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ARTICLE
Trace-element geochemistry of transform-fault serpentinite in
high-pressuresubduction mélanges (eastern Cuba): implications for
subduction initiationJ. Cárdenas-Párraga a, A. García-Casco a,b, J.
A. Proenza c, G. E. Harlow d, I. F. Blanco-Quintero e,C. Lázaro a,
Cristina Villanova-de-Benavent c and K. Núñez Cambraf
aDepartamento de Mineralogía y Petrología, Universidad de
Granada, Granada, Spain; bInstituto Andaluz de Ciencias de la
Tierra, CSIC-Universidad de Granada, Granada, Spain; cDepartament
de Mineralogia, Petrologia i Geologia Aplicada, Universitat de
Barcelona, Barcelona,Spain; dDepartment of Earth and Planetary
Sciences, American Museum of Natural History, New York, NY, USA;
eDepartamento deGeociencias, Universidad de los Andes, Bogotá,
Colombia; fInstituto de Geología y Paleontología, San Miguel del
Padrón, Cuba
ABSTRACTThe Sierra del Convento and La Corea mélanges (eastern
Cuba) are vestiges of a Cretaceoussubduction channel in the
Caribbean realm. Both mélanges contain blocks of oceanic crust
andserpentinite subducted to high pressure within a serpentinite
matrix. The bulk composition ofserpentinite indicates
spinel-harzburgite and -herzolite protoliths. The samples preserve
fertileprotolith signatures that suggest low melting degrees. High
concentration of immobile elementsZr, Th, Nb, and REE contents
(from ~0.1 to ~2 CI-chondrite) point to early melt–rock
interactionprocesses before serpentinization took place. Major- and
trace-element compositions suggest anoceanic
fracture-zone–transform-fault setting. A mild negative Eu anomaly
in most samplesindicates low-temperature fluid–rock interaction as
a likely consequence of seawater infiltrationduring oceanic
serpentinization. A second, more important, serpentinization stage
is related toenrichment in U, Pb, Cs, Ba, and Sr due to the
infiltration of slab-derived fluids. The mineralassemblages are
mainly formed by antigorite, lizardite, and chlorite, with local
minor talc,tremolite, anthophyllite, dolomite, brucite, and relict
orthopyroxene. The local presence of antho-phyllite and the
replacements of lizardite by antigorite indicate a metamorphic
evolution from thecooling of peridotite/serpentinite at the oceanic
context to mild heating and compression in asubduction setting. We
propose that serpentinites formed at an oceanic transform-fault
settingthat was the locus of subduction initiation of the
Proto-Caribbean basin below the Caribbeanplate during early
Cretaceous times. Onset of subduction at the fracture zone allowed
thepreservation of abyssal transform-fault serpentinites at the
upper plate, whereas limited down-ward drag during mature
subduction placed the rocks in the subduction channel where
theytectonically mixed with the upward-migrating accreted block of
the subducted Proto-Caribbeanoceanic crust. Hence, we suggest that
relatively fertile serpentinites of high-pressure mélangeswere
witness to the onset of subduction at an oceanic transform-fault
setting.
ARTICLE HISTORYReceived 23 December 2016Accepted 16 March
2017
KEYWORDSSerpentinite; high-P mélanges;Cuba; Caribbean;
subductioninitiation; transform-fault
Introduction
The incorporation of up to 15–16 wt.% H2O intometaultramafic
rocks during the serpentinization oflithospheric mantle (e.g. Vils
et al. 2008) controls muchof the geochemical and geophysical
characteristics ofthe oceanic lithosphere (e.g. Hacker et al. 2003;
Hattoriand Guillot 2007). This in turn affects the global
geo-chemical cycle of lithosphere creation and consumption(Ulmer
and Trommsdorff 1995; Tatsumi 2005).Serpentinized ultramafic rocks
occur in a variety ofgeodynamic settings, including active plate
margins,such as mid-ocean ridges, oceanic abyssal fracture
zones, mantle zones above subducting plates, fore-arcand
back-arc basins, and passive continental margins(ocean–continent
transition; OCT). The identification ofthe geodynamic setting of
the ultramafic protolith ofexhumed serpentinite bodies is, however,
challenging(e.g. Deschamps et al. 2013; Martin et al. 2016).
At (or near) the seafloor, abyssal serpentinites occurat
slow-spreading mid-ocean ridges and associatedtransform-faults
(Kerrick 2002) as a result of the exhu-mation of upper mantle
peridotites, which are hydratedafter interaction with downwelling
seawater (e.g.Cannat et al. 2010; Kodolányi et al. 2012) and/or
byhot fluids (~350ºC) released from ocean-ridge
CONTACT J. Cárdenas-Párraga [email protected] Departamento
Mineralogía y Petrología Facultad de Ciencias Avda, Fuentenueva,
s/nUniversidad de Granada, Granada, 18002 Spain
The supplemental data for this article can be accessed here.
INTERNATIONAL GEOLOGY REVIEW, 2017VOL. 59, NO. 16,
2041–2064https://doi.org/10.1080/00206814.2017.1308843
© 2017 Informa UK Limited, trading as Taylor & Francis
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http://orcid.org/0000-0002-2787-0829http://orcid.org/0000-0002-8814-402Xhttp://orcid.org/0000-0001-8738-7305http://orcid.org/0000-0003-2580-2635http://orcid.org/0000-0001-9644-1916http://orcid.org/0000-0002-8140-1660http://orcid.org/0000-0002-3973-2271https://doi.org/10.1080/00206814.2017.1308843http://www.tandfonline.comhttp://crossmark.crossref.org/dialog/?doi=10.1080/00206814.2017.1308843&domain=pdf
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hydrothermal activity (e.g. Früh-Green et al. 2003).
Attransform-faults, serpentinization reaches great depthsbelow the
oceanic Moho (Peacock 1990), creating zonesof lithospheric weakness
that may be favourable forsubduction initiation (Müeller and
Phillips 1991; Stern2004; Gerya 2011).
In the subduction scenario, the infiltration of seawaterinto the
subducting oceanic lithosphere at trenches,favoured by normal
faults developed during plate bend-ing, causes serpentinization of
the underlying oceaniclithospheric mantle (e.g. Ranero et al.
