Jean-Pierre Lorand
email: jean-pierre.lorand@univ-nantes.fr

Sylvain Pont

Rosario Guttierez-Narbona

Fernando Gervilla

Chalcophile-siderophile element systematics and regional-scale magmatic percolation in the Ronda peridotite massif (Spain)

Keywords:

Eighteen samples from the south-western part of the Ronda lherzolitic massif have been analysed with bulk-rock and in-situ techniques to unravel the fate of Cu, platinum-group element and chalcogens (S, Se) in a middle Proterozoic subcontinental lithospheric mantle segment variably overprinted by kilometre-scale porous flow percolation of asthenosphere-derived silicate melts during the Alpine orogeny. Chalcogen elements (S, Se Cu) and PGE systematics fit well the published data base for orogenic mantle peridotites as a whole. Positive correlations between S, Se, Cu and fertility result from progressive removal of sulfides from the mantle at increasing degrees of melting. A few harzburgites preserved the S-, Se-and Pd-depleted (Pd/Ir < 1)-chondrite normalized PGE patterns of residues after partial melting. The Oligocene thermo-mechanical erosion event triggered secondary partial melting of the sulfide phase liberating a Cu-Ni-rich sulfide melt now identified through Cu-Ni-rich sulfide inclusions (pentlandite + chalcopyrite ± bornite) and a wide range of intergranular Cu-rich sulfides and alloys. Residual monosulfide solid solution (coexisting with refractory platinum group minerals (laurite-erlichmanite) in spinel tectonites) survived throughout all of the tectonometamorphic domains, thus preserving relative and absolute abundances of compatible platinum group elements (Os, Ir, Ru, Rh). Local scale redistribution of the Cu-Ni-rich sulfide melt accounts for the enrichment/depletion trends of Te, Pd, Pt, Au, Ag, Cu identified in granular peridotites. On cooling, the sulfide melt produced pentlandite by reacting with monosulfide solid solution at T < 870 °C while transfering incompatible elements that generated micrometric Pt-Cu-Te-As-bearing platinumgroup mineral inclusions (e.g. malanite CuPt 2 IrS 4 , moncheite PtTe 2 , Pt arsenide, secondary Pt-Cu alloys), in addition to superchondritic Pd/Ir and nearly chondritic Se/Te identified in mantle sulfides of metasomatic origin. By contrast, micrometer-sized Au particles identified in Au-enriched spinel harzburgites are clearly primary precipitates from volatile-rich small melt fractions.

Introduction

Highly siderophile elements (HSE = platinum-group elements (PGE) + gold + rhenium) are currently used to adress fundamental issues of the earth's mantle relevant to planetary accretion, core-mantle differentiation as well as mantle melting, melt percolation and metasomatism involving the mantle at shallow depth (e.g. Walker, 2016 and references therein;Luguet and Reisberg, 2016 and references therein;Lorand and Luguet, 2016 and references therein). HSEs also offer great potentialities for dating long-term magmatic and metasomatic events thanks to two long-period radiogenic isotope pairs ( 187 Re-187 Os and 186 Os-190 Pt; Walker, 2016 and references therein). Unlike other geochemical tracers such as lithophile elements (e.g. Rare Earth Elements; REE), HSEs are ultra-trace elements carried by trace Cu-Fe-Ni sulfide phases (hereafter referred to as "Base Metal Sulfides", BMS) and micrometric platinum-group minerals (PGM) incorporating some PGE, chalcogens (Te, Se) and semi-metals (Bi, As, Sb) (e.g. [START_REF] Alard | Non-chondritic distribution of the highly siderophile elements in mantle sulphides[END_REF][START_REF] Lorand | Platinum-group element abundances in the upper mantle: New constraints from in situ and whole-rock analyses of massif central xenoliths (France)[END_REF][START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF][START_REF] Griffin | Lithosphere evolution beneath the Kaapvaal Craton: Re-Os systematics of sulfides in mantle-derived peridotites[END_REF]Lorand et al., 2010;[START_REF] Marchesi | Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): influence of hydrothermal and magmatic processes[END_REF]Lorand and Luguet, 2016 and reference therein). The extent to which these minor sulfides and PGM microphases are resistent to magmatic percolation is however still debated. [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF]Lorand et al. ( , 2010) ) identified a wide spectrum of discrete PGMs carrying compatible PGEs (Os, Ir, Ru, Pt) in secondary refertilized pyrenean lherzolites. They conclude that such relict phases remained undissolved and survived melt/rock reactions that occurred during refertilization. The Re-Os isotopic system provided separate evidence that Os-bearing refractory minerals can preserve ancient Os isotopic signatures [START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF][START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF][START_REF] González-Jiménez | Transfer of Os isotopic signatures from peridotite to chromitite in the subcontinental mantle: insights from in situ analysis of platinum-group and base-metal minerals (Ojén peridotite massif, southern Spain)[END_REF]Luguet and Reisberg, 2016 and reference therein). On the other hand, opensystem magmatic percolation at high melt fraction can trigger complete dissolution/reequilibration of BMS/PGM, resulting in deep modification of the HSE patterns of host peridotites [START_REF] Büchl | Melt percolation monitored by Os isotopes and HSE abundances: a case study from the mantle section of the Troodos Ophiolite[END_REF][START_REF] Griffin | Lithosphere evolution beneath the Kaapvaal Craton: Re-Os systematics of sulfides in mantle-derived peridotites[END_REF][START_REF] Delpech | In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean[END_REF][START_REF] Lorand | Platinum-group element systematics and petrogenetic processing of the continental upper mantle: a review[END_REF][START_REF] Ackerman | Highly siderophile element geochemistry of peridotites and pyroxenites from Horní-Bory, Bohemian Massif: Implications for HSE behaviour in subduction-related upper mantle[END_REF][START_REF] Marchesi | Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts[END_REF]Luguet and Reisberg, 2016 and reference therein).

The issue is addressed here from a multiscale investigation of the six PGEs, Au and related chalcogens (S, Se) and chalcophile elements (Cu) in the Ronda peridotite massif, southern Spain. This massif is well suited for this purpose because structural and petrogenetic studies of its southwestern part [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF][START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF][START_REF] Van Der Wal | Structural petrology of the Ronda peridotite, SW Spain: Deformation history[END_REF] have revealed a kilometric-scale porous flow percolation of asthenosphere-derived silicate melts and limited melt extraction (<5%) overprinting a middle Proterozoic subcontinental lithospheric mantle protolith [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF][START_REF] Reisberg | The Re-Os systematics of the Ronda Ultramafic complex of Southern Spain[END_REF][START_REF] Reisberg | Longevity of the sub-continental mantle lithosphere from osmium isotope systematic in orogenic peridotite massifs[END_REF][START_REF] Reisberg | Further Sr and Nd isotopic results from peridotites of the Ronda Ultramafic Complex[END_REF]. To date, only 5 highly fertile lherzolites (7-8 wt% Al 2 O 3 ) sampled within the recrystallization front were analysed for bulk-rock PGE and Re concentrations [START_REF] Marchesi | Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts[END_REF]. Other papers on PGE by [START_REF] Gueddari | Differentiation of platinum-group elements (PGE) and of gold during partial melting of peridotites in the lherzolitic massifs of the Betico-Rifean range (Ronda and Beni Bousera)[END_REF], [START_REF] Garuti | Platinum-group-element distribution in subcontinental mantle: evidence from the Ivrea Zone (Italy) and the Betic-Rifean cordillera (Spain and Morocco)[END_REF] and [START_REF] Lorand | Highly siderophile element geochemistry of the Earth's mantle: new data for the Lanzo (Italy) and Ronda (Spain) orogenic peridotites bodies[END_REF] published bulk-rock PGE analyses of samples collected mainly outside the percolation area and some elements (e.g. Pt, Ir) were clearly affected by analytical bias, thus making their results disputable (see below). Our paper reports new bulk rock analyses of chalcophile (Cu), chalcogens (S, Se) and PGE + Au contents of 18 samples collected from all of the various tectonometamorphic subdomains defined by [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. We combine these bulk rock analyses with insitu analyses of BMS with laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) and a systematic search of PGE carriers in optical reflected light and by scanning electron microscope (SEM). This well-constrained data set allows the fate of PGE and related elements (S, Se, Te) in a km-scale percolation process to be discussed within a well documented petrogenetic framework.

Petrogenesis of the Ronda peridotite massif

The Ronda ultramafic massif, the largest outcrop of sub-continental lithospheric mantle on Earth (300 km 2 ) is located in the western part of the Malaga province (southern Spain), within the Alpujarride Complex, in the Internal Zones of the Betic Cordillera. It represents a portion of lithospheric mantle emplaced at high temperature into the continental crust, about 22 Ma. ago [START_REF] Zindler | Nd and Sr isotopic study of a mafic layer from Ronda ultramafic complex[END_REF]. [START_REF] Obata | The Ronda peridotite: Garnet-, spinel-and plagioclase-lherzolites facies and the P-T trajectories of a high-temperature mantle intrusion[END_REF] recognised four zones (Fig. 1) characterized by garnet-lherzolite facies, ariegite subfacies of the spinel-lherzolite facies, seiland subfacies of the spinel-lherzolite facies and plagioclase-lherzolite facies.

In their seminal work, [START_REF] Frey | The Ronda high temperature peridotite: geochemistry and petrogenesis[END_REF] showed that geochemical variations of the Ronda peridotite could be explained by various degrees of melt extraction from a fertile precursor. [START_REF] Frey | The Ronda high temperature peridotite: geochemistry and petrogenesis[END_REF] also showed that the eastern part of the massif, or the plagioclase facies, had on average a far more depleted major element composition than the spinel and garnet facies defined by [START_REF] Obata | The Ronda peridotite: Garnet-, spinel-and plagioclase-lherzolites facies and the P-T trajectories of a high-temperature mantle intrusion[END_REF]. Clinopyroxenes collected from river sediments throughout the massif gave Sm-Nd model ages suggesting a middle-Proterozoïc age for this partial melting event [START_REF] Reisberg | Further Sr and Nd isotopic results from peridotites of the Ronda Ultramafic Complex[END_REF]. This age is supported by correlation of peridotite major element compositions (including the highly depleted plagioclase samples from the eastern part of the massif) with Os isotope ratios [START_REF] Reisberg | The Re-Os systematics of the Ronda Ultramafic complex of Southern Spain[END_REF][START_REF] Reisberg | Longevity of the sub-continental mantle lithosphere from osmium isotope systematic in orogenic peridotite massifs[END_REF].

The recrystallization front associated with the regional scale magmatic mercolation developed in the western part of the massif that had experienced smaller amount of Proterozoic melt extraction. This fertile region was nevertheless heterogeneous on a small scale and included numerous mafic layers, at least some of which formed during the 1.3 Ga event [START_REF] Reisberg | The Re-Os systematics of the Ronda Ultramafic complex of Southern Spain[END_REF]. There detailed petrological, structural and geochemical investigations [START_REF] Garrido | Diversity of mafic rocks in the Ronda peridotites: evidence for pervasive meltr-rock reaction during heating of subcontinental lithosphere by upwelling asthenosphere[END_REF][START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF][START_REF] Soustelle | Deformation and reactive melt transport in the mantle lithosphere above a large-scale partial melting domain: the Ronda peridotite massif[END_REF][START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF][START_REF] Van Der Wal | Structural petrology of the Ronda peridotite, SW Spain: Deformation history[END_REF] identified three tectono-magmatic domains which broadly correspond to Obata's zones (Fig. 1). From northwest to southeast (representing a top to bottom cross section), these are: (1) a spinel (±garnet) tectonite domain subdivided into an outer zone of garnet-spinel mylonites, which delineates the northern and western boundaries of the massif, and a domain of foliated spinel tectonites to the south. 2) a granular-peridotite domain separated from the spinel tectonite domain by a recrystallization front and 3) a plagioclase-tectonite domain.

The spinel-tectonite domain is composed of foliated porphyroclastic spinel peridotites and mylonitic garnet-spinel peridotites that record a decompression and cooling event from 1150 °C and 2.7 GPa to 900 °C and 1.9 GPa [START_REF] Precigout | Strain localisation in the subcontinental mantle-a ductile alternative to the brittle mantle[END_REF]. Peridotite modal compositions (Table 1) range from fertile lherzolites to harzburgites. The melting event that created this range of peridotite modal composition is dated at 1.3-1.7 Ga by Re/Os chronometry [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF]. Cryptic metasomatism features such as LREE enrichments were detected in most harzburgites [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]see below).

