The aim of this study is to analyze natural clinkers (= calcined clays by coal combustion) from a lower Cretaceous coal outcrop in Ariño (Teruel, NE Spain) in order to describe mineral and textural transformations produced during the spontaneous combustion of coal. To achieve this aim, samples were analyzed using X-ray diffraction and optical and electron microscopy. Spontaneous combustion resulted in the melting of the surrounding clays, with the generation of an Al–Si-rich vitreous phase. Subsequently, high-temperature phases crystallized from this vitreous phase. These new minerals are interesting due to their similarity with those formed during ceramic processes, used in the manufacture of stoneware and ceramic tiles, as well as in refractory ceramics, and with natural events such as metamorphic and igneous processes. The studied natural clinkers are composed of vitreous phase mullite, hematite, hercynite, cristobalite, quartz, pyroxenes, cordierite, gypsum, pyrite, and calcium oxides. A trend from hematite to hercynite composition indicates compositional variations at sample scale, which evidence d-spacing differences in hercynite and may be related to the Al and Fe content in hercynite depending on its texture. The mullite shows higher Si/Al ratio (1.21) than the theoretical composition (0.35), indicating that this mullite is more Si-rich. Three pyroxene-type compositions (diopside-type, ferrosilite-type, and a Ca–Al-rich pyroxene) were found. Both the mullite and the pyroxenes are nonstoichiometric.

The facies and clay mineral study of clay/marl-rich levels from the Torrelapaja Formation (latest Hauterivian–early Barremian, NW Iberian Range, NE Spain) allowed to establish the palaeoclimatic and palaeoenvironmental conditions under they were generated. The muddy levels and pisoids contained therein of two logs were sampled and studied by X-ray diffraction and optical and electron microscopy. A similar mineralogical upwards trend is recorded in both logs, with a decrease in calcite coupled with an increase in quartz and orthoclase content and constant proportions in goethite, hematite, diaspore, anatase, rutile, ilmenite, and clay mineral content. The lower muddy levels have higher kaolinite content than the upper levels, where illitic phases are the dominant clay minerals. Smectite and intergrowths of illitic phases and kaolinite are also detected upwards. The kaolinite and smectite textures indicate an authigenic origin, whereas the illitic phases are former phases acting as a substrate for kaolinite crystallization. Pisoids mineralogy and texture show an in-situ origin, but some are fractured, indicating reworking processes. The mineral association found in the muddy levels is characteristic of oxisols formed under warm and humid conditions. The upward decrease in kaolinite content is coeval with an increase in the illitic phases and quartz content, related to siliciclastic input, but is also coeval with the presence of authigenic smectite. This indicates a decrease in chemical weathering, not fully registered due to the siliciclastic contribution, which was possibly associated with a change to colder, drier conditions during the latest Hauterivian–early Barremian in the studied area.

The Mallorca coastal caves present large amounts of speleothems that have been studied for decades. However, the sedimentary deposits also present in these cases have not been given the same attention. This work is the first study entirely focused on these deposits, specifically the ones found in the Ases cave. These deposits are formed by clay minerals (illitic phases, kaolinite, smectite, and chlorite), calcite and quartz, and minor proportions of dolomite, albite, orthoclase, hematite, and goethite. The grain size and the electron microscopy studies suggested the presence of different sedimentation processes (bedrock degradation, creep or saltation, and suspension) and different origins (authigenic and detrital origins) for the different sediments. Based on these differences, two types of deposits were characterized: autochthonous and allochthonous deposits. The first ones are located on the floor of chambers and corridors in subaqueous zones, indicating the stability of the mixing zone (and therefore the sea level) over time. The second ones appear filling voids on the walls and the ceiling in the terrestrial zone, evidencing the filling of the cavity in the presence of water (during a wet period). These results are very important to complete the understanding of the caves and their evolution and support the relevance of these materials in paleoenvironmental studies.