 504B, Initial Rep. Deep Sea Drill. Proj.,
69, 687 – 695, 1983a.
Karato, S., Physical properties of basalts from the Galapagos,
Leg 70, Initial Rep. Deep Sea Drill. Proj., 70, 423 – 428,
1983b.
Karson, J. A., Internal structure of oceanic lithosphere: a per-
spective from tectonic windows, in Faulting and Magmatism
at Mid-Ocean Ridges, Geophys. Monogr. Ser., vol. 106, edi-
ted by W. R. Buck et al., 177 – 218, AGU, Washington, D.C.,
1998.
Karson, J. A., Geologic structure of the uppermost oceanic
crust created at fast- to intermediate-rate spreading centers,
Annu. Rev. Earth Planet. Sci., 30, 347 – 384, 2002.
Kasahara, J., A. Kamimura, G. Fujie, and R. Hino, Influence of
water on earthquake generation along subduction zones,
Bull. Earthquake. Res. Inst. Univ. Tokyo, 76, 291 – 303, 2001.
Kastner, M., H. Elderfield, and J. B. Martin, Fluids in conver-
gent margins: What do we know about their composition,
origin, role in diagenesis and importance for oceanic chemi-
cal fluxes, Philos. Trans. R. Soc. London, Ser. A, 335, 243 –
259, 1991.
Kastner, M., et al., Geochemical and isotopic evidence for fluid
flow in the western Nankai subduction zone, Japan, Proc.
Ocean Drill. Program Sci. Results, 131, 397 – 413, 1993.
Kato, T., and Y. Kotake, Tectonics of the Philippine Sea plate
as seen from GPS observations, Eos Trans. AGU, 83(47),
Fall Meet. Suppl., F1321, 2002.
Kerrick, D. M., Present and past nonanthropogenic CO2 degas-
sing from the solid Earth, Rev. Geophys., 39, 565 – 585,
2001.
Kerrick, D. M., and J. A. D. Connolly, Subduction of ophicar-
bonates and recycling of CO2 and H2O, Geology, 26, 375 –
378, 1998.
10.1029/2002GC000392
Kerrick, D. M., and J. A. D. Connolly, Metamorphic devola-
tilization of subducted oceanic metabasalts: Implications for
seismicity, arc magmatism and volatile recycling, Earth Pla-
net. Sci. Lett., 189, 19 – 29, 2001.
Kirby, S. H., E. R. Engdahl, and R. Denlinger, Intraslab earth-
quakes and arc volcanism: dual physical expressions of crus-
tal and uppermost mantle metamorphism in subducting slabs,
in Subduction Top to Bottom, Geophys. Monogr. Ser., 96,
edited by G. E. Bebout et al., pp. 195 – 214, AGU,
Washington, D.C., 1996.
Kominz, M. A., Oceanic ridge volumes and sea-level change:
An error analysis, in Interregional Unconformities and Hy-
drocarbon Accumulation, edited by J. S. Schlee, Mem. Am.
Assoc. Petrol. Geol., 36, 109 – 127, 1984.
Larson, R. L., Geological consequences of superplumes, Geol-
ogy, 19, 547 – 550, 1991.
Lawrence, J. R., J. J. Drever, and M. Kastner, Low temperature
alteration of basalts predominates at DSDP Site 395, Initial
Rep. Deep Sea Drill. Proj., 45, 609 – 612, 1978.
Lecuyer, C., M. Brouxel, and F. Albarede, Elemental fluxes
during hydrothermal alteration of the Trinity Ophiolite (Ca-
lifornia, USA) by seawater, Chem. Geol., 89, 87 – 115,
1990.
Leeman, W. P., Boron and other fluid-mobile elements in vol-
canic arc lavas: Implications for subduction processes, in
Subduction Top to Bottom, Geophys. Monogr., vol. 96, edited
by G. E. Bebout et al., pp. 269 – 276, AGU, Washington,
D.C., 1996.
Le Pichon, X., P. Henry, and the Kaiko-Nankai Scientific
Crew, Water budgets in accretionary wedges: A compari-
son, Philos. Trans. R. Soc. London Ser. A, 335, 315 – 330,
1991.
Le Pichon, X., P. Henry, and S. Lallemant, Accretion and
erosion in subduction zones: The role of fluids, Annu. Rev.
Earth Planet. Sci., 21, 307 – 331, 1993.
