Geoscience Frontiers 10 (2019) 1223e1254

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China University of Geosciences (Beijing)

Geoscience Frontiers
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Focus Paper

Subduction zone geochemistry

Yong-Fei Zheng
CAS Key Laboratory of Crust-Mantle Materials and Environments, School of Earth and Space Sciences, University of Science and Technology of China, Hefei 230026,
China

a r t i c l e i n f o a b s t r a c t

Article history: Crustal recycling at convergent plate boundaries is essential to mantle heterogeneity. However, crustal
Received 14 November 2018 signatures in the mantle source of basaltic rocks above subduction zones were primarily incorporated in
Received in revised form the form of liquid rather than solid phases. The physicochemical property of liquid phases is determined
14 February 2019
by the dehydration behavior of crustal rocks at the slab-mantle interface in subduction channels. Because
Accepted 25 February 2019
of the significant fractionation in incompatible trace elements but the full inheritance in radiogenic
Available online 28 March 2019
Handling Editor: M. Santosh isotopes relative to their crustal sources, the production of liquid phases is crucial to the geochemical
transfer from the subducting crust into the mantle. In this process, the stability of specific minerals in
Keywords:
subducting crustal rocks exerts a primary control on the enrichment of given trace elements in the liquid
Subduction zone phases. For this reason, geochemically enriched oceanic basalts can be categorized into two types in
Basalts terms of their trace element distribution patterns in the primitive mantle-normalized diagram. One is
Element mobility island arc basalts (IAB), showing enrichment in LILE, Pb and LREE but depletion in HFSE such as Nb and Ta
Geochemical differentiation relative to HREE. The other is ocean island basalts (OIB), exhibiting enrichment in LILE and LREE,
Crustal metasomatism enrichment or non-depletion in HFSE but depletion in Pb relative to HREE. In either types, these basalts
Mantle geochemistry show the enhanced enrichment of LILE and LREE with increasing their incompatibility relative to normal
mid-ocean ridge basalts (MORB).
The thermal regime of subduction zones can be categorized into two stages in both time and space.
The first stage is characterized by compressional tectonism at low thermal gradients. As a consequence,
metamorphic dehydration of the subducting crust prevails at forearc to subarc depths due to the
breakdown of hydrous minerals such as mica and amphibole in the stability field of garnet and rutile,
resulting in the liberation of aqueous solutions with the trace element composition that is considerably
enriched in LILE, Pb and LREE but depleted in HFSE and HREE relative to normal MORB. This provides the
crustal signature for the mantle sources of IAB. The second stage is indicated by extensional tectonism at
high thermal gradients, leading to the partial melting of metamorphically dehydrated crustal rocks at
subarc to postarc depths. This involves not only the breakdown of hydrous minerals such as amphibole,
phengite and allanite in the stability field of garnet but also the dissolution of rutile into hydrous melts.
As such, the hydrous melts can acquire the trace element composition that is significantly enriched in
LILE, HFSE and LREE but depleted in Pb and HREE relative to normal MORB, providing the crustal
signature for the mantle sources of OIB. In either case, these liquid phases would metasomatize the
overlying mantle wedge peridotite at different depths, generating ultramafic metasomatites such as
serpentinized and chloritized peridotites, and olivine-poor pyroxenites and hornblendites. As a conse-
quence, the crustal signatures are transferred by the liquid phases from the subducting slab into the
mantle.
Ó 2019, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction

Subduction zones are a dynamic site of mass and energy ex-

change between the asthenosphere, lithosphere, hydrosphere, at-
E-mail address: yfzheng@ustc.edu.cn. mosphere, and biosphere, with significant implications for the
Peer-review under responsibility of China University of Geosciences (Beijing). evolution of the Earth’s surface and interior (e.g., Tatsumi and

https://doi.org/10.1016/j.gsf.2019.02.003
1674-9871/Ó 2019, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1224 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Eggins, 1995; Stern, 2002; Bebout, 2007; Zheng and Chen, 2016). In
subduction zones, lithospheric plates are descending into the
mantle, giving rise to earthquakes, volcanic eruptions, and con-
centrations of economic ores (Fig. 1). Subduction’s delivery of
crustal materials to the mantle means that it plays a primary role in
cycling of terrestrial elements. On a larger scale, subduction drives
plate tectonics, as plate movement is chiefly driven by the down-
ward pull of oceanic slabs sinking into the asthenospheric mantle
(Forsyth and Uyeda, 1975; Jarrard, 1986; Conrad and Lithgow-
Bertelloni, 2004). Lithosphere and asthenosphere are trapped
above this slab, forming a wedge of mantle material (van Keken,
2003; Wiens et al., 2008; Zheng and Zhao, 2017). Subduction
generates strong thermal and chemical disequilibrium, leading to
dehydration and hydration, mineral transformations, and partial
melting of crustal and mantle rocks. This results in different types
of subduction zone processes such as metamorphism, meta-
somatism and magmatism. Understanding these three types of
geological processes is essential to the geochemical transfer from
the subducting crust into the mantle.
Crustal recycling at convergent plate boundaries has been
accepted as the fundamental mechanism for geochemical het-
erogeneity of the mantle (e.g., Armstrong, 1968; Chase, 1981;
Allègre, 1982; Hofmann and White, 1982; Ringwood, 1982;
Zindler and Hart, 1986; Hofmann, 1997; Stracke, 2012). In this
regard, the trace element and radiogenic isotope composition of
subduction zone magmas is primarily dictated by element transfer
from the subducting crust into the overlying mantle wedge (e.g.,
McCulloch and Gamble, 1991; Woodhead et al., 1993; Tatsumi and
Eggins, 1995; Turner and Hawkesworth, 1997; Stern, 2002;
Spandler and Pirard, 2013; Kelemen et al., 2014; Zheng and
Chen, 2016). It has also been recognized that the geochemical
signature of subducted crust is also present in intraplate basalts
(e.g., Sun, 1980; Allègre, 1982; Zindler and Hart, 1986; Sun and
McDonough, 1989; Hofmann, 1997; Stracke, 2012; Farmer, 2014;
Zhao et al., 2015; Huang and Zheng, 2017; Xu and Zheng, 2017).
Although major inputs at subduction zones can be fingerprinted in
volcanic outputs, there remain considerable uncertainties as to
the nature of element transfer during subduction from forearc
depths of <60e80 km through subarc depths of 80e160 km to
postarc depths of >200 km.
A great deal of geochemical studies have been devoted to
dehydration behavior and element mobility of the subducting crust
at different depths. They are generally categorized into two
Figure 1. Schematic diagram of a typical subduction zone showing the mass transfer processes and the location of seismic events (modified after Angiboust et al., 2012).
approaches. One deals with the igneous rocks of mafic composition
(e.g., Elliott et al., 1997; Tatsumi and Kogiso, 1997; Churikova et al.,
2001; Regelous et al., 2010; Cai et al., 2014; Kelemen et al., 2014;
Ryan and Chauvel, 2014), and the other focuses on high-pressure
(HP) to ultrahigh-pressure (UHP) metamorphic rocks (e.g.,
Tribuzio et al., 1996; Becker et al., 2000; Zack et al., 2001; Spandler
et al., 2003, 2004; Bebout et al., 2007, 2014; Gao et al., 2007; Miller
et al., 2007; Zhao et al., 2007; Zhang et al., 2008; El Korh et al., 2009;
Xiao et al., 2016). While some of the results from both approaches
converge toward consistent answers, many of them are still
divergent without coherent definitions. This is particularly so for
the interpretation of geochemical data for fluid action and element
transport when dealing with the origin of crustal signatures in
enriched basalts above subduction zones relative to the composi-
tion of fluids liberated from HP to UHP metamorphic rocks. By
contrast, laboratory experimental studies of trace element parti-
tioning coefficients between fluids and minerals yield almost
consistent results (e.g., Kogiso et al., 1997; Kessel et al., 2005;
Klimm et al., 2008; Hermann and Rubatto, 2009; Skora and
Blundy, 2010; Schmidt and Poli, 2014), which provides a basis for
deciphering the geochemical variation and element transfer at the
slab-mantle interface in subduction channels.
As the typical product of interplate magmatism, island arc ba-
salts (IAB) are generally characterized by their trace element dis-
tribution patterns in the primitive mantle-normalized diagram
(Fig. 2), showing more enrichment in large ion lithophile elements
(LILE), Pb and light rare earth elements (LREE), but depletion in
high field strength elements (HFSE) such as Nb and Ta relative to
neighboring elements, and less enrichment in heavy rare earth
elements (HREE) relative to the primitive mantle (e.g.,
Hawkesworth et al., 1991; Tatsumi and Eggins, 1995; Pearce et al.,
2005; Spandler and Pirard, 2013; Kelemen et al., 2014). As the
product of intraplate magmatism, by contrast, oceanic island ba-
salts (OIB) are also characteristized by the specific patterns of trace
element distribution (Fig. 2), exhibiting elevated abundances of not
only LILE and LREE but also HFSE relative to IAB, with depletion in
Pb (e.g., Zindler and Hart, 1986; Sun and McDonough, 1989;
Weaver, 1991). Although the enrichments in LILE and LREE are
traditionally ascribed to origination from the lower mantle, a proxy
for the primitive mantle (DePaolo and Wasserburg, 1976;
Wasserburg and DePaolo, 1977; Allègre et al., 1979; O’Nions et al.,
1979; Hofmann, 1988; Allègre and Lewin, 1989), available mantle
samples provide no geochemical evidence for the lower mantle
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Figure 2. Trace element distribution of mafic volcanics in the primitive mantle-normalized diagram. The plotted data are the average compositions of island arc basalts (IAB),
continental arc andesites (CAA) and mid-ocean ridge basalts (MORB) from Kelemen et al. (2014), and those for oceanic island basalts (OIB) are from Sun and McDonough (1989). The
primitive mantle values are from McDonough and Sun (1995).
origin (White, 2010; Huang and Zheng, 2017). In addition, both IAB
and OIB show similar enrichments in radiogenic Sr isotopes but
depletions in radiogenic Nd isotopes relative to the primitive
mantle. These have challenged the petrogenetic interpretation of
OIB and its relationship to mantle geochemistry. In this regard, it is
critical to assess the relative contributions of crustal and mantle
components to interplate and intraplate magmas in order to eval-
uate the flux of crustal material recycled into the mantle. Therefore,
a central issue in subduction zone geochemistry is to decipher how
the crustal components were incorporated into the mantle source
of basaltic rocks.
In order to advance our understanding of subduction zone
geochemistry, this article presents a state-of-the-art review on the
trace element transfer from the subducting crust at different depths
into the mantle. I first give a synthesis of current studies on the
thermal regime of subduction zones, which is a key to the dehy-
dration and melting behaviors of crustal rocks at the slab-mantle
interface in subduction channels. This is followed by examining
the geochemistry of subduction zone fluids, which may occur in the
forms of aqueous solutions, hydrous melts and even supercritical
fluids. The physicochemical property of these liquid phases has
great bearing on the fractionation behavior of both major and trace
elements in the geochemical transfer from the subducting crust
into the mantle. For this reason, more attention is paid to the for-
mation of supercritical fluids and the geochemical behavior of HFSE
in subduction channels. Then these updated results are linked to
the enrichment of crustal signatures in basaltic rocks, in which the
crustal signatures are represented by an integration of major ele-
ments, trace elements and radiogenic isotopes. This leads to a
common mechanism for the geochemical transfer at the different
depths in subduction zones.
2. The thermal regime of subduction zones
The thermal regime of subduction zones is defined as the
thermal structure and its variations through time (Agard and
Vitale-Brovarone, 2013). The thermal structure of subduction
zones is transient and its steady state depends on a number of
1225
variables (e.g., Peacock, 1996; Kelemen et al., 2003; Kincaid and
Griffiths, 2003; Lallemand et al., 2005; Peacock et al., 2005;
Currie and Hyndman, 2006; Syracuse et al., 2010; van Keken
et al., 2011; Hall, 2012; Sharples et al., 2014). Traditionally, it is
correlated with the following five variables (Fig. 3): (1) the rate of
plate convergence, (2) the age of descending slabs, (3) subduction
dip angle, (4) the property of the mantle wedge, and (5) the effi-
ciency of shear heating at the slab-mantle interface. Further studies
indicate that it is also dictated by the thickness of upper plate and
the depth of decoupling between the subducting slab and the
mantle wedge. In modern subduction zones, active compression in
the overriding plate is always associated with shallowly dipping
slabs (<30
), whereas active extension in backarc sites is always
observed for steeply dipping slabs (>50
). In combination with the
metastable occurrence of hydrous minerals in eclogite facies UHP
metamorphic rocks (Zheng, 2009), it appears that the convergent
rate exerts the first-order control on the thermal regime of sub-
ducting zones (Zheng and Chen, 2016). As a consequence, the
fastest convergence leads to the lowest temperatures at the slab-
mantle interface in subduction channels. On the other hand, the
thermal structure of subduction zones changes with time, so that it
is dynamic in both time and space and its variation leads to the
difference of thermal gradients for orogenic processes above sub-
duction zones (Zheng and Chen, 2017).
In subducting zones, cold slabs descend into the warm mantle,
resulting in cooling of the mantle wedge on the one hand and
warming of the slab surface on the other hand. More importantly,
crustal rocks in the subducting slabs undergo metamorphic dehy-
dration and partial melting at lithospheric depths, releasing
aqueous solutions and hydrous melts for metasomatism of the
mantle wedge. Which liquid phase is released from the descending
crust depends on the thermal structure of subducting zones (e.g.,
Kelemen et al., 2003; Zheng et al., 2016). Therefore, the thermal
structure of subduction zones is not only important for meta-
morphic dehydration and partial melting but also to understand
the development of orogenic processes in different phases. In
general, the thermal regime of subduction zones is dictated not
only by the nature of the upper plate (ancient craton vs. juvenile
1226 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

Figure 3. Schematic diagram showing the major variables that control the thermal structure of subducting zones (modified from Peacock, 1996).

arc) and the nature of the lithosphere being subducted (oceanic vs.
continental) but also by the tectonic coupling between the sub-
ducting slab and the lithospheric mantle. In addition, previously
subducted zones may be reactivated by rifting tectonism (Zheng
and Chen, 2017).
Temperature (T) and pressure (P) are two principal variables at
the slab-mantle interface in subduction channels, and their varia-
tions are the key to understanding of mass transfer and
geochemical cycling in subduction zones (e.g., Manning, 2004;
Bebout, 2007; Zheng et al., 2011), arc volcanism (e.g., Kelemen
et al., 2003; Spandler and Pirard, 2013), crustal rheology and
shallow interplate seismicity (e.g., Peacock and Wang, 1999; Hacker
et al., 2003; Hyndman, 2013; Wang and Tréhu, 2016), and water
release vs. storage in the subducting crust and the overlying mantle
wedge (e.g., Hacker, 2008; van Keken et al., 2011; Zheng et al., 2016;
Abers et al., 2017). Interpretation of all these processes is primarily
dictated by the thermal regime of subduction zones (e.g., Peacock
and Wang, 1999; Kelemen et al., 2003; Hacker, 2008; Syracuse

