Herein is presented a rare example of salt/ cocrystal polymorphism involving the adduct between ethionamide (ETH) and salicylic acid (SAL). Both the salt and cocrystal forms have the same stoichiometry and composition and are both stable at room temperature. The synthetic procedure was successfully optimized in order to selectively obtain both polymorphs. The two adducts' structures were thoroughly investigated by means of singlecrystal X-ray diffraction, solid-state NMR spectroscopy, and density functional theory (DFT) calculations. From the solidstate NMR point of view, the combination of mono-and multinuclear experiments ( 1 H MAS, 13 C and 15 N CPMAS, 1 H-{ 14 N} D-HMQC, 1 H− 14 N PM-S-RESPDOR) provided undoubted spectroscopic evidence about the different positions of the hydrogen atom along the main N•••H•••O interaction. In particular, the 1 H− 14 N PM-S-RESPDOR allowed N−H distance measurements through the 1 H detected signal at a very high spinning speed (70 kHz), which remarkably agree with those derived by DFT optimized X-ray diffraction, even on a natural abundance real system. The thermodynamic relationship between the salt and the cocrystal was inquired from the experimental and computational points of view, enabling the characterization of the two polymorphs as enantiotropically related. The performances of the two forms in terms of dissolution rate are comparable to each other but significantly higher with respect to the pure ETH.
Calcium oxalates are naturally occurring biominerals and can be found as a byproduct of some industrial processes. Recently, a new and green method for carbon capture and sequestration in stable calcium oxalate from oxalic acid produced by carbon dioxide reduction was proposed. The reaction resulted in high-quality weddellite crystals. Assessing the stability of these weddellite crystals is crucial to forecast their reuse as solid-state reservoir of pure CO2 and CaO in a circular economy perspective or, eventually, their disposal. The thermal decomposition of weddellite obtained from the new method of carbon capture and storage was studied by coupling in-situ high-temperature X-ray powder diffraction and thermogravimetric analysis, in order to evaluate the dehydration, decarbonation, and the possible production of unwanted volatile species during heating. At low temperature (119–255 °C), structural water release was superimposed to an early CO2 feeble evolution, resulting in a water-carbon dioxide mixture that should be separated for reuse. Furthermore, the storage temperature limit must be considered bearing in mind this CO2 release low-temperature event. In the range 390–550 °C, a two-component mixture of carbon monoxide and dioxide is evolved, requiring oxidation of the former or gas separation to reuse pure gases. Finally, the last decarbonation reaction produced pure CO2 starting from 550 °C.
The balance between lichen biodeterioration and bioprotection processes on stone surfaces depends on many variables and is crucial to understanding the role of lichens in biogeomorphology and their threat to stone heritage conservation. However, stones colonized by lichens have still been mostly examined in terms of affected volumes and physico-chemical modes of interactions, overlooking the overall effects on properties related to surface durability. In this study, the impact of lichen colonization patterns on Cortemilia sandstone was examined beneath thalli of three lichen species. Rock hardness, a proxy for rock durability, was measured at different depths from the surface using an Equotip hardness tester and compared to that of freshly cut surfaces and exposed surfaces uncolonized by lichens. Mineralogical analyses were performed by X-ray powder diffraction on rock beneath lichen colonization, in comparison with unweathered rock. Equotip analyses quantified a differential, species-specific decrease in stone hardness. This variability was related to differences in hyphal penetration patterns and, possibly, calcite (re-)precipitation. In particular, in the case of the species most impacting rock hardness, X-ray diffraction patterns of calcite showed a remarkable stability of crystallographic plane (01-12), known to be enhanced in the presence of organic chelants. These results confirm that decisions on lichen removal from stone surfaces should consider species-specific behaviour. Moreover, the innovative approach of measuring stone hardness variation in association with the analysis of biomineralization processes contributes to unveil the extension of the sphere of lichen interaction within the stone substrate beyond the limit of the hyphal penetration.
The two most common polymorphs of MnO 2 , ramsdellite and pyrolusite, are often found in natural association. Our starting sample is from the Mistake mine (Arizona) containing macroscopic crystals of both ramsdellite (a = 4.5131( 6), b = 9.2689(13), c = 2.8610(4) Å, V = 119.69(3) Å 3 ; S.G. Pbmn) and pyrolusite (a = 4.4030(2), c = 2.87392(16) Å, V = 55.715(5) Å 3 ; S.G. P4 2 /mnm), along with a smaller amount of "groutellite". A mixed powder was used to study the ramsdellite→pyrolusite transformation by in situ high-temperature X-ray powder diffraction. Our results reveal that this transformation is not a direct transition, but it occurs in two steps, as a function of temperature; ramsdellite transforms into an amorphous phase, which then recrystallizes into pyrolusite. Amorphization of ramsdellite and crystallization of pyrolusite kinetics were studied by the universal equation for solid-solid reactions. The two activation energies are comparable, but the pre-exponential factor of the ramsdellite amorphization is two orders of magnitude larger than pyrolusite crystallization's. As a consequence, ramsdellite→pyrolusite transformation implies the formation of an amorphous transition, due to a mismatch between the conversion rates, that reaches its maximum at around 630 K and then decreases at higher T, when pyrolusite crystallization is strongly promoted.
