Footprints of element mobility during metasomatism linked to a late Miocene peraluminous granite intruding a carbonate host (Campiglia Marittima, Tuscany)

The Campiglia Marittima magmatic-hydrothermal system includes a peraluminous granite, its carbonatic host, and skarn. The system evolved generating a time-transgressive exchange of major and trace elements between granite, metasomatic fluids, and host rock. The process resulted in partial metasomatic replacement of the granite and severe replacement of the carbonate host rocks. The fluid activity started during a late-magmatic stage, followed by a potassic–calcic metasomatism, ending with a lower temperature acidic metasomatism. During the late-magmatic stage, B-rich residual fluids led to the formation of disseminated tourmaline–quartz orbicules. High-temperature metasomatic fluids generated a pervasive potassic–calcic metasomatism of the granite, with replacement of plagioclase, biotite, ilmenite, and apatite by K-feldspar, phlogopite–chlorite–titanite, titanite–rutile, and significant mobilization of Fe, Na, P, Ti, and minor HFSE/REE. The metasomatized granite is enriched in Mg, K, Rb, Ba, and Sr, and depleted in Fe and Na. Ca metasomatism is characterized by crystallization of a variety of calc-silicates, focusing along joints into the granite (endoskarn) and at the marble/pluton contact (exoskarn), and exchange of HFSE and LREE with hydrothermal fluids. Upon cooling, fluids became more acidic and fluorine activity increased, with widespread crystallization of fluorite from disequilibrium of former calc-silicates. At the pluton-host boundary, fluids were accumulated, and pH buffered to low values as temperature decreased, leading to the formation of a metasomatic front triggering the increasing mobilization of REE and HFSE and the late crystallization of REE–HFSE minerals.