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The increasing use of photoselective nets (PNs) raises the question of their influence on pollen traits. We aimed to evaluate the effect of PNs (yellow, pearl, and grey) on the pollen of ‘Matua’ and ‘Tomuri’ Actinidia deliciosa cultivars. The pollen size and the exine were studied with a light microscopy and a scanning electron microscopy, and the fertility was analysed by a viability assay and in vitro germination. The total soluble proteins (TSPs) and sugars (TSSs) were quantified by colorimetric assays. The molecular structure of the pollen grain’s wall was analysed by a Raman spectroscopy. The pollen from the plants under the PNs had a larger width and area and a lower germination rate. No significant changes were observed in the exine’s microperforations. The TSP and TSS contents were influenced by the cultivar and PNs (particularly the pearl PN). The Raman spectra of the pollen from the plants grown under the nets presented some bands that significantly shifted from their original position, indicating differences in the vibration modes of the molecules, but no overall changes at their structural or organisation level were found. Our study showed that the PNs could influence several pollen traits, with the pearl PN inducing greater modifications. Our results also support the idea that cultivars affect the outcome of some characteristics.

4-nitrophenol (4-NPh) is a harmful compound produced in large amounts in the chemical industry, and its reduction to aminophenol (4-APh) using noble metals as catalysts is one of the most studied processes. The development of noble metal-free catalysts represents an economic advantage in large-scale applications and contributes to the sustainability of raw materials. Coal fly ash (FA), a major waste stream from coal combustion, contains an easily recoverable magnetic fraction (FAmag sample) composed of Fe-rich particles that could substitute noble metal catalysts in 4-NPh reduction, with the concomitant advantage of being easily recovered via magnetic separation. For this purpose, a new composite material containing copper ferrite nanoparticles (FAmag@CS@CuFe) was prepared via a facile, environmentally friendly and cost-effective method based on three components: FAmag as the core, a biobased polymer chitosan (CS) as the linker and copper ferrite CuFe2O4 nanoparticles (CuFe) as the active sites. The structure, morphology, composition and magnetic properties of the FAmag@CS@CuFe material were studied to assess the efficiency of the preparation. It was found that the biopolymer prevented the aggregation of CuFe nanoparticles and enabled a synergistically outstanding activity towards the reduction of 4-NPh in comparison to the pristine FAmag and bare CuFe nanoparticles. The FAmag@CS@CuFe catalyst showed efficiency and stability in the conversion of 4-NPh of up to 95% in 3 min over four consecutive cycles. Such remarkable catalytic results demonstrate the potential of this catalyst as a substitute for expensive noble metals.

To unveil and shape the molecular connectivity in (metallo)porphyrin–carbon nanotube hybrids are of main relevance for the multiple medicinal, photoelectronic, catalytic, and photocatalytic applications of these materials. Multi-walled carbon nanotubes (MWCNTs) were modified through 1,3-dipolar cycloaddition reactions with azomethine ylides generated in situ and carrying pentafluorophenyl groups, followed by immobilization of the β-amino-tetraphenylporphyrinate Zn(II). The functionalities were confirmed via XPS and FTIR, whereas Raman spectroscopy showed disruptions on the graphitic carbon nanotube surface upon both steps. The functionalization extension, measured via TGA mass loss and corroborated via XPS, was 0.2 mmol·g−1. Photophysical studies attest to the presence of the different porphyrin–carbon nanotube connectivity in the nanohybrid. Significantly different emission spectra and fluorescence anisotropy of 0.15–0.3 were observed upon variation of excitation wavelength. Vis-NIR absorption and flash photolysis experiments showed energy/charge transfer in the photoactivated nanohybrid. Moreover, evidence was found for direct reaction of amino groups with a carbon nanotube surface in the presence of molecular dipoles such as the zwitterionic sarcosine amino acid.

Critical raw materials, such as graphite and lithium metal oxides (LMOs), with a high supply risk and high economic importance are present in spent lithium-ion batteries (LIBs). The recovery and recycling of these critical raw materials from LIBs will contribute to the circular economy model, reduce the environmental footprint associated with the mining of these materials, and lower their high supply risk. The main aim of this paper is to present a separation process to recover graphite from black mass (BM) from spent LIB. Simultaneously, LMO and copper (Cu) and aluminum (Al) foils were also recovered as by-products from the process. The process used a combination of simple and/or low environmental footprint technologies, such as sieving, sink-float, citric acid leaching, and milling through ultrasound and soft attrition, to allow separation of the LIB valuable components. Three graphite-rich products (with purities ranging between 74 and 88 wt.% total carbon and a combined yield of 14 wt.%) with three different sizes (

