Understanding mass transfer associated with fluids circulation and deformation in the Alpine orogeny is often complex due to common multistage crystallization. For example, in two emblematic and historic Pb-Ag deposits of the French Alps, Macôt-la Plagne (MP) and Peisey-Nancroix (PN), a sedimentary or orogenic origin is still debated. To discriminate between the metallogenic models of the two deposits, an integrative methodology combining field, microstructural, mineralogical, thermobarometrical, and geochronological data was here applied for establishing detailed Pressure–Temperature–Time–Deformation (P-T-t-d) mineralization conditions. Both deposits are located in Permo-Triassic quartzite of the External Briançonnais domain along the Internal Briançonnais Front (Internal Western Alps). The ore mainly occurs as veins and disseminated textures containing galena, pyrite, and variable content of tetrahedrite–tennantite and chalcopyrite. Quartz porphyroclasts and sulfide microstructures indicate a dynamic recrystallization of the quartzite during the main fluid mineralization episode. Chlorites and K-white micas (phengite) chemical analysis and thermodynamic modeling from compositional maps indicate an onset of the mineralization at 280 °C, with a main precipitation stage at 315 ± 35 °C and 6.25 ± 0.75 kbar. In situ U-Pb dating on monazite, cogenetic with sulfides, gives ages around 35 Ma for both deposits. The integrative dataset converges for a cogenetic MP-PN Alpine Pb-Ag mineralization during deformation in relation to the thrusting of the “Nappe des Gypses” and the Internal Briançonnais at the metamorphic peak.
In this study, the removal of benzotriazole (BTA), a pervasive aquatic contaminant widely used for its anti-corrosion, UV-stabilizing, and antioxidant properties, by nanomagnetite, biochar, and nanomagnetite–biochar composite is investigated. Nanomagnetite and nanomagnetite–biochar composite were synthesized under anoxic conditions and tested for BTA removal efficiency at neutral pH under both oxic and anoxic conditions at different time scales. Within the short time scale (up to 8 h), the removal of BTA by nanomagnetite–biochar composite was shown to be due to BTA deprotonation by the nanomagnetite surface. Through proton liberation, Fe²⁺ is released in accordance with the reaction Fe₃O₄ + 2H⁺ → Fe₂O₃ + Fe²⁺ + H₂O, which likely influences BTA complexation and its possible redox degradation. On the longer time scale, biochar achieved higher removal efficiency: 50% BTA removed within 48 h, due to formation of a ternary complex with surface Ca2+ ions, or 75% BTA removed after HCl biochar acid wash followed by Ca2+ surface saturation. As BTA presents significant environmental risks due to its extensive industrial applications, the present study offers critical insights into the mechanisms of BTA removal by nanomagnetite–biochar composite, and highlights the potential of such materials for water treatment applications.
Smectite interlayer water plays a key role in the mobility of elements and molecules and affects a variety of geological processes. In trioctahedral smectites, in contrast to saponite and hectorite, the layer charge of which originates from isomorphic substitutions, the stevensite layer charge originates from the presence of octahedral vacancies. Despite its common occurrence in lacustrine environments, stevensite hydration has received little attention compared to saponite and hectorite. Early reports mention a specific hydration behaviour, however, with the systematic presence of a low-angle reflection attributed to the regular interstratification of various hydration states. The present study aims to revisit this specific hydration behaviour in more depth. Within this scope, the hydration behaviour of the three smectite varieties above are compared using synthetic trioctahedral smectites of similar layer charge and various compositions of their octahedral sheets. The chemical composition of the octahedral sheet does not appear to influence significantly smectite hydration for saponite and hectorite. Compared to its saponite and hectorite equivalents, H2O content in stevensite is lower by ~2.0 mmol H2O per g of dry clay. Consistent with this lower H2O content, Zn-stevensite lacks a stable monohydrated state, with dehydrated layers prevailing from 60% to 0% relative humidity. The presence of the regular interstratification of 0W and 1W layers is responsible for the low-angle reflection commonly observed for stevensite under air-dried conditions. Finally, the stevensite identification method based on X-ray diffraction of heated and ethylene glycol-solvated samples is challenged by the possible influence of the octahedral sheet chemical composition (Zn or Mg in the present study) on hectorite swelling behaviour in synthetic Zn-smectites. The origin of this effect remains undetermined and further work is needed to propose a more general identification method.
Calcium silicate hydrate (C-S-H) is a disordered, nanocrystalline material acting as the primary binding phase in Portland cement. Thin films of water are present on the surfaces and inside the nanopores of C-S-H and related phases such as calcium-aluminum-silicate-hydrate (C-A-S-H), an Al-bearing substitute present in low-CO2 C-S-H cement. These water films control many of the chemical and mechanical properties of C-S-H, including drying shrinkage, ion transport, creep, and thermal behavior. Therefore, obtaining a fundamental understanding of their properties is essential. In this work, we have applied a combination of inelastic incoherent neutron scattering and molecular dynamics simulation methods to unravel the dynamics of water in synthetic C-(A)-S-H samples conditioned at five hydration states (from dry to fully hydrated) and with three different Ca/Si ratios (0.9, 1, and 1.3). Our results converge towards a picture where the evolution from thin layers of adsorbed water to bulk capillary water is dampened by the structure of C-(A)-S-H, in particular by the availability of Ca2+ sites which tend to keep the water in the form of structured surface layers.