2003).Furthermore, tectonic extension in the fore-arc and
theassociated infiltration of seawater, in addition to therelease
of fluids after dehydration of the subducted crustandmantle, are
responsible for the serpentinization of theupper-plate fore-arc
mantle (Peacock 1993; O’Hanley1996). Continued subduction during
tens of millions ofyears releases considerable amounts of fluid to
the upper-plate mantle as a result of dehydration of
subductedserpentinite, hydrated mafic crust, greenschist,
blueschist,eclogite, and sediments, promoting large-scale
serpenti-nization of the mantle at the slab–mantle interface
atmoderate to low temperatures (
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mélanges (eastern Cuba), which formed early in thesubduction
history of the region. Using mineral assem-blages, textural
relations, and major and trace-elementwhole-rock compositions, we
discuss the geologic set-ting of serpentinization and of mantle
protoliths in aneffort to decipher the implications of subducted
ser-pentinite for the geodynamic evolution of subductionzones.
Geological setting
The Greater Antillean Arc formed by the convergence ofthe North
American and the Farallon/Caribbean platesduring the Lower
Cretaceous to Tertiary (Burke 1988).After the Jurassic
fragmentation of Pangea and theopening of the Proto-Caribbean
oceanic basin, subduc-tion of the latter underneath the Caribbean
plate (ofPacific–Farallon plate-origin) created the Caribbean
vol-canic arc (Pindell et al. 2006; Pindell and Kennan
2009;Boschman et al. 2014; and references therein).Subduction
initiation has been dated at ca. 135 Ma inthe leading northern edge
of the Caribbean plate(Rojas-Agramonte et al. 2011, 2016; Lázaro et
al. 2016;see also Torró et al. 2016, 2017, for subduction
initiationbasaltic magmatism in the Dominican Republic), likelyin a
transform-fault plate boundary termed the inter-American transform
(Pindell et al. 2012; Boschman et al.2014). This event does not
appear to be related to themid-late Cretaceous plume-induced
subduction sce-nario proposed for the western and southern edges
ofthe Caribbean plate (Gerya et al. 2015; Whattam andStern 2015).
In the northern leading edge, the intra-oceanic Caribbean arc
system was tectonicallyemplaced by northward collision with the
Maya block,the Caribeana terrane, and the Bahamas platform dur-ing
the latest Cretaceous–Tertiary time (Iturralde-Vinentet al. 2008;
García-Casco et al. 2008b; Van Hinsbergenet al. 2009; Solari et al.
2013). This collision event isrecorded in obducted ophiolite bodies
and serpentinitemélanges containing high-pressure blocks
fromGuatemala through Cuba to Hispaniola (Figure 1(a)).
In eastern Cuba, the orogenic belt includes oceanic unitsof
Cretaceous volcanic arcs, ophiolites, and closely asso-ciated
serpentinite-matrix subduction mélanges (Figure 1(b)). All these
units constitute tectonic nappes with a gen-eral vergence towards
the NE and accreted in the lateCretaceous–earliest Palaeocene
(Cobiella et al. 1984;Nuñez Cambra et al. 2004; Iturralde-Vinent et
al. 2006).The ophiolite belt comprises two allochthonous
massifs:the Mayarí–Cristal massif to the west, with a mantle
sectionover 5 km thick, and the Moa–Baracoa massif to the east,with
about 2.2 km of peridotite section (Proenza et al. 1999;Marchesi et
al. 2006). Harzburgitic tectonites are dominant,
with subordinate dunites, chromitite bodies, banded gab-bros,
and discordant microgabbro and pyroxenite, trocto-lite, wehrlite,
and diabase bodies. Basaltic rocks withtholeiitic to boninitic
signature and radiolarites tectonicallyunderlie the mantle-plutonic
section (Kerr et al. 1999;Iturralde-Vinent et al. 2006; Marchesi et
al. 2006, 2007;Proenza et al. 2006). Although Dilek and Furnes
(2011)have classified Cuban ophiolites as plume-related,
easternCuba ophiolites have supra-subduction geochemical
sig-natures (Proenza et al. 1999, 2006; Gervilla et al.
2005;Marchesi et al. 2006, 2007). Recently, Lázaro et al. (2013)and
Lázaro et al. (2015) identified the Guira de Jaucoamphibolite
complex (650–665°C and 8.5–8.7 kbar) as themetamorphic sole of the
Moa–Baracoa ophiolite sheet andrelated it to the inception of a new
SW-dipping subductionof Late Cretaceous age (85 Ma) in the back-arc
of theCretaceous Caribbean arc. The ophiolitic massifs were
tec-tonically emplaced over the tholeiitic to
calc-alkalineAptian–Campanian volcanic arc units during the
lateCampanian–Maastrichtian times (Iturralde-Vinent et al.2006 and
references therein) shortly after the volcanic arc-related El
Purial complex subducted to greenschist toblueschist facies
(Boiteau et al. 1972; Somin and Millán1981; Cobiella et al. 1984)
during the latest Cretaceous(75 ± 5 Ma; Somin et al. 1992;
Iturralde-Vinent et al. 2006).
Zircon from an ophiolitic gabbroic body from CayoGrande
(Moa–Baracoa ophiolitic massif) yielded a206Pb/238U age of ca. 124
Ma (Rojas-Agramonte et al.2016). Similar early Cretaceous ages
characterize low-pressure serpentinite-matrix mélanges
containingblocks of fore-arc metadiabase/metamicrogabbrowhose
basaltic protoliths formed at >123 Ma (Lázaroet al. 2016). The
correlated Gaspar–Hernández serpenti-nite mélange in the Dominican
Republic containsblocks of similar (meta)micrograbbro crystallized
at136 Ma from Mid-Ocean-Ridge Basalt (MORB) magmasformed in the
proto-Caribbean oceanic lithosphere(Escuder-Viruete et al. 2011) or
fore-arc basalts (Lázaroet al. 2016) formed during subduction
initiation. Theseages predate ages of the exhumed products of
subduc-tion recorded in high-pressure subduction mélanges,
asdescribed next.
Subduction mélanges
Two serpentinitic mélanges bearing high-P blocks, namelythe
Sierra del Convento and La Corea mélanges (Millán1996b; Figure
1(b)), record early to late stages of subduc-tion of the
Proto-Caribbean below the Caribbean plate(García-Casco et al.