High amounts of coal combustion products, such as fly ash and bottom ash, are generated every year; however, only 64% are used, which means that a significant part is landfilled despite containing valuable materials such as ferrospheres, which may be used as catalysts, substituting critical raw materials (e.g., platinoids). In commercial coals, pyrite contents are reduced as a pre-combustion S-emissions control measure, so low amounts of ferrospheres are expected in the respective ashes. However, given the large amounts of ash being generated from these coals, it may provide a reliable source of catalysts, with ferrospheres being easily recovered via magnetic separation. Several studies have been conducted regarding these morphotypes; however, there is a lack of investigation considering the ash derived from highly beneficiated coals and the variations with location and time. In this study, bottom ash, economizer grits, and fly ash samples from a Portuguese power plant burning Colombian commercial coal were fractionated using ferrite (Fe-MC fraction) and Nd (Nd-MC fraction) magnets, and a multi-technique approach was used to assess their properties (magnetic parameters, particle size distribution, mineralogy, particle morphology, microtexture, and chemical composition). The Fe-MC presented higher Fe concentrations (up to 44 wt.% Fe2O4) than the Nd-MC (up to 7 wt.% Fe2O4). Once it was a sequential process, Nd magnets essentially collected Fe-bearing aluminosilicate glass, and Fe-bearing minerals were residual when compared to the Fe-MC, where magnetite, magnesioferrite, hematite, and maghemite accounted for up to 30 wt.%. Among the Fe-MC, the sample collected from electrostatic precipitator fly ash (ESP FA), despite having a lower yield, presented higher Fe concentrations than the ones from bottom ash and economizer grits, which was related to the mode of occurrence of Fe-bearing phases: in the Fe-MC from ESP FA, discrete ferrospheres predominated, while in the remaining Fe-bearing phases, they were often embedded in aluminosilicate glass. All Fe-MC samples showed an increase of Fe-substituting elements (e.g., Mn and Ni) and their concentration tended to increase with decreasing particle size along with Fe. The integrated study of cross-sections enabled the identification of oxidation rims, martitization aspects, and the co-existence of hematite and magnesioferrite.

The target of this study was the tungsten Regoufe mine, whose exploitation stopped in the 1970s. When the mine closed, an unacceptable legacy constituted of mining waste tailings and the ruins of infrastructure was left behind. This work assessed the soil, plants, and water contamination in the mining area; namely their content in potentially toxic elements (PTEs). The global impact of PTEs in the Regoufe mine surface soil points to a very high to ultrahigh degree of contamination of the area having a serious ecological risk level, mainly related to As and Cd contributions. However, establishing the direct relation between As contamination and the anthropogenic effects caused by the mining process cannot be carried out in a straightforward manner, since the soils were already enriched in metals and metalloids as a result of the geological processes that gave origin to the mineral deposits. The studies performed on the plants revealed that the PTE levels in the plants were lower than in the soil, but site-specific soil concentrations in As and Pb positively influence bioaccumulation in plants. The magnetic studies showed the presence of magnetic technogenic particles concentrated in the magnetic fraction, in the form of magnetic spherules. The magnetic technogenic particles probably result from temperature increases induced by some technological process related to ore processing/mining activity. The PTEs in the surface and groundwater samples were similar and relatively low, being unlikely to pose potential health and environmental risks. Arsenic (As) constituted the exception, with levels above reference for drinking water purposes.

The increasing demand for rare earth elements (REEs), which is associated with their economic importance and the supply risk, has motivated the research for alternative secondary sources of these elements. Coal and coal combustion ash have been pointed out as promising REE raw materials. This research seeks to understand REE fractionation, from feed coals to ashes, considering seasonal variations, and to assess the trends within the ash fractions that can be used for further beneficiation processes. Colombian commercial feed coals, combustion ashes, and their respective fractions were sampled from a Portuguese power plant and were characterized via petrographical, mineralogical, and chemical analyses. The total REE concentrations in the feed coals studied range between 6.97 and 23.15 ppm, while, in the ashes, they vary from 159.9 to 266.6 ppm. Fly ash (FA) from electrostatic precipitator (ESP) presented higher concentrations than the bottom (BA) and economizer (ECO) ashes. Furthermore, REEs and the LREE/HREE ratio increased slightly towards the back rows of the ESP. In the feed coals, the REEs are significantly correlated with ash, and they occur in micrometric phosphate minerals intermixed with clays. In the ashes, the REEs were mostly detected in micrometric particles, with P and Al-Si as the major components. The results from the fractioned samples show that the REEs were enriched in the fine (

In this study, we propose a predictive model for maceral discrimination based on Raman spectroscopic analyses of dispersed organic matter. Raman micro-spectroscopy was coupled with optical and Rock-Eval pyrolysis analyses on a set of seven samples collected from Mesozoic and Cenozoic successions of the Outer sector of the Carpathian fold and thrust belt. Organic petrography and Rock-Eval pyrolysis evidence a type II/III kerogen with complex organofacies composed by the coal maceral groups of the vitrinite, inertinite, and liptinite, while thermal maturity lies at the onset of the oil window spanning between 0.42 and 0.61 Ro%. Micro-Raman analyses were performed, on approximately 30–100 spectra per sample but only for relatively few fragments was it possible to perform an optical classification according to their macerals group. A multivariate statistical analysis of the identified vitrinite and inertinite spectra allows to define the variability of the organofacies and develop a predictive PLS-DA model for the identification of vitrinite from Raman spectra. Following the first attempts made in the last years, this work outlines how machine learning techniques have become a useful support for classical petrography analyses in thermal maturity assessment.

