German Montes-Hernandez

Goethite as an alternative origin of the 3.1 μm band on dark asteroids

Context. The reflectance spectra of some main-belt asteroids contain a 3-μm band, which is explained by the presence of water or hydroxyl groups in minerals. Recent observations of 24-Themis have been found to display evidence of water ice. Aims. We synthesize iron oxy-hydroxide materials and in the laboratory measure their near-infrared spectra under dry conditions to compare with asteroid observations. Methods. The syntheses are performed using either the well-established titration method or a non-conventional hydrothermal method. Bi-directional near-infrared reflectance spectra are obtained using the spectrogonio radiometer available at LPG/IPAG. Spectra are measured in a vacuum to avoid contamination by adsorbed water. Results. The reflectance spectra that we measure for synthesized goethite are consistent with published transmission spectra. The 3-μm band in goethite has a minimum around 3.10 μm, similar to observations of 24-Themis. Its overall shape matches well Themiss 3-μm band; goethite-like oxy-hydroxydes are a viable alternative way of explaining 24-Themis near-IR spectra.

Removal of oxyanions from synthetic wastewater via carbonation process of calcium hydroxide: Applied and fundamental aspects

Removal of oxyanions (selenite, selenate, arsenate, phosphate and nitrate) during calcite formation was experimentally studied using aqueous carbonation of calcium hydroxide under moderate pressure (P(CO2) congruent with 20 bar) and temperature (30 degrees C). The effects of Ca(OH)(2) dose (10 and 20 g), Ca(OH)(2) source (commercial pure material or alkaline paper mill waste) and oxyanion initial concentration (from 0 to 70 mg atom/L) were investigated for this anisobaric gas-liquid-solid system. The Ca(OH)(2) carbonation reaction allowed successfully the removal of selenite (>90%), arsenate (>78%) and phosphate (congruent with 100%) from synthetic solutions. Conversely, nitrate and selenate had not any physicochemical affinity/effect during calcite formation. The rate of CO(2) transfer during calcite formation in presence of oxyanions was equal or slower than for an oxyanion-free system, allowing to define a retarding kinetic factor RF that can vary between 0 (no retarding effect) to 1 (total inhibition). For selenite and phosphate RF was quite high, close to 0.3. A small retarding effect was detected for arsenate (RF approximately 0.05) and no retarding effect was detected for selenate and nitrate (RF approximately 0). In general, RF depends on the oxyanion initial concentration, oxyanion nature and Ca(OH)(2) dose. The presence of oxyanions could also influence the crystal morphology and aggregation/agglomeration process. For example, a c-axis elongation of calcite crystals was clearly observed at the equilibrium, for calcite formation in presence of selenite and phosphate. The oxyanions removal process proposed herein was inspired on the common physicochemical treatment of wastewater using calcium hydroxide (Ca(OH)(2)). The particularity, for this novel method is the simultaneous calcium hydroxide carbonation with compressed carbon dioxide in order to stabilise the solid matter. This economical and ecological method could allow the removal of various oxyanions as well as the ex situ mineral sequestration of CO(2); particularly, when the Ca(OH)(2) source comes from alkaline solid waste.

Experimental assessment of CO2-mineral-toxic ion interactions in a simplified freshwater aquifer: implications for CO2 leakage from deep geological storage.

The possible intrusion of CO2 into a given freshwater aquifer due to leakage from deep geological storage involves a decrease in pH, which has been directly associated with the remobilization of hazardous trace elements via mineral dissolution and/or via desorption processes. In an effort to evaluate the potential risks to potable water quality, the present study is devoted to experimental investigation of the effects of CO2 intrusion on the mobility of toxic ions in simplified equilibrated aquifers. We demonstrate that remobilization of trace elements by CO2 intrusion is not a universal physicochemical effect. In fact goethite and calcite, two minerals frequently found in aquifers, could successfully prevent the remobilization of adsorbed Cu(II), Cd(II), Se(IV), and As(V) if CO2 is intruded into a drinking water aquifer. Furthermore, a decrease in pH resulting from CO2 intrusion could reactivate the adsorption of Se(IV) and As(V) if goethite and calcite are sufficiently available in underground layers. Our results also suggest that adsorption of cadmium and copper could be promoted by calcite dissolution. These adsorbed ions on calcite are not remobilized when CO2 is intruded into the system, but it intensifies calcite dissolution. On the other hand, arsenite As(III) is significantly adsorbed on goethite, but is partially remobilized by CO2 intrusion.