According to [START_REF] Van Der Wal | Structural petrology of the Ronda peridotite, SW Spain: Deformation history[END_REF]Van der Wal and[START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]Lenoir et al., 2001, structural and geochemical data suggest that the granular subdomain was produced from the older, porphyroclastic spinel tectonite by a recent (Cenozoic) porous melt flow process of regional extent and thermomechanical erosion of the Proterozoic lithosphere (see also [START_REF] Garrido | Diversity of mafic rocks in the Ronda peridotites: evidence for pervasive meltr-rock reaction during heating of subcontinental lithosphere by upwelling asthenosphere[END_REF][START_REF] Soustelle | Deformation and reactive melt transport in the mantle lithosphere above a large-scale partial melting domain: the Ronda peridotite massif[END_REF]. The granular domain was further subdivided into three subdomains from NW to SE: 1) a coarse-granular subdomain 2) a fine-granular subdomain and 3) a layered-granular subdomain. Compared with spinel tectonites, coarse-granular peridotites are chemically more homogeneous, more refractory in terms of major elements and more depleted in incompatible trace elements (Table 1). The increasing diameter of olivine grains by up to a factor of five compared to that in the spinel tectonite domain, the rounded orthopyroxene with diameters up to 2 cm and the lack of deformation in both minerals are typical features of silicate grain growth and annealing caused by pervasive infiltration of basaltic melts at high-temperature (1250 °C) ( [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. Resorbtion of clinopyroxene+spinel yielded olivine-rich lherzolites. These features are consistent with a process involving partial melting, km-scale migration of melts by diffuse porous flow and limited melt extraction [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF]. Os model ages are generally younger compared to spinel tectonite domain [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF].

Fine-granular peridotites are mostly olivine-rich lherzolites with modal compositions (56-67% ol; 23-29% opx; 7-14% cpx) and mgnumbers (89-90) deviating from mantle melting trend. Olivine microstructures are similar to those of coarse-granular peridotites; the orthopyroxene grain size is strongly reduced owing to the olivineforming reactions that are inferred to have occurred at increasing melt fractions and increasing temperature (Van der [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. Moreover, melt/rock reactions at decreasing melt volume and temperature produced a late Cr-rich interstitial clinopyroxene (hereafter referred to as cpx II) often forming diffuse cpx ± spinel microlayers. Cpx II becomes more abundant than in fine-granular peridotites, occurring with Cr-poor spinel in diffuse microlayers. Layered-granular peridotites consist of layered olivine-rich lherzolites, harzburgites and dunites hosted by fertile plagioclase lherzolites.

In some coarse granular and layered granular samples, Cr spinel is replaced by a low-Ti pargasite and geochemical data indicate that a grain boundary component (0.9% ilmenite +0.07% phlogopite) is necessary to balance the whole-rock budget of some highly incompatible trace elements such as Rb and Ba in the harzburgites [START_REF] Garrido | Incompatible trace element partitioning and residence in anhydrous spinel peridotites and websterites from the Ronda orogenic peridotite[END_REF]. Those minor phases crystallized from volatile-rich smallvolume melts generated from the recrystallization front after pyroxene-forming melt-rock reactions reactions [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF][START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. These late-stage small-volume melts derive from melts that reacted with, and partly replaced pargasiteand ilmenite-rich pyroxenites defined as Group C pyroxenites by [START_REF] Garrido | Diversity of mafic rocks in the Ronda peridotites: evidence for pervasive meltr-rock reaction during heating of subcontinental lithosphere by upwelling asthenosphere[END_REF]. These latter melt fractions were highly mobile and escaped from the recrystallization front, migrating upward to the spinel tectonite domain representing the thermal boundary of the recrystallization front [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF]. They infiltrated harzburgites which now show LREE-enrichments (Ce N /Sm N = 1.06-6.41) proportional to the distance to the recrystallization front. [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF] interpreted this REE pattern as resulting from a chromatographic fractionation of the LREE. Then, when the percolation system cooled, the recrystallization front moved downwards, thus liberating new batches of small-volume melts which infiltrated the coarse-granular peridotites first and, subsequently the fine-granular peridotites [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF].

The plagioclase domain in the south western formed at the expense of the granular peridotites during crustal emplacement of the massif. Plagioclase peridotites record late low-pressure cooling (1 GPa) associated with strain localization in subsolidus shear zones that obliterated older magmatic and deformation structures before the final emplacement into the crust (Van der [START_REF] Van Der Wal | Structural petrology of the Ronda peridotite, SW Spain: Deformation history[END_REF].

Sampling and analytical methods

Eighteen peridotite samples collected from each tectonometamorphic domain from the westernmost part of the Ronda massif were selected for the present study. All of these samples but three were studied by [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. The rest of the studied samples are a fertile spinel lherzolite from the spinel tectonite domain (CHR2; Al 2 O 3 = 3.78 wt% and CaO = 3.25 wt%), a fine-granular depleted lherzolite (RO 203) and a fertile (Al 2 O 3 = 3.4 wt% and CaO = 2.97 wt%) plagioclase lherzolite (RO 144) from the layered granular subdomain. To minimise the effect of serpentinization, rock powders were prepared from large (1 kg) masses free from weathered surfaces and fracture planes. Sulfur was analysed with a high-temperature combustion iodometric tritation method at the National Museum of Natural History of Paris (France). Accuracy and precision were Fig. 1. Location of the peridotite samples studied in the southwestern part of the Ronda peridotite massif. Geological background after [START_REF] Gervilla | Geology and Metallogeny of the upper mantle rocks from the Serrania de Ronda[END_REF]. The three sub-domains of the granular peridotite facies (CG, LG and FG), as well as the recrystallization front (RF) are from [START_REF] Van Der Wal | Structural petrology of the Ronda peridotite, SW Spain: Deformation history[END_REF] and [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF].

reported by [START_REF] Gros | Determination of total sulfur contents in international rock standard SY-2 and other mafic and ultramafic rocks using an improved scheme of combustion/iodometric titration[END_REF]. Copper was analysed by XRF and ICP-MS at the University of Granada. Selenium was analysed at Geosciences Laboratory (Sudbury, Canada) by hydride generation and inductively coupled plasma mass spectrometry (ICPMS), after digestion of rock powders in hot concentrated acids (hydrofluoric, hydrochloric, nitric, and perchloric) in open vessels. Large (10 g) powder aliquots ensured detection limits of 3.5 ppb. Accuracy tests were reported by [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF], Lorand and Alard (2010) and [START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF]. Platinum-group elements and Au were analysed by ICP-MS (inductively coupled plasma-mass spectrometry) using a Thermofisher Element II ICPMS at the University of Montpellier (France). PGEs were separated from 15 g powder aliquots by the NiS-fire assay-Te coprecipitation procedure described by [START_REF] Gros | Analysis of platinum-group elements in geological materials using NiS-fire assay and Te-coprecipitation: the NiS dissolution step revisited[END_REF] and modified by [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF] to improve the recovery of PGE (i.e. second NiS-fire assay step and amount of Te increased to 28 ml). Blanks and accuracy tests were reported by [START_REF] Lorand | Platinum-group element signature of the Primitive Upper Mantle in highly residual ophiolitic peridotites[END_REF]Lorand et al. ( , 2010) ) on several peridotite samples, including UB-N. [START_REF] Savard | Comparison between nickel-sulfur fire assay Te co-precipitation and isotope dilution with high-pressure asher acid digestion for the determination of platinum-group elements, rhenium and gold[END_REF] demonstrated the good agreement between NiS fireassay analyses and the CT-ID-ICPMS procedure. Further analyses of one international rock standard (WGB1) are reported Table 2.

Polished thin sections of each sample were examined in reflected light microscopy at high magnification (500-1000×) to locate BMS and any HSE-bearing phases (see [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF]Lorand et al., , 2010)). PGMs were searched for and studied with a Tescan VEGA II LSU Scanning Electron Microscope (SEM) operating in conventional (high-vacuum) back scattered electron (BSE) mode, and equipped with an energy dispersive Si(L) SD3 detector with a resolution of 129 eV full width at half maximum at the Fe peak (Muséum National d'Histoire Naturelle, Paris, France, MNHN). PGMs were located by manual scan on carefully polished 200 μm-thick standard-sized (40 × 25 mm) sections at an acceleration voltage of 15 kV and a working distance of 8 mm to identify PGM qualitatively in the BSE mode.

Platinum-group element contents of BMS grains large enough (>100 μm) to be probed were determined along with several other chalcophile trace elements (Se, Zn, Te, Bi, Pb) by laser-ablation inductively coupled plasma mass spectrometry (LA-ICPMS). A GEOLAS excimer UV laser operating at 193 nm, coupled with a Thermo-Finnigan Element 2 magnetic-sector ICP-MS inductively coupled plasma mass spectrometer (ICP-MS) (University of Montpellier II) was used. Analytical conditions were reported in [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF]Lorand et al. ( , 2010)). The laser beam diameter was set up at 51 μm, with a 5 Hz laser frequency and a beam energy of about 12-15 J/cm 2 . Native copper and synthetic sulfides (i.e., NiS) known to be devoid of PGE (< ppb concentration levels) were analysed for evaluating mass interference between Niand Cu-argides ( 62 Ni 40 Ar, 63 Cu 40 Ar and 65 Cu 40 Ar) and the isotopes 102 Ru and 103 Rh. Rh and Ru concentrations were corrected accordingly. The gas blank (laser off) was collected for 240 s prior to laser ablation. Each ablation run was analysed in detail in time-integrated count diagrams to detect PGE and associated elements (Se, Te, Bi) hosted in metal-rich microparticles.

Raw data reduction was done using GlitterTM software. The analyses of pentlandite were quantified with S as an internal standard, using the mean S concentration measured by EMPA [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF]. Apart from a few analyses having sampled "pure" minerals, most are mixtures of several phases, BMS and/or alloys, as indicated by their large range of Ni and Cu contents (see below). The compositions of such mixtures were quantified using either S, Cu and/or Ni as internal standards and linear mixing between pentlandite/native copper and pentlandite/awaruite volume ratio calculated from Cu/S and Ni/S count rates in timeintegrated count diagrams. The detection limits in each quantification were calculated for each analysis from the gas blank and the sensitivity of the reference materials following the equations in [START_REF] Longerich | Laser ablation inductively coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation[END_REF]. As usually observed for LA-ICPMS analyses of sulfides, the detection limits for each element can vary significantly from one analysis to another, as a function of the size of the analysed grain, gas blanks and duration of the signal. A total of 68 spot analyses were conducted on 52 sulfide grains. Accuracy tests were performed with an in-house standard (NiS bead doped with SARM 7 rock standard powder; Table 3) which was reanalyzed at the «Laboratoire de Planétologie et Géodynamique à Nantes» using a Photon Machine Analyte G2 equipped with an excimer laser (193 nm laser wavelength) coupled with a Bruker quadrupole ICPMS [START_REF] Lorand | Chalcophile-siderophile element systematics of hydrothermal pyrite from martian regolith breccia NWA 7533[END_REF].

Petrographic data on BMS

All the studied samples show accessory BMS, as several tens of grains per single polished thin section of lherzolites (<0.1 vol%) and in lesser amounts in the harzburgites that display depleted bulk-rock S contents (Table 3). By contrast, there is no correlation between BMS modal abundances and the tectonometamorphic domains (see also [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF]. BMS occur either as rare, small (<20 μm) droplet-like (or euhedrally shaped) inclusions in the silicates (orthopyroxene, olivine) and Cr-spinel or as 200-300 μm polyhedral (not spherical) blebs with convex-inward grain boundaries forming dihedral angles (>60°) with adjacent silicates (Fig. 2). On average, due to strong deformation, BMS grain size tends to be somewhat smaller in garnet-spinel tectonites (6 × 18 to 45 × 20 μm) compared to granular samples. Such grains are commonly located at orthopyroxene-olivine grain boundaries in granular peridotites as documented in mantle peridotites that have been pervasively percolated by basaltic melts (e.g. [START_REF] Lorand | The Cu-Fe-Ni sulfide assemblages of tectonic peridotites from the Maqsad district, Sumail ophiolite, southern Oman: implications for the origin of the sulfide component in the oceanic upper-mantle[END_REF][START_REF] Seyler | Pervasive melt percolation reactions in ultra-depleted réfractory harzburgites at the Mid-Atlantic Ridge, 15°20' N: ODP Hole 1274[END_REF]. Where present, serpentine veinlets generally surround and coat (or cross-cut) these coarser BMS grains.