The sustainability of primary resources depends on recycling, resource efficiency and the search for alternative materials [...]

The knowledge of pollen sensitivity and tolerance to stress factors such as air pollution is important for forest sustainability, ensuring the most efficient production with the highest benefits and lowest resource losses. This study intended to evaluate the influence of common air pollutants in four forest trees species, Betula pendula Roth, Corylus avellana L., Acer negundo L. and Quercus robur L., through a comparative analysis at the same experimental conditions. We aimed to investigate the effect that may occur in pollen fertility, protein content, oxidative stress and wall composition after exposure in vitro to ozone and nitrogen dioxide at concentration levels for vegetation protection in Europe. Our results suggest changes in pollen viability, protein content and differential sensitivity related to ROS synthesis, NADPH oxidase activity, as well as in wall composition. The results indicate that NO2 exposure affected more the pollen species studied mostly at the highest concentration exposure. As for ozone, there were less significant differences between samples; however, a different behavior occurs in O3 expositions, where the most influence happens at the legal limit for vegetation protection in Europe. Our study showed that significant pollen functions could be compromised even at common air pollutant’s concentrations.

In order to assess a source rock for economical exploitation purposes, many parameters should be considered; regarding the geochemical aspects, the most important ones are the amount of organic matter (OM) and its quality. Quality refers to the thermal maturity level and the type of OM from which it was formed. The origin of the OM affects the ability of the deposited OM between sediments to generate oil, gas, or both with particular potential after going through thermal maturation. Vitrinite reflectance and programmed pyrolysis (for instance, Rock-Eval) are common methods for evaluating the thermal maturity of the OM and its potential to generate petroleum, but they do not provide us with answers to what extent solid bitumen is oil-prone or gas-prone, as they are bulk geochemical methods. In the present study, Raman spectroscopy (RS), as a powerful tool for studying carbonaceous materials and organic matter, was conducted on shale and coal samples and their individual macerals to show the potential of this technique in kerogen typing and to reveal the parent maceral of the examined bitumen. The proposed methodology, by exhibiting the chemical structure of different organic matters as a major secondary product in unconventional reservoirs, can also detect the behavior of solid bitumen and its hydrocarbon production potential for more accurate petroleum system evaluation.

The oxygen reduction reaction is an essential reaction in several energy conversion devices such as fuel cells and batteries. So far, the best performance is obtained by using platinum-based electrocatalysts, which make the devices really expensive, and thus, new and more affordable materials should be designed. Biomass-derived carbons were prepared by hydrothermal carbonization in the presence of carbon nanotubes with different oxygen surface functionalities to evaluate their effect on the final properties. Additionally, nitrogen functional groups were also introduced by ball milling the carbon composite together with melamine. The oxygen groups on the surface of the carbon nanotubes favor their dispersion into the precursor mixture and the formation of a more homogenous carbon structure with higher mechanical strength. This type of structure partially avoids the crushing of the nanotubes and the carbon spheres during the ball milling, resulting in a carbon composite with enhanced electrical conductivity. Undoped and N-doped composites were used as electrocatalysts for the oxygen reduction reaction. The onset potential increases by 20% due to the incorporation of carbon nanotubes (CNTs) and nitrogen, which increases the number of active sites and improves the chemical reactivity, while the limiting current density increases by 47% due to the higher electrical conductivity.

During a study aiming to recover strategic elements and minerals from coal fly ash and bottom ash (RAREASH and CHARPHITE projects funded, respectively, by the 2nd ERA-MIN and 3rd ERA-MIN Programs of the European Union Commission), it was found that in coal fly ash and bottom ash from Romania and Poland, several morphotypes did not fit into the general fly ash classifications, unless grouped together as “undifferentiated inorganics”. However, the combination of reflected light optical microscopy under oil immersion, scanning electron microscopy, and X-ray microanalysis (SEM/EDS) showed that many of these morphotypes not only have distinctive petrographic patterns but are also characterized by a chemical assemblage dominated by Ca, Mg, and P. In this paper, a survey of the literature is presented together with several detailed studies of samples from the RAREASH and CHARPHITE projects from which the following nomenclature are proposed: “calcispheres” for spongy Ca-rich morphotypes, “calcimagnesiaspheres” for (Ca + Mg)-rich morphotypes with visible MgO nodules and/or periclase (MgO) exsolved from Ca aluminate-silicate glass, and “magnesiaspheres” divided into “magnesiaferrospheres” for (Mg + Fe)-rich morphotypes with magnesioferrite, and “magnesiaoxyspheres” for magnesiaspheres mainly composed of (Mg + Fe)-rich amorphous material with visible MgO nodules and/or periclase.