Tiina Torvela

Particulate Matter from Both Heavy Fuel Oil and Diesel Fuel Shipping Emissions Show Strong Biological Effects on Human Lung Cells at Realistic and Comparable In Vitro Exposure Conditions

Background Ship engine emissions are important with regard to lung and cardiovascular diseases especially in coastal regions worldwide. Known cellular responses to combustion particles include oxidative stress and inflammatory signalling. Objectives To provide a molecular link between the chemical and physical characteristics of ship emission particles and the cellular responses they elicit and to identify potentially harmful fractions in shipping emission aerosols. Methods Through an air-liquid interface exposure system, we exposed human lung cells under realistic in vitro conditions to exhaust fumes from a ship engine running on either common heavy fuel oil (HFO) or cleaner-burning diesel fuel (DF). Advanced chemical analyses of the exhaust aerosols were combined with transcriptional, proteomic and metabolomic profiling including isotope labelling methods to characterise the lung cell responses. Results The HFO emissions contained high concentrations of toxic compounds such as metals and polycyclic aromatic hydrocarbon, and were higher in particle mass. These compounds were lower in DF emissions, which in turn had higher concentrations of elemental carbon (“soot”). Common cellular reactions included cellular stress responses and endocytosis. Reactions to HFO emissions were dominated by oxidative stress and inflammatory responses, whereas DF emissions induced generally a broader biological response than HFO emissions and affected essential cellular pathways such as energy metabolism, protein synthesis, and chromatin modification. Conclusions Despite a lower content of known toxic compounds, combustion particles from the clean shipping fuel DF influenced several essential pathways of lung cell metabolism more strongly than particles from the unrefined fuel HFO. This might be attributable to a higher soot content in DF. Thus the role of diesel soot, which is a known carcinogen in acute air pollution-induced health effects should be further investigated. For the use of HFO and DF we recommend a reduction of carbonaceous soot in the ship emissions by implementation of filtration devices.

Effect of fuel zinc content on toxicological responses of particulate matter from pellet combustion in vitro.

Significant amounts of transition metals such as zinc, cadmium and copper can become enriched in the fine particle fraction during biomass combustion with Zn being one of the most abundant transition metals in wood combustion. These metals may have an important role in the toxicological properties of particulate matter (PM). Indeed, many epidemiological studies have found associations between mortality and PM Zn content. The role of Zn toxicity on combustion PM was investigated. Pellets enriched with 170, 480 and 2300 mg Zn/kg of fuel were manufactured. Emission samples were generated using a pellet boiler and the four types of PM samples; native, Zn-low, Zn-medium and Zn-high were collected with an impactor from diluted flue gas. The RAW 264.7 macrophage cell line was exposed for 24h to different doses (15, 50,150 and 300 μg ml(-1)) of the emission samples to investigate their ability to cause cytotoxicity, to generate reactive oxygen species (ROS), to altering the cell cycle and to trigger genotoxicity as well as to promote inflammation. Zn enriched pellets combusted in a pellet boiler produced emission PM containing ZnO. Even the Zn-low sample caused extensive cell cycle arrest and there was massive cell death of RAW 264.7 macrophages at the two highest PM doses. Moreover, only the Zn-enriched emission samples induced a dose dependent ROS response in the exposed cells. Inflammatory responses were at a low level but macrophage inflammatory protein 2 reached a statistically significant level after exposure of RAW 264.7 macrophages to ZnO containing emission particles. ZnO content of the samples was associated with significant toxicity in almost all measured endpoints. Thus, ZnO may be a key component producing toxicological responses in the PM emissions from efficient wood combustion. Zn as well as the other transition metals, may contribute a significant amount to the ROS responses evoked by ambient PM.

A Method to Study Agglomerate Breakup and Bounce During Impaction

The impaction behavior of agglomerates plays a significant role in nanoparticle technology. In order to be able to evaluate the process of de-agglomeration, the agglomerates are impacted onto a surface and forces are estimated from the breakup of the agglomerates. Several studies have used this principle; however, the simultaneous bounce and breakup of the agglomerates has received little attention. In this study, a method was devised to study both agglomerate breakup and bounce during impaction. In this method, the agglomerates were impacted onto an impaction plate located in a single stage micro-orifice uniform deposit impactor and the bounced particles were collected into a sampling chamber specially designed for this task. This way, the properties of the deposited and bounced particles can be examined with transmission electron microscopy, but in addition, the bounced particles can be analyzed with online measurement instruments, such as the scanning mobility particle sizer. Titanium dioxide (TiO2) and copper particles were used to test and validate the system, and the first impaction behavior results with this system were acquired using TiO2 agglomerates. It was evident that the agglomerates broke up during impaction under the conditions used in this study; the diameter of the particles decreased from 269 nm to 143 nm. It was found that half of the particles bounced. The particle diameter and the fractal dimension of the bounced particles were very similar to those of the particles that did not bounce. Copyright 2012 American Association for Aerosol Research

Effective Density and Morphology of Particles Emitted from Small-Scale Combustion of Various Wood Fuels

