Lisard Torró
email: lisardtorro@hotmail.com

Diego Benites

Jean Vallance

Oscar Laurent

Brayam A Ortiz- Benavente

Cyril Chelle-Michou

Joaquín A Proenza

Lluís Fontboté D A Ge G Ca E G Ee G P G A , Fac

ETH Ce

Dr Lisard

Trace element geochemistry of sphalerite and chalcopyrite in arc-hosted VMS deposits

Keywords: Sulfide, LA-ICP-MS, Coupled Substitution, Compositional Profile, Volcanic Arc, Latin America

Trace element compositions of sphalerite and chalcop rite have been investigated for four arc-hosted Cretaceous VMS deposits (Palma, Perubar, and Mar a Teresa in Peru, and Cerro de Maim n in the Dominican Republic) using laser ablation inductivel -coupled plasma mass spectrometr . In sphalerite, Fe, Mn, Cd, Hg, Ag, Sb, Se, In, Ge, and Ga are latticebound, whereas Sn, Tl, Bi, and Pb occur at least partl as mineral microinclusions.

Significant variations in the contents of minor and trace elements are observed in sphalerite grains from individual deposits. A strong negative correlation between Fe (Inter-Quartile Range [IQR] 44009-18168 ppm) and Zn indicates a dominant Fe 2+ Zn 2+ simple isovalent substitution. Regarding potential g -ec b -products, the contents of In (IQR 42-1.6 ppm, up to 415 ppm) and Ga (IQR 31-5.9 ppm, up to 96 ppm) in the studied sphalerite are normall much higher than those of Ge (IQR 0.85-0.16 ppm, up to 9.3 ppm).

Correlation trends suggest Cu + + In 3+ 2Zn 2+ , Cu + + Ga 3+ 2Zn 2+ , and additional, more complex substitution mechanisms of Zn involving combinations of monovalent (Cu + , Ag + ), divalent (Ge 2+ ?), trivalent (In 3+ , Ga 3+ , [Sn 3+ ?]), and quadrivalent (Ge 4+ , Sn 4+ ) cations.

As for chalcop rite, Zn, Ag, Sn, Cd, Se, In, Ga, and Ge are interpreted to be lattice-bound, whereas Mo, Au, Tl, Sb, Pb, and Bi probabl occur as microinclusions. Relative to sphalerite, chalcop rite is depleted in In (IQR 28-8.4 ppm, up to 49 ppm) and Ga (IQR 8.3-2.9 ppm, up to 24 ppm) and enriched in Ge (IQR 5.9-0.70 ppm, up to 80 ppm). Of the other trace elements, Zn (IQR 426-190 ppm) is the most highl concentrated in the studied chalcop rite, followed b Ag (IQR 136-23 ppm), Se (IQR 64-22 ppm), Sn (IQR 53-1.3 ppm), and Cd (IQR 12-6.0 ppm). General positive correlation trends between Zn, Cd, In, Ge, and Ga in chalcopyrite suggest varied coupled substitution mechanisms of Fe and Cu with fluctuating valences due to covalent bonding. Trace-element distribution patterns in sphalerite and chalcop rite were studied for the one-refined Sof a-D massive sulfide bod in the Mar a Teresa deposit, which comprises a core of dominant pyrite sheathed outward with zones of chalcopyrite (Cu zone), sphalerite (Zn zone) and galena + sphalerite ± fahlore ± barite (Pb Zn Ag zone). Bottom to top of the sulfide bod , sphalerite records progressive depletion in In, Cu, Mn, and Se, and enrichment in Ge. This distribution pattern agrees with increasing crystallization temperatures and/or volatile magmatic influx towards the core of the massive mineralization. Distribution of trace elements in chalcopyrite is rather uneven except for a sustained enrichment in Se towards the basal portion of the sulfide body. The fact that such trends are preserved in spite of extensive recrystallization during thermal metamorphism in parts of the Sofía-D massive sulfide mineralization suggests i) a closed metamorphic system and ii) that element interdiffusion was prominently local. Accordingly, we propose that sphalerite lattice-bound trace elements distribution patterns described in this article can help determine the polarity of massive sulfide bodies in VMS districts in metamorphosed and tectonized terranes.

Introduction

Volcanogenic massive sulfide (VMS) deposits are exhalative and/or replacive accumulations of sulfide minerals formed at or near the seafloor where uprising hydrothermal fluids driven by synchronous magmatism are entrained with cold seawater or porewaters [START_REF] Doyle | Subsea-floor replacement in volcanic-hosted massive sulfide deposits[END_REF][START_REF] Shanks | Volcanogenic massive sulfide occurrence model[END_REF][START_REF] Tornos | Controls on the sitting and style of volcanogenic massive sulphide deposits[END_REF]. VMS mineralization occurs as sulfide mounds to tabular stratiform bodies, which are often underlain by a stockwork or feeder zone [START_REF] Galley | Mineral Deposits of Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and Exploration Methods[END_REF][START_REF] Tornos | Controls on the sitting and style of volcanogenic massive sulphide deposits[END_REF]. Their formation responds to the convergence in the time and space of anomalously high thermal gradients and extensional tectonic regimes that promote the circulation of evolved hydrothermal fluids through, and leaching of metals from, the oceanic strata [START_REF] Ohmoto | Formation of volcanogenic massive sulfide deposits: The Kuroko perspective[END_REF][START_REF] Tivey | Generation of seafloor hydrothermal vent fluids and associated mineral deposits[END_REF][START_REF] Piercey | The setting, style, and role of magmatism in the formation of volcanogenic massive sulfide deposits[END_REF]. Such geological features are primarily met in oceanic spreading ridges, arc environments, and rifted continental margins.

Most VMS deposits are preserved in suprasubduction zones either in back-arc, intra-arc, or forearc basins on both oceanic and continental crust [START_REF] Franklin | Arc-related volcanogenic massive sulfide deposits[END_REF][START_REF] Nimis | Peculiarities of some mafic ultramafic-hosted massive sulfide deposits from southern Urals A likely forearc occurrence[END_REF][START_REF] Herrington | 6: classification of VMS deposits: lessons from the uralides[END_REF][START_REF] Hollis | Petrochemistry and hydrothermal alteration within the Tyrone igneous complex, Northern Ireland: implications for VMS mineralization in the British and Irish Caledonides[END_REF][START_REF] Peter | Geochemical constraints on the tectonic setting of basaltic host rocks to the Windy Craggy Cu-Co-Au massive sulphide deposit, northwestern British Columbia[END_REF]Torró et al., 2016a). In arc-related systems, contrasting water depths in massive sulfide formation exert a major control on the ore and hydrothermal alteration mineral assemblages and the metalliferous contents [START_REF] Sillitoe | High sulfidation deposits in the volcanogenic massive sulfide environment[END_REF][START_REF] Dubé | Mineral Deposits of Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and Exploration Methods[END_REF][START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF]. VMS deposits in back-arc and forearc basins form at water depths typically in the range between 1500 to 3700 m, whereas those in arc volcanoes and arc-related rifts are normally restricted to water depths in the range between 700 to 2000 m. The latter are often associated with elevated magmatic gas contents and boiling of the hydrothermal fluids may occur in shallower arc volcanoes and rifted intra-arc submarine hydrothermal systems [START_REF] Gemmell | Sulfur Isotope Evidence for Magmatic Contributions to Submarine and Subaerial Gold Mineralization: Conical Seamount and the Ladolam Gold Deposit, Papua New Guinea[END_REF][START_REF] Dubé | Mineral Deposits of Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and Exploration Methods[END_REF][START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF].

VMS deposits are important sources of Cu, Zn, Pb, Au, and Ag [START_REF] Galley | Mineral Deposits of Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of Geological Provinces, and Exploration Methods[END_REF]. In addition, a wealth of other metals and metalloids that are potentially economically recoverable as byproducts (e.g., Sn, Co, Ni, In, Ga, Ge, Mo, Re, Se, Te) or deleterious (i.e., harmful or unwanted elements; e.g., Mn, As, Sb, Hg, Tl) may occur in remarkable concentrations in VMS deposits and even determine their economic viability (Benzaazoua et al., 2003;Zaccarini and Garuti, 2008;[START_REF] Koski | Deposit type and associated commodities in volcanogenic massive sulfide occurrence model[END_REF][START_REF] Ridley | Geochemical characteristics in volcanogenic massive sulfide occurrence model[END_REF][START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF][START_REF] Frenzel | The geometallurgical assessment of by-products geochemical proxies for the complex mineralogical deportment of indium at Neves-Corvo, Portugal[END_REF]. Minor and trace elements can either precipitate as native elements or substitute into the crystal lattice of major sulfide minerals [START_REF] Cook | Trace and minor elements in sphalerite: a LA-ICPMS study[END_REF][START_REF] Cook | Determination of the oxidation state of Cu in substituted Cu-In-Fe-bearing sphalerite via mu-XANES spectroscopy[END_REF][START_REF] Cook | Distribution and substitution mechanism of Ge in a Ge-(Fe)-bearing sphalerite[END_REF]Ye et al., 2011;[START_REF] Ridley | Geochemical characteristics in volcanogenic massive sulfide occurrence model[END_REF]Murakami and Ishihara, 2014;[START_REF] George | Trace and minor elements in galena: A reconnaissance LA-ICP-MS study[END_REF][START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF]Benites et al., 2021a,b). The understanding of the mineralogical expression of either potential by-product or deleterious minor and trace elements in a given deposit or mineralization style is essential to predict their metallurgical behavior (e.g., [START_REF] Cook | The mineralogy and mineral chemistry of indium in sulphide deposits and implications for mineral processing[END_REF].

This study aims at understanding the mineralogical expression of minor and trace elements in sphalerite and chalcopyrite from arc-related VMS deposits and their distribution across massive sulfide bodies. To do so, we have systematically determined the trace element budget on these ore minerals from four arc-related VMS deposits in the Andes (Palma, Perubar, and María Teresa in Peru) and the Caribbean (Cerro de Maimón in the Dominican Republic). The obtained contents are compared with published data on other VMS deposits worldwide. In addition, a comprehensive set of samples has allowed the study of ore bodyscale zoning of certain trace elements in a zone-refined massive sulfide body in the María Teresa deposit. The obtained results are used to assess the incorporation mechanisms of some high-tech elements to the crystal lattice of major sulfides (sphalerite and chalcopyrite) and contribute to revealing element distribution patterns across massive sulfide bodies in VMS districts; such patterns can be used to target the most prospective zones of zoned massive sulfide bodies for potential by-products and complementarily also to constrain sulfide body polarity during exploration in tectonized terranes.

Geological Setting

2.1. Volcanogenic massive sulfide deposits in Peru 2.1.1. General geologic framework In Peru, several VMS deposits occur along the coastal region and are hosted by rocks of Cretaceous age [START_REF] Steinmüller | Volcanogenic massive sulfides in Peru[END_REF][START_REF] Fontboté | Volcanogenic Zn-Pb±Cu massive sulfide deposits in the Upper Cretaceous plutono-volcanic arc in central Peru[END_REF]. In northern Peru, the giant Tambogrande deposits represent the largest VMS endowment in this country and probably in South America, and include the TG1 deposit with resources of 109 million metric tons (Mt) grading 1.6 % Cu, 1.0 % Zn, 0.5 g/t Au, and 22 g/t Ag, plus 16.7 Mt grading 3.5 g/t Au and 64 g/t Ag in oxide ore, and the TG3 deposit with resources of 82 Mt grading 1.0 % Cu, 1.4 % Zn, 0.8 g/t Au, and 25 g/t Ag (Manhattan Minerals, 2002in Winter et al., 2010).

There, VMS mineralization is hosted by subalkaline (calc-alkaline and tholeiitic) basaltic pillowed and brecciated lavas and lesser amounts of felsic volcanic rocks that filled N and NW-oriented sub-basins in the lower portion of the Lancones basin (Fig. 1; [START_REF] Tegart | Regional setting, stratigraphy, alteration and mineralization of the Tambo Grande VMS district, Piura department, northern Peru[END_REF]Winter et al., 2004Winter et al., , 2010)). The formation of the Lancones basin is connected to the break-up of Gondwana and coincided with a period of intense extension and rifting due to trench-rollback (Winter et al., 2010 and their references). Minimum age of massive sulfide formation (and likely synchronous with or slightly postdating massive sulfide formation) is constrained by U-Pb zircon dating of felsic volcaniclastic rocks at 104.8 ± 1.3 to 100.2 ± 0.5 Ma (middle Albian; Winter et al. 2010). The volcanic and sedimentary pile in the Lancones basin was intruded by Late Cretaceous to Tertiary arc-related granitoids of the Coastal Batholith (cf. [START_REF] Pitcher | A multiple and composite batholith[END_REF][START_REF] Atherton | The Coastal Batholith of Peru: the product of rapid recycling of new crust formed within rifted continental margin[END_REF][START_REF] Cobbing | The Coastal Batholith and other aspects of Andean magmatism in Peru[END_REF][START_REF] Hildebrand | Arc and Slab-Failure Magmatism in Cordilleran Batholiths I The Cretaceous Coastal Batholith of Peru and its Role in South American Orogenesis and Hemispheric Subduction Flip[END_REF]).