Figure 4. The pressure-temperature diagrams of metamorphic facies in terms of petrology (a) and tectonics (b), with PeT fields for given mineral assemblages (modified after
Stüwe, 2007). The vertical axes are the same in both diagrams but labeled in GPa for petrology (a) and in km for tectonics (b). Bands delineating fields in (a) indicate that boundaries
vary according to bulk composition of metamorphic lithologies. Green lines denote the thermal gradients of subduction zone processes, and red curve denotes the granite wet
solidus. Mineral abbreviations: Ab, albite; And, andalusite; Coe, coesite; Jd, jadeite; Ky, kyanite, Sil, sillimanite; Qz, quartz. Metamorphic facies abbreviations: LG ¼ low grade;
GS ¼ greenschist facies; BS ¼ blueschist facies; EC ¼ eclogite facies; UHP ¼ ultrahigh-pressure facies; GP ¼ garnet pyroxenite facies; HGR ¼ high-P granulite facies; GR ¼ granulite
facies; PA ¼ plagioclase amphibolite facies; UHT ¼ ultrahigh-temperature facies.
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
et al., 2010; van Keken et al., 2011). In this regard, subduction zone
processes can be categorized into five types in terms of their
thermal gradients: (1) ultracold (5
C/km), (2) cold (5e10
C/km),
(3) warm (10e30
C/km), (4) hot (30e60
C/km), and (5) ultrahot
(>60
C/km). This is illustrated by the PeT phase diagram for
metamorphic facies of crustal rocks (Fig. 4). Because the subducting
slab is generally coupled with the overlying mantle wedge at lith-
ospheric depths, cold subducting zones are produced at low ther-
mal gradients of <10
C/km. This leads to progressive
metamorphism in Alpine facies series from HP blueschist through
HP eclogite to UHP eclogite (Zheng and Chen, 2017), with the
common occurrence of hydrous minerals such as glaucophane,
lawsonite, phengite and zoisite (Schmidt and Poli, 2014; Zheng
et al., 2016). If two plates are converged at very fast rates, an ul-
tracold subducting zone results with metastable preservation of
these hydrous minerals at the postarc depths (Zheng and Chen,
2016).
With decreasing convergent rates, on the other hand, warm to
hot subducting zones may be produced at moderate thermal gra-
dients of 10e30
C/km to result in progressive metamorphism in
Barrovian facies series from low-P greenschist through mid-P
amphibolite to HP granulite (Zheng and Chen, 2017). High ther-
mal gradients of 30e60
C/km are often invoked for flat subduction
of oceanic lithosphere, but it is necessary for the overlying litho-
sphere to be as thin as 40e60 km. Otherwise this is problematic
because either oceanic or continental lithosphere generally has a
thickness of >80 km (Stüwe, 2007). Nevertheless, the very high
thermal gradients of >60
C/km may occur at crustal depths if the
lithosphere-asthenosphere boundary is shallowed for convective
heat transfer from the upwelling asthenospheric mantle into the
thinned lithosphere after foundering of orogenic roots (Zheng and
Chen, 2016, 2017). This can bring high heat flow for rifting orogeny
through superimposition on previously subducted zones,
resulting in high-temperature (HT) to ultrahigh-temperature (UHT)
granulite-facies metamorphism at the forearc depths (Zheng and
Chen, 2017). Such high heat flow is common at continental
Figure 5. Schematic diagram showing the thermal structure of an oceanic subduction zone at its early stage (revised after Scambelluri et al., 2006). The temperature of the mantle
wedge base is reduced to a value consistent with the surface of a subducting slab after achieving thermal equilibration. Pink denotes the subducting plate and green denotes the
overriding plate.
1227
backarc lithosphere (Hyndman et al., 2005; Currie and Hyndman,
2006; Currie et al., 2008). It also can be acquired at the subarc to
postarc depths if a subducting slab is rollback to decouple with the
overlying mantle wedge, leading to the lateral flow of the
asthenospheric mantle into the space between the mantle wedge
base and the slab surface (Zheng et al., 2016).
A great deal of petrological studies have demonstrated that
continental subduction always proceeds at the low thermal gradi-
ents and thus belongs to the cold subduction (Liou et al., 2009;
Zheng et al., 2016). By contrast, oceanic subduction zones may
span a wide spectrum of thermal gradients from ultracold to ul-
trahot ones (Peacock and Wang, 1999; van Keken et al., 2002, 2011;
Abers et al., 2006; Syracuse et al., 2010), which is dictated not only
by the rate of plate convergence but also by the thickness of the
overlying plate. Nevertheless, the temperature of subducting slabs
is always lower than that of the mantle wedge (Peacock, 2003;
Syracuse et al., 2010; Hall, 2012; Zheng et al., 2016). Before sub-
duction, there is a vertical geotherm inside the mantle wedge, with
temperatures varying from about 500e600
C at its top to about
1200e1400
C at its bottom (Stüwe, 2007). During subduction, the
subducting slab is coupled with the mantle wedge at lithospheric
depths, resulting in cooling of the wedge base due to thermal
conduction from the cold slab. This yields two opposite vertical
thermal gradients inside the mantle wedge, with the highest
temperature in the wedge center but the lowest temperature in the
forearc corner. With continuation of subduction, the wedge bottom
temperature decreases with time and becomes increasingly close to
the slab surface temperature. It eventually approaches the same
lowest temperature at the slab-mantle interface when being sub-
ducted to the subarc depths (Fig. 5). Such lowest temperatures
would be generally reached at the highest pressures, corresponding
to the peak UHP metamorphism in cold subduction zones.
The lowest temperature at the slab-mantle interface is variably
lower than the wedge center temperature, with differences ranging
from less than one hundred to several hundred degrees (Toksöz
et al., 1971; Schubert et al., 2001; Hall, 2012). Convection inside
1228 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
the mantle wedge becomes weaker and weaker during the sub-
duction and stops finally. The difference in temperature between
the slab surface and the wedge center is primarily dictated by the
nature of the mantle wedge (Leng and Mao, 2015; Zheng and Chen,
2016). The mantle wedge center may keep the relatively higher
temperatures for a while, but there is no convection any more as
soon as it cools down to temperatures below those for the thermal
boundary layer between lithosphere and asthenosphere. If the
subduction continues, free convection of the mantle wedge may be
renewed by lateral heating from the convective mantle at the
backarc position (Peacock et al., 1994). This also brings heat into the
wedge base close to the subducting slab. Nevertheless, rollback of
the subducting slab is a more effective mechanism for heating of
both wedge base and slab surface by lateral flow of the astheno-
spheric mantle (e.g., Kincaid and Griffiths, 2003, 2004; Zheng et al.,
2016). In this context, the thermal regime of subducting zones can
be categorized into two stages in both time and space. The first
stage is characterized by compressional tectonism at the low
thermal gradients due to the tectonic coupling between the mantle
wedge and the subducting slab, corresponding to thermal locking
of subducting zones. The second stage is indicated by extensional
tectonism at the high thermal gradients due to the tectonic
decoupling between the mantle wedge and the subducting slab,
corresponding to thermal unlocking of the subducting zones.
In cold subducting zones, the descending oceanic crust would
not undergo significant dehydration at the forearc depths. For this
reason, the subducting oceanic crust at the subarc depths can still
release a large amount of aqueous solutions to hydrate the over-
lying mantle wedge and thus to eventually produce abundant arc
volcanics (Peacock and Wang, 1999; van Keken et al., 2002, 2011;
Hacker, 2008). In warm to hot subducting zones, in contrast, the
descending oceanic crust may be significantly dehydrated at the
forearc depths. This is also the reason why Juan de Fuca slab
entering Cascadia subduction zone is relatively dry (Canales et al.,
2017). Nevertheless, the dehydrated oceanic crust may undergo
partial melting at the postarc depths due to the thermally unlock-
ing of subduction zones. This is primarily caused by rollback of the
Figure 6. Trace element characteristics of island arc basalts in the primitive mantle-normalized diagram (data from Elliott, 2003).
subducting slab, leading to heating by the laterally flowed
asthenospheric mantle (e.g., Kincaid and Griffiths, 2003, 2004;
Zheng and Chen, 2017). In this case, a lot of arc volcanics can
occur in the hot subducting zones such as Cascadia and Mexico.
Therefore, the temporal change in the thermal structure of sub-
duction zones controls whether the subducting oceanic crust can
provide sufficient amounts of liquid phases to metasomatize the
mantle wedge at the subarc to postarc depths (van Keken et al.,
2002, 2011; Hacker, 2008; Zheng et al., 2016).
3. The composition of subduction zone fluids
It is well known that IAB are enriched in LILE, Pb and LREE but
depleted in HFSE such as Nb and Ta relative to HREE in the primitive
mantle-normalized diagram (Figs. 2 and 6). Thus, IAB-like
geochemical signatures are indicated by high LILE/HFSE and
LREE/HREE ratios but low Nb/U and Ce/Pb ratios. By contrast,
normal mid-ocean ridge basalts (MORB) are depleted in LILE, Pb
and LREE relative to HREE, so that MORB-like geochemical signa-
tures are indicated by low LILE/HFSE and LREE/HREE ratios. Because
of the seawater hydrothermal alteration, igneous oceanic crust
(IOC) acquires variably elevated abundances for LILE and Pb relative
to normal MORB; seafloor sediments show significant enrichment
in LILE, Pb, LREE, Nb and Ta relative to normal MORB despite the
Nb-Ta trough in the diagram (Fig. 7).
Based on the geochemistry of IAB and their differences relative
to normal MORB, there is the consensus that LILE and Pb are added
to the mantle sources of IAB via liquid phases rather than solid
rocks from the subducting oceanic crust (e.g., Hawkesworth et al.,
1991; Pearce and Peate, 1995; Bebout et al., 1999; Elliott, 2003;
Spandler and Pirard, 2013). Such distinctive geochemical signa-
tures have frequently been linked to the flux of aqueous solutions
derived from dehydration reactions in the subducting slab, which
are expected to carry a significant amount of water-soluble trace
elements. The subarc mantle is thus expected to be enriched in LILE
(such as Cs, Rb, Ba, U and Sr) and Pb relative to the depleted MORB
mantle (Hawkesworth et al., 1991; Spandler and Pirard, 2013), and
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Figure 7. Trace element characteristics of altered oceanic basalt and seafloor sediment at subduction zones in the primitive mantle-normalized diagram. Data sources: altered
oceanic basalt at ODP Sites 417 (Staudigel et al., 1996) and 801 (Kelley et al., 2003), and globally subducting sediment (GLOSS II) composite (Plank, 2014).
this group of elements is soluble in water and thus termed as water-
soluble elements. Nevertheless, mafic arc volcanics are also
enriched in LREE and Th (e.g., Weaver, 1991; Elliott, 2003; Spandler
and Pirard, 2013; Kelemen et al., 2014), which are insoluble in water
but soluble in hydrous silicate melts. Thus, all of LILE, Pb, LREE and
Th are collectively referred to as fluid-mobile elements (e.g., Kogiso
et al., 1997; Kessel et al., 2005). On the other hand, trace elements
that have higher charge density, most notably HSFE such as Nb, Ta,
Ti, Zr and Hf but also HREE, are usually viewed as immobile in
subduction zone fluids (e.g., Tatsumi et al., 1986; Brenan et al., 1994,
1995a; Keppler, 1996), so that they are generally referred to as fluid-
immobile elements. Therefore, the mantle sources of mafic arc
volcanics appear relatively depleted in HFSE but enriched in Pb,
resulting in negative Nb-Ta anomalies but a positive Pb anomaly in
IAB (Figs. 2 and 6).
In addition to the water-soluble elements such as LILE and Pb,
IAB also show variable enrichment in the water-insoluble elements
such as Th and LREE relative to normal MORB (e.g., Weaver, 1991;
Elliott, 2003; Spandler and Pirard, 2013; Kelemen et al., 2014).
This is often ascribed to contributions from the seafloor sediment,
because this crustal component is strongly enriched in LILE, Pb, Th
and LREE relative to HREE (Fig. 6). Nevertheless, the sedimentary
input to subduction zones is widely variable, heavily depending on
the composition of subducting crust (upper vs. lower continental
crust). Continental margins adjacent to oceanic subduction zones
generally undergo chemical weathering during subduction, trans-
porting various materials, including both water-soluble elements
and water-insoluble detritus, into the trench. The trench sediment
is generally heterogeneous in lithology, varying from pure silica
chert to nearly pure calcium carbonate chalks and metal-rich red
clays (Plank, 2014). In the trench, they are physical mixtures of
variable amounts of terrigenous detritus, biogenic accumulates of
primarily carbonate, opal and apatite organism hard parts, and
hydrothermal particulates as the complements to seafloor alter-
ation. Globally, the trench sediment is dominated by terrigenous
detritus and so has a geochemical composition very similar to that
1229
of the post-Archean average shales and the upper continental crust
(Plank and Langmuir, 1998). Biogenic phases are largely diluents to
most chemical species in the detritus, except Sr, Ba, and U in car-
bonates, REE in phosphates, and Ba associated with biogenic opal.
In oceanic regions far away from the terrigenous input, the pelagic
sediment is dominated by hydrogenetic or hydrothermal compo-
nents, rich in Fe-Mn oxides, REE, Th, Pb, Co, and other metals. In
general, the seafloor sediment may have characteristic Nd-Hf iso-
topic compositions due to the strong enrichment of REE in some
phases and the lack of the heavy mineral zircon in the pelagic
sediment (Vervoort et al., 2011). The oceanic realm also may lead to
the distinctive fractionation of quadrivalent Ce from the other
dominantly trivalent REE.
Subduction zone fluids are commonly categorized into two
types in terms of their origin (Zheng and Hermann, 2014): (1)
metamorphic fluids, which are produced by metamorphic reactions
at temperatures below the wet solidus of crustal rocks and occur in
the form of aqueous solutions; (2) anatectic melts, which are pro-
duced by peritectic reactions at temperatures above the wet solidus
of crustal rocks and occur in the form of hydrous melts. Meta-
morphic and peritectic minerals, particularly some accessory
minerals such as zircon and rutile, are also produced by meta-
morphic and peritectic reactions, respectively. It is important to
acknowledge that the two accessory minerals cannot precipitate
from either metamorphic fluids or anatectic melts, because the two
types of subduction zone fluids are highly undersaturated with
HFSE, including Zr and Ti. Nevertheless, silica is highly soluble in
metamorphic fluids and thus quartz is common in metamorphic
veins. Likewise, felsic components are susceptible to dissolution in
anatectic melts and thus quartz and feldspar are common in ana-
tectic veins (e.g., leucosomes in migmatites). Like magmatic melts,
on the other hand, anatectic melts may be evolved through the
fractional crystallization of Zr-poor minerals, resulting in the local
oversaturation of Zr for zircon growth. For these reasons, we have
different terms for different origin of zircon, with metamorphic
zircon from metamorphic reactions, peritectic zircon from
1230 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

Figure 8. Simplified phase relations for silicate-water systems at the second critical endpoint, where there are continuum properties of a supercritical fluid (revised after Schmidt
and Poli, 2014). (a) With no hydrous minerals stable above the solidus (as applicable for basalt at >3 GPa). (b) With hydrous minerals stable above the solidus (as applicable for
pelites where the hydrous phase is phengite). Capital A denotes the anhydrous silicate mineral and H denotes the hydrous silicate mineral. (c) PeT diagram showing the wet solidus
(red line), the critical curve (green line) that corresponds to the crest of the fluid-melt immiscibility gap, and the fluid-absent solidus for a hydrous mineral (red dashed line). The T-x
sections on the backside of panels (a) and (b) give the continuum curves for pressures above the second critical endpoint. Dehydration melting is not affected by the endpoint, and
the peritectic reaction H ¼ A þ melt is stable at all pressures of (b) and (c). The field labels in italic refer to the T-x section at the back face of (a) and (b). Abbreviations: SCP, second
critical endpoint of the solidus; SCF, supercritical fluid (supercritical with respect to the endpoint of the solidus).

