Lithos 334–335 (2019) 205–230

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Lithos

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Seismicity and mineral destabilizations in the subducting mantle up to

6 GPa, 200 km depth
Thomas P. Ferrand ⁎
Earthquake Research Institute, University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan

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

Article history: In the subducting oceanic lithosphere, a significant part of the seismicity is triggered in the mantle, especially
Received 28 June 2018 along the upper and lower Wadati-Benioff planes. Several studies have investigated the potential involvement
25 February 2019 of dehydration reactions in the triggering mechanism of mantle earthquakes. Recent experimental results reveal
Accepted 11 March 2019
that, under subduction conditions, mechanical instabilities nucleate in strong stable mineral aggregates during
Available online 15 March 2019
the destabilization of minor amounts of antigorite, i.e. the high-temperature serpentine, through a stress transfer,
Keywords:
without any fluid overpressure. Here I confront these laboratory results to seismological observations. On one
Earthquakes hand, most of the natural hydrous magnesium silicates seem to be known, with experimentally deduced stability
Intraslab limits up to 7 GPa, at least, available as relatively accurate estimates. On the other hand, recent achievements in
DDST thermal structure of subduction zones combined with precise hypocentre relocation give access to pressure and
Dehydration temperature conditions at earthquakes hypocentres. A series of P-T diagrams summarizes the stability limit of
Transformation minerals that may be part of natural peridotites or serpentinites with variable compositions at pressures from
Mantle 0.5 to 6 GPa and temperatures from 200 to 950 °C, and compares it with seismicity. Both hydrous and anhydrous
Stress transfer
phases are considered. A myriad of minor metamorphic reactions could participate in a transformation-driven
Lower Wadati-Benioff plane
stress transfer, even if the stability limits of serpentine minerals seem to correlate with most of the observed
Double seismic structure
Peridotite seismicity.
Hydration © 2019 Elsevier B.V. All rights reserved.
Hydrous phases
Water transfer
Serpentine
Antigorite
Chlorite
Clinochlore
Talc
DHMS

1. Introduction
Mantle earthquakes occur in different geological contexts, such as
shearing oceanic transform faults (e.g. Abercrombie and Ekström,
2001; Antolik et al., 2006; Delescluse and Chamot-Rooke, 2007;
Deplus et al., 1998; Henry, 2000), continental strike-slip faults (e.g.
Ferrand et al., 2018; Ueda et al., 2008) and, for most, subduction zones
(e.g. Yamaoka et al., 1986; Burbach and Frohlich, 1986; Abers and
Sarker, 1996; Peacock, 2001; Abers et al., 2006, 2009, 2013; Andersen
et al., 2014; Scambelluri et al., 2017). Among the latter, geophysicists
distinguish between intermediate-depth (≈35–400 km) and deep-
focus (N400–700 km; Frohlich, 2006) earthquakes, respectively related
to dehydration reactions (e.g. Jung and Green, 2004; Ferrand et al.,
2017) and phase transitions of olivine (e.g. Green and Houston, 1995;
⁎ Corresponding author.
E-mail address: ferrand@eri.u-tokyo.ac.jp (T.P. Ferrand).
Kirby, 1987; Schubnel et al., 2013) and/or enstatite (Akashi et al.,
2009; Xu et al., 2018). In this study, I focus on subduction mantle earth-
quakes (30–200 km), a large amount of which is triggered 10–40 km be-
neath the subduction interface in the lower Wadati-Benioff plane
(Brudzinski et al., 2007; Burbach and Frohlich, 1986; Hacker et al.,
2003; Hasegawa et al., 1978; Peacock, 2001; Yamaoka et al., 1986). A
recent study (Abers et al., 2013) calculated the pressure and tempera-
ture conditions at earthquakes hypocentres using both thermal models
of subduction zones (Syracuse et al., 2010; van Keken et al., 2011) and
precise hypocentre relocation techniques (e.g. Kita et al., 2010a,
2010b). They concluded that in warm subduction zones (Cascadia,
Tokai and Kii) most of the earthquakes are triggered in the mantle,
near the Moho or some kilometres deeper, whilst earthquakes clearly
form two distant planes, i.e. the upper and lower Wadati-Benioff planes,
in cold subduction zones (e.g. Tohoku and Hokkaido).
The mechanism of mantle earthquakes is still a matter of debate
(Section 2.4), but recent studies have demonstrated mantle hydration

https://doi.org/10.1016/j.lithos.2019.03.014
0024-4937/© 2019 Elsevier B.V. All rights reserved.
206 T.P. Ferrand / Lithos 334–335 (2019) 205–230
tens of kilometres below the Moho (e.g. Cai et al., 2018; Shillington et al.,
2015) and the presence of transient aqueous fluid within the lower
Wadati-Benioff plane (Bloch et al., 2018). High-pressure dehydration
experiments have evidenced a stress transfer upon antigorite destabili-
zation (DDST; Ferrand et al., 2017; Fig. 1), which would explain recent
seismological observations (Kita and Ferrand, 2018). Up to now, the
lower Wadati-Benioff plane has been proposed to correspond to the de-
hydration “isotherm” of antigorite (e.g. Abers et al., 2013; Hacker et al.,
2003; Peacock, 2001) or to the hydration limit of the oceanic lithosphere
(Ferrand et al., 2017; Kita and Ferrand, 2018). Other studies consider
that antigorite has nothing to do with lower-plane seismicity
(Reynard et al., 2010) and that it could be due to self-localizing thermal
runaway within peridotite above 600 °C (e.g. Kelemen and Hirth, 2007;
Ohuchi et al., 2017).
For the five above-mentioned populations of mantle earthquakes
(Fig. 2; Abers et al., 2013), constraints on earthquake location and ther-
mal structure are independent, and hypocentre depth error is lower
than 5 km for Cascadia (Abers et al., 2013; Parsons et al., 1998) and
only 2 km beneath northern Japan (e.g. Kita et al., 2010b; Zhao et al.,
1997) and Nankai (Tokai and Kii; e.g. Hirose et al., 2008). As shown on
Fig. 2, a large variability of P-T conditions at hypocentres exist, especially
in the cold mantle slab northeastern Japan (Tohoku and Hokkaido).
Hypocentre P-T conditions presented in Fig. 2 show a partial correlation
with major dehydration reactions, e.g. chrysotile and antigorite, i.e. ser-
pentine minerals.
Natural serpentinites, mostly made of antigorite and other serpen-
tine minerals, present significant chemical variations from place to
place (e.g. John et al., 2011; Kendrick et al., 2011; Scambelluri et al.,
2001, 2004; Trommsdorff and Evans, 1980), which have a significant
impact on the structural properties of antigorite (Uehara and Shirozu,
1985). Notably, the Al3+ content may significantly impact its stability
by MgSi-AlAl Tschermak substitution (Bromiley and Pawley, 2003;
Padrón-Navarta et al., 2013). Chemical variations are also widely ob-
served in other hydrous phases, such as humites (e.g. Trommsdorff and
Evans, 1980; Evans & Trommsdorff, 1983). Talc composition does not
usually vary much from the end-member formula Mg3Si4O10(OH)2
Fig. 1. Dehydration-driven stress transfer from the lab to the slab. Geometrical relationships between serpentinites and peridotites both in the lab and in natural systems and implications
on earthquakes triggering: (a) Situation within experimental samples (adapted from Ferrand et al., 2017) and near the tip of deep serpentinized faults; (b) Situation within a subducting
slab (modified after Kita and Ferrand, 2018); (b) Recap of the up-to-date understanding of mantle earthquakes mechanisms within a subducting slab undergoing dehydration.
(Pawley and Wood, 1995), but compositional variations, e.g. Tschermak
substitution, are observed in HP hydrated talc-like phases (e.g. Chinnery
et al., 1999; Fumagalli and Poli, 2005). Considering the complexity of
serpentinized faults (Fig. 3), this study aims to show to what extent dehy-
dration reactions could suffice to explain all lower-plane earthquakes in
the subducting mantle at the Nankai, Japan, Kuril and Cascadia trenches
(Abers et al., 2013).
Furthermore, using recent relocation data (Sippl et al., 2018) and
slab thermal structure (Wada and Wang, 2009) for northern Chile, I es-
timated the P-T conditions at hypocenters in the subducting mantle as
was previously done for other subduction zones (Abers et al., 2013).
This intermediate-age lithosphere (≈ 45 Ma) shows two distinct seis-
micity planes within the subducting mantle, separated by ≈ 25 km
and merging into a highly seismic body between 90 and 150 km.
Thus, this study also discusses how such puzzling seismicity could be re-
lated to mineral destabilizations within the subducting mantle of the
Nazca plate.
2. Geological and experimental contexts
2.1. Hydration and carbonation of oceanic peridotites
At least 25% of the oceanic floor, forming either at magma-poor
(slow spreading) or magma-rich (fast spreading) ridges could be only
composed by serpentinized mantle (e.g. Cannat et al., 2010). At slow-
spreading oceanic trenches, the “seismic Moho” indicates the depth at
which pervasive alteration of the peridotites stops, i.e. limit of high
reaction-induced fracturation (e.g. Dunn et al., 2017). The seismic
Moho is usually not very deep, only 2–4 km below the seafloor near
the ridge axis (Dunn et al., 2017; Escartín et al., 1997). But it varies
and the impact of alteration on seismic velocities can reach about
10 km below the seafloor, especially along normal faults, detachments
and fracture zones (e.g. Canales et al., 2000). Along seismic faults this
depth may significantly increase as fluid flows are favored by brittle de-
formation. Thus maximum alternation, i.e. localized serpentinization, is
deeper than the “seismic Moho” (Andreani et al., 2007).
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 207

Fig. 2. Seismicity in the mantle of subducting slabs and stability of major hydrous phases. Diagram showing P-T conditions at hypocentres in the subducting mantle beneath Hokkaido,
Tohoku, Kii, Tokai and Cascadia as calculated by Abers et al. (2013). Curves show the stability limits of chrysotile (Chr), antigorite (Atg), talc (Ta) and clinochlore (Chl). For each of
these phases, colour shades indicate the destabilization P-T window depending on local variations of peridotite bulk composition in the MSH and/or MASH systems. For composition
and abbreviation of mineral phases, see Tables 1 and 2. For details see Figs. 4–7. For additional phases see Figs. 8–10. References: B.1986 = Berman et al. (1986); P.2003 = Pawley
(2003); P.2005 = Perrillat et al. (2005); S&S.1977 = Staudigel and Schreyer (1977); U&T.1999 = Ulmer and Trommsdorff (1999); W&S.1997 = Wunder and Schreyer (1997).