In the central coastal segment of Peru, where the deposits studied in this paper are located, VMS mineralizations emplaced in the Huarmey and Cañete basins of the West Peruvian Trough (WPT; Fig. 1) and are now exposed along the Peruvian Western Cordillera to the Coastal region. The opening of the WPT has been assigned to an aborted back-arc or true ocean floor extensional marginal basin (e.g., [START_REF] Atherton | The Mesozoic marginal basin of Central Peru: a geochemical study of within-plate-edge volcanism[END_REF][START_REF] Aguirre | The link between metamorphism, volcanism and geotectonic setting during the evolution of the Andes[END_REF][START_REF] Atherton | Thermal and geotectonic setting of Cretaceous volcanic rocks near Ica, Peru, in relation to Andean crustal thinning[END_REF] or to an intra-arc extensional pull-apart basin [START_REF] Soler | El volcanismo Casma del Perú Central: cuenca marginal abortada o simple arco volcanico?[END_REF]Jaillard, 1994;[START_REF] Polliand | Formation of intra-arc volcano-sedimentary basins in the western flank of the central Peruvian Andes during Late Cretaceous oblique subduction field evidence and constraints from U-Pb ages and Hf isotopes[END_REF][START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF]. Stratigraphic relationships in the WPT led [START_REF] Scherrenberg | Stratigraphic variations across the Marañón Fold-Thrust Belt, Peru: Implications for the basin architecture of the West Peruvian Trough[END_REF] to delineate i) a western intra-arc basin, which is dominated by igneous rocks and that geographically coincides with the VMS mineralization; and ii) an eastern, deeper back-arc basin in which volcanic rocks overlie continental clastic rocks and marine carbonates. Major basin filling in the WPT occurred from latest Jurassic to Late Cretaceous [START_REF] Mégard | The Andean orogenic period and its major structures in central and northern Peru[END_REF]Benavides-Cáceres, 1999). The stratigraphy of the WPT (at least in its western portion sensu [START_REF] Scherrenberg | Stratigraphic variations across the Marañón Fold-Thrust Belt, Peru: Implications for the basin architecture of the West Peruvian Trough[END_REF] is largely composed of a volcano-sedimentary sequence including bimodal mafic-felsic volcanic rocks, limestones, shales, sandstones, and local evaporites that was intruded by the Peruvian Coastal Batholith, which in part is coetaneous with the volcano-sedimentary sequence [START_REF] Mégard | The Andean orogenic period and its major structures in central and northern Peru[END_REF][START_REF] Atherton | Thermal and geotectonic setting of Cretaceous volcanic rocks near Ica, Peru, in relation to Andean crustal thinning[END_REF][START_REF] Vela | Nueva concepción estratigráfica de la subcuenca de Lima. IX Congreso Peruano de Geología[END_REF]Benavides-Cáceres, 1999;[START_REF] Polliand | Formation of intra-arc volcano-sedimentary basins in the western flank of the central Peruvian Andes during Late Cretaceous oblique subduction field evidence and constraints from U-Pb ages and Hf isotopes[END_REF][START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF][START_REF] Hildebrand | Arc and Slab-Failure Magmatism in Cordilleran Batholiths I The Cretaceous Coastal Batholith of Peru and its Role in South American Orogenesis and Hemispheric Subduction Flip[END_REF]. The stratigraphy of the WPT is complex and includes abrupt lateral facies changes greatly limiting the stratigraphic correlation and age estimates of the sedimentary units. Since the scope of this article is limited to the geochemical composition of some ore minerals in selected VMS deposits, we will not elaborate on the nomenclature of hosting units but will simply conform with Casma Group embracing the Albian-Cenomanian volcano-sedimentary sequence versus the ounger Upper Cretaceous-Paleocene volcano-sedimentar sequence [START_REF] Romero | Los depósitos de la cuenca Maastrichtiano -Daniano: relación con los yacimientos tipo sulfuros masivos volcanogénicos de Pb -Zn -Cu; Perú central[END_REF]Cueva et al., 2010;[START_REF] Fontboté | Volcanogenic Zn-Pb±Cu massive sulfide deposits in the Upper Cretaceous plutono-volcanic arc in central Peru[END_REF].

From north to south, the most representative VMS mineralization in the Huarmey and Cañete basins are the María Teresa, Aurora Augusta, Perubar, Palma, and Cerro Lindo (Fig. 1). Geochronology has given two groups of ages for these deposits: uppermost Cretaceous and mid-Cretaceous. High-resolution U-Pb zircon geochronology performed by [START_REF] Polliand | Formation of intra-arc volcano-sedimentary basins in the western flank of the central Peruvian Andes during Late Cretaceous oblique subduction field evidence and constraints from U-Pb ages and Hf isotopes[END_REF] on rhyolitic lavas at the bottom and top of massive ore bodies in Perubar yields dates of 69.71 ± 0.18 and 68.92 ± 0.16 Ma, and on intrusive rocks, dates of 67.91 ± 0.17 and 67.89 ± 0.18 Ma. These dates ascribe the hosting rocks to the Upper Cretaceous-Paleocene volcano-sedimentary sequence and point to largely coeval subsidence, submarine volcanism, and plutonic activity within the Andean magmatic arc during the Late Cretaceous [START_REF] Polliand | Formation of intra-arc volcano-sedimentary basins in the western flank of the central Peruvian Andes during Late Cretaceous oblique subduction field evidence and constraints from U-Pb ages and Hf isotopes[END_REF][START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF]. At María Teresa, a date of 68 ± 6 Ma (Rb/Sr in hydrothermal sericite; [START_REF] Romero | Los depósitos de la cuenca Maastrichtiano -Daniano: relación con los yacimientos tipo sulfuros masivos volcanogénicos de Pb -Zn -Cu; Perú central[END_REF]) points also to VMS mineralization in the latest Cretaceous. In contrast, the Cerro Lindo VMS mineralization is described to be hosted by a volcano-sedimentary sequence whose age has been attributed to the mid-Cretaceous (Casma Group) according to U-Pb zircon dating of host rhyolites at 105.7 ± 0.2 and 106.9 ± 0.2 Ma (Gariépy and Hinostroza, 2003;Votorantim, 2017;Bueno Carreón, 2019;Bueno Carreón and Mendoza Mondragón, 2019). Recent U-Pb zircon dating at 101 Ma of a diorite dike crosscutting the mineralization suggests that the Palma VMS deposit is also mid Cretaceous [START_REF] Choquehuanca | Petrology, geochronology and geochemistry of the Lower Cretaceous in Palma volcanogenic massive sulfide (VMS) deposit[END_REF]. At Aurora Augusta, hydrothermal sericite yielded inconclusive both mid-and late Cretaceous ages (K-Ar;Vidal, 1987).

Hydrothermal alteration in the María Teresa, Perubar, and Palma typically comprises intense sericite ± chlorite in the footwall and epidote + albite + chlorite + carbonates in the hanging wall and distal domains of sulfide bodies [START_REF] Fontboté | Volcanogenic Zn-Pb±Cu massive sulfide deposits in the Upper Cretaceous plutono-volcanic arc in central Peru[END_REF]. Sericite alteration is particularly well developed in the María Teresa deposit due to the exclusive igneous nature (i.e., plagioclase-rich) of the host rocks unlike in Perubar and Palma, where the presence of sedimentary rocks in the host sequence distorts the hydrothermal alteration halos. At María Teresa, the identification of a prospective hori on outlined b an intense sericite alteration front has been interpreted as a paleo-horizon in which ascending hydrothermal fluids mixed with seawater in the volcanic pile in the sub-seafloor [START_REF] Fontboté | Volcanogenic Zn-Pb±Cu massive sulfide deposits in the Upper Cretaceous plutono-volcanic arc in central Peru[END_REF][START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF]. Sulfur and Sr isotope data at Perubar support that mixing between a hydrothermal fluid (dominated by H2S) and seawater triggered the mineralization [START_REF] Polliand | Tracing back sulfur isotope reequilibration due to contact metamorphism: A case study from the Perubar VMS deposit, Central Peru[END_REF][START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF]. The setting of the María Teresa, Palma, and Perubar in a plutono-volcanic arc and the likely involvement of acidic-oxidizing fluids indicated by alteration and ore mineral assemblages are used by [START_REF] Fontboté | Volcanogenic Zn-Pb±Cu massive sulfide deposits in the Upper Cretaceous plutono-volcanic arc in central Peru[END_REF] to argue for a magmatic origin of the ore-forming hydrothermal fluids.

Geology of the María Teresa deposit

The Zn-Pb-Cu-Ag María Teresa mine is located 11 km NW of Huaral and 85 km N of Lima (Fig. 1) and is owned and operated by Minera Colquisiri SA since 1985.

Mineralization at María Teresa (>18 Mt high-grade Zn-Pb-Ag±Cu ore, [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF] occurs as replacement of volcanic and subvolcanic rocks that were intruded by a series of subvertical, N150E-oriented andesitic and dacitic dykes and, in places, by granodiorite and diorite plutons. Volcanic rocks at María Teresa comprise basaltic andesites and andesites and less abundant rhyodacites which, akin plutonic rocks in the district, show calc-alkaline affinity [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF]. Basaltic andesites and andesites show aphanitic, porphyritic textures drawn by plagioclase and amphibole phenocrysts.

Amygdaloidal and brecciated textures are also common and, towards the upper section of the sequence, pillow lavas and hyaloclastites occur. Despite that the limit between individual lava flows is often blurred, the locally observed bedding is horizontal to slightly W-dipping. The N160E-oriented El Abra strike-slip fault dismembered and displaced clockwise the minerali ation in the prospective hori on so that the Calera sector has been displaced about 500 m to the south in relation to the Mine 2 and Bubulina sectors. In addition, the N140E-oriented Sofía reverse fault has slid the western block on top of the eastern block with an approximate vertical displacement of 90 m (Fig. 2). The mineralization in the María Teresa deposit occurs mostly as N150E-oriented irregular to lenticular massive sulfide bodies and underlying stockwork structures associated with abundant alteration to sericite and quartz [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF]. Close to the contact with granodiorite intrusions chiefly to the east of the Calera zone, a mineral assemblage including cordierite and garnet porphyroblasts along with biotite, phlogopite, and tremolite is interpreted as the contact metamorphic product of the hydrothermal sericite alteration [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF]. The ore mineralization includes sphalerite, chalcopyrite, tetrahedrite-group minerals, and galena, which occur along with variable proportions of pyrite ± pyrrhotite ± barite. The Sofía-D massive sulfide body is the largest in the deposit (~ 8 Mt grading 7.1% Zn, 1.37% Cu, 0.64% Pb, 60.3 g/t Ag; [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF] and shows clear metal zoning (Fig. 2). Metal zoning, ore mineral assemblages, and textures observed in this ore body are described in detail below. Due to the well-defined metal zoning in Sofía-D, it was selected in this study to trace the distribution of trace elements in sphalerite and chalcopyrite in zone-refined massive sulfide bodies.

Geology of the Perubar deposit

The Zn-Pb-Ba Perubar deposit is located 50 km E of Lima (Fig. 1) and was exploited between 1978 and 2000 with a production of 6 Mt with an average grade of 11.8% Zn and 1.4 % Pb [START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF]. The massive sulfide mineralization is hosted by an uppermost Cretaceous volcano-sedimentary sequence composed of submarine volcanic rocks and pyroclastic deposits of intermediate to felsic composition, intercalated with detrital sediments, volcaniclastic sandstones, tuffaceous mudstones, calcareous volcaniclastics, and limestones. Monzodiorite and monzogranite stocks belonging to the Coastal Batholith intruded in the area < ~1 Myr after the mineralizing event causing contact metamorphism at the Perubar deposit [START_REF] Polliand | Tracing back sulfur isotope reequilibration due to contact metamorphism: A case study from the Perubar VMS deposit, Central Peru[END_REF]see Fig. 3 in Polliand et al., 2005;[START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF].