peritectic reactions, anatectic zircon from the evolved anatectic
melts, and magmatic zircon from the evolved magmatic melts
(Chen and Zheng, 2017).
With increasing pressure along the wet solidus, aqueous solu-
tions may dissolve more silicate components to become hydrous
silicate melts, eventually reaching the second critical endpoint
where the two liquid phases become one phase of the supercritical
fluid (Fig. 8). It appears that supercritical fluids can be generated
under UHP metamorphic conditions (Manning, 2004; Hermann
et al., 2006a; Zheng et al., 2011; Ni et al., 2017). However, this is
only a necessary condition in chemical thermodynamics. A suffi-
cient condition in chemical kinetics is to achieve the complete
miscibility between aqueous solutions and hydrous melts. In other
words, both aqueous solutions and hydrous melts can be produced
under UHP conditions, but it takes time to achieve the complete
miscibility at the subarc depths. Hermann et al. (2006a) suggest
that aqueous solutions contain solutes of <30 wt.% whereas hy-
drous melts contain dissolved water of <35 wt.%, and thus super-
critical fluids are considered to exhibit intermediate compositions
(a kind of transitional fluids). Physicochemically, there are indeed
immiscibility gaps between aqueous solutions and hydrous melts at
supersolidus temperatures. In view of the complete miscibility for
supercritical fluids, nevertheless, there are variable proportions
between aqueous solutions and hydrous melts (Zheng et al., 2011;
Frezzotti and Ferrando, 2015).
The composition of subduction zone fluids is a function of
element solubility at different temperatures and pressures
(Hermann et al., 2006a; Zheng et al., 2011; Zheng and Hermann,
2014). The amount of water in fluids is inversely correlated with
that of solutes and thus also changes as a function of pressure and
temperature. The major solutes are Si, Al and alkalis (Na, K) with
minor amounts of Ca, Fe and Mg (Manning, 2004; Hermann et al.,
2013). While Al is not significantly fractionated during partial
melting, aqueous solutions preferentially dissolve Si. Aqueous so-
lutions and hydrous melts have different capacities of dissolving
and transporting trace elements during subduction zone processes
(e.g., Hermann et al., 2006a; Zheng et al., 2011). A number of
experimental studies were performed to determine the concen-
tration of major and trace elements in aqueous solutions and hy-
drous melts relative to the pelitic protolith that has a common
crustal composition (Fig. 9). Upon the metamorphic dehydration
and partial melting at lithospheric depths, aqueous solutions are
only enriched with water-soluble trace elements such as LILE, Pb
and U. In comparison, hydrous melts can be enriched with all fluid-
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254 1231

Figure 9. Experimentally determined major and trace element distribution of fluids at mantle conditions normalized to the starting materials of pelitic composition (revised after
Zheng and Hermann, 2014). Blue-green curves denote aqueous solutions, where data at 2.2 GPa are after Spandler et al. (2007); data at 2.5e4.5 GPa, 600
C and 700
C are after
Hermann and Spandler (2008) for major elements and Zheng and Hermann (2014) for trace elements from the same experiments. Red-orange curves denote hydrous melts with
data after Hermann and Rubatto (2009).

mobile trace elements, including LREE and Th. Residues are highly may persist to the postarc depths in peridotite if subduction pro-
enriched with fluid-immobile trace elements such as HFSE and ceeds at very low thermal gradients (Ulmer and Trommsdorff,
HREE. The concentrations of fluid-mobile trace elements in 1995; Zheng et al., 2016). At higher temperatures, subduction
aqueous solutions are at least an order of magnitude lower than zone fluids evolve during the breakdown of lawsonite, amphibole
those in hydrous melts (Zheng and Hermann, 2014). and mica, and become more solute rich, containing Si, Al and alkalis
Similar results are obtained from the experimental determi- (Manning, 2004; Zheng and Hermann, 2014). If influxed with
nation of trace element partition coefficients between fluid and aqueous solutions, the slab top may partially melt at T  700
C and
solid for basalt-water systems (Kessel et al., 2005; Klimm et al., P  3 GPa (Mann and Schmidt, 2015).
2008; Skora and Blundy, 2010; Kawamoto et al., 2012, 2013).
Fig. 10 presents a comparison of fluid/solid partition coefficients
4. The possible existence of supercritical fluids in subduction
for liquid phases based on experimental data. Despite the limited
zones
database, the available data indicate that fluid/solid partition co-
efficients for hydrous melts are greater than for aqueous solutions
Subduction zone magmas contain crustal components that were
but lesser than for supercritical fluids. The partition coefficients
primarily carried by liquid phases from the subducting slab.
represent a somewhat relative mobility of characteristic elements,
Whether the crustal components are present in the form of
which may change with their reactive volumes and equilibrium
aqueous solutions, hydrous melts, or supercritical fluids is critical to
scales during metamorphic dehydration and partial melting.
the mass transfer at the slab-mantle interface in subduction
While the supercritical fluids can efficiently transport trace ele-
channels. Although supercritical fluids could be identified by the
ments than the hydrous melts, their physicochemical property is
intermediate compositions (Hermann et al., 2006a, 2013; Ni et al.,
primarily dictated by the miscibility between water and melt
2017), it does not mean that there is a given range of water con-
above the second critical endpoints, regardless of the relative
centrations to distinguish a supercritical fluid from an aqueous
proportions between water and melt (Bureau and Keppler, 1999;
solution and a hydrous melt at given PeT conditions. Geochemical
Hermann et al., 2006a; Hack et al., 2007; Zheng et al., 2011; Ni
studies of metamorphic and peritectic minerals formed under
et al., 2017).
eclogite facies UHP conditions indicate that the compositions of
With slab subduction to the forearc depths, dominant minerals
supercritical fluids are typically high in trace elements such as not
in metabasalts are lawsonite, garnet and clinopyroxene (Hacker,
only LREE and LILE but also HREE and HFSE (e.g., Ferrando et al.,
2008; Klimm et al., 2008), while quartz and mica also form in
2005; Zhang et al., 2008; Xia et al., 2010). In this regard, it is
metasediments. Water-soluble elements are mobile at such depths
important to find the geochemical evidence for the existence of
and thus transported by aqueous solutions (Bebout and Penniston-
supercritical fluids in subduction zones.
Dorland, 2016). A series of accessory minerals and their T-depen-
The action of supercritical fluids has been increasingly invoked
dent solubility can exert a primary control on the behavior of some
in geochemical studies of subduction zone rocks (e.g., Stockhert
trace elements, such as REE, Th, and U in monazite and allanite, Nb
et al., 2001, 2009; van Roermund et al., 2002; Ferrando et al.,
and Ta in rutile, and Zr, Hf, U, and HREE in zircon (Hermann and
2005, 2009; Gao et al., 2007, 2012; Scambelluri et al., 2008;
Rubatto, 2009; Skora and Blundy, 2010; Zheng et al., 2011).
Vrijmoed et al., 2008; Malaspina et al., 2010; Xia et al., 2010;
Although serpentine minerals only have a maximum stability of
Huang and Xiao, 2015; Wang et al., 2017). There is also a signifi-
600e700
C (Schmidt and Poli, 1998; Spandler et al., 2014), they
cant increase in our knowledge of the origin and evolution of
1232 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

Figure 10. Fluid/solid partition coefficients for MORB-water systems at mantle conditions (revised after Schmidt and Poli, 2014). Symbols: solution/MORB (blue diamonds), melt/
MORB (red diamonds and red array), supercritical fluid/MORB (green array), and melt/pelite (gray array). In all cases, the residue is composed of garnet þ clinopyroxene  quartz/
coesite with rutile þ epidote/allanite for the gray melt/MORB field, and with phengite þ ilmenite þ rutile for the red melt/pelite field. Data from Kessel et al. (2005) e K05: di-
amonds and green array; Klimm et al. (2008) e K08: red array; and Skora and Blundy (2010) e SB10: gray array.

supercritical fluids in subduction zones (e.g., Manning, 2004;
Hermann et al., 2006a; Hack et al., 2007; Zheng et al., 2011;
Schmidt and Poli, 2014; Frezzotti and Ferrando, 2015; Ni et al.,
2017). However, a prominent problem in those studies of natural
samples is to determine the real existence of supercritical fluids in
subduction zones. Both hydrous melt and supercritical fluid can be
produced through peritectic reactions under PeT conditions above
the critical curve. The peritectic minerals so produced may have a
wide range of geochemical compositions, making their identifica-
tion challenging. Ferrando et al. (2005) observed the occurrence of
primary crystal inclusions in peritectic garnet and kyanite in the
UHP eclogite and kyanite quartzite from the Sulu orogen, China.
Some of the crystal inclusions contain very high amounts of ele-
ments Si, Al and Ti (in the order of tens of wt.%), suggesting the
possible existence of a supercritical fluid with transitional character
between a aqueous solution and a hydrous melt. Zhang et al. (2008)
suggest that the supercritical fluid attending the UHP conditions is
mainly composed of SiO2 þ Al2O3 þ CaO þ MgO þ FeO þ
Na2O þ H2O and enriched in LREE, HFSE and P, V, Sr, Ba and Pb.
By using an in situ observation technique, Kawamoto et al.
(2012) determined the second critical endpoint between aqueous
solutions and hydrous melts under UHP conditions. The results
suggest that the depth for the second critical endpoint changes
with the composition of silicate rocks in aqueous systems. It is at
92 km (2.8 GPa) and 750
C for the andesiteeH2O system, and at
83 km (2.5 GPa) and 700
C for the sediment-H2O system. It is
possible that the sediment-derived supercritical fluid is generated
first, and then it is fed to the mantle wedge from the subducting
crust. It is during this process that the supercritical fluid is sepa-
rated into an aqueous solution and a hydrous melt at 92 km depth.
The aqueous solution is reacted with the mantle wedge peridotite
to generate the source of island arc basalts, whereas the hydrous
melt is reacted with the peridotite to generate the source of island
arc andesites.
Elliott et al. (1997) recognized two slab-derived components in
IAB: a hydrous melt from the subducting sedimentary layer and an
aqueous solution from the subducting basaltic layer. The melt and
solution components can coexist in the mantle wedge if the su-
percritical slab-derived fluids supplied from the downgoing slabs
separate into a hydrous melt and an aqueous solution (Kawamoto
et al., 2012). The newly determined second critical endpoint sug-
gests that slab-derived fluids are expected to be under supercritical
conditions at the slab-mantle interface in cold subduction zones,
where the supercritical fluid is presumably generated by reaction of
the sediment-derived supercritical fluids with the overlying mantle
wedge peridotite at the subarc depths. Therefore, no isolated liquid
phase exists at that time, but there is a single supercritical fluid
phase (with a continuum characteristic between aqueous solution
and hydrous melt in the downgoing sediments) at the subarc
depths. Two such distinct slab-derived components have also been
suggested to explain the geochemistry of many arc basalts. Sepa-
ration of slab-derived supercritical fluids into hydrous melts and
aqueous solutions can commonly occur in most subduction zones.
Gao et al. (2012) observed the coexistence of silicate and sulfate
inclusions in the peritectic garnet of UHP eclogite from the Dabie
orogen. These crystal inclusions show variable mineral paragenesis
from pure K-feldspar to pure quartz, with predominance of inter-
mediate compositions consisting of K-feldspar þ quartz  silicate
(plagioclase or epidote)  barite. The barite exhibits significant
heterogeneity in major element composition, with total contents of
only 57e73 wt.% and highly variable SiO2 contents of
0.32e25.85 wt.% that are positively correlated with the BaO and
SO3 contents. While the occurrence of silicate inclusions indicates
their crystallization from hydrous melts, the occurrence of barite
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Figure 11. Schematic diagrams showing a subduction path at low thermal gradients
from high-pressure blueschist to ultrahigh-pressure eclogite facies. Also shown is the
difference in temperature between slab dehydrationand mantle melting for arc mag-
matism above oceanic subduction zones. Thin lines denote the thermal gradients at
5
C/km, 10
C/km, 30
C/km and 60
C/km, respectively, in oceanic subduction zones.
Abbreviations: GS, greenschist facies; BS, blueschist facies; AM, amphibolite facies;
EC1, high-pressure eclogite facies; EC2, ultrahigh-pressure eclogite facies; GP, garnet
pyroxenite; LH, lherzolite.
aggregates with variably high SiO2 contents suggests the coexis-
tence of aqueous solutions with hydrous melts. Although these
hydrous melts and aqueous solutions were immiscible within the
UHP slice, they would be miscible at UHP metamorphic conditions
(Zheng et al., 2011). It is possible that the hydrous melts and
aqueous solutions were generated by phase separation of the su-
percritical fluids (Kawamoto et al., 2012). For this reason, Gao et al.
(2012) suggest that the immiscible melt-solution phases would be
produced by phase separation of the miscible phases during
decompressional exhumation of the deeply subduction continental
crust. In this regard, a S-rich supercritical fluid would be generated
within the UHP slice in the peak UHP metamorphic stage.
Although the action of supercritical fluids in subarc subduction
zones has been suggested by a number of studies, caution is must
be exercised when linking some specific metamorphic products to
the action of supercritical fluids because such products may be
precipitated from hydrous melts during decompressional exhu-
mation of the deeply subducted continental crust. In this regard, it
remains to be resolved which composition of minerals can be used
as the geochemical evidence for the former existence of super-
critical fluids in the subduction zones. Therefore, it is critical to find
natural samples that can be attributed to the product of super-
critical fluids at the subarc depths.
5. Geochemical differentiation during crustal melting in
subduction zones
In general, aqueous solutions are only capable of dissolving and
transporting water-soluble trace elements such as LILE, Pb and U
(Kogiso et al., 1997; Kessel et al., 2005; Hermann et al., 2006a;
Zheng et al., 2011). Nevertheless, hydrous melts have the capacity
to dissolve and transport LREE and Th (Figs. 9 and 10), so that they
have been considered as an important component for continental
arc magmatism (e.g., Kelemen et al., 2014; Zheng et al., 2015; Chen
1233
and Zhao, 2017). In doing so, it is important to know the physico-
chemical conditions under which crustal rocks can meta-
morphically dehydrate and partially melt at the subarc depths in
subduction zones (Fig. 11), which have great bearing on the
geochemical fractionation in major and trace elements between
subducting crustal rocks and their derived liquid phases (Manning,
2004; Zheng and Hermann, 2014). Fluid-immobile compatible el-
ements tend to retain in the subducting crust, whereas fluid-mobile
incompatible elements are mobilized by metamorphic dehydration
and partial melting and then transported to the mantle wedge. The
concentration of silicate components derived from the subducting
crust increases with rising temperature, leading to reduction of the
immiscibility gap between aqueous solutions and hydrous melts in
subduction zone fluids (Zheng et al., 2011).
As soon as crustal rocks are carried into subduction zones, they
are metamorphosed at lithospheric depths to deliver liquid phases
that occur in the form of aqueous solutions at temperatures below
the wet solidus but hydrous felsic melts at temperatures above the
wet solidus. Although Be and Th are relatively insoluble in aqueous
solutions, they are highly soluble in hydrous silicate melts. Thus,
their efficient recycling indicates the partial melting of subducting
sediments (e.g., Morris et al., 1990; Brenan et al., 1995a, 1995b;
Elliott et al., 1997; Johnson and Plank, 1999). As such, these liquid
phases would serve as metasomatic agents to react with the
overlying mantle wedge peridotite, transferring the crustal signa-
tures from the subducting slab into the subarc mantle (Elliott et al.,
1997; Bebout, 2007; Zheng et al., 2016). This gives rise to unique
geochemical characteristics of each sedimentary site that is shared
by its adjacent arc volcanics (Plank, 2005), indicating crustal recy-
cling through subduction. In particular, the addition of sediment-
derived hydrous melts to the mantle wedge has not only a similar
effect in the LILE and Pb enrichment to the addition of aqueous
solutions but also an additional effect in the Th and LREE enrich-
ment (Elliott et al., 1997; Plank and Langmuir, 1998). It appears that
the hydrous melts may play a significant role in transporting the
water-insoluble elements from the subducting crust to the mantle
wedge (Elliott et al., 1997). However, which liquid phase was pro-
duced is primarily dictated by the thermal structure of subduction
zones (Fig. 4). This has bearing on the stability of specific hydrous
and accessory minerals during metamorphic dehydration and
partial melting of crustal rocks at the slab-mantle interface in
subduction channels (Klimm et al., 2008; Hermann and Rubatto,
2009; Skora and Blundy, 2010; Zheng et al., 2011).
Melting temperatures of the assemblage phengite þ omphacite
þ coesite in the presence of aqueous solution are w700
C at 3 GPa
and w800
C at 4.5 GPa (Hermann and Spandler, 2008). Melting
temperatures for K-rich basalts, graywackes, and pelites are very
similar as long as the assemblage phengite þ coesite þ omphacite is
present; partial melting of the three lithologies produces felsic
melts, which become increasingly potassic with pressure as resid-
ual clinopyroxene becomes increasingly more abundant and
jadeitic (Schmidt et al., 2004a). Large percentages of hydrous melts
were produced by the melting experiments of Skora and Blundy
(2010) at 3.0 GPa and 700e1250
C with 7e15 wt.% H2O for radi-
olarian clay (compositionally similar to pelite). The melting begins
at w750
C for the assemblage phengite þ clinopyroxene þ coesite,
yielding a hydrous melt in coexistence with mostly
garnet þ kyanite þ quartz up to around 1250
C. Very high degrees
of melting, up to w54% at 800
C in the presence of 15 wt.% H2O,
were obtained at the relatively low, supersolidus temperatures.
If a significant amount of free water is not available, only minor
melting can occur at the wet solidus, and major melt fractions are
only produced through the dehydration reaction of
phengite þ clinopyroxene þ coesite ¼ garnet þ hydrous
melt  kyanite. This reaction takes place about 150e200
C above
1234 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
the wet solidus (at 3 GPa to 5 GPa), leading to 20e30 wt.% melt in
metasediments but only a few percent melt in metabasalts
(Schmidt and Poli, 2014). Melting temperatures for the assemblages
phengite þ jadeite þ coesite, phengite ¼ calcite þ jadeite þ coesite,
and K-feldspar þ calcite þ jadeite þ coesite are 910e960
C at 3 GPa
and 1030e1100
C at 4.5 GPa (Thomsen and Schmidt, 2008; Tsuno
and Dasgupta, 2011). The large melt percentages are in marked
contrast to dehydration melting of similar lithologies in the ex-
periments of Schmidt et al. (2004a), which yield small melt per-
centages of 5%e10% at similar temperatures.
Schmidt et al. (2004a) experimentally investigated dehydration
melting of greywacke and pelite, the latter being chemically similar
to the radiolarian clay used in the experiments of Skora and Blundy
(2010). At a temperature of 50
C overstepping the sediment soli-
dus, only small percentages of melt (<10%) are produced from the
dehydration melting. Substantial melting up to 50% can be achieved
only at relatively high temperatures (w1000
C) where phengite
disappears. This is consistent with previous studies indicating that
the phengite breakdown is a key to the dehydration melting of
metasediment (Hermann and Spandler, 2008). The melt percent-
ages in the experiments of Skora and Blundy (2010) at phengite-out
(w830e870
C) approximate the phengite-out melt percentages of
Schmidt et al. (2004a) at w1000
C. The difference in melting
temperature is obviously dictated by the water content of starting
materials between the two sets of melting experiments. In this
regard, the water contents of subducting sediment are proportional
to melting degrees at the same PeT conditions. If a large amount of
water could be added to the previously dehydrated crust, it would
result in hydration melting of the subducting crust. Whereas the
dehydration melting only brings small amounts of crust-derived
melts into the mantle wedge for metasomatism, the hydration
melting can produce large amounts of such melts in subduction
channels. This leads to different compositions of metasomatites in
the mantle wedge. Therefore, the partial melting of subducting
crustal rocks at the slab-mantle interface in subduction channels
plays a substantial role in dictating the composition of mantle
sources for mafic arc volcanics.
Although the depletion in LILE, Pb and LREE relative to HREE is
prominent in the subducting IOC (Fig. 7), fluid-mobile trace ele-
ments become relatively enriched in crust-derived melts (Figs. 9
and 10). This is particularly so for low-degree anatexis of the sub-
ducting IOC, which can largely fractionate highly incompatible
elements so long as the anatectic extent is of the same order as the
bulk partition coefficient of trace elements between residue and
melt (McKenzie, 1989; Donnelly et al., 2004; Xu et al., 2017). This
has been quantitatively documented by modeling the budget of
trace elements in enriched MORB from the Mid-Altlantic Ridge
(e.g., Cooper et al., 2004; Donnelly et al., 2004). Such geochemical
differentiation results in elevated LILE/HFSE and LREE/HREE ratios
for the crust-derived melts. Trace element modeling based on the
geochemistry of OIB also suggest that partial melting of the sub-
ducting IOC in the mantle would have very low degrees, typically
below 3% (Stracke et al., 2003; Willbold and Stracke, 2006),
sometimes between 0.5% and 1.5% (Jacques et al., 2013). Therefore,
the anatexis of subducting IOC at very small extent is the key to the
high-degree fractionation of trace elements between the subduct-
ing IOC and its derived melts. As such, the hydrous felsic melts
would transfer the crustal signature to the mantle wedge, where
fertile, enriched metasomatites would be generated to serve as the
sources of both interplate and intraplate basalts. Such mass transfer
processes have been generally accepted for the origin of IAB (e.g.,
Ringwood, 1974; Kay, 1980; Tatsumi, 1986; Hawkesworth et al.,
1993; Pearce et al., 1995; Schiano et al., 2000), and they are also
applicable to the origin of OIB-like continental basalts (Zhang et al.,
2009; Wang et al., 2011; Xu et al., 2012, 2017).
It is known at thermodynamic equilibrium that low-degree
partial melting, if the degree of melting (F) is of the same order
as the residue/melt bulk partition coefficient (D), can fractionate
highly incompatible elements with preservation of crustal isotope
signatures (Donnelly et al., 2004; Xu and Zheng, 2017). The con-
centration of an element in a melt (Cl) is related to the source
abundance (C0) by the batch fractionation model in the case of
high-degree melting: C1 ¼ C0/[F þ D(1  F)]. On the other hand, the
Rayleigh fractionation model is more appropriate for low-degree
melting: C1 ¼ C0  F(D1). Elements with D < 0.01, such as Ba, Th
and La, require very low degrees of partial melting to achieve the
large fractionations. Although many elements are incompatible
during partial melting, their mobilities are different from each
other (e.g., Hofmann, 2003; Pertermann et al., 2004; Stracke and
Bourdon, 2009). As a result, silicate melts produced by congruent
melting of the subducting crust can acquire significant enrichment
in fluid-mobile trace elements with increasing incompatibility. The
lowest degree of crustal anataxis can produce felsic melts with the
highest enrichment in incompatible elements. As such, the
enriched geochemical signatures can be transferred from the sub-
ducting crust via the metasomatic agents into the mantle sources of
both IAB and OIB.
On the other hand, crustal and mantle rocks may undergo
incongruent melting, whereby partial melts preferentially sample
the most fertile and most trace-element enriched portions of
source rocks. It is known from diffusion coefficients for liquid and
solid silicates in the mantle that partially molten rocks generally
come to local equilibrium between partial melt and residual min-
eral (Hofmann and Hart, 1978; Hart and Zindler, 1989; Tommasini
and Davies, 1997; Harris and Ayres, 1998). However, partial melts
may be at disequilibrium with mineral grains in parental rocks if
they are formed and extracted very rapidly (Hart and Zindler, 1989;
Hammouda et al., 1996; Knesel and Davidson, 1996, 1999; Farina
and Stevens, 2011). This inference can be extended to crustal ana-
taxis at the subarc to postarc depths, where fertile portions in the
subducting crust can be preferentially melted and the resulted
melts be rapidly extracted without geochemical equilibration with
refractory portions. It is possible that the incongruent melting of
crustal rocks is a rule rather than an exception during subduction
zone processes, leading to more significant enrichment of highly
incompatible trace elements in felsic melts relative to the sub-
ducting crust than the congruent melting.
In summary, either congruent or incongruent melting can cause
considerable enrichment of fluid-mobile trace elements in partial
melts relative to parental rocks, regardless of their origination from
the subducting crust or the metasomatized mantle. In either case,
the nature of fertile portions in the subducting crust determines the
radiogenic isotope composition of felsic melts. The two types of
partial melting may take place simultaneously in the mantle,
providing the physicochemical mechanism for geochemical frac-
tionation between various elements with contrasting compatibil-
ities. As a consequence, either felsic or mafic melts produced by
partial melting of the crustal or mantle rocks in the mantle can
acquire enhanced enrichment of fluid-mobile trace elements with
increasing incompatibility. Because the ultramafic metasomatites
had acquired significant pre-enrichment with fluid-mobile trace
elements, their partial melting can produce basaltic melts with
further enrichment of these elements in both IAB and OIB. More
alkaline basalts tend to be more enriched in these elements.
Therefore, the crustal signature in both IAB and OIB can be linked to
the nature of metasomatic agents, whose trace element composi-
tion is primarily dictated by that of fertile portions in the sub-
ducting slab.
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254 1235