Carbon oxidizing conditions at depth in the oceanic lithosphere is
unknown, but carbonation could occur along with serpentinization,
for instance in deep hydrothermal systems within ophicarbonates of
mid-oceanic ridges (Escartín et al., 1997; Trommsdorff and Evans,
1977). Experiments reveal that serpentinization triggers carbonation
in CO2-rich systems (e.g. Klein and McCollom, 2013). In addition, field
observations reveal that the back-reaction of serpentinite with the
COH-fluid promotes deep carbonation during subduction (Scambelluri
et al., 2016). Major uncertainties exist regarding deep carbon cycles,
but recent studies about deep life reveal that serpentinites can host mi-
crobial activity (Ménez et al., 2012), especially within hydrothermal
systems (Kelley et al., 2005; McCollom, 2007), which could lead to effi-
cient carbon storage within the hydrated lithospheric mantle.
Reaction-driven cracking is expected to play a critical role in the sus-
tainability of fluid flow during either hydration or carbonation
(e.g. Jamtveit et al., 2008; Jamtveit et al., 2009; Kelemen and Hirth,
2012; Rudge et al., 2010). Fluid migration is usually favored by
preexisting heterogeneities within the uppermost mantle (e.g. Debret
et al., 2013). Moreover, neutron scattering techniques reveal nano-
scale pore spaces within the structure of serpentine minerals that can
serve as fluid pathways (Tutolo et al., 2016), allowing further hydration
of ultramafic rocks (Schwarzenbach, 2016).
2.2. Extent of mantle hydration and carbonation in subduction context
Observational facts show evidence of deep faults at numerous sub-
duction trenches (Cai et al., 2018; Ivandic et al., 2010; Naif et al., 2015,
2016; Ranero et al., 2003; Shillington et al., 2015). At the Mariana sub-
duction zone, ocean-bottom seismic data recently revealed that signifi-
cant serpentinization reaches at least 24 km below the Moho (Cai et al.,
2018), consistently with the flexure model that predicts a neutral plane
at around 30 km below the seafloor (Emry et al., 2014). For other sub-
duction zones, despite the absence of substantially reduced seismic
velocities at 10 km and deeper (Reynard et al., 2010), seismic reflection
surveys have revealed deep reflections that can be interpreted as
bending-related serpentinized faults at the Middle America Trench
(Ivandic et al., 2010; Ranero et al., 2003) and offshore Alaska
(Shillington et al., 2015). These observations indicate that the litho-
spheric mantle is partially hydrated at least 8 km and 15km below the
Moho, respectively, through serpentinization of deep faults, which can
be extended to 35 km based on an estimate of the brittle-ductile transi-
tion of the lithosphere (Ranero et al., 2003). Evidence of the direct link
between mantle hydration and the generation of dehydration-
induced intermediate-depth seismicity is also demonstrated offshore
Alaska (Shillington et al., 2015). Such hydration up to the lower plane
is also consistent with full waveform modeling performed both for Hok-
kaido (Garth and Rietbrock, 2014) and Chile (Garth and Rietbrock,
2017).
Slower velocities in the lower-plane (Nakajima et al., 2009) have
been confirmed by high-resolution data (Bloch et al., 2018), which indi-
cate a higher VP/VS ratio (≥2.0 ± 0.1) typical of free fluid. Bloch et al.
(2018) demonstrated a deep hydration of the lithospheric mantle of
the subducting Nazca plate up to the lower-plane and suggested that
dehydration-induced fluids escape through a transient crack network
(porosity ~0.1 vol%). The higher VP/VS values at the lower plane most
likely indicate the presence of minor fluids that cannot immediately es-
cape, whereas higher connectivity of/within serpentinized zones
(Fig. 1) between the planes would allow permanent permeable path-
ways, especially thanks to the structure of serpentine minerals
(Schwarzenbach, 2016; Tutolo et al., 2016). Indeed, the abnormally
high VP/VS ratio is only observed in the vicinity of the lower-plane and
not in the inter-plane aseismic region.
Carbonates are soluble in aqueous fluids at relatively low tempera-
tures (e.g. Caciagli and Manning, 2003; Facq et al., 2014; Frezzotti
et al., 2011; Milesi et al., 2015) suggesting that, if hydrous fluids are in-
volved, efficient slab decarbonation should occur at relatively shallow
depths (Debret et al., 2018). But numerous studies prove that carbon
reaches great depth through subduction, in the form of graphite
(Pasteris, 1981) or aragonite inclusions found within olivine (N100 km
depth; Humphreys et al., 2010). Notably, dehydration fluids are charac-
terized by high oxygen fugacity (e.g. Debret and Sverjensky, 2017),
which slightly delays further dehydration reactions (Bretscher et al.,
2018), especially via the change of iron oxidation state due to
serpentinizaion (e.g. Debret et al., 2015; Merkulova et al., 2016). Such
dehydration-induced oxidizing conditions would allow further carbon-
ation reaction, i.e. transfer of CO2 to greater depths.
Most importantly, with increasing pressure and temperature, H2O is
a supercritical fluid in case of H2O saturation (e.g. Ferrando et al., 2005).
208 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Fig. 3. An incomplete correlation between dehydration and lower-plane seismicity? (a) Sketch of a representative unit of fault surface and gouge in the MSH system considering only
antigorite and brucite, and associated P-T diagram questioning the “correlation” between dehydration reactions and lower-plane seismicity; (b) Situation in the MASH system
considering antigorite and clinochlore; (c) Suggested situation for a natural mantle vs natural seismicity. For references, see Fig. 2.

In such conditions, H2O is a solvent and CO2 may be a solute. But, as
most of the hydrated mantle only contains few H2O, it is mainly
adsorbed at grain boundaries or integrated as defects within crystals
(e.g. Bai and Kohlstedt, 1992; Martin and Donnay, 1972). In a
subducting slab, as long as H2O is preferentially integrated into hydrous
phases (b600 °C), slab decarbonation would occur only in case of H2O
saturation, i.e. depending on hydrous phases connectivity and aqueous
fluids pathways.
2.3. Multiple destabilizations of hydrous phases within serpentinites
Antigorite (Schweizer, 1840) is the high-temperature serpentine va-
riety and carries in its structure about 12–13 wt% of bound H2O on aver-
age (e.g. Kunze, 1961; Mellini et al., 1987; Uehara, 1998; Uehara and
Kamata, 1994). It is a rock-forming mineral and the most abundant hy-
drous phase in the mantle undergoing subduction. The stability field of
antigorite is thus commonly used to predict the depth where fluid is
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 209

released in subduction zones (e.g. Hacker et al., 2003; Peacock, 2001;
Schwartz et al., 2013). A first-order model of serpentinized fault in the
MSH system would be an antigorite gouge with variable thickness, but
it would only correlate with part of the seismological observations
(Fig. 3a).
Actually, a large number of hydrous phases may coexist with serpen-
tine minerals within serpentinites (Section 4.1), such as talc (4.7 wt%
H2O, e.g. Berman et al., 1986; Pawley and Wood, 1995) or chlorite
(12.97 wt% H2O, e.g. Staudigel and Schreyer, 1977; Pawley, 2003).
Table 1 lists the hydrous phases (Section 4.1) that are likely within
serpentinites, at least in small amounts and for limited P-T conditions.
The natural complexity of serpentinized faults is questioned in this
study, such as phases diversity and fluid pathways (Fig. 3b,c).
One of the most important differences between hot and cold
subducting slabs is that major dehydration reactions, e.g. serpentine
minerals, are respectively associated with positive and negative volume
change (solid + fluid; e.g. Hacker et al., 2003; Abers et al., 2013; Gasc
et al., 2011; Incel et al., 2017; Ferrand et al., 2017). Nevertheless, nega-
tive volume change also occurs within the mantle of hot subducting
slabs, for instance during the dehydration of talc or chlorite (Fig. 2).
2.4. Decades of debate about (de)serpentinization and earthquakes
mechanisms
The link between the dehydration of serpentinites and mantle seis-
micity has been a matter of debate for decades (e.g. Abers et al., 2013;
Ferrand et al., 2017; Frohlich, 2006; Hacker et al., 2003; Incel et al.,
2017; Kirby et al., 1996; Raleigh and Paterson, 1965). Potential mecha-
nisms are recapped in Fig. 1c. In the followings, I distinguish between
triggering and nucleation mechanisms.
Embrittlement upon dehydration of deforming antigorite occurs in
the laboratory at low pressure (0.5 GPa, i.e. 16 km) and is the root of
the “dehydration embrittlement” model (Raleigh and Paterson, 1965).
In this model, fluid overpressure due to dehydration drives brittle yield-
ing (e.g. Frohlich, 2006; Hacker et al., 2003). Fluid overpressure is also
proposed to trigger high-pressure hydrofracturing in the cold top-slab
mantle (Padrón-Navarta et al., 2010). The limitations of such fluid-
induced processes have been discussed in several studies (e.g. Ferrand
et al., 2017; Thielmann et al., 2015).
Consequently, the weakening of dehydrating serpentinites, i.e.
mostly rock-forming antigorite and other hydrous phases, has been

Table 1
Hydrous phases and associated formula considered in this study.

CaO-MgO-Al2O3-SiO2-H2O system (CMASH) for pressures between 0.5 and 6.5 GPa. DHMS refers to “Dense Hydrous Magnesium Silicates”. For carbonates, see Table 3. Except for goethite,
iron is not indicated in the table. The substitution of Mg2+ by Fe2+ in magnesium silicates is common, but the iron content does not exceed 1%, which, for most phases, has minor impact on
stability. Besides, Fe3+ and Ti3+ may exist in hydrous silicates, especially replacing Al3+ in Al-bearing minerals. As titanium and fluorine have a major impact on humites stability (see Fig. 9),
Ti3+ and F− are indicated for chondrodite and clinohumite. In most mantle peridotites, hydrous phases are minor phases. P-T diagrams that direclty deal with the stability of a phase are
indicated with a bold number. When numbers are not bold, it means that the phase is involved in a reaction in a P-T diagram that does not focus on this phase.
210 T.P. Ferrand / Lithos 334–335 (2019) 205–230
considered as the cause for dynamic rupture nucleation in the mantle
(e.g. Hacker et al., 2003). However, at mantle pressures (N1 GPa),
dehydrating antigorite is not seismic (Chernak and Hirth, 2010, 2011;
Gasc et al., 2011, 2017; Okazaki and Hirth, 2016). Nevertheless,
dehydration-driven embrittlement is observed in serpentinized perido-
tites at subducting-mantle P-T conditions (e.g. Ferrand et al., 2017; Jung
et al., 2004; Jung and Green, 2004; Xia, 2013).
These results are confirmed by field observations, where pseu-
dotachylytes, i.e. fossilized earthquakes, are observed in large dry peri-
dotite bodies (Ferrand et al., 2018; Scambelluri et al., 2017) or
partially/locally serpentinized peridotites (Andersen and Austrheim,
2006; Andersen et al., 2014; Deseta et al., 2014a, 2014b; Dunkel et al.,
2017). Concurrently with these observations of brittle features in peri-
dotite, only ductile deformation is reported in dehydrating serpentinites
(Plümper et al., 2017), consistently with experiments (e.g. Chernak and
Hirth, 2010, 2011). The Erro Tobbio serpentinite of the Voltri massif,
which reached 100 km depth (i.e. 3 GPa) 30 million years ago (e.g.
Scambelluri et al., 1995; Scambelluri et al., 2004), shows dehydration
features organized as anastomosed channels (Plümper et al., 2017).
The dehydration reaction in serpentinites seems to drive ductile defor-
mation, and no connexion between dehydrating serpentinite bodies
and faults could be observed on the field.
Another mechanism, which would not require the presence of hy-
drous phases, has been proposed to explain the double Wadati-Benioff
structure, especially concerning the lower plane (Reynard et al., 2010). In-
deed, until recently (Bloch et al., 2018; Cai et al., 2018), seismic imaging
has generally documented the absence of substantially reduced velocities
deep below the oceanic Moho, thus demonstrating little hydration if any
(Reynard et al., 2010). Earthquakes would be triggered by the nucleation
of self-sustained shear-heating instabilities (John et al., 2009; Kelemen
and Hirth, 2007; Prieto et al., 2013), as supported by recent high-
pressure deformation experiments on dunite (Ohuchi et al., 2017).
Shear heating in dry ultramafic mylonitic layers would lead to viscous
rupture between 600 and 800 °C (Kelemen and Hirth, 2007). It is however
important to note that, such thermal runaway (John et al., 2009; Kelemen
and Hirth, 2007) must be preceded by an initial grain size reduction
(Thielmann, 2018a), easily obtained during localized mineral transforma-
tions (Green II et al., 2015; Thielmann, 2018b). In the laboratory (Ohuchi
et al., 2017) the shear strength of the dunite sample is reached at sample
scale; for natural intraslab earthquakes, a trigger is needed, and mineral
transformations are good candidate for it. A thermal runaway process
that would be associated with mineral transformations, e.g. antigorite de-
hydration, could participate in paving the way for reconciliation of these
apparently contradictory studies. Nonetheless, the endothermique nature
of dehydration reactions would constitute a negative feedback in models
considering thermal runaway activated by frictional heating (e.g. Brantut
et al., 2011; Yamashita and Schubnel, 2016).
The impact of sliding on a fault segment on the stress state along the
rest of the fault and along neighbouring faults varies depending on their
geometries, the lithologies they go through and the fluids that circulate
in their gouges (e.g. Guéguen and Palciauskas, 1994). Mineral reactions
necessarily induce grain size reduction, which could drive nanometric
flow and cause extreme weakening during fault slip (Green II et al.,
2015). Local transformation and associated grain size reduction may
also drive stress transfers and trigger earthquakes (Ferrand et al.,
2017). It has also been noted that slow seismic events may lead to stress
transfers triggering large earthquakes in Japan (Obara and Kato, 2016).
Recent experimental results (Ferrand et al., 2017) revealed that
antigorite destabilization is the trigger for dynamic failure in slightly
serpentinized peridotites (5 vol% antigorite), leading to the radiation
of elastic waves and pseudotachylytes formation (Ferrand et al.,
2017). These laboratory observations lead to the establishment of a
new phenomenological model, the DDST (Dehydration-Driven Stress
Transfer), which may describe how intraslab mantle earthquakes are lo-
cated along the LWBP. The latter seismicity zone is neither a tectonic
contact nor a thermal limit. Its position seems mainly controlled by
the amount and the distribution of antigorite in slightly/locally
serpentinized peridotite bodies (Ferrand et al., 2017).
To understand the complex phenomenon of transformation-driven
earthquakes, two models could be integrated: the thermal runaway
model (Kelemen and Hirth, 2007) and the stress transfer model
(DDST, Ferrand et al., 2017). In other words, dynamic weakening, re-
quired for rupture at depth, could be operated by thermal runaway,
which would be triggered by local antigorite dehydration in the vicinity
of the future fault (Fig. 1).
2.5. About the upper Wadati-Benioff plane
Salty brines have been found in eclogitized hydrous peridotites from
the Erro-Tobbio massif, i.e. former plate interface, which suggests that
significant amounts of Cl, Na and K could be incorporated into peridotites
during subduction (Scambelluri et al., 1997). Then, many other hydrous
minerals may exist within metasomatized peridotites, such as Na- and
K-bearing minerals, e.g. pargasite NaCa2Mg4Al3Si6O22(OH)2 (e.g. Lykins
and Jenkins, 1992) and phlogopite KMg3AlSi3O10(OH)2 (e.g. Fumagalli
et al., 2009). These minerals may form within serpentinites but only in
near-surface conditions, when peridotite reaches the seafloor. Similarily,
as lawsonite CaAl2Si2O7(OH)2·H2O and zoizite Ca2Al3[Si2O7][SiO4]O(OH)
(Schmidt and Poli, 1994) do not contain Mg and are generally not found
within peridotites, these minerals are not considered in this study.
From a petrological point of view, the lower Wadati-Benioff plane is
the simpliest part of the double-seismic zone, as it consists at first order
of locally and/or slightly hydrated peridotite. Considering this relatively
simple composition, it is likely that this seismicity has only one trigger-
ing mechanism. As long as we do not know whether there is oceanic
crust or not and/or how many triggering mechanisms exist near the
plate interface, I do not focus on the upper plane. Experiments have
shown that mineral destabilizations within the oceanic crust, such as
lawsonite and glaucophane dehydration, trigger seismicity (e.g. Incel
et al., 2017; Okazaki and Hirth, 2016). The numerous dehydration and
other metamorphic reactions that may occur within the oceanic crust
should be recapped, but it is not the point of this study.
2.6. Experimental stability curves vs pseudosections
It should be recalled here that the experimental stability curves de-
tailed in this review fundamentally differ from pseudosections. Experi-
mental P-T curves are deduced from direct observations of samples
after experiments mimicking the geological processes; pseudosections,
constrained from experimental results, are based on thermodynamic
calculations in equilibrated systems. Used in many petrological and
mineralogical studies (e.g. Bretscher et al., 2018; Fumagalli and Poli,
2005; Padrón-Navarta et al., 2013), pseudosections are a powerful tool
to understand metamorphic parageneses.
Nonetheless, pseudosections only consider phases that are defined as an
input in the calculation. Moreover, considering relatively low temperatures
(b600 °C) in subduction context and variable amount of minor hydrous/
carbonated phases within fault gouges (Fig. 3), local equilibria within
serpentinized faults should be considered. In other words, rocks are not
expected to be equilibrated at the fault scale. In sake of clarity, this paper
contains only experimental P-T curves and no pseudosection. It leaves
also the door open to potential undiscovered or misunderstood phases,
such as high-pressure hydrated talc phases (Section 4.1.1), with various
H2O contents, which could consist of a polysomatic series (Section 4.2.4.2).
3. Methods and results
3.1. Review of all experimental studies on the stability of mantle minerals
Stability limits of a wide spectrum of major and minor mantle phases
are presented in a series of P-T diagrams (Figs. 4–11). These diagrams
summarize prograde stability limits and take into account potential
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 211

