Multicoloured tourmalines from Elba Island, commonly display dark-coloured terminations due to incorporation of Fe, and also occasionally Mn. The mechanisms which led to the availability of these elements in the late-stage residual fluids are not yet completely understood. For this purpose, we investigated a representative tourmaline crystal found naturally in two fragments within a wide miarolitic cavity in the Rosina pegmatite (San Piero in Campo, Elba Island, Italy), and characterised by late-stage dark-coloured overgrowths. Microstructural and paragenetic observations, together with compositional and spectroscopic data (electron microprobe and optical absorption spectroscopy), provide evidence which shows that the formation of the dark-coloured Mn-rich overgrowths are the result of a pocket rupture. This event caused alteration of the cavity-coating spessartine garnet by highly-reactive late-stage cavity fluids by leaching processes, with the subsequent release of Mn to the residual fluids. We argue that the two fragments were originally a single crystal, which underwent natural breakage followed by the simultaneous growth of Mn-rich dark terminations at both breakage surfaces. This conclusion supports the evidence for a pocket rupture event, responsible for both the shattering of the tourmaline crystal and the compositional variation of the cavity-fluids related to the availability of Mn, which was incorporated by the tourmaline crystals. Additionally, a comparison of the dark overgrowths formed at the analogous and the antilogous poles, provides information on tourmaline crystallisation at the two different poles. The antilogous pole is characterised by a higher affinity for Ca, F and Ti, and a selective uptake of Mn2+, even in the presence of a considerable amount of Mn3+ in the system. This uneven uptake of Mn ions resulted in the yellow–orange colouration of the antilogous overgrowth (Mn2+ dependent) rather than the purple-reddish colour of the analogous overgrowths (Mn3+ dependent).

Two tourmaline crystals with a blue growth zone at the analogous pole, respectively from the San Silvestro and the Fucili pegmatites, located in the San Piero in Campo village, Elba Island (Tyrrhenian Sea, Italy), have been described for the first time using compositional and spectroscopic data to define their crystal-chemical aspects and the causes of the colour. Compositional data obtained by electron microprobe analysis indicate that both tourmalines belong to the elbaite–fluor-elbaite series. The upper part of each crystal is characterised by an increased amount of Fe (FeO up to ~1 wt.%) and a Ti content below the detection limit. Optical absorption spectra recorded on the blue zone of both samples show absorption bands caused by spin-allowed d-d transitions in [6]-coordinated Fe2+, and no intervalence charge transfer Fe2+-Ti interactions, indicating that Fe2+ is the only chromophore. Mössbauer analysis of the blue zone of the Fucili sample confirmed the Fe2+ oxidation state, implying that the redox conditions in the crystallisation environment were relatively reducing. The presence of colour changes at the analogous termination during tourmaline crystal growth suggests a change in the composition of the crystallisation environment, probably associated with a partial opening of the system.

Geothermal systems in terrains affected by polyphase deformation have reservoirs with a 3D geometry that is always difficult to predict. In this paper we describe a fossil exhumed geothermal system exposed in eastern Elba Island that developed in a polyphase folded and faulted setting, which can help us to understand how geothermal fluids circulate in geological bodies with inherited structures. Geothermal circulation at Elba allowed the deposition of Fe-ore deposits (haematite/magnetite and pyrite) and altered rock volumes, which represent tracers of the palaeo-fluid flow. Normal and oblique-slip faults dissected a polyphase folded metasiliciclastic succession and produced a secondary permeability in the range of 5 × 10−13 to 5 × 10−16 m2. From the permeable fault zones acting as feeder conduits, geothermal fluids permeated the hydraulically connected metasiliciclastic rock bodies previously deformed by two generations of folds. Geothermal fluids followed the already defined geometry, thus giving rise to apparent folded mineralized levels. Fluid migration into the metasiliciclastic rocks was possible due to their chemical aggression, which favoured the dissolution and reprecipitation of quartz, and Fe-oxide and sulphide deposition. Renewed fluids maintained their chemical properties (pH value and temperature, mostly). This conclusion provides inputs for reconstructing geothermal conceptual models and evaluating the geothermal potentiality of exploitable areas developing in similar geological settings.