Nucleation and Growth of Chrysotile Nanotubes in H2SiO3/MgCl2/NaOH Medium at 90 to 300 °C

Herein, we report new insights into the nucleation and growth processes of chrysotile nanotubes by using batch and semi-continuous experiments. For the synthesis of this highly carcinogenic material, the influences of temperature (90, 200, and 300 °C), Si/Mg molar ratio, and reaction time were investigated. From the semi-continuous experiments (i.e., sampling of the reacting suspension over time) and solid-state characterization of the collected samples by XRPD, TGA, FTIR spectroscopy, and FESEM, three main reaction steps were identified for chrysotile nucleation and growth at 300 °C: 1) formation of the proto-serpentine precursor within the first 2 h of the reaction, accompanied by the formation of brucite and residual silica gel; 2) spontaneous nucleation and growth of chrysotile between about 3 and 8 h reaction time, through a progressive dissolution of the proto-serpentine, brucite, and residual silica gel; and 3) Ostwald ripening growth of chrysotile from 8 to 30 h reaction time, as attested to by BET and FESEM measurements. Complementary results from batch experiments confirmed a significant influence of the reaction temperature on the kinetics of chrysotile formation. However, FESEM observations revealed some formation of chrysotile nanotubes at low temperatures (90 °C) after 14 days of reaction. Finally, doubling the Si/Mg molar ratio promoted the precipitation of pure smectite (stevensite-type) under the same P (8.2 MPa)/T (300 °C)/pH (13.5) conditions.

Sequestration of selenium on calcite surfaces revealed by nanoscale imaging.

Calcite, a widespread natural mineral at the Earths surface, is well-known for its capacity to sequester various elements within its structure. Among these elements, selenium is important because of its high toxicity in natural systems and for human health. In the form of selenite (Se((IV))), selenium can be incorporated into calcite during growth. Our in situ atomic force microscopy observations of calcite surfaces during contact with selenium-bearing solutions demonstrate that another process of selenium trapping can occur under conditions in which calcite dissolves. Upon the injection of solutions containing selenium in two states of oxidation (either Se((IV)) or Se((VI))), precipitates were observed forming while calcite was still dissolving. In the presence of selenate (Se((VI))), the precipitates formed remained small during the observation period. When injecting selenite (Se((IV))), the precipitates grew significantly and were identified as CaSeO3·H2O, based on SEM observations, Raman spectroscopy, and thermodynamic calculations. An interpretation is proposed where the dissolution of calcite increases the calcium concentration in a thin boundary layer in contact with the surface, allowing the precipitation of a selenium phase. This process of dissolution-precipitation provides a new mechanism for selenium sequestration and extends the range of thermodynamic conditions under which such a process is efficient.

Formation of porous calcite mesocrystals from CO2–H2O–Ca(OH)2 slurry in the presence of common domestic drinks

This study reports a simple, innovative and fast method to synthesize porous calcite mesocrystals with high specific surface area from Ca(OH)2–water–CO2 slurry in the presence of common domestic drinks (soluble coffee, orange juice, carrot juice, white wine, sugar–water and milk). As already reported in previous studies, calcite nanoparticles (<100 nm) can be obtained at low temperature (≤30 °C) in the absence of additives. We demonstrate herein that the use of common domestic drinks as additives can induce the formation of calcite mesocrystals with a peanut-like morphology, i.e. the formation of a nanostructured material in which the constituent calcite nanoparticles (10 < size < 50 nm) are aligned and/or oriented, forming regular micrometric (<3 μm) 3D porous aggregates. We note that the additives used in the system did not induce polymorphism because only calcite was measured/observed in the solid products using XRD, FESEM and TEM or in collected-time suspensions using Raman spectroscopy. This innovative method for synthesizing porous calcite mesocrystals has significant relevance because only a few hours (6 h < time < 24 h) were required and synthesis was possible using a dispersed triphasic gas–liquid–solid system under high non-constant CO2 pressure (anisobaric conditions), contrary to available methods requiring days or weeks, in which reactant diffusion is typically imposed since these systems were initially designed to mimic biomineralization processes. Moreover, this new synthesis method could easily be scaled to industrial processes to produce calcite mesocrystals with high specific surface area (up to 30 m2 g−1). The nanostructured state, the mesoporosity and the high specific surface area for these synthesized calcite mesocrystals could improve the typical industrial and medical uses for synthetic calcite.

