Mario Commodo

SOOT AND NANOPARTICLE FORMATION IN LAMINAR AND TURBULENT FLAMES

A new optical diagnostic method has been developed based on the interaction of a pulsed UV laser source with combustion-generated aerosols. This method allows characterization of nanoparticles of organic carbon (NOC) and soot by point measurements. Fluorescence and incandescence measurements induced by the fifth harmonic of a Nd-YAG laser at 213 nm are used for the determination of the volume fractions of particulates in a laminar premixed flame and in a turbulent non-premixed flame of ethylene/air. The selected light source enhances the fluorescence of NOC, which exhibit a large absorption band between 200 and 250 nm and also heats up soot particles to give incandescent emission. Ultraviolet emission signals are correlated with NOC extinction coefficients, while LII signals are correlated with extinction coefficients in the visible region. Laser light scattering measurements are used to estimate the mean sizes of both classes of particles.

Characterization of Combustion-Generated Carbonaceous Nanoparticles by Size-Dependent Ultraviolet Laser Photoionization

Photoelectric charging of particles is a powerful tool for online characterization of submicrometer aerosol particles. Indeed photoionization based techniques have high sensitivity and chemical selectivity. Moreover, they yield information on electronic properties of the material and are sensitive to the state of the surface. In the present study the photoionization charging efficiency, i.e., the ratio between the generated positive ions and the corresponding neutral ones, for different classes of flame-generated carbonaceous nanoparticles was measured. The fifth harmonics of a Nd:YAG laser, 213 nm (5.82 eV), was used as an ionization source for the combustion generated nanoparticles, whereas a differential mobility analyzer (DMA) coupled to a Faraday cup electrometer was used for particle classification and detection. Carbonaceous nanoparticles in the nucleation mode, i.e., sizes ranging from 1 to 10 nm, show a photoionization charging efficiency clearly dependent on the flame conditions. In particular, we observed that the richer the flame is, i.e., the higher the equivalent ratio is, the higher the photon charging efficiency is. We hypothesized that such an increase in the photoionization propensity of the carbonaceous nanoparticles from richer flame condition is associated to the presence within the particles of larger aromatic moieties. The results clearly show that photoionization is a powerful diagnostic tool for the physical-chemical characterization of combustion aerosol, and it may lead to further insights into the soot formation mechanism.

Flame-Formed Carbon Nanoparticles: Morphology, Interaction Forces, and Hamaker Constant from AFM

Interaction forces acting between combustion-generated carbon particles were studied by using atomic force microscopy (AFM). To this aim, carbon nanoparticles were produced in fuel-rich ethylene/air laminar premixed flames with different equivalent ratios Φ, and analyzed at a fixed residence time in the flame. Particles were collected on mica substrates by means of a thermophoretic sampling system and then analyzed by AFM. A characterization of particle dimension and morphology were performed operating AFM in semicontact mode, showing that the shape of the particles collected on a sampling plate is never spherical. Increasing the flame-equivalent ratio, particle shape moves from an almost atomically thick object to thicker compounds, indicating the transformation from particles made of small, defective graphene-like sheets to particles containing stacked aromatic layers. Attractive and adhesive forces between a titanium nitride probe and sampled particles were calculated from force–distance curves acquired in AFM force spectroscopy mode. Assuming that van der Walls forces are the main contribution to attractive forces, the measurement of attractive forces allowed the evaluation of the Hamaker constant for the carbon particles as a function of the flame-equivalent ratio. The comparison of the measured Hamaker constants with the values for benzene and HOPG, suggests a continuous increase of the aromatic domains and the three-dimensional order within the particles when the flame-equivalent ratio increases. Copyright 2015 American Association for Aerosol Research

An Experimental and Modelling Study of Particulate Formation in Premixed Flames Burning Methane

In this article we present an experimental and modeling study of Organic Carbon (OC) particles, with a typical size range of 1–10 nm, and soot particles, with sizes in the range 10–100 nm, formed in premixed methane flames at atmospheric pressure. An optical diagnostic method based on the interaction of an ultraviolet source, corresponding to the fifth harmonic of a Nd:YAG laser, with combustion-generated aerosols was used in order to measure the concentration profiles of both OC and soot particles with high spatial resolution. The high energy of the selected harmonic induces fluorescence from aromatic chromophoric groups and also allows soot particles to heat up and emit incandescent radiation. Optical measurements data are compared with numerical modeling simulations. The experimental data, in agreement with the model results, show that methane burned in slightly rich conditions forms prevalently organic particulate with mean size lower than 10 nm, while soot formation is observable only in very rich conditions.