<p>The management of waste and its sustainable reuse is one of the most important concern in our society in recent years, together with the increasing need to find primary materials without resorting to new extraction of resources. In this context, the thermovalorization of municipal solid waste (MSW) is currently the method that is spreading and replacing landfill disposal; the thermal treatment allows to reduce the volumes significantly, producing energy and returning bottom ashes (BA) and fly ashes (FA) in the measure of 20% and 5% of the total waste respectively.<br>The MSW incineration BA are classified as non-hazardous waste and can be reused as a raw material after some physical-chemical treatments.<br>The FA, on the contrary, are classified as hazardous waste and according to current legislation, they are usually subjected to vitrification treatments and stored in dedicated landfills. The hazard is due to the high content of soluble salts (chlorides and sulfates) and heavy metals (mainly Zn and Pb). Therefore, for their possible reuse as construction materials (e.g. ceramic, cement, concrete aggregates) or base roads, a preliminary stabilization step is required which often requires the use of significant quantities of energy.<br>In the present work, low energy cost methods are considered to reduce the dangerousness of FA and consequently make them more easily treatable for their reintegration into the production cycles.<br>Among the methods, washing of FA with water is examined, to find the lowest L / S ratio in the reduction of salts and heavy metals, analyzing the dissolution kinetics and the mineralogical content of fly ash before and after each washing treatment.<br>For a better definition of the kinetics, the FA are previously submitted to particle size separation to understand in which fractions the most dangerous substances are concentrated.<br>Washing treatments can be useful to remove or reduce soluble salts, in particular chlorides, by using a different liquid / solid (L / S) ratio, in order to obtain a more suitable material for the solidification / stabilization treatments carried out by geopolymerization or in cement.<br>The eluates of washing are also taken into consideration to evaluate the recovery of elemental species of interest and the purification of the liquid phase with biochar.</p>
Treatments to reduce the leaching of contaminants (chloride, sulfate, heavy metals) into the environment from bottom ash (BA) are investigated, as a function of the ash’s particle size (s). The aim is to make BA suitable for reuse as secondary raw material, in accordance with the legal requirements. Such treatments must be economically feasible and, possibly, have to use by-products of the plant (in this case, steam in excess from the turbine). For the sake of completeness and comparison, carbonation is performed on those BA particle size classes that are not positively responsive to steam washing. BA is partitioned into four different particle size classes (s ≥ 4.75, 4.75 > s ≥ 2, 2 > s ≥ 1 and s < 1 mm, corresponding to 36, 24, 13 and 27 wt%, respectively). In the case of s ≥ 2 mm (60 wt%), steam washing is effective in reducing to under the legal limits the leaching of chlorides, sulfate and heavy metals (Zn, Cu, Cd, Pb). It has been observed that steam washing causes both removal and dissolution of thin dust adherent to the BA’s surface. BA with 2 > s ≥ 1 (~13 wt% of total BA) requires a combination of steam washing and carbonation to achieve a leaching below the legal limits. The finest BA fraction, s < 1 mm (~27 wt% of total BA), is treated by carbonation, which reduces heavy metals leaching by 85%, but it fails to sufficiently curb chlorides and sulfates.
<p>Municipal solid waste incinerator (MSWI) fly ash can represent a sustainable source of construction materials, but it needs to be treated in order to remove dangerous substances as chlorides, sulfates, and heavy metals. The concentration of salts and heavy metals in fly ash usually exceeds the law threshold and so they are considered a hazardous waste, unsuitable for reuse in concrete and civil engineering applications.In this work, a complete characterization of fly ash coming from a northern Italy thermovalorization plant was investigated, both on the solid and leachates composition, focused on the particle size, by X-Ray fluorescence and X-Ray diffraction on the solid matrices and ICP-MS analysis on the leachates.Using mechanical sieving on several subsamples of fly ash, six different particle size were separated and analyzed, and compared to the bulk fly ash composition.The most abundant elements are represented by Ca, Cl, S, and Si; trace elements and heavy metals are mainly represented by Zn, Fe, Al, Pb. The XRF and ICP-MS analysis show a general increasing trend, as the particle size decrease, of Na, K, Cl, S, as well as Cr, Cd, Cu, Pb, Sb, Zn, Ba, both on solid and leachates composition; on the contrary Ca and Si decrease.After leaching Cl and K decrease consistently, while it can be observed an increase of all the other elements, due to the weight loss attributable mainly to the leaching of Na-K chlorides, that is confirmed also by the X-Ray diffraction analysis.</p>
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