Figure 12. Partition coefficients for trace elements between rutile and melt from experiments on the tonalite composition (revised after Foley et al., 2000).

6. The behavior of HFSE in subduction zones
A prominent difference in trace element composition between
IAB and OIB is the abundance of Nb and Ta in the primitive mantle-
normalized diagram (Fig. 2). While IAB are generally depleted in Nb
and Ta, OIB are enriched, at least not depleted, in Nb and Ta. The
depletion of Nb and Ta in IAB is generally attributed to their in-
heritance from metasomatic agents (e.g., Ringwood, 1974; Kay,
1980; Tatsumi, 1986; Hawkesworth et al., 1993; Pearce et al.,
1995), which are assumed to be produced by metamorphic dehy-
dration and partial melting of the subducting crust in the stability
field of rutile (Green, 1981; Ryerson and Watson, 1987; Brenan
et al., 1994; Foley et al., 2000; Zack et al., 2002; Schmidt et al.,
2004b; Gaetani et al., 2008; Xiong et al., 2011; Chen et al., 2018).
This issue has been central to the difference in trace element
composition between IAB and OIB, which merits discussing in
detail.
Rutile is a major repository for HFSE (mainly Nb, Ta and Ti), with
a preference to retain pentavalent elements. Experimental studies
do demonstrate that rutile is a key host mineral for Nb and Ta
(Fig. 12). This paradigm has been used to explain the depletion of
Nb and Ta in mafic arc volcanics above oceanic subduction zones
(e.g., Morris and Hart, 1983; Foley and Wheller, 1990; McDonough,
1991; Brenan et al., 1994; Rudnick et al., 2000; Foley et al., 2000;
Gómez-Tuena et al., 2011). As such, aqueous solutions produced
by metamorphic dehydration in the rutile stability field are
depleted in Nb and Ta, whereas the abundances of Nb and Ta are
elevated in hydrous melts or supercritical fluids if rutile breaks
down. Therefore, the stability of rutile during dehydration melting
of the subducting crustal rocks (mainly eclogite at the subarc to
postarc depths) is a key to the composition of HFSE in metasomatic
agents.
The presence of crustal signatures in the magma sources of OIB
is indicated not only by enrichment in LILE, Pb and LREE but also by
enrichment in radiogenic Sr-Nd-Pb isotope compositions (e.g.,
Chase, 1981; Eiler et al., 1996; Hauri, 1996; Blichert-Toft et al., 1999).
In particular, the magma source of some OIB contains enriched
signatures such as high HFSE abundances, which are generally