Lippard, S. J., A. W. Shelton, and I. G. Gass, The Ophiolite of
Northern Oman, 178 pp., Blackwell Sci., Malden, Mass.,
1986.
Liu, J., S. R. Bohlen, and W. G. Ernst, Stability of hydrous
phases in subducting oceanic crust, Earth Planet. Sci. Lett.,
143, 161 – 171, 1996.
Livingstone, D. A., Chemical composition of rivers and lakes,
U. S. Geol. Survey Prof. Paper, 440-G, G1 – G64, 1963.
Magenheim, A. J., A. J. Spivack, P. J. Michael, and J. M.
Gieskes, Chlorine stable isotope composition of the oceanic
crust: Implication for Earth’s distribution of chlorine, Earth
Planet. Sci. Lett., 131, 427 – 432, 1995.
Martin, W. R., and F. L. Sayles, Seafloor diagenetic fluxes, in
Material Fluxes on the Surface of the Earth, edited by W. W.
Hay, et al., pp. 143 – 163, Natl. Acad. Press, Washington,
D.C., 1994.
Marty, B., and I. N. Tolstikhin, CO2 fluxes from midocean
ridges, arcs and plumes, Chem. Geol., 145, 233 – 248, 1998.
McCaffrey, R., Influences of recurrence times and fault zone
temperatures on the age-rate dependence of subduction zone
seismicity, J. Geophys. Res., 102, 22,839 – 22,854, 1997.
McCulloch, M. T., The role of subducted slabs in an evolving
earth, Earth Planet. Sci. Lett., 115, 89 – 100, 1993.
46 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
McGovern, P. J., and G. Schubert, Thermal evolution of the
Earth: Effects of volatile exchange between atmosphere and
interior, Earth Planet. Sci. Lett., 96, 27 – 37, 1989.
Meade, C., and R. Jeanloz, Deep-focus earthquakes and recy-
cling of water into the Earth’s mantle, Science, 252, 68 – 72,
1991.
Meybeck, M., Concentrations des eaux fluviales en éléments
majeurs et apports en solution aux océans, Rev. Geol. Dyn.
Geogr. Phys., 21, 215 – 246, 1979.
Meybeck, M., Atmospheric inputs and river transport of dis-
solved substances, in Dissolved Load of Rivers and Surface
Water Quantity/Quality Relationships, Proceedings of Ham-
burg Symposium, IAHS Publ., 141, edited by B. W. Webb,
pp. 173 – 192, Int. Assoc. of Hydrol. Sci. Press, Wallingford,
Oxfordshire, U.K., 1983.
Meybeck, M., Origin and variable composition of present day
riverborne material, in Material Fluxes on the Surface of the
Earth, edited by W. W. Hay et al., pp. 61 – 73, Natl. Acad.
Press, Washington, D.C., 1994.
Milliman, J. D., and R. H. Meade, World-wide delivery of
river sediment to the oceans, J. Geology, 91, 1 – 21, 1983.
Milliman, J. D., and J. P. M. Syvitski, Geomorphic/tectonic
control of sediment discharge to the ocean: the importance of
small mountainous rivers, in Material Fluxes on the Surface
of the Earth, edited by W. W. Hay, et al., pp. 74 – 85, Natl.
Acad. Press, Washington, D.C., 1994.
Minster, J. B., and T. H. Jordan, Present-day plate motions,
J. Geophys. Res., 83, 5331 – 5354, 1978.
Miyazaki, S., and K. Heki, Crustal velocity field of southwest
Japan: Subduction and arc-arc collision, J. Geophys. Res.,
106, 4305 – 4326, 2001.
Moore, J. C., and D. Saffer, Updip limit of the seismogenic
zone beneath the accretionary prism of southwest Japan: An
effect of diagenetic to low-grade metamorphic processes and
increasing effective stress, Geology, 29, 183 – 186, 2001.
Moore, J. C., and P. Vrolijk, Fluids in accretionary prisms, Rev.
Geophys., 30, 113 – 135, 1992.
Moos, D., and D. Marion, Morphology of extrusive basalts and
its relationship to seismic velocities in the shallow oceanic
crust, J. Geophys. Res., 99, 2985 – 2994, 1994.
Mottl, M. J., and C. G. Wheat, Hydrothermal circulation
through mid-ocean ridge flanks: Fluxes of heat and magne-
sium, Geochim. Cosmochim. Acta, 58, 2225 – 2237, 1994.