2008a; Blanco-Quintero et al. 2010,2011d). Both mélanges share
similar geological, petrologi-cal, and geochemical characteristics.
The Sierra delConventomélange occurs below a body of partly
hydrated
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ultramafic rocks lacking high-P tectonic blocks, and abovethe
metamorphosed Cretaceous volcanic arc Purial com-plex
(Iturralde-Vinent 1998; García-Casco et al. 2008a). Thedistribution
of field exposures of the mélange allows defin-ing four
sub-mélanges: El Palenque, Posango, Sabanalamar,and Macambo,
respectively, to the north, east, west, andsouth of the hydrated
ultramafic body (Figure 2(a)). The LaCorea mélange is completely
surrounded by ultramaficrocks of the Mayarí–Cristal ophiolitic
massif and its corre-sponding footwall rocks are not exposed
(Figure 2(b)). Thetectonic relations suggest that the mélange is
overriddenby the ophiolitic massif, and that both override
theCretaceous volcanic arc Santo Domingo unit.
Chaotic tectonic blocks of subducted material
includeMORB-derived garnet-epidote amphibolite and lower-
grade metavolcanic and metasedimentary blueschist-and
greenschist-facies rocks derived from abyssal
andvolcanic-arc-related settings (Millan 1996b). The
earliestproduct of subduction is garnet-epidote amphibolite
thatreached supersolidus temperature atmantle depths (700–750ºC, 15
kbar, 50 kmdepth), as documented by anatecticleucocratic
segregations and veins of trondhjemitic com-position that
crystallized at similar depths (García-Casco2007; Lázaro and
García-Casco 2008; Lázaro et al. 2011;Blanco-Quintero et al. 2011b,
2011c, 2011e). SHRIMPU–Pbages of magmatic zircons from anatectic
rocks range from113 to 105 Ma (Lázaro et al. 2009; Blanco-Quintero
et al.2011e). Blocks of jadeitite occur at the Macambo region ofthe
Sierra del Conventomélange (García-Casco et al.
2009;Cárdenas-Párraga et al. 2010, 2012). The rock crystallized
Figure 1. (a) Schematic map of Greater Antilles with indication
of ophiolite bodies (modified from Wadge et al. 1984). (b)
Geologicalmap of eastern Cuba showing the geological units
mentioned in the text and the location of the Sierra del Convento
and La Coreaserpentinite mélanges (modified from Pushcharovsky
1988).
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from Al2O3-Na2O-SiO2-rich fluids in open veins at
hightemperature (550–625ºC, the highest temperature ofjadeitite
reported so far; see review in Harlow et al.2015). SHRIMP
206Pb/238U ages of hydrothermal zirconyielded 107–108 Ma
(Cárdenas-Párraga et al. 2012), indi-cating a close
temporal/spatial relation between hydro-thermal jadeite forming
fluids and slab-derived hydroustrondhjemitic melts. All these early
subduction-relatedrocks show retrograde blueschist facies
overprint, docu-menting counterclockwise P-T-t paths. The
metamorphic/magmatic/hydrothermal evolution indicates the
subduc-tion of young hot oceanic lithosphere (close to a mid-ocean
ridge) at ca. 120 Ma, accretion to the upper plate(near-isobaric
cooling stage at 50 km depth dated at115–105 Ma), and slow
syn-subduction exhumation toca. 25 km depth within the evolving
serpentinitic channeluntil ca. 75 Ma (Lázaro et al. 2009;
Blanco-Quintero et al.2010, 2011a, 2011e), when subduction of the
Purial vol-canic arc complex accreted blocks of greenschist
andblueschist to the mélange. At 70 Ma, arc-Caribeana
ter-rane–Bahamas margin collision triggered exhumation tothe
surface, as documented by the Maastrichtian–Danianolistostromic
synorogenic sediments of Micara and LaPicota formations containing
detrital ophiolitic material(Cobiella et al. 1984; Iturralde-Vinent
et al. 2008).
Serpentinites
Serpentinites from the Sierra del Convento mélangeshow similar
textural (see below) and field relations.Fourteen fresh
serpentinite samples were selected
from different outcrops at the Macambo sub-mélange(Figure 2(a)).
The samples occur as plastically or brittlydeformed bodies (massive
to foliated fabrics; Figures 3(a,b)), surrounded by the sheared
serpentinite. At thehand-sample scale, they present green-coloured
veinsin a dark-green matrix, and inherited deformation
fromperidotite protoliths, which are locally defined by elon-gated
(retrograde) Cr-bearing magnetite/ferrian chro-mite grains (Figures
3(c)). Other primary minerals arelacking, and only bastite
pseudomorphs, after orthopyr-oxene, as an irregular occurrence of
green pseudomor-phosed porphyroblasts/clasts (≤8 mm in size),
wereobserved.
Blanco-Quintero et al. (2011d) identified two types
ofserpentinite of harzburgitic protolith in the La Coreamélange
(Figure 2(b)) based on petrographic andmajor-element composition:
i) large blocks of massive/sheared antigorite serpentinite
interpreted as deepfragments of the channel developed after
mantle-wedge peridotite and ii) lizardite–antigorite serpenti-nite
of abyssal origin accreted from the incomingplate at shallow
depths. Both types occur intermixedat the dm scale and display
massive to foliated texturesin the field, with massive serpentinite
blocks and otherlithologies included as boudins in a strongly
shearedserpentinite matrix (Figures 3(d)); Blanco-Quintero et
al.2011d). The lizardite–antigorite type occurs withinfoliated
varieties. In this article, the published major-element and
platinum-group element (PGE) data ofBlanco-Quintero et al. (2011d)
are considered in addi-tion to new trace-element data of these
samples.
Figure 2. (a) Geologic maps of the Sierra del Convento mélange,
showing the location of Posango, El Palenque, Sabanalamar,
andMacambo sub-mélanges and (b) the La Corea mélange (after
Kulachkov and Leyva 1990). Both maps with indication of sample
sites.
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Analytical procedures
A volume of about 40 cm3 per sample was crushed formajor and
trace-element analyses. Major elements wereanalysed with a PHILIPS
Magix Pro (PW-2440) X-ray fluor-escence (XRF) equipment (Centro de
InstrumentaciónCientífica – CIC, University of Granada).
