Potentially toxic elements speciation in bottom ashes from a municipal solid waste incinerator: A combined SEM-EDS, µ-XRF and µ-XANES study

Bottom Ashes from Municipal Solid Waste Incinerators and Waste to Energy plants represent an interesting source of secondary raw materials for many applications, like urban mining and inclusion in concrete, and road pavement. However, Bottom Ashes may contain potentially toxic elements, whose actual toxicity depends essentially on their oxidation state and mineralogical environment. For this reason, a representative sample of bottom ashes from Parma Waste to Energy plant has been selected to investigate the chemical speciation of Cr, Ni, Pb, Co, Zn and Cu by means of complementary techniques: Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDS), micro X-Ray Fluorescence (µ-XRF) mapping and X-Ray Absorption Near Edge Structure (XANES) measurements by synchrotron radiation. This multi-technique approach allowed to obtain a general image of the mineralogical and chemical environment in which these elements are found. SEM-EDS analyses show the presence of Zn and Pb both in minerals and in glass matrix. Cr has been detected in the form of oxide and in spinel structure (chromite) whereas Co and Cu are found as alloy or metal inclusions. µ-XRF mapping reveals that Cu, Ni and Cr are generally associated to Na, K and Si suggesting their presence in glass matrix. XANES investigations exhibit that Cu has a variable oxidation state that suggesting its presence in the form of oxide, hydroxide, acetate and metal. Zn is mainly found as +II and in a number of different phases (including Zn-carbonates, in agreement with SEM-EDS data). Cr has been found only as +III, with XANES features resembling those of chromite, whereas as +VI was never identified. Ni and Co were found either as metal form and oxides. Pb spectra show a good match with oxides

A target repurposing approach identifies N-myristoyltransferase as a new candidate drug target in filarial nematodes

Myristoylation is a lipid modification involving the addition of a 14-carbon unsaturated fatty acid, myristic acid, to the N-terminal glycine of a subset of proteins, a modification that promotes their binding to cell membranes for varied biological functions. The process is catalyzed by myristoyl-CoA:protein N-myristoyltransferase (NMT), an enzyme which has been validated as a drug target in human cancers, and for infectious diseases caused by fungi, viruses and protozoan parasites. We purified Caenorhabditis elegans and Brugia malayi NMTs as active recombinant proteins and carried out kinetic analyses with their essential fatty acid donor, myristoyl-CoA and peptide substrates. Biochemical and structural analyses both revealed that the nematode enzymes are canonical NMTs, sharing a high degree of conservation with protozoan NMT enzymes. Inhibitory compounds that target NMT in protozoan species inhibited the nematode NMTs with IC50 values of 2.5-10 nM, and were active against B. malayi microfilariae and adult worms at 12.5 µM and 50 µM respectively, and C. elegans (25 µM) in culture. RNA interference and gene deletion in C. elegans further showed that NMT is essential for nematode viability. The effects observed are likely due to disruption of the function of several downstream target proteins. Potential substrates of NMT in B. malayi are predicted using bioinformatic analysis. Our genetic and chemical studies highlight the importance of myristoylation in the synthesis of functional proteins in nematodes and have shown for the first time that NMT is required for viability in parasitic nematodes. These results suggest that targeting NMT could be a valid approach for the development of chemotherapeutic agents against nematode diseases including filariasis

Comprehensive Analysis of Two H13-Type Starting Materials Used for Laser Cladding and Aerosol Particles Formed in This Process

Laser cladding with H13 steel powders was performed and the related material transformations were studied for the particles emitted during this process. Fractions of various sizes of the aerosol particles formed during the laser cladding were collected on a cascade impactor, while the electromobility and the aerodynamic size of the particles were measured using a scanning mobility particle spectrometer and an aerodynamic particle sizer, respectively. The aerosol particles deposited onto the impactor plates were analyzed using scanning electron microscopy–energy-dispersive X-ray spectroscopy, as well as total-reflection X-ray fluorescence and X-ray absorption near-edge structure spectroscopy. Both the concentration and mean oxidation state of the major components were correlated with the aerosol particle size. The ultrafine aerosol particles (with a diameter less than about 100 nm) were predominantly oxidized and formed as the result of an evaporation–oxidation–condensation process sequence. The larger particles (>200 nm in geometric diameter) were primarily the residues of the original metal powder and exhibited a composition change as compared to the as-received metal powder. Correlations between the changes in the concentration ratio of the components were detected and explained