large chemical variations due to fluids. Based on geophysical imaging
studies (Ivandic et al., 2010; Ranero et al., 2003; Reynard et al., 2010;
Shillington et al., 2015), experimental datasets (Bromiley and Pawley,
2003; Chinnery et al., 1999; Evans, 1977; Evans, 2004; Evans et al.,
1976; Fockenberg, 1995; Fransolet and Schreyer, 1984; Fumagalli
et al., 2014; Guggenbuehl, 1994; Johannes, 1968; Massonne et al.,
1981; Merkulova et al., 2016; Pawley, 2003; Pawley and Wood, 1995,
1996; Pawley and Wood, 1996; Perrillat et al., 2005; Schreyer, 1988;
Staudigel and Schreyer, 1977; Ulmer and Trommsdorff, 1995; Ulmer
and Trommsdorff, 1999; Wunder, 1998), field observations (e.g.
Trommsdorff, 1983; Chopin, 1984; Schwartz et al., 2013) and associated
thermodynamic considerations (e.g. Berman et al., 1986; Wunder and
Schreyer, 1997; Holland and Powell, 1998; Hilairet et al., 2006), I con-
sider a large spectrum of phases in the MSH and MASH systems
(Figs. 4–9), with a wide range of variations both in their chemical com-
positions and possible paragenesis. Transformations in anhydrous peri-
dotite are also considered (Fig. 10), as well as decarbonation reactions
and other carbonate mineral stability limits (Fig. 11).

Fig. 4. Stability of antigorite on a prograde metamorphic path and sketch of antigorite lattice. (a) P-T diagram presenting up-to-date knowledge on the stability limit of antigorite up to
6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry and H2O saturation as expected in a subduction context. Background coloured dots
correspond to P-T conditions at hypocentres of intermediate-depth mantle earthquakes for well-studied subducting slabs beneath Hokkaido, Tohoku, Kii, Tokai and Cascadia (see
Fig. 2). For composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations and thermodynamic
equilibrium numerical studies, see the text. References: B.1986 = Berman et al. (1986); B&N.1998 = Bose and Navrotsky (1998); B&P.2003 = Bromiley and Pawley (2003); E.1976 =
Evans et al. (1976); E.2004 = Evans (2004); H.2006 = Hilairet et al. (2006); P.2005 = Perrillat et al. (2005); U&T.1999 = Ulmer and Trommsdorff (1999); W&S.1997 = Wunder and
Schreyer (1997). (b) Antigorite crystal lattice 3D structure (m = 17; adapted from Uehara, 1998). Silica tetrahedra SiO4− 4 (lilac) share three of their four oxygen atoms (red) with each
other, i.e. “silica layer”, and share one with the octahedral sites, i.e. “brucite layer”. Ideally, the latter are occupied by bivalent cations (orange spheres, mostly Mg2+ and Fe2+). Protons
+ −
(H ) of the hydroxyles (OH ), represented with small blue dots, connect the silica and brucite layers (hydrogen bond). For sake of clarity, the geometry of the brucite layer is
represented separately, showing the six oxygen atoms at the octahedron edges.
212 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Fig. 5. Stability of chrysotile, lizardites and amesite on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limit of serpentine minerals chrysotile,
lizardites and amesite up to 6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry and H2O saturation as expected in a subduction context. See
Fig. 2 for the background coloured dots. The stability of amesite is not certain as it and clinochlore could get mixed up (Ackermand et al., 1975). For composition and abbreviation of mineral
phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations and thermodynamic equilibrium numerical studies, see the text. References: A.1975 =
Ackermand et al. (1975); B.1986 = Berman et al. (1986); C&C.1979 = Caruso and Chernosky (1979); C.1973a = Chernosky (1973a); C.1973b = Chernosky (1973b); E.1976 = Evans et al.
(1976); E.1977 = Evans (1977); E.2004 = Evans (2004); J.1968 = Johannes (1968); P; S.2013 = Schwartz et al. (2013); T.1983 = Trommsdorff (1983); U&T.1999 = Ulmer and
Trommsdorff (1999).

Antigorite is the most studied hydrous magnesium silicate and the
most common hydrous phase in the subducting mantle. Its stability
limits are shown in Fig. 4a. Antigorite lattice structure is detailed in
Fig. 4b, with description of “silica” and “brucite” layers, often referred
to in descriptions of phyllosilicates such as serpentine, talc and chlorite
minerals. Documented reactions involving other serpentine minerals
(chrysotile, lizardites and amesite) are summarized in Fig. 5. The stabil-
ity limits of chlorite and Mg-chloritoid are summarized in Fig. 6. Most
reactions involving talc and HP hydrous talc-like minerals are presented
in Fig. 7, except reactions involving chlorite or Mg-chloritoid (Fig. 6).
The stability of Phase A and amphiboles are presented in Fig. 8. Reac-
tions involving other Mg- and/or Al-rich hydrous silicates are presented
in Fig. 9. Complementally, Fig. 10 summarizes reactions of anhydrous
phases, some of which typical of ultramafic rocks (e.g. forsterite,
enstatite, diopside), some other possibly locally present due to fluid cir-
culation at faults and metasomatism (e.g. Bonnemains et al., 2017). Fi-
nally, as the peridotite is likely to be partially carbonated, at least in
the first kilometres below the Moho, decarbonation reactions and
other carbonate mineral stability limits are summarized in Fig. 11.
Additional works on antigorite polysomatism and on the impact of
H2O saturation on the stability of antigorite are recapped in Fig. 12.
All the references used are specified in captions and discussed in the
following sections. Mineral compositions and abbreviations considered
in this study are listed in Table 1, 2 and 3 respectively for hydrous
phases except carbonates, anhydrous phases except carbonates and car-
bonate minerals.
was previously done for other subduction zones (Abers et al., 2013).
The thermal structure calculated by Wada and Wang (2009), at latitude
23.5°S, is the most accurate up to date for this region. It gives similar re-
sults as the model of van Keken et al. (2011) for a given slab geometry
and boundary conditions (Ikuko Wada, personal communication). The
thermal model of Wada and Wang (2009) is also consistent with atten-
uation tomography results (Schurr et al., 2006).
Down to 120 km depth, a constant dip of the subduction interface of
21° is considered and well consistent with both the slab surface imaging
and the relocated seismicity (Sippl et al., 2018). At great depths, how-
ever, a change occurs in the slab geometry between latitudes 22°S and
22.5°S (Sippl et al., 2018), which constrains to consider an additional
bend of 14°, leading to a total dip of 35° from 120 to 200 km depth.
In Fig. 13, I present the cross-section at latitude 21.5°S with results of
P and T estimates for the case of an extrapolation of the thermal struc-
ture with constant dip of 21° (Fig. 13a and b), and considering the addi-
tional bend at 120 km depth (Fig. 13c and d). I consider no change in the
thermal structure of the slab between these two scenarios. For compar-
ison, the same exercise at latitude 23°S, close to the determined thermal
structure (23.5°S), is displayed in Fig. 13e and f.
Errors for hypocentre relocation do not exceed 2 km (Sippl et al.,
2018), which means that pressure estimates are accurate with uncer-
tainties lower than 60 MPa. In contrast, the temperature estimates are
strongly affected by uncertainties about the thermal structure of the
subducting slab. For a given thermal structure, the T estimates are ob-
tained considering a linear T increase between the displayed isotherms.

3.2. Estimate of the P-T conditions at hypocentres beneath northern Chile 4. Discussion

In this study, I use high-quality relocation data recently published for Major advances have been made in the understanding of mineralogical
northern Chile (Sippl et al., 2018), at latitude 21.5°S and 23°S, to esti- diversity and stability limits for various bulk compositions thanks to ex-
mate the P-T conditions at hypocentres in the subducting mantle as tended experimental studies and associated thermodynamic calculations
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 213

Fig. 6. Stability of chlorite and Mg-Chloritoid on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limit of chlorite (clinochlore and sudoite) and
Mg-chloritoid up to 6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry and H2O saturation as expected in a subduction context. See Fig. 2 for
the background coloured dots. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations
and thermodynamic equilibrium numerical studies, see the text. When not specified, the curves are adapted from Chopin and Schreyer (1983). References: A.1975 = Ackermand et al.
(1975); C.1984 = Chopin (1984); E.1976 = Evans et al. (1976); E.1977 = Evans (1977); E.2004 = Evans (2004); F&S.1984 = Fransolet and Schreyer (1984); F.1995 = Fockenberg
(1995); F.1998a = Fockenberg (1998a); F.1998b = Fockenberg (1998b); F.2014 = Fumagalli et al. (2014); G.1994 = Guggenbuehl (1994); J.1968 = Johannes (1968); M.1981 =
Massonne et al. (1981); P&W.1995 = Pawley and Wood (1995); P.2003 = Pawley (2003); S.1988 = Schreyer (1988); S.2013 = Schwartz et al. (2013); S&S.1977 = Staudigel and
Schreyer (1977); T.1983 = Trommsdorff (1983); U&T.1999 = Ulmer and Trommsdorff (1999).