Measurementswere carried out on glass beads prepared with 0.6 g
ofpowdered sample diluted in 6 g of Li2B4O7. Precision wasbetter
than ±1.5–2% and ±4% (relative) for concentrationsof ≥10 wt.%
and
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Petrography
All studied samples are strongly to completely serpen-tinized
peridotites, as supported by the loss on ignition(LOI) values
higher than 10 wt.% (SupplementaryTable 2 and Blanco-Quintero et
al. 2011d). Primary
silicates and Cr-spinel are completely absent and onlyCr-bearing
magnetite and ferrian chromite are found asalteration products of
the latter. As in La Corea, most ofthe samples from the Sierra del
Convento mélangeshow a general massive to fragmented mesh
texture(Figures 4 and 5(a)). Samples 09-SC-3 g and MCB-2f
Figure 4. Scanned thin sections showing a summary of the
different characteristic macroscopic textures of samples (a)
09-SC-8aV;(b) 09-SC-27t; and (c) 09-SC-7f.
Figure 5. Cross-polarized light (a–d) and BSE images (e–f)
showing serpentinite microtextures. (a) and (b) Mesh textures and
bladesof antigorite (Atg) in sample 09-SC-08aV (note some grains of
altered spinel). (c) Interpenetrating (interlocking) needles in
theantigoritic matrix, containing scattered chlorite (Chl) (sample
09-SC-3 g). (d) Chlorite rims around magnetite/ferrian chromite
fromalteration of spinel, all surrounded by the interlocking
antigoritic matrix (sample 09-SC-31k). (e) Fine-grained
clinopyroxene (Di)associated with tremolite (Tr) in sample
09-SC-9d. (f) Anhedral granules of relict anthophyllite (Ath)
overprinted by the antigoriticmatrix and associated with altered
spinel (sample 09-SC-7k).
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show a strong deformation fabric (Figures 3 and 5(c)).Antigorite
is the main constituent in all samples (>90%;Supplementary Table
1) forming pseudomorphic micro-textures (mesh textures; Figure
5(a,b)), millimetricblades that overprint the original peridotite
texture(Figure 5(b)), and non-pseudomorphic massively
recrys-tallized microtextures characterized by
interpenetratingneedles (interlocking texture; Figure 5(c,d)).
Bastite tex-tures are frequent and made of elongate
serpentinecrystals parallel to the orientation of
exfoliationplanes/exolution lamellae of former orthopyroxene.These
petrographic observations were confirmed withmicro-Raman and PXRD
spectra obtained from Sierradel Convento samples, which show very
intense andsharp bands at ~228, 371–374, ~680, and ~1043 cm−1,
aweaker band at 456–459 cm−1, and a shoulder/peak at636–637 cm−1 in
the low-wave-number spectral region(Figure 6(a–d)). According to
Rinaudo and Gastaldi(2003), Groppo et al. (2006), and Schwartz et
al. (2013),these typical bands of serpentine group minerals
arelocated at relatively low Raman shifts and are assignedto
antigorite. In addition, in the high spectral region,two very
intense bands at 3663–3670 and3695–3699 cm−1 are observed (Figure
6(a–d)), whichcan be related to antigorite, according to
Petriglieriet al. (2014). The calculated PXRD profiles of four
representative samples are shown in Figure 6(e–h).These samples
consist mainly of antigorite (from 100%to 63.9%) associated with
talc (up to 35.7% in thesample MCB-2f) or tremolite (4.93% in the
sample 09-SC-31b), and minor chlorite (from 0.32% to
0.63%).Notably, brucite is absent in the samples, suggestinghigher
temperature than in lizardite–brucite-bearingsamples from the La
Corea mélange.
Chlorite is present in all studied samples(Supplementary Table
1). It forms fine-grained idioblas-tic flakes (around 0.3 mm;
Figure 5(c,f)) and xenoblasticfelt-like aggregates (Figure 5(e)).
Both types appeardispersed in the serpentine matrix and usually
occurat the edge of mesh texture bodies (Figure 5(a)).Chlorite
systematically envelopes ferrian chromite-mag-netite that formed
after the complete replacement ofdisseminated primary Cr-spinel
(Figure 5(d)). Chlorite isalso locally interlocked with calcic
amphibole (tremo-lite) grains (Figure 5(e)) in replacement textures
afterprimary pyroxene(s). Talc is common in all sample
types(Supplementary Table 1). It forms fine anhedral gran-ules or
dusty grains dispersed in the matrix, which areassociated with
chlorite and rare fine- to medium-grained sub-idioblastic tremolite
(Figure 5(a);Supplementary Table 1). Tremolite (Figure 5(e)) is
locallyincluded within carbonates. Anthophyllite occurs in one
Figure 6. Representative micro-Raman spectra in the 150–1200
cm−1 and 3200–4000 cm−1 regions (central panel) and
thecorresponding optical photomicrographs (left panel) indicating
the analysed spots (yellow circles) in samples (a) 09-SC-8aV;
(b)09-SC-7k; (c) 09-SC-31b; and (d) 09-SC-31k. The numbered yellow
circles indicate the location of the micro-Raman spectrumdisplayed.
Peaks labelled in black are characteristic of antigorite.
Representative PXRD results (right panel) for samples (e)
09-SC-6c;(f) MCB-2f; (g) 09-SC-27 u; and (h) 09-SC-31b with the
experimental (blue) and calculated (red) profiles.
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sample (09-SC-7k) as dispersed, anhedral granules over-printed
by matrix antigorite and associated with mag-netite and ferrian
chromite after spinel (Figure 5(f)).Fine-grained neo-formed
clinopyroxene occurs in sam-ple 09-SC-09d (Figure 5(e)) associated
with tremoliteand in the cores of pseudomorphic serpentine
textures.
Antigorite serpentinite from La Corea mélange ischaracterized by
non-pseudomorphic textures of inter-penetrating needles of
antigorite, which is locally par-tially replaced by dolomite. Talc
is variably abundant.Primary Cr-spinel grains are completely
altered to fer-rian chromite and magnetite generally surrounded
bychlorite. On the other hand, antigorite–lizardite serpen-tinite
from this mélange shows pseudomorphic fea-tures, such as the
hourglass texture of lizardite andantigorite replacing the
orthopyroxene in bastite, fine-grained clinopyroxene, chlorite,
magnetite, and ferrianchromite that overgrew/replaced primary
clinopyrox-ene porphyroblasts, and spinel. Veins of andradite
gar-net crosscut these rocks (see Blanco-Quintero et al.2011d for
additional petrographic information).