The hydrothermal alteration of the host rocks comprises a siliceous core in the stockwork zone that grades outward to chlorite + pyrite ± sericite; extensive quartz + sericite developed in the footwall below the sulfide lenses, as well as distal quartz + K-feldspar. The deposit consists of four main massive barite-sulfide ore bodies (Graciela, Juanita, Cecilia Norte, and Cecilia Sur). According to [START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF], the original (i.e., before tectonic deformation) ore zonation included a stockwork, which is now located north of the deposit, and massive mineralization that comprised pyrite(-magnetite) and pyrite-rich semi-black ores topped by a massive black ore, which graded laterally to banded barite-sulfide ores. The ore included pyrrhotite, pyrite, marcasite, magnetite, sphalerite, galena, barite, and lesser proportions of chalcopyrite, tetrahedrite, and arsenopyrite [START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF]. In addition, during our survey, tiny amounts of molybdenite and electrum were identified (Fig. S1). Representative photomicrographs of the samples containing the analyzed sphalerite from Perubar are shown in Figure S1. [START_REF] Polliand | Genesis, evolution, and tectonic setting of the Upper Cretaceous Perubar Ba-Pb-Zn volcanic-hosted massive sulfide deposit[END_REF] suggests that the conspicuously low proportion of chalcopyrite in the ore mineralization constrains the temperature of the mineralizing fluids < ~ 300 ºC.

Geology of the Palma deposit

The Zn-Pb Palma deposit is located 55 km SE of Lima and 15 km south of Perubar (Fig. 1).

Ongoing exploration by Volcan Cía. Minera since 2009 has revealed a resource of 14.5 Mt including 9.6 Mt indicated at 5% Zn, 0.7% Pb, and 22 g Ag/t and 4.9 Mt inferred at 6% Zn, 1% Pb, and 21 g Ag/t, all reported with a cut-off of 3.5% Zn [START_REF] Farfán | Palma, yacimiento de Zn-Pb tipo VMS en una cuenca intra-arco del Cretácico Superior en Perú central, nuevos avances en exploración para un gran potencial[END_REF]. The mineralization is hosted in a volcano-sedimentary sequence consisting of sills and NNW-SSE trending dykes of basaltic to andesitic composition and local peperitic textures, organic matter-rich and framboidal-pyrite-bearing pelites, and shallow-water limestones. This sequence is cut by NNW-SSE-oriented felsic dykes. The igneous suite in the district displays calc-alkaline affinity [START_REF] Farfán | Palma, yacimiento de Zn-Pb tipo VMS en una cuenca intra-arco del Cretácico Superior en Perú central, nuevos avances en exploración para un gran potencial[END_REF]. Hydrothermal alteration includes deep, poorly developed sericite alteration and much widespread albite + epidote + chlorite + pyrite alteration The mineralization occurs as stacked massive sulfide bodies roughly parallel to the bedding and replaced chiefly limestone and subordinately pelitic and mafic and intermediate igneous rocks belonging to the lower section of the volcano-sedimentary sequence in the > 250-m-thick Palma Unit (see Fig. 3 in [START_REF] Farfán | Palma, yacimiento de Zn-Pb tipo VMS en una cuenca intra-arco del Cretácico Superior en Perú central, nuevos avances en exploración para un gran potencial[END_REF]. Stringer and stockwork mineralization are also documented by these authors. [START_REF] Farfán | Palma, yacimiento de Zn-Pb tipo VMS en una cuenca intra-arco del Cretácico Superior en Perú central, nuevos avances en exploración para un gran potencial[END_REF] describe that the mineralogy of the upper semi-massive sulfide bodies comprises mainly pyrite, sphalerite, galena, and barite, with subordinate pyrrhotite and chalcopyrite, while the proportion of these two minerals increases in lower massive sulfide bodies. In addition, minor amounts of arsenopyrite and marcasite were identified during this survey. The samples analyzed in this work come from the upper semi-massive sulfide bodies. Representative microphotographs of samples containing the analyzed sphalerite from Palma are presented in Fig. S2. Ore and host rock have partly undergone contact metamorphism induced by arc plutons [START_REF] Farfán | Palma, yacimiento de Zn-Pb tipo VMS en una cuenca intra-arco del Cretácico Superior en Perú central, nuevos avances en exploración para un gran potencial[END_REF].

Geology of the Cerro de Maimón deposit, Dominican Republic

The Cerro de Maimón VMS deposit is located 70 km northwest of Santo Domingo in central Dominican Republic (Fig. 3). It stands as the only VMS deposit currently under production in the Caribbean region. It is owned and operated by Perilya Limited through its subsidiary Corporación Minera Dominicana (CORMIDOM). The Cerro de Maimón massive sulfide body contains 4.8 Mt of proven and probable reserves grading 2.54% copper, 0.96 g/t Au, and 34.9 g/t Ag [START_REF] Perilya | Cerro de Maimón[END_REF]. VMS mineralization and the metallogenic evolution of the Caribbean Greater Antilles are summarized and discussed by [START_REF] Nelson | The metallogenic evolution of the Greater Antilles[END_REF]Torró et al. (2018a). The Cerro de Maimón massive sulfide mineralization is hosted by the Aptian Maimón Formation (Fig. 3), which is composed mostly of bimodal mafic-felsic volcanic and volcaniclastic rocks of boninitic and tholeiitic affinities emplaced in the forearc portion of the nascent Caribbean island-arc (Torró et al., 2016a[START_REF] Torró | Petrogenesis of meta-volcanic rocks from the Maimón Formation (Dominican Republic): Geochemical record of the nascent Greater Antilles paleo-arc[END_REF](Torró et al., , 2018b)). Massive sulfides and hosting volcanic rocks were deformed and metamorphosed to peak metamorphic conditions in the greenschist/blueschist facies transition (Torró et al., 2016b). The mineralization is composed of pyrite grains with both cataclastic/blow-apart and metablastic welding textures and an interstitial assemblage of chalcopyrite + sphalerite + quartz + tennantite ± galena (paragenetic sequence and photomicrographs available in Fig. 6 in Torró et al., 2016a).

Materials and Methods

The study is based on 36 ore samples from the María Teresa (n = 24), Palma (n = 4), and Perubar (n = 5) deposits in Peru and the Cerro de Maimón deposit (n = 3) in the Dominican Republic. A list of the samples, their location, and brief textural descriptions are given in Table S1 in the Supplementary Material. In the María Teresa deposit, 15 ore samples picked up at different depths along a single drill core (34-18-S) that cut the zone-refined Sofía-D sulfide body (Calera sector) have been used to monitor mineralogical and mineral geochemical variations with depth. A total of 34 thick polished sections were produced at the QEMSCAN laboratory of the Pontificia Universidad Católica del Perú (PUCP) and examined using petrographic and scanning electron (SEM) microscopy. SEM images and major element mineral compositions were acquired on an environmental SEM Thermo Fisher Quanta 650 FEI equipment with an EDAX-Octane Pro EDS microanalysis system at PUCP (Centro de Caracterización de Materiales CAM-PUCP) and a VEGA II XMU Tescan equipment with a Bruker QUANTAX EDS microanalysis system at BIZALAB at operating conditions of 5 nA and 20 kV accelerating voltage.

Minor and trace element compositions of sphalerite and chalcopyrite were determined by means of electron microprobe (EPMA), at the University of Barcelona, and laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS), at the ETH Zürich, using the same equipment and methodology as described in Benites et al. (2021a). For samples from the María Teresa, Palma, and Perubar deposits, representative EPMA analyses of sphalerite and chalcopyrite are displayed in Table S2 in Supplementary Material. For samples from the Cerro de Maimón deposit, representative EPMA analyses of sulfide minerals are provided in Torró et al. (2016a). LA-ICPMS data are reported in Table S3 in Supplementary Material. Content statistical data for sphalerite and chalcopyrite are shown in Tables 12.

Results

Ore mineral geochemistry

Major and trace element compositions of sphalerite and chalcopyrite show, in general, a wide range of elements at measurable contents. Summaries of their compositions, including minimum, maximum, geometric mean, standard deviation, and interquartile range (IQR) values are displayed in Tables 1 and2. Content values will be hereinafter reported as IQR unless otherwise specified. Significant effort was made to report only the content of elements whose variations respond to solid solutions and not to mixed mineral analyses by analyzing mineral volumes free of obvious inclusions and by selecting only stable signal intervals in LA-ICP-MS spectra (Fig. S3 in Supplementary Material).

However, it should be noted that evenly distributed nano-inclusions may also yield flat ablation profiles (e.g., [START_REF] Gregory | Trace element content of sedimentary pyrite in black shales[END_REF] and that, therefore, the possibility of mixed mineral analyses cannot be completely discarded due to the relatively low spatial resolution of the used methods.

Sphalerite

Iron, Mn, Cd, Hg, and Cu (Fig. S3 in Supplementary Material) yield smooth and constant ablation profiles. Studied sphalerite shows a relatively wide range of Fe contents in samples from the María Teresa deposit (40675-17122 ppm), which are higher than in samples from the Cerro de Maimón (585-535 ppm) and generally lower than in samples from the Perubar (67570-39965 ppm) and Palma (63423-30015 ppm) deposits (Table 1). Manganese also shows a relatively wide range of contents in sphalerite from María Teresa (2343-326 ppm), which overlaps with the composition of grains from Cerro de Maimón (482-446 ppm) and are in general lower than in grains from Perubar (5964-907 ppm) and Palma (7751-6734 ppm). The contents of Cd are constantly high in all analyzed sphalerite samples (7373-5290 ppm in María Teresa, 6665-4297 ppm in Perubar, 7109-4782 ppm in Palma, and 3829-3574 ppm in Cerro de Maimón). Mercury contents are higher in sphalerite from the Palma (667-593 ppm) and María Teresa (448-326 ppm) deposits than in sphalerite from the Perubar (107-18 ppm) and Cerro de Maimón (26-22 ppm) deposits. The content of Cu is generally higher in sphalerite samples from the Cerro de Maimón (138-113 ppm) and María Teresa (98-36 ppm) deposits than in sphalerite samples from the Perubar (41-25 ppm) and Palma (31-11 ppm) deposits.

At generally lower contents and also showing smooth ablation spectra are Ag, In, Ge, and Ga (Table 1; Fig. S3 in Supplementary Material). Silver content ranges mostly overlap in sphalerite grains from the four studied deposits (12-4.2 ppm in María Teresa, 7.1-3.6 ppm in Perubar, 17-3.8 ppm in Palma, and 4.2-3.1 ppm in Cerro de Maimón). The contents of In are in general much higher in sphalerite from the María Teresa deposit (68-4.4 ppm, up to 415 ppm) than in sphalerite from the Cerro Maimón (10-9.5 ppm), Perubar (2.3-0.78 ppm) and Palma (0.22-0.0091 ppm; Table 1) deposits. Gallium contents are higher in sphalerite from the Cerro de Maimón deposit (95-78 ppm, up to 96 ppm) than in sphalerite from the María Teresa (32-11 ppm, up to 94 ppm), Perubar (30-4.7ppm), and Palma (2.4-1.9 ppm) deposits. Germanium contents are in general very low in analyzed sphalerite grains (0.65-0.17 ppm in María Teresa, 0.19-0.15 ppm in Perubar, 3.5-0.16 ppm in Palma, and 1.2-0.68 ppm in Cerro de Maimón).

The content of other elements are in general very low (Pb: 9.3-1.1 ppm; Sb: 3.7-0.31 ppm; Tl: 0.66-0.045; Sn: 0.49-0.23 ppm; Bi: 0.60-0.0055 ppm; detailed results for individual deposits are available in Table 1). Some analyses show slightly ragged ablation spectra (Fig. S1 in Supplementary Material).

Chalcopyrite

Chalcopyrite grains from the María Teresa and Cerro de Maimón VMS deposits have been analyzed. Zinc, Ag, Sn, Cd, Se, In, Ge, and Ga show relatively constant ablation profiles (Fig. S3 in Supplementary Material). Zinc is the trace element most highly concentrated in studied sphalerite grains; its contents are higher in chalcopyrite from the María Teresa deposit (425-194 ppm) than in chalcopyrite from the Cerro de Maimón deposit (a single analysis >d.l. yields a concentration of 71 ppm; Table 2). Silver, Sn, and Cd are relatively enriched in chalcopyrite grains from the María Teresa deposit (150-71 ppm Ag, 77-33 ppm Sn, 12-6.2 ppm Cd) relative to grains from the Cerro de Maimón deposit (23-15 ppm Ag, 1.6-1.4 ppm Sn, 0.53-0.41 ppm Cd). Selenium is more concentrated in chalcopyrite from the Cerro de Maimón deposit (89-79 ppm) than in chalcopyrite from the María Teresa deposit (31-19 ppm). Indium values are relatively constant in analyzed grains from the studied deposits and are systematically higher in chalcopyrite from María Teresa (32-12 ppm) than in chalcopyrite from Cerro de Maimón (8.1-7.3 ppm). The contents of Ga and Ge are in general lower than those of In (9.2-2.6 ppm Ga and4.3-0.66 ppm Ge in María Teresa; 3.6-3.3 ppm Ga and6.1-5.3 ppm Ge in Cerro de Maimón).

Downhole ablation spectra reveal very irregular profiles for Mo and Au and in some samples, slightly irregular profiles for Tl, Sb, and Bi (Fig. S3 in Supplementary Material).