The same opaque mineral parageneses as those documented by [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF] in Beni Bousera and Ronda peridotites were found in our samples. No sharp difference of BMS assemblages has been detected in our sample set between each tectonometamorphic domain (Table 1). Enclosed BMS consist in Ni-rich (0.5 < Fe/Ni <1) pentlandite (ideally (Fe, Ni) 9 S 8 ) + chalcopyrite (ideally (CuFe)S 2 )) ± bornite (ideally Cu 5 FeS 4 ) ± pyrrhotite (Fe 1-x S) whereas a S-deficient assemblage (Fe-rich pentlandite + troïlite (FeS) + native copper + awaruite (Ni 3 Fe) + magnetite ± native iron) characterizes intergranular BMS (Fig. 2). Relict troïlite was identified in a few BMS grains from granular peridotites (Fig. 2b). Intergranular pentlandite grains are veined along the ( 100) and ( 111) cleavage planes by chalcopyrite and/or mackinawite, ideally Fe 1+x S (Fig. 2b). Valleriite (ideally 4(Fe,Cu)S 3 (Mg, Al)(OH) 2 ) is a secondary alteration product of chalcopyrite and/or bornite. [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF] interpreted enclosed BMS as primary (mantle-derived) sulfide phases and the intergranular sulfides + alloys assemblages as mantle-derived BMS altered to variable extents by serpentinization. Native copper and awaruite occur as external granules, as discontinous coronas or as fracture-filling veins cutting across BMS grains, as does magnetite (Fig. 2c,e). Such native metal-rich assemblages are typical of low-T (<300 °C) retrogressive serpentinization under olivine-excess conditions (low fluid/rock ratios) that generated strongly reducing conditions stabilizing native iron [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF]. Secondary BMS were also identified as serpentine veins-filling small-sized grains (<20 μm). These BMS of likely hydrothermal origin are Co-rich euhedral pentlandite (c.f. [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF] that are especially abundant in five samples (DR-12, DR-22, DR-4, DR-37 and DR-17).

Bulk-rock abundances of chalcogens and HSE

Chalcogen element systematics (S, Se) are similar to those reported so far for orogenic peridotites [START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF][START_REF] Lorand | Platinum-group element systematics and petrogenetic processing of the continental upper mantle: a review[END_REF]Lorand and Alard, 2010;[START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF][START_REF] Wang | Ratios of S, Se and Te in the silicate Earth require a volatile-rich late veneer[END_REF]. Sulfur concentrations range between 336 and 51 ppm (Table 4) and decrease from the lherzolites to the harzburgites. The five samples that show indisputable evidence of hydrothermal S addition as veinlet-filling euhedral pentlandite plot markedly above the S vs. Al 2 O 3 positive correlation of Fig. 3A, thus indicating S input from serpentinization fluids. Ignoring these five outliers, sulfur concentrations positively correlates with Al 2 O 3 , taken here as a fertility index (Fig. 3A). The regression line (r = 0.79) intercepts the Primitive Mantle Al 2 O 3 content at c.a. 250 ppm, as usually reported for orogenic peridotites [START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF]Wang and Becker, 2013 and references therein). Selenium, a close geochemical proxy for S under the reduced conditions of the upper mantle [START_REF] Lorand | S/Se systematics of the sub-continental lithospheric mantle beneath the Massif Central[END_REF][START_REF] Queffurus | A review of sulfur to selenium ratios in magmatic nickel-copper and platinum-group element deposits[END_REF], closely follows S systematics. Taken as a whole, Se concentrations positively correlate with Al 2 O 3. The compositional field of our Ronda peridotites in the Se vs. Al 2 O 3 plot of Fig. 3B fit well the various data sets documented for orogenic peridotites (Lorand and Alard, 2010;[START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF][START_REF] Lorand | Platinum-group element systematics and petrogenetic processing of the continental upper mantle: a review[END_REF][START_REF] Wang | Ratios of S, Se and Te in the silicate Earth require a volatile-rich late veneer[END_REF]Lorand and Luguet, 2016 and reference therein). However, Fig. 3 A and B indicates second-order erratic variations within granular peridotites. The three coarse granular lherzolites analysed are marginally Sand Se-depleted compared to tectonite spinel lherzolites. The depleted lherzolites from the fine-granular domain show highly variable S (54-180 ppm) and Se contents (30-77 ppb) for a narrow range of Al 2 O 3 contents. The three amphibole-cpxII-bearing samples DR-17, DR-37 and RO-203 display the highest S and Se contents. In a S vs. Se plot, our Ronda peridotites show broadly chondritic S/Se ratios, regardless of the tectonometamorphic domain they come from and whether they show secondary Cpx and/or disseminated Ti amphibole (Fig. 4A). Only the five samples presumably contaminated by serpentinizationderived S show the superchondritic S/Se ratios (3.10 3 -10 4 ) that characterize hydrothermal sulfides (e.g. [START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF]Queffurus and Barnes, 2015 and references therein). Such ratios exceed the accepted mantle range (3000 ± 200;[START_REF] Lorand | S/Se systematics of the sub-continental lithospheric mantle beneath the Massif Central[END_REF][START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF][START_REF] Wang | Ratios of S, Se and Te in the silicate Earth require a volatile-rich late veneer[END_REF][START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]. The Cu concentration range (7.8-34 ppm; Table 4) closely matches the published data base for orogenic mantle peridotites [START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF][START_REF] Wang | Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle[END_REF] and references therein), including the Ronda massif [START_REF] Frey | The Ronda high temperature peridotite: geochemistry and petrogenesis[END_REF][START_REF] Gueddari | Differentiation of platinum-group elements (PGE) and of gold during partial melting of peridotites in the lherzolitic massifs of the Betico-Rifean range (Ronda and Beni Bousera)[END_REF][START_REF] Garuti | Platinum-group-element distribution in subcontinental mantle: evidence from the Ivrea Zone (Italy) and the Betic-Rifean cordillera (Spain and Morocco)[END_REF]. [START_REF] Frey | The Ronda high temperature peridotite: geochemistry and petrogenesis[END_REF] documented a good positive Cu vs. Al 2 O 3. correlation for 17 Ronda peridotites collected in the easternmost part of the Ronda peridotite massif that escaped to regional-scale melt percolation. Such a correlation is also preserved in the spinel tectonite domain in Western Ronda (Fig. 3C). There is no difference in S, Se and Cu contents between fine layered granular lherzolite RO-144 and spinel tectonite lherzolite CHR-2. By contrast, granular peridotites of lower fertility (Al 2 O 3 < 3.0 wt%) show erratic variations in their Cu contents, that mimic those documented above for S and Se. The coarse-granular depleted lherzolites are slightly Cu-depleted compared to tectonite spinel lherzolites. Conversely, the depleted lherzolites (Al 2 O 3 < 2 wt%) from the fine-granular domain, namely the three S-and Se-enriched cpxIIbearing fine-granular lherzolites DR-17, DR-37 and RO-203, display highly variable Cu contents (7.8-33.1 ppm; Table 4). Likewise, the Cu vs. Se plot of Fig. 4B clearly highlights similar scatter for Se <60 ppb; depleted lherzolites from the fine-granular subdomain show greater variability of Cu/Se ratios compared to the fertile lherzolites that align quite well on the Cu vs. Se correlation defined by spinel tectonites.

The analysed peridotites display the PGE concentration range of orogenic peridotites at 0.05 to 0.1 x CI-chondrites (Table 4; Fig. 5). The lherzolites (Al 2 O 3 > 2 wt%) preserve quite similar PGE concentrations and PGE relative abundances throughout the four subdomains defined by [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. Their CI chondrite-normalized PGE patterns display Ru N /Ir N (1.6-2.6) and Rh N /Ir N (1.16-1.36) that are distinctly higher than CI-chondritic ratios (N = CI-chondrite normalized). These fertile samples also display higher than chondritic Pd N /Ir N (1.1-1.6; Table 4); the highest value (1.6) corresponding to sample CHR-2, the most fertile lherzolite analysed in the spinel tectonite domain. Similar excesses of Ru, Rh and Pd relative to Ir and Pt and to chondritic ratios are a characteristic feature of orogenic lherzolites worldwide [START_REF] Becker | Highly siderophile element composition of the Earth's primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths[END_REF]Lorand et al., 2013 and reference therein). Previous bulk-rock PGE analyses of Ronda lherzolites produced mostly similar CI-chondrite normalized PGE patterns, except however, a much larger scatter of Pt contents (5.9 to 22 ppb) [START_REF] Garuti | Platinum-group-element distribution in subcontinental mantle: evidence from the Ivrea Zone (Italy) and the Betic-Rifean cordillera (Spain and Morocco)[END_REF][START_REF] Gueddari | Differentiation of platinum-group elements (PGE) and of gold during partial melting of peridotites in the lherzolitic massifs of the Betico-Rifean range (Ronda and Beni Bousera)[END_REF]. This large variability of Pt within and between the different data sets most likely reflects the heterogeneous distribution of this element within discrete Pt-rich microminerals that generate strong nugget effects if bulk-rock analysis is performed from sample aliquots that are too small (<1 g) [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF]. Our analyses performed on 15 g of sample powder achieved much better reproducibility for Pt analyses. The NiS fire-assay Instrumental Neutron Activation (INA) procedure of [START_REF] Lorand | Highly siderophile element geochemistry of the Earth's mantle: new data for the Lanzo (Italy) and Ronda (Spain) orogenic peridotites bodies[END_REF] underestimated the contents of Ir and Ru, as shown by the abnomally high Pd N /Ir N (1.96) and Os N /Ir N (1.6) of sample RO-144 which was reanalyzed with both ID-ICMS and our NiS procedure (Table 4).

Correlation between PGE absolute abundances and fertility index (Al 2 O 3 ) are lacking (Fig. 6A). Fertile lherzolites (bulk-rock Al 2 O 3 > 2 wt%) show rather homogeneous PGE absolute abundances and Pd N /Ir N ratios and no clear variations can be identified between each tectonometamorphic domain. Pd N /Ir N slightly decreases (Pd N /Ir N = 1.0) in the granular harzburgites DR41 and DR4, the most Pd depleted Ronda harzburgite analysed in the present study (Fig. 6B). However, all of the depleted peridotites (bulk-rock Al 2 O 3 < 2 wt%) analysed here show Pd N /Pt N > 1 and higher absolute Pd abundances compared with similar rocks of residual origin from other orogenic peridotites (Fig. 5). This is especially true for the refractory lherzolites (DR-33, DR37; DR-17 and RO-203) that contain modal metasomatic phases (magmatic clinopyroxene +/-Ti pargasite) (1 < Pd N /Ir N < 1.56), and for cpx-poor lherzolites from the spinel tectonite domain (DR-12; DR 27; Fig. 6). The Au concentration range in western Ronda peridotites is also larger than usually reported in fertile mantle peridotites from orogenic peridotite massifs (<2 ppb: [START_REF] Fischer-Gödde | Rhodium, gold and other highly siderophile elements in orogenic peridotites and peridotite xenoliths[END_REF][START_REF] Wang | Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle[END_REF] (Fig. 5). Extreme Au enrichments (14.4 ppb) were detected in two spinel tectonites DR-27 and DR-12, that are also rich in serpentinizationderived hydrothermal sulfide veinlets as shown by their superchonditic S/Se ratios (Table 4; Fig. 4B). The other three granular samples that display S excess coupled with petrographical evidence of hydrothermal sulfides (DR-4; DR-37 and DR-17; Table 3) are poorer in Au. Measured bulk Au content may be highly unreproducible (e.g. . No correlation between Au and Pd N /Ir N was detected, nor between Au and Cu, Au and L.O•I values or S/Se (not shown).