Figure 13. Experimentally determined phase relations for the rutile stability during eclogite melting (revised after Spandler et al., 2008). The numbers below the dots denote the
percentage melting of the experiments. Mineral abbreviations: Coe, coesite; Qtz, quartz; Ksp, K-feldspar; Grt, garnet; Cpx, clinopyroxene.
1236 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
ascribed to involvement of the subducted oceanic crust (e.g.,
Hofmann and White, 1982; Hofmann et al., 1986; Weaver et al.,
1986; McKenzie, 1989; Prytulak and Elliott, 2007; Jackson et al.,
2008). Nevertheless, the geochemical behavior of HFSE changes
dramatically when residual rutile in the UHP eclogite is eliminated
in the subducting crust because these elements exhibit highly
incompatible behavior in garnet and clinopyroxene. Experimental
studies indicate that rutile may be dissolved into liquid phases
during partial melting of the subducting oceanic crust at greater
mantle depths (Green and Pearson, 1986; Ryerson and Watson,
1987; Iizuka and Nakamura, 1995; Klemme et al., 2002; Longhi,
2002; Bromiley and Redfern, 2008; Gaetani et al., 2008; Spandler
et al., 2008; Skora and Blundy, 2010; Chen et al., 2018). In other
words, when eclogite facies UHP metamorphically dehydrated
oceanic crust is subducted to the postarc depths, it undergoes
further dehydration melting with the rutile breakdown (Fig. 13). For
this reason, the dissolution of rutile into metasomatic agents is
advocated as the physicochemical mechanism for enrichment of
Nb, Ta and Ti in intraplate basalts (Ringwood, 1990; Zheng, 2012).
As such, the HFSE are transferred together with both LILE and LREE
by the liquid phases from the subducting crust into the mantle.
Experimental studies indicate that the rutile stability during
crustal melting is a function of not only temperature and pressure
but also the concentrations of SiO2, H2O and CO2 in subduction zone
fluids (Green and Pearson, 1986; Ryerson and Watson, 1987; Iizuka
and Nakamura, 1995; Klemme et al., 2002; Longhi, 2002;
Pertermann and Hirschmann, 2003a, 2003b; Hayden and Watson,
2007; Bromiley and Redfern, 2008; Gaetani et al., 2008; Spandler
et al., 2008; Skora and Blundy, 2010; Chen et al., 2018). Early ex-
periments suggest that the solubility of TiO2 in garnet increases
with elevating pressures and temperatures, which would
contribute towards the elimination of residual rutile. Iizuka and
Nakamura (1995) experimentally investigated the dehydration re-
action of natural hydrous minerals in a subducting oceanic crust
and thereby resulted metasomatism in the mantle wedge at pres-
sures of 3e8 GPa and a temperature of 850
C. Their starting ma-
terials were blueschist facies metabasite from New Caledonia and
olivine separate of spinel lherzolite from San Carlos, respectively,
representing the subducting oceanic crust and the overlying wedge
mantle. Their results indicate that the HP metabasite was changed
to rutile-bearing UHP eclogite at 3 and 6 GPa, respectively, corre-
sponding to 100 and 200 km in depth. The observed phases in the
mantle side are the primary olivine and the metasomatic enstatite
generated by reaction of the olivine with silica-rich fluids from the
crustal side. At 8 GPa, the crustal rock was further transformed to
rutile-free UHP eclogite, and the phases in the mantle side are Ti-
clinohumite in addition to the olivine and enstatite. The Ti-
clinohumite was generated by reaction of the olivine with a Ti-
bearing fluid which was supplied from the crustal side. Because
the hydrous Ti-phase is a host reservoir of HFSE, the formation of
Ti-clinohumite at 8 GPa, corresponding to 250 km in depth, sug-
gests that the fluid can be a carrier of HFSE from the subducting
crust to the mantle.
The experiments of Ryerson and Watson (1987) indicate that the
TiO2 solubility in silicate melts varies significantly as a function of
composition, especially silica content. If the melts have SiO2 con-
tents of 60e70 wt.%, the TiO2 solubility would be enhanced to the
extent that rutile would no longer occur in the eclogite residuum at
950e1100
C. Further experiments indicate that the TiO2 contents
of low-degree melts increase dramatically with pressures at
3.0e5.0 GPa and temperatures of >1250
C (Spandler et al., 2008).
Partitioning experiments of Bromiley and Redfern (2008) for HFSE
between rutile, its high-pressure polymorph TiO2(II) and silicate
melt suggest that characteristic depletion of Nb and Ta in felsic
melts due to the presence of rutile in solid residues is primarily
dictated by the pressure of crustal melting in the absence of free
water. With increasing pressure, changes in melt structure lead to
significant decreases in the partition coefficients of HFSE between
TiO2 (II) and melt. If the experimental results are applicable to the
OIB genesis, the enrichment or non-depletion of Nb, Ta and Ti in OIB
implies that partial melting of the subducting oceanic crust would
take place at depths of >300 km.
Pertermann and Hirschmann (2003a, 2003b) made melting
experiments at 2e3 GPa on MORB-like eclogite under nominally
anhydrous conditions. The results indicate that rutile was present
at temperatures above the eclogite solidus at 1315
C, but started to
disappear at 1325e1335
C and completely disappeared at
1335e1350
C. Furthermore, rutile melts out after about >5%e10%
of eclogite melting. Thus, rutile starts to dissolve in silicate melts at
temperatures about 10e20
C higher than those for the eclogite
solidus. A key feature of the silicate melts, which were quenched as
the experimental glasses, is their enrichment in TiO2, particularly
near the solidus. At 3 GPa, the TiO2 concentrations are similar:
w5.76.7 wt.% at 1315e1335
C, conditions corresponding to the
rutile saturation in the silicate melts. With rising temperature and
increasing melt fraction, the TiO2 concentrations diminish to
2 wt.%, the TiO2 content of the starting material. At 2 GPa, partial
melt has 6.7 wt.% TiO2 near the solidus, which diminishes to
2.4 wt.% at 1375
C.
Gaetani et al. (2008) made rutile saturation calculations for
partial melting of MORB-like eclogite at different conditions. The
results indicate that partial melts may contain 2 wt.% TiO2 at
4.0 GPa and 1440
C. At 1% partial melting, the concentration of
TiO2 in the melt is w5.4 wt.%, and w0.45 wt.% rutile is present in
the residual eclogite. With decreasing pressure and increasing
extent of partial melting, the concentration of TiO2 in the melt
decreases to a minimum of w4.45 wt.% at w3.4 GPa and w17%
partial melting, and then increases slightly to w4.5 wt.% at
w3.3 GPa and w22% partial melting. Exhaustion of rutile at w22%
partial melting is an upper limit, as near-Rayleigh melting can
deplete TiO2 in the eclogite much more rapidly. These results
suggest that eclogite melting can exhaust rutile at temperatures
below the peridotite solidus. Therefore, the dissolution of rutile into
partial melts from deeply subducting oceanic crust has the capacity
to produce a detectible signal of HFSE in OIB.
Furthermore, water addition significantly enhances the rutile
solubility in silicate melts. According to the experimental studies of
Skora and Blundy (2010) on hydrous melting of radiolarian clay at
3.0 GPa, 700e1250
C and 7e15 wt.% H2O, rutile is present at
T < 1000
C. The amount of rutile in the metasediment steadily
decreases with increasing temperature (Fig. 14), indicating its
increased solubility in the resulted melts until its exhaustion in the
metasediment above 1000
C. On the other hand, the content of
TiO2 in the melts also increases steadily from 750
C to 1100
C,
consistent with enhanced rutile solubilities in hydrous melts at
higher temperatures (e.g., Ryerson and Watson, 1987; Schmidt
et al., 2004b; Xiong et al., 2011). Given that rutile is not actually
present in the melts at 1100
C, the increase of TiO2 in the melts
from 1000
C to 1100
C suggests that rutile is exhausted in the
metasediment at temperatures closer to 1100
C than 1000
C. As
such, more and more rutile is dissolved into the hydrous melts
during the partial melting of subducting crustal rocks at the subarc
to postarc depths. Therefore, the solubility of rutile in hydrous
melts is the key to the HFSE concentrations of hydrous melts from
the subducting crust. More rutile is dissolved into the hydrous
melts, more HFSE are delivered to the mantle sources of basalts
above oceanic subduction zones. If these experimental data are
applicable to natural eclogites beneath the mantle wedge, the
enrichment of Nb and Ta in intraplate basalts indicates the signif-
icant rutile dissolution at the postarc depths.
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Figure 14. Experimentally determined solubility of TiO2 in hydrous melts during
partial melting of radiolarian clay at 3 GPa (revised after Skora and Blundy, 2010).
7. Subduction zone metasomatism
It is known that there are a series of compositional differences
between the mantle and the crust (e.g., Palme and O’Neill, 2014;
Rudnick and Gao, 2014; White and Klein, 2014; Huang and
Zheng, 2017). The mantle has the ultramafic composition in lith-
ochemistry, and its lithology is dominated by peridotite with minor
amounts of pyroxenite and hornblendite. Geochemically, these ul-
tramafic rocks may be depleted or enriched in fluid-mobile
incompatible trace elements and their pertinent radiogenic iso-
topes. On the other hand, the oceanic crust is primarily of mafic
composition and its lithology is dominated by basalt-gabbro asso-
ciations, whereas the continental crust is mainly of felsic compo-
sition and its lithology is dominated by granite-amphibolite-
granulite associations. Sedimentary cover is thin on oceanic crust
but thick on continental crust. Geochemically, the basalt-gabbro
associations in the oceanic crust are derived from decompres-
sional melting of the asthenospheric mantle at spreading ridges
and characterized by depletions in melt-mobile incompatible trace
elements and their pertinent radiogenic isotopes (White and Klein,
2014). In contrast, the granite-amphibolite associations and their
cover sediment in the continental crust are the product of crustal
reworking and generally characterized by enrichments in melt-
mobile incompatible trace elements and their pertinent radio-
genic isotopes (Rudnick and Gao, 2014). The differences between
crustal and mantle compositions are a basic driving force for the
geochemical exchange at elevated pressure-temperature condi-
tions in subduction zones (Bebout, 2007, 2014; Hermann and
Rubatto, 2014; Zheng and Chen, 2016; Zheng and Zhao, 2017).
In subduction zones, crustal signatures are directly transferred
from the descending slab into the mantle wedge at different depths,
leading to crustal metasomatism of the mantle (Zheng, 2012). This
generates ultramafic metasomatites such as serpentinized and
chloritized peridotites, and olivine-poor pyroxenites and horn-
blendites (e.g., Tatsumi, 1986, 1989; Ulmer and Trommsdorff, 1995;
Kushiro, 2001; Kogiso et al., 2004; Kogiso and Hirschmann, 2006;
Lambart et al., 2013; Green et al., 2014; Zheng et al., 2016). These
metasomatites are more susceptible to partial melting than normal
peridotite in the asthenospheric mantle (e.g., Hirschmann and
Stolper, 1996; Kushiro, 2001; Pertermann and Hirschmann,
2003a,b; Kogiso et al., 2004; Kogiso and Hirschmann, 2006;
Lambart et al., 2013, 2016). This may give rise to mafic melts that
react with the overlying peridotite, resulting in fertile, enriched
mantle domains in the ordinary mantle (Kelemen, 1995; Yaxley and
1237
Green, 1998; Sobolev et al., 2005). In this regard, the composition of
metasomatic products can be linked to the composition of meta-
somatic agents in subduction zones. In general, the metasomatism
by crust-derived felsic melts generates low MgO metasomatites,
whereas the metasomatism by mantle-derived mafic melts brings
about high MgO metasomatites. In either case, these metasomatites
provide our actual samples of the rocks that record the subduction
zone metasomatism if they are available for various observations.
Orogenic peridotites can be used as prime samples of the mantle
in the study of crustal metasomatism at subduction zones (e.g.,
Rampone and Morten, 2001; Malaspina et al., 2006a, 2009;
Scambelluri et al., 2006, 2010; Bodinier and Godard, 2014; Chen
et al., 2015, 2017; Li et al., 2016, 2018a). They exhibit a large vari-
ation in lithology from lherzolites (plagioclase lherzolite, spinel
lherzolite and garnet lherzolite) to harzburgite. Also occur are py-
roxenite and dunite in many cases (e.g., Garrido and Bodinier, 1999;
Downes, 2007; Bodinier et al., 2008; Bodinier and Godard, 2014).
These lithological variations are ascribed not only to metasomatic
reaction with felsic melts but also to significant extraction of mafic
melts. On the other hand, there are significant differences in the
trace element composition of orogenic peridotites, varying from
the relative depletion to the relative enrichment of fluid-mobile
elements such as LILE, Pb and LREE in the primitive-normalized
diagram. Furthermore, their radiogenic isotope compositions vary
from depleted to enriched with reference to the primitive mantle.
The geochemical variations in these orogenic ultramafics can be
used to indicate the crustal recycling in subduction zones (e.g.,
Zanetti et al., 1999; Rampone and Morten, 2001; Malaspina et al.,
2006a, 2009; Scambelluri et al., 2006, 2010; Vrijmoed et al., 2013;
Bodinier and Godard, 2014; Chen et al., 2015, 2017).
A number of UHP garnet peridotites occur in collisional orogens,
which are categorized into M-type and C-type, respectively (e.g.,
Brueckner and Medaris, 2000; Nimis and Morten, 2000; Zhang
et al., 2000). The M-type peridotites were primarily located in the
lowermost part of the mantle wedge above the continental sub-
duction zones, and they were tectonically eroded by the subduct-
ing/exhuming continental crust. Thus, there are metasomatic
reactions of the mantle wedge peridotite with subducting crust-
derived fluids in subduction channels during the subduction/
exhumation of the continental crust. In contrast, the C-type peri-
dotites were originally crystallized as ultramafic cumulates from
mafic magmas and emplaced as complexes into the continental
crust before subduction. They were subducted together with the
host continental crust to the subarc depths for UHP metamorphism.
Petrologically, the C-type peridotites can be distinguished from the
Figure 15. The trace element composition of garnet peridotites from Zhimafang in the
Sulu orogen of east-central China in the primitive mantle-normalized diagram (revised
after Zhang et al., 2011). Thick green line denotes the depleted MORB mantle.
1238 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

M-type peridotites by their lower Mg numbers and Ni contents in 2003, 2014; Hermann et al., 2006b; Vrijmoed et al., 2013; Li et al.,
olivine and pyroxene but higher contents of HREE, Al2O3 and CaO in 2016; Chen and Zheng, 2017; Chen et al., 2017). Zircon is not a
garnet. Although the two types of orogenic peridotites underwent common accessory mineral in the primary peridotite because of its
UHP metamorphism at the subarc depths, both show petrological low Zr content and low Si activity. However, zircons of different U-
and geochemical records of crustal metasomatism in continental Pb ages have been found in metasomatic pyroxenite veins inside
subduction zones (Malaspina et al., 2006a, 2006b, 2009; Chen et al., peridotite xenoliths entrained by Cenozoic continental basalts in
2015, 2017; Li et al., 2016, 2018a, 2018b). In particular, the refractory North China (Liu et al., 2010) and in chromitites hosted in the
property of peridotitic minerals makes petrological and geochem- mantle of supra-subduction-zone ophiolites (Yamamoto et al.,
ical inheritance possible. Nevertheless, it is critical to distinguish 2013; Robinson et al., 2015), indicating incorporation of terrige-
the supra-subduction-zone M-type peridotites from the sub- nous sediments into the mantle by subduction. Furthermore,
subduction-zone C-type peridotites in view of the difference be- crustal recycling is indicated by the presence of old, terrigenous
tween their tectonic implications. zircon grains in oceanic mantle-derived basaltic rocks (e.g.,
The M-type orogenic peridotites in continental subduction Hargrove et al., 2006; Kröner et al., 2007; Ali et al., 2009; Grimes
zones are an important lithology recording the geochemical et al., 2009; Lissenberg et al., 2009; Portner et al., 2011; Torsvik
transfer from the subducted continental crust into the overlying et al., 2013; Tapster et al., 2014; Buys et al., 2014; Cheng et al.,
subcontinental lithospheric mantle (SCLM) in subduction channels. 2016). In this regard, understanding the origin of zircons in
Variable extents of fluid metasomatism are evident in orogenic orogenic peridotites has great bearing on the mechanism of crustal
peridotites from the Dabie-Sulu orogenic belt in east-central China recycling at subduction zones.
(e.g., Malaspina et al., 2006a, 2006b, 2009; Zhang et al., 2011; Chen Zircon is also common in refertilized peridotites, such as the
et al., 2015; Li et al., 2016, 2018a, 2018b). This is particularly so at garnet peridotite at Zhimafang in the Sulu orogen (Zhang et al.,
the contacts between contrasting lithological units, in which fluid- 2005; Zheng et al., 2006), with tens to hundreds of zircon grains
peridotite reactions represent an analog to the crust-mantle available for SIMS U-Pb dating. According to the observations of
interaction at the subarc depths. As a consequence, the M-type Zhang et al. (2005), some zircon grains are visible on thin sections;
peridotites provide a direct record of crustal metasomatism at the the majority of zircon-bearing peridotites are characterized by
continental subduction zone in the Triassic (Zheng, 2012). The abundant hydrous phases (phlogopite  Ti-clinohumite). In addi-
presence of hydrous minerals, such as amphibole and phlogopite, is tion, the zircon contains crystal inclusions of olivine (Fo91e92),
also a mineralogical evidence for the crustal metasomatism of M- enstatite, apatite, Ti-clinohumite, phlogopite and diopside, whose
type peridotites. A case in point is the garnet peridotite at Zhima-
fang close to the Chinese Continental Deep Drilling (CCSD) main
hole, within the mid-T/UHP eclogite facies zone in the Sulu orogen.
The peridotite shows significant enrichment in LILE and LREE
relative to HFSE and HREE with negative Nb, Zr and Ti anomalies
(Fig. 15), indicating involvement of crustal components in the M-
type peridotite.
Petrological studies indicate that the Zhimafang peridotite
contains seven generations of mineral assemblage (Yang and Jahn,
2000; Zhang et al., 2005, 2007; Malaspina et al., 2009; Ye et al.,
2009). Typically, olivines develop abundant exsolution lamellae of
Fe-Ti oxides; porphyroblastic orthopyroxenes are common with
development of clinopyroxene and chromite (or Cr-spinel) exso-
lution lamellae; reconstruction of its metamorphic PeT path in-
dicates a very low geothermal gradient of <5
C/km, corresponding
to an ultracold subduction zone (Fig. 4); several stages of fluid
metasomatism are identifiable. Zhang et al. (2005) considered that
the peridotite was originated from the mantle wedge with its pri-
mary crystallization at 6.0e7.0 GPa and 1100e1200
C, and was
tectonically entrained by the deeply subducted continental crust to
experience UHP metamorphism at 4.2e6.0 GPa and 800e900
C.
Malaspina et al. (2009) suggested that the peridotite experienced
an early stage of metasomatism by an alkaline melt at w1000
C
and >5.0 GPa, and a late stage one by a transitional fluid rich in
fluid-mobile elements during the Triassic UHP metamorphism.
Zhang et al. (2007) suggested that the peridotite underwent three
episodes of metasomatism: (1) crystallization of phlogopite in the
mantle by infiltration of K-rich fluids; (2) formation of magnesite
and magnesite  phlogopite  Ti-clinohumite veins by infiltration
of carbonatitic melts with a hydrous silicate component; and (3)
replacement of magnesite, garnet and diopside by dolomite and
secondary hydrous phases by a crust-derived, CO2-bearing,
aqueous solution. Figure 16. The trace element composition of peak and retrograde minerals in garnet
In addition to the fertile, enriched compositions of orogenic peridotite at Duria in Central Alps of Europe in the primitive mantle-normalized dia-
peridotites, the occurrence of zircon in them is a piece of miner- grams (revised after Hermann et al., 2006b). (a) Comparison between peak meta-
morphic and retrograde clinopyroxene and amphibole. (b) Peak metamorphic minerals
alogical evidence for metasomatism by crust-derived fluids during (open diamond ¼ garnet; red circle ¼ amphibole; green square ¼ clinopyroxene,
continental collision (e.g., Gebauer, 1996; Bea et al., 2001; Lopez cross ¼ orthopyroxene) and calculated bulk rock composition (blue line) compared to
Sanchez-Vizcaino et al., 2001; Katayama et al., 2003; Zheng et al., the depleted MORB mantle (green line).
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
parageneses and compositions are consistent with derivation from
the peridotite rather than contamination from the other source.
Phlogopite- and Ti-clinohumite-rich peridotites contain more
zircon grains than the other peridotites. The presence of abundant
apatite inclusions, and a few aqueous fluid inclusions in the zircon
is consistent with the crustal metasomatism. Based on the major
and trace element compositions of zircon-bearing peridotites,
Zhang et al. (2005) suggested that the metasomatic fluids were
enriched not only in LILE (such as Rb, Ba and K) and LREE but also in
Zr. SIMS U-Pb dating of the zircon grains yielded consistent ages of
221  3 Ma to 224  8 Ma (Zheng et al., 2003, 2006; Zhang et al.,
2005). Most of the zircon grains have Th/U ratios of 0.1e1.03
(Zhang et al., 2005; Zheng et al., 2006), suggesting their growth
primarily through peritectic reaction. Because these U-Pb ages are
slightly younger than the known ages of 225e240 Ma for the UHP
metamorphism (Zheng et al., 2009), the crustal metasomatism
occurred at the slab-mantle interface during the initial exhumation
(Zheng et al., 2011). Therefore, the orogenic peridotite at Zhimafang
was offscraped from the overlying SCLM of the North China Block
by the subducting/exhuming slab of the South China Block (Zheng,
2012). This records the crust-mantle interaction during the conti-
nental collision in the Triassic.
The occurrence of zircon in garnet peridotites was also found at
Duria in Central Alps of Europe. Gebauer (1996) obtained SIMS
zircon U-Pb ages of w35 Ma for garnet peridotite, garnet pyroxenite
and eclogite at Arami. Hermann et al. (2006b) acquired two groups
of SIMS zircon U-Pb ages at 34.2  0.2 Ma and 32.9  0.3 Ma,
respectively, for two types of zircon domain in garnet peridotite at
Duria in the Adula nape. The authors interpreted the younger age as
indicating zircon growth during exhumation of the garnet perido-
tite. This suggests crustal metasomatism by anatectic melts derived
from partial melting of the deeply subducted crustal rocks during
the exhumation. The garnet peridotite at Duria exhibits a por-
phyroblastic texture and is not associated with eclogites or meta-
rodingites. As documented by Hermann et al. (2006b), mineral
assemblages in the garnet peridotite contain both peak and retro-
grade amphiboles that are enriched in Rb, Ba and Pb (Fig. 16a). In
addition, a LILE-rich phlogopite occurs as an inclusion in garnet.
The calculated whole-rock patterns of trace element distribution
from peak metamorphic minerals exhibit very similar REE, Ti and Zr
abundances to the depleted MORB mantle but much higher LILE
abundances (Fig. 16b). The presence of these lithophile elements
suggests that the garnet peridotite experienced the crustal meta-
somatism in the subduction channel. This is consistent with
mineralogical observations that show abundant, fine-grained,
newly formed clinopyroxene, orthopyroxene and amphibole in
the garnet peridotite, with the occasional occurrence of textures
related to the replacement of olivine (Hermann et al., 2006b). These
phases are associated with spinel and ilmenite, indicating that the
metasomatism occurred during exhumation due to the influx of an
anatectic melt rich in SieCaeAleNaeK. The newly formed amphi-
bole contains elevated levels of water-soluble elements such as Rb,
Ba and Pb with respect to LREE. The texture and mineral compo-
sition suggest that the peridotite also underwent the meta-
somatism due to infiltration of a metamorphic fluid that is enriched
in typical crustal elements such as Ba, Rb, Pb and U.
However, caution must be exercised when interpreting the core
U-Pb ages of zircon in orogenic peridotites as the timing of crust-
mantle differentiation. A case in point is SIMS zircon U-Pb dating
of the garnet peridotite from the Kokchetav UHP terrane in
Kazakhstan. Katayama et al. (2003) obtained concordant U-Pb ages
of 494e554 Ma (a weighted mean of 528 Ma) for metamorphic rims
of flat HREE patterns, consistent with the UHP metamorphic ages of
530e540 Ma (Claoue-Long et al., 1991; Hermann et al., 2001;
Katayama et al., 2001). In addition, Katayama et al. (2003)
1239
estimated the discordia upper-intercept U-Pb ages of about
1.1e2.2 Ga for residual cores with steep HREE patterns. While it is
correct for the authors to interpret the rim U-Pb ages for crustal
metasomatism of the overlying mantle wedge during the conti-
nental subduction-zone processes, it is problematic to interpret the
core U-Pb ages as dating the Precambrian growth of magmatic
zircon inside the mantle wedge peridotite. This is because the ul-
tramafic mantle lithology is principally undersaturated with Zr
(Palme and O’Neill, 2014), no zircon is able to crystallize from it. An
alternative explanation is that the zircon cores were physically
extracted by the metasomatic agent from the subducting crustal
rocks at the subarc depths. In other words, the crustal zircon of
different sizes was physically transported by the metasomatic
agent melt into the mantle wedge peridotite during the slab-
mantle interaction in the continental subduction channel. On the
other hand, there would be the chemical dissolution of zircon
grains at different degrees in the metasomatic agent (Zheng and
Hermann, 2014). Because the metasomatic agent was produced at
temperatures above the wet solidus of crustal rocks, crustal ana-
taxis was significant at the subarc depths. This led to peritectic
growth of zircon in the metasomatic agent during its infiltration
into the mantle wedge peridotite, with metamorphic recrystalli-
zation of the relict cores at the same time. Thus, the relict zircon
grains are those large ones that survived the dissolution in the
metasomatic agent.
Amphibole is a secondary mineral in mantle peridotites and it is
generally produced by metasomatic reaction of pyroxene with
fluids at mantle conditions. Its geochemical features can be used to
fingerprint the signatures of metasomatic agents. Coltorti et al.
(2007) made a geochemical study of metasomatic amphiboles
mainly in mantle xenoliths from a number of interplate and
intraplate basalts. The results show depletion of Nb and Ta in
interplate amphiboles (Fig. 17) with mainly suprachondritic Ti/Nb
and Zr/Nb ratios (Fig. 18), but enrichment of Nb and Ta in intraplate
amphiboles with exclusively subchondritic Ti/Nb and Zr/Nb ratios.
The authors ascribed such complementary features to meta-
somatism by Nb- and Ta-depleted fluids from the subducting
oceanic crust, leaving a rutile-bearing eclogite residuum. In this
regard, rutile-bearing eclogite was produced by metamorphic
dehydration at the subarc depths, releasing Nb- and Ta-depleted
aqueous solutions that metasomatized the mantle wedge perido-
tite to form the interplate amphiboles. With continuous subduction
of the dehydrated oceanic crust to the postarc depths, the Nb and Ta
may be transferred by supercritical fluids (Hayden and Manning,
2011) from the rutile-bearing eclogite into the intraplate amphi-
boles. Nevertheless, the Nb and Ta would be transported in the form
of dissolved complexes rather than rutile grains (Antignano and
Manning, 2008; Manning et al., 2008), otherwise the amphiboles
cannot form in the absence of water. In this context, the residual
eclogite would have undergone dehydration melting at the postarc
depths to allow for the dissolution of rutile into the metasomatic
agent at elevated temperatures (Ringwood, 1990; Zheng, 2012). The
incorporation of such fluids into the depleted MORB mantle can
generate the ultramafic metasomatites that are enriched, at least
not depleted, in Nb and Ta. Partial melting of the metasomatites
ultimately contribute to the origin of intraplate basalts, character-
ized by high Nb and Ta abundances.
The complementary relationship in geochemical composition
between the interplate and intraplate amphiboles can be extended
to metasomatic pyroxenes in the asthenospheric mantle, providing
a petrogenetic link between interplate calc-alkaline and intraplate
alkaline magmas. This is in agreement with the temporal sequence
of subduction, calc-alkaline volcanism and alkaline magmatism in
the circum-Pacific regions and in many subduction zones world-
wide (e.g., Tatsumi et al., 2000; Gómez-Tuena et al., 2011; Kita et al.,
1240 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