Whole-rock composition
Major-element geochemistry
The bulk composition of the analysed samples fromSierra del
Convento has LOI values from 9.69 wt.% to12.36 wt.% (Supplementary
Table 2). The contents ofMgO and SiO2 are variable, in the range of
36.59–42.93 wt.% and 46.13–50.79 wt.%, respectively(Supplementary
Table 2, Figure 7(a,c)), as a likely con-sequence of mobilization
during serpentinization (Snowand Dick 1995; Niu 2004). The content
of Al2O3 varies inthe range of 1.62–3.66 wt.% (Figure 7). Narrower
rangesare observed for FeOtot (7.0–8.95 wt.%, (Figure 7(b)),Mg#
(100 x Mg/[Mg+Fe2+tot], 88.48–91.55;Supplementary Table 2), and
TiO2 (0.02–0.17 wt.%;Figure 7(d)). The CaO contents are generally
low, butone sample reaches 1.10 wt.% (09-SC-27t) as a
likelyconsequence of limited carbonation, whereas the typi-cal
values are around 0.5 wt.% (Supplementary Table 2and Figure 7(e)).
These compositions are similar to thepublished values from the La
Corea mélange (Blanco-Quintero et al. 2011d).
We have classified the samples in the Ol-Opx-Cpxternary diagram
calculated in oxy-equivalent or (gram-oxygen) units (Figure 8).
This measure of mineral pro-portions was obtained from the
molecular proportionsof oxides in whole-rock samples using standard
alge-braic methods and has the advantage of being a mea-sure of the
volume of solids in which oxygen is the onlymajor anion (Brady and
Stout 1980; Thompson 1982).
We have performed the calculations and ternary projec-tion using
software CSpace (Torres-Roldán et al. 2000),which makes use of the
Singular Value Decompositiontechnique for solving linear equations
(Fisher 1989,1993). According to the fields defined by Le Maîtreet
al. (2002), most samples of Sierra del Convento ser-pentinite show
a harzburgitic protolith in this diagram,except for samples MCB-2f
and 09-SC-8aV, which havean apparent olivine orthopyroxenite
composition. Asexpected, these two samples contain a relatively
hightalc content, which may indicate a
silica-metasomatictransformation of a former harzburgite. On the
otherhand, the sample 09-SC-27t, with the highest calculatedCpx
content, shows relatively abundant tremolite andcarbonate, the
latter suggesting metasomatic (carbona-tion) alteration. In this
diagram, the serpentinite sam-ples from the La Corea mélange of
Blanco-Quinteroet al. (2011d) plot as harzburgite and lherzolite
compo-sitions that overlap the field of the Sierra del
Conventoserpentinites, although a trend towards higher Ca
isapparent. To a certain extent, this is the result of thepresence
of carbonates (dolomite).
Figure 9 shows the relationships between the MgO/SiO2 and
Al2O3/SiO2 ratios of the studied serpentinitesfrom both eastern
Cuba mélanges. All compositions arerelatively consistent with an
abyssal origin (values ofAl2O3/SiO2 above 0.03 are considered
typical of sub-ducted abyssal harzburgitic serpentinite;
Deschampset al. 2013). Two samples plot within the field of
thecompositional evolution trend of melting residue (‘ter-restrial
array’ after Jagoutz et al. 1979 and Hart andZindler 1986),
although most samples have depletedcompositions with respect to the
‘terrestrial array’.
Trace-element geochemistry
The rare earth element (REE) contents of the Sierra delConvento
and La Corea serpentinites (SupplementaryTables 2 and 3,
respectively) range from ~0.1 to ~2times CI-chondrite (Figure
10(a,b)). The abundance ofother trace elements is, in general,
depleted relativeto estimates of the primitive mantle (PM), with
excep-tions in the large ion lithophile elements (LILE)(Figure
10(c,d)). The REE patterns vary from nearlyflat with a mild
negative Eu anomaly to slightlyHREE-enriched (>CI-Chondrite) and
LREE-depleted(Figure 10(a)). PM-normalized trace-element patternsof
serpentinites are characterized by similar or slightlyenriched Cs,
Ba, U, and Rb contents and Th depletion(Figure 10(c,d)). In
general, all samples show markedHf and Sr depletion and Pb
enrichment (Pb was notanalysed for the La Corea mélange), although
a localprominent positive spike in Sr and a negative spike in
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Rb characterize some samples, suggesting mobiliza-tion of
fluid-mobile trace elements duringserpentinization.
PGE composition
The total concentration of PGE in the Sierra delConvento
serpentinite samples ranges from 18 ppb to36 ppb (Supplementary
Table 4). These low values arecharacterized by concentrations of
Ir-type PGE (IPGE)from 10 ppb to 15 ppb (Os = 1–3 ppb; Ir = 3–4
ppb;
Ru = 6–9 ppb) and concentrations of Pd-type PGE(PPGE) from 8 to
21 ppb (Rh = 1–2 ppb; Pt = 5–10ppb; Pd = 2–9 ppb; Supplementary
table 4). The sam-ples have similar values to the primitive upper
mantle(PUM; Becker et al. 2006) for Ir, Ru, Pt, and Pd, althoughone
sample shows depletion in Pt and Pd and all sam-ples show depletion
in Os (Figure 11). Serpentinitesfrom the La Corea mélange have
similar concentrationsof IPGE (Os, Ir, Ru) and PPGE (Rh, Pt, Pd),
although theydo not show a marked depletion in Os and Pd and
havehigher values of PPGE.
Figure 7. Major-element diagrams displaying the composition of
the studied serpentinites (La Corea mélange from Blanco-Quinteroet
al. 2011d), with oxides recalculated to the anhydrous basis. (a)
SiO2 content (wt.%); (b) FeOtotal content (wt.%); (c) MgO
content(wt.%); (d) TiO2 content (wt.%); and (e) CaO content (wt.%)
versus Al2O3 content (wt.%). Silicate Earth (primitive mantle, PM)
fromMcDonough and Sun (1995). Samples from different formation
environments are plotted for comparison.