6. In-situ analyses

LA-ICPMS analyses

As usually documented in mantle rocks, PGE, Au and the chalcogens Se, Te, Bi and As occur at ppm to tens of ppm concentrations levels in Ronda peridotitic sulfides [START_REF] Alard | Non-chondritic distribution of the highly siderophile elements in mantle sulphides[END_REF][START_REF] Delpech | In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean[END_REF][START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF]Luguet et al., 2004, and references therein). Apart from three pyrrhotite grains (analyses ab-6po, ab-8po and ab-9po) in the layered granular peridotite RO-144 and one native copper grain (analysis ab-27), large enough to be probed in the fine granular sample DR-29, all the other in-situ analyses are analyses of mixed grains dominated by pentlandite, the major sulfide in Ronda peridotites [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF]. Awaruite was inferred in mixed analyses that show Ni contents above the average value reported for Ronda intergranular pentlandite (25% [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF]. Note that half of the analysed BMS (37/60) display Cu content >5 wt%, reflecting widespread Cu-rich minerals, in agreement with observations in reflected light microscopy. Native copper/chalcopyrite-pentlandite mixes were identified through their elevated Cu contents and metal/sulfur counts ratios.

Taken as a whole, the analysed Ronda sulfides display CI-chondrite normalized patterns of orogenic pentlandites [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF](Lorand et al., , 2010;;[START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF], i.e. broadly chondritic Os N /Ir N , Ru N /Ir N and Rh N /Ir N ratios coupled with deep Pt and Au negative anomalies and highly variable Pd contents; Se/Te ratios vary significantly around the chondritic ratio (Fig. 7). Platinum contents vary by four orders of magnitude, irrespective of the other HSE absolute and relative abundances. Despite the good reproducibility of bulk-rock analyses at 15 g subsample size, in-situ analysed Iridium-group PGE (IPGE = Os, Ir, Ru), Rh and Se concentrations spread over two orders of magnitude. It has long been shown that the missing Pt in mantle rocks is hosted in discrete Pt-rich microphases [START_REF] Alard | Non-chondritic distribution of the highly siderophile elements in mantle sulphides[END_REF][START_REF] Lorand | Platinum-group element abundances in the upper mantle: New constraints from in situ and whole-rock analyses of massif central xenoliths (France)[END_REF][START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF]Lorand et al., 2010;Lorand and Luguet, 2016 and reference therein). This is confirmed for Ronda peridotites by the SEM study (see section 6.2) and a close inspection of time-integrated laser ablation output signals. For example, the time-integrated laser signal collected during the laser microprobe analyses of several grains (qb-4, sample DR-3; ab-1, sample RO 144) display Pt, Te and Bi peaks corresponding to micrometric Pt-(Pd)-Te-Bi phases (Fig. 8). If incorporated in the calculation of PGE concentrations, such Te-rich phases produce nearly flat CI-chondrite normalized PGE pattern (Fig. 7 C,D). [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF] also detected Pt-rich micronuggets up to several microns across in their LA-ICPMS analyses.

Pentlandite compositions vary according to the coexisting mineral assemblage intercepted by the laser beam and to a lesser extent, the tectonometamorphic domain they come from. [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF] interpreted their extreme Os tenors (up to 908 ppm) as likely caused by Os-rich minerals (alloys or sulfides) inside the targets of the laser spots. We did not find such extreme Os contents in our LA-ICPMS data set. However, several pentlandite analyses in DR-7 (analyses Qa-11 and Qa-16 in Table S1), a spinel tectonite lherzolite, produced laurite-type chondrite-normalized HSE patterns characterized by positive Os, Ru and (Rh) anomalies with respect to Ir (Fig. 7A; see [START_REF] González-Jiménez | Transfer of Os isotopic signatures from peridotite to chromitite in the subcontinental mantle: insights from in situ analysis of platinum-group and base-metal minerals (Ojén peridotite massif, southern Spain)[END_REF]Lorand et al., 2010;[START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF]. "Pure" Pn analyses (14.8-17.5 wt% Ni) in granular peridotites produces high IPGE contents (10-50 x CI-chondritic abundances) coupled with highly reproducible Pt, Pd and Au contents, close to limits of detection leading to Pd N / Ir N < 0.01. The Cu-rich pentlandite analyses show more scattered Pd contents, resulting in Pd N /Ir N ranging from higher than chondritic (8.2) to lower than chondritic (0.01; Table S1). Such random variations may result from the Cu-rich mineral contaminant, whether native Cu or chalcopyrite. Apart from the two Pt-rich outliers qb-4 and ab-1, there is no correlation between Pt and Te contents: pentlandite-native copper and pentlandite-awaruite mixes (e.g. DR-29) incorporate significant amount of Te (Fig. 7C,D). Silver contents positively correlate with Cu (not shown). Zinc, Cd and Pb are associated with high Cu. The only analysis of "pure" native Cu in one fine-granular peridotite (ab-27; DR-29) indicates high Pd (20 ppm) and Ag (121 ppm) contents coupled with Pt and Au contents close to limits of detection (Table S1; Fig. 9A). Like native copper, awaruite may incorporate much Pd (up to 40 ppm in sample DR 29; analysis ab 26 in Table S1; Fig. 9B). Some pentlanditeawaruite intergrowths (e.g. analysis ab-28; sample DR-29) also display higher-than chondritic Pd N /Ir N (Table S1). The analysed Po (ab-8po and ab-9po, Table S1) are uniformly PGE depleted with Pd N /Ir N < 0.01, and close to limits of detection Pt and Pd contents (Fig. 7D) while containing trace amounts of chalcophiles/chalcogens (Cd, Pb, Bi, Se, Te).

SEM study

SEM observations provide further evidence for discrete platinumgroup minerals (PGM) in nine (of the fourteeen) studied Ronda peridotites (Table 4). Taken as a whole, the PGM assemblage identified in Ronda peridotite does not differ significantly from those reported in other orogenic lherzolites [START_REF] Lorand | Abundance and distribution of platinum-group elements in orogenic lherzolites; a case study in a Fontête Rouge lherzolite (French Pyrénées)[END_REF](Lorand et al., , 2010;;[START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF][START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF]. All PGMs were identified inside Fe-Ni-Cu sulfides (or their serpentinization-derived products). The highest PGM abundance (ten grains in four samples) and the largest mineralogical diversity were found in spinel tectonites. As suggested by LA-ICPMS analyses, laurite-erlichmanite (Ru,Os)S 2 compounds were identified in sample DR-12, as a 4 × 2 μm euhedral inclusion in pentlandite and a 10 × 1 μm external granule embedded in another pentlandite (Fig. 10A,B). Only Pt-rich minerals (malanite, CuPt 2 IrS 4 , moncheite, PtTe 2 and secondary Pt-Cu alloys) were identified in the other studied samples (CHR-2; DR-7 and DR-27), with Cu-Pt-rich minerals predominating over the other species. Micrometric inclusions of moncheite and Pt-Fe alloys were identified in DR-27 and DR-7 pentlandites, respectively. Malanite occurs inside pentlandite as anhedral external granules or rod-shaped exsolutions with sharp boundaries (Fig. 10D). Cu-Pt(Pd) alloys are closely associated with serpentinization-related alteration products, as μm-sized particles inside spongy awaruite or magnetite or inside chlorite in the immediate vicinity of sulfide blebs. Systematic scanning also identified gold microparticles disseminated within interstitial (serpentinized or not) pores of spinel tectonites, along with several silver sulfide microphases, galena and barite (Table S1). These latter minerals are found to occur away from Cu-Fe-Ni sulfides.

Granular peridotites are poorer in PGM (7 detections for seven samples studied). Apart from a two-phase inclusion of Pt(Ir)As (200 nm across) + Ni arsenide in RO 203 pentlandite (Fig. 11E), all the other PGMs studied are Cu-Pt rich minerals akin to those described above in spinel tectonites, i.e. malanite within unaltered pentlandite blebs and Cu-Pt-(Pd) alloys in the altered area around pentlandite, associated with native Cu, awaruite or magnetite (Fig. 10E). Silver sulfides, lead sulfides and barite were also detected, within serpentine mesh, at some distance from Cu-Fe-Ni sulfides.

Discussion

The preserved correlations with fertility index might suggest that the chalcophile/siderophile element systematics inherited from the Proterozoïc melting event identified by radiogenic isotope studies remained immune from the regional-scale magmatic percolation event recorded by the southwestern portion of the Ronda peridotite massif. However, several features argue for subtle but significant modifications affecting mostly the distribution of incompatible elements (S, Se, Cu, Pd, Au) in the depleted lherzolites from the granular tectonometamorphic domain (Al 2 O 3 < 2 wt%). Before to adress these points in terms of mantle processes, a short discussion of the effect of serpentinization is made necessary by the extent of this alteration materialized by high Loss on Ignition (L.O•I.) values of some bulk-rock analyses. et al. (1997) found a much larger S concentration range (291-1093 ppm) mostly exceeding the accepted mantle range in 10 peridotite samples collected from the central part of the Ronda massif. Because their S concentrations positively correlate with loss on ignition (L.O•I.) values, these authors concluded that much of the sulfur in the Ronda massif had been disturbed by serpentinization. No such correlation has been observed in southwestern Ronda samples and most of our S contents agree with the accepted mantle concentration range despite L.O.I. values of similar magnitude as those of [START_REF] Garuti | Platinum-group-element distribution in subcontinental mantle: evidence from the Ivrea Zone (Italy) and the Betic-Rifean cordillera (Spain and Morocco)[END_REF]. Sulfur was remobilized on a local scale only, as shown by the 5 samples (DR-12, DR-27, DR-4; DR-29, DR-26) that display unambiguous mineralogical and geochemical evidence of hydrothermal S addition. The same is true for other chalcogens, semi metals and PGEs. Observations in nature, theoretical modelling and experiments, all demonstrate a greater mobility of Au and the less refractory PGE (Pd and Pt) over Os, Ir and Ru in hydrothermal fluids [START_REF] Wood | The aqueous geochemistry of the platinum group elements with applications to ore deposits[END_REF]Barnes and Liu, 2012 and references therein). However, our data base does not produce a statistically reliable correlation between Au and S/Se: the highest Au contents (DR-12, DR 27) correspond to highly variable S/Se ratios (9834-3553). At Ronda, the retrogressive serpentinization event generated oxygen fugacities low enough to stabilise native iron. Under such conditions, Au, Pt and Pd should occur in hydrothermal solutions mainly as bisulfides rather than as chloride or hydroxide complexes [START_REF] Wood | The aqueous geochemistry of the platinum group elements with applications to ore deposits[END_REF]. Remobilization of Pd, Pt and Au as bisulfide complexes cannot be precluded on the hand-sample scale, because some sulfur was liberated from the primary sulfide assemblages to form secondary sulfides in serpentine mesh lines (c.f. [START_REF] Lorand | The behaviour of the upper mantle sulfide component during the incipient serpentinization of "alpine-type" peridotites as exemplified by the Beni Bousera (Northern Morocco) and Ronda (Southern Spain) ultramafic bodies[END_REF]. Desulfurization also resulted in the evolution of Pt-rich PGM from sulfides and tellurides when trapped inside BMS to alloys when adjacent to serpentine. However, even considering the five samples where the S contents were obviously upgraded by serpentinization fluids, correlations between Pt or Pd (or Pd/Ir) and L.O.I are lacking at the bulk-rock scale. The same is also true for Au, suggesting that these three elements remained largely immune from serpentinization-related mobilisation. This lack of mobility can be explained by the fact that Au was sequestered in native gold, Pd in BMS and alloys stable during serpentinization (pentlandite, native copper and awaruite), and Pt in sulfides, tellurides, arsenides and secondary alloys. Moreover, experiments suggest that the solubilities of PGE-tellurides and bismuthides in hydrothermal fluids are significantly low under the T conditions of serpentinization [START_REF] Barnes | Pt and Pd mobility in hydrothermal fluids: evidence from komatiites and from thermodynamic modelling[END_REF].