Muehlenbachs, K., The alteration and aging of the basaltic
layer of the sea floor: oxygen isotope evidence from
DSDP/IPOD Legs 51, 52, and 53, Initial Rep. Deep Sea
Drill. Proj., 51 – 53, 1159 – 1167, 1979.
Nakamori, T., Global carbonate accumulation rates from Cre-
taceous to Present and their implications for the carbon cycle
model, Island Arc, 10, 1 – 8, 2001.
Nockolds, S. R., Average chemical compositions of some
igneous rocks, Geol. Soc. Am. Bull., 65, 1007 – 1032, 1954.
Nur, A., Effects of stress on velocity anisotropy in rocks with
cracks, J. Geophys. Res., 76, 2022 – 2034, 1971.
Omori, S., S. Kamiya, S. Maruyama, and D. Zhao, Morphol-
ogy of the intraslab seismic zone and devolatilization phase
equilibria of the subducting slab peridotite, Bull. Earthquake
Res. Inst. Univ. Tokyo, 76, 455 – 478, 2001.
10.1029/2002GC000392
Ono, S., Stability limits of hydrous minerals in sediment and
midocean ridge basalt compositions: Implications for water
transport in subduction zones, J. Geophys. Res., 103,
18,253 – 18,267, 1998.
Parsons, B., The rates of plate creation and consumption, Geo-
phys. J. R. Astron. Soc., 67, 437 – 448, 1981.
Pawley, A. R., The pressure and temperature stability limits of
lawsonite: Implications for H2O recycling in subduction
zones, Contrib. Mineral. Petrol., 118, 99 – 108, 1994.
Pawley, A. R., and J. R. Holloway, Water sources for subduc-
tion zone volcanism: New experimental constraints, Science,
260, 664 – 667, 1993.
Peacock, S. M., Fluid processes in subduction zones, Science,
248, 329 – 337, 1990.
Peacock, S. M., Numerical simulation of subduction zone pres-
sure temperature time paths - constraints on fluid production
and arc magmatism, Philos. Trans. R. Soc. London Ser. A,
335, 341 – 353, 1991.
Peacock, S. M., The importance of blueschist-eclogite dehy-
dration reactions in subducting oceanic crust, Geol. Soc.
Amer. Bull., 105, 684 – 694, 1993.
Peacock, S. M., Thermal and petrological structure of subduc-
tion zones, in Subduction Top to Bottom, Geophys. Monogr.
Ser., vol. 96, edited by G. E. Bebout et al., pp. 119 – 133,
AGU, Washington, D.C., 1996.
Peacock, S. M., Are the lower planes of double seismic zones
caused by serpentine dehydration in subducting oceanic
mantle?, Geology, 29, 299 – 302, 2001.
Peacock, S. M., and R. D. Hyndman, On the importance of
serpentine in the subduction factory, Eos Trans. AGU,
82(47), Fall Meet. Suppl., F1154, 2001.
Peacock, S. M., T. Rushmer, and A. B. Thompson, Partial
melting of subducting oceanic crust, Earth Planet. Sci. Lett.,
121, 227 – 244, 1994.
Pearson, P. N., and M. R. Palmer, Atmospheric carbon dioxide
concentrations over the past 60 million years, Nature, 406,
695 – 699, 2000.
Pezard, P. A., Electrical properties of mid-ocean ridge basalt
and implications for the structure of the upper oceanic
crust at Hole 504B, J. Geophys. Res., 95, 9237 – 9264,
1990.
Pezard, P. A., F. Einaudi, D. Hermitte, J.-J. Cocheme, C. Cou-
lon, and C. Laverne, MORB emplacement and structure;
Insights from the Semail Ophiolite, Oman, Geophys. Res.
Lett., 27, 3933 – 3936, 2000.
Philippot, P., P. Agrinier, and M. Scambelluri, Chlorine cycling
during subduction of altered oceanic crust, Earth Planet. Sci.
Lett., 161, 33 – 44, 1998.
Plank, T., and C. H. Langmuir, Tracing trace elements from
sediment input to volcanic output at subduction zones, Nat-
ure, 362, 739 – 743, 1993.
Plank, T., and C. H. Langmuir, The chemical composition of
subducting sediment and its consequences for the crust and
mantle, Chem. Geol., 145, 325 – 394, 1998.