in the MSH system (e.g. Pawley and Wood, 1995; Wunder and Schreyer,
1997; Chinnery et al., 1999; Pawley, 2003). An important parameter con-
trolling the stability of major hydrous phases appears to be the bulk com-
position of the peridotite, e.g. the presence or absence of brucite shifting
the stability of serpentine minerals by 100–150 °C and 2–3 GPa (Figs. 4
and 5). The fluids also significantly impact serpentinization, especially re-
action kinetics (e.g. Pens et al., 2016). Additional work in the MASH system
(e.g. Chollet et al., 2009; Bromiley and Pawley, 2002, 2003) and comple-
mentary studies considering additional minor amounts of cations (e.g.
Fe2+, Fe3+, Cr3+ and Ti3+; e.g. Ulmer and Trommsdorff, 1995; Fumagalli
et al., 2014) or anions (e.g. F−, Cl−; e.g. Weiss, 1997) allow to better con-
strain the stability of natural phases. Both deep H2O and CO2 cycles have
been reappraised in light of experiments, geological observations and ther-
modynamic calculations (e.g. Irifune et al., 1998; Comodi et al., 2007;
Scambelluri et al., 2016; Dunn et al., 2017; Cai et al., 2018; Sverjensky
et al., 2014). Complementary studies explored deep fluid processes and el-
ements cycling especially through antigorite burying and deep destabiliza-
tion (Scambelluri et al., 1997, 2001, 2004; John et al., 2011). Section 4.1
summarizes the state of the art in the MSH and MASH systems, and ad-
dresses the question of “metastability”.
In Section 4.2, I highlight several parameters that undoubtedly influ-
ence the position of reaction curves in the P-T diagrams presented above
(Figs. 4–11). The parameters are (4.2.1) bulk composition, (4.2.2) min-
eral chemistry, (4.2.3) fluid composition and saturation level, (4.2.4)
mineral structure and (4.2.5) structural interactions between phases.
Taken all together, these factors are likely to allow substantial variations
in the stability of either major or minor mantle phases. Finally, I discuss
the importance of these stability fluctuations on the relevance and ap-
plicability of transformation-driven stress transfers such as the one evi-
denced by recent experimental results (DDST; Ferrand et al., 2017). To
do so, this paper deliberately puts the emphasis on well-studied and
widely-observed phases as much as on rarer or less observed minerals.
4.1. A diversity of phases with abrupt stability limits
4.1.1. A continuous discovery of new phases in transforming serpentinites
Many studies have tried to refine thermodynamic calculations to
fit experimental data in internally consistent datasets (e.g. Berman
et al., 1986; Berman, 1988; Holland and Powell, 1998; Wunder and
Schreyer, 1997; Wunder, 1998) and this work is still progressing. Fur-
ther updates of reaction curves positions are likely. This review shows
a first-order general agreement between all the experimental works
which have been conducted since the 70s, as illustrated by the series
of P-T diagrams (Figs. 4–11).
Below 6 GPa, antigorite is the most abundant hydrous phase in the
mantle between 300 and 700 °C (Fig. 4). It is the rock-forming mineral
of serpentinites, which may include various other phases. Serpentinite
volumes transport large amounts of water into the mantle (Irifune et al.,
1998). During its transportation at depth, serpentine minerals transfer
water to other phases of the MSH system such as talc (e.g. Pawley and
Wood, 1995; Bose and Navrotsky, 1998; Bromiley and Pawley, 2003;
Figs. 4a and 5), HP hydrated talc (i.e. 10-Å and talc-like phases, e.g.
Chinnery et al., 1999; Fumagalli and Poli, 2005; Comodi et al., 2007) or
phase A (e.g. Pawley and Wood, 1996; Chinnery et al., 1999; Chollet
214 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Fig. 7. Stability of talc and 10-Å phase on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limit of talc and 10-Å phase up to 6 GPa, i.e. 200 km.
Reactions are indicated with coloured curves referring to different chemistry and H2O saturation as expected in a subduction context. See Fig. 2 for the background coloured dots. For
composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations and experiments-based numerical
studies, see the text. For sake of clarity, the stability of talc in the presence of chlorite or chloritoid is only drawn on Fig. 6. When not obvious, small black arrows refer to the reaction
sense as indicated in the reactions list. References: B.2000 = Bailey and Holloway (2000); B.1986 = Berman et al. (1986); C.1999 = Chinnery et al. (1999); C.2009 = Chollet et al.
(2009); C.1984 = Chopin (1984); E.1977 = Evans (1977); G.1984 = Guggenbuehl (1994); K.1966 = Kithara et al. (1966); P.1998 = Pawley (1998); P&W.1995 = Pawley and Wood
(1995); U&T.1999 = Ulmer and Trommsdorff (1999); W&S.1997 = Wunder and Schreyer (1997); Y&A.1977 = Yamamoto and Akimoto (1977).

Fig. 8. Stability of phase A and Mg-amphiboles on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limit of phase A, anthophyllite,
cummingtonite, tremolite and tschermakite up to 6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry. See Fig. 2 for the background
coloured dots. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations and experiments-based
numerical studies, see the text. When not obvious, small black arrows refer to the reaction sense as indicated in the reaction list. References: B.1986 = Berman et al. (1986);
B&N.1998 = Bose and Navrotsky (1998); H.2006 = Hilairet et al. (2006); J.1983 = Jenkins (1983); P&W.1995 = Pawley and Wood (1995); P&W.1996 = Pawley and Wood (1996);
T.1983 = Trommsdorff (1983); U&T.1999 = Ulmer and Trommsdorff (1999); W&S.1997 = Wunder and Schreyer (1997); W.1998 = Wunder (1998).
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 215

Fig. 9. Stability of other relevant hydrous minerals on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limits of brucite, diaspore, clinohumites,
chondrodites, staurolite, carpholite and Sursassites up to 6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry. See Fig. 2 for the background
coloured dots. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations and experiments-based
numerical studies, see the text. When not obvious, small black arrows refer to the reaction sense as indicated in the reaction list. When not specified, the curves are adapted from
Chopin and Schreyer (1983). The gray shaded region corresponds to the reaction 2 Gth → Hmt + H2O (FO system; Majzlan et al. (2003)). References: B.1986 = Berman et al. (1986);
F.1998a = Fockenberg (1998a); F.1998b = Fockenberg (1998b); P&W.1996 = Pawley and Wood (1996); P.2000 =Pawley (2000); U&T.1999 = Ulmer and Trommsdorff (1999);
W.1997 = Weiss (1997); W&S.1997 = Wunder and Schreyer (1997); W.1998 = Wunder (1998).

Fig. 10. Stability of minerals in anhydrous peridotites on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limits of anorthite, spinel, garnets,
quartz, enstatite, corundum, kyanite and sapphirine in unhydrous peridotites up to 6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry. See
Fig. 2 for the background coloured dots. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details about the catalogue of published experimental investigations
and experiments-based numerical studies, see the text. When not obvious, small black arrows refer to the reaction sense as indicated in the reaction list. References: A.1975 = Ackermand
et al. (1975); B.1986 = Berman et al. (1986); B.1991 = Bohlen et al. (1991); H&P1998 = Holland and Powell (1998); H&E1971 = Hensen and Essene (1971); M&K.1998 = Morishita and
Kodera (1998); M.2001 = Morishita et al. (2001); O.1976 = Obata et al. (1976); O'H.1971 = O'Hara et al. (1971); U&S.2001 = Ulmer and Stalder (2001).
216 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Fig. 11. Stability of carbonate minerals in peridotites on a prograde metamorphic path. P-T diagram presenting up-to-date knowledge on the stability limits of carbonated peridotites up to
6 GPa, i.e. 200 km. Reactions are indicated with coloured curves referring to different chemistry. See Fig. 2 for the background coloured dots. For composition and abbreviation of mineral
phases, see Tables 2 and 3. For details about the catalogue of published experimental investigations and experiments-based numerical studies, see the text. When not obvious, small black
arrows refer to the reaction sense as indicated in the reaction list. The impact of CO2 saturation within the aqueous fluid is indicated for some decarbonation reactions in the CMSH system
(light and dark green; Tenthorey and Cox, 2003; Trommsdorff and Evans, 1977) and in the CMS system (light and dark gray lines after Zhou and Hsu, 1992). The shaded gray area refers to
all plausible positions of the stability curves in wet natural systems. Purple lines are contours of log10mCaCO 3 (calcite concentration in aqueous fluid) as a function of P and T, without
considering the calcite-aragonite transition (Caciagli and Manning, 2003). References: J&P.1971 = Johannes and Puhan (1971); K.1975 = Kushiro et al. (1975); M.1996 = Martinez
et al. (1996); W&H.1976 = Wyllie and Huang (1976); Z&H.1992 = Zhou and Hsu (1992).

et al., 2009; Fig. 8). Especially, 10-Å phase, i.e. a HP hydrated talc bearing stability field (Comodi et al., 2007). Other hydrated talc phases (e.g.
13.6 wt% H2O (Yamamoto and Akimoto, 1977), has been identified as a Chinnery et al., 1999; Perrillat et al., 2005) have been discovered experi-
good candidate for water transfer into the mantle beyond the antigorite mentally. Such HP phyllosilicates are inexistent or extremely rare on the

Fig. 12. Antigorite metasomatism and influence of H2O saturation on its stability. P-T diagram presenting the evolution of antigorite a-axis wavelength m (green numbers and lines;
Wunder et al., 2001) and stability limit depending on H2O saturation (blue numbers and lines; Perrillat et al., 2005). See Fig. 2 for seismicity (background coloured dots). See Fig. 4 for
references of reaction curves (black lines).
 T.P. Ferrand / Lithos 334–335 (2019) 205–230 217

Table 2
Anhydrous phases and associated formula considered in this study.

CaO-MgO-Al2O3-SiO2 system (CMAS), except carbonates (see Table 3), for pressures between 0.5 and 6.5 GPa. Here the Fe2+ content is only indicated for hematite, olivine and ilmenite, but
minor substitution of Mg2+ by Fe2+ is common in all magnesium silicates. The last column indicates in which figures the phases are involved. P-T diagrams that direclty deal with the
stability of a phase are indicated with a bold number. When numbers are not bold, it means that the phase is involved in a reaction in a P-T diagram that does not focus on this phase.

Earth surface, as they are prone to localize deformation, which prevents
preservation throughout exhumation. For instance, a “talc-like” phase
was initially observed thanks to in-situ X-ray diffraction during HP-HT ex-
periments investigating the stability limit of antigorite (Perrillat et al.,
2005; Fig. 4), and a similar phase was recently observed on the field
(Plümper et al., 2017). The 10-Å phase has an intermediate composition
and structure between talc and vermiculite (Pawley and Wood, 1995).
The “talc-like” phase has an intermediate composition between talc and
the 10-Å phase (Perrillat et al., 2005) and should have intermediate struc-
ture. The water-poor 10-Å phase evidenced by Chinnery et al. (1999; “10-
Å(0.65)” in Table 1) could actually be one of the so-called “talc-like” phases.
The relative stabilities of HP hydrated talc phases should depend, as for
serpentines and talc, on H2O saturation (e.g. Perrillat et al., 2005;
Hilairet et al., 2006) and SiO2 activity (e.g. Worden et al., 1991;
Manning, 1995).
In the MSH system, it seems that a large diversity of high-grade
phases exists, some of which having close composition or structure.
Most of the dense hydrous phases would be stable in a P-T range of a
few GPa and some hundreds of degrees. In addition, hot slabs may en-
dure seismicity due to Mg-amphiboles destabilization (e.g.

Table 3
Carbonate phases and associated formula considered in this study.

Carbonate phases in the CaO-MgO-Al2O3-SiO2-CO2-H2O system for pressures between 0.5 and 6.5 GPa. The mentioned hydrated carbonates are stable in serpentinite, but their stability
limits have not been determined yet. P-T diagrams that direclty deal with the stability of a phase are indicated with a bold number. When numbers are not bold, it means that the
phase is involved in a reaction in a P-T diagram that does not focus on this phase.
218 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Fig. 13. Seismicity in the subducting mantle beneath northern Chile. (a) Relocated events from 2007 to 2014 on a W-E profile 21.5°S after Sippl et al. (2018), with thermal model from
Wada and Wang (2009) with extrapolation from 150 to 200 km depth considering a constant slab dip of 21°; (b) P-T diagram showing conditions at hypocentres within the subducting
mantle according to section (a); (c) Same as (a) considering an additional bend of 14° from the centre of the highly seismic body, consistently with the slab geometry at that latitude (Sippl
et al., 2018) as confirmed by attenuation tomography (Schurr et al., 2006); (d) P-T diagram showing conditions at hypocentres within the subducting mantle according to section (c);
(e) W-E cross-section at latitude 23°S; (f) P-T diagram for section (e). For the cross-sections, the horizontal axis indicates the distance from the trench. On the P-T diagrams, the curves
show the stability limits of chrysotile (Chr), antigorite (Atg), talc (Ta) and clinochlore (Chl). For each of these phases, colour shades indicate the destabilization P-T window depending
on local variations of peridotite bulk composition in the MSH and/or MASH systems. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details see Figs. 4–7.
For additional phases see Figs. 8–10. References: B.1986 = Berman et al. (1986); P.2003 = Pawley (2003); P.2005 = Perrillat et al. (2005); S&S.1977 = Staudigel and Schreyer
(1977); U&T.1999 = Ulmer and Trommsdorff (1999); W&S.1997 = Wunder and Schreyer (1997).