Molybdenum yields relatively erratic contents, which are much higher in analyzed chalcopyrite from Cerro de Maimón (83-23 ppm) than in chalcopyrite from María Teresa (0.034-0.021 ppm, and mostly <d.l.). The contents of Tl (< 11 ppm), Sb (< 31 ppm), Bi (< 10 ppm), and Au (< 0.40 ppm) are relatively low (Table 2).

Metal zonation, mineralogy and trace-element distribution patterns in the zonerefined Sofía-D body

The metal zonation in Sofía-D massive sulfide body includes, bottom to top, i) a Cu zone composed dominantly of chalcopyrite and lesser amounts of sphalerite grading downward to massive pyrite; ii) a Zn zone in which sphalerite is the most abundant phase and appears along with lesser amounts of galena and chalcopyrite and minor fahlore; and iii) a Pb Zn Ag zone with abundant galena and sphalerite, and lesser proportions of fahlore and barite (Fig. 2).

On the hand sample scale, sphalerite occurs as mm-to cm-sized grains of yellow-pale brown (Fig. 4A-C) and red-brownish (Fig. 4D-E) color. In places, the massive sphalerite aggregates are cut by irregular, chalcopyrite-rich veinlets (Fig. 4A, D-E). In the eastern part of the María Teresa deposit, i.e., close to the granodiorite stock as is the case for the Sofia D ore body, coarse-grained pyrrhotite ± magnetite is observed and, similarly to in Perubar (see Vidal, 1987;[START_REF] Polliand | Tracing back sulfur isotope reequilibration due to contact metamorphism: A case study from the Perubar VMS deposit, Central Peru[END_REF], interpreted as the metamorphic product after pyrite.

An example is shown in Figure 4F coming from a 20-cm-wide band composed of coarsegrained pyrrhotite ± magnetite at the contact with and andesitic dyke. In volcaniclastic rocks in the immediate host of the Sofía-D body, chalcopyrite selectively replaced some of the clasts and the matrix (Fig. 4G). Silicified dykes that cut the Sofía-D body typically contain patches and irregular veinlets of chalcopyrite (Fig. 4H).

Under the petrographic microscope, pyrite grains, which have sizes typically in the range between 100 and 600 µm, draw a variety of textures including anhedral isolated grains with roundish and embayed outlines, aggregates of several grains often with foam equilibrium textures (i.e., contacts at 120º) and, in some cases, internal irregular fractures (Fig. 5A-D).

Arsenopyrite is relatively scarce in the studied samples and appears as isolated euhedral and subhedral fractured grains and sizes in the range between 50 and 200 µm (Fig. 5C-D).

The other sulfides, fahlore (tennantite-(Fe) ± argentian tetrahedrite), and traces of other sulfosalts such as bournonite, boulangerite, and polybasite (petrographic observations complemented with EDS analyses) occupy interstitial space between, and line porosity and fractures within, pyrite ± arsenopyrite grains (Fig. 5). According to these observations, pyrite and arsenopyrite crystallized early in the paragenetic sequence (Fig. 6) and, in places, underwent thermal re-equilibration connected to dyke and granodiorite intrusions [START_REF] Pichardo | El yacimiento de Zn-Pb-Cu-Ag tipo VMS María Teresa, Perú: Geología y exploración[END_REF]. Internal fractures of pyrite and arsenopyrite (Fig. 5C) also point to fragile deformation, probably due to movements along the Sofía reverse fault (Fig. 2). Sphalerite grains in the Zn zone show clean surfaces (Fig. 5B,E), whereas in the Cu zone they have been pervasively replaced by chalcopyrite and show dense chalcopyrite disease textures (Fig. 5D, F-G). Chalcopyrite floods the interstitial space between pyrite ± arsenopyrite in the Cu zone along with relicts of sphalerite and in places shows sharply bounded exsolutions of cubanite laths up to 150 µm in length (Fig. 5G). Auriferous silver (73 wt.% Ag, 27 wt.% Au, EDS analysis) has been observed in one sample and appears as minute grains (< 2 µm) in fractured arsenopyrite along with chalcopyrite (Fig. 5H).

The systematic sampling developed along the drill core 34-18-S from 72.85 to 128 m (Table S1 in the Supplementary Material) allows for the assessment of vertical trends in trace-element contents in sphalerite and chalcopyrite. Bottom to top in sphalerite, there is a relatively sustained decrease in the contents of Mn, Cu, Se, Bi, and In and an increase of m,) to shallower (80-74 ppm in sample 2019-MT-007at 90.5 m) chalcopyrite samples (Fig. 8J). Although probably hosted as sub-microscopic mineral inclusions, the content of Bi in chalcopyrite also shows significant variation and tends to increase with depth (Fig. 8G).

Discussion

Trace-element budget in sphalerite and chalcopyrite from arc-hosted VMS deposits

The minor and trace element contents measured in sphalerite and chalcopyrite from the Palma, Perubar, María Teresa (Perú), and Cerro de Maimón (Dominican Republic) VMS deposits will be compared along the following lines with available data from other VMS deposits, and particularly with those formed in arc systems. We have compared our results with the comprehensive compilation by [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF] of whole-rock and mineral geochemical data from both active seafloor massive sulfide (SMS) and fossil equivalent deposits emplaced in a variety of tectonic settings worldwide.

Sphalerite from the four investigated deposits yields fairly variable Fe contents (Table 1), the content of the other analyzed trace elements being largely subordinated to that of Fe. The content of Fe in sphalerite samples from the Cerro de Maimón deposit analyzed in this study is particularly low (Table 1); a more complete geochemical dataset based on EPMA analyses on sphalerite samples from this deposit reported by Torró et al. (2016a) indicates average Fe contents of 1.16 wt.%. Iron contents in the studied deposits are compatible with sphalerite crystallized in intermediate to high-intermediate sulfidation environments in equilibrium with pyrite (Barton and Toulmin 1964;[START_REF] Hannington | Sulfidation equilibria as guides to gold mineralization in volcanogenic sulfides: evidence from sulfide mineralogy and the composition of sphalerite[END_REF]. Co-crystallization of fahlore (tennantite and tetrahedrite) along with sphalerite in the studied ore samples is a further indication of intermediate-sulfidation state of the hydrothermal mineralizing fluids.

Similar Fe contents to those in the studied Andean VMS deposits are reported in sphalerite samples from the Zinkgruvan, Marketorp, and Sauda VMS deposit (Table 3 and references therein). Iron contents similar to those found in sphalerite from the Cerro de Maimón deposit are reported in the Vorta, Eskay Creek, and Çayeli VMS deposits. In contrast, sphalerite from the VMS Laochang deposit (South China) systematically yields higher Fe contents.

The relatively high content of Cd in sphalerite from the studied deposits (Table 1) are comparable with those in sphalerite from other VMS deposits such as Vorta, Eskay Creek, Zinkgruvan, Marketorp, and Laochang, and higher than in Sauda (Table 3). Cadmium contents of several hundreds of parts per million are typical of SMS emplaced in arc settings compared to contents in the range of some tens of parts per million in those emplaced in mid-ocean ridge systems, sphalerite and wurtzite bein the main Cd hosts in VMS deposits according to [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF]. According to our (Table 1) and previous (Table 3) data, Cd in sphalerite from VMS deposits in arc systems typically yields contents of several thousands of parts per million. The content of Hg varies between some tens (Perubar and Cerro de Maimón) and some hundreds (María Teresa and Palma) of parts per million in the studied sphalerite samples; the content of Hg is not provided for sphalerite from other VMS deposits in arc systems in the revised literature. [START_REF] Petersen | Drilling shallow-water massive sulfides at the Palinuro volcanic complex, Aeolian island arc, Italy[END_REF] reported contents between <0.02 and 7.4 wt.% Hg (median = 0.37 wt.% Hg; EPMA data) in sphalerite from the Palinuro SMS deposit in the Aeolian arc (transitional arc setting). [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF] found out that the content of Hg in SMS is higher in mineralization emplaced in arc volcanoes and rifted arcs (some tens of ppm) relative to mineralization emplaced in backarc spreading centers and mid-ocean ridges; also, that Hg usually shows a strong positive correlation with Sb in mineralized samples from SMS which normally results from the chief concentration of Hg in tetrahedrite and tennantite over other ore minerals. The contents of Sb in the studied sphalerite are mostly in the 1-10 parts per million range or below (Table 1), similar to sphalerite from other VMS mineralization such as Vorta, Zinkgruvan, and Laochang, and lower than in Eskay Creek and Çayeli (Table 3). The content of Tl in the studied sphalerite samples is normally below 1 ppm (Table 1), similar to sphalerite from other VMS deposits with the exception of Çayeli, in which the content of Tl is much higher (13-4.9 ppm; Table 3). The contents of Sb and Tl are usually higher in sulfide samples from SMS mineralization emplaced in arc volcanoes and rifted arcs than in SMS mineralization emplaced in back-arc spreading centers and mid-ocean ridges according to data compiled by [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF].

The studied sphalerite samples yield In contents largely in the range between <1 ppm and some tens of parts per million (Table 1), similar to sphalerite from Vorta, Eskay Creek, Zinggruvan, Marketorp, and Sauda, and lower than in Laochang (Table 3). The measured In contents are also much lower than in sphalerite from the Neves Corvo VMS deposit (up to 2.1 wt.%, EPMA data: [START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF]. The contents of Ga in the sphalerite samples analyzed here are largely of the same order of magnitude (from a few ppm to 100 ppm) as contents reported for sphalerite from other VMS deposits (Table 3), whereas the contents of Ge (mostly <1 ppm) are generally lower than those reported in the literature. The contents of In, Ge, and Ga are mostly indistinguishably low in SMS sulfides irrespective of their tectonic environment of emplacement [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF].

In the studied chalcopyrite samples from the Andean VMS deposits, the content of Zn is of some hundreds of parts per million (Table 2), similar to chalcopyrite from Vorta, Sulitjelma, and Kutlular, and lower than in chalcopyrite from Çayeli (Table 4 and references therein); Zn content in sphalerite from the Cerro de Maimón deposit is significantly lower. The contents of Ag are mostly in the range between a few to some hundreds of parts per million in the analyzed chalcopyrite (Table 2), like chalcopyrite from VMS reported in the literature (Table 4). Selenium contents in the studied chalcopyrite samples are of some tens of parts per million (Table 2), and therefore lower than Se contents in chalcopyrite from other subduction-related VMS deposits, which are mostly in the hundreds of parts per million range (Table 4). According to [START_REF] Monecke | Constraints on Water Depth of Massive Sulfide Formation: Evidence from Modern Seafloor Hydrothermal Systems in Arc-Related Settings[END_REF], chalcopyrite is the main host of Se in VMS and SMS deposits along with pyrite and, typically, higher Se contents are found in sulfide samples collected in SMS formed in mid-ocean ridges relative to those in subduction related systems. Cadmium shows contents of a few to some tens of parts per million in the analyzed chalcopyrite samples (Table 2), similar to chalcopyrite from other VMS deposits (Table 4); therefore, as expected, Cd contents are much lower in chalcopyrite than in sphalerite from the same deposit (Tables 1 and3). Similarly, Hg contents in chalcopyrite (up to a few ppm, Table 2) are much lower than in sphalerite (Table 1) from the respective deposits, and similar to or slightly higher than Hg content in chalcopyrite from the Vorta and Sulitjelma VMS deposits (Table 4).

Indium content in analyzed chalcopyrite grains, mostly at the level of tens of parts per million, is only slightly lower than In content in sphalerite grains from the same deposits (Tables 1 and2), and steadily higher than in chalcopyrite grains from the Vorta and Sulitjelma VMS deposits (Table 4). Germanium content in the analyzed chalcopyrite samples is mostly at the level of some parts per million (Table 2) and usually higher than in sphalerite from the respective deposits (Table 1); Ge content is not provided in reference data for chalcopyrite from other VMS deposits (Table 4). The content of Ga (mostly at the level of a few ppm to some tens of ppm) is lower in chalcopyrite than in sphalerite from the same deposit (Tables 1 and2); the content of Ga in chalcopyrite from the Vorta and Sulitjelma VMS deposits is systematically lower than in the samples analyzed here (Table 4).

Correlation trends and substitution mechanisms

Sphalerite

The dataset shows a marked negative correlation trend between Fe and Zn with a slope of 1 (Fig. 9A) that indicates a dominant Fe 2+ Zn 2+ simple isovalent substitution. Fair positive correlations between Ag and both Pb (Fig. 9B) and Sb (Fig. 9C) suggest that these three elements likely occur in solid solution in the studied sphalerite samples. Tin is also positively correlated with Ag and the reasonable positive correlation in the Sb+Sn vs. Ag+Pb plot (Fig. 9D) with a slope 1 suggests incorporation of these elements via coupled substitutions of the type Ag + + Pb 2+ + (Sn,Sb) 3+ 3Zn 2+ and likely also via independent variations of this scheme [START_REF] Cook | Trace and minor elements in sphalerite: a LA-ICPMS study[END_REF]. Nevertheless, the observation of slight ragged downhole ablation spectra for Sn and Pb in a few analyses (e.g., Fig. S3D in Supplementary Material) might suggest the local presence of sub-microscopic inclusions of galena and/or Sn-Pb sulfosalts.

