Plastic deformation and trace element mobility in sphalerite
Authors: Cugerone Alexandre , Oliot Emilien , Muñoz Manuel , Barou Fabrice , Motto-Ros Vincent , Cenki Bénédicte 
Published: March 2024

Abstract
Sphalerite (ZnS) is a sulfide found in a large variety of ore deposits and is frequently hosted in meta-morphic terranes that have undergone deformation and related recrystallization. However, the deformation mechanisms of sphalerite are still poorly understood because recrystallization evidence is barely visible under an optical microscope and may reflect complex and frequently multistage mechanisms. Furthermore, sphalerite may host up to a few thousands of parts per million of critical metals such as gallium (Ga), germanium (Ge), and indium (In). Metamorphic conditions and dynamic recrystallization may have induced local or total redistribution of these elements. Modern techniques such as electron backscattered diffraction analyses (EBSD) and laser-induced breakdown spectroscopy (LIBS) applied on sphalerite allow for the examination of grain boundaries, crystal-plastic deformation, and internal chemical diffusion, which classically reflect active deformation mechanisms. In this study, a microstructural and in situ chemical comparison between four sphalerite types (types 1, 2, 3, and 4) has been made for the first time. The four sphalerite types present different deformation imprints, although they are hosted in a similar geological setting: the Pyrenean Axial Zone and the Montagne Noire Variscan massifs (France). Based on EBSD and LIBS mapping, we describe two regional sphalerite growth stages composed of dark red crystals with polygonal shape (type 1, Bentaillou-Liat deposit) and light- to dark-brown euhedral crystals (type 3, Saint Salvy deposit). New investigation at microscale on sphalerite grains from the Saint-Salvy deposit shows late Cu-Ge-Ga enrichment not only in specific sector zonings but also along grain boundaries, growing crystal edges, and in low-angle misorientations or twin boundaries. Following a deformation event that probably occurred during the Pyrenean-Alpine orogeny, these two sphalerite mineralizations have both endured plastic deformation in a dislocation creep regime and dynamically recovered by subgrain rotation (SGR) mechanism. Two mechanisms of Cu-Ga-Ge spatial redistribution are observed and are key processes for the crystallization of Cu-Ga-Ge-rich minerals in sphalerite veins. The first mechanism involved the in situ redistribution of Cu-Ga-Ge contents from a pre-existing concentration in the sphalerite lattice (type 3, Arre deposit), creating Ge-sulfides (briartite), probably during Pyrenean-Alpine orogeny. Formation of this type of Ge-mineral may be related to solid-state diffusion processes. The second mechanism is associated with the circulation of a Cu-Ga-Ge-rich fluid in surrounding rocks. In the pre-existing polygonal sphalerite from Late-Variscan veins (type 2, Pale Bidau deposit), millimeter-size bands of small (&lt;50 µm), recrystallized sphalerite grains are locally observed. Those domains contain inclusions of Cu (chalcopyrite) and Ga and Ge minerals (brunogeierite, carboirite). Fluid-induced diffusion in the polygonal sphalerite aggregates may occur with superimposed dynamic recrystallization, such as the Late-Variscan veins (type 2, Pale Bidau-type). During post-Variscan time, this fluid enriched in Cu-Ga-Ge largely circulated in the upper-crust of this Variscan terrane. This study highlights the key importance of coupled textural (EBSD) and in situ chemical analyses (LIBS) of diverse sphalerite types at a regional scale to indirectly unravel the origin of vein mineralization, and their related critical metal distribution.