Crystal structure refinements were performed on five Al-rich phlogopite-1M crystals (1.50 ⩽ Al3+ ⩽ 1.97 atoms per formula unit) from skarns of the Predazzo and Monzoni Hills petrographic area (north-east Italy) with the aim of characterizing geometrical variation produced by Al3+ increase. The charge imbalance was mostly compensated for by substitutions of highly charged cations in the octahedral sheet (Al3+ and/or Fe3+ for Mg2+). The refinements were carried out in the mean space group C2/m and gave agreement values (R) between 0.025 and 0.030. For some additional crystals, only chemistry and/or unit cell parameters were determined. In all samples the tetrahedra are more regular and larger than those previously reported in the literature for phlogopite crystals and the misfit between tetrahedral and octahedral sheets, produced by the increase in the tetrahedral edges, is mostly compensated for by the tetrahedral ring angle rotation α (10.2 °⩽ α ⩽ 12.5°), whereas the octahedral sheet features seem affected only by local crystal-chemical variations.

Two Ca-Zr-Ti oxides, zirconolite CaZrTi2O7 and calzirtite Ca2Zr5Ti2O16, occur as minute interstitial crystals in skarn (forsterite-spinel-calcite, with rhythmic banding) ejecta from the 1631 eruption of Vesuvius. The substitutions in zirconolite observed here mainly include Nb-for-Ti (typical for zirconolites in alkaline magmatic surroundings) and (Th,U)-for-Ca, and produce a crystal-chemical formula Ca0.9–1Th0.04–0.12U0.04–0.10ZrTi1.36–1.61Nb0.09–0.22(Fe,Mg,Al)0.29–0.47O7. The skarn, which occurs in contact with a pyroxenite of magmatic origin, displays a mineralogical zoning with Zr-, Ti-, Nb- and (U,Th)-rich oxides (e.g. Nb-perovskite and zirconolite) close to the pyroxenite (<2 mm), whereas those oxides observed further from the pyroxenite (>1 cm) are richer still in Zr but (Ti, Nb, U, Th)-poor or free (e.g. calzirtite and baddeleyite ZrO2). Textural relationships between minerals provide evidence for a metasomatic development of the skarn at the expense of the pyroxenite, through drastic leaching of Na, K, Si, Fe. The same process is responsible for the zoning in the skarn (leaching of Fe, Si, Ti, Nb, U and Th), in which Zr was less mobilized than other HFSE. This process, related to the circulation of fluids equilibrated with carbonates, is responsible for those forsterite-spinel (± calcite) skarns which can be observed as remnants in a large part of the 1631 ejecta. Such endoskarns probably formed repeatedly during at least the last millennia of Vesuvius’ history, and existed prior to the emplacement at shallow depth of the 1631 magma whose chamber walls were different from the limestone/dolostone classically assumed to host the Vesuvius magmas (Fulignati et al., 2005).

In the Artikutza area, near the contact with the southern Aya granite, skarns containing hedenbergite, grandite, epidote, quartz, calcite, actinolite, idocrase and magnetite occur and have been found to contain ilvaite layers. This is the second reported occurrence of ilvaite in Spain; spectral reflectances, colour values. Vickers hardness numbers and chemical composition are given. The monomineralic ilvaite lens intercalation developed by hydrothermal alteration of hedenbergite in a second stage of skarn formation.

Numerical models that account for fluid flow, magmatic and metamorphic fluid production, topography and thermal expansion of the fluid following emplacement of a granitic magma in the upper crust reveal controls on the distribution of magmatic fluids during the evolution of a hydrothermal system. Initially, fluid pressures are close to lithostatic in and near an intrusion, and internally generated magmatic and metamorphic fluids are expelled. Later, fluid pressures drop to hydrostatic values and meteoric fluids circulate throughout the system. High permeabilities and low rates of fluid production accelerate this transition. Fluid production in the magma and wallrocks is the dominant mechanism elevating fluid pressures to lithostatic values. For granitic intrusions, about three to five times as much magmatic fluid is produced as metamorphic fluid. Continuous fluid release from a granitic magma with a vertical dimensions of 10 km produces a dynamic permeability of up to several tens of microdarcies.

Near the surface, topography associated with a typical volcano acts to maintain a shallow meteoric flow system and drive fluids laterally. The exponential decay with depth of the influence of topography on fluid pressures results in a persistent zone of mixing at a depth of 1-2 km between these meteoric fluids and magmatic fluids despite variations in the strength of the magmatic hydrothermal system. However, in shallow systems where fluid release is episodic, dramatic changes in the region of mixing are still possible because fluid pressure is sensitive to variations in the rates of fluid production. At depth, high rates of metamorphic fluid production in the wallrocks and low permeabilities (< 1 μD) produce elevated fluid pressures, which hinder the lateral flow of magmatic fluids. Together, these patterns are consistent with the distribution and evolution of skarns and hydrothermal ore deposits around granitic magmas.