The dataset shows a marked correlation trend between Cu and In in samples from María Teresa, particularly in those with the highest In contents, with a slope 1 (Fig. 10A) thus pointing to a Cu + + In 3+ 2Zn 2+ coupled substitution [START_REF] Cook | Determination of the oxidation state of Cu in substituted Cu-In-Fe-bearing sphalerite via mu-XANES spectroscopy[END_REF][START_REF] Trofimov | The State of Trace Elements (In, Cu, Ag) in Sphalerite Studied by X-Ray Absorption Spectroscopy of Synthetic Minerals[END_REF]Benites et al., 2021a,b). Gallium yields a fair positive correlation with Cu with some [START_REF] Cook | Trace and minor elements in sphalerite: a LA-ICPMS study[END_REF][START_REF] Cook | Distribution and substitution mechanism of Ge in a Ge-(Fe)-bearing sphalerite[END_REF]Bellisont et al., 2014). The low content of both Sn and Ge in the studied sphalerite grains and the apparent lack of individual correlation trends with other analyzed elements do not allow to give a definitive conclusion on their incorporation in the crystal lattice.

Chalcopyrite

Unlike sphalerite, chalcopyrite is not a fully ionic mineral but bonding between atoms in its structure is effectivel covalent with valencies of Fe fluctuating between divalent and trivalent and valencies of Cu, between monovalent and divalent [START_REF] Donnay | Symmetry of magnetic structures: magnetic structure of chalcopyrite[END_REF][START_REF] Hall | The crystal structure refinement of chalcopyrite, CuFeS2[END_REF][START_REF] Li | A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite[END_REF]. Therefore, the incorporation mechanism of trace elements in chalcopyrite is far more complex to draw than for sphalerite (see [START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF]. Weak to fair positive correlation trends between Zn, Cd, In, Ge, and Ga are observed across our dataset (Fig. 11). [START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF] also noticed the positive correlation between Zn and Cd in chalcopyrite samples from a variety of mineralization styles and argued that systematic variations of Cd:Zn ratio are strongly dependent on crystallization temperature (this question is further addressed in the following section). Our data would suggest that the incorporation of Zn, Cd, In, Ge, and Ga to the structure of chalcopyrite is not completely independent (i.e., simple substitution) but that coupled substitutions involving cations of these elements are likely (see also [START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF] and their references).

Trace element distribution profiles and conditions of crystallization (and recrystallization)

Metal and mineral onation (Fig. 2) and the overprinting and replacement of earlier sulfides (e.g., sphalerite) b minerals that are stable at higher temperature (e.g., chalcop rite; Figs.

4-6) as described for Sof a-D in the Mar a Teresa deposit denote a thermall intensif ing h drothermal s stem during the growth of the massive sulfide bod ; in VMS s stems, this process is commonl known as one refining [START_REF] Eldridge | Mineral textures and their bearing on formation of the Kuroko orebodies[END_REF][START_REF] Hannington | Comparison of the TAG mound and stock-work complex with Cyprus-type massive sulfide deposits[END_REF][START_REF] Grant | Distribution and controls on silver mineralization in the Hackett River Main Zone, Nunavut, Canada: An Ag-and Pbenriched Archean volcanogenic massive sulfide deposit[END_REF][START_REF] Almodóvar | Massive sulfide ores in the Iberian Pyrite Belt: Mineralogical and textural evolution[END_REF]. According to the GGIMFIS geothermometer of [START_REF] Frenzel | Gallium, germanium, indium and other trace and minor elements in sphalerite as a function of the deposit type A metaanalysis[END_REF] which uses the contents of Fe, Mn, In, Ga, and Ge in sphalerite, the analyzed sphalerite from the María Teresa deposit crystallized at temperatures in the range between 320 and 257 ºC (IQR). Such a temperature range is in good agreement with a VMS mineralization containing fair abundant chalcopyrite (Hannington et al., 1995;[START_REF] Ohmoto | Formation of volcanogenic massive sulfide deposits: The Kuroko perspective[END_REF][START_REF] Franklin | Volcanogenic Massive Sulfide Deposits[END_REF]. Assuming that fO2 and fS2

were stable during the crystallization of sphalerite (see Hannington and[START_REF] Hannington | Sulfidation equilibria as guides to gold mineralization in volcanogenic sulfides: evidence from sulfide mineralogy and the composition of sphalerite[END_REF][START_REF] Keith | Effect of temperature, sulfur and oxygen fugacity on the composition of sphalerite from submarine hydrothermal vents[END_REF] in the Sofía-D sulfide body, sphalerite composition would record a relatively sustained decrease in the crystallization temperature bottom to top (335-327 ºC for sample 2019-MT-015 at 128 m to 255-249 ºC for sample 2019-MT-002 at 74.6 m; Fig. 7J). This decrease in the calculated crystallization temperature is actually a numerical translation of the depletion in In and Mn (directly proportional to the GGIMFIS temperature) and the enrichment in Ge (inversely proportional to the GGIMFIS temperature) bottom to top in sphalerite of the Sofía-D massive sulfide body (Fig. 7).

Noteworthy, an increase in the availability of Cu in the mineralizing fluid towards the Cu zone probably also enhanced the incorporation of In to the sphalerite crystal lattice through the coupled substitution mentioned above (Cu + + In 3+ 2Zn 2+ ) during zone refining processes.

The Cd:Zn ratio in chalcopyrite is commonly used to trace variations in physicochemical conditions during its crystallization. Higher Cd:Zn ratios are typically ascribed to higher temperatures of crystallization [START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF]). In the Sofía-D sulfide body, chalcopyrite shows rather constant Cd:Zn ratios at different depths and sections (Fig. 8K)

suggesting relatively homogeneous physicochemical conditions during the crystallization of this mineral throughout the Cu zone of the mineralized body (Fig 2). In contrast, the increase of Se contents in chalcopyrite (and sphalerite) with depth would suggest an increase in the temperature and/or magmatic volatile influx [START_REF] Auclair | Distribution of selenium in high-temperature hydrothermal sulfide deposits at 13º North, East Pacific Rise[END_REF][START_REF] Huston | Trace elements in sulfide minerals from eastern Australian volcanic-hosted massive sulfide deposits; Part I, Proton microprobe analyses of pyrite, chalcopyrite, and sphalerite, and Part II, Selenium levels in pyrite; comparison with delta 34 S values and implications for the source of sulfur in volcanogenic hydrothermal systems[END_REF][START_REF] Layton-Matthews | Distribution, Mineralogy, and Geochemistry of Selenium in Felsic Volcanic-Hosted Massive Sulfide Deposits of the Finlayson Lake District, Yukon Territory, Canada[END_REF][START_REF] Martin | Trace element systematics and ore-forming processes in mafic VMS deposits: Evidence from the Troodos ophiolite, Cyprus[END_REF]. The concentration of Se, and most trace elements indeed, in the structure of chalcopyrite is distinguishingly strongly influenced by the co-crystallizing phases so that the continuous crystallization of galena during zone refining probably partitioned Se and depleted chalcopyrite in this element [START_REF] Cook | Mineralogy of the sulphide deposits at Sulitjelma, northern Norway[END_REF][START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF][START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF]). The progressively increasing abundance of galena towards the upper sections of the Sofía-D body may therefore explain the progressive depletion of Se in chalcopyrite at shallower levels.

In short, our results suggest that in zone-refined VMS mineralization such as the Sofía-D massive sulfide body in the María Teresa deposit, chalcopyrite and particularly sphalerite register systematic changes in their trace element compositions across the mineralized body. Bottom to top of the sulfide body, observed trends include i) in sphalerite, depletion in In, Cu, Mn, Se, and Bi and enrichment in Ge; and ii) in chalcopyrite, depletion in Se and Bi (the latter probably in microinclusions). Furthermore, these patterns agree with expected physicochemical trends involving decreasing temperatures and influx of hydrothermal fluids with a direct magmatic contribution towards the margins of the sulfide body [START_REF] Auclair | Distribution of selenium in high-temperature hydrothermal sulfide deposits at 13º North, East Pacific Rise[END_REF][START_REF] Huston | Trace elements in sulfide minerals from eastern Australian volcanic-hosted massive sulfide deposits; Part I, Proton microprobe analyses of pyrite, chalcopyrite, and sphalerite, and Part II, Selenium levels in pyrite; comparison with delta 34 S values and implications for the source of sulfur in volcanogenic hydrothermal systems[END_REF][START_REF] Layton-Matthews | Distribution, Mineralogy, and Geochemistry of Selenium in Felsic Volcanic-Hosted Massive Sulfide Deposits of the Finlayson Lake District, Yukon Territory, Canada[END_REF]Yeats et al., 2014;[START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF]Schmidt et al., 2018;[START_REF] Martin | Trace element systematics and ore-forming processes in mafic VMS deposits: Evidence from the Troodos ophiolite, Cyprus[END_REF].

Ore mineralization at the Sofía-D massive sulfide body in the María Teresa deposit underwent contact metamorphism connected to nearby granodiorite intrusions (Fig. 2). The identification of key trace-element distribution patterns in sphalerite and chalcopyrite across this body and their reconciliation with expected original trends suggest that contact metamorphism occurred in a closed system and more importantly, that body-scale trace element distribution was largely unaffected. Similarly, [START_REF] Polliand | Tracing back sulfur isotope reequilibration due to contact metamorphism: A case study from the Perubar VMS deposit, Central Peru[END_REF] determined that in the Perubar VMS deposit, sulfur isotope re-equilibration between sulfate-sulfide pairs during contact metamorphism occurred in a closed system and only between adjacent mineral grains. [START_REF] Lockington | Trace and minor elements in sphalerite from metamorphosed sulfide deposits[END_REF] found out that the content of lattice-bound trace elements in sphalerite (e.g., Mn, Fe, Cd, Cu, In, Ge, Hg, and Se) from metamorphosed VMS deposits worldwide showed no correlation with the metamorphic grade but were defined primarily by physicochemical conditions during initial deposition; in contrast, the contents of elements that typically occur as micro-and nano-inclusions in sphalerite (e.g., Pb and Bi) decreased with increasing metamorphic grade. Therefore, the use of trace element patterns defined by Mn, In, Ge, and Se in sphalerite, and of Se in chalcopyrite, are likely to reflect primary trends.

Conclusions and implications

In this stud , s stematic trace element determinations have been conducted in sphalerite Regarding potential g -ec b -products in the studied sphalerite grains, In (42-1.6 ppm, up to 415 ppm) and Ga (31-5.9 ppm, up to 96 ppm) contents are mostl higher than Ge contents (0.85-0.16 ppm, up to 9.3 ppm). In samples from the Mar a Teresa deposit, the concentrations of In and Cu ield a positive correlation trend with a slope 1 corroborating a Cu + + In 3+ 2Zn 2+ coupled substitution. The dataset also shows a positive correlation trend between Ga and Cu; anal ses of sphalerite from the Mar a Teresa, Perubar and Cerro de Maim n deposits lie close to the Ga:Cu 1:1 ratio line thus pointing to a Cu + + Ga 3+ 2Zn 2+ coupled substitution. Furthermore, the narrow arrangement of most anal ses along the 1:1 ratio line in a In + Ga + Ge + Sn vs. Cu + Ag plot suggests the occurrence of additional, more complex substitution mechanisms involving different combinations of monovalent (Cu + , Ag + ), divalent (Ge 2+ ?), trivalent (In 3+ , Ga 3+ , [Sn 3+ ?]), and quadrivalent (Ge 4+ , Sn 4+ ) cations.

The [START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF], Cook et al., 2019[START_REF] Revan | Mineralogy and trace-element geochemistry of sulfide minerals in hydrothermal chimneys from the Upper-Cretaceous VMS deposits of the eastern Pontide orogenic belt (NE Turkey)[END_REF], and Ye et al., 2011). [START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF], Cook et al., 2019[START_REF] Revan | Mineralogy and trace-element geochemistry of sulfide minerals in hydrothermal chimneys from the Upper-Cretaceous VMS deposits of the eastern Pontide orogenic belt (NE Turkey)[END_REF], and Ye et al., 2011). .9 24-8.9 3.9-2.9 4.1-0.93 2.5-1.0 n.a.

Figure captions

7.5-5.9 8853-8562 235-164 7.7-3.9 ; SD: standard deviation; IQR: interquartile range Table S2 Click here to access/download Supplementar Material Table S2_EPMA VMS.xlsx Table S3 C c e e acce /d ad S e e a Ma e a Tab e S3_LAda a.

