Notice on a methodology for characterizing emissions of ultrafine particles/nanoparticles in microenvironments

Bearing in mind the potential adverse health effects of ultrafine particles, it is of paramount importance to perform effective monitoring of nanosized particles in several microenvironments, which may include ambient air, indoor air, and also occupational environments. In fact, effective and accurate monitoring is the first step to obtaining a set of data that could be used further on to perform subsequent evaluations such as risk assessment and epidemiologic studies, thus proposing good working practices such as containment measures in order to reduce occupational exposure. This paper presents a useful methodology for monitoring ultrafine particles/nanoparticles in several microenvironments, using online analyzers and also sampling systems that allow further characterization on collected nanoparticles. This methodology was validated in three case studies presented in the paper, which assess monitoring of nanosized particles in the outdoor atmosphere, during cooking operations, and in a welding workshop.

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Characterization of airborne particles generated from metal active gas welding process

This study is focused on the characterization of particles emitted in the metal active gas welding of carbon steel using mixture of Ar + CO2, and intends to analyze which are the main process parameters that influence the emission itself. It was found that the amount of emitted particles (measured by particle number and alveolar deposited surface area) are clearly dependent on the distance to the welding front and also on the main welding parameters, namely the current intensity and heat input in the welding process. The emission of airborne fine particles seems to increase with the current intensity as fume-formation rate does. When comparing the tested gas mixtures, higher emissions are observed for more oxidant mixtures, that is, mixtures with higher CO2 content, which result in higher arc stability. These mixtures originate higher concentrations of fine particles (as measured by number of particles by cm 3 of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more severe worker's exposure.

The effect of metal transfer modes and shielding gas composition on the emission of ultraafine particles in MAG steel welding

The present study aims to characterize ultrafine particles emitted during gas metal arc welding of mild steel and stainless steel, using different shielding gas mixtures, and to evaluate the effect of metal transfer modes, controlled by both processing parameters and shielding gas composition, on the quantity and morphology of the ultrafine particles. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the main welding parameters, namely the current intensity and the heat input of the Welding process. The emission of airborne ultrafine particles increases with the current intensity as fume formation rate does. When comparing the shielding gas mixtures, higher emissions were observed for more oxidizing mixtures, that is, with higher CO2 content, which means that these mixtures originate higher concentrations of ultrafine particles (as measured by number of particles. by cubic centimeter of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding welders exposure.

Quantitative description of the self-assembly of patchy particles into chains and rings

We numerically study a simple fluid composed of particles having a hard-core repulsion complemented by two patchy attractive sites on the particle poles. An appropriate choice of the patch angular width allows for the formation of ring structures which, at low temperatures and low densities, compete with the growth of linear aggregates. The simplicity of the model makes it possible to compare simulation results and theoretical predictions based on the Wertheim perturbation theory, specialized to the case in which ring formation is allowed. Such a comparison offers a unique framework for establishing the quality of the analytic predictions. We find that the Wertheim theory describes remarkably well the simulation results.

Contribuição para a caracterização da emissão de nanopartículas em processos de soldadura e avaliação de riscos decorrentes do processo

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de processos químicos

Phase diagrams of particles with dissimilar patches: X-junctions and Y-junctions

We use Wertheim's first-order perturbation theory to investigate the phase behaviour and the structure of coexisting fluid phases for a model of patchy particles with dissimilar patches (two patches of type A and f(B) patches of type B). A patch of type alpha = {A, B} can bond to a patch of type beta = {A, B} in a volume nu(alpha beta), thereby decreasing the internal energy by epsilon(alpha beta). We analyse the range of model parameters where AB bonds, or Y-junctions, are energetically disfavoured (epsilon(AB) < epsilon(AA)/2) but entropically favoured (nu(AB) >> nu(alpha alpha)), and BB bonds, or X-junctions, are energetically favoured (epsilon(BB) > 0). We show that, for low values of epsilon(BB)/epsilon(AA), the phase diagram has three different regions: (i) close to the critical temperature a low-density liquid composed of long chains and rich in Y-junctions coexists with a vapour of chains; (ii) at intermediate temperatures there is coexistence between a vapour of short chains and a liquid of very long chains with X-and Y-junctions; (iii) at low temperatures an ideal gas coexists with a high-density liquid with all possible AA and BB bonds formed. It is also shown that in region (i) the liquid binodal is reentrant (its density decreases with decreasing temperature) for the lower values of epsilon(BB)/epsilon(AA). The existence of these three regions is a consequence of the competition between the formation of X- and Y-junctions: X-junctions are energetically favoured and thus dominate at low temperatures, whereas Y-junctions are entropically favoured and dominate at higher temperatures.

On the assessment of exposure to airborne ultrafine particles in urban environments

The aim of this study was to contribute to the assessment of exposure levels of ultrafine particles in the urban environment of Lisbon, Portugal, due to automobile traffic, by monitoring lung deposited alveolar surface area (resulting from exposure to ultrafine particles) in a major avenue leading to the town center during late spring, as well as in indoor buildings facing it. Data revealed differentiated patterns for week days and weekends, consistent with PM2.5 and PM10 patterns currently monitored by air quality stations in Lisbon. The observed ultrafine particulate levels may be directly correlated with fluxes in automobile traffic. During a typical week, amounts of ultrafine particles per alveolar deposited surface area varied between 35 and 89.2 μm2/cm3, which are comparable with levels reported for other towns in Germany and the United States. The measured values allowed for determination of the number of ultrafine particles per cubic centimeter, which are comparable to levels reported for Madrid and Brisbane. In what concerns outdoor/indoor levels, we observed higher levels (32 to 63%) outdoors, which is somewhat lower than levels observed in houses in Ontario.