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Discussion
The mineral assemblages and textures characterized
byantigorite±lizardite, chlorite, tremolite, diopside, talc,and,
importantly, anthophyllite, with antigorite replace-ments after
lizardite, and the composition of the ana-lysed samples indicate a
complex geodynamic historyof serpentinite from both mélanges. In
this section, wediscuss the geochemical characteristics of the
studiedsamples and their P-T evolution, and propose a tectonicmodel
within the framework of Cretaceous Caribbeantectonics, which may be
extended to other regions.
Environment of formation
Since extensive serpentinization is characteristic of thestudied
mélanges, the mobility of elements during thealteration/metamorphic
processes may obscure proto-lith provenance (e.g. Niu 2004).
Serpentinization is char-acterized by MgO loss, as illustrated by
the trend ofserpentinized peridotites from the fracture
zone/abyssal(Figure 9). In a similar way, enrichment of SiO2
and/orCaO in several samples (Figures 4(b), 7(a,d) and 9) maybe
related to the serpentinization of oceanic peridotiteby seawater
(e.g. Marchesi et al. 2011). Indeed, thesamples have PGE
concentrations similar to PUM,denoting only local variations in the
extent of residualcharacter (Becker et al. 2006), except for Os,
Pt, and Pdin the Sierra del Convento mélange (Figure 11),
whichshows depletions likely caused by limited mobility dur-ing
serpentinization (Lorand et al. 2003; Luguet et al.2003; Pearson et
al. 2004; Harvey et al. 2006; Wang et al.2008; Liu et al. 2009;
Lorand and Alard 2010; Marchesiet al. 2013; Penniston-Dorland et
al. 2014). Talc, found insome deformation textures (Figures 5(a)
and 2(b,c) inBlanco-Quintero et al. 2011d), is present in the
mineralassemblage of several antigorite and antigorite–lizar-dite
serpentinites of both mélanges. The local presenceof talc can be
related to the variable degree of infiltra-tion of metasomatic
fluids. This type of alterationcauses a mildly negative Eu anomaly,
as shown bymost analysed samples (Figure 12; cf. Paulick et
al.2006; Boschi et al. 2006). We hence suggest that asecondary Eu
anomaly caused by alteration in the ocea-nic environment is still
preserved.
Despite the effects of alteration, the abundance ofmajor and
trace elements suggests that serpentinitefrom both mélanges has
similar geochemical signatures(Figures 7–12) and that all samples
broadly conform tothe compositional evolution trend of mantle melt
resi-dues (terrestrial array; Figure 9) with only a
somewhatrefractory Al2O3/SiO2 signature (>0.03).
Furthermore,
Figure 8. Ternary diagram showing oxy-equivalent molar
pro-portions of olivine (Ol), orthopyroxene (Opx), and
clinopyrox-ene (Cpx) within the ultramafic rocks classification
scheme ofLe Maître et al. (2002). Bulk rock major- and
trace-elementcompositions (SiO2, TiO2, Al2O3, FeOtotal, MnO, MgO,
CaO,Cr2O3, and NiO) of La Corea (Blanco-Quintero et al. 2011d)and
Sierra del Convento serpentinite samples are mapped inthe space
defined by forsterite, enstatite, diopside, and spinel(measured in
oxy-equivalent units) and the exchange vectorsTiMgAl−2 (Ti-spinel),
FeMg−1, MnFe−1, CrAl−1, and NiMg−1. Thisprocedure allows
approximating the volume proportions ofolivine, ortho- and
clinopyroxene. Calculations were executedby means of the CSpace
software (Torres-Roldán et al. 2000).Serpentinites and
serpentinized peridotites from oceanic frac-ture-zone/abyssal
environments are plotted for comparison.
Figure 9. MgO/SiO2 versus Al2O3/SiO2 diagram of the
studiedserpentinite samples. The ‘terrestrial array’ is after
Jagoutz et al.(1979) and Hart and Zindler (1986) and primitive
mantle (PM) isfrom McDonough and Sun (1995). Samples from different
for-mation environments are plotted for comparison.
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major- and trace-element compositions show no coin-cidence with
the drilled/dragged serpentinites/perido-tites from the mantle
wedges (Pearce et al. 2000;
Kodolányi et al. 2012). Importantly also, they do notshow
coincidence with the drilled/dragged abyssal ser-pentinites derived
from harzburgite (Paulick et al. 2006),except if melt-related
re-fertilization processes affectedthese rocks (Figures 7, 9, and
12; see below).
Immobile trace elements must be used to gain addi-tional
insight. Titanium and La/Yb versus Yb relations(Figure 13(a,c))
confirm a less-refractory composition(enrichment in Ti and Yb) than
drilled/dragged harzbur-gitic abyssal and mantle wedge
serpentinites/perido-tites and are similar to the compositions of
fracture-zone/abyssal serpentinized peridotites and drilled/dragged
abyssal serpentinites with melt impregnationprocesses. In a similar
way, the Nb versus La diagram(Figure 13(b)) shows a positive trend
and moderate fitto the linear regression for abyssal peridotites
(Paulicket al. 2006). These characteristics may be related to
re-fertilization controlled by melt–rock interaction pro-cesses.
Mafic and differentiated melts percolating andreacting with mantle
peridotite are identified as
Figure 10. Trace-element patterns normalized to CI-chondrite (a
and b) and silicate earth/primitive mantle (c and d) (McDonoughand
Sun 1995) for the La Corea (a and c) and Sierra del Convento
mélanges (b and d). Subducted, abyssal, and mantle wedgeharzburgite
serpentinites data compiled by Deschamps et al. (2013; samples from
exhumed interpreted bodies and drilled/draggedin oceanic basins)
are plotted for comparison.
Figure 11. CI-chondrite-normalized PGE patterns of easternCuba
mélanges. PGE of oceanic and continental peridotitescompiled by
Marchesi et al. (2013) are plotted for comparison.Normalizing
values are from Palme and Jones (2003). Primitiveupper mantle (PUM)
is from Becker et al. (2006).
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responsible for HFSE and REE enrichment in samplesdrilled from
transform settings (Niu 2004; Paulick et al.2006). Higher REE, Zr,
Th, and Nb contents than abyssaland mantle wedge fields, as
illustrated in Figure 10(c,d)and 13(b), would suggest melt
impregnation processesthat cannot be related to serpentinization
due to theirimmobility in aqueous solutions (e.g. Paulick et al.