  Ge, and the contents of elements such as Cd and Ga show irregular distributions (Fig. 7A-G). The contents of In significantly decrease from sample 2019-MT-015 (128 m, 167-158 ppm) to sample 2019-MT-001 (72.85 m, 4.4-4.1 ppm), although the maximum contents occur in sample 2019-MT-004 (81.4 m, 409-399 ppm; Fig. 7G). The distribution of Cu contents almost mimics that of In, with a decrease from sample 2019-MT-015 (128 m, 203-160 ppm) to sample 2019-MT-001 (72.85 m, 27-24 ppm), although with maximum contents at intermediate depths in samples 2019-MT-004 (81.4 m, 335-321 ppm) and 2019-MT-011 (105.5 m, 597-115 ppm; Fig. 7C). Germanium contents show a moderately irregular distribution pattern with a general increase in its content from sample 2019-MT-015 (128 m, 0.33-0.23 ppm) to sample 2019-MT-002 (74.6 m, 1.3-0.73 ppm; Fig. 7I). As for chalcopyrite, vertical distribution patterns are mostly irregular (Fig. 8). The most remarkable exception is Se, which content tends to decrease steadily at shallower levels (45 ppm single value in sample 2019-MT-015 at 128 m, 31-27 ppm in sample 2019-MT-012 at 109.4 m, 11-10 ppm in sample 2019-MT-007 at 90.5 m; Fig. 8E). An opposite trend is defined by the content of Ge, with general enrichment from deeper (2.2 ppm single value in sample 2019-MT-015 at 128 m, 0.84-0.60 ppm in sample 2019-MT-012 at 109.4

  analyses plotting along or close to the 1:1 correlation line (Fig.10B) suggesting a Cu + + Ga 3+ 2Zn 2+ coupled substitution. Germanium contents do not show clear correlation trends with the other analyzed elements. The alignment of the analyses in the Sn+In+Ge+Ga vs. Cu + Ag plot (R = 0.55; Fig. 10C) would suggest supplementary complex substitution mechanisms involving combinations of coupled substitutions of trivalent cations (i.e., In, Ga) with monovalent cations (i.e., Cu, Ag) and direct substitution of quadrivalent cations (Sn, Ge) with vacancies for Zn. However, the lacking consensus on the oxidation state of Ge (+2 or +4) and Sn (+3 or +4) in sphalerite leaves open the possibility of other substitution schemes (see

  and chalcop rite from the Cretaceous arc-related Palma, Perubar, and Mar a Teresa VMS deposits in Peru and the Cerro de Maim n VMS deposits in the Dominican Republic. Sphalerite from the four deposits incorporated Fe, Mn, Cd, Hg, Ag, Sb, Se, In, Ge, and Ga in solid solution. The incorporation of other elements such as Sn, Tl, Bi, and Pb possibl resulted in some cases from microinclusions as suggested b occasional ragged ablation spectra. The contents of minor and trace elements in anal ed sphalerite show significant variations even between samples from an individual deposit. Iron contents (44009-18168 ppm) correlate negativel with Zn suggesting a dominant Fe 2+ Zn 2+ simple isovalent substitution. Cadmium (7082-4972 ppm), Mn (4578-140 ppm), and Hg (453-107 ppm) are much concentrated than Pb (9.5-1.1 ppm), Sb (3.7-0.31 ppm), Tl (0.70-0.045 ppm), and Bi (0.60-0.0055 ppm).

  trace element composition of chalcop rite was investigated for the Mar a Teresa and Cerro de Maim n deposits as chalcop rite is a trace phase in the Palma and Perubar deposits. Trace elements such as Zn, Ag, Sn, Cd, Se, In, Ga, and Ge are present in solid solution as opposed to the likel occurrence of Mo, Au, Tl, Sb, Pb, and Bi in microinclusions. Deleterious elements show low contents ppm, Sn = 53-1.3 ppm, Cd = 12-6.0 ppm, Tl < 11 ppm, Bi < 10 ppm, Ni < 2.5 ppm, As < 2.0 ppm, Hg < 3.8 ppm) relative to reference maximum contents before charge is incurred sensuFontain (2013). The contents of Ag (136-23 ppm, up to 296 ppm) and Au (< 0.40 ppm) are also relatively low. In analyzed chalcopyrite grains, the contents of the potential high-tech by-products In (28-8.4 ppm, up to 49 ppm) and Ga (8.3-2.9 ppm, up to 24 ppm) are lower, and the contents of Ge (5.9-0.70 ppm, up to 80 ppm), higher, than in sphalerite from the respective deposits. General positive correlation trends between Zn, Cd, In, Ge, and Ga in chalcopyrite suggest varied coupled substitution mechanisms of Fe (+2 and +4) and Cu (+1 and +3) with fluctuating valences due to covalent bonding in this mineral.A comprehensive sampling across the Sof a-D massive sulfide bod in the Mar a Teresa deposit revealed significant mineral and trace-element onation. Mineral ones in Sof a-D include a core of dominant barren pyrite sheathed with facies of chalcopyrite (Cu zone) that grades outwards to sphalerite ± fahlore ± galena ± chalcopyrite (Zn zone) and galena + sphalerite ± fahlore ± barite (Pb Zn Ag zone) carapaces. Strong replacement of early sphalerite by chalcopyrite and metalliferous zonation strongly suggest one refining. The contents of some trace elements in sphalerite and to a lesser extent in chalcop rite displa s stematic vertical distribution patterns. In sphalerite, these include, bottom to top of the sulfide body, depletion in In, Cu, Mn, and Se and enrichment in Ge. This distribution agrees with the expected decrease of the crystallization temperature and/or volatile magmatic influx from the feeders of the massive mineralization. In chalcopyrite, the distributions of trace elements and Sc/Zn ratios are rather uneven except for constant enrichment in Bi (probably present as microinclusions) and Se towards the basal portion of the sulfide body. Unlike sphalerite, the trace element composition of chalcopyrite is strongly dependent on the co-crystallizing phases over physicochemical conditions. Cocrystallization and/or reequilibration of chalcopyrite with galena at shallower levels may therefore account for progressive depletion of Se in chalcopyrite.The Sofía-D massive sulfide mineralization shows strong textural and mineralogical evidence of recrystallization during thermal metamorphism caused by nearby granodiorite intrusions. The impact of the thermal metamorphism in the absolute trace elements contents in sphalerite and chalcopyrite is unknown. However, the preservation of expected original trace element distribution patterns would suggest a closed metamorphic system and that element interdiffusion was local, probably attaining only contiguous sulfide grains. Accordingly, we propose that the distribution patterns described in this article for lattice-bound trace elements in sphalerite and chalcopyrite may be useful during exploration in order to trace the polarity of massive sulfide bodies in metamorphosed and tectonized terranes.

Fig. 1 .

 1 Fig. 1. Geologic map of the Peruvian Coastal Batholith and Mesozoic Western Peruvian Trough (WPT) with related volcano-sedimentary basins hosting massive sulfide deposits. Modified from Polliand et al. (2005). Distribution of the Cretaceous Peruvian Costal Batholith and strata after the digital version of the geological map of Peru (INGEMMET, 2000).

Fig. 2 .

 2 Fig. 2. Representative schematic cross-section across the Sofía D massive sulfide body in the María Teresa VMS deposit, Peru (redrawn from geological documents of the María Teresa Mine geological department as of December 2020).

Fig. 3 .

 3 Fig. 3. (A) Geographic location of the Early Cretaceous boninite and island arc tholeiite volcanic series and ophiolitic peridotites along the Greater Antilles. (B) Geological map of the Maimón Formation and surrounding Early Cretaceous arc-related volcanic units (modified from[START_REF] Martín | Mapa geológico de la hoja 6172-I (Hatillo) a escala[END_REF].

Fig. 4 .Fig. 5 .Fig. 6 .

 456 Fig. 4. Drill core photographs of sulfide mineralization from the Sofía-D massive sulfide body in the María Teresa VMS deposit. (A-C) Semi-massive sulfide ore dominated by medium-grained pale-brown sphalerite grains partially replaced by an assemblage of pyrite and chalcopyrite. (D) Massive sulfide ore composed of coarse-grained red-brownish sphalerite grains cut by irregular veinlets of chalcopyrite and pyrite. (E) Dark red, mediumsized sphalerite partially replaced by an assemblage of pyrite and chalcopyrite and the whole assemblage cut by thin, irregular chalcopyrite veinlets. (F) Coarse-grained pyrrhotite and chalcopyrite in a sample picked up close to a contact with a porphyritic andesitic dyke. (G) Silicified volcaniclastic rock with chalcopyrite mineralization along clast contacts. (F) Irregular veinlets of chalcopyrite in a silicified intrusive rock. Key: cpy = chalcopyrite; po = pyrrhotite; py = pyrite; qz = quartz; sl = sphalerite.

Fig. 7 .

 7 Fig. 7. Boxplots of log-transformed element contents (A-I) and crystallization temperature (J) according to the GGIMFis geothermometer of Frenzel et al. (2016) for sphalerite at different depths along the drill core 34-18-S in the mine section 300 across the Sofía-D massive sulfide body, María Teresa deposit (LA-ICP-MS data). Box-and-whisker plots provide IQR (box), 1.5 IQR (whiskers), median (line), and outliers (circles).

Fig. 8 .

 8 Fig. 8. Boxplots of log-transformed element contents in chalcopyrite at different depths along the drill core 34-18-S in the mine section 300 across the Sofía-D massive sulfide body, Calera sector, María Teresa deposit (LA-ICP-MS data). Box-and-whisker plots provide IQR (box), 1.5 IQR (whiskers), median (line), and outliers (circles).

Fig. 9 .

 9 Fig. 9. Binary plots showing inter-element correlations in sphalerite: (A) Fe vs. Zn, (B) Ag vs. Pb, (C) Ag vs. Sb, and (D) Sb+Sn vs. Ag+Pb. Dashed lines represent 1:1 molar correlation. Additionally, contents are presented in box-and-whisker plots, which provide IQR (box), 1.5 IQR (whiskers), median (line) and outliers (circles). The composition of sphalerite from other VMS deposits worldwide are shown for comparison (data from

Fig. 10 .

 10 Fig. 10. Binary plots showing inter-element correlations in sphalerite: (A) In vs. Cu, (B) Ga vs. Cu, and (C) Sn+In+Ge+Ga vs. Cu+Ag. Dashed lines represent 1:1 molar correlation. Additionally, contents are presented in box-and-whisker plots, which provide IQR (box), 1.5 IQR (whiskers), median (line) and outliers (circles). The composition of sphalerite from other VMS deposits worldwide are shown for comparison (data from

Fig. 11 .

 11 Fig. 11. Binary plots showing inter-element correlations in chalcopyrite: (A) Bi vs. Cu, (B) In vs. Cu, (C) Ga vs. Cu, and (D) Sn+In+Ge+Ga vs. Cu+Ag. Dashed lines represent 1:1molar correlation. Additionally, contents are presented in box-and-whisker plots, which

Fig. S2 .

 S2 Fig. S2. Photomicrographs (reflected light) of textural features in samples used for this study from the Palma deposit. A) Aggregates of spheroidal and subhedral p rite grains cemented b sphalerite and galena. B) Mass of sphalerite and minor galena along with relictic p rrhotite. C) Sphalerite replacement of p rrhotite; sphalerite also lines voids in cariated p rite. D) P rite partl showing "atoll-like texture" in massive sphalerite. E) Pyrrhotite aggregates replaced by massive sphalerite and galena. F) Subhedral pyrite in massive sphalerite with pyrrhotite relicts. Fine disseminations of chalcopyrite in sphalerite.Abbreviations: cp : chalcop rite; gn: galena; p : p rite; po: p rrhotite; l: sphalerite.

Fig. S3 .

 S3 Fig. S3. Representative downhole LA-ICP-MS spectra for selected elements in sphalerite (A-D) and chalcopyrite (E-F).