Figure 17. Trace element distribution patterns of metasomatic amphiboles in the primitive mantle-normalized diagrams (revised after Coltorti et al., 2007). (a) Interplate am-
phiboles from Val d’Ultimo, and (b) intraplate amphiboles from Antarctica.

2012; Jacques et al., 2013; Espanon et al., 2014; Brenna et al., 2015;
Mullen and Weis, 2015). In this context, fluid-immobile trace ele-
ments such as Nb and Ta are depleted in aqueous solutions derived
from metamorphic dehydration of the subducted oceanic crust at
the subarc depths. On the other hand, these elements are relatively
enriched, at least not depleted, in hydrous felsic melts (and even
supercritical fluids) due to the dissolution of rutile in them during
the crustal anatexis at the postarc depths. As soon as the depleted
MORB mantle is metasomatized by such liquid phases, it becomes
rich in pyroxene but poor in olivine due to the melt-peridotite re-
action at the slab-mantle interface in oceanic subduction channels.
This generates ultramafic metasomatites that exhibit enrichment
not only in Nb and Ta but also in LILE and LREE. Partial melting of
such metasomatites gives rise to basaltic melts with OIB-like
geochemical composition. This model of melt-peridotite reaction
at the slab-mantle interface in oceanic subduction channel has
been applied to Cenozoic continental basalts in eastern China
(Zhang et al., 2009; Wang et al., 2011; Xu et al., 2012, 2017) and
Early Cretaceous continental basalts in central China (Dai et al.,
2017). It is also applicable to mid-Cretaceous continental basalts
in New Zealand (McCoy-West et al., 2010) and Permian continental
flood basalts (CFB) in southwestern China (Hou et al., 2013).

Figure 18. Diagrams of Zr/Nb vs. Ti/Nb ratios for interplate and intraplate amphiboles (revised after Coltorti et al., 2007).
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Therefore, the property of metasomatic agents at the slab-mantle
interface in subduction channels is the key to the composition of
metasomatites and eventually to that of basaltic rocks.
Geochemical studies of oceanic basalts indicate the presence of
terrigenous components in different proportions (Zindler and Hart,
1986; Hofmann, 1997; Stracke, 2012; Huang and Zheng, 2017).
However, only a few percent of liquid phases from crustal rocks are
required to account for the enrichment of fluid-mobile trace ele-
ments and their pertinent radiogenic isotopes in mantle sources
(McKenzie, 1989; Stracke et al., 2003; Donnelly et al., 2004; Xu and
Zheng, 2017; Xu et al., 2017). This is because the abundances of
fluid-mobile trace elements in the liquid phases are generally much
higher than those in the depleted MORB mantle. Then very small
amounts of the liquid phases can significantly modify the trace
element compositions of the mantle wedge. While the crustal
components predominate the budget of fluid-mobile trace ele-
ments, the mantle peridotite predominates the budget of major
elements (Xu and Zheng, 2017; Xu et al., 2017). This corollary is also
applicable to the origin of enriched Nd-Sr-Pb isotope signatures in
the mantle sources of mafic igeous rocks.
8. Implications for the enrichment of crustal isotope
signatures in oceanic basalts
A fundamental observation in mantle geochemistry is that OIB
and normal MORB show systematic differences in their radiogenic
Sr-Nd-Hf-Pb isotope compositions (Zindler and Hart, 1986;
Hofmann, 1988, 2003). In general, OIB range to higher Sr and Pb
isotope ratios but lower Nd and Hf isotope ratios than normal
MORB (Fig. 19), and are isotopically more diverse. These differences
were recognized about a half of century ago (Gast et al., 1964; Hart
et al., 1973; Schilling, 1973; Sun et al., 1975). The presence of
enriched isotope signatures in OIB is prominent, leading to their
classification into three isotope endmembers (White, 1985; Zindler
and Hart, 1986): EM1, EM2 and HIMU (high m, m ¼ 238U/204Pb). In
doing so, normal MORB were assumed to represent the depleted
isotope endmember (depleted MORB mantle). As such, recycling of
IOC with different types of sediment was suggested as the most
plausible mechanism for the generation of isotope and trace
element systematics in oceanic basalts (Chase, 1981; Hofmann and
White, 1982; Ringwood, 1982; Zindler and Hart, 1986; Weaver,
1991; Chauvel et al., 1992; Eiler et al., 1996; Hofmann, 1997;
Stracke et al., 2005; Stracke, 2012). So is the recycling of upper
and lower continental crust (Willbold and Stracke, 2010; Huang
and Zheng, 2017). In these studies, it is generally assumed that
the upper continental crust of ancient age is high in radiogenic Sr
isotope ratios but low in radiogenic Nd isotope ratios, which are
traditionally referred to as enriched radiogenic isotope composi-
tions. By contrast, the depletion in radiogenic isotope compositions
denotes the low Sr isotope ratios but high Nd isotope ratios, which
are typical of the depleted MORB mantle and its derived juvenile
crust.
Furthermore, it was found that each of these isotope end-
members shows certain common trace element characteristics
that distinguish them from one another (Weaver, 1991; Condie,
2005; Pearce, 2008). In addition, it was hypothesized that these
enriched mantle domains have been isolated from each other for a
long time (over hundreds of million years) in the depleted MORB
mantle, resulting in long-lived heterogeneities in the mantle
(Zindler and Hart, 1986; Hofmann, 1989). Although the enriched
isotope signatures in OIB are generally linked to the recycling of
oceanic crust, it is problematic because common IOC generally
show increasing depletion of trace elements with increasing in-
compatibility (Hofmann, 1988; Salters and Stracke, 2004;
Workman and Hart, 2005), opposite to OIB (Niu et al., 2002; Niu
1241
and O’Hara, 2003). In addition, typical OIB are alkaline and often
undersaturated with silica, whereas partial melts of IOC are
saturated with silica (Green et al., 1967; Rapp et al., 1991; Rapp
and Watson, 1995; Klemme et al., 2002), making the problem
with the subducted IOC as the direct source of OIB (Niu and
O’Hara, 2003).
For the trace elements of lithophile isotope systems (e.g., Rb-Sr,
Sm-Nd and U-Th-Pb), both U and Pb are water soluble and thus
susceptible to liberation from the subducting crust into aqueous
solutions during metamorphic dehydration at the forearc to subarc
depths, where uranogenic Pb isotope signatures are transferred
into the mantle wedge. On the other hand, Rb, Sr, Sm, Nd and Th are
melt mobile and thus susceptible to transport during partial
melting at the subarc to postarc depths. The hydrous melts so
produced generally have high Sr and Nd abundances, transferring
radiogenic Sr and Nd isotope signatures as well as thorogenic Pb
isotope signatures into the mantle wedge. Therefore, the radiogenic
Sr-Nd-Pb isotope compositions are largely controlled by the trace
element compositions of both parental and daughter isotopes in
the crustal components rather than in the mantle wedge with
respect to their contributions to the magma sources of both IAB and
OIB.
Traditionally, the oceanic basalts of positive εNd(t) values were
attributed to their direct derivation from partial melting of the
depleted MORB mantle, whereas those of negative εNd(t) values
were linked to long-lived heterogeneities in the mantle (e.g.,
Zindler and Hart, 1986; Hofmann, 1989). However, the juvenile
crust also shows positive εNd(t) values because of its extraction from
the depleted MORB mantle at a recent time (DePaolo and
Wasserburg, 1976; O’Nions et al., 1979). As a consequence, its
mixing with the mantle wedge does not considerably change their
Nd isotope compositions, regardless of the difference in their Nd
abundances. For the oceanic basalts of negative εNd(t) values, on the
other hand, their mantle sources were hypothesized to form a long
time ago, with isolation of the enriched mantle domains from each
other for over hundreds of million years in the depleted MORB
mantle (Zindler and Hart, 1986; Hofmann, 1989). However, such
negative εNd(t) values can be acquired by addition of the negative
εNd(t) melts to the mantle wedge, because the crust-derived melts
always have significantly higher LREE abundances than the mantle
peridotite. Thus, the negative εNd(t) mantle sources can be gener-
ated by incorporating the high Nd melts of ancient crust into the
depleted MORB mantle at a recent time, with no appeal for the
long-lived heterogeneities in the mantle.
Likewise, the oceanic basalts of high (87Sr/86Sr)i and
(206Pb/204Pb)i ratios were traditionally attributed to mantle sources
that contain the upper continental crust component with high Rb/
Sr and U/Pb ratios for the long-term accumulation of radiogenic
87
Sr and 206Pb isotopes, whereas those of low (87Sr/86Sr)i and
( Pb/204Pb)i ratios were linked to mantle sources that contain the
206
lower continental crust component with low Rb/Sr and U/Pb ratios
for the long-term deficiency of radiogenic 87Sr and 206Pb isotopes
(e.g., Hofmann, 1997; Willbold and Stracke, 2010). In either case, the
two types of mantle sources were hypothesized to form a long time
ago, so that the enriched mantle domains were isolated from each
other for over hundreds of million years in the depleted MORB
mantle (e.g., Zindler and Hart, 1986; Hofmann, 1989). In fact, the
mantle sources with such abnormal (87Sr/86Sr)i and (206Pb/204Pb)i
ratios can be generated by incorporating the high Sr and Pb melts of
ancient crust into the depleted MORB mantle at a recent time.
Because the crustal melts always have significantly higher fluid-
mobile trace element abundances than the mantle peridotite,
those abnormal isotope ratios can be obtained by addition of the
ancient crust-derived melts to the mantle wedge. Therefore, the
enrichment of fluid-mobile trace elements in the liquid phases can
1242 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254