2006;Augustin et al. 2012). Thus, the enriched patterns dis-played
by the studied samples, with REE and IPGE con-centrations close to
1 CI-chondrite (Figures 10(a,b) and12(a,b)) and PUM (Figure 11),
respectively, and therelatively high concentrations in HFSE can be
inter-preted as fracture-zone/abyssal peridotites that experi-enced
modest percentages of partial melting and likelyre-fertilization
processes (Pearce et al. 2000; Niu 2004;Choi et al. 2008a; Chen et
al. 2015).
Enriched patterns of Cs, Rb, and Ba with respect
todrilled/dragged abyssal serpentinites, on the otherhand, might
have been related to the influence ofmetasomatic fluids in the
mantle wedge by slab-derived agents (Figure 10(c,d); for example,
Schmidtand Poli 1998; Bebout and Barton 2002; Hyndman andPeacock
2003; Scambelluri et al. 2004). Eastern Cuba
serpentinites are similar to serpentinites from the sub-duction
environment and show strong enrichment inBa relative to
serpentinized peridotites from fracturezones (Figure 14(b)),
pointing to an influence of fluidsevolved from subducted crust.
Indeed, they also showdepletion in U and Li (Figure 14(a,c))
relative to fracture-zone/abyssal serpentinized peridotite,
indicating theeffects of subduction-related fluids (e.g. Vils et
al.2011). Thus, despite their fracture-zone/abyssal
origin,serpentinites were hydrated in a subduction scenariowhere
they experienced interactions with slab-derivedfluids (cf. Choi et
al. 2008a, 2008b; Deschamps et al.2012).
Metamorphic evolution
A first seafloor serpentinization event is documented bythe
presence of low-pressure mineral phases.Anthophyllite, present
locally in the Sierra delConvento mélange (Supplementary Table 1;
Figure 5(f)), is typical of metaultramafic rocks formed at a
rela-tively high temperature of 600–700ºC and a relativelylow
pressure of
-
Figure 13. (a) Ti versus Yb, (b) Nb versus La, and (c) La/Yb
versus Yb diagrams for the studied samples. Re-fertilization,
magmaticdepletion, fluid–rock interaction, and melt–rock
interaction trends are after Deschamps et al. (2013) and the
references therein.Linear regression for abyssal peridotites is
shown by a dashed line (Paulick et al. 2006). PM is from McDonough
and Sun (1995) andGLOSS after Plank and Langmuir (1998). Note the
rupture of the Ti and La scales in A and B, respectively.
Figure 14. Fluid mobile element compositions of the studied
serpentinites, (a) Li, (b) Ba, and (c) U versus Yb content (ppm).
PM isfrom McDonough and Sun (1995) and GLOSS after Plank and
Langmuir (1998).
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are incompatible with the mature and warm subduc-tion-related
thermal gradients (Figure 15). Instead, theymay be related to a hot
subduction scenario related tothe subduction initiation of the
young oceanic litho-sphere (as in eastern Cuba mélanges) or to
ocean-floormetamorphism characterized by high thermal gradi-ents.
The evidence from the associated tectonic blocksof MORB-derived
amphibolite in the studied mélangesindicates a hot thermal gradient
of ca. 15ºC/km relatedto the subduction of the young oceanic
lithosphere(García-Casco et al. 2008a; Lázaro et al. 2009;
Blanco-Quintero et al. 2010). This gradient is however
incom-patible with >31.2ºC/km, expected for the formation
ofanthophyllite at 31.2ºC/km. For this reason, and thelack of
evidence of such a high thermal gradient ineastern Cuba mélanges,
our preferred interpretation isthat anthophyllite represents a
relict of mid-ocean ridgemetamorphism. Other minerals, like
antigorite, talc, tre-molite, and diopside, might have also formed
uponcooling of the oceanic lithosphere down to 300–400ºCand further
fluid infiltration (Figure 15). However, heat-ing is documented by
lizardite transformation to anti-gorite (Blanco-Quintero et al.
2011d; cf Schwartz et al.2013). This prograde metamorphic event can
hardly berelated to the thermal evolution at a transform-zone
Figure 15. P-T diagram showing the metamorphic evolution of the
serpentinite rocks of the Sierra del Convento and La Coreamélanges
from the oceanic to the subduction environments. The red lines
represent the reaction relationships in the CaO-MgO-SiO2-H2O system
after Spear (1995) and Padrón-Navarta et al. (2012). The thick red
reaction curves denote the calculated maximumstability of
antigorite in the MgO-SiO2-H2O system. This reaction is almost
coincident with the experimental stability limit of MSH-antigorite
(denoted as ‘MSH-Atg out (BP)’ in the figure, after Bromiley and
Pawley 2003). Also shown is the experimental stabilitylimit of
Al-rich antigorite (denoted as ‘MASH-Atg out (UT)’ after Ulmer and
Trommsdorff 1995). The orange shaded regionencompasses additional
experimental stability limits of antigorite with variable Al after
Bromiley and Pawley (2003), Wunder andSchreyer (1997), and Wunder
et al. (2001). The phase relations between lizardite and antigorite
(green and blue reaction bands) arefrom Evans et al. (2013) and
Schwartz et al. (2013). For reference, the thermal gradients of the
top (slab–mantle interface) andbottom of the subducted oceanic
crust in cold and warm subduction scenarios (Peacock and Wang 1999)
and the wet basalticsolidus (Green 1982) are shown. The P-T paths
of subducted MORB Grt-amphibolite blocks of the Sierra del Convento
and La Coreamélanges followed counterclockwise P-T paths, reaching
peak conditions appropriate for partial melting at ca. 750ºC at 15
kbar(García-Casco et al. 2008a; Lázaro et al. 2009; Blanco-Quintero
et al. 2010, 2011e). Note that the related abyssal serpentinite
from thedown-going plate subducted at this stage would have been
transformed into metaharzburgite/meta-olivine orthopyroxenite,
whichis lacking in the mélanges. The timing and P-T conditions of
jadeitite formation in the Sierra del Convento mélange are after
García-Casco et al. (2009) and Cárdenas-Párraga et al. (2012).