Greenwood, 1963; Berman et al., 1986; Evans and Ghiorso, 1995; Fig. 8);
in cold slabs, humites could be involved (Akimoto et al., 1977;
Trommsdorff and Evans, 1980; Evans and Trommsdorff, 1983; Dymek
et al., 1988; Weiss, 1997; Fig. 9).
In nature, mostly due to chemical variability (see Section 4.2), even
more phases exist, a significant number of which may have not been
discovered yet. In this study I especially emphasize the MASH system,
in which many phases have stability limits fitting seismological
observations, e.g. chlorite (e.g. Staudigel and Schreyer, 1977; Pawley,
2003; Fumagalli et al., 2014), Mg-Chloritoid (Vidal et al., 1994), Mg-
Carpholite (Viswanathan, 1981; Ferraris et al., 1992; Vidal et al.,
1992), Mg-Staurolite (Fockenberg, 1998a), Yoderite (Schreyer, 1988),
and Mg-Sursassites (also known as MgMgAl-pumpellyite; Schreyer
et al., 1991; Fockenberg, 1998b; Bromiley and Pawley, 2002). Except
chlorite, these phases of the MASH system have not been reported in
natural HP chlorite-bearing harzburgites that formed via serpentinite
dehydration (Evans and Trommsdorff, 1978; Trommsdorff et al.,
1998). It is important to recall here that, as most phases are involved
in retrograde reactions during exhumation processes (e.g. Figs. 6 and
9), they could be rare on outcrops and still have an important role at
depth.
4.1.2. Diversity of phases within serpentinites
Serpentinite bodies contain additional phases, such as serpentine-
like hydrated inosilicates, i.e. carlosturanite (Compagnoni et al., 1985;
17.14 wt% H2O), and balangeroite (Compagnoni et al., 1983;
Bonaccorsi et al., 2012; 11.95 wt% H2O). Depending on bulk composition
and H2O saturation, carlosturanite forms in the stability field of
antigorite through the reaction 6 Chr + 3 Br + 3 H2O → Crl and
balangeroite through the reaction 8 Chr + 18 Br → Bal + 14 H2O
(Evans, 2004). The stability limits of these minerals are unknown but
they have been evidenced as stable together with antigorite and chrys-
otile (Ferraris et al., 1987; Groppo and Compagnoni, 2007). Even if they
are rarely observed in natural samples, we cannot exclude that such
phases could reach higher ratios at depth within H2O-saturated
serpentinized faults.
Other serpentine minerals may also share part of the stability field of
chrysotile, lizardite and antigorite, such as polygonal serpentine (e.g.
Mellini, 1986; Mitchell and Putnis, 1988; Viti, 2010; Baronnet and
Devouard, 1996), conical serpentine and polyhedral serpentine
(Andreani et al., 2008; Cressey et al., 2008). These serpentine minerals
were found stable within antigorite-rich rocks (e.g. Banfield et al.,
1995) but their stability limits are unknown.
 T.P. Ferrand / Lithos 334–335 (2019) 205–230
Bulk composition (Section 4.2.1), mineral chemistry (Section 4.2.2)
and fluids (Section 4.2.3) are known as the key parameters controlling
relative stabilities of these phases within serpentinites, along with
antigorite polysomatism (Section 4.2.3). Especially, structural reorgani-
zation and H2O redistribution in serpentinites or serpentinized perido-
tites is likely to occur.
4.1.3. The question of “metastability”
Chrysotile is said to be “metastable” (Evans, 2004) as it may trans-
form to other serpentine minerals with same composition and different
structure through recrystallization under hydrothermal conditions.
Lizardite has also been noticed as “metastable” (e.g. O'Hanley et al.,
1989; Mellini and Zanazzi, 1989). A significant number of studies refer
to “metastability”, “metastable dehydration reactions” or “metastable
extension” of the antigorite stability field (e.g. Trommsdorff and
Evans, 1980; Wunder and Schreyer, 1997). Many studies questioned
the potential link between subduction seismicity and the dehydration
of serpentine minerals (e.g. Peacock, 2001; Hacker et al., 2003; Abers
et al., 2013).
Antigorite “metastability” is especially invoked to explain why its
dehydration curve does not fully fit the lower Wadati-Benioff plane of
double seismic structures (e.g. Peacock, 2001). Indeed, as shown in
Fig. 4, a significant part of the seismicity does not fit antigorite destabi-
lization, even when bulk composition and phases chemical variability
are considered (Fig. 4; Sections 4.2.1 and 4.2.2). However, experimental
work evidenced that, for pressures between 1 and 6 GPa, antigorite de-
stabilizes quickly in the stability field of Fo + En + H2O (above 600–700
°C), which suggests that “metastable” antigorite does not exist in a
subducted slab (Inoue et al., 2009; Ferrand et al., 2017).
The kinetics of antigorite dehydration is fast enough to trigger brittle
failure in subduction conditions (Perrillat et al., 2005; Ferrand et al.,
2017; Liu et al., 2019), it is not metastable (Inoue et al., 2009; Ferrand,
2019). Hence, other phases (Fig. 4), are likely not to be metastable,
which was demonstrated for talc and 10-Å phase (Chollet et al., 2009).
By definition, metastability is the ability of a mineral to persist for an
unbounded time in an unstable equilibrium or metastable state. The ki-
netics of metamorphic reactions depends on the presence of a fluid
phase, which dramatically increases the mobility of atoms within a
rock volume (e.g. Fyfe, 1958; Rubie, 1990, and reference therein). In
other words, the absence of fluids is known to favor metastability. But
for dehydration reactions, this kinetic effect is in competition with
H2O saturation. Indeed, as a reaction product, H2O stabilizes antigorite
(Figs. 4 and 12; Perrillat et al., 2005). “Metastability” in transforming
serpentinites at subduction conditions could actually be due to fluid cir-
culations within serpentinized faults, allowing ions mobility between
different regions of the serpentinized peridotite. Fluid percolation and
repeated circulation events may allow reaction products to migrate, as
a supercritical fluid, up to the subduction channel. In other words, igno-
rance on local variations of mantle composition and connectivity of
potential fluid pathways seems to be called “metastability”. The latter
may also refer to the difference in the position of stability limit in the
P-T diagram between theoretical pure phases and natural minerals
with variable ions diversity (Section 4.2.2).
4.2. Parameters controlling phases stability
4.2.1. Impact of bulk composition on the stability of mineral assemblages
As summarized in Fig. 2. Bulk composition seriously impacts the sta-
bility limit of major mantle hydrous phases, especially depending on the
presence of brucite, enstatite and forsterite in the vicinity of the latter.
Figs. 4–7 detail the various reactions that could affect antigorite
(Fig. 4), chrysotile, lizardite (Fig. 5), chlorite, Mg-chloritoid (Fig. 6)
and talc (Fig. 7) in the MSH system and other systems that are relevant
for serpentinized mantle.
219
4.2.1.1. Stability of each phase depending on bulk composition. In the MSH
system, antigorite dehydration occurs at pressures and temperatures
respectively ≈2 GPa and ≈150 °C lower in brucite-saturated condi-
tions (Fig. 4). Similar observations are made for chrysotile (Fig. 5),
even if the reaction Chr + Br → A + 10Å + H2O is deduced
from the overall topology of the system and was not directly tested
with dedicated experiments. Similar observations are made in the
MASH and CMASH systems or for any other chemistry, e.g. includ-
ing minor amounts of Fe, Ni or Cr, which do not change the topol-
ogy of the overall system.
Within peridotites the stability of clinochlore, the Mg-chlorite,
depends on the presence of enstatite in the system, but it only shifts
the stability curves by ≈50 °C down (Fig. 6). Other minerals, such as ky-
anite, diapore and corundum, which would reduce clinochlore stability
by tens of degrees, are not expected in the deep mantle, except if local
high-Al, low-Mg metasomatism exists in near Moho-conditions. Espe-
cially, between 2 and 5 GPa, Mg-chloritoid, poor in Mg compared to
clinochlore, may form from chlorite between 400 and 550 °C and desta-
bilize between 600 and 750 °C depending on the presence of Al-rich
minerals. Furthermore, in a talc-rich system, Mg-chloritoid is
destabilized at ≈3.5 GPa, leading to the formation of Mg-sursassite
(Fockenberg, 1998b).
Quartz or aqueous SiO2 may also be present within peridotites (e.g.
Bonnemains et al., 2017), which, at 2 GPa, lowers the stability of
clinochlore by 300 °C and 4 GPa. On the contrary, moderate SiO2 activity
transforms chrysotile and lizardite into antigorite and tends to stabilize
antigorite; furthermore, high SiO2 activity transforms serpentine min-
erals into talc (Schwartz et al., 2013). Chrysotile also transforms to
antigorite in the presence of talc or tremolite (Fig. 5). The extent of
talc occurrence depends, as the latter, on the bulk Mg-Si ratio (Pawley
and Wood, 1995). Especially, the presence of forsterite decreases the
stability of talc by ≈100 °C at 1 GPa to ≈250 °C at 2.5 GPa (Berman
et al., 1986; Pawley, 1998). Hence considering near-Moho forsterite-
poor bulk composition, talc may stay stable or heterogeneously trans-
form, especially depending on fluid circulation and ion charge of these
fluids.
4.2.1.2. Coexisting hydrous phases. In nature, various minor phases may
coexist within serpentinite bodies or along serpentinized faults. Nota-
bly, coexisting phases may be less stable than each phase of the mixture.
For example, at 3 GPa, antigorite (Fig. 4) and talc (Fig. 7) are stable up to
≈650 °C and ≈750 °C respectively, and the association of those phases
destabilizes around 570 °C (Figs. 4 and 7). Note that similar behavior is
observed with brucite, as the latter dehydrates above 1000 °C at those
pressures (e.g. Berman et al., 1986; Kanzaki, 1991; Fig. 9). Between 2
and 4 GPa, the association talc-chlorite-chloritoid is also less stable
than any of the three phases involved (Figs. 6 and 7).
Within peridotites, talc is generally considered stable up to 1.5 GPa
and 700 °C only and most studies show pseudosections in which talc
is absent at higher pressures (e.g. Fumagalli and Poli, 2005; Padrón-
Navarta et al., 2013). Nevertheless, talc itself can be stable to much
higher P and T, depending on its chemistry and on the mineralogical en-
vironment (e.g. Yamamoto and Akimoto, 1977; Pawley and Wood,
1995). Experimental data (Fig. 7) show that talc within peridotites can
only be stable up to 2 GPa at 500 °C and 1.5 GPa at 600 °C; but talc within
antigorite-rich serpentinites is, depending on chemistry, stable to
3–4 GPa at 500 °C and 2.5–4 GPa at 600 °C. As a consequence,
considerding potential high hydration in near-Moho conditions or
along deep bending faults, talc may locally exist within deep
serpentinites.
Potential structural associations of hydrous phases are discussed in
Section 4.2.5.
4.2.2. Impact of chemical composition on mineral stability
In dry mantle peridotite, Al is mostly present in spinel and garnets,
but some Al also integrates clinopyroxenes. In contrast, in serpentinized
220 T.P. Ferrand / Lithos 334–335 (2019) 205–230

Table 4
Composition of antigorite samples from various studies.

Composition of oxides. Contributions below 0.05 for all samples are not indicated.
a
Corrected for Carbonate impurity and absorbed water; *This study.
Depending on the study, bulk analysis (Bulk an.) was performed by electron microprobe (EMP), X-ray fluorescence (XRF) or XRD (X-ray diffraction; this study). When investigated, H2O
m M mFe3þ
and iron ions determination (det.) is specified. X Mg ¼ 1=ð1 þ mFe Mg
Mg MFe
Þ; X Fe3þ ¼ ðm þmFe2þ Þ. References: E.1976 = Evans et al. (1976); J&S.1981 = Johannes and Schreyer (1981); W&S.1997
Fe3þ

= Wunder and Schreyer (1997); U&T.1995 = Ulmer and Trommsdorff (1995); B&P.2003 = Bromiley and Pawley (2003); P.2005 = Perrillat et al. (2005); I.2009 = Inoue et al. (2009);
G.2011 = Gasc et al. (2011); G.2017 = Gasc et al. (2017); F.2017 = Ferrand et al. (2017).