Hydrothermal input of serpentinization-related fluids

Garuti

Monosulfide solid solution and the longevity of PGE and chalcogen/ chalcophile systematics inherited from the Proterozoïc protolith

The nearly flat CI-chondrite normalized PGE patterns that characterize the Primitive Mantle estimate [START_REF] Becker | Highly siderophile element composition of the Earth's primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths[END_REF] is the best evidence that except for Pd, our southwestern Ronda peridotites preserved the PGE systematic inherited from the Proterozoïc melting event. Our conclusion is consistent with the long-term stability of Osbearing minerals documented by [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF] who identified Fe-Ni sulfides carrying similar Proterozoic model ages in peridotites from both the protolith and the recrystallized domain(s). Most of the grains they analysed by LA-MC-ICPMS have 187 Os/ 188 Os lower than PUM (γOs up to -2.1), high Os contents and low Re/Os, suggesting derivation from former BMS residual after melt extraction mostly protected from reactions with intergranular melt films by inclusion in spinel and silicates. According to [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF], monosulfide solid solution (Mss; ideally complete pyrrhotite solid solution between Fe 1-x S and Ni 1- x S) may account for these well preserved Proterozoic Re-Os model ages. Mss has octahedral sites for sequestering Re, Os, Ir, Ru, and Rh at wt% concentration levels (e.g. [START_REF] Ballhaus | Phase relations in the Fe-Ni-Cu-PGE-S system at magmatic temperature and application to massive sulfide ores of the Sudbury igneous complex[END_REF][START_REF] Bockrath | Stabilities of Laurite RuS 2 and monosulfide liquid solutions at magmatic temperatures[END_REF][START_REF] Helmy | Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulfide melts[END_REF][START_REF] Li | Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: effects of composition and temperature[END_REF]Liu and Brenan, 2015 and references therein), i.e. 100 x the actual Os contents measured in Ronda BMS. These solubility data account for preservation of broadly-chondritic relative abundances now measured in southwestern Ronda peridotites. In the [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF] model, the coarse granular subdomain beneath the recrystallization front was simply reheated at 1250 °C by the thermal input of the percolating melt. This temperature estimate lies below the melting point of Mss which is the stable BMS phase during mantle melting [START_REF] Alard | Non-chondritic distribution of the highly siderophile elements in mantle sulphides[END_REF][START_REF] Griffin | Lithosphere evolution beneath the Kaapvaal Craton: Re-Os systematics of sulfides in mantle-derived peridotites[END_REF][START_REF] Bockrath | Stabilities of Laurite RuS 2 and monosulfide liquid solutions at magmatic temperatures[END_REF][START_REF] Zhang | Experimental constraints on mantle sulfide melting up to 8 GPa[END_REF]Fig. 11). According to experiments and studies of natural rocks (e.g. [START_REF] Guo | Geochemistry and origin of sulphide minerals in mantle xenoliths: Qilin, Southeastern China[END_REF][START_REF] Etschmann | A kinetic study of the exsolution of pentlandite (Ni, Fe) 9 S 8 from the monosulfide solid solution (Fe,Ni)[END_REF][START_REF] Fleet | Phase equilibria at high temperatures[END_REF]Lorand and Luguet, 2016 and reference), the Mss phases decompose on cooling by a series of subsolidus reactions yielding to the low-temperature BMS assemblage now observed in tectonically emplaced mantle peridotites: pentlandite + pyrrhotite. Because the Mss can dissolve several percents Cu (2.2-6.1 wt% at 950-1020 °C according [START_REF] Helmy | Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulfide melts[END_REF], it exsolve chalcopyrite at T < 500 °C (e.g. [START_REF] Fleet | Phase equilibria at high temperatures[END_REF]. The few pentlandite+pyrrhotite±chalcopyrite inclusions isolated in silicates and preserved from serpentinization-related desulfidation are likely such Mss decomposition products. Silicates-or spinel-hosted BMS inclusions in our samples were much too small to be probed with the LA-ICPMS. However, Mss precursors can be identified by the high IPGE contents in all of the intergranular pentlandite grains analysed by LA-ICPMS. Moreover, several grains in the coarse granular lherzolite (Fig. 7B) display the strongly Pt-Pd-depleted CI-chondrite normalized PGE patterns (Pd N /Ir N < 0.1) predicted for residual Mss by laboratory partitioning experiments that report almost similar incompatible behaviour for both elements in the Mss structure [START_REF] Li | Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: effects of composition and temperature[END_REF][START_REF] Ballhaus | Phase relations in the Fe-Ni-Cu-PGE-S system at magmatic temperature and application to massive sulfide ores of the Sudbury igneous complex[END_REF][START_REF] Liu | Partitioning of platinum-group elements (PGE) and chalcogens (Se, Te, As, Sb, Bi) between monosulfide-solid solution (Mss), intermediate solid solution (Iss) and sulfide liquid at controlled fO 2 -fS 2 conditions[END_REF] and reference therein). The good positive correlation between S and Se of Fig. 4A can also be inherited from the proterozoic partial melting event because both elements are accomodated in the Mss lattice [START_REF] Delpech | In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean[END_REF][START_REF] Helmy | Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt -Application to magmatic sulfide deposits[END_REF][START_REF] Liu | Partitioning of platinum-group elements (PGE) and chalcogens (Se, Te, As, Sb, Bi) between monosulfide-solid solution (Mss), intermediate solid solution (Iss) and sulfide liquid at controlled fO 2 -fS 2 conditions[END_REF]Lorand and Alard, 2010).

The positive correlations between chalcogens (S, Se), chalcophile Cu, and fertility index are usually interpreted in terms of progressive removal of sulfides from the mantle at increasing degrees of melting (e.g. [START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF][START_REF] Luguet | Highly siderophile element and 187 Os signatures in noncratonic basalt-hosted peridotite xenoliths: unravelling the origin and evolution of the post-Archean lithospheric mantle[END_REF] and reference therein), although the strong linearity of some plots can also be better reconcilied with ancient refertilisation events of the protolith predating the Oligocène event (e.g. Lorand et al., 2010;[START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF]. It was better preserved in spinel peridotites from spinel/garnet tectonite domain that escaped thermal/chemical effects of this regional scale porous melt flow processing. For 5% melting, as assumed by [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF], BMS are marginally extracted from residual peridotites [START_REF] Guo | Geochemistry and origin of sulphide minerals in mantle xenoliths: Qilin, Southeastern China[END_REF][START_REF] Lorand | Platinum-group element systematics and petrogenetic processing of the continental upper mantle: a review[END_REF][START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF] and references therein) and sulfide melt -silicate melt partition coefficients are so high (>10 5 ) that they preserve PGE inside BMS from significant fractionation. By contrast, the erratic variations of Cu, S and Se contents identified in Figs. 3 and4 point to thermal/chemical effects of melt percolation on BMS in the Granular domain as a whole. Likewise, the Pd N /Pt N > 1 of refractory peridotites, whether from the granular or the spinel tectonite domain, cannot be a partial melting feature. Although both elements are in theory Mss-incompatible, they fractionate during mantle melting processes because Pt exsolves as Pt-rich alloys during the desulfidation process of Mss coeval to partial melting, thus making Pt more compatible than Pd which does not enter such high-T Pt-alloys [START_REF] Lorand | Chalcophile and siderophile elements in mantle rocks: trace elements controlled by trace minerals[END_REF][START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF]Peregoedova et al., 2004 and references therein). Likewise the Au-enrichment compared to Primitive Mantle estimates cannot be a partial melting feature.

Cu-Ni sulfide melt mobility and expected distribution of Mssincompatible elements

According to Fig. 11, BMS were partially molten during the Oligocène thermo-mechanical erosion of Ronda peridotites. Hence, residual Mss coexisted with a sulfide melt that experiments on the Cu-Fe-Ni-S system predict to be more metal rich (atomic metal/sulfur ratio close to 1) and enriched in both Cu and Ni relative to Mss (e.g. Ballhaus et al., (2008,2010) and [START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF]. CI chondrite normalizing values after [START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]. The different colors represent the four tectonometamorphic subdomains defined in [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF].

2001; [START_REF] Craig | Phase relations in the Cu-Fe-Ni-S system and their applications to magmatic ore deposits[END_REF][START_REF] Fleet | Phase equilibria at high temperatures[END_REF]Lorand and Luguet, 2016 and references therein). This Cu-Ni-rich sulfide melt can accommodate Pt and Pd in its square-planar sites, along with Au, Se, semi-metals (Te, As, Bi) and other chalcophile elements (Cu, Ag, Zn…) [START_REF] Helmy | Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt -Application to magmatic sulfide deposits[END_REF][START_REF] Li | Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: effects of composition and temperature[END_REF][START_REF] Liu | Partitioning of platinum-group elements (PGE) and chalcogens (Se, Te, As, Sb, Bi) between monosulfide-solid solution (Mss), intermediate solid solution (Iss) and sulfide liquid at controlled fO 2 -fS 2 conditions[END_REF]. D Mss/sulfide melt decreases from 1 to 0.6 for S and Se to 0.1-0.2 for Cu, Pt and Pd and less than 0.05 for Te and Ag [START_REF] Helmy | Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulfide melts[END_REF][START_REF] Wang | Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle[END_REF]. One may infer that remobilization of this Cu-Ni rich sulfide melt by the Oligocene thermomechanical erosion of the mantle lithosphere accounts for the erratic variation of bulk-rock Cu, S and Se contents detected in granular peridotites. The Cu-Ni rich sulfide melt shows up wetting properties against the silicate matrix and could easily be physically separated from the Mss [START_REF] Ballhaus | Phase relations in the Fe-Ni-Cu-PGE-S system at magmatic temperature and application to massive sulfide ores of the Sudbury igneous complex[END_REF][START_REF] Delpech | In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean[END_REF]Lorand et al., 2010). Accumulation of this sulfide melt also account for the S-Cu-Se enrichment trend coupled with a selective increase of Pd relative to Pt (Pd N /Pt N > 1) that characterize several olivine-rich refractory lherzolites from the fine-granular subdomain (i.e. . Here, this accumulation pattern correlates with precipitation of a late Cr-rich, interstitial clinopyroxene (hereafter referred to as cpx II), resulting from melt-rock reaction at decreasing melt fractions and decreasing temperature [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF][START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF]. The same sequence of event producing the same Curich BMS assemblage (Ni pentlandite + chalcopyrite + bornite) enclosed in Cr spinel and silicates was documented in oceanic and continental peridotites that display evidence of melt percolation [START_REF] Lorand | The Cu-Fe-Ni sulfide assemblages of tectonic peridotites from the Maqsad district, Sumail ophiolite, southern Oman: implications for the origin of the sulfide component in the oceanic upper-mantle[END_REF][START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF][START_REF] Seyler | Pervasive melt percolation reactions in ultra-depleted réfractory harzburgites at the Mid-Atlantic Ridge, 15°20' N: ODP Hole 1274[END_REF], Marchesi et al., 2013).

Despite serpentinization-related desulfurization reactions, intergranular BMS in our Ronda samples also bear evidence for Cu-rich BMS compositions such as chalcopyrite networks inside coarsegrained pentlandite, coupled with widespread occurrences of native copper and secondary Cu sulfides (valleriite). If those coarse-grained pentlandites with abundant chalcopyrite networking had formed only via subsolidus decomposition of a Mss, it would be expected to be almost devoid of Pd and other Mss-incompatible chalcogens and chalcophile elements (e.g. Te, As, Bi, Zn, Cd....) while being Cu-poor [START_REF] Mansur | Textural and compositional evidence for the formation of pentlandite via peritectic reaction: Implications for the distribution of highly siderophile elements[END_REF]. More likely, our coarse-grained pentlandite is a Fig. 6. Plots of Total PGE contents and Pd/Ir ratio vs. Al 2 O 3 . CI-chondritic ratio after [START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]. Total PGE contents estimated as Ir + Ru + Rh + Pt + Pd. Symbols as in Fig. 3.