Poli, S., and M. W. Schmidt, H2O transport and release in
subduction zones: Experimental constraints on basaltic and
andesitic systems, J. Geophys. Res., 100, 22,299 – 22,314,
1995.
47 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Purdy, G. M., L. S. L. Kong, G. L. Christeson, and S. C.
Solomon, Relationship between spreading rate and the seis-
mic structure of mid-ocean ridges, Nature, 355, 815 – 817,
1992.
Raitt, R. W., The crustal rocks, in The Sea, vol. 3, edited by
M. N. Hill, pp. 85 – 102, Wiley-Interscience, New York, 1963.
Raleigh, C. B., and M. S. Paterson, Experimental deformation
of serpentinite and its tectonic implications, J. Geophys.
Res., 70, 3965 – 3985, 1965.
Rangin, C., and E. Silver, Geological setting of the Celebes
and Sulu Seas, Proc. Ocean Drill Program Initial Rep., 124,
35 – 42, 1990.
Ransom, B., and H. C. Helgeson, A chemical and thermody-
namic model of dioctehedral 2:1 layer clay minerals in di-
agenetic processes: Dehydration of dioctahedral aluminous
smectite as a function of temperature and depth in sedimen-
tary basins, Am. J. Sci., 295, 245 – 281, 1995.
Rea, D. K., Geologic records in deep-sea muds, GSA Today, 3,
205 – 210, 1993.
Rea, D. K., and L. J. Ruff, Composition and mass flux of
sediment entering the world’s subduction zones: Implications
for global sediment budgets, great earthquakes, and volcan-
ism, Earth Planet. Sci. Lett., 140, 1 – 12, 1996.
Reymer, A., and G. Schubert, Phanerozoic addition rates to the
continental crust and crustal growth, Tectonics, 3, 63 – 77,
1984.
Robertson, A. H. F., and Shipboard Scientific Party, Tectonic
introduction, Proc. Ocean Drill. Program Init. Rep., 160, 5 –
20, 1996.
Robinson, P. T., M. F. Flower, H. Staudigel, and D. A. Swan-
son, Lithology and eruptive stratigraphy of Cretaceous ocea-
nic crust, western Atlantic, Initial Rep. Deep Sea Drill. Proj.,
51 – 53, 1535 – 1556, 1979.
Robinson, P. T., H. J. B. Dick, D. Von Herzen, and R. Pierre,
Metamorphism and alteration in oceanic layer 3: Hole 735B,
Proc. Ocean Drill. Program Sci. Results, 118, 541 – 562,
1991.
Ronov, A. B., and A. A. Yaroshevskiy, A new model for the
chemical structure of the Earth’s crust, Geochem. Int., 13,
89 – 121, 1976.
Rubey, W. W., Geologic history of sea water: an attempt to
state the problem, Geol. Soc. Am. Bull., 62, 1111 – 1147,
1951.
Ruff, L., and H. Kanamori, Seismicity and the subduction
process, Phys. Earth Planet. Int., 23, 240 – 252, 1980.
Ruff, L. J., and B. W. Tichelaar, What controls the seismogenic
plate interface in subduction zones?, in Subduction Top to
Bottom, Geophys. Monogr. Ser., vol. 96, edited by G. E.
Bebout et al., pp. 105 – 111, AGU, Washington, D.C., 1996.
Ryan, J., J. Morris, G. Bebout, and B. Leeman, Describing
chemical fluxes in subduction zones: insights from ‘‘depth
profiling’’ studies of arc and forearc rocks, in Subduction Top
to Bottom, Geophys. Monogr. Ser., vol. 96, edited by G. E.
Bebout et al., pp. 263 – 268, AGU, Washington, D.C., 1996.
Saffer, D. M., and B. A. Bekins, Episodic fluid flow in the
Nankai accretionary complex: Timescale, geochemistry, flow
rates, and fluid budget, J. Geophys. Res., 103, 30,351 –
30,370, 1998.
10.1029/2002GC000392
Saffer, D. M., and B. A. Bekins, Hydrologic controls on the
morphology and mechanics of accretionary wedges, Geol-
ogy, 30, 271 – 274, 2002.
Sager, W., Argo abyssal plain magnetic lineations revisited:
Implications for the onset of seafloor spreading and tectonic
evolution of the Eastern Indian Ocean, Proc. Ocean Drill.