peridotites substantial Al is preferentially integrated into various hy-
drous phases, such as chlorite or other Al-rich phases (Fig. 6), but also
in smaller amounts in MSH minerals, e.g. antigorite (Fig. 4), lizardite
(Fig. 5) or talc (Fig. 7).
4.2.2.1. Antigorite composition and stability. Natural antigorite has sys-
tematic compositional variations depending on its origin due to differ-
ent formation contexts (Uehara and Shirozu, 1985), as confirmed by
various analyses using electron microprobe or X-ray fluorescence
(Table 4). Comparing the MSH and MASH compositions (Bromiley and
Pawley, 2003), the reaction Atg → 14 Fo + 20 En + 31 H2O is shifted
by 40–100 °C at 2 and 5 GPa, respectively (Fig. 4). This stabilizing effect
of Al3+ on antigorite seems even greater with increasing cations diver-
sity, e.g. adding Fe2+ or Ni2+ in antigorite, or adding Ca2+ or Cr3+ in the
serpentinite (e.g. Ulmer and Trommsdorff, 1995), which is likely for
most of the unpublished natural compositions (e.g. Bose and
Navrotsky, 1998). Such inclusive compositions would stretch the stabil-
ity limit by 60–150 °C compared to the MSH composition (Fig. 4). In ad-
dition, it is important to note that the “Al-bearing” sample of Bromiley
and Pawley (2003) is also Fe-rich and that Fe determination was not
performed. When Fe3+, as a trivalent cation, could stabilize antigorite
to higher T and P (Bromiley and Pawley, 2003; Padrón-Navarta et al.,
2008, 2013; Debret et al., 2014; Debret et al., 2015) via Tschermak sub-
stitutions (Evans et al., 2012; Padrón-Navarta et al., 2013), Fe2+ is
known to decrease its stability by ≈ 15 °C (Fig. 4, CMASH system, 0.8
b XFe b 1%; Ulmer and Trommsdorff, 1999). Considering these two an-
tagonist effects, 10 wt% FeO reduces antigorite stability by only 25 °C
(Merkulova et al., 2016).
4.2.2.2. Composition and stability of other hydrous phases. Chrysotile and
polygonal serpentine may bear some Al (e.g. Andreani et al., 2007, 0.5
and 4 wt% of Al2O3). On the contrary, lizardite naturally bears substan-
tial Al. The impact of Al on the stability of lizardite has been studied at
low pressure (Chernosky, 1973a, 1973b; Caruso and Chernosky,
1979), i.e. a shift by ≈ 60 °C between Lz(0.2) and Lz(0.5) (Fig. 5; see
Table 1 for compositions). The stability of amesite, the Al-serpentine,
often confused with chlorite, is not well known but is likely to be
much greater (Ackermand et al., 1975).
Clinochlore is the hydrous silicate that stays stable the longest in pe-
ridotites below 5 GPa (Staudigel and Schreyer, 1977; Pawley, 2003;
Fumagalli et al., 2014). Its stable structure may include various cations,
such as Fe2+ or Cr3+ in significant quantities (e.g. Ulmer and
Trommsdorff, 1999; Fumagalli et al., 2014). Notably, such compositional
variations may delay the reaction Chl + 2 En → 2 Fo + Py + H2O by
30–80 °C.
Talc composition does not usually vary much from the end-member
formula Mg3Si4O10(OH)2 (Pawley and Wood, 1995), with as most com-
mon substitutions up to ≈0.15 Al replacing Si and ≈ 0.1 Fe replacing Mg
(Deer and Zussman, 1962). Nonetheless, such substitutions may shift
talc stability by 80–100 °C (Fig. 7; Ulmer and Trommsdorff, 1999). Com-
paring talc stability in the CMSH and CMASH systems, Al3+ appears to
stretch the reaction Ta + Fo → 5 En + H2O by N100 °C at 2 GPa. Compar-
ing the MSH and CMASH systems, the reaction Ta → 3 En + Coe + H2O
is shifted by N120 °C at 4 GPa (Fig. 7).
The stability fields of the 10-Å phase (Fig. 7) and phase A (Fig. 8) are
also shifted to higher pressures due to ions diversity, so that their ther-
mal limit decreases by some tens of degrees (e.g. Chollet et al., 2009;
Ulmer and Trommsdorff, 1999).
According to the literature, chemistry has limited impact on the sta-
bility of Mg-amphiboles (Fig. 8). However, substantial amounts of triva-
lent cations, especially Al3+ and Fe3+, are preferentially incorporated in
amphiboles by Tschermak substitution (e.g. Ulmer and Trommsdorff,
1999), which leads to various structures and stabilities. For instance,
tschermakite, i.e. Al-tremolite (Jenkins, 1983), is stable to ≈ 880 °C
(i.e. limit shifted by 70 °C) at low pressure. Also, and most importantly,
it should be noticed that cummingtonite, the monoclinic polymorph of
anthophyllite, is stable to 2 GPa at ≈740 °C (MSH system), which can
be extended to ≈780 °C if the iron content reaches 25% (Evans and
Ghiorso, 1995). Thus, as for serpentine minerals, the breakdown of am-
phiboles could explain a large part of mantle earthquakes within hot
subducting slabs (Fig. 8).
Finally, clinohumite, which could be seen as a HP hydrated olivine, is
widely observed in antigorite rocks, stabilizing by adapting its
 T.P. Ferrand / Lithos 334–335 (2019) 205–230
composition to P-T conditions (e.g. Trommsdorff and Evans, 1980;
Evans and Trommsdorff, 1983; Scambelluri et al., 1991; Weiss, 1997).
Indeed, clinohumite can bear substantial Fe2+, Fe3+, Ti3+ and F−,
stretching its stability limit by hundreds of degrees (Fig. 9; e.g. López
Sánchez-Vizcaíno et al., 2005).
4.2.2.3. Anhydrous phases. Anhydrous phases (Fig. 9; Table 2) also have
varying compositions. Various proportions of Al3+ or Ca2+ in pyroxens
and garnets significantly change their stability fields (e.g. Morishita
et al., 2001; O'Hara et al., 1971). Nevertheless, as the latter form solid so-
lutions, they are not likely to destabilize abruptly, but rather gradually
adjust their composition to the P-T evolution. For this reason, only a
few compositions are considered in Fig. 9.
4.2.2.4. Carbonated peridotites. Below 1 GPa, mechanical instabilities in
carbonates are involved in seismicity (e.g. Kurzawski et al., 2016). At
higher pressures, considering carbonated peridotites and CO2 in the
aqueous fluid (e.g. Trommsdorff and Evans, 1977; Zhou and Hsu,
1992), additional reactions should be considered (Fig. 11). Carbonate
phases that are expected in carbonated peridotites are listed in
Table 3. Some serpentinite decarbonation reactions are considered
(Tenthorey and Cox, 2003; Trommsdorff and Evans, 1977), but most
of the knowledge focuses on anhydrous systems up to date (Kushiro
et al., 1975; Martinez et al., 1996; Wyllie and Huang, 1976; Zhou and
Hsu, 1992). As suggested by Fig. 11, some of these reactions fit mantle
seismicity. Near the Moho, peridotite carbonation is expected (e.g.
Wyllie and Huang, 1976) and associated decarbonation reactions
seem to fit part of the mantle seismicity. Hydrous carbonates (Table 4)
are most likely in hydrated peridotites but, unfortunately, their stability
fields have not been studied yet.
4.2.2.5. Phase transitions. Enstatite, one of the most abundant phases in
peridotites, endures two transitions in the P-T window considered in
this study. Both of them fit some mantle seismicity (Fig. 10). Especially,
the transition lcEn → oEn surprisingly fits seismicity beneath Hokkaido
at 5–5.5 GPa. Furthermore, recent experimental work (Xu et al., 2018)
suggests that the high-pressure transition in orthoenstatite above
12 GPa (≈400 km) triggers part of the deep earthquakes.
The quartz-coesite transition correlates particularly well with the
seismicity beneath Hokkaido and Tohoku at ≈2.5 GPa. But quartz is
not expected in deep peridotites, except if quartz is locally present as
a minor phase. These earthquakes also correlate with the destabilization
of serpentine + brucite, which is more likely.
Several transitions in carbonates also correlate with seismological
observations (Fig. 10). For near-Moho mantle earthquakes (e.g.
Cascadia), the transition Ca → Ara could be involved in seismicity. For
the lower Wadati-Benioff plane of cold slabs (e.g. northern Japan), the
presence of carbonates is less probable, but the question of fluid circula-
tion in deep bending faults at trenches is still debated. If so, dolomite
could locally form in deep faults down to the brittle-ductile transition,
i.e. 20–40 km depth, and its decomposition during subduction could
play a role in seismicity.
Hence, surprisingly, this review highlights potential involvement of
phase transitions within serpentinites, peridotites or serpentinized pe-
ridotites between 1 and 6 GPa.
4.2.3. Impact of fluid composition and saturation level
4.2.3.1. Impact of H2O on antigorite stability. Antigorite stability is
known to depend on H2 O saturation (e.g. Perrillat et al., 2005;
Hilairet et al., 2006; Fig. 4). At 2.5 GPa, H2O saturation shifts the sta-
bility limit from 570 °C (Perrillat et al., 2005) to 670 °C at least
(Bromiley and Pawley, 2003; Ulmer and Trommsdorff, 1995).
Perrillat et al. (2005) showed that a “talc-like” phase forms in H2O-
unsaturated conditions, whereas antigorite remains stable in H2O-
saturated conditions. The stability limit gradually shifts to higher T
221
with increasing H2O activity, with a maximum in H2O-saturated con-
ditions (Fig. 12; Perrillat et al., 2005). Chrysotile dehydration (Fig. 5)
may contribute to H2 O saturation and delay antigorite instability.
Similarly, if brucite is present in the system in limited amounts,
part of antigorite could react at about 500 °C, stabilizing the system
via H2 O saturation, which would allow stress to rise again in the
fresh peridotite surrounding serpentinized zones (i.e. serpentinized
faults or ductile zones, e.g. Scambelluri et al., 2017).
It should be recalled that H2O saturation at high P most likely refers
to defects diffusing within crystals. In other words, neither sustainable
porosity nor fluid pressure is required.
4.2.3.2. Impact of H2O on the stability of other phases. Presumably, for any
phase, variations in H2O saturation could explain most of the remaining
discrepancies that cations variability does not account for. Furthermore,
supposing H2O-saturated conditions for most of the experimental
results, a reduction of the saturation in near-instability conditions for
any of the listed phases might shift the curves 50–100 °C toward
lower temperatures.
The H2O content may vary in the 10-Å phase (e.g. Pawley and Wood,
1995; Chinnery et al., 1999; Chollet et al., 2009), which has a large impact
on its stability (Fig. 7). Its ideal composition in the MASH system has been
established to be Mg3-y/2Aly/3Si4O10(OH)2·2H2O (Yamamoto and
Akimoto, 1977), with possible substitution of Mg2+ by Fe2+. As discussed
above (Section 4.1.1), Chinnery et al. (1999) actually studied the stability
of a near-10-Å phase, that could actually be one of the "talc-like" phases.
A possible explanation for the uncertainty in H2O-saturation during
talc stability tests (Fig. 7) is directly related to the existence of "talc-like"
phases that form during loading and heating, progressively integrating
H2O in their structure. In other words, to get H2O-saturated conditions
near the talc stability limit, a significant oversaturation is needed. As
argued by Chinnery et al. (1999), the H2O content of HP hydrated talc
should depend on the composition of the starting material, especially
trivalent cations. And, as the stability of all hydrated phases itself de-
pends on chemistry, little chemical variations are likely to significantly
change the stability limit of such partially hydrated talc minerals.
Ulmer and Trommsdorff (1999) reported large differences in the
experimentally deduced reaction Ta + Fo → 5 En + H2O (Kithara
et al., 1966; Yamamoto and Akimoto, 1977; Guggenbuehl, 1994;
Pawley, 1998) and argued that the only likely explanation they could
offer is possible differences in the activity of H2O in the different studies.
In other words, the results of Yamamoto and Akimoto (1977) would
correspond to water-saturated conditions whilst the experiments of
Pawley (1998) would represent water-free conditions.
4.2.3.3. Impact of CO2 on decarbonation reactions and antigorite stability.
Aqueous fluid circulating in faulted peridotites are likely to contain up
to 0.1 wt% CO2 (Trommsdorff and Evans, 1977; Zhou and Hsu, 1992).
If so, CO2 saturation influences (de)carbonation reactions:
Di þ Ca → Ak þ CO2
Wo þ Mc þ CO2 → Di þ Ca
These reactions are shifted to higher pressures by ≈1 GPa by de-
creasing CO2 saturation from 0.1 wt% down to 0.02 wt% (Fig. 11). As it
stabilizes carbonates, increasing CO2 saturation stabilizes antigorite,
but this effect is very limited (Tenthorey and Cox, 2003; Trommsdorff
and Evans, 1977).
4.2.4. Polysomatism, water content and mineral stability
4.2.4.1. Antigorite self-stabilized by polysomatism. Antigorite is an atypical
serpentine variety for several reasons that are detailed below. In the
MSH system, antigorite exhibits 12 ideal discrete compositions depend-
ing on P-T conditions (Wunder et al., 2001). According to Kunze (1961),
222 T.P. Ferrand / Lithos 334–335 (2019) 205–230

antigorite compositional variations can be expressed by the formula
M3m-3T2mO5m(OH)4m-6 where M are octahedral cationic sites (Mg2+,
Fe2+, Ni2+, Al3+), T are tetrahedral cationic sites (Si4+, Al3+, Fe3+)
and m is the number of tetrahedra in a single chain along the a-axis,
i.e. wavelength. Notably, antigorite H2O content depends on m. For nat-
ural antigorite, m = ⟦13;24⟧, which corresponds to [12.09;12.52] wt% of
H2O (Mellini et al., 1987), and m decreases with increasing metamor-
phic grade of serpentinites (Kunze, 1961; Uehara and Kamata, 1994).
In subduction P-T conditions, increasing T or decreasing P reduces m
(Fig. 12), which corresponds to a volume reduction of the antigorite
crystal lattice (Wunder et al., 2001). For 18 N m N 14 and depending
on relative amounts of brucite (stable to 400–500 °C in subduction
zones, Fig. 4a, 5 and 9) and H2O, successive polysomatism reactions
can be written as follows (Wunder et al., 2001; Fig. 12):
This means that H2O saturation should not favor the transformation
Chr → Atg or its reverse reaction (Wunder et al., 2001). Hence, as it is
not a dehydration reaction, antigorite could contribute to almost 100%
of serpentinites in brucite-poor environments, as suggested by field
observations.
Finally, even if most of the studies do not consider it as a key param-
eter, the stability limit of antigorite varies with P and m, as follows:
5 Atgð14Þ → 72 Fo þ 17 Ta þ 108 H2 O ðP ¼ ½0:5; 1:5 GPaÞ
AtgðmÞ → ðm−3Þ Fo þ ðm þ 3Þ En þ ð2m−3Þ H2 O ð14 bm b16Þ
5 AtgðmÞ → ðm−3Þ A þ ð2m þ 6ðm þ 1ÞÞ En
þ ðm þ 6ðm−1ÞÞ H2 O ð16 bm b18Þ

ð3 þ mÞ Atgðmþ1Þ → ð4 þ mÞ AtgðmÞ þ 6 Fo þ 9 H2 O
As explained in Section 4.2.3 and 4.2.1, these dehydration reactions
ðmþ1Þ ðmÞ are likely to be delayed depending H2O saturation and potential compo-
m Atg → ð1 þ mÞ Atg þ 3 Br
sitional variations.