Retrograde hydration of peridotite down to ca. 300ºC in the context
of atransform-fault zone and the ensuing down-drag of the
upper-plate serpentinite (which experienced limited subduction down
to ca.30 km, up to 450ºC after the onset of subduction) are
indicated by deep-red arrows. Massive antigoritite formed at depths
of ca.15 kbar (Blanco-Quintero et al. 2011d). Exhumation of all
types of blocks and serpentinite along the subduction channel
allowed theformation of the mélanges with low-T serpentinite at
-
environment characterized by cooling and must berelated to the
subduction of serpentinite (Figure 15).
Tectonic blocks in eastern Cuba serpentinite mélangesrecord
subduction of the oceanic and volcanic arc litho-sphere. The
earliest subducted metamorphic blocks areMORB-derived
garnet-epidote amphibolite and asso-ciated partial melting-derived
segregations and veins oftrondhjemitic to tonalitic composition.
They formed athigh temperature and moderate pressure (700–750ºC,15
kbar; Figure 15) as the result of subduction of a near-ridge
lithosphere (García-Casco 2007; Lázaro and García-Casco 2008;
Blanco-Quintero et al. 2011b; c, e; Lázaro et al.2011). At similar
depth (50 km) but lower temperature(550–625ºC), jadeitite rocks
were formed in the Sierra delConvento subduction channel
(García-Casco et al. 2009;Cárdenas-Párraga et al. 2012; Figure 15).
Metamorphicoverprints bearing glaucophane and lawsonite
documentcounterclockwise P-T paths and progressive cooling of
the
channel during accretion (Figure 15). Subduction of thePurial
volcanic arc complex during the latest Cretaceous(75–70 Ma)
provided blocks of blueschist and greenschistto the mélanges,
shortly before arc–terrane collisionexhumed the ophiolitic units
and the associatedmélanges (García-Casco et al. 2008b). In this
context,before 75 Ma, lizardite-free antigorite serpentinitesformed
at an imprecise range of 10–14 kbar and450–600ºC (Blanco-Quintero
et al. 2011d; Figure 15). Onthe other hand, since lizardite is
locally preserved andantigorite replaced lizardite in some samples,
this materialreached less than ca. 30 km depth during heating
andcompression in the channel (
-
As a result of the plastic behaviour of serpentinite,large-scale
convective circulation is a process documen-ted in subduction
channels predicted by numericalmodels (Gerya et al. 2002; Gorczyk
et al. 2007). A naturalexample of large-scale convective
circulation inmélanges was first presented by Blanco-Quintero et
al.(2011a), who documented large P-T recurrences inamphibolite
blocks from the La Corea mélange coupledwith counterclockwise P-T
paths documenting coolingand exhumation from ca. 50 km depth
(García-Cascoet al. 2008a; Lázaro et al. 2009; Blanco-Quintero et
al.2011b, 2011e). Metasomatic rinds of actinolite-
andchlorite-bearing rocks associated with amphibolite andjadeitite
blocks document, in turn, a long-lasting historyof fluid–rock
interactions in the subduction channel(Blanco-Quintero et al.
2011d; Cárdenas-Párraga et al.2012). These evidences point to the
large-scale tectonictransport of blocks and matrix in the
subduction chan-nel involving mixing of the deeper parts of the
channelwith the shallower parts where a large volume of low-grade
serpentinite forms (Shervais et al. 2011; Shervaisand Choi 2012),
rather than exhumation, sedimentation,and re-subduction
(Wakabayashi 2012, 2015).
Tectonic model
In the model of Figure 16, a scenario of subduction andmixing in
a subduction channel mélange is conceptualizedwithin the
currentmodels of plate tectonic evolution of theCaribbean region.
Pindell et al. (2012) proposed that sub-duction nucleated at an
inter-American transform-fault sys-tem developed upon the
detachment of North Americafrom Gondwana related to Pangea break-up
in the region.Boschman et al. (2014) discussed the plate-tectonic
config-uration of this fault and concluded that it separated
theProto-Caribbean and Panthalassa (Farallon) lithospheresand that
subduction of the former below the latter initiatedalong it during
the early Cretaceous. Transform-fault is onepossible general
scenario for the onset of subduction (Stern2004; `Stern et al.
2012) that has been proposed inmélanges, such as the
proto-Franciscan subduction zone(Shervais and Choi 2012).
Our data and inferences support a transform-fault sce-nario for
subduction initiation in the northern Caribbeanduring the early
Cretaceous (Figure 16(a,b)). Serpentiniticmasses formed along the
inter-Americas transform contrib-uted to the mechanical weak zone
needed for subductioninception (Figure 16(c,d); cf. Blanco-Quintero
et al. 2011band references therein). In an ideal model with only
onetransform-fault plate boundary (rather than a fault zone),once
subduction initiated, the fault-bounded Proto-Caribbean lithosphere
rich in serpentinite was draggeddown, whereas the Caribbean-
(Farallon-) plate counterpart
was trapped in the fore-arc region close to the trench at
arelatively shallow depth (Figures 15 and 16(d); cf. Shervaisand
Choi 2012). In a more realistic wider fault boundaryzone, fragments
of subducted serpentinite accreted to theupper plate and
contributed to the evolving serpentiniticchannel. Upon development
at 50 km depth (ca. 10 millionyears after subduction initiation,
Blanco-Quintero et al.2011b), subducted oceanic crust (partially
melted garnetamphibolites) accreted to the channel. Further
develop-ment of the channel allowed the shallower part formedby the
lizardite-bearing serpentinite to be draggeddown to
-
Serpentinization affected peridotite in this tectonic con-text
as a consequence of the infiltration of seawater,triggering the
formation of talc, tremolite, diopside,anthophyllite, and lizardite
and the remobilization of ele-ments (SiO2, CaO, Sr, and Pb
enrichment, and Mg, Os, Pt,Pd, and Eu depletion). Subduction
initiation along thetransform-fault zone at ca. 135 Ma, identified
as theinter-Americas transform zone, caused subduction of
theProto-Caribbean half-fault zone serpentinite
(antigoriteserpentinite) and capture of the Caribbean
(Farallon)counterpart at the shallow upper plate close to the
trench(lizardite-serpentinite). Upon establishment of mass flowin
the channel shortly after the onset of subduction, sub-ducted
oceanic crust accreted and shallower serpentinitewas dragged down
to
-
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