J.-P. Lorand, S. Pont, R. Guttierez-Narbona et al. Lithos 380-381 (2021) 105901

subsolidus decomposition product of a Cu-bearing high temperature pentlandite. A series of experimental studies [START_REF] Kitakaze | Phase relations in the Fe-Ni-S system from 875 °C to 650 °C[END_REF][START_REF] Sugaki | High form of pentlandite and its thermal stability[END_REF] have demonstrated that such coarse-grained pentlandite starts crystallizing at 870 °C via a peritectic reaction between Mss and the sulfide melt and keeps growing from the sulfide melt down to 739 °C [START_REF] Kitakaze | Phase relations in the Fe-Ni-S system from 875 °C to 650 °C[END_REF]. It is well known that pentlandite can accommodate relatively high amounts of all IPGE in its structure (e.g., up to 12.9 wt% Ru and at 500 °C; [START_REF] Makovicky | Experimental studies on the solubility and distribution of platinum group elements in base metal sulfides in platinum deposits[END_REF]. Thus, its IPGE budget was directly inherited from precursor Mss, while the highly variable Pd contents (0.01 < Pd N /Ir N <8.2; Table S1) testify to variable input of Cu-Ni rich melt. Reequibration between Mss and this sulfide melt also explains why the depleted lherzolites show bulk-rock Pd N /Pt N ratios (N = CI-chondrite normalized) close to 1.

Of course, any remobilization of the Cu-Ni sulfide melt should affect all the Mss-incompatible trace elements other than Se, Cu and Pd. As shown by numerous papers [START_REF] Helmy | Partitioning of Se, As, Sb, Te and Bi between monosulfide solid solution and sulfide melt -Application to magmatic sulfide deposits[END_REF][START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF]Lorand andAlard, 2001, 2010 andreferences therein) the Cu-Ni sulfide melt incorporates preferentially Te over Se, and Pd over Ir. Hence, the Cu-Ni sulfide melt is expected to display low Se/Te coupled with high (superchondritic) Pd/Ir while Mss shows opposite characteristics. Our LA-ICPMS analyses define a wide array between those two end-members in a Pd/Ir vs. Se/Te diagram (Fig. 12A). However, it is worth noting that this diagram may be subject to sampling bias. In sample DR4 from the coarsegranular subdomain, BMS display broadly chondritic Se/Te coupled with a stong Pd-depletion whereas in the layered granular sample RO 144, all of the analysed BMS show a strong Te-depletion for similar Se contents compared to peridotites from the other subdomains, yielding to extreme Se/Te ratios up to 110 (Fig. 12B; Table S1). For DR-4, a secondary disturbance of BMS assemblages during serpentinization that generated native copper and awaruite is to be considered. Both minerals are two important Pd-carriers that may disturb the in-situ analyses in being not fully intercepted by the laser beam owing to their location in contorted veinlets at grain boundaries and within fractures of primary BMS. The same line of reasoning can also apply to RO-144 that show evidence for micrometersized tellurides that are difficult to pick up during LA-ICPMS analyses.

In spite of such second-order disturbances, one may assume that the diagrams of Fig. 12 testify to a mixing trend between Mss and a Cu-Ni-rich sulfide melt, not necessarily cogenetic.

In summary, our Ronda samples only bear evidence for local scale redistribution of the Cu-Ni sulfide melt triggered by reheating and low-degree partial melting rather than suggesting massive input of chalcophile-siderophile elements coming from the percolating magmas. The high modal abundance of Cu sulfides was likely an original compositional feature of the protolith antedating the regional-scale Oligocene thermomechanical erosion. On average, orogenic lherzolites are Curicher compared to other mantle samples [START_REF] Lorand | S/Se systematics of the sub-continental lithospheric mantle beneath the Massif Central[END_REF](Lorand et al., , 2010[START_REF] Lorand | Platinum-group element systematics and petrogenetic processing of the continental upper mantle: a review[END_REF][START_REF] Wang | Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle[END_REF]. No difference of BMS assemblages was detected between the granular domain and the spinel tectonite domain that remained mostly immune from the Cenozoïc thermomechanical erosion. In the granular domain, only the most refractory olivine-rich lherzolites were involved by sulfide melt remobilization, perhaps because olivine-rich rocks were more permeable to silicate melt/sulfide film infiltrations [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF]. It is also worth noting that none of our granular peridotites as a whole show the drastic depletion in HSE + chalcophile elements documented in mantle peridotites that have lost their BMS by percolating melts (e.g. [START_REF] Ackerman | Highly siderophile element geochemistry of peridotites and pyroxenites from Horní-Bory, Bohemian Massif: Implications for HSE behaviour in subduction-related upper mantle[END_REF][START_REF] Büchl | Melt percolation monitored by Os isotopes and HSE abundances: a case study from the mantle section of the Troodos Ophiolite[END_REF][START_REF] Delpech | In-situ geochemistry of sulfides in highly metasomatized mantle xenoliths from Kerguelen, southern Indian Ocean[END_REF]. Likewise, none of our samples display the pyroxenite-type CI-chondrite normalized hybrid HSE patterns (e.g., Pt N /Os N = 3.4-7.8 coupled with highly radiogenic 187 Os/ 188 Os (0.1372-0.1411)) identified by [START_REF] Marchesi | Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts[END_REF] in some highly fertile lherzolites (7-8 wt% Al 2 O 3 ) sampled within the recrystallization front of the Ronda peridotite massif. These author suggested that the mass fraction of percolating melt dramatically modified their HSE chalcophile element patterns of these samples by triggering complete dissolution/reequilibration of their mineral carriers in an open system melting process [START_REF] Marchesi | Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts[END_REF].

If valid for the granular domain, our interpretation linking the erratic variations of Mss-incompatible elements to a secondary mobility of Cu-Ni-rich sulfide melt does not account for the Au enrichment trend of spinel harzburgites frrom the spinel tectonite domain. This latter is clearly related to the LREE enrichments trend documented by [START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF] who suggested that spinel harzburgites were infiltrated by volatile-rich small-melt fractions (<<0.1% by volume) migrating upward from the granular domain through the recrystallization front (see also [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF]. It is the progressive fractionation and volume reduction of the intruding melt by melt-rock reaction in the granular domain that led to accumulation of volatiles [START_REF] Garrido | Incompatible trace element partitioning and residence in anhydrous spinel peridotites and websterites from the Ronda orogenic peridotite[END_REF]. Such small-melt fractions were able to develop a chromatographic fractionation effect on the most incompatible lithophile elements. A similar chromatographic explanation also holds for the strong Au and to a lesser extent Pd enrichments that were detected in these rocks (e.g. Fig. 5). The behaviour of both elements (compared to other PGEs) is consistent with their stronger affinity for the volatile phase [START_REF] Ballhaus | The Partitioning of Fe, Ni, Cu, Pt, and Au between Sulfide, Metal, and Fluid Phases -a Pilot-Study[END_REF][START_REF] Fleet | Volatile transport of precious metals at 1000°C; Speciation, fractionation and effect of base metal sulfides[END_REF][START_REF] Wood | The aqueous geochemistry of the platinum group elements with applications to ore deposits[END_REF], coupled with their highly incompatible behaviour with respect to Mss, which is expected to be the dominant residual BMS in such refractory rocks at mantle temperatures (e.g. [START_REF] Alard | Non-chondritic distribution of the highly siderophile elements in mantle sulphides[END_REF][START_REF] Griffin | Lithosphere evolution beneath the Kaapvaal Craton: Re-Os systematics of sulfides in mantle-derived peridotites[END_REF][START_REF] Guo | Geochemistry and origin of sulphide minerals in mantle xenoliths: Qilin, Southeastern China[END_REF][START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF]. Gold discrete grains detected with the SEM in spinel tectonite harzgurgites are independent from BMS, and thus, are interpreted as primary precipitates from this volatile-rich phase. Palladium was detected in gold micronuggets by semi quantitave SEM analyses; however, these latter are too small sized to be analysed with EMP or LA-ICPMS. Hence, although preserved from pervasive magmatic percolation, the spinel tectonite domain in the western Ronda massif also bears evidence of local modification of its HSE budget by this event.

Platinum-group minerals and the Oligocene thermomechanical erosion event

Unlike gold, PGM are intimately associated with BMS and their origin is therefore intimately linked with that of BMS. Because they were Fig. 8. Time-resolved LA-ICPMS spectra collected during one analysis of pentlandite (count per second (cp/s) vs. time (s)). The spikes of Pt, Te, Bi are interpreted to be submicrometer-sized Pt tellurides intercepted by the laser beam. Note that Pd is not present inside this telluride (analysis qb-4; fine-granular peridotite DR-3). identified in peridotite sampled from both sides of the recrystallization front, Pt rich minerals (CuPt 2 S 4 , PtFe, PtTe 2 ) at first sight do not seem to be controlled by the Oligocene thermomechanical erosion event. Their intimate association with BMS points to a single exsolution origin, as does their laths elongated, rod-shaped morphology. Malanite (CuPt 2 S 4 ) was reported to be stable at 760 °C [START_REF] Melcher | Petrogenesis of the ophiolitic giant chromite deposits of Kempirsai, Kazakhstan; a study of solid and fluid inclusions in chromite[END_REF][START_REF] Peregoedova | Collectors of Pt, Pd and Rh in a S-poor Fe-Ni-Cu sulfide system at 760 C: experimental data and application to ore deposits[END_REF] while pentlandite does not accomodate Pt at any temperature [START_REF] Lorand | Platinum-group element abundances in the upper mantle: New constraints from in situ and whole-rock analyses of massif central xenoliths (France)[END_REF][START_REF] Luguet | A multi-technique study of platinumgroup elements systematic in some Ligurian ophiolitic peridotites[END_REF][START_REF] Makovicky | Experimental studies on the solubility and distribution of platinum group elements in base metal sulfides in platinum deposits[END_REF][START_REF] Mansur | Textural and compositional evidence for the formation of pentlandite via peritectic reaction: Implications for the distribution of highly siderophile elements[END_REF]. The most likely scenario is that Pt in Ronda peridotites was transferred by the Cu-Ni sulfide melt that reacted with the Mss to produce single-phase Cu-rich high-T pentlandite at temperatures below 870 °C. Then malanite exsolved from pentlandite on cooling. A similar scenario holds true for Pt-Te phases. Moncheite (PtTe 2 ) has higher thermal stabilities (above 950 °C; Helmy et al., 2013 and reference therein). Interestingly, some Pt-Te inclusions are not elongated and aligned, but rather blocky and located towards the edge of the blocky pentlandite grain. [START_REF] Helmy | Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulfide melts[END_REF] suggested that semi metals (Te, Bi) minerals may nucleate by using preexisting nanophases and nanoparticles as building blocks. High temperature exsolution favours heterogeneous nucleation of a few grains that may grow by temperature-driven solid state growth (cf. [START_REF] Etschmann | A kinetic study of the exsolution of pentlandite (Ni, Fe) 9 S 8 from the monosulfide solid solution (Fe,Ni)[END_REF]. Therefore, the Pt-tellurides may have formed at high temperature as nanoparticles (i.e., >870 °C) perhaps before blocky pentlandite and then were pushed towards the grain boundary during the continuous growth of this BMS between 870 and 600 °C, as postulated by [START_REF] Kitakaze | Phase relations in the Fe-Ni-S system from 875 °C to 650 °C[END_REF] experiments.

The origin of the two-phase inclusion of Pt(Ir)As + Ni arsenide in RO 203 pentlandite is puzzling because Ni is a major element of pentlandite while As strongly concentrates into BMS at magmatic temperatures: [START_REF] Bai | Sperrylite saturation in magmatic sulfide melts: Implications for formation of PGE-bearing arsenides and sulfarsenides[END_REF] reported huge As contents (2300-4600 ppm to 22,000-46,000 ppm) in synthetic sulfide melts saturated with respect to PtAs 2 . At first sight, the very low As contents of Ronda pentlandite (<11 ppm, Table S1) argue for a low-T exsolution of Ni-As and Pt-As phases. Like Pt-Te phases, Ni, Pt and As may have started nucleating as atomic clusters in the Cu-Ni-rich sulfide melts and then coalesced forming discrete Pt arsenides and Ni arsenides before crystallization of pentlandite (see [START_REF] Helmy | Noble metal nanoclusters and nanoparticles precede mineral formation in magmatic sulfide melts[END_REF]. According to [START_REF] Gervilla | Geology and Metallogeny of the upper mantle rocks from the Serrania de Ronda[END_REF], arsenides are unusually abundant in Betic peridotite massifs (Ronda and Ojen) as Ni-As ores, as disseminated Ni-arsenides in peridotites (see also [START_REF] Lorand | L'orcélite des péridotites de Beni Bousera (Maroc), Ronda (Espagne), Table Mountain et Blow-Me-Down-Montain (Terre neuve) et du Pinde Septentrional (Grèce)[END_REF], as well as as PGE arsenides/sulfarsenides in associated chromitites. This high As activity may also explain the Pt-As-Ni phase observed in RO-203. Taken as a whole, the unusual diversity of arsenides at Ronda supports the idea of a high volatility activity at the end of the Oligocène magmatic percolation event [START_REF] Gervilla | Geology and Metallogeny of the upper mantle rocks from the Serrania de Ronda[END_REF].