  Figure 3 C c acc /d ad;F ;F 3_GEO RD. d

  Figure 6 C c e e acce /d ad;F e;F e 6_Pa a e e c e MT. df

  Fig reS2

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  Cu 6 (Cu 4 Fe 2 )As 4 S 13 Sofía-D, Calera sector, María Teresa VMS deposit

	Arsenopyrite FeAsS
	Galena PbS
	Boulangerite Pb 5 Sb 4 S 11 Bournotite PbCuSbS 3 Sphalerite ZnS Polybasite [(Ag,Cu) 6 (Sb,As) 2 S 7 ][Ag 9 CuS 4 ]	Zone re ning
	Chalcopyrite CuFeS 2
	Cubanite CuFe 2 S 3
	Auriferous Ag (Ag,Au)
	Pyrrhotite Fe 1-X S
	Magnetite Fe 2+ Fe 3+	2 O 4

  In (ppm) Sn (ppm) Sb (ppm)* Au (ppm)* Hg (ppm) Tl (ppm)* Pb (ppm)*

	Ta Ta	1 2						C c he e acce /d C ic he e acce /d	ad;Tab e;Tab e 1_S ge che . ad;Tab e;Tab e 2_C ge che .
				Cecilia Sur
		B.D.L.		(n = 22) 33 0.82	0.19 0.43	5.4 4.0			4.4 117	0.20 1.0	14	17
		Deposit Zn (ppm) 569500 605057 7381 Cd (ppm) 6422 518 Bi (ppm)* B.D.L. B.D.L. B.D.L. Deposit Cu (ppm) 340000 Bi (ppm)* Ga Cd (ppm) 3.5 0.0092	Ge 11 23	Sector / Body / Section All samples Ga (ppm) Ge (ppm) 1.4 B.D.L. 25 0.16 7 0.03 In (ppm) Sn (ppm)* Sb (ppm) Hg (ppm) Tl (ppm)* Mn (ppm) Fe (ppm) Min. 107 9772 As (ppm) Se (ppm) Mo (ppm) Ag (ppm) Cu (ppm) 3.8 4.6 B.D.L. B.D.L. 2.2 4.7 1.7 0.085 6.8 0.3 1.3 0.031 2.2 Pb (ppm)* 0.44 0.14 B.D.L. 98 B.D.L. 0.038 0.10 0.31 0.6 97 0.10 2.5 0.39 0.07 1.1 16 0.23 4.1 Sector/Body/Section Fe (ppm) Co (ppm) Ni (ppm) Min. 264304 B.D.L. B.D.L. Zn (ppm) Ga (ppm) Ge (ppm) As (ppm) Se (ppm) Mo (ppm)* Ag (ppm) 152 0.070 0.18 0.18 10 B.D.L. 3.2 As Se Mo Ag Cd In Sn 4.3 1.4 B.D.L. B.D.L. 0.019 1.4 n.a. 1.4 149 21 5088 0.060 0.24
		Max. 4998 GM 1353 SD 1236 IQR 2343-326 Min. 3139 9.3 32 6.0 6.4 0.8 9.3 4.8-4.6 3.2-1.1 4.0 3.2 4.7 4.2 48 788 4.3 392 7.2 135 0.75-0.0060 0.35-0.26 1.9-0.23 (n = 141) Bubulina / Bubulina 1180 Graciela (n = 10) 94 2.3 25 0.51 19 0.56 614400-600000 31-20 663300 623168 22726 0.17-0.14 572900 17 B.D.L. 575100 22 0.20 415 20 6605** 60 1.2 89 2.8 6797-5833 108-79 4799 1.9 0.17 B.D.L. 37 5135 2.1 0.23 0.59 43 3.5 0.44 0.77 B.D.L. B.D.L. B.D.L. Max. 373972 GM 331188 SD 24272 352700 647 24 80 1.9 15 49 201 31 0.40 3.8 5.5 75 2.7 n.a. 0.82 8.0 1.4 4169 63534 29317 13930 40675-17122 98-36 740 96 106 13000 79 1.6 66 0.16 11 0.19 10 0.098-0.071 7.8-5.7 0.39 1.7 0.55 2.8 19 44 1.0 6.2 2.1 7.2 0.20-0.047 5.8-1.2 0.045 0.18 0.17 3.2 0.087 2.2 0.075 1.5 0.010 0.4 59 0.044 295 11 82 0.040 0.050 All samples 346217 277 4.0 1.6 0.43 25 0.027 82 8.8 20 43 6.8 0.069 1.1 0.8 7.8 1.0 8.0 n.a. 1.1 40 3.7 4734 0.049 0.080 (n = 40) 3871 133 6.4 19.4 0.41 13 0.008 67 3.3 12 40 7.3 0.091 1.1 3.0 16.4 1.6 7.2 n.a. 0.18 50 6.7 337 0.014 0.072 Perubar 641300-608100 32-11 0.65-0.17 6.5-5.5 5.3-1.6 0.20-0.047 12-4.2 574430 21 0.18 4.3 3.7 0.48 2.0 7373-5290 68-4.4 0.61-0.25 5.2-0.52 448-326 1.2-0.060 8.7-1.4 4983 2.0 0.20 0.13 40 0.076 0.56 0.60-0.0055 B.D.L. IQR 348538-319792 0.079-0.070 1.9-1.2 348300-343900 425-194 9.2-2.6 4.3-0.66 0.74-0.29 31-19 0.034-0.021 150-71 12-6.2 32-12 77-33 12-3.2 0.12-0.039 1.9-0.69 2.4-0.28 12-4.3 2.5-0.54 171-79 12-5.8 n.a. 1.2-1.0 71-20 5.3-2.0 5044-4562 0.055-0.045 0.080-0.055 (Peru) 630300 17 B.D.L. 4.7 4.3 0.25 3.2 699 2 0.01 0.2 0.3 0.04 0.3 21 0.30 0.048 664 B.D.L. 0.21 89 0.0 0.02 0.20 2 0.043 0.93 B.D.L. B.D.L. Min. 264304 B.D.L. B.D.L. 342000 152 0.070 0.18 0.18 10 B.D.L. 3.2 3.5 11 4.3 1.4 B.D.L. B.D.L. 0.019 1.4 0.0092 14 1550 4.1 31 2785 4955 14 31
		Max. 4998 GM 4474 SD 550 5.8 5.3 0.3 4.3-4.2 4.7 6.1 1.1 0.28 0.37 0.21-0.19 0.27-0.053 41-39 0.16 5.3 0.16 4.8 -0.4 0.19-0.18 4.0-3.5 B.D.L. 2.5 0.49 3.9 3.2 788 1.0 724 1.0 35 0.19 0.38 15 1.4 3.0 17 Max. 373972 GM 331249 SD 25625 24 80 1.9 31 0.40 3.8 1.3 0.15 6.8 2720 18702 16628 2135 0.73 0.37 0.15 0.49-0.46 0.12 0.17 0.0081 0.0067 0.0010 0.10-0.055 0.0060 0.49 0.087 2.2 174 126 26 5.2 4.2 0.7 2.1-1.9 3.6 7.4 4.3 1.2 1.7 1.2-0.22 0.63 1.3 0.075 1.4 0.010 0.4 45 0.044 295 11 82 0.10 2.6 Calera / Sofía D / 300 (n = 9) 94 51 23 575100-574200 22-21 648500 640091 6640 557900 4.5 567000 8.1 99 59 118 36 5039-4952 2.0-2.0 3977 6.7 4388 7.1 B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. B.D.L. María 352700 529 15 49 201 5.5 19 0.47 1 Teresa 347222 263 3.5 1.2 0.45 22 0.027 89 9.2 18 42 6.6 0.077 1.0 0.8 8.8 1.0 86 1.2 27 2.1 0.63 102 3796 0.29 9.1 (n = 25) (Peru) 3155 124 6.8 20.9 0.43 8 0.008 68 3.2 11 43 7.4 0.095 0.9 3.2 17.2 1.6 3.7 435 1.3 8.7 872 679 3.9 11
		IQR 4747-4492 5.4-5.1 5.0-4.6 5.2 3.1 1.7-0.35 0.54-0.15 737-704 0.16-0.16 0.25 0.35 0.91 16 IQR 348538-319792 0.079-0.070 1.8-1.2 18088-15614 138-118 0.36-0.31 4.6-3.8 0.14 4.6 0.0076-0.0061 4.1-0.62 0.05 0.83 349700-345000 425-192 8.1-2.6 643900-633600 68-43 562010 6.5 4964-4804 94-25 4208 6.9 B.D.L. B.D.L. 2.2-0.64 0.80-0.29 30-16 0.035-0.021 166-76 12-8.2 23-12 78-30 10-3.2 0.13-0.041 1.5-0.69 2.4-0.28 14-6.0 2.6-0.86 123-61 1.4-0.89 196-3.9 3.3-1.5 0.77-0.29 575-15 4394-3294 0.45-0.10 19.8-5.2
		569500 4813 185 B.D.L. B.D.L. 340000 4.1 0.45 2.8	34 1.2	Calera / Sofía-D, all 1.4 B.D.L. 1.5 0.26 0.44 0.14 0.2 0.57 276 8.9 43 3.6 n.a. 1.9	Min. 107 4.6 0.6 B.D.L. 1.19 Min. 312109 7.3 0.25 B.D.L. 0.6 98 1 0.016 0.57 49 9772 B.D.L. 0.03 B.D.L. 0.23 B.D.L. 0.62 B.D.L. 3.8 2.2 1.8 B.D.L. 0.038 0.31 44 1.5 n.a. 13 3943 0.32	0.25
		Max. 2857 GM 716 SD 939 9.3 6.0 0.8 5.4-5.0 4.4 4.9 48 1.7 7.3 0.56-0.20 1.4-0.59 2.3 0.33 0.56 0.40-0.22 B.D.L. 0.22 20 0.48 2.86 0.19 0.14 0.36 5.4 Max. 350244 GM 330803 SD 15609 11 12 0.36 32 3.1 9.6 3.3-2.9 6.5 10 677 349 107 17-16 17 20 17 0.075 3.7 1.9 n.a. 4.6 3661 63534 26558 13984 1.6 0.09 0.18 0.16-0.12 0.33 0.45 19 0.28 2.18 0.18-0.031 B.D.L. 0.12 B.D.L. 1.9 740 61 109 66 7.9 10.6 5.2-3.6 2.5 10 44 3.4 7.3 1.0-0.64 0.22 2.7 -1.9 -0.1 59 0.033 68 3.4 7.9 0.26 0.080 Calera / Sofía D / 500 samples (n = 132) 70 17 17 565725-557900 7.4-6.4 663300 621589 22982 549400 3.4 552400 4.8 415 19 91 4341-4110 7.0-6.9 3996 2.1 4436 2.4 3.46 0.04 0.77 B.D.L. B.D.L. 0.0037 340000 647 9.6 44 53 2.5 1.9 0.82 n.a. 340000 374 10 9.4 0.30 53 0.025 52 6.6 37 49 7.8 0.036 1.9 1.7 3.6 1.0 2.2 1.1 n.a. 1.9 n.a. 6.0 3811 0.29 0.13 (n = 4) -170 1 2.4 0.05 4 0.007 10 2.4 5 4 7.2 0.029 1.5 1.1 3.2 1.0 0.38 0.15 n.a. -n.a. 3.5 126 0.026 0.077
		IQR 1771-303 6.5-5.5 5.5-1.5 4.6 8.6 0.58-0.24 5.5-0.65 0.66-0.17 0.17 438-318 0.25 0.47 18 IQR 336816-325247 -40842-17173 87-36 0.17-0.045 13-4.2 0.38 4.4 1.3-0.084 8.8-1.6 0.011 0.52 1.9-1.8 340000-340000 425-303 10-9.1 639625-605100 31-11 551092 4.2 7411-5446 54-4.3 4235 2.3 0.60-0.0055 0.0033 11-7.8 0.33-0.28 54-50 0.028-0.022 55-48 8.4-5.4 38-34 52-47 16-3.8 0.065-0.020 3.5-1.5 2.5-1.5 7.0-1.9 1.8-0.52 2.4-1.9 1.2-1.1 n.a. 1.9-1.9 n.a. 6.1-4.6 3933-3718 0.31-0.27 0.21-0.090
		Min. 107 Max. 2857 GM 828 SD 967 IQR 2343-251 5.2 B.D.L. 9.3 32 6.1 3.3 0.7 10.6 6.4-5.7 5.6-1.5 0.2 1.1 4.8-4.6 9.3-8.3 3.6 B.D.L. 6.3 1.6 4.9 0.94 B.D.L. 98 48 485 2.0 345 7.7 97 0.48-0.22 5.9-0.79 Calera / Sofía-D / 300 (n = 105) All samples (n = 37) 3.1 B.D.L. 38 2.3 15 0.37 10 0.60 639600-602500 27-10 María Teresa (Peru) 569500 663300 621999 24203 0.79-0.17 1010 0.5 0.03 551600-550625 4.6-4.0 0.20-0.15 543300 0.61 B.D.L. 625100 3.1 9.3 591619 1.9 0.6 3.9 0.14 415 16 33 0.37 967 98 2.19 7239-5290 78-12 438-315 104 0.1 0.04 1.40 1 4291-4185 2.3-2.2 0.27-0.22 0.75-0.20 19-18 4335 0.0059 0.15 B.D.L. 213 7951 1.6 0.90 28 1215 5703 0.046 0.30 2.2 603 B.D.L. 3.5 0.053 0.801 0.72-0.0057 0.0005 0.0035-0.0031 B.D.L. 0.015 0.004 Min. 270450 Max. 316435 GM 296657 SD 14668 IQR 307234-285613 2.0-1.5 9772 63534 25631 14897 42100-15748 90-36 20 740 66 120 B.D.L. 2.2 1.6 66 0.11 7.5 0.19 10.5 0.20-0.050 13-3.9 0.04 2.1 0.42-0.35 4.1-3.9 0.13 1.7 0.69 32 0.44 8.5 0.0072 0.038 19 33 0.35 3.9 2.39 6.5 1.7-0.13 9.0-2.0 0.034 0.73 0.028-0.0044 1.0-0.26 B.D.L. 0.17 6.2 140 0.2 14 1.2 B.D.L. 3.1 2.5 1.8 1.7 0.6 0.4 1.9-1.5 346300 B.D.L. 3.1 4.8 0.36 60 5.4 8.3 B.D.L. 6.7 1.2 0.05 0.015 B.D.L. 0.026 5.1 1.5 9.6 13 n.a. 36 0.68 34 3619 28 0.81 Cerro de Maimón (Dominican 346300 71 3.9 6.6 2.0 94 250 33 0.59 8.7 1.8 0.34 0.13 0.27 0.42 39 10 0.61 1.8 n.a. 29 0.11 7.4 2968 25 0.090 Cerro de Maimón 346300 71 3.4 5.6 0.86 81 40 18 0.45 7.7 1.5 0.16 0.043 0.17 0.078 12 3.8 1.5 2.7 n.a. 33 0.27 12 3246 26 0.20 (n = 11) --0.2 0.6 0.54 11 69 7 0.17 0.6 0.2 0.10 0.034 0.06 0.123 12 3.4 3.1 3.7 n.a. 1.8 0.40 8.8 191 1.1 0.26 Republic) 346300-346300 -3.6-3.3 6.1-5.3 1.3-0.56 89-79 83-23 23-15 0.53-0.41 8.1-7.3 1.6-1.4 0.25-0.10 0.071-0.027 0.21-0.14 0.15-0.042 21-7.1 8.0-2.2 1.8-0.87 2.6-1.9 n.a. 34-33 0.54-0.25 14-8.7 3304-3135 27-26 0.29-0.13
	591600 31430 1212 B.D.L. 0.006 SD: standard deviation 8.6 1.4	Calera / Sofía D / 340 1.4 B.D.L. 0.6 2.6 0.44 0.18 0.421 0.16 n.a. 109	Min. 113 6.7 0.7 0.10 6.2 0.17 5.5 B.D.L. 0.25 213 316	18062 B.D.L. 0.15 B.D.L. 1.4 3488	3.8 4.1 8.8 42	0.28 42	1.3
	Max. 1662 7.1 5.3-4.3 1.1 0.22-0.0091 0.41-0.20 7.1-0.78 (n = 10) 38 0.21 619200-557400 2.4-1.9 642900 3.5-0.16 42 1.8 7109-4782 0.0051 0.0066-0.0025 roinclusions 4.1 0.86 n.a. 89 0.17 2.4 7.1 1.1-0.8 443 667-593 1973 42132 0.13 0.58-0.41 0.32 1.4-0.020	76 9.2 17-3.8 2.5 71-3.9 27	0.27
		614743 557400 4335 0.0046 B.D.L. 5.5	1.0	Old mine 8 0.61 5 0.0059 n.a.	0.16 B.D.L. 0.46 0.15 94	GM 468 6.9 3.6 0.40 B.D.L. 0.17 3.7 3.1 B.D.L. 300 213	31839 0.06 0.13 0.05 B.D.L. 2170	19 6.9 1.7 29	0.83 0.17	0.56
		22717 625100 656 7293 0.0006 0.015 1.4	(n = 28) 19 3.1 22 1.6 0.16 n.a.	0.04 9.3 0.45 0.63 6.0	SD 0.1 6.3 0.39 16 -	799 1.0 2.8 1.6 105 667	9365 0.05 0.58 0.12 6.2 455	35 1.8 32 4.4	0.74 140	0.38
		Palma (Peru) 634275-594450 38-1.5 605878 1.8 6899-5632 42-0.56 5227 0.0 0.0050-0.0044 0.005 6.0-4.7 1.1-0.92 n.a.	IQR 1646-139 7.0-6.9 6.6-1.3 4.8 1.0 0.58-0.29 0.87-0.24 409-219 0.19-0.13 0.9 0.27 2 487 96-90 0.17-0.17 4.5-3.1 2117-2031 41573-27114 70-5.3 0.11-0.027 8.6-5.7 0.39 8 0.17-0.019 1.5-0.48 0.3 19 30-28 0.97-0.38
		608000 22214 848 B.D.L. 0.007 n.a.	n.a.	Calera / Sofía D / 500 22 0.12 0.7 2.7 1.1 0.34 0.52 0.14 7261 62	Min. 320 4.9 0.84 0.31 4.1 222 450 1.3 0.29 329 166	15296 0.033 0.12 0.085 1.5 8957	40 11 10 n.a.	3.9 44	512
		Max. 584 5.6 5.6-4.0 24 0.032-0.0072 0.36-0.18 5.8-0.47 (n = 5) 59 0.95 620375-603350 2.4-1.8 645800 4.6-0.18 1.8 2.2 5382-4742 0.0061 0.0089-0.0025 n.a. n.a. 0.19 0.13 0.030 0.80 3.7 1.2-0.8 677 621-504 1051 38233 0.61 0.47-0.39 0.71 1.7-0.034	82 46 18-3.6 44 77-4.5 n.a.	0.43
		637688 543300 7109 0.0061 B.D.L. n.a.	n.a.	Sta Lidia 28 2.0 1.6 0.13 345	0.37 B.D.L. 0.95 0.26 7.1	GM 502 5.3 4.7 3.3 1.1 5.0 51 2.1 B.D.L. 574 1147	19140 0.07 0.64 0.23 0.0056 3234	53 24 3.7 n.a.	10 1.1	14
		14717 555300 166 7951 -0.0037 n.a.	n.a.	(n = 9) 14 2.9 0.2 0.28 1874	0.31 0.23 0.71 0.90 12	SD 0.2 5.3 9.6 28 45	97	0.9 1.1 130 1215 98	8832 0.23 0.69 0.24 0.21 1936	15 14 23 n.a.	15 16	81
		IQR 557-520 5.4-5.3 2.4-1.7 5.1 0.86 1.6-0.64 13-1.4 0.64-0.29 0.16 654-620 0.40 6.1 1169 1693-275 13-5.0 18-0.99 138-40 3430-2636 17392-16548 55-47 645150-641800 25-24 0.065-0.038 38-18 549369 2.3 0.66 9.3 9152-9054 1.7-1.6 0.44-0.12 16-6.0 7481 0.21 0.034 5.0 0.0061-0.0061 0.0037 n.a. n.a. n.a.	44-4.4
		608000 4919 251 B.D.L. -	15	Calera / Sofía D / 540 58 B.D.L. 0.2 0.04 1.0 0.61 0.06 0.19 36 4.0	Min. 214 4.6 0.2 0.02 8.8 n.a. 10 2.1 0.12 325 21	35835 0.037 0.02 0.014 0.070 9600	82 5.7 6.7 566	0.10 5.1	38
		(n = 12) 70 552500-543300 2.4-2.2 619700 1.5 7647-7315 0.27-0.17 0.011 0.0037-0.0037 2.3 2.1 0.33	Max. 357 5.4 5.3-4.9 11 0.42-0.33 15-3.7 1.2 0.19-0.14 20 0.62 n.a. 4.8 3.7 0.9-0.8 356 1177-1156 0.11-0.018 38973 0.67 0.67-0.64 1.2 8306 66 137 27 16-5.6 31 10-3.0	2.2
		GM 322 SD 36 IQR 339-326 min 667 max 7639 5.0 2.8 3.6 17 0.9 338 0.026 21 n.a. 6.7 6.1 10 4.4-3.9 61-57 5.4 117 0.50-0.23 0.26-0.052 26-22 Cerro de Maimón All samples (n = 50) 64 0.22 70 0.23 1.2 3.1 5.9 0.14 2.2 1.6 33 0.49 650000-650000 95-78 614685 650000 3413 0.0069 0.054 15 3.8 Cerro de 617700 1.2-0.68 7.1 1.4 3829-3574 10-9.5 0.0037 1.1-0.33 Republic) 549400 3.4 B.D.L. 4.0 B.D.L. 5894 9.0 1.4 1.6 17 0.0056 0.17 B.D.L. 15 146 1.3 0.60 0.77 2.9 B.D.L. 1.0 (Dominican 616125-613700 68-63 0.23-0.16 5.2-4.9 3.0-2.6 652622 85.2 0.9 4.4 49 8951-8784 1.2-1.1 8.4-1.1 3.1-0.28 344-331 8736 37824 1036 38681-37310 89-84 91 16 30747 16 73876 789 0.06 8.9 B.D.L. 2.6 0.14 1.7 0.036 1.9 184 0.55 14 0.30-0.090 4.2-3.1 1.0 17 0.23-0.061 17-6.6 0.046 1.7 0.52 5.3 B.D.L. 0.038 0.38 8.2 0.055-0.042 11-6.5 0.20 4.4 0.38-0.052 4.7-0.45 5.6 3684 9.5 0.37 0.15 23.8 0.15 9.9 0.0084-0.0053 0.5 Maimón (n = 17) 2950 4 0.33 0.3 0.4 0.18 6.2 665000 96 6.2 10 67 1.7 21 158 0.2 5.6 4.0 11 0.45 8.6 3905 11 2.5 3.3 30 1.51 30 0.0035 3.5 24 2.5 9.7 1.1 n.a. 1.3 240 89 6
	579909.2969 D: standard deviation 0.0033	13 1.0	0.17 0.27	GM 2421 4.6 0.45	3.5 44	51935 0.19 0.05	35 4.6	1.1
	24068.28288 ccur as sub-microinclusions 11 1.8 0.0005	0.08 0.17	SD 0.4 1.15	2738	3.0 39	15233 0.17 0.18	108 2.7	3.3
	600000-551800 30-4.7 verevaluated by 48-57% 6664.9-4296.6 2.3-0.78 0.0035-0.0031	IQR 5964-907 4.8-4.4 8.2-2.5 0.31-0.22 1.2-0.18 0.19-0.15 107-18	67570-39965 41-25 0.42-0.089 7.1-3.6 0.13-0.025 2.9-0.39
		599800 B.D.L.		Cecilia Sur 11 0.0056	B.D.L. 0.20	Min. 667 4.3 B.D.L.	B.D.L. 71	30747 0.046 0.013	20 4.3	0.038
				(n = 22)