Program Sci. Results, 123, 659 – 669, 1992.
Salisbury, M. H., N. I. Christensen, and R. H. Wilkens, Nature
of the Layer 2/3 transition from a comparison of laboratory
and logging velocities and petrology at the base of Hole
504B, Proc. Ocean Drill. Program Sci. Results, 148, 409 –
414, 1996.
Sansone, F. J., M. J. Mottl, E. J. Olson, C. G. Wheat, and M. D.
Lilley, CO2-depleted fluids from mid-ocean ridge-flank hy-
drothermal springs, Geochim. Cosmochim. Acta, 62, 2247 –
2252, 1998.
Schilling, J.-G., C. K. Unni, and M. L. Bender, Origin of
chlorine and bromine in the oceans, Nature, 273, 631 –
636, 1978.
Schmidt, M. W., Experimental constraints on recycling of po-
tassium from subducted oceanic crust, Science, 272, 1927 –
1930, 1996.
Schmidt, M. W., and S. Poli, Experimentally based water bud-
gets for dehydrating slabs and consequences for arc magma
generation, Earth Planet. Sci. Lett., 163, 361 – 379, 1998.
Schmincke, H.-U., and U. Bednarz, Pillow-, sheet flow-, and
breccia volcano-tectonic-hydrothermal cycles in the Extru-
sive Series of the northwestern Troodos Ophiolite (Cyprus),
in Proceedings Symposium Troodos 87 – Ophiolites and
Oceanic Lithosphere, edited by J. Malpas et al., pp. 185 –
207, Geol. Surv. Dept., Nicosia, Cyprus, 1990.
Schreiber, E., and P. J. Fox, Compressional wave velocities and
mineralogy of fresh basalts from the FAMOUS area and the
Oceanographer Fracture Zone and the texture of Layer 2A of
the oceanic crust, J. Geophys. Res., 81, 4071 – 4076, 1976.
Schreiber, E., and P. J. Fox, Density and P-wave velocity of
rocks from the FAMOUS region and their implication to the
structure of the oceanic crust, Geol. Soc. Am. Bull., 88, 600 –
608, 1977.
Seno, T., S. Stein, and A. E. Gripp, A model for the motion of
the Philippine Sea plate consistent with NUVEL-1 and geo-
logical data, J. Geophys. Res., 98, 17,941 – 17,948, 1993.
Serra, O., Fundamentals of Well Log Interpretation, vol. 2, The
Interpretation of Logging Data, 684 pp., Elsevier, New
York, 1986.
Shaw, P., Age variations of oceanic crust Poisson’s ratio: In-
version and a porosity inversion model, J. Geophys. Res., 99,
3057 – 3066, 1994.
Shimakawa, Y., and Y. Honkura, Electrical conductivity struc-
ture beneath the Ryukyu Trench-Arc system and its relation
to subduction of the Philippine Sea plate, J. Geomag. Geoe-
lect., 43, 1 – 20, 1991.
Shipboard Scientific Party, Site 395, Initial Rep. Deep Sea
Drill. Proj., 45, 131 – 264, 1978.
Shipboard Scientific Party, Site 562, Initial Rep. Deep Sea
Drill. Proj., 82, 255 – 278, 1985.
Shipboard Scientific Party, Site 735, Proc. Ocean Drill. Pro-
gram Initial Rep., 118, 89 – 222, 1989.
48 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
Shipboard Scientific Party, Site 768, Proc. Ocean Drill. Pro-
gram Initial Rep., 124, 195 – 297, 1990a.
Shipboard Scientific Party, Site 770, Proc. Ocean Drill. Pro-
gram Initial Rep., 124, 343 – 397, 1990b.
Shipboard Scientific Party, Site 504, Proc. Ocean Drill. Pro-
gram Initial Rep., 140, 37 – 200, 1992.
Shipboard Scientific Party, Site 894, Proc. Ocean Drill. Pro-
gram Initial Rep., 147, 45 – 108, 1993.
Shipboard Scientific Party, Site 735 [online], Proc. Ocean
Drill. Program Initial Rep., 176, 1 – 314, 1999. (Available at
http://www-odp.tamu.edu/publications/176_IR/VOLUME/
CHAPTERS/CHAP_03.PDF).
Shipboard Scientific Party, Site 801 [online], Proc. Ocean Drill.