This means that antigorite polysomatism reactions are minor
dehydration reactions, which may, to a certain extent, maintain H2O-
saturated conditions, i.e. self-stabilization (Perrillat et al., 2005;
Fig. 12). Depending on bulk composition and potential fluids, these
structural adjustments of antigorite may occur or not, which is likely
to shift its stability limit.
In addition, when chrysotile destabilizes in the stability field of
Atg(m), brucite is formed regardless of m as follows:
m Chr → AtgðmÞ þ 3 Br ð16bmb18Þ
4.2.4.2 H2O content of high-pressure hydrated talc phases: A polysomatic
series? As shown in previous sections, investigations on HP hydrated
talc are still very active, especially questioning the composition, struc-
ture and stability of “talc-like” phases (e.g. Perrillat et al., 2005; Chollet
et al., 2009). The 10-Å phase (e.g. Yamamoto and Akimoto, 1977),
which can be seen as one of the so-called “talc-like” phases, can be
written in the MASH system as (Mg,Al)3(Si,Al)4O10(OH)2·2H2O.
Complementary experiments evidenced a similar phase with lower
H2O-content, which is written (Mg,Al)3(Si,Al)4O10(OH)2·0.65H2O
(Chinnery et al., 1999), that I suggest as one of the “talc-like” phases.
Such variation in H2O content significantly changes the stability field

Fig. 14. Examples of interlayering and other close associations of hydrous minerals. (a) Scanning electron microscopy image showing an association between sudoite, clinochlore,
muscovite (Ms) and pyrophyllite in metasediments from Verrucano, Italy (adapted from Giorgetti et al., 1997). (b) High-resolution Transmission Electron Microscopy (TEM) image
(adapted from Dódony and Buseck, 2004) showing an intimate intergrowth interlayer of clinochlore, lizardite and chrysotile in the Baltimore mafic complex. Each of these structures
shows coherent, continuous boundaries with the others. (c-d) TEM images showing various associations between antigorite, clinochlore, dozyite (D), chrysotile and polygonal serpentine
(PS) in a serpentinite from Wood's Mine, Pennsylvania (adapted from Banfield et al., 1995). Polygonal serpentine develops as connexions between larger grains, mostly clinochlore. Ab-
breviations that are not specified here are detailed in Table 1.
 T.P. Ferrand / Lithos 334–335 (2019) 205–230
of HP hydrated talc (Fig. 7) and is considered to be due to H2O unsatu-
rated conditions during its formation (Chinnery et al., 1999).
Most probably, “talc-like” phases are a population of phases with
slightly variable lattice structures, close to talc and 10-Å phase, i.e.
with different water contents (e.g. Fumagalli and Stixrude, 2007), and
only formed in narrow P-T conditions. However, even if some enstatite
crystals are observed after antigorite dehydration, a “talc-like” phase is
formed and preserved above 800 °C (Ferrand et al., 2017), which indi-
cates that “talc-like” phases are stable at higher T than (low-pressure)
talc. Once these phases are formed, their stability could extend to high
pressure and temperature as for talc and 10-Å phase (e.g. Pawley and
Wood, 1995; Chollet et al., 2009).
In light of this review, and by comparison with antigorite, I propose
that talc and HP hydrated talc phases could be regarded as a
polysomatic series. Further investigations are required to understand
whether “talc-like” phases have discrete or continuous compositions.
4.2.5. Interlayering and other close mineral associations
Minerals of the serpentine, talc and chlorite groups are phyllosilicates.
As mentioned in Section 4.2.1, the stability fields of many hydrous silicates
discussed in this study overlap. Interactions between coexisting phases
may significantly reduce destabilization temperatures. However, close as-
sociation of phases may drive additional stability. In particular, associated
phases may stabilize each other by forming fully-fledged minerals, such
as kulkeite (e.g. Schreyer et al., 1982) or dozyite (Bailey et al., 1995).
Interlayering has been documented for various assemblages, such as
muscovite + chlorite (e.g. Giorgetti et al., 1997), lizardite + chlorite
(Dódony and Buseck, 2004) and chlorite + berthierine (Fe-Al-serpen-
tine; Xu and Veblen, 1996). Various associations between antigorite,
clinochlore, dozyite, chrysotile and polygonal serpentine were evi-
denced by Banfield et al. (1995). The latter studies presented SEM and
TEM images showing interlayered minerals and other close mineral as-
sociations forming coherent boundaries (Fig. 14).
In the MASH system, Al-free chrysotile may form depending on stoi-
chiometry within synthetic lizardite samples (Liz(0.2); Chernosky,
1973a). Lizardite and chlorite coexist and could stabilize each other
(Caruso and Chernosky, 1979). Intimate relations have been imaged be-
tween chrysotile, lizardite and clinochlore (Dódony and Buseck, 2004).
Dozyite (Bailey et al., 1995; Banfield et al., 1995) is a natural 1:1 regular
interstratification of trioctahedral serpentine and chlorite, with an inter-
mediate formula between clinochlore and amesite (Al-serpentine).
Kulkeite is a natural interlayered talc-chlorite mineral (Schreyer
et al., 1982). On the field, it may be confused with mica because of sim-
ilar shape and aspect. It is important to notice that the talc layer of
kulkeite is hydrated, and that observations suggest intermediate stabil-
ity between talc and chlorite (Schreyer et al., 1982), relevant for hot
subducted slabs (Figs. 4 and 5). Similarily, a mixed layered structure
formed of clinochlore and 10-Å phase was synthetized (Fumagalli and
Poli, 2005) and could thus be called HP (hydrated) kulkeite.
As stated by Fumagalli and Poli (2005), kulkeite would destabilize in
the presence of clinopyroxene (Ca,Mg)2Si2O6. For example, diopside
and kulkeite would transform into enstatite and garnet as follows:
Ku þ Di → 5 En þ Fo þ GtCaMg2 þ 5 H2 O
Kulkeite is qualified as “metastable” in chlorite-rich rocks (Schreyer
et al., 1982) and dozyite would also be stable up to 800 °C at least
(Banfield et al., 1995). However, as closely associated phases, they could
endure much faster transformation once the assembly becomes unstable.
Finally, interlayering is an alternative explanation for the most ex-
treme observed stability of talc (Fig. 7; e.g. Yamamoto and Akimoto,
1977) compared to theoretical reactions (Pawley, 1998). Possible
interlayered talc-like phases, i.e. with various H2O contents, could also
participate in the high stability of “talc-like” phases observed in the lab-
oratory (e.g. Ferrand et al., 2017).
223
4.3. A joint effect of successive minor transformation-driven stress
transfers?
4.3.1. A full correlation between seismicity and mineral transformations
Considering all the factors that control the stability of mineral assem-
blages in natural peridotite below 6 GPa (Section 4.2), I demonstrate that
a large majority of the stability limits drawn in Figs. 4–11 correlate with
mantle earthquakes beneath Japan, Cascadia and northern Chile. Thus, it
is reasonable to think that, if present, any of these reactions could partic-
ipate in peridotite embrittlement. Moreover, as suggested by geophysical
imaging (Ranero et al., 2003; Ivandic et al., 2010; Shillington et al., 2015)
and confirmed by most recent studies (Cai et al., 2018; Bloch et al., 2018),
the H2O transfer into the mantle is likely to occur thanks to deep
serpentinized faults, although almost all the peridotite remains fresh
within the downgoing slab (Reynard et al., 2010).
4.3.2. Transformation-driven grain size reduction and stress transfers
Intermediate-depth earthquakes are thought to initiate by thermal
runaway processes (e.g. John et al., 2009; Kelemen and Hirth, 2007).
Such strain localization is grain size sensitive and is likely to propagate
and accelerate by grain size reduction up to the unstable propagation,
i.e. seismic rupture (Thielmann et al., 2015; Thielmann, 2018a, 2018b).
Dehydration reactions of single phases are fast phenomena, as dem-
onstrated for antigorite (Perrillat et al., 2005; Inoue et al., 2009; Ferrand
et al., 2017) and talc (Chollet et al., 2009). Such transformations sud-
denly lead to extremely fine mineral aggregates (Ferrand, 2017), and
any other reaction is likely to induce grain size reduction. Grain size is
the key parameter driving strain localization by thermal runaway
(Thielmann et al., 2015; Thielmann, 2018a, 2018b). If hydrous phases
are present in a future fault zone, it is reasonable to include its dehydra-
tion in the strain localization process. For instance, antigorite dehydra-
tion may be either a cause or a consequence of strain localization (e.g.
Brantut et al., 2010, 2011; Brantut and Sulem, 2012; Platt et al., 2015).
Furthermore, any new HP phase or reaction discovered in the past
years allows imagining successive grain size reduction events, which
could actually participate in keeping relatively small grain size at some
places. For example, the discovery of yoderite (Schreyer, 1988), stable
from ≈750 to ≈870 °C between 1.5 and 2 GPa, adds a reaction curve
to Fig. 6, which correlates with earthquakes around 770 °C beneath Kii
or Cascadia. Such localized grain size reduction events could be accom-
panied by slow slab-scale continuous stress transfers, equivalent of
what was observed in the laboratory during the dehydration of slightly
serpentinized peridotites (Ferrand et al., 2017). These stress transfers
would largely be accommodated by “self-localizing” thermal runaway
(e.g. John et al., 2009), i.e. viscous flow in the periphery of transforming
mineral assemblies, i.e. planar patches. In other words, mineral transfor-
mations induce grain size reduction, which initiates strain localization
(e.g. Thielmann, 2018a, 2018b), driving local viscous flow propagating
by thermal runaway up to a regional mechanical instability, i.e. perido-
tite embrittlement.
According to the DDST model (Ferrand et al., 2017), at uppermost
mantle pressures, i.e. between 1 and 2 GPa, the dehydration reaction
is likely to drive a mechanical instability in peridotites only if the
dehydrating mineral constitutes a minor phase, e.g. 5 vol% in the exper-
iments (Ferrand et al., 2017). This volume ratio cannot be directly ex-
trapolated, as the phase network connectivity mostly depends on the
shape of the inclusions, which should be closer to surfaces than volumes
in nature, i.e. deep faults. Thus, some minor phases discussed in this
study may have major importance.
On one hand, increasing the number of phases should dispatch po-
tential stress transfers along a fault network, which would favor
aseismic deformation. On the other hand, regional variability in both
fault network geometry and phases diversity may drive significant
stress accumulations where reactions are rare or inexistent. It is then
important to keep in mind that antigorite (Fig. 4) and chlorite (Fig. 6),
in spite of significant influence of above-mentioned parameters on
224 T.P. Ferrand / Lithos 334–335 (2019) 205–230

their stability, are the most widely stable rock-forming hydrous phases
below 5 GPa and that their stability limits vary much less than the ones
of talc (Fig. 7) for example. Furthermore, considering local variations of
all above-mentioned parameters, N90% of the mantle earthquakes cor-
relate with antigorite destabilization; chlorite remains a good candidate
for earthquakes at higher temperatures.
Seismic fault nucleation in peridotites could originate in a chain
mechanism with grain size as central parameter. Sliding would become
unstable after a critical displacement at a certain scale, as suggested by
the DDST model (Ferrand et al., 2017). Considering potential fluid per-
colation and repeated circulation events, which would allow reaction
products to migrate up to the subduction channel, understanding the
triggering mechanisms of earthquakes in the slab mantle remains
challenging.
4.3.3. Dehydration embrittlement vs dehydration-driven stress transfer
The “dehydration-embrittlement” model (Raleigh and Paterson,
1965) hypothesizes fluid-induced embrittlement. According to this
model, brittle yielding of the rocks would be due to fluid overpressure
due to the dehydration of phases (e.g. Hacker et al., 2003; Frohlich,
2006). Firstly evidenced at low pressure in the laboratory (Raleigh and
Paterson, 1965), it could contribute to the triggering mechanism of
earthquakes in the upper Wadati-Benioff plane, especially during the
dehydration of lawsonite (Incel et al., 2017; Okazaki and Hirth, 2016).
As discussed by several papers (e.g. Reynard et al., 2010; Thielmann,
2018a), overpressure requires available fluids, which are not likely in
the subducting mantle, especially at depth N5 km below the Moho.
Moreover, most of the dehydration reactions (Figs. 4–8) induce a nega-
tive volume change (solid + fluid) between 1.5 and 5 GPa, which is in-
compatible with fluid overpressure (e.g. Jung et al., 2004; Gasc et al.,
2011).
Using both a rupture criterion (Ohnaka, 2003) and the percola-
tion theory (Stauffer and Aharony, 1992), the DDST model (Dehy-
dration-Driven Stress Transfer, Section 4.3.4) predicts that
mechanical instabilities could nucleate due to high stress intensity
at the tip of antigorite clusters in olivine-antigorite aggregates
(Ferrand et al., 2017). If so, depending on the regional stress
state, any unstable minor phase could locally induce a critical stress
transfer. The most important parameters controlling the earth-
quake triggering should be the relative dimensions of clusters of
unstable phase and volumes of stable peridotite, as well as the spa-
tial distribution of the clusters.

