X-ray absorption near edge structure (XANES) spectroscopy was used on zoned sphalerites (ZnS) from two world-class Mississippi Valley Type deposits, the Central and Eastern Tennessee Mining district, USA, in order to investigate germanium oxidation states. Due to the low germanium concentrations of these samples, it was necessary to perform the X-ray absorption spectroscopy (XAS) in fluorescence mode. The overlapping of the Zn Kβ and Ge Kα emission lines meant that a high energy-resolution was required. This was achieved using crystal analysers and allowed a bandwidth of 1.3 eV to be obtained. Experimental spectra were compared to XANES calculations and three configurations of germanium incorporation into sphalerite were identified. The first two, the most prevalent, show germanium (II) and (IV) surrounded by sulphur atoms in tetrahedral coordination, suggesting the replacement of Zn by Ge. In the third configuration, germanium (IV) is surrounded by oxygen atoms. This third configuration is unexpected for a zinc sulphide mineral and it resembles that of argutite (GeO₂).

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.

Near the Segura pluton, hyper-differentiated magmas enriched in F, P, and Li migrated through shallowly dipping fractures, which were sub-perpendicular to the schistosity of the host Neoproterozoic to Lower Cambrian metasedimentary series, to form two swarms of low-plunging aplite–pegmatite dykes. The high enrichment factors for the fluxing elements (F, P, and Li) compared with peraluminous granites are of the order of 1.5 to 5 and are a consequence of the extraction of low-viscosity magma from the crystallising melt. With magmatic differentiation, increased P and Li activity yielded the crystallisation of the primary amblygonite–montebrasite series and Fe-Mn phosphates. The high activity of sodium during the formation of the albite–topaz assemblage in pegmatites led to the replacement of the primary phosphates by lacroixite. The influx of external, post-magmatic, and Ca-Sr-rich hydrothermal fluids replaced the initial Li-Na phosphates with phosphates of the goyazite–crandallite series and was followed by apatite formation. Dyke emplacement in metasediments took place nearby the main injection site of the muscovite granite, which plausibly occurred during a late major compression event.