Program Initial Rep., 185, 1 – 222, 2000a. (Available at
http://www-odp.tamu.edu/publications/185_IR/VOLUME/
CHAPTERS/IR185_03.PDF).
Shipboard Scientific Party, Site 1149 [online], Proc. Ocean
Drill. Program Initial Rep., 185, 1 – 190, 2000b. (Available at
http://www-odp.tamu.edu/publications/185_IR/VOLUME/
CHAPTERS/IR185_04.PDF).
Shipboard Scientific Party, Site 1222 [online], Proc. Ocean
Drill. Program Initial Rep., 199, 1 – 57, 2002. (Available at
http://www-odp.tamu.edu/publications/199_IR/VOLUME/
CHAPTERS/IR199_15.PDF).
Sleep, N. H., Thermal history and degassing of the Earth; some
simple calculations, J. Geol., 87, 671 – 686, 1979.
Sleep, N. H., and T. J. Wolery, Sediment subduction and al-
teration of oceanic crust, a chemical constraint (abstract),
Eos Trans. AGU, 60, 392, 1979.
Small, C., Global systematics of mid-ocean ridge morphology,
in Faulting and Magmatism at Mid-Ocean Ridges, Geophys.
Monogr. Ser., vol. 106, edited by W. R. Buck et al., pp. 1 –
25, AGU, Washington, D.C., 1998.
Sobolev, A. V., and M. Chaussidon, H2O concentrations in
primary melts from supra-subduction zones and midocean
ridges: Implications for H2O storage and recycling in the
mantle, Earth Planet. Sci. Lett., 137, 45 – 55, 1996.
Spivack, A. J., and H. Staudigel, Low-temperature alteration of
the upper oceanic crust and the alkalinity budget of seawater,
Chem. Geol., 115, 239 – 247, 1994.
Sprague, D., and H. N. Pollack, Heat flow in the Mesozoic and
Cenozoic, Nature, 285, 393 – 395, 1980.
Staudigel, H., and S. D. King, Ultrafast subduction: The key to
slab recycling efficiency and mantle differentiation, Earth
Planet. Sci. Lett., 109, 517 – 530, 1992.
Staudigel, H., S. R. Hart, and S. Richardson, Alteration of the
oceanic crust: Processes and timing, Earth Planet. Sci. Lett.,
52, 311 – 327, 1981.
Staudigel, H., S. R. Hart, H.-U. Schmincke, and B. M. Smith,
Cretaceous ocean crust at DSDP sites 417 and 418; Carbon
uptake from weathering versus loss by magmatic outgassing,
Geochim. Cosmochim. Acta, 53, 3091 – 3094, 1989.
Staudigel, H., T. Plank, B. White, and H.-U. Schmincke,
Geochemical fluxes during seafloor alteration of the basal-
tic upper oceanic crust; DSDP sites 417 and 418, in Sub-
duction Top to Bottom, Geophys. Monogr. Ser., vol. 96,
edited by G. E. Bebout et al., pp. 19 – 38, AGU, Washing-
ton, D.C., 1996.
10.1029/2002GC000392
Staudigel, H., et al., Geochemical Earth Reference Model
(GERM); Description of the initiative, Chem. Geol., 145,
153 – 159, 1998a.
Staudigel, H., A. Yayanos, R. Chastain, G. Davies, E. A. T.
Verdurmen, P. Schiffman, R. Bourcier, and H. de Baar, Bio-
logically mediated dissolution of volcanic glass in seawater,
Earth Planet. Sci. Lett., 164, 233 – 244, 1998b.
Stein, C. A., and S. Stein, Constraints on hydrothermal heat
flux through the oceanic lithosphere from global heat flow,
J. Geophys. Res., 99, 3081 – 3095, 1994.
Stephen, R. A., Data report: physical properties measurements
in ODP Hole 735B [online], Proc. Ocean Drill Program Sci.
Results, 176, 2001. (Available at http://www-odp.tamu.edu/
publications/176SR/chap.02/chap.02.htm)
Sugisaki, R., Chemical characteristics of volcanic rocks: Rela-
tion to plate movements, Lithos, 9, 17 – 30, 1976.
Tatsumi, Y., and T. Kogiso, Trace-element transport during
dehydration processes in the subducted oceanic crust: 2.
Origin of chemical and physical characteristics in arc mag-
matism, Earth Planet. Sci. Lett., 148, 207 – 221, 1997.
