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 jcardenas_1@ugr.es 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

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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

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 (

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

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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