Characterization of unique aerosol pollution episodes in urban areas using TXRF and TXRF-XANES

Identifying sources of unique, short-time aerosol pollution episodes in urban areas is a difficult task since they could last only for a couple of hours. With the combination of size-fractioned sampling with May-type cascade impactor and total-reflection X-ray fluorescence (TXRF) in addition to X-ray absorption near-edge structure spectroscopy various sources could be identified in samples collected in Budapest (Hungary) and Cassino (Italy). Using short-time (1–4 h), size-fractionated (70 nm up to 10 μm into 7 stages) sampling method, TXRF is capable of detecting transition metals in the order of 0.1 ng/m3. The present study discusses pollution episodes with Cu and Br concentrations in the range of 1–40 ng/m3. The contribution of both exhaust and non-exhaust type traffic-related emission sources were found to be dominant in the Cu species. Wear products of brake system were identified in coarse particles in addition to resuspension of roadside dust. The ratio of organic/inorganic Br could be determined for a pollution episode with elevated Br concentration

Experimental quantification of the Fe-valence state at amosite-asbestos boundaries using acSTEM dual-electron energy-loss spectroscopy

Determination of the oxidation state and coordination geometry of iron in Fe-bearing minerals expands our knowledge obtained by standard mineralogical characterization. It provides information that is crucial in assessing the potential of minerals to interact with their surrounding environment and to generate reactive oxygen species, which can disrupt the normal function of living organisms. Aberration-corrected scanning transmission electron microscopy dual-electron energy-loss spectroscopy (acSTEM Dual-EELS) has only rarely been applied in environmental and medical mineralogy, but it can yield data that are essential for the description of near-surface and surface mechanisms involved in many environmental and health-related processes. In this study, we have applied the energy loss near-edge structure (ELNES) and L2,3 white-line intensity-ratio methods using both the universal curve and progressively larger integrating windows to verify their effectiveness in satisfactorily describing the valence state of iron at amosite grain boundaries, and, at the same time, to estimate thickness in the same region of interest. The average valence state obtained from acSTEM Dual-EELS and from a simplified geometrical model were in good agreement, and within the range defined by the bulk and the measured surface-valence states. In the specific case presented here, the use of the universal curve was most suitable in defining the valence state of iron at amosite grain boundaries. The study of ELNES revealed an excellent correspondence with the valence state determined by the L2,3 white-line intensity-ratio method through the use of the universal curve, and it seems that the spectra carry some information regarding the coordination geometry of Fe. The combination of visual examination, reconstruction of the grain boundaries through a simple geometrical model, and Dual-EELS investigation is a powerful tool for characterizing the grain boundaries of hazardous minerals and foreseeing their potential activity in an organism, with the possibility to describe toxic mechanisms in a stepwise fashion

Primary Mandibular Condyle Xanthoma: Case Report and Literature Review

Bone xanthoma is a rare benign primary bone lesion histologically characterized by sheets of foamy cells which are macrophages with a cytoplasm filled with droplets of fat. It is usually associated with endocrine or metabolic diseases, in the absence of which the lesion is called primary xanthoma. Because of the lack of pathognomonic radiologic and clinical features, they require a differential diagnosis with a broad spectrum of lesions with a varying degree of malignant potential. We describe a case of primary mandibular xanthoma of a 16-year-old girl without typical cutaneous manifestations and alterations in lipid values. The temporomandibular joint involvement at the mandibular condyle is peculiar in the case described here. We present even a qualitative systematic review of the literature on primary xanthoma of the jaws in others to draw up treatment guidelines