It is worth noting that compared to similar orogenic peridotites worldwide (Lorand and Luguet, 2016 and reference therein), the Ronda samples investigated in the present study show no Pt-Ir-Os alloys whereas their bulk-rock Pt abundances are consistent with a partial melting model involving such alloys. According to observations in mantle samples [START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF] and experiments [START_REF] Peregoedova | The formation of Pt-Ir alloys and Cu-Pd-rich sulfide melts by partial desulfuration of Fe-Ni-Cu sulfides: results of experiments and implications for natural systems[END_REF], Pt-Ir-Os alloys are expected to exsolve from the Mss during mantle melting because of S consumption into partial melts. Desulfidation experiments produced rod-shaped Pt-Ir-Os alloys ressembling our malanite exsolutions in pentlandite [START_REF] Peregoedova | The formation of Pt-Ir alloys and Cu-Pd-rich sulfide melts by partial desulfuration of Fe-Ni-Cu sulfides: results of experiments and implications for natural systems[END_REF]. However, malanite is stable along with chalcopyrite and bornite for fS 2 conditions twice higher than those controlling Pt-Ir-Os alloys [START_REF] Makovicky | Ternary and Quaternary phase Systems with PGE. The Geology Geochemistry, Mineralogy and Mineral Beneficiation of Platinum-Group Elements[END_REF].

One may speculate that these alloys were converted into Pt sulfides by an increase of fS 2 , very likely triggered by the high volatile activity taking place at the end of the Oligocène magmatic percolation event.

Unlike the Pt-rich PGMs discussed above, the scarce, single, thick laurite inclusions in pentlandite from the spinel tectonite domain do not show textural features of exsolution. Laurite can exsolve only at very low temperature because Ru and Os are strongly soluble in Mss or pentlandite, with theoretical solubility values well in excess of their concentrations measured in Ronda pentlandite (<50 ppm; Table S1) [START_REF] Bockrath | Stabilities of Laurite RuS 2 and monosulfide liquid solutions at magmatic temperatures[END_REF][START_REF] Li | Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: effects of composition and temperature[END_REF][START_REF] Makovicky | Experimental studies on the solubility and distribution of platinum group elements in base metal sulfides in platinum deposits[END_REF]. Alternatively, Lorand et al. (2010) interpreted laurite-erlichmanite inclusions in Lherz refertilized orogenic lherzolites as Proterozoic partial melting products that have survived refertilization, while recrystallizing as euhedral crystals. The same interpretation may also hold true for Ronda spinel tectonites. However, at Ronda, the distribution of lauriteerlichmanite was clearly modified by the regional scale Oligocene percolation event that eliminated this mineral from the granular domain while preserving it in the spinel tectonite domain. Experimental works indicate an upper thermal limit for pure laurite (RuS 2 ) at ~1275 °C for log fS 2 of -2.0 (Brenan and Andrews, 2001), i.e. within [START_REF] Zhang | Experimental constraints on mantle sulfide melting up to 8 GPa[END_REF]. Star refers to the P-T conditions recorded by coarse-granular peridotites during the Oligocene thermo-mechanical erosion event [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF].

uncertainty of the peak temperature reached by coarse-granular peridotites during the Oligocene magmatic percolation event (1250 °C; [START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF]. However, the same experiments also showed that the solubility of Os in laurite decreases its temperature of stability. According to EDS semi quantitative analyses, Ronda laurite may incorporates as much Os as Ru, so the regional-scale thermal input of the Oligocene magmatic percolation event alone could be responsible for its resorbtion from the granular domain. Other parameters may also have Fig. 12. Plots of Se/Te vs. Pd/Ir and Te (in-situ LA-ICPMS analyses). Mss and Cu\ \Ni sulfide melt after [START_REF] König | Selenium and tellurium systematics of the Earth's mantle from high precision analyses of ultradepleted orogenic peridotites[END_REF]. Thick grey lines indicate the putative primitive mantle ratios (after Wang and[START_REF] Wang | Ratios of S, Se and Te in the silicate Earth require a volatile-rich late veneer[END_REF]Palme and[START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]. Symbols as in Fig. 3.

interacted such as the redox conditions that controlled this event. [START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF] show that at 1250 °C, laurite has a very narrow range of stability of c.a. 1 log unit in terms of fugacity of sulfur, being replaced by Mss at elevated fS 2 , or Ru alloys at low fS 2 . Any small change of fS 2 around that range may have enhanced its dissolution. Increasing oxygen fugacity in the residual melt fraction after extensive magma percolation may increase octaedral vacancies inside the Mss structure and its ability to accomodate high-valence elements such as Os, Ir and Ru [START_REF] Bockrath | Stabilities of Laurite RuS 2 and monosulfide liquid solutions at magmatic temperatures[END_REF][START_REF] Li | Partitioning of nickel, copper, iridium, rhenium, platinum, and palladium between monosulfide solid solution and sulfide liquid: effects of composition and temperature[END_REF][START_REF] Liu | Partitioning of platinum-group elements (PGE) and chalcogens (Se, Te, As, Sb, Bi) between monosulfide-solid solution (Mss), intermediate solid solution (Iss) and sulfide liquid at controlled fO 2 -fS 2 conditions[END_REF]. Finally, a number of other, unconstrained parameters such as original grain size, morphology or structural damages in original laurite crystals may also have controlled its dissolution. By dissolving into BMS, minerals from the laurite-erlichmanite series are good candidate for transferring the oldest Os isotope model ages now measured inside the granular domain by [START_REF] Marchesi | Persistence of mantle lithospheric Re-Os signature during asthenospherization of the subcontinental lithospheric mantle: insights from in situ isotopic analysis of sulfides from the Ronda peridotite (southern Spain)[END_REF].

Conclusions

Chalcogen elements (S, Se Cu) and PGE systematics fit well the published data base for orogenic mantle peridotites as a whole. Positive correlations between S, Se, Cu and fertility result from progressive removal of sulfides from the mantle at increasing degrees of melting. A few harzburgites preserved the S-, Se-and Pt-depleted chondrite normalized PGE patterns of residues after partial melting.

The Oligocene thermo-mechanical erosion event triggered secondary partial melting of the sulfide phase liberating a Cu-Ni-rich sulfide melt now identified through Ni-Cu-rich sulfide inclusions (pentlandite + chalcopyrite ± bornite) and a wide range of intergranular Cu-rich sulfides and alloys. Residual Mss (coexisting with refractory PGM (laurite-erlichmanite) in spinel tectonites) survived throughout all of the tectonometamorphic domains, thus preserving Mss-compatible PGE (Os, Ir, Ru, Rh) relative and absolute abundances. Mss and laurite-erlichamniate also preserved Proterozoïc Os model ages.

Local scale redistribution of the Cu-Ni-rich sulfide melt accounts for the enrichment/depletion trends of Mss-incompatible elements (Pd, Au, Cu, Se) identified in the bulk-rock analyses of coarse granular and fine granular depleted peridotites. On cooling, the sulfide melt produced pentlandite by reacting out with Mss at T < 870 °C while transfering Mssincompatible element that generated micrometric Pt-Cu-Te-As-bearing platinum-group mineral inclusions, in addition to superchondritic Pd N / Ir N and nearly chondritic Se/Te identified in mantle sulfides of metasomatic origin.

Although preserved from percolation of large melt fractions, the spinel tectonite domain in the western Ronda massif also bear evidence of local modification of its HSE budget. The Au and Pd enrichment of spinel harzburgites track infiltration of volatile-rich small melt fractions coming from beneath the recrystallization front. There, Au micronuggets are primary precipitates.

Fig. 2 .

 2 Fig. 2. Microphotographs of base metal sulfides (BMS). a: intergranular pentlandite bleb showing convex-inward grain boundaries (BSE image); note mackinawite (mw) flakes inside pentlandite. Cleavage and fracture planes filled with magnetite and/or awaruite. b: intergranular pentlandite-troïlite (Tr) mix (reflected light optical microscope). c. intergranular pentlandite with chalcopyrite network and partial magnetite (mt) rim (BSE image). d: native copper (Cu) embedded in intergranular pentlandite bleb (reflected light optical microscope). e. partly weathered ellipsoïdal pentlandite bleb at olivine-clinopyroxene-Cr spinel triple junction; note the fracture planes partly filled with awaruite (aw) and/or magnetite (mt) (BSE image). f: serpentine-hosted native iron spherules that are variably replaced by magnetite (BSE image).

Fig. 3 .

 3 Fig. 3. Plots of S, Se and Cu vs. Al 2 O 3 (bulk-rock concentrations). Thin lines were arbitrarily drawn to delineate the covariation trends in spinel tectonites. Note the broad positive correlation trends between each element and fertility index as represented by Al 2 O 3 and the erratic variations of Se and Cu concentrations in coarse-granular and fine granular depleted lherzolites. Sample numbers correspond to the five S-enriched outliers that contain serpentinization-derived secondary sulfides. Sp: spinel; CG: Coarse granular; FG: fine granular; LG: layered granular.

Fig. 4 .

 4 Fig. 4. S vs. Se and Cu vs. Se diagrams (bulk-rock analyses). CI chondrite values after Palme and O'Neill (2014). Note erratic variations of Se and Cu concentrations in coarse-granular and finegranular depleted lherzolites. Symbols as in Fig. 3.

Fig. 5 .

 5 Fig. 5. CI Chondrite-normalized PGE and Au bulk-rock concentrations. The two compositional fields for Pyrenean lherzolites and Pyrenean harburgites were drawn from Lorand et al.(2008, 2010) and[START_REF] Luguet | Residual platinumgroup minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle[END_REF]. CI chondrite normalizing values after[START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]. The different colors represent the four tectonometamorphic subdomains defined in[START_REF] Van Der Wal | Origin of the recrystallization front in the Ronda peridotite by km-scale pervasive porous flow[END_REF].

Fig. 7 .

 7 Fig. 7. Chondrite-normalized highly siderophile element contents of Ronda sulfides (LA-ICPMS analyses). A: spinel tectonites; B: coarse-granular peridotites; C: fine-granular peridotites; D: layered granular peridotites. CI-chondrite values after Palme and O'Neill (2014). Po = pyrrhotite; Cu: native copper; Pt-Te-Bi: Pt-Te-Bi phases encountered during laser drilling. All of the other analysed sulfides (in black) are pentlandite-dominated grains (+ subordinated amounts of native copper, awaruite, magnetite and/or chalcopyrite/pyrrhotite).

Fig. 7

 7 Fig. 7 (continued).

Fig. 9 .

 9 Fig. 9. Pd vs. Cu and Pd vs. Ni plots for LA-ICPMS analyses. Symbols as in Fig. 3.

Fig. 10 .

 10 Fig. 10. Microphotographs of platinum-group minerals (BSE images). a: euhedral laurite-erlichmanite inclusion in pentlandite. b: Pt\ \Te inclusion in pentlandite. c: external grains of laurite-erlichmanite in pentlandite. d: rod-shaped external malanite exsolution in pentlandite. e: Pt-As/Ni-As inclusions in pentlandite. f: serpentinization-derived Cu-Pt-Pd alloy inside magnetite-pentlandite intergrowth.

Fig. 11 .

 11 Fig. 11. Comparison of Mss solidus and liquidus with mantle geotherms after[START_REF] Zhang | Experimental constraints on mantle sulfide melting up to 8 GPa[END_REF]. Star refers to the P-T conditions recorded by coarse-granular peridotites during the Oligocene thermo-mechanical erosion event[START_REF] Lenoir | The recrystallization front of the Ronda peridotite: evidence for melting and thermal erosion of subcontinental lithospheric mantle beneath the Alboran Basin[END_REF].