Fig. 15. Comparison between mantle earthquakes beneath Japan, Cascadia and Chile. (a) P-T diagram showing P-T conditions at hypocentres in the subducting mantle beneath Hokkaido,
Tohoku, Kii, Tokai and Cascadia (Abers et al., 2013), with additional data for northern Chile (latitude 23°S); (b) Same as (a) with additional data for northem Chile (21.5°S), i.e. where un-
certainties remain regarding the thermal structure due to both the change in subduction obliquity and the additional bend of the slab. Curves show the stability limits of chrysotile (Chr),
antigorite (Atg), talc (Ta) and clinochlore (Chl). For each of these phases, colour shades indicate the destabilization P-T window depending on local variations of peridotite bulk compo-
sition in the MSH and/or MASH systems. For composition and abbreviation of mineral phases, see Tables 1 and 2. For details see Figs. 4–7. For additional phases see Figs. 8–11. References:
B.1986 = Berman et al. (1986); P.2003 = Pawley (2003); P.2005 = Perrillat et al. (2005); S&S.1977 = Staudigel and Schreyer (1977); U&T.1999 = Ulmer and Trommsdorff (1999);
W&S.1997 = Wunder and Schreyer (1997).
 T.P. Ferrand / Lithos 334–335 (2019) 205–230
Stress state description in a polyphasic mineral aggregate depends
on the observation scale. Indeed, as experimentally demonstrated by
Ferrand et al. (2017), low sample-scale stress state can coexist with
local high stress intensities, especially due to local mineral transforma-
tions. Both experimental and seismological observations are consistent
with the DDST model, which appears more accurate than “dehydration
embrittlement” to explain mantle earthquakes. Recent field work
(Dunkel et al., 2017; Scambelluri et al., 2017; Ferrand et al., 2018) and
seismological data (Cai et al., 2018; Bloch et al., 2018; Kita and
Ferrand, 2018) together support DDST rather than dehydration embrit-
tlement to explain the earthquakes of the lower Wadati-Benioff plane.
4.3.4. Heterogeneity, phases connectivity and transformation-driven stress
transfers
In natural materials, homogeneity can be defined at a certain scale.
Nonetheless, rocks are usually assemblages of various minerals, con-
taining impurities at the grain scale, e.g. fluid inclusions, or at crystal lat-
tice scale, e.g. dislocations or ions substitution. At larger scales, lithology
contrasts have various origins and faults constitute additional heteroge-
neity. In other words, homogeneity remains a concept. During deforma-
tion, heterogeneities may interact. The evolution of this interaction has
been studied using percolation models (e.g. Lockner and Madden, 1991;
Hansen et al., 1991; Reuschle, 1998).
The percolation theory (Broadbent and Hammersley, 1957) allows
describing clusters connectivity in a system close to its critical state,
i.e. “percolation threshold”. Near the threshold, power laws describe
fractal evolution of clusters geometry (Stauffer and Aharony, 1992).
Widely used to study fluid circulations, the percolation theory has re-
cently been used to study mechanical stress (Tordesillas et al., 2009,
2011; Burnley, 2013). Mechanical interaction between clusters can be
numerically studied like interactions between fault segments (e.g.
Baud and Reuschlé, 1997). Moreover, statistical models of cracks and
crack length distribution give access to relative dimensions and specific
surfaces of the different phases in the system (e.g. Dienes, 1982;
Guéguen and Dienes, 1989).
A rock volume may deform and/or transform faster depending on
confinement and drainage conditions (e.g. Wong et al., 1997).
Dehydrating antigorite is first localized in veins containing the dehydra-
tion products (Hermann et al., 2000; López Sánchez-Vizcaíno et al.,
2005) and prone to form anastomosed channels within serpentinites
(Plümper et al., 2017). As discussed in Section 4.2.3, dehydration prod-
ucts mobility may strongly depend on the connectivity of hydrous
phases networks, leading to potential apparent metastability (Section
4.1.3). Finally, recent seismic attenuation studies (e.g. Shiina et al.,
2018) suggest that the lower Wadati-Benioff plane correlates with
slightly lower seismic velocities, which would be consistent with re-
peated strong rheological contrast on the waves pathway, e.g. between
serpentinized faults and fresh peridotite volumes, as argued by Ferrand
et al. (2017) and Kita and Ferrand (2018). Finally, recent high-
resolution data show that the lower plane of the subducting Nazca
plate contains a minor fluid phase (Bloch et al., 2018), which transiently
escapes through the slab toward the subduction interface. This is quite
consistent with theoretical calculations on generation and maintenance
of pore pressure excess in a dehydrating system (Wong et al., 1997). But
pore fluids in such conditions are transient, as the connectivity of fluid
pathways would be favored by preexisting heterogeneities (Debret
et al., 2013) and by the structure of serpentine minerals itself (Tutolo
et al., 2016; Schwarzenbach, 2016).
4.4. About northern Chile
Using relocated hypocenters (Sippl et al., 2018) and an accurate
thermal model (Wada and Wang, 2009), I show that the mantle earth-
quakes within the subducting Nazca plate beneath northern Chile could
be all triggered by mineral transformations (Fig. 13), consistently with
previous results for other subduction zones (Fig. 15; Abers et al., 2013).
225
Two distinct seismicity planes exist within the subducting mantle of
the Nazca Plate, separated by ≈25 km and merging into a highly seismic
body between 90 and 150 km depth (Sippl et al., 2018). The upper-
plane mantle seismicity could partly originate in somehow large back-
ground stresses in the vicinity of the subducting interface (b10 km
away), but could also be triggered by the destabilization of chrysotile
and lizardite, i.e. transition to antigorite (Fig. 5; Evans et al., 1976;
Evans, 2004; Schwartz et al., 2013).
The earthquakes of the lower Wadati-Benioff plane fully correlate
with the destabilization of serpentine minerals, i.e. dehydration reac-
tions (Fig. 13f and 15a). At latitude 21.5°S, however, it seems that the
lower-plane seismicity extends up to the limit of stability of talc
(Fig. 13b). This shift in temperature estimations (40 °C between
Fig. 13d and f), is likely to be due to a slight change in subduction obliq-
uity (Plunder et al., 2018), which happens around latitude 22°S (Sippl
et al., 2018).
The increase of seismicity at 90–100 km depth (Fig. 13), also ob-
served in Japan (Fig. 15), well correlates with pressure-induced
antigorite dehydration, i.e. transition to phase A in brucite-saturated
conditions (Atg + 71 Br → 17 A + 51 H2O). At higher pressures and
temperatures, the highly seismic body could be explained by a series
of transformations releasing minor amounts of H2O and forming HP
hydrated talc and phase A (Figs. 4 and 5). Taking into account the addi-
tional bend of the slab near 120 km depth (Fig. 13c), most of the seis-
micity between 3 and 6 GPa (90–200 km) correlates quite well with
serpentine and chlorite destabilizations. Notably, the highly seismic
body between 90 and 150 km (3–4.5 GPa) correlates with a series of de-
hydration reactions affecting chrysotile, antigorite and chlorite with
highly negative volume changes, which facilitates rupture nucleations.
Such observations are well consistent with experimental results, show-
ing that dehydration-induced earthquakes are triggered at much lower
temperatures above 3 GPa (Ferrand et al., 2017).
Because of its intermediate age (≈45 Ma), the Nazca plate
subducting beneath northern Chile and the Altiplano completes the
dataset of P-T conditions corresponding to the nucleation of mantle
earthquakes. Altogether, the relocated hypocenters show a wide range
of nucleation P-T conditions, confirming that, if mineral transformations
are involved in earthquakes triggering mechanisms, several reactions
are involved. Nonetheless, the destabilization of serpentine minerals
in various conditions (Figs. 4 and 5) remains sufficient to explain the
majority of the seismicity (Fig. 15), along with chlorite minerals for
the highest temperatures.
5. Conclusions
This study participates in checking the validity of the DDST model
(Dehydration-Driven Stress Transfer) compared to other models such
as dehydration embrittlement and self-localizing thermal runaway in
light of most recent experimental and seismological achievements. Min-
erals stability limits, which significantly vary with bulk composition,
phases chemistry (especially Al3+), fluid saturation, fluid composition
and other factors, show correlations with seismicity. Thus, if present,
any unstable mineral, listed in Tables 1, 2 and 3 or not, is likely to con-
tribute in the initiation of strain localization by significant grain size re-
duction, which drives further propagation by thermal runaway. As a
major part of the seismicity questioned here corresponds to P-T condi-
tions leading to significant negative volume changes upon dehydration,
fluid overpressure is not expected, especially for the lower Wadati-
Benioff plane of cold subducting slabs.
Previous experiments have shown that hydrous phases are not
metastable in the P-T window considered in this study (Perrillat et al.,
2005; Inoue et al., 2009; Chollet et al., 2009; Chollet et al., 2011). More-
over, studies on dehydrating antigorite show stable sliding and aseismic
deformation in deep serpentinites (Chernak and Hirth, 2010, 2011; Gasc
et al., 2011, 2017; Okazaki and Hirth, 2016) when serpentinized
226 T.P. Ferrand / Lithos 334–335 (2019) 205–230
peridotite show embrittlement in the same conditions (Jung et al.,
2004; Jung and Green, 2004; Xia, 2013; Ferrand, 2017; Ferrand et al.,
2017).
Antigorite destabilization correlates with most of the mantle seis-
micity studied. However, the series of P-T diagrams presented here
show that antigorite stability alone does not explain all observed mantle
seismicity (Fig. 4), and that other serpentine minerals (Fig. 5), along
with other hydrous phases should be involved. For instance, as sug-
gested by previous studies (e.g. Hacker et al., 2003; Abers et al., 2013),
chlorite remains a good candidate to explain HT seismicity in hot mantle
slabs (e.g. Kii, Tokai and Cascadia; Fig. 6) as well as beneath northern
Chile (Figs. 13 and 15). Notably, the transitions from serpentine min-
erals to phases A and 10-Å correlate with higher mantle seismicity be-
tween 90 and 150 km depth.
Mantle earthquakes between 0.5 and 6 GPa, at least, are very likely
to be triggered by dehydration reactions. This could also play a role in
the triggering process of other earthquakes, such as upper-plane earth-
quakes. Disqualified in the laboratory (Gasc et al., 2011, 2017; Okazaki
and Hirth, 2016; Ferrand et al., 2017), “dehydration embrittlement” is
not likely in the slab mantle at intermediate depths. Up to date, DDST
(Ferrand et al., 2017) remains the most accurate model to explain the
earthquakes of the lower Wadati-Benioff plane. Furthermore, as
discussed in this paper, DDST would not be contradictory with thermal
runaway models, but complementary.
Water-free transformations (e.g. antigorite formation; Fig. 5) and
anhydrous reactions (Fig. 10), especially the enstatite transitions,
might be involved in the triggering mechanism of earthquakes within
slabs at cold subduction zones. The paragenetic evolution of Al reparti-
tion in peridotite (Fig. 10) and decarbonation reactions (Fig. 11) also
show meaningful correlations, which require further investigations. In
any case, the “Transformation-Driven Stress Transfer” (TDST) involves
minor phases that are prone to induce local grain size reduction. These
local metamorphic transformations are likely to drive stress transfers
that initiate catastrophic strain localization in the mantle.
Acknowledgments
I thank Christian Sippl for his explanations about recent relocation
data beneath Chile, Ikuko Wada for giving me access to the up-to-date
thermal structure at latitude 23°S, and Nadège Hilairet and Javier
Escartín for the thoughtful discussions. Many thanks to Natsumi
Hokanishi for her help with XRF analysis and to Hatsuki Yamauchi and
Takehiko Hiraga for great support. I thank the International Research Pro-
motion Office of the Earthquake Research Institute for supporting this
study. I also thank Philippe Agard, associate editor of the special issue,
and two anonymous reviewers, whose comments strongly improved
the paper.
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