Particle Inception in a Laminar Premixed Flame of Benzene

Spectral optical techniques, including light extinction and laser induce fluorescence and incandescence measurements, are combined to characterize large-molecule soot precursors and soot in a slightly sooting flame of benzene at atmospheric pressure. Light absorption coupled to in-situ light scattering measurements and ex-situ Atomic Force Microscopy also allowed the evaluation of particle sizes. In the benzene flame high molecular mass structures with typical sizes of 3–4 nm are formed in the main oxidation region of the flame. The radical-rich flame environment in which these compounds are formed promotes their dehydrogenation increasing the level of their aromaticity. As a result, nanoparticles with typical sizes of about 5 nm, absorbing and fluorescing in the visible are formed. These compounds reach a maximum concentration just before the appearance of incandescent soot particles.

Human peripheral blood mononuclear cells (PBMCs) from smokers release higher levels of IL-1-like cytokines after exposure to combustion-generated ultrafine particles

Ultrafine particles (UFP) generated by combustion processes are often associated with adverse health effects. However, little is known about the inflammatory processes generated by UFP that may underlie their toxicological activity. Murine macrophages (J774.1 cells) and human peripheral blood mononuclear cells (PBMCs) were used to evaluate the molecular mechanism underlying the pro-inflammatory activity of UFP. The addition of soot particles to J774.1 cells induced a concentration-dependent release of IL-1α, IL-1β and IL-33 This effect was not associated with cell death and, in contrast to literature, was pronounced at very low concentrations (5–100u2009pg/ml). Similarly, UFP induced the release of IL-1α, IL-18 and IL-33 by PBMCs. However, this effect was solely observed in PBMCs obtained from smokers, as the PBMCs from non-smokers instead released higher levels of IL-10. The release of these cytokines after UFP exposure was caspase-1- and NLRP3 inflammasome-dependent in PBMCs from healthy smokers, whereas IL-1α release was calpain-dependent. These results show that UFP at very low concentrations are able to give rise to an inflammatory process that is responsible for IL-1α, IL-18 and IL-33 release, which is pronounced in PBMCs from smokers, confirming that these individuals are especially susceptible to inflammatory-based airway diseases once exposed to air pollution.

Antimicrobial activity of flame-synthesized nano-TiO2 coatings

TiO2 in the form of nanocrystals possesses photocatalyst properties leading to excellent capability of degrading a number of environmental contaminants such as organics, bacteria, and viruses. However, the antimicrobial activity of nano-TiO2 coatings against different microorganisms is not yet well established. Candida albicans, Aspergillus niger, Staphylococcus aureus and Streptococcus mutans are common nosocomial and environmental pathogens responsible for biofilm-associated infections especially in indoor environments. In this study, we produced thin coatings of TiO2 nanoparticles on aluminum substrates and assessed whether they may prevent fungi and bacteria biofilm formation and whether this may be a synergistic effect of TiO2 nanoparticles with UV irradiation, which is more representative of the natural conditions for passive devices. Coatings of flame-synthesized nanoparticles were produced by direct thermophoretic deposition on aluminum substrates through a rotating disk inserted in the flame. Particle and coating characterization was performed by means of differential mobility analysis, Raman and X-ray diffraction spectroscopy. Microbial biofilm formation on substrates with different TiO2 thicknesses were evaluated by the colorimetric crystal violet method and quantified by spectrophotometry in four different fungi and bacteria strains; the results were corroborated by scanning electron microscopy analysis. Substrates with minimal TiO2 nanoparticle layers demonstrated a strong anti-biofilm effect against both fungi and bacteria, due to the well-known cellular component photo-oxidation and to the enhanced nanomaterial surface area. Interestingly, UV irradiation of the substrates at a low intensity for a short time demonstrated a significant enhancement of the titania antimicrobial activity. TiO2 nanoparticle coatings may be proposed as self-cleaning and self-disinfecting materials able to reduce microbial infections, especially in indoor environments where hygiene is needed.

