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Glaucony occurrences have been reported both from exposed transgressive and overlying highstand system tracts. However, its occurrences within highstand deposits are often invoked as the result of underlying condensed section reworking. Detailed textural, mineralogical and geochemical reports of glaucony grains in highstand deposits remain elusive. The northern Gulf of Cadiz shelf (SW Iberia) offers a unique opportunity to investigate late Holocene glaucony authigenesis in a well-documented time-stratigraphic context, where transgressive deposits are locally exposed on the seafloor and are laterally draped by highstand muddy deposits. In this study, glaucony grains extracted from a core retrieved from a highstand muddy depocenter off the Guadiana River were investigated by means of digital microscopy, X-ray diffraction (XRD), and electron microscopic methods (FESEM-EDX and TEM-HRTEM). To better constrain the glaucony origin (autochthonous vs. allochthonous) in highstand muddy deposits, glaucony grains from surficial samples—taken from exposed transgressive deposits—were also investigated. Glauconitization in the studied core can be largely attributed to the replacement of faecal pellets from c. ~4.2–1.0 cal. ka BP. Both XRD and TEM-HRTEM analyses indicate that glaucony consists mainly of an R1, with a minor presence of R0, smectite-rich (nontronite) glauconite-smectite mixed-layer silicate, made up of 35–75% glauconitic layers and 65–25% of interstratified smectite layers. At the mineral lattice level, minor individual 7Å layers (berthierine) were also identified by HRTEM. Shallow radial cracks at the pellet surface, along with globular and vermiform-like biomorphic to low packing density lamellar-flaky nanostructures, mineralogical properties, and K-poor content (average 0.4 atoms p.f.u.) indicate a scarcely mature glauconitization process, attesting to formation of the grains in situ (autochthonous). Glaucony grains from exposed transgressive deposits, i.e., in the tests of calcareous benthic foraminifera, do not share a genetic relationship with the grains investigated in the highstand deposits, thus supporting the autochthonous origin of glaucony within the highstand deposits. Our combined dataset provides evidence of a multiphase history for autochthonous glaucony formation in the Guadiana shelf, as its genesis is traced to both transgressive and highstand conditions. While eustatic sea-level changes favoured glaucony formation under transgressive conditions, factors such as protracted low sediment supply and the establishment of a strong nutrient-rich upwelling system in the study area promoted glaucony development during late Holocene highstand conditions., Fundacao para a Ciencia e a Tecnologia (FCT) PDCTM/P/MAR/15289/1999, Spanish Government CGL2011-30302-C02-02, MCIN/AEI FJC2021-047046-I

Clay dehydration at great depth generates fluids and overpressures in organic-rich sediments that can release isotopically light boron from mature organic matter, producing 10B-rich fluids. The B can be incorporated into the tetrahedral sites of authigenic illite during the illitization of smectite. Therefore, the crystal-chemical and geochemical characterization of illite, smectite or interlayered illite&ndash, smectite clay minerals can be an indicator of depth (temperature) and reactions with the basin fluids. The aim of this study was to determine the detailed clay mineralogy, B-content and isotopic composition in illite&ndash, smectite rich samples of mud volcanoes from the Gulf of C&aacute, diz, in order to evaluate interactions of hydrocarbon-rich fluids with clays. Molecular modeling of the illite structure was performed, using electron density functional theory (DFT) methods to examine the phenomenon of B incorporation into illite at the atomic level. We found that it is energetically preferable for B to reside in the tetrahedral sites replacing Si atoms than in the interlayer of expandable clays. The B abundances in this study are high and consistent with previous results of B data on interstitial fluids, suggesting that hydrocarbon-related fluids approaching temperatures of methane generation (150 &deg, C) are the likely source of B-rich illite in the studied samples.

We report the first results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of zoned laurite (RuS2)-erlichmanite (OS2) in mantle-hosted chromitites. These platinum-group minerals form isolated inclusions (&lt, 50 &micro, m across) within larger crystals of unaltered chromite form the Oj&eacute, n ultramafic massif (southern Spain). High-magnification electron microscopy (HMEM), high angle-annular dark field (HAADF) and precession electron diffraction (PED) data revealed that microscale normal zoning in laurite consisting of Os-poor core and Os-rich rims observed by conventional micro-analytical techniques like field emission scanning electron microscope and electron microprobe analysis (FE-SEM and EPMA) exist at the nanoscale approach in single laurite crystals. At the nanoscale, Os poor cores consist of relatively homogenous pure laurite (RuS2) lacking defects in the crystal lattice, whereas the Os-richer rim consists of homogenous laurite matrix hosting fringes (10&ndash, 20 nm thickness) of almost pure erlichmanite (OsS2). Core-to-rim microscale zoning in laurite reflects a nonequilibrium during laurite crystal growth, which hampered the intra-crystalline diffusion of Os. The origin of zoning in laurite is related to the formation of the chromitites in the Earth&rsquo, s upper mantle but fast cooling of the chromite-laurite magmatic system associated to fast exhumation of the rocks would prevent the effective dissolution of Os in the laurite even at high temperatures (~1200 &deg, C), allowing the formation/preservation of nanoscale domains of erlichmanite in laurite. Our observation highlights for the first time the importance of nanoscale studies for a better understanding of the genesis of platinum-group minerals in magmatic ore-forming systems.