The main event responsible for the deposition of tungsten at Panasqueira was closely associated with strong tourmalinization of the wall rocks. Tourmaline is coeval with a W-rich rutile (up to 8–10 wt % W), and both minerals record an early introduction of W in the system, just before the main W deposition. Uranium-Pb dating of the rutile by LA-ICP-MS yielded an age of 305.2 ± 5.7 Ma, which is 6 to 10 m.y. older than the K-Ar age of 296.3 ± 1.2 Ma obtained on muscovite, which was therefore not coeval with wolframite. Major and trace element concentration variations in tourmaline record fluid mixing between two end members, both considered to be of metamorphic derivation on the basis of rare earth element profiles. We report evidence for a fluid rich in Co, Cu, Pb, Sc, Sr, V, Cr, Nb, Ta, and Sn interpreted to be of local origin—e.g., well equilibrated with the host formations—and a fluid rich in Li, F, Fe, Mn, and W inferred to be of deep origin and related to biotite dehydration. The second fluid carried the metals (in particular Fe and Mn) that were necessary for wolframite deposition and that were not necessarily inherited from the wall rocks through fluid-rock interaction. Micrometer-scale variations in tourmaline and rutile crystal chemistry are indicative of pulsatory fluid input during tourmalinization.

Elucidation of time-space relationships between a given wolframite deposit and the associated granites, the nature of the latter, and their alterations, is a prerequisite to establishing a genetic model. In the case of the world-class Panasqueira deposit, the problem is complicated because the associated granites are concealed and until now poorly known. The study of samples from a recent drill hole and a new gallery allowed a new approach of the Panasqueira granite system. Detailed petrographic, mineralogical, and geochemical studies were conducted, involving bulk major and trace analyses, BSE and CL imaging, EPMA, and SEM-EDS analyses of minerals. The apical part of the Pansqueira pluton consisted of a layered sequence of separate granite pulses, strongly affected by polyphase alteration. The use of pertinent geochemical diagrams (major and trace elements) facilitated the discrimination of magmatic and alteration trends. The studied samples were representative of a magmatic suite of the high-phosphorus peraluminous rare-metal granite type. The less fractionated members were porphyritic protolithionite granites (G1), the more evolved member was an albite-Li-muscovite rare metal granite (G4). Granites showed three types of alteration processes. Early muscovitisation (Ms0) affected the protolithionite in G1. Intense silicification affected the upper G4 cupola. Late muscovitisation (Fe–Li–Ms1) was pervasive in all facies, more intense in the G4 cupola, where quartz replacement yielded quartz-muscovite (pseudo-greisen) and muscovite only (episyenite) rocks. These alterations were prone to yield rare metals to the coeval quartz-wolframite veins.

Abundant W-rich rutile in the tourmalinized wall-rocks from the Panasqueira W-deposit appears to be a marker of the onset of the main wolframite depositing event. Rutile displays spectacular zoning, both sector (SZ) and oscillatory (OZ). An extensive set of compositional data obtained on crystals, beforehand studied using back-scattered electron images and X-ray maps, was used to address (i) the effects of SZ on differential trapping of minor elements, and (ii) the significance of the OZ in deciphering fluid sources and fluid circulation dynamics. Particular attention was paid to Sn, W (Nb, Ta) concentrations in rutile as pathfinders of the W deposition. Concerning the sector zoning, W is more incorporated than (Nb, Ta) onto more efficient faces, whereas Sn contents are nearly not impacted. The net effect of the sector zoning is thus a progressive increase of the relative weight of Sn from pyramid to prism faces, in combination with a less significant increase in the relative weight of Nb + Ta. The oscillatory zoning concerns most minor elements: W, Nb (Ta), Fe, V, Cr and Sn. In the frequent doublets, the clear bands are in general enriched in W relatively to the dark ones, whereas the inverse is true for Nb and Ta. The doublets may be viewed as the result of the successive influx of (i) a W-rich, Nb + Ta poor fluid, abruptly replaced by (or mixed to) (ii) a Nb + Ta-rich and W-poor fluid. The Nb + Ta-rich fluid could be in turn related to a rare-metal granite layer observed atop of the Panasqueira granite.