Figure 19. Radiogenic Sr-Nd-Pb isotope compositions of oceanic island basalts and mid-ocean ridge basalts (revised after Harmon and Hoefs, 1995).

exert the first-order control on the pertinent radiogenic isotope
compositions of mantle sources for basaltic rocks.
The very low degree of crustal anataxis can produce felsic melts
with the radiogenic isotope characteristics of the highest
incompatible-element enrichment. In particular, the radiogenic
isotope composition of partial melts is primarily dictated by that of
fertile portions. The partial melts acquire relatively enriched sig-
natures in radiogenic isotope compositions if the fertile portions
are dominated by the ancient terrigenous sediment. By contrast,
the partial melts are relatively depleted if the fertile portions are
dominated by the juvenile IOC. As such, the enriched isotope sig-
natures can be transferred from the subducting crust via the
metasomatic agents into the mantle source of OIB. At a later time,
the ultramafic metasomatites underwent partial melting to pro-
duce OIB. As a consequence, the enriched isotope signatures in the
mantle domains can be linked to metasomatism of the depleted
MORB mantle by ancient crust-derived melts, with no appeal for
long-lived separation of the enriched domains from each other in
the depleted MORB mantle (Xu and Zheng, 2017; Xu et al., 2017).
Because pelagic and terrigenous sediments are variably
enriched in fluid-mobile trace elements relative to IOC (Plank and
Langmuir, 1998; Plank, 2014), they were suggested to contribute
more significant enrichment of radiogenic isotopes to OIB. This led
to the consensus that the three enriched isotope endmembers were
generated by IOC plus pelagic sediment for EM1, IOC plus terrige-
nous sediment for EM2, and altered IOC for HIMU (Zindler and Hart,
1986; Weaver, 1991; Chauvel et al., 1992; Hofmann, 1997). Although
the terrigenous sediment is significantly enriched in these ele-
ments, it cannot explain the high Nb/U and Ce/Pb ratios, a common
feature for both MORB and OIB (Hofmann et al., 1986). Furthermore,
the terrigenous sediment generally shows distinct signatures in
trace elements (e.g., high Ba/La) and radiogenic isotopes (e.g., high
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
207
Pb/204Pb) from common OIB. For example, its Ba/La ratios are a
factor of w10 higher than normal MORB, whereas moderately
incompatible element ratios such as Sm/La differ by less than a
factor of 5. Even if the variable enrichment of fluid-mobile trace
elements and their pertinent radiogenic isotopes are taken into
account when interpreting the geochemical variations in OIB, one
still has a big problem with contributions from the bulk oceanic
crust to the enriched components.
Alternatively, it was suggested that the enriched components
could be the metasomatized oceanic or continental lithospheric
mantle that was recycled into the mantle (Sun and McDonough,
1989; Halliday et al., 1992, 1995; McKenzie and O’Nions, 1995;
Niu et al., 2002; Niu and O’Hara, 2003; Workman et al., 2004;
Pilet et al., 2005, 2008; Panter et al., 2006). The alternative inter-
pretation has challenged the classic model of mantle plumes for the
origin of OIB. It was even claimed that recycled oceanic crust and
sediment may be much less common in OIB sources than is
commonly assumed (Pilet et al., 2005). This leads to the superficial
difference that the two hypotheses with crustal recycling vs met-
asomatized lithosphere were mutually exclusive in the origin of
mantle heterogeneity (Hofmann, 1997; Niu and O’Hara, 2003).
However, both types of the enriched components may play roles in
the chemical and isotopic variability of the mantle sources of
intraplate basalts (Workman et al., 2004; Pilet et al., 2008). In
particular, little addition of the metasomatic agents to the depleted
MORB mantle can generate ultramafic metasomatites with
considerably enriched geochemical signatures, provided that the
agents predominate the composition of trace elements and their
pertinent radiogenic isotopes in the metasomatites. The key is that
the subducting oceanic crust underwent low-degree partial
melting to induce the significant fractionation in incompatible
trace elements between the subducting crustal rocks and their
derived liquid phases.
9. Perspective on the future
It is remarkable to see what we have achieved at the core of
subduction zone geochemistry. All of our major progresses are
primarily based on observations not only from geochemistry but
also from geology and geophysics. By doing so, an integrated
interpretation of these observations is critical to understanding of
the geochemical transfer from the subducting crust into the mantle
at different depths. Although these have informed us much more
about the chemical geodynamics of subduction zones than our
predecessors would have obtained before, it still remains to be
answered what controls the mass transfer at the slab-mantle
interface in subduction channels. This is because subduction zone
geochemistry is an all-encompassing discipline that borrows
heavily the approaches and techniques from a broad range of dis-
ciplines e from physics to chemistry, from material science to
mathematics, from kinematics to dynamics, and from thermody-
namics to kinetics e and in return delivers new insights into the
structures, processes and products of subduction zones; and
sometimes new problems. Because the discipline is rapidly
evolving, this review has only provided a snapshot of its state at the
present stage. The significant development of technology and
methodology will surely bring new exciting ideas and results on the
stage in the next decades.
The present review has mainly focused on the behavior of trace
elements during the crust-mantle interaction at subduction zones.
The results indicate that both IAB and OIB share the same property
of geochemical enrichment in their fluid-mobile trace element
composition and the difference between the two types of oceanic
basalts is primarily dictated by the property of crustal materials in
their mantle source. By doing so, it is realized that a lot of issues still
1243
remain to be resolved in the study of subduction zone geochem-
istry. These can be outlined in the following eight aspects: (1)
changes in the thermal gradient of subduction zone processes with
both time and space; (2) the behavior of various minerals, not only
major, minor and accessory but also hydrous and nominally anhy-
drous, during metamorphic dehydration and partial melting of
subducting crustal rocks; (3) the species of liquid phases produced
by dehydration and melting during crustal subduction to different
depths; (4) metasomatic reaction of the mantle wedge peridotite
with liquid phases derived from subducting crust; (5) the behavior
of mafic to ultramafic metasomatites in the mantle wedge during
and after subduction; (6) the geochemical differentiation of
incompatible relative to compatible elements during crustal and
mantle melting; (7) the progressive enrichment of fluid-mobile
trace elements in liquid phases, metasomatites and mafic melts
relative to fluid-immoble elements in different stages of subduction
zone processes; (8) the mass budget in major and trace elements
between crustal rocks, liquid phases, mantle peridotites, meta-
somatites under different PeT conditions.
Although the thermal gradient of subduction zones has been
inferred from both geodynamic models and natural rocks, there are
still disagreements in the results from the two approaches. With
respect to the commonly referenced thermal models of modern
subduction zones (Syracuse et al., 2010), for instance, Penniston-
Dorland et al. (2015) found that model temperatures are about
100e300
C colder at forearc depths of 30e80 km than PeT con-
ditions determined by the geothermobarometry of many exhumed
HP metamorphic rocks in both oceanic and continental subduction
zones. While nearly one half of the HP rocks were metamorphosed
at low thermal gradients of 5e10
C/km due to crustal subduction
from the forarc to subarc depths, the other half of these rocks were
metamorphosed at moderate thermal gradients of 10e20
C/km at
the forearc depths. It is in the second half that the metamorphic
temperatures are about 100e300
C hotter than the results from
thermal models. As argued by Penniston-Dorland et al. (2015), the
model-data discrepancies for this half cannot be explained by bias
to the calculated PeT conditions through postpeak processes such
as transport to the hangwall, prolonging of residence time, and
isothermal exhumation, because prograde PeT paths also show the
same PeT distribution as thermobarometry. Kohn et al. (2018)
compiled surface heat flow data from global subduction zones
and found that adding shear heating to the thermal models can
reproduce not only the surface heat flow but also the PeT condi-
tions of exhumed HP metamorphic rocks. Thus, the authors
concluded that the metamorphic record may have underrepre-
sented hot-young subduction and overrepresented old-cold sub-
duction. By contrast, van Keken et al. (2018) found that the addition
of reasonable amounts of shear heating leads to less than 50
C
heating of the oceanic crust compared to models that exclude this
heat source. Through comparing two sets of thermal models for
global subduction zones with the rock record, the authors found
that the average exhumed mafic rock record is systematically
warmer than the average thermal structure of mature modern
subduction zones. In this regard, it is intriguing to examine how
large amount of the shear heating can be produced at the slab-
mantle interface of lithospheric depths.
Because the composition of many exhumed HP rocks appears to
represent generally warmer conditions than predicted by the ther-
mal models (Penniston-Dorland et al., 2015), it has been a challenge
to reconcile the results from the thermal models with the geo-
thermobarometric results from those natural rocks. It is noticed that
the thermal models only provide the steady-state results for the
thermal structure of subduction zones in their early stage, whereas
the geothermobarometries tend to give the dynamic results of
metamorphic PeT conditions in different stages. In essence, the
1244 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
thermal gradient of subduction zones is dynamically evolved in both
time and space. As illustrated in Fig. 11, there are significant differ-
ences in temperature between slab dehydration and arc magmatism.
In general, low temperatures of 730e900
C are common for slab
dehydration at the subarc depths (Cooper et al., 2012), high tem-
peratures of 1200e1400
C are generally required for mantle melting
to yield arc magmatism (Kelemen et al., 2003; Kelley et al., 2010;
Perrin et al., 2016; Plank and Forsyth, 2016). In this regard, there is
not only the subarc heating for the mantle melting but also the
subarc lag between dehydration metasomatism and arc magmatism.
This can be explained by the inference that the low thermal gradi-
ents prevail in the locking stage of subduction zones, whereas the
high thermal gradients are common in the unlocking stage of sub-
duction zones. As such, it is possible for HP to UHP metamorphic
rocks in collisional orogens to have experienced cold subduction at
the low thermal gradients but warm exhumation at the moderate
thermal gradients (Zheng and Wu, 2018). In other words, plate
covergence would generally proceed in two stages, with the early
one in the compressional regime at the low thermal gradients but
the late one in the extensional regime at the moderate to high
thermal gradients. Nevertheless, the moderate thermal gradients
would occur at the slab-mantle interface if subduction could proceed
in a regime between compression and extension, which may be
caused by slow rates of plate convergence or moderate slab dips of
40e50
C. Thus, it remains to be tested whether the change in the
thermal gradient of subduction zones is responsible for the obser-
vation that the some HP metamorphic rocks record higher temper-
atures than the results from the thermal models. However, it is often
assumed that a flatly subducting oceanic slab would have the high
thermal gradients for crustal anataxis to yield adakatic magmatism.
This requires the overriding plate as thin as 40e60 km, which could
occur in such sites where mid-ocean ridges were transformed into
subduction zones. This situation may be more common in the
Archean to Paleoproterozoic than in the Neoproterozoic to Phaner-
ozoic. Therefore, further studies are required to determine not only
the differences in temperature and time between dehydration
metasomatism and arc magmatism but also the tectonic mechanism
for adakitic magmatism above subduction zones.
In nature, mafic to ultramafic metasomatites have much poorer
exposure than mafic igneous rocks and HP to UHP metamorphic
rocks above both oceanic and continental subduction zones. For
this reason, the geochemical study of HP to UHP metamorphic
rocks is a common way to deduce the composition of subduction
zone fluids (e.g., Hermann et al., 2006a; Bebout, 2007; Zheng, 2009;
Hermann et al., 2013; Zheng and Hermann, 2014). A number of
recent studies show insignificant loss of fluid-mobile trace ele-
ments such as LILE and LREE during prograde HP metamorphism
from blueschist to eclogite facies (e.g., Chalot-Prat et al., 2003;
Spandler et al., 2003, 2004; Volkova et al., 2004; Miller et al.,
2007; Deschamps et al., 2011; Xiao et al., 2012, 2013). This sug-
gests the decoupling between metamorphic dehydration and
element transport at the forearc depths, in contrast to the con-
ventional assumption that significant amounts of these trace ele-
ments can be mobilized and transported from subducting crustal
rocks during their dehydration at the subarc depths (e.g., Arculus
et al., 1999; Becker et al., 2000; Scambelluri et al., 2001; John
et al., 2004). It has been enigmatic why such coupling-decoupling
relationships occur during subduction zone metamorphism.
Although the stability of given hydrous minerals may exert a critical
control on the abundance of specific trace elements in meta-
morphic products (e.g., Hermann, 2002; Feineman et al., 2007; El
Korh et al., 2009; Hermann and Rubatto, 2009; Xiao et al., 2014),
it remains to be resolved which hydrous minerals are critical during
the metamorphic dehydration in oceanic subduction zones.
In view of the difference in the trace element composition of
mafic arc volcanics, various combinations of aqueous solutions and
hydrous felsic melts in different proportions are called upon to
transfer given trace elements into the mantle sources (e.g.,
McCulloch and Gamble, 1991; Elliott et al., 1997; Hermann et al.,
2006a). While the water-soluble elements are susceptible to
transport by aqueous solutions into the magma source of arc vol-
canics, the water-insoluble elements require transport by hydrous
melts. This dichotomy in the behavior of trace elements led to the
conclusion that the sediment melts and the IOC dehydrates in
studies of arc magma genesis. Thus, it is a critical issue in inter-
preting the geochemical data of mafic arc volcanics is to decide how
much of the geochemical signatures results from subarc transport
processes and how much is due simply to the composition of
subducting crustal rocks.
Whether fluid-immobile trace elements were transported by
subduction zone fluids is a critical issue in the study of geochem-
ical transfer from the subducting crust into the mantle. For
instance, HFSE are usually hosted by common accessory minerals
such as zircon and rutile, which may form during dehydration-
driven mineralogical reactions under HP to UHP conditions.
Indeed, the two HFSE-enriched accessory minerals have been
found in eclogite facies veins in UHP metamorphic rocks (e.g.,
Rubatto and Hermann, 2003; Gao et al., 2007; Zheng et al., 2007).
They were interpreted as precipitates from metamorphic fluids
during veining. In particular, Gao et al. (2007) presented field ob-
servations from eclogite outcrops in the southwestern Tianshan of
northwestern China, where centimeter-sized rutile grains occur as
prismatic crystals in a vein and as needle-like crystals in a meta-
morphic segregation. The authors interpreted these observations
as indicating mobilization and transportation of HFSE such as Ti,
Nb, and Ta by metamorphic fluids during subduction zone dehy-
dration. Such observations were viewed as mineralogical evidence
for the mobility of HFSE during the flow of metamorphic fluids in
subduction zones. However, it is noted that the vein is composed of
omphacite, rutile, quartz, apatite and ankerite, with minor
amounts of glaucophane, barroisite and phengite; the segregation
also contains garnet, omphacite and quartz with minor apatite,
phengite and amphibole. It is known from experimental
geochemistry that metamorphic fluids have the very limited sol-
ubility of HFSE at the forearc to subarc depths (Ayers and Watson,
1993; Audetat and Keppler, 2005; Tropper and Manning, 2005;
Antignano and Manning, 2008; Manning et al., 2008; Rapp et al.,
2010). Thus, TiO2 is not able to achieve oversaturation for rutile
precipitation, challenging the classic interpretation. In this regard,
it is asked whether the rutile crystals can be produced through
retrograde metamorphic reactions during the decompressional
exhumation of UHP eclogite to HP blueschist, whereby these rutile
crystals were physically transported by the metamorphic fluids
into both vein and segregation rather than directly precipitated
from the subsolidus fluids. It remains to be examined whether the
metamorphic reactions were accomplished by the decomposition
of eclogitic minerals with release of Ti and other HFSE into the
fluids. If so, it may yield the geochemical gradients as observed by
Gao et al. (2007), in that the Ti contents of garnet and omphacite,
the modal abundances of rutile and titanite and the whole-rock Ti,
Nb and Ta contents decrease towards its enclosed rutile-bearing
segregations and veins. Likewise, newly grown zircon grains and
domains in eclogite facies veins are usually interpreted as
precipitating from metamorphic fluids (Rubatto and Hermann,
2003; Zheng et al., 2007). However, it remained to be examined
whether they were produced through dehydration reactions of
UHP eclogites and then physically transported by the metamorphic
fluids into the veins. Therefore, it remains to be resolved whether
the occurrence of either rutile or zircon in metamorphic veins does
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254 1245