Comparison of deposited surface area of airborne ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

Impact of Sahara dust transport on Cape Verde atmospheric element particles

The objectives of this study were to (1) conduct an elemental characterization of airborne particles sampled in Cape Verde and (2) assess the influence of Sahara desert on local suspended particles. Particulate matter (PM10) was collected in Praia city (14°94'N; 23°49'W) with a low-volume sampler in order to characterize its chemical composition by k0-INAA. The filter samples were first weighed and subsequently irradiated at the Portuguese Research Reactor. Results showed that PM10 concentrations in Cape Verde markedly exceeded the health-based air quality standards defined by the European Union (EU), World Health Organization (WHO), and U.S. Environmental Protection Agency (EPA), in part due to the influence of Sahara dust transport. The PM10 composition was characterized essentially by high concentrations of elements originating from the soil (K, Sm, Co, Fe, Sc, Rb, Cr, Ce, and Ba) and sea (Na), and low concentrations of anthropogenic elements (As, Zn, and Sb). In addition, the high concentrations of PM measured in Cape Verde suggest that health of the population may be less affected compared with other sites where PM10 concentrations are lower but more enriched with toxic elements.

Monitorization of alveolar deposited surface area of nanoparticles and ultrafine particles in different environments

Nanotechnology is an important emerging industry with a projected annual market of around one trillion dollars by 2015. It involves the control of atoms and molecules to create new materials with a variety of useful functions. Although there are advantages on the utilization of these nano-scale materials, questions related with its impact over the environment and human health must be addressed too, so that potential risks can be limited at early stages of development. At this time, occupational health risks associated with manufacturing and use of nanoparticles are not yet clearly understood. However, workers may be exposed to nanoparticles through inhalation at levels that can greatly exceed ambient concentrations. Current workplace exposure limits are based on particle mass, but this criteria could not be adequate in this case as nanoparticles are characterized by very large surface area, which has been pointed out as the distinctive characteristic that could even turn out an inert substance into another substance exhibiting very different interactions with biological fluids and cells. Therefore, it seems that, when assessing human exposure based on the mass concentration of particles, which is widely adopted for particles over 1 μm, would not work in this particular case. In fact, nanoparticles have far more surface area for the equivalent mass of larger particles, which increases the chance they may react with body tissues. Thus, it has been claimed that surface area should be used for nanoparticle exposure and dosing. As a result, assessing exposure based on the measurement of particle surface area is of increasing interest. It is well known that lung deposition is the most efficient way for airborne particles to enter the body and cause adverse health effects. If nanoparticles can deposit in the lung and remain there, have an active surface chemistry and interact with the body, then, there is potential for exposure. It was showed that surface area plays an important role in the toxicity of nanoparticles and this is the metric that best correlates with particle-induced adverse health effects. The potential for adverse health effects seems to be directly proportional to particle surface area. The objective of the study is to identify and validate methods and tools for measuring nanoparticles during production, manipulation and use of nanomaterials.

Emission of airborne ultrafine particles during welding of steel plates

The present study is focused on the characterization of ultrafine particles emitted in welding of steel using mixtures of Ar+CO2, and intends to analyze which are the main process parameters which may have influence on the emission itself. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the distance to the welding front and also from the main welding parameters, namely the current intensity and heat input in the welding process. The emission of airborne ultrafine particles seem to increase with the current intensity as fume formation rate does. When comparing the tested gas mixtures, higher emissions are observed for more oxidant mixtures, that is, mixtures with higher CO2 content, which result in higher arc stability. The later mixtures originate higher concentrations of ultrafine particles (as measured by number of particles by cm3 of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding worker's exposure. © 2014 Sociedade Portuguesa de Materiais (SPM). Published by Elsevier España, S.L. All rights reserved.

Comparison of deposited surface area of airbone ultrafine particles generated from two welding processes

This article describes work performed on the assessment of the levels of airborne ultrafine particles emitted in two welding processes metal-active gas (MAG) of carbon steel and friction-stir welding (FSW) of aluminium in terms of deposited area in alveolar tract of the lung using a nanoparticle surface area monitor analyser. The obtained results showed the dependence from process parameters on emitted ultrafine particles and clearly demonstrated the presence of ultrafine particles, when compared with background levels. The obtained results showed that the process that results on the lower levels of alveolar-deposited surface area is FSW, unlike MAG. Nevertheless, all the tested processes resulted in important doses of ultrafine particles that are to be deposited in the human lung of exposed workers.

On the assessment of exposure to airborne ultrafine particles in urban environments

The aim of this study was to contribute to the assessment of exposure levels of ultrafine particles in the urban environment of Lisbon, Portugal, due to automobile traffic, by monitoring lung deposited alveolar surface area (resulting from exposure to ultrafine particles) in a major avenue leading to the town center during late spring, as well as in indoor buildings facing it. Data revealed differentiated patterns for week days and weekends, consistent with PM2.5 and PM10 patterns currently monitored by air quality stations in Lisbon. The observed ultrafine particulate levels may be directly correlated with fluxes in automobile traffic. During a typical week, amounts of ultrafine particles per alveolar deposited surface area varied between 35 and 89.2 mu m2/cm3, which are comparable with levels reported for other towns in Germany and the United States. The measured values allowed for determination of the number of ultrafine particles per cubic centimeter, which are comparable to levels reported for Madrid and Brisbane. In what concerns outdoor/indoor levels, we observed higher levels (32 to 63%) outdoors, which is somewhat lower than levels observed in houses in Ontario.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.