Metamorphic degassing of carbonates in the contact aureole of the Aguablanca Cu–Ni–PGE deposit, Spain

Analysis of magmatic and sedimentary rocks of several large igneous provinces has demonstrated that the release of gas during plutonic-metamorphic processes may be linked to global climate change and mass extinctions. Aguablanca, one of the largest Cu–Ni–PGE deposits in Europe, formed during the Variscan orogeny when a mafic magma intruded limestones and shales, creating a contact aureole composed of marble, skarn and hornfels. Our petrological and geochemical investigation of the aureole provides evidence that a combination of the two processes led to the formation of the ore deposit: The assimilation of terrigenous sediments supplied S to the magma while the assimilation of carbonates changed the oxygen fugacity and decreased the solubility of sulfur in the magma. The metamorphic assemblages in the contact aureole are directly related to heterogeneity of the protolith and particularly to the original proportions of calcite and clay. We modeled carbon dioxide degassing during contact metamorphism and showed that pure limestone is relatively unproductive because of its high reaction temperature. The presence of clay, however, leads to the formation of calc-silicates and significantly enhances CO 2 degassing. Our estimations suggest that degassing of the Aguablanca contact aureole released about 74.8 Mt of CO 2 , a relatively low volume that we attribute to the composition of the host rock, mainly a pure limestone. A far larger volume of carbon dioxide was emitted by the contact metamorphism of dolostones in the contact aureole of Panzhihua (part of Emeishan large igneous province, SW China). We propose that the level of emission of carbon dioxide depends strongly on the nature of the protolith and has to be considered when predicting environmental impact during the emplacement of large igneous provinces.