Origin and evolution of the calcic and magnesian skarns hosting the El Valle-Boinás copper–gold deposit, Asturias (Spain)

The El Valle-Boinás copper–gold deposit is located in the southern part of the Rio Narcea Gold Belt 65 km west of Oviedo (NW Spain), within the Cantabrian Zone (Iberian Hercynian Massif). The deposit is related to the Boinás stock, which ranges from quartz-monzonite to monzogranite and intruded (303 Ma) the carbonated Láncara Formation (early Cambrian) and the siliciclastic Oville Formation (middle-late Cambrian).A copper–gold skarn was developed along the contact between the igneous rock and the carbonated sedimentary rocks. The skarn distribution and mineralogy reflects both structural and lithologic controls. Two types of skarn exists: a calcic skarn mainly developed in the upper calcic member of the Láncara Formation, and a magnesian skarn developed in the lower dolomitic and organic-rich member. The former mainly consists of garnet, pyroxene and wollastonite. Retrograde alteration consists of K-feldspar, epidote, quartz, calcite, magnetite, ferroactinolite, titanite, apatite, chlorite and sulfides. Magnesian skarn mainly consists of diopside with interbedded forsterite zones. Pyroxene skarn is mainly altered to tremolite, with minor phlogopite and serpentine. Olivine skarn is pervasively altered to serpentine and magnetite, and is commonly accompanied by high sulfide and gold concentrations. This altered skarn results in a very dark rock, referred to as “black skarn”, which has great importance in gold reserves. Sulfide mineralization mainly consists of chalcopyrite, bornite, arsenopyrite, pyrrhotite and pyrite, while wittichenite, sphalerite, digenite, bismuthinite, native bismuth and electrum occur as accessory minerals.After extensive erosion, reactivation of the northeast-trending fracture zone provided conduits for the subsequent emplacement of porphyritic dikes (285±4 Ma) and diabasic dikes (255±5 Ma). Alteration, characterized by sericitization, silicification, carbonatization and hypogene oxidation took place, as did sulfide mineralization (pyrite, arsenopyrite, sphalerite, chalcopyrite, galena, bournonite, and Fe–Pb–Sb sulfosalts). Veins with quartz, carbonate, adularia and sulfide minerals crosscut all previous lithologies. Jasper and jasperoid breccias developed at the upper parts of the deposits.The fluid inclusion and stable isotope studies suggest a predominantly magmatic prograde-skarn fluid characterized by high-salinity (26–28 wt.% KCl and 32–36 wt.% NaCl) and high temperature, above 580°C. This fluid evolved into two immiscible fluids: a CO₂- and/or CH₄-rich, high-salinity aqueous fluid. Temperatures for the first retrograde-stage are between 350 and 425°C. A second stage is related to a more diluted aqueous fluid (3–6.2 wt.% NaCl eq.) and temperatures from 280 to 325°C. The fluid inclusion study performed on quartz from low-temperature mineralization indicates a very low salinity (0.2–6.2 wt.% NaCl eq.), low-temperature aqueous fluid (from 150 to 250°C), and trapping pressure conditions less than 0.2 kbar. In addition, the stable isotope study suggests that an influx of metamorphic waters derived from the country rocks produced these lower temperature fluids. The last control for the Au mineralization is the Alpine tectonism, which developed fault breccias (cataclasites to, locally, protomylonites) and gold remobilization from previous mineralization.