Physico-chemical characterization of crystalline phases in fly ashes

Fuel oil combustion in power plants, domestic heating systems and diesel engines, causes the emission in the environment of particles with a typical structure and composition: the cenospheres.These particles are produced during the microdrop fuel oil combustion, when air and fuel are injected into the combustion chamber; they have a spheroidal morphology and a spongy structure.Cenospheres are constituted by an amorphous component rich in C, S, Si, Fe and Al; phases composed by microcrystals of sulphates, oxides and pure metallic elements or their alloys, are frequently present in the cenospheres.These crystalline phases are important from environmental and toxicological points of view both because they are composed of heavy metals, and because they can play an important role in heterogeneous catalysis.We started to study these crystalline phases by analytical electron microscopy techniques and electron energy loss spectrometry to define and characterise their structure and composition.     

Quantitative energy dispersive X-ray analysis of submicrometric particles using a scanning electron microscope

The quantitative scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis of a horneblende and two augite prismatic samples reduced to submicrometric particles was performed, and error due to the particle effects ("absent mass" and the "reduced absorption" effect) was minimized. Correction factors as a function of fragment size were obtained for O, Na, Mg, Si, Ca, and Fe. In addition, the influence of chemical composition of the samples used as standards (the matrix effect) on correction factors was evaluated. The results indicate that the absent mass effect is dominant for all elements except for the light elements O and Na, for which the reduced absorption effect is dominant. No significant matrix effect has been observed. By using corrected SEM-EDX data, the error on quantification of the element concentration has been estimated to be 3% relative for light elements and below 2% relative for heavy elements (notably, about 1% relative for Fe).     

Combined use of X-ray photoelectron and Mössbauer spectroscopic techniques in the analytical characterization of iron oxidation state in amphibole asbestos

Asbestos fibers are an important cause of serious health problems and respiratory diseases. The presence, structural coordination, and oxidation state of iron at the fiber surface are potentially important for the biological effects of asbestos because iron can catalyze the Haber–Weiss reaction, generating the reactive oxygen species ?OH. Literature results indicate that the surface concentration of Fe(III) may play an important role in fiber-related radical formation. Amphibole asbestos were analyzed by X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy, with the aim of determining the surface vs. bulk Fe(III)/Fe_tot ratios. A standard reference asbestos (Union Internationale Contre le Cancer crocidolite from South Africa) and three fibrous tremolite samples (from Italy and USA) were investigated. In addition to the Mössbauer spectroscopy study of bulk Fe(III)/Fe_tot ratios, much work was dedicated to the interpretation of the XPS Fe2p signal and to the quantification of surface Fe(III)/Fe_tot ratios. Results confirmed the importance of surface properties because this showed that fiber surfaces are always more oxidized than the bulk and that Fe(III) is present as oxide and oxyhydroxide species. Notably, the highest difference of surface/bulk Fe oxidation was found for San Mango tremolite—the sample that in preliminary cytotoxicity tests (MTT assay) had revealed a cell mortality delayed with respect to the other samples.     

Strong CP problem and mirror world: the Weinberg–Wilczek axion revisited

A new possibility for solving the strong CP problem is suggested. It is based on the concept of a mirror world of particles, with the gauge symmetry and Lagrangian completely identical to that of the observable particles. We assume that the ordinary and mirror sectors share the same Peccei–Quinn symmetry realized à la Weinberg–Wilczek, so that the θ-terms are simultaneously canceled by the axion VEV in both worlds. This property remains valid even if the symmetry between two sectors is spontaneously broken and the weak scale of the mirror world is larger than the ordinary weak scale, in which case also the mirror QCD scale becomes larger than the ordinary one. In this situation our axion essentially represents a Weinberg–Wilczek axion of the mirror world with quite a large mass, while it couples the ordinary particles like an invisible axion. The experimental and astrophysical limits are discussed and an allowed parameter window is found with the Peccei–Quinn scale f_a10⁴–10⁵ GeV and the axion mass m_a1 MeV, which can be accessible for future experiments. We also show that our solution to the strong CP problem is stable against the Planck scale induced effects.     

Surface chemistry and surface reactivity of fibrous amphiboles that are not regulated as asbestos

Three fibrous amphiboles that are not regulated as asbestos—two from Biancavilla (Sicily, Italy) and one from Libby (MT, USA)—were studied in order to establish relationships between surface chemistry and surface reactivity. The three fibrous samples, plus one prismatic fluoro-edenite from Biancavilla that was used for comparison, were investigated by X-ray photoelectron spectroscopy (XPS) in order to obtain their quantitative surface compositions and to determine the chemical environment of the Fe in each case. In particular, the Fe 2p_3/2 peak was fitted and, for the first for these materials, the binding energies of Fe(II) oxide, Fe(III) oxide and Fe(III) oxyhydroxide were identified. Bulk chemistries and Fe oxidation states were obtained from previous studies for the samples from Biancavilla, and were investigated in the present work by electron microprobe (EMP) and ⁵⁷Fe Mössbauer spectroscopy (MS) for the sample from Libby. Comparison between surface and bulk data revealed that the sample with the lowest bulk Fe oxidation state was the one most affected by surface oxidation, while the samples with bulk highly-oxidised Fe were showing very high signal of Fe (III) oxy-hydroxide probably due to weathering. The surface reactivities of the fibrous amphiboles were investigated by measuring the production of the [DMPO, HO]? radical adduct using electron paramagnetic resonance (EPR) spectroscopy. Notably, significant chemical reactivity was observed; it was found to be comparable with—or, for the Libby sample, even higher than—that of fibrous tremolite (one of the six asbestos minerals). A positive linear correlation was observed when the production of HO? radical was plotted versus the Fe(II) content on the fibre surface. Data on fibrous tremolite obtained from previous studies were added to substantiate the correlation. These results provide evidence that Fe(II) at the fibre surface controls the production of radicals at the fibre surface. The observed relationship provides further confirmation that Fe topochemistry is strictly related to—though not solely responsible for—the toxicity of asbestos and other fibrous amphiboles that are not regulated as asbestos.