The effective density of fine particles emitted from small-scale wood combustion of various fuels were determined with a system consisting of an aerosol particle mass analyzer and a scanning mobility particle sizer (APM-SMPS). A novel sampling chamber was combined to the system to enable measurements of highly fluctuating combustion processes. In addition, mass-mobility exponents (relates mass and mobility size) were determined from the density data to describe the shape of the particles. Particle size, type of fuel, combustion phase, and combustion conditions were found to have an effect on the effective density and the particle shape. For example, steady combustion phase produced agglomerates with effective density of roughly 1 g cm(-3) for small particles, decreasing to 0.25 g cm(-3) for 400 nm particles. The effective density was higher for particles emitted from glowing embers phase (ca. 1-2 g cm(-3)), and a clear size dependency was not observed as the particles were nearly spherical in shape. This study shows that a single value cannot be used for the effective density of particles emitted from wood combustion.

Reference Particles for Toxicological Studies of Wood Combustion: Formation, Characteristics, and Toxicity Compared to Those of Real Wood Combustion Particulate Mass

Multiple studies show that particulate mass (PM) generated from incomplete wood combustion may induce adverse health issues in humans. Previous findings have shown that also the PM from efficient wood combustion may induce enhanced production of reactive oxygen species (ROS), inflammation, and cytotoxicity in vitro and in vivo. Underlying factors of these effects may be traced back to volatile inorganic transition metals, especially zinc, which can be enriched in the ultrafine fraction of biomass combustion particulate emission. In this study, nanoparticles composed of potassium, sulfur, and zinc, which are the major components forming inorganic fine PM, were synthesized and tested in vitro. In addition, in vitro toxicity of PM from efficient combustion of wood chips was compared with that of the synthesized particles. Cytotoxicity, cell cycle arrest, ROS generation, and tumor necrosis factor alpha release were related to zinc concentration in PM. Potassium sulfate and potassium carbonate did not induce toxic responses. In light of the provided data, it can be concluded that zinc, enriched in wood combustion emissions, caused the toxicity in all of the measured end points.

Break-Up and Bounce of TiO2 Agglomerates by Impaction

In this study, the impaction behavior of titanium dioxide (TiO2) agglomerates is evaluated, and the described method allows for the break-up and bounce of the particles to be monitored simultaneously. The degree of sintering and the primary particle size of the TiO2 agglomerates were varied. The agglomerates were impacted onto the impaction plate of a single-stage micro-orifice uniform impactor, after which the bounced particles were collected in a low-pressure sampling chamber for subsequent analyses. The particle trajectories were simulated to accurately estimate the impaction velocity, which is one of the key parameters in the impaction process. A high degree of sintering significantly reduced the number of broken bonds, whereas reducing the primary particle size caused only minor differences in the number of broken bonds. The particles that bounced but did not break up either had a smaller primary particle size or were sintered. Decreasing the primary particle size also reduced the mass-based fraction of the bouncing particles. Copyright 2014 American Association for Aerosol Research

In vitro toxicological effects of zinc containing nanoparticles with different physico-chemical properties

Nanomaterials (NM) exhibit novel physicochemical properties that determine their interaction with biological substrates and processes. Recent nano-technological advances are leading to wide usage of metallic nanoparticles (NPs) in various fields. However, the increasing use of NPs has led to their release into environment and the toxicity of NPs on human health has become a concern. Moreover, there are inadvertently generated metallic NPs which are formed during various human activities (e.g. metal processing and energy production). Unfortunately, there are still widespread controversies and ambiguities with respect to the toxic effects and mechanisms of metallic NPs, e.g. metal oxides including ZnO. In this study, we generated zinc containing NMs, and studied them in vitro. Different nano-sized particles containing Zn were compared in in vitro study to elucidate the physicochemical characteristics (e.g. chemical composition, solubility, shape and size of the particles) that determine cellular toxicity. Zn induced toxicity in macrophage cell line (RAW 264.7) was detected, leading to the cell cycle disruption, cell death and excitation of release of inflammatory mediators. The solubility and the size of Zn compounds had a major role in the induced toxic responses. The soluble particles reduced the cell viability, whereas the less soluble NPs significantly increased inflammation. Moreover, uptake of large ZnO NPs inside the cells was likely to play a key role in the detected cell cycle arrest.

Films of Graphene Nanomaterials Formed by Ultrasonic Spraying of Their Stable Suspensions

Graphene, a two-dimensional carbon allotrope, exhibits excellent optoelectronic properties. The assembly of graphene into films provides a platform to deepen the study of its interaction with varying surfaces, to engineer devices, and to develop functional materials. A general approach to produce graphene films consists of preparing a dispersion and laying it on a substrate of choice, followed by solvent evaporation. Here, we report the preparation of stable suspensions of new types of graphene nanomaterials namely, graphene nanoflowers (GNFs) and multi-layer graphene (MLG) flakes, in ethanol, N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP). Sprayable suspensions of both GNFs and MLG were prepared in DMF/ethanol, which showed high stability, without addition