Characterization of the ultrafine and fine particles formed during laser cladding with the Inconel 718 metal powder by means of X-ray spectroscopic techniques

Additive manufacturing is a rapidly growing industrial technology. Still, there is a lack of knowledge regarding the fine particle emission and new particle formation during the processes and their consequences on the performance of the operation and the operator's health as well. Therefore, we studied the properties of the emitted particles during the 3D printing process using the Inconel 718 (Ni-based) superalloy. The number and the mass concentrations were measured with a Scanning Mobility Particle Counter and Sizer. Size-fractionated samples were collected by a cascade impactor, and the elemental composition of the particles was determined by total-reflection X-ray fluorescence analysis, Scanning Electron Microscopy, Energy Dispersive Spectroscopy, and microscopic X-ray fluorescence analysis in the different size fractions. The oxidation states of the metals (Cr, Mn, Fe, Ni) in the samples were determined with the X-ray absorption near-edge structure (XANES) method. Most of the particles were found in the ultrafine region with a size below 100 nm, and the mass size distribution had the maximum at 85 nm. In the original powder, Ni was dominating with appr. 52 wt%, and the proportion of Cr was around 20 wt%, and Mn was below 1 wt%. In the released particles, the Ni content decreased to appr. 26 wt%, the Cr content increased to appr. 47 wt% and Mn increased to around 10 wt% for particles with a size between 0.07 and 10 μm. According to the XANES results, Cr, Mn and Fe were found to be oxidized significantly, whereas Ni remained in the metallic form in the total emitted aerosol containing mostly ultrafine particles. The enrichment and oxidation of metals were correlated with each other

Large scale synthesis of copper nickel alloy nanoparticles with reduced compressibility using arc thermal plasma process

Among the various methods employed in the synthesis of nanostructures, those involving high operating temperature and sharp thermal gradients often lead to the establishment of new exotic properties. Herein, we report on the formation of Cu-Ni metallic alloy nanoparticles with greatly enhanced stiffness achieved through direct-current transferred arc-thermal plasma assisted vapour-phase condensation. High pressure synchrotron X-ray powder diffraction (XRPD) at ambient temperature as well as XRPD in the temperature range 180 to 920 K, show that the thermal arc-plasma route resulted in alloy nanoparticles with much enhanced bulk modulus compared to their bulk counterparts. Such a behaviour may find an explanation in the sudden quenching assisted by the retention of a large amount of local strain due to alloying, combined with the perfect miscibility of the elemental components during the thermal plasma synthesis process

Heavy metals concentrations and speciation of Pb and Ni in airborne particulate matter over two residential sites in Greater Cairo - reflection from synchrotron radiation

Synchrotron radiation-based techniques [X-ray absorption near-edge structure (XANES) and X-ray fluorescence (XRF)] combined with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the assessment of heavy metals concentrations as well as lead (Pb) and nickel (Ni) speciation in airborne particulate matter (PM10) over two residential sites in Greater Cairo. Nineteen 24 h high-volume samples collected at Giza (G) Square and Helwan (H) University (Egypt) were selected for this study. Mean concentrations of heavy metals in PM10 at both sites were found to have the same descending order of Pb > Cu > Ni > Cd > Co > As, of which concentrations of Pb, Cu, Ni and Cd in H samples were higher than those in G samples. For Pb, synchrotron-based XRF results were in good agreement with concentrations obtained by ICP-MS. The XANES spectra of PM10 at the Pb L 2-edge and Ni K-edge were compared with those of Pb and Ni in model standard compounds to provide information on the potential oxidation states as well as the chemical forms of those elements. The data show that Pb has similar chemical environments in both series G and H with the predominance of Pb2+oxidation state. Nickel was found as Ni(OH)2, NiO and Ni metal in the analyzed samples. However, the content of Ni in the background filter shows a very strong interference with that of the collected PM10. Carcinogenic and non-carcinogenic risks resulting from the inhalation of the studied heavy metals were assessed for children and adult residents and were found below the safe limits, at both sites