B.D.L.: Below detection limit; IQR: interquartile range; GM: geometric mean; SD: standard deviation *Ragged ablation spectra indicate that these elements may occur as sub-microinclusions

Acknowledgments

This study was economically supported by the Peruvian CONCYTEC-FONDECYT-World Bank project 107-2018-FONDECYT-BM-IADT-AV, the Spanish projects CGL2015 65824 and PID2019-105625RB-C21, and a Huiracocha Ph. D granted by the PUCP to D.B. Minera Colquisiri provided field and logistical support, access to the mine area, and the documents to prepare Fig. 2; its staff is most gratefully acknowledged, particularly Juan José Herrera, Edgar Pichardo, and Óscar Chirinos. We also thank Perilya-CORMIDOM for providing specimens from the Cerro de Maimón deposits. The analyzed material from Perubar and Palma was sampled (1998)(1999)(2000) by Marc Polliand in the frame of his PhD thesis at the University of Geneva. The senior author acknowledges C.E.

Nelson for insightful debate on the origin and classification of VMS deposits hosted in

Cretaceous arc-related volcanic units in Cuba and the Dominican Republic. We appreciate the technical support by Xavier Llovet (CCiT-UB) during the acquisition of EPMA data, and by Peter Tollan (ETHZ) during the acquisition of LA-ICP-MS data. We are grateful to two anonymous reviewers for their constructive comments.

provide IQR (box), 1.5 IQR (whiskers), median (line) and outliers (circles). The composition of sphalerite from other VMS deposits worldwide are shown for comparison (data from [START_REF] Carvalho | Indium and selenium distribution in the Neves-Corvo deposit, Iberian Pyrite Belt, Portugal[END_REF][START_REF] George | Trace elements in hydrothermal chalcopyrite[END_REF][START_REF] Revan | Mineralogy and trace-element geochemistry of sulfide minerals in hydrothermal chimneys from the Upper-Cretaceous VMS deposits of the eastern Pontide orogenic belt (NE Turkey)[END_REF].

Supplementary material

Table S1. List of samples and their location.

Table S2.

Representative EPMA analyses of sphalerite and chalcopyrite from the María Teresa, Palma and Perubar VMS deposits in Peru. Structural formula of sphalerite was normalized to S = 1. Structural formula of chalcopyrite was normalized to S = 2. Table S3. LA-ICP-MS trace element analyses on sulfides and reference materials.