Photoionization Study of Soot Precursor Nanoparticles in Laminar Premixed Ethylene/Ethanol Flames

The effect of ethanol addition in ethylene laminar premixed flames on the characteristics of soot precursor nanoparticles was investigated by aerosol photoionization technique. The fifth harmonic of a Nd:YAG laser, 213 nm (5.82 eV), was used as ionization source, while a differential mobility analyzer (DMA) coupled to a Faraday cup electrometer was used for ionized particle classification and detection. Carbonaceous nanoparticles in the nucleation mode, i.e., with sizes ranging from 1 to 10 nm, show a photoionization charging efficiency clearly dependent on the percentage of ethanol used as dopant in the flame. In particular, we observed that the more ethanol was added as fuel, the lower the particle photo-charging efficiency was. This result indicates a modification in the nanoparticle chemical structure as the amount of ethanol is increased. These experimental evidences may be explained by a decrease of aromaticity of the particles and/or by the presence of oxygen bonds within the nanoparticles.

Probing the equivalence ratio in partially premixed flames by combining optical techniques and modeling results

ABSTRACT Chemiluminescence and laser-induced breakdown spectroscopy (LIBS) measurements have been carried out in laminar ethylene/air partially premixed flames for real-time local equivalence ratio monitoring. OH* and CH* chemiluminescence measurements have been performed in the region where combustion processes mainly occur. Using LIBS measurements, the hydrogen to oxygen emission signal ratio has been obtained as an indicator of the fuel to air ratio and consequently of the mixing processes. Through a calibration procedure performed in nitrogen-diluted ethylene/air premixed flames of known equivalence ratio, the local values of the equivalence ratio have been derived in the flames under analysis. Target flames, proposed in the framework of the International Sooting Flame (ISF) workshop, have been investigated along the radius at different heights above the burner. Correspondingly, chemical kinetic modeling analysis has been performed and the results were compared with the experimental data in order to cross-check the reliability of both experimental techniques and modeling approach.

Chronic Obstructive Pulmonary Disease-Derived Circulating Cells Release IL-18 and IL-33 under Ultrafine Particulate Matter Exposure in a Caspase-1/8-Independent Manner

Chronic obstructive pulmonary disease (COPD) is considered the fourth-leading causes of death worldwide; COPD is caused by inhalation of noxious indoor and outdoor particles, especially cigarette smoke that represents the first risk factor for this respiratory disorder. To mimic the effects of particulate matter on COPD, we isolated peripheral blood mononuclear cells (PBMCs) and treated them with combustion-generated ultrafine particles (UFPs) obtained from two different fuel mixtures, namely, pure ethylene and a mixture of ethylene and dimethylfuran (the latter mimicking the combustion of biofuels). UFPs were separated in two fractions: (1) sub-10u2009nm particles, named nano organic carbon (NOC) particles and (2) primarily soot particles of 20–40u2009nm and their agglomerates (200u2009nm). We found that both NOC and soot UFPs induced the release of IL-18 and IL-33 from unstable/exacerbated COPD-derived PBMCs. This effect was associated with higher levels of mitochondrial dysfunction and derived reactive oxygen species, which were higher in PBMCs from unstable COPD patients after combustion-generated UFP exposure. Moreover, lower mRNA expression of the repairing enzyme OGG1 was associated with the higher levels of 8-OH-dG compared with non-smoker and smokers. It was interesting that IL-18 and IL-33 release from PBMCs of unstable COPD patients was not NOD-like receptor 3/caspase-1 or caspase-8-dependent, but rather correlated to caspase-4 release. This effect was not evident in stable COPD-derived PBMCs. Our data suggest that combustion-generated UFPs induce the release of caspase-4-dependent inflammasome from PBMCs of COPD patients compared with healthy subjects, shedding new light into the biology of this key complex in COPD.