The mineralogy and physicochemical features of Saharan dust particles help to identify source areas and determine their biogeochemical, radiative, and health effects, but their characterization is challenging. Using a multianalytical approach, here we characterized with unprecedented level of detail the mineralogy and physicochemical properties of Saharan dust particles massively wet deposited ( ∼ 18 g m⁻²) following an extreme red rain event triggered by a northern African cyclone that affected the southern Iberian Peninsula during 21–23 February 2017. Abundant palygorskite and illite, and relatively high carbonate contents, well-known northern and north-western Saharan dust indicators, along with low chlorite content and significant amounts of smectites and kaolinite, whose abundance increases southwards in the western Sahara, complemented by satellite imagery and back/forward trajectories, show that the most probable dust source areas were (i) southern/central Algeria, northern Mali, and northwestern Niger, and (ii) northern Algeria, southern Tunisia, and northwestern Libya. Scanning and transmission electron microscopy analyses, including Z-contrast high angle annular dark field (HAADF) imaging and analytical electron microscopy (AEM), show that clay minerals include abundant structural Fe (55 % of the total Fe) and typically form nanogranular aggregates covered or interspersed with amorphous/poorly crystalline iron oxyhydroxide nanoparticles (ferrihydrite), which account for ∼ 18 % of the free Fe, the rest being goethite and hematite. These nanogranular aggregates tend to form rims lining large silicate and carbonate particles. Such internally mixed iron-containing phases are the main contributors to the observed absorption of solar and thermal radiation, and along with the abundant coarse/giant particles ( > 10 µm) strongly affect the dust direct radiative forcing. The lack of secondary sulfates in aggregates of unaltered calcite internally mixed with clays/iron-rich nanoparticles shows that iron-rich nanoparticles did not form via atmospheric (acid) processing but were already present in the dust source soils. Such iron-rich nanoparticles, in addition to iron-containing clay (nano)particles, are the source of the ∼ 20 % soluble (bioavailable) iron in the studied desert dust. The dust particles are a potential health hazard, specifically the abundant and potentially carcinogenic iron-containing palygorskite fibers. Ultimately, we show that different source areas are activated over large desert extensions, and large quantities of complex dust mixtures are transported thousands of kilometers and wet-deposited during such extreme events, which dwarf any other Saharan dust event affecting southwestern Europe. The past, present, and future trends, as well as impacts, of such extreme events must be taken into account when evaluating and modeling the manifold effects of the desert dust cycle.

One of the most promising strategies for the safe and permanent disposal of anthropogenic CO₂ is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO₂ capture and storage (CCS). Here, we studied the different steps of wollastonite (CaSiO₃) carbonation (silicate dissolution → carbonate precipitation) as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA), a natural enzyme that catalyzes the reversible hydration of CO_2(aq), and biomimetic metal-organic frameworks (MOFs). Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl)-specific). CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.

Mineralization of hydroxylapatite (HAp), the main inorganic phase in bone, follows nonclassical crystallization routes involving metastable precursors and is strongly influenced by organic macromolecules. However, the effect of small organic molecules such as citrate on the formation of HAp is not well constrained. Using potentiometric titration experiments and titration calorimetry, in combination with a multianalytical approach, we show that citrate stabilizes prenucleation species as well as a liquid-like calcium phosphate precursor formed before any solid phase nucleates in the system. The stabilization of a liquid-like precursor phase could facilitate infiltration into the cavities of the collagen fibrils during bone mineralization, explaining the enhancement of collagen-mediated mineralization by citrate reported in previous studies. Hence, citrate can influence bone mineralization way before any solid phase (amorphous or crystalline) is formed. We also show that HAp formation after amorphous calcium phosphate (ACP) in the absence and presence of citrate results in nanoplates of about 5–12 nm thick, elongated along the c axis. Such nanoplates are made up of HAp nanocrystallites with a preferred c axis orientation and with interspersed ACP. The nanoplatelet morphology, size, and preferred crystallographic orientation, remarkably similar to those of bone HAp nanocrystals, appear to be an intrinsic feature of HAp formed from an amorphous precursor. Our results challenge current models for HAp mineralization in bone and the role of citrate, offering new clues to help answer the long-standing question as to why natural evolution favored HAp as the mineral phase in bone.

Incorporation of heavy metal ions in cement hydrates is of great interest for the storage and immobilization of toxic, hazardous, and radioactive wastes using cementitious matrix. Magnesium silicate hydrate (M-S-H) is a low pH alternative cementitious binder to commonly used Portland cement. Low pH cements have been considered as promising matrix for municipal and nuclear waste immobilization in the last decades. It is however crucial to assure that the incorporation of secondary ions is not detrimental for the formation of the hydration products. Herein, we investigate the early stages of formation of M-S-H from electrolyte solutions in presence of a wide range of metal cations (Li^I, Ba^II, Cs^I, Cr^III, Fe^III, Co^II, Ni^II, Cu^I, Zn^II, Pb^II, Al^III). The final solid products obtained after 24 h have been characterized via powder X-ray diffraction (PXRD), attenuated total reflectance-Fourier transformed infrared spectroscopy (FTIR-ATR), elemental analysis via energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HR-TEM). In all the experiments, the main precipitated phase after 24 h was confirmed to be M-S-H with a ratio (total metal/Si) close to one. The obtained M-S-H products showed strong immobilization capacity for the secondary metal cations and can incorporate up to 30% of the total metal content at the early stages of M-S-H formation without significantly delaying the nucleation of the M-S-H. It has been observed that presence of Cr, Co, and Fe in the solution is prolonging the growth period of M-S-H. This is related to a higher average secondary metal/total metal ratio in the precipitated material. Secondary phases that co-precipitate in some of the experiments (Fe, Pb, Ni, and Zn) were also effectively trapped within in the M-S-H matrix. Barium was the only element in which the formation of a secondary carbonate phase isolated from the M-S-H precipitates was detected.