Figure 20. A schematic cartoon showing the composition of subduction zone fluids produced by metamorphic dehydration and partial melting of crustal rocks at high pressures
(HP) and ultrahigh pressures (UHP), respectively, corresponding to forearc to subarc depths for crustal metasomatism of the mantle wedge (revised after Hermann et al., 2006a).
Different kinds of fluid-mobile trace elements are mobilized at different depths and then transported from the subducting crust to the mantle wedge.

mean the transport of HFSE by metamorphic fluids at the forearc to
subarc depths.
The presence of crustal signatures in the mantle source of
basaltic rocks indicates the crustal metasomatism at the slab-
mantle interface in subduction channels. However, it is uncertain
at which depth the crustal components were transferred from the
subducting crust into the mantle. The petrological outcome of
crustal metasomatism is directly recorded by peridotite and
pyroxenite in collisional orogens (e.g., Zanetti et al., 1999; Rampone
and Morten, 2001; Malaspina et al., 2006a, 2006b, 2009;
Scambelluri et al., 2006, 2010; Zhang et al., 2011; Bebout, 2013;
Vrijmoed et al., 2013; Bodinier and Godard, 2014; Chen et al.,
2015, 2017; Li et al., 2018a, 2018b). Its effect on the composition
of metasomatites is primarily dictated by the property of liquid
phases derived from the subducting crust. In order to link this to
subduction zone magmatism, it is generally assumed that HP

Figure 21. A schematic cartoon showing the formation of a mantle wedge during subduction of an oceanic plate beneath a continental plate. The mantle wedge becomes larger and
larger with subduction, and its size increases from a small one at subarc depths to a big one at postarc depths. Different properties of liquid phases would be produced by
dehydration and melting of the subducting oceanic crust at different depths.
1246 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
metamorphism is responsible for processes at the forearc depths
and UHP metamorphism for those at the subarc depths (Fig. 20).
Metamorphic petrology provides a number of diagnostic features
for identification of dehydration and anatectic depths (e.g., Chopin,
2003; Liou et al., 2009). Subduction zone metasomatism may also
occur at the postarc depths (e.g., Scambelluri et al., 2008), but dif-
ficulty has been encountered in determining its depth for the
mantle source of OIB. Although many publications have speculated
the crust-mantle interaction at depths above or below the mantle
transition zone, no attempt has been made to determine the depth
of interaction. Therefore, further studies are required to focus on
the depth of crust-mantle interaction in subduction zones.
Crustal signatures in IAB are often used to retrieve the
geochemical transfer from the subducting crust into the mantle
wedge (e.g., Tatsumi and Kogiso, 1997; Churikova et al., 2001;
Tamura et al., 2007; Regelous et al., 2010; Cai et al., 2014; Haase
et al., 2015). These IAB also record the geochemical heterogeneity
of mantle sources that were generated at the subarc depths by
metasomatic reaction of the mantle wedge with oceanic crust-
derived liquid phases. Nevertheless, the IAB are only the indirect
products of such crust-mantle interaction. On the other hand,
mantle xenoliths and alkali basalts contain fertile, enriched signa-
tures due to chemical reactions in the mantle (e.g., Frey and Green,
1974; Menzies and Murthy, 1980; Bailey, 1982; O’Reilly and Griffin,
1988). Such processes were traditionally referred to as mantle
metasomatism (e.g., Roden and Murthy, 1985; Bailey, 1987; O’Reilly
and Griffin, 2013), without further distinction in the origin of
metasomatic agents between crustal and mantle sources. Because
mafic to ultramafic metasomatites in the mantle are more fertile
than peridotite, they are susceptible to partial melting to produce
mafic melts for mantle metasomatism. On the other hand, sub-
ducted crustal rocks are more fertile than the metasomatites, they
are more susceptible to partial melting to produce felsic melts for
crustal metasomatism. Therefore, further studies are required to
distinguish the origin of metasomatic agents in the mantle at the
subarc to postarc depths.
The mantle source of OIB would be generated at much greater
depths than that of IAB (Ringwood, 1990; Zheng et al., 2015, 2018;
Xu and Zheng, 2017). This corresponds to a significant difference in
the metasomatic formation of mantle sources with crustal sub-
duction from the subarc to postarc depths. It is the difference in
metasomatic depth that results in the difference in the physico-
chemical property of metasomatic agents at the slab-mantle
interface in subduction channels. In this regard, the mantle
wedge would increase its size with slab subduction from the
forearc via subarc to postarc depths, eventually forming a big
mantle wedge overlying the subducting slab above the mantle
transition zone (Fig. 21). However, it is unclear when a subducting
slab becomes rollback and how long it takes to make the big mantle
wedge above the mantle transition zone. This may be dictated by
the rates of slab subduction, slab rollback and slab sinking. There-
fore, it is intriguing how the subducting slab would change its angle
from low to high to make the mantle wedge biger and biger and
how long it would take for the change in slab position from the
lithospheric base to the mantle transition zone.
Since the original suggestion by Allègre and Turcotte (1986), the
model of a marble-cake mantle has gained wide acceptance as a
paradigm for mantle composition and components. The marble-
cake mantle was conceived as an ultramafic migmatite on the
macroscale, with many types of enriched veins and layers in the
ordinary asthenospheric mantle. The model postulates that the
subducted oceanic lithosphere would initially exist in the form of
elongate strips, which would be stretched and thinned at first by
the normal and shear strain in the convection mantle, and then
destroyed by being reprocessed on the centimeter scale by
dissolution processes. The fertile components of the mantle are
preferentially melted in ascending mantle flow, even beneath
cratonic lithosphere, giving rise to basaltic melts for intraplate
magmatism. The model was inspired by the occurrence of garnet
pyroxenites, comprising a great diversity of pyroxene- and garnet-
rich layers at different length scales, in orogenic peridotite massifs
such as Ronda in South Spain and Beni Bousera in North Morocco,
where only UHP pyroxenites are highly stretched and tectonically
mixed with peridotites (Garrido and Bodinier, 1999; Frets et al.,
2014). Although the garnet pyroxenites were hypothesized as the
fertile components for the mantle sources of isotopically enriched
basalts, no statement was given for the dissolution processes at the
slab-mantle interface in oceanic subduction channels. In this re-
gard, it is intriguing to assess whether these UHP pyroxenites were
generated by metasomatic reaction of the mantle wedge peridotite
at the subarc depths with hydrous felsic melts derived from the
subducting oceanic crust and whether the enriched components in
the mantle were dissolved from the subducting rather than sub-
ducted oceanic lithosphere.
Our understanding of the way in which the Earth works has
undergone a radical change since the advent of plate tectonics a
half of century ago (e.g., Wilson, 1965; Vine, 1966; Dickinson and
Hatherton, 1967; McKenzie and Parker, 1967; Isacks et al., 1968;
Morgan, 1968). In the last quarter of the last century, mantle geo-
chemists argued successfully that the mantle is layered, in which
the lower mantle is sampled by OIB that are enriched in fluid-
mobile trace elements such as LILE and LREE relative to HREE,
whereas the upper mantle is sampled by normal MORB that are
depleted in LILE and LREE relative to HREE (e.g., DePaolo and
Wasserburg, 1976; Wasserburg and DePaolo, 1977; Zindler and
Hart, 1986; Hofmann, 1988, 1997, 2003; Allègre and Lewin, 1989;
Sun and McDonough, 1989). Because of the plate subduction,
crustal material has been transported into the mantle at different
depths (e.g., Amstrong, 1968; Allègre et al., 1979; DePaolo, 1979;
O’Nions et al., 1979; Jacobsen and Wasserburg, 1980; Allègre,
1982; Hofmann and White, 1982; Ringwood, 1982; Zindler and
Hart, 1986; Hofmann, 1997; Huang and Zheng, 2017). This also
leads to different types of mafic magmatism in interplate and
intraplate regions (e.g., Zindler and Hart, 1986; Sun and
McDonough, 1989; Spandler and Pirard, 2013; Farmer, 2014;
Kelemen et al., 2014; Zhao et al., 2015; Zheng et al., 2015, 2018;
Huang and Zheng, 2017). Typically, IAB and CAA are regarded as
the products of interplate magmatism above oceanic subduction
zones, whereas OIB and CFB are considered as the products of
intraplate magmatism far away from modern oceanic subduction
zones (e.g., Zindler and Hart, 1986; Wilson, 1989; Hofmann, 1997;
White, 2010; Farmer, 2014; Kelemen et al., 2014). However, this
paradigm has been severely challenged by more and more studies
from geochemistry and geophysics in the past two decades. They
have posed a significant problem for mantle geochemists: how the
mantle has changed its composition with time and space?
In principle, geochemical transfer from the subducting crust to
the mantle operates as a series of transient, dynamic processes in
subduction channels (Stern, 2002; Manning, 2004; Bebout, 2007;
Zheng and Chen, 2016). It involves the macroscopic motions of
gas, liquid and solid materials at the slab-mantle interface and the
forces that produce these motions in geological systems. Because
the forces are directly related to the time rate of change of mo-
mentum of a system, these motions are collectively referred to as
momentum transfer. The forces acting on the system include
gravity, pressure and shear stress, leading to differences in the
speed of material motion at the slab-mantle interface. Although the
momentum transfer in subduction zones is realized by the trans-
port of liquid phases, the liquid phases may carry tiny mineral
grains from the subducting crust to the mantle wedge (Zheng and
 Y.-F. Zheng / Geoscience Frontiers 10 (2019) 1223e1254
Hermann, 2014; Li et al., 2016). This is indicated by the occurrence
of crustal zircons in mafic igneous rocks above oceanic subduction
zones (e.g., Rojas-Agramonte et al., 2016; Xu et al., 2018). However,
it remains to be resolved how these crustal zircons have survived
during partial melting of both crustal and mantle rocks at the
subarc to postarc depths.
Much progresses have been made in the past five decades since
the quantitative insights of Amstrong (1968) into the recycling of
subducted crustal materials. While quantitative simulations pro-
vide the test to petrogenetic models for the origin of basaltic rocks
above subduction zones (e.g., Stracke et al., 2003; Kimura et al.,
2009; Kimura and Kawabata, 2015; Xu et al., 2017; Xu and Zheng,
2017), qualitative interpretations are the key to the petrogenetic
models (e.g., Ringwood, 1974; Tatsumi and Eggins, 1995; Zhao et al.,
2013, 2015; Chen and Zhao, 2017). In either case, it is critical to have
reasonable estimates of both mass and energy at the slab-mantle
interface in subduction channels. In doing so, it is intriguing to
know: (1) how much subducting crust-derived material, whether
aqueous solutions, hydrous melts or supercritical fluids, is required
to account for the magnitude of trace element and isotopic
enrichment observed in IAB and OIB; (2) how much the mantle
wedge-derived material is required to account for the composition
of IAB and OIB; (3) whether such estimates are consistent with
those obtained from laboratory experiments and field-based
studies of UHP metamorphic rocks and orogenic to xenolith peri-
dotites, respectively. It is important to have the metasomatic do-
mains in the mantle wedge that can exactly account for the degree
of enrichment in various basalts above subduction zones. There-
fore, it remains to be resolved how such variables as major ele-
ments, trace elements, radiogenic isotopes and stable isotopes can
be integrated in the study of subduction zone geochemistry in
addition to constraints from both geology and geophysics.
10. Concluding remarks
All basaltic rocks in interplate and intraplate regions contain the
geochemical signature of crustal components. Inspection of the
mass balance in major and trace elements between mantle sources
and melting products indicates that subducting crustal rocks were
not directly incorporated into the mantle sources. Instead, the
crustal components were transferred into the mantle sources in the
form of liquid phases (metasomatic agents) that are significantly
enriched in fluid-mobile trace elements and their pertinent radio-
genic isotopes. Thus, the composition of basaltic rocks is deter-
mined by the budget of different elements between mantle and
crustal materials during metasomatism of the mantle wedge by the
subduction zone fluids. As such, their trace elements and pertinent
isotope compositions are primarily dictated by the composition of
metasomatic agents, whereas their major elements are dictated by
the mantle wedge peridotite.
The subducting crust undergoes metamorphic dehydration and
partial melting at different depths, producing different properties
of the liquid phases that react with the mantle wedge peridotite to
generate different compositions of metasomatites. Partial melting
of these metasomatites gives rise to different types of basalts in
terms of their trace element distribution patterns. One is the IAB,
showing enrichment in LILE, Pb and LREE but depletion in HFSE
relative to HREE; its mantle source was generated by metasomatic
reactions at the subarc depths. The other is the OIB, exhibiting
enrichment in LILE, HFSE and LREE but depletion in Pb relative to
HREE; its mantle source was generated by metasomatic reactions at
the postarc depths. Although shallow IAB and deep OIB magmas
would originate from compositionally distinct mantle sources, they
share a common crustal signature (enrichment in LILE and LREE)
that is distinct from the depleted MORB mantle. The persistence of
1247
such a signature in the mantle suggests the presence of specific
mantle domains in the mantle wedge, which are fertile in lith-
ochemistry and enriched in radiogenic isotopes. It is these domains
that contain the geochemical signature of crustal components and
serve as the magma source of basaltic rocks in both interplate and
intraplate regions.
While the dehydration melting of crustal rocks in subduction
zones has delivered the liquid phases to the mantle wedge, the
metasomatic reactions at the slab-mantle interface in subduction
channels have primed the magma sources of both IAB and OIB. For
this reason, the geochemical composition of subduction zone
magmas is primarily determined by that of metasomatic agents,
which is principally dictated by the thermal structure of subduction
zones at different depths. Although low thermal gradients prevail
in the early stage of subduction when the subducting slab is
coupled with the mantle wedge, high thermal gradients are ob-
tained in the late stage when the subducting slab is decoupled with
the mantle wedge. It is the high thermal gradients that cause partial
melting of the subducting crust with the rutile breakown, pro-
ducing hydrous silicate melts with the signature of HFSE enrich-
ment in the mantle sources of OIB. Because such sources can be
generated by the crust-mantle interaction at the postarc depths
above the mantle transition zone, it is intriguing whether it is
necessary to invoke the origin of OIB from mantle plumes at the
core-mantle boundary.
Acknowledgments
This study was supported by funds from the Chinese Academy of
Sciences (XDB18020303), the Chinese Ministry of Science and
Technology (2015CB856100) and the National Natural Science
Foundation of China (41590620). Thanks are due to two anonymous
reviewers for their comments, which greatly helped the improve-
ment of the presentation.
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Zheng, Y.F., Xu, Z., Zhao, Z.F., Dai, L.Q., 2018. Mesozoic mafic magmatism in North (1985) from Nanjing University in China, and a Dr. rer. nat.
China: implications for thinning and destruction of cratonic lithosphere. Sci- (1991) from University of Goettingen in Germany. He did
ence China: Earth Sciences 61, 353e385. postdoc in University of Tuebingen in Germany. He is
Zindler, A., Hart, S., 1986. Chemical geodynamics. Annual Review of Earth and specialized with not only the geochemical tracing of stable
Planetary Sciences 14, 493e571. and radiogenic isotopes but also the isotope geochro-
nology in high-temperature geological processes. His
research interests started from the geochemistry of light
element stable isotopes in minerals, the geochemistry of
hydrothermal ore deposits, and the theoretical modeling
Yong-Fei Zheng is a Chair Professor of geochemistry in
of isotopic systematics and its geochemical applications
University of Science and Technology of China, Academi-
through the geochemistry of metamorphic and magmatic
cian of the Chinese Academy of Sciences, a fellow of the
rocks in collisional orogens to the chemical geodynamics
Mineralogical society of America, and a fellow of the
of continental and oceanic subduction zones.
Geochemical Society. He received a B.S. (1982) and a M.Sc.