Dissolution-reprecipitation and self-assembly of serpentine nanoparticles preceding chrysotile formation: Insights into the structure of proto-serpentine

Abstract Any poorly crystalline serpentine-type mineral with a lack of recognizable textural or diffraction features for typical serpentine varieties (i.e., chryotile, lizardite, and antigorite) is usually referred to as proto-serpentine. The formation of the so-called proto-serpentine seems ubiquitous in serpentinization reactions. It is related to dissolution-precipitation of strongly reactive particles prior to true serpentine formation (e.g., in veins where both chrysotile and proto-serpentine are described). However, the structural characteristics of proto-serpentine and its relation with serpentine crystalline varieties remain unclear. In this study a model describing the transformation from proto-serpentine to chrysotile is presented based on experimental chrysotile synthesis using thermogravimetric analyses, transmission electron microscopy, and high-energy X-ray diffraction with pair distribution function analyses. The combination of the high-resolution TEM and high-energy X-ray diffraction enables to resolve the local order of neo-formed particles and their structuration processes occurring during pure chrysotile formation (i.e., during the first three hours of reaction). The formation of individual nanotubes is preceded by the formation of small nanocrystals that already show a chrysotile short-range order, forming porous anastomosing features of hydrophilic crystallites mixed with brucite. This is followed by a hierarchical aggregation of particles into a fiber-like structure. These flake-like particles subsequently stack forming concentric layers with the chrysotile structure. Finally, the individualization of chrysotile nanotubes with a homogeneous distribution of diameter and lengths (several hundreds of nanometer in length) is observed. The competitive precipitation of brucite and transient serpentine during incipient serpentinization reaction indicates that both dissolution-precipitation and serpentine-particle aggregation processes operate to form individual chrysotile. This study sheds light into mineralization processes and sets a first milestone toward the identification of the factors controlling polymorph selection mechanisms in this fascinating system.

Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging

Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca2Sb2O7). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

Hydrothermal Valorization of Steel Slags—Part I: Coupled H2 Production and CO2 Mineral Sequestration

A new process route for the valorization of BOF steel slags combining H2 production and CO2 mineral sequestration is investigated at 300°C (HT) under hydrothermal conditions. A BOF steel slag stored several weeks outdoor on the production site was used as starting material. To serve as a reference, room temperature (RT) carbonation of the same BOF steel slag has been monitored with in situ Raman spectroscopy and by measuring pH and PCO2 on a time-resolved basis. CO2 uptake under RT and HT are, respectively, 243 and 327 kg CO2/t of fresh steel slag, which add up with the 63 kg of atmospheric CO2 per ton already uptaken by the starting steel slag on the storage site. The CO2 gained by the sample at HT is bounded to the carbonation of brownmillerite. H2 yield decreased by about 30% in comparison to the same experiment performed without added CO2, due to sequestration of ferrous iron in a Mg-rich siderite phase. Ferric iron, initially present in brownmillerite, is partitioned between an Fe-rich clay mineral of saponite type and metastable hematite. Saponite is likely stabilized by the presence of Al, whereas hematite may represent a metastable product of brown-millerite carbonation. Mg-rich wustite is involved in at least two competing reactions, i.e., oxidation into magnetite and carbonation into siderite. Results of both water-slag and water-CO2-slag experiments after 72 h are consistent with a kinetics enhancement of the former reaction when a CO2 partial pressure imposes a pH between 5 and 6. Three possible valorization routes, (1) RT carbonation prior to hydrothermal oxidation, (2) RT carbonation after hydrothermal treatment, and (3) combined HT carbonation and oxidation are discussed in light of the present results and literature data.