Table 1

 1 Main petrographic features and modal composition of the studied peridotites.

	Sample Ref. Rock type	Domain ol	opx	cpx	sp	CpxII CaO	Al 2 O 3	L.O.I	Mg#	Ce N /Sm N Sm N /Yb N Yb N
					(wt%)	(wt%)	(wt%)	(wt%)		(wt%)	(wt%)	(wt%)
	CHR-2	1	Gn-and Sp-bearing lherzolite	ST	50	33	16	1		3.3	3.78	3.81	0.888 0.57	0.82	2.87
	DR-18	2	Lherzolite	ST	50	33	16	1		3.45	3.39	5.85	0.884 0.67	0.86	2.45
	DR-7	2	Lherzolite	ST	51	32	15	2		2.71	3.18	5.55	0.887 0.6	0.77	2.17
	DR-27	2	Lherzolite	ST	52	32	15	1		2.15	2.36	5.16	0.9	0.55	0.78	1.42
	DR-12	2	Harzburgite	ST	71	23	5	1		1.25	1.35	6.75	0.905 2.13	0.24	0.38
	DR-22	2	Harzburgite	ST	72	21	6	1	(+)	1.36	1.28	7.9	0.906 1.06	0.04	0.39
	DR-5	2	Lherzolite	CGP	61	28	10	1		2.17	2.84	6.8	0.9	0.27	0.52	1.71
	DR-26	2	Lherzolite	CGP	60	28	11	1		2.53	2.78	7.15	0.898 0.51	0.76	1.96
	DR-4	2	Harzburgite	CGP	74	20	4	2		0.95	1.18	7.7	0.911 0.51	0.49	0.55
	DR-16	2	Lherzolite	FGP	58	27	14	1		2.86	3.14	5.3	0.903 0.45	0.52	2.22
	DR-29	2	Lherzolite	FGP	56	29	13	2		2.95	3.34	6.3	0.896 0.69	0.88	2.42
	DR-3	2	Lherzolite	FGP	62	28	9	1		2.02	2.22	5.6	0.904 0.67	0.37	1.24
	DR-41	2	Cpx-poor lherzolite	FGP	65	27	7	1		1.64	1.97	6.00	0.902 0.6	0.68	1.22
	DR-37	2	Cpx-poor lherzolite	FGP	63	28	7	2		1.64	1.91	8.7	0.903 1.56	0.22	0.85
	RO-203 1	Cpx-poor and Pl-bearing lherzolite FGP	67	23	9	1	(+)	1.9	1.75	3.96	0.9	1.48	0.28	0.55
	DR-33	2	Cpx-poor lherzolite	FGP	67	23	9	1	+	1.99	1.89	6.1	0.902 1.35	0.43	0.81
	DR-17	2	Cpx-poor lherzolite	FGP	64	27	7	2	+	1.79	1.67	9.35	0.9	1.9	0.46	0.63
	RO-144 1	Sp-and Pl-bearing lherzolite	LGP	60	23	15	2		2.97	3.39	0.34	0.896 0.38	0.81	2.75
	1 = this study; 2 = Van der Wal and Bodinier (1996) (ST = spinel tectonites; CGP = coarse-granular peridotites; FGP = fine-granular peridotites; LGP = layered-granular peridotites;
	italics: modal composition estimated by Van der Wal and Bodinier (1996); whole rock major elements and REE after Van der Wal and Bodinier (1996) and Gutiérrez-Narbona (unpub-
	lished data); L.O.I.: loss on ignition; Mg# = Mg/(Mg + Fe); ol: olivine; opx: orthopyroxene; cpx: clinopyroxene; Sp: spinel; CpxII: late magmatic clinopyroxene; (+) = trace amount;
	+ = minor phase; N = CI-chondrite-normalized (Palme and O'Neill, 2014).

Table 3

 3 Chalcophile-siderophile element contents of SARM-7-10 in-house NiS standard (ppm).

		Theoretical	LPGN	Montpellier	MRAC
			(France)	Geosciences	Tervuren
				(France)	(Belgium)
	N =		30	12	20
	S		297,390 (12572)
	Fe		19,940 (7000)
	Ni	710,000 (IS)	710,000 (IS)	710,000 (IS)	710,000 (IS)
	Co		140 (29)
	Cu	1740	2435 (433)	1740 (356)
	As		1.344 (0.65)	1.58 (0.46)
	Se	3.99	4.43 (0.95)	4.09 (0.30)
	Mo		0.044 (0.019)
	Ru	0.86 (0.1)		1.30 (0.90)	1.30 (1.06)
	Rh	0.50 (0.02)		0.75 (0.30)	0.67 (0.42)
	Pd	3.06 (0.06)	3.31 (0.64)	3.95 (1.55)	4.07 (1.33)
	Ag		2.04 (1.13)	1.56 (0.24)
	Cd		0.217 (0.06)
	Sn		2.20 (1.13)
	Sb		1.23 (0.31)
	Te		1.36 (0.434)	1.70 (0.4)
	Os	0.126 (0.012)	0.10 (0.04)	0.17 (0.10)	0.16 (0.13)
	Ir	0.15 (0.035)	0.11 (0.14)	0.38 (0.26)	0.31 (0.25)
	Pt	7.48 (0.1)	7.48 (1.35)	7.49 (0.98)	7.23 (1.54)
	Au	0.48 (0.03)	0.57 (0.11)	0.66 (0.19)	0.74 (0.22)
	Tl		0.314 (0.47)
	Pb		48.0 (12.23)
	Bi		0.67 (0.11)	1.02 (0.75)

N = number of analyses. Theoretical values after South African Bureau of Standard. One sigma value between parentheses; IS = internal standard. LPGN:

[START_REF] Lorand | Chalcophile-siderophile element systematics of hydrothermal pyrite from martian regolith breccia NWA 7533[END_REF]

, Mass 1 as external calibration standard; Montpellier; PGE-A as external calibration standard

(Lorand et al., 2010)

. MRAC

(Lorand et al., 2010)

.

Table 4 :

 4 Whole-rock S, Se, Cu, Au and PGE contents, Base Metal Sulfides (BMS) and Platinum-group minerals (PGM) in western Ronda peridotites.

	Sample	S	Se	Cu	BMS	BMS assemblages	Os	Ir	Ru	Rh	Pt	Pd	Au	PdN/IrN Platinum group	Native
		(ppm)	(ppb)	(ppm)	abundance		(ppb)	(ppb)	(ppb)	(ppb)	(ppb)	(ppb)	(ppb)		minerals	Au
	CHR-2 (ST) 234	99	32.5	++	Pn, Mw, Aw, Cu, Vall, Mt 3.33	3.29	6.13	1.2	7.0	6.38	1.58	1.60	Ma (x2) inside Pn
							3.31	3.28	6.12	1.24	7.0	6.41	1.30	1.60	Pt-Cu alloys inside Mt
	DR-12	305	31	9.6	++	Cu, Pn, Aw	n.a.	3.68	8.02	1.25	5.55	5.02	14.40 1.13	La(x2); Pt\ \Cu (Pd)	5
		(S)													alloys
	DR-22	59	37	9.4	+	Pn, Cu, (Mt, Aw)	n.a.	3.1	5.69	1.22	4.4	4.19	4.34	1.13		1
	DR-18	172	93	31.9		Pn, (Mt, Aw)	n.a.	2.9	5.4	1.00	5.02	4.62	4.7	1.33
	DR-7	200"	91	24.1	++	Pn, Mt., Cu, Vall, (Aw)	3.16	3.03	7.24	1.2	5.32	3.18	4.11	1.54	Pt-Fe and Pt\ \Cu
															alloys
							3.72	3.57	6.42	1.26	6.57	6.00	4.20	1.39
	DR-27	265	75	20.3	+	Pn, Aw, Cu, Mw, Mt	n.a.	3.1	6.59	1.08	5.58	3.71	11.76 1.0	Mo inside Pn
		(S)
							3.62	3.32	6.05	1.13	5.79	4.69	n.a.	1.17		3
	DR-26	276	59	19.8	++	Pn, Mw, Mt., Cp, Cu,	n.a.	2.9	4.6	0.88	4.36	4.6	4.46	1.33
	(CGP)	(S)				(Vall)
	DR-4	214	33	18.8	+	Pn, Mw, Fe	n.a.	3.17	6.44	0.78	3.36	2.35	2.75	0.62
		(S)
	DR-5	166	48	18.0	++	Pn, Aw, Mt., Cu, Mw, Cp n.a.	3.2	6.21	1.2	6.7	5.00	2.82	1.30	Cu-Pd alloy
	DR-16	155	55	22.6			n.a.	2.64	4.31	0.83	4.36	4.6	5.53	1.44
	(FGP)
	DR-29	336	78	23.9		Pn, Aw, Mt., Cu, Mw, Cp,	n.a.	3.82	5.87	1.25	6.5	6.00	3.20	1.42
		(S)				Po
	DR-3	119	59	16.0	++	Pn, Cu, Aw, Mt., Mw	3.42	2.91	6.79	1.03	4.65	3.91	5.74	1.21	Ma inside Pn
	DR-33	153	77	21.7	++	Pn, Aw, Mt., Cu, (Mw,	n.a.	3.9	7.7	1.27	6.25	5.81	2.40	1.23
						Cp, Po)
	DR-41	54	30	15.2	+	Pn, Cu, Mt	n.a.	3.00	6.85	0.93	4.32	3.4	3.19	1.06
	DR-37	180	52	7.8	+	Pn, Aw, Cu, Mt	n.a.	3.17	6.72	1.06	4.385 4.2	4.34	1.10
	RO-203	180	62	33.1	++	Pn + Cp, Aw, Cu, Mt.,	4.94	4.62	6.67	1.44	4.72	4.62	1.70	1.20
							4.1	3.84	6.88	1.3	9.19	6.05	1.5	1.32	CuPt(Pd) alloy; Pt(Ir)
															As
	DR-17	156	63	15.3	+	Pn, Aw, Mt., Cu, Mw, Cp,	4.17	3.83	7.01	1.16	5.88	5.8	4.70	1.25
						Po
							3.62	3.32	6.03	1.18	6.27	6.28	0.86	1.56
	RO-144	240	96	34.0	++	Pn, Po, Cp, Mw, Cu	n.a.	3.78	6.33	1.31	6.68	6.12	1.27	1.35	Pt-Pd-Te-Bi
	(LGP)
	RO-144						3.94	3.94	7.13	n.a.	7.17	6.3	n.a.	1.61
	(CT)
	RO-144 (I)						4.05	2.61	5.21	1.4	n.a.	6.28	1.93	1.96

ST: spinel tectonites; CGP: coarse granular peridotites; FGP: fine-granular peridotites; LGP: layered granular peridotites. (S): serpentinization-derived hydrothermal sulfides; CT: Carius Tube digestion procedure

[START_REF] Becker | Highly siderophile element composition of the Earth's primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths[END_REF]

; I: INAA: Instrumental Neutron Activation analysis after NiS preconcentration step

[START_REF] Lorand | Highly siderophile element geochemistry of the Earth's mantle: new data for the Lanzo (Italy) and Ronda (Spain) orogenic peridotites bodies[END_REF]

; n.a.: not analysed. BMS: Base Metal Sulfides; +: accessory; ++: minor;Pn = pentlandite; Mw: mackinawite; Aw: awaruite; Cu: native copper; Vall: valleriite; Mt.: magnetite; Po: pyrrhotite; Cp: chalcopyrite; Ma = Malanite CuPt 2 S 4 ; La = laurite (Os,Ru)S 2 ; Mo = moncheite (PtTe 2 ). N = CI-chondrite normalized

[START_REF] Palme | Cosmochemical estimates of mantle composition[END_REF]

.

Acknowledgements

The authors thanks Monique Marot for the polished thick sections and Olivier Alard and Olivier Bruggier for their help with the LA-ICPMS analyses. Financial funding was provided by CNRS (UMR 7160 and 6112), the University of Granada (Junta de Andalucia), a French-Spanish integrated action (HF1997-0082) and the Spanish DGES (Project PB97-1211). The final version was greatly improved thanks to comments from Laurie Reisberg and two anonymous reviews, and editorial suggestions from associate editor Michael Roden.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi. org/10.1016/j.lithos.2020.105901.