Thompson, A. B., Water in the Earth’s upper mantle, Nature,
358, 295 – 302, 1992.
Thompson, G., Metamorphic and hydrothermal processes: ba-
salt-seawater interaction, in Oceanic Basalts, edited by P. A.
Floyd, pp. 148 – 173, Van Nostrand Reinhold, New York,
1991.
Toh, H., Electrical conductivity structure of the Izu-Bonin Arc
revealed by seafloor electromagnetic observations, Ph.D.
thesis, Ocean Research Inst., Univ. of Tokyo, Tokyo, 1993.
Tregoning, P., F. Tan, J. Gilliland, H. McQueen, and K. Lam-
beck, Present-day crustal motion in the Solomon Islands
from GPS observations, Geophys. Res. Lett., 25, 3627 –
3630, 1998.
Ulmer, P., and V. Trommsdorff, Serpentine stability to mantle
depths and subduction-related magmatism, Science, 268,
858 – 861, 1995.
Underwood, M. B., et al., Sediment geochemistry, clay miner-
alogy, and diagenesis: A synthesis of data from Leg 131,
Nankai Trough, Proc. Ocean Drill. Program Sci. Results,
131, 343 – 363, 1993.
Vera, E. E., and J. C. Mutter, Crustal structure in the ROSE
area of the East Pacific Rise: One-dimensional travel time
inversion of sonobuoys and expanded spread profiles,
J. Geophys. Res., 93, 6635 – 6648, 1988.
Von Herzen, R., Geothermal evidence for continuing hydro-
thermal circulation in older (>60 M.y.) ocean crust, in Hy-
drology of the Oceanic Lithosphere, edited by E. Davis and
H. Elderfield, Cambridge Univ. Press, New York, in press,
2003.
von Huene, R., and D. W. Scholl, Observations at convergent
margins concerning sediment subduction, subduction ero-
sion, and the growth of continental crust, Rev. Geophys.,
29, 279 – 316, 1991.
Wang, K., and E. E. Davis, In the pursuit of hydrothermal
circulation and hydration depths of oceanic plates, Eos
Trans. AGU, 83(47), Fall Meet. Suppl., F1252, 2002.
Wannamaker, P. E., J. R. Booker, A. G. Jones, A. D. Chave,
J. H. Filloux, H. S. Waff, and L. K. Law, Resistivity cross
49 of 50
 Geochemistry 3
Geophysics
Geosystems G jarrard: subduction fluxes of water
section through the Juan de Fuca subduction system and its
tectonic implications, J. Geophys. Res., 94, 14,127 – 14,144,
1989.
White, R. S., D. McKenzie, and R. K. O’Nions, Oceanic crustal
thickness from seismic measurements and rare earth element
inversions, J. Geophys. Res., 97, 19,683 – 19,715, 1992.
Wilkens, R. H., N. I. Christensen, and L. Slater, High-pressure
seismic studies of Leg 69 and 70 basalts, Initial Rep. Deep
Sea Drill. Proj., 69, 683 – 686, 1983.
Wilkens, R. H., G. J. Fryer, and J. Karsten, Evolution of por-
osity and seismic structure of upper oceanic crust: impor-
tance of aspect ratios, J. Geophys. Res., 96, 17,981 –
17,995, 1991.
Williams, Q., and R. J. Hemley, Hydrogen in the deep earth,
Ann. Rev. Earth Planet. Sci., 29, 365 – 418, 2001.
10.1029/2002GC000392
Wyllie, M. R. J., A. R. Gregory, and G. H. F. Gardner, Elastic
wave velocities in heterogeneous and porous media, Geo-
physics, 21, 41 – 70, 1956.
Zhang, Y., and A. Zindler, Distribution and evolution of car-
bon and nitrogen in Earth, Earth Planet. Sci. Lett., 117, 331 –
345, 1993.
Zhou, W., D. R. Peacor, J. C. Alt, R. Van der Voo, and L.-S.
Kao, TEM study of the alteration of interstitital glass in
MORB by inorganic processes, Chem. Geol., 174, 365 –
376, 2001a.
Zhou, W., R. Van der Voo, D. R. Peacor, D. Wang, and Y. Zhang,
Low-temperature oxidation in MORB of titanomagnetite to
titanomaghemite: A gradual process with implications for
marine magnetic anomaly amplitudes, J. Geophys. Res.,
106, 6409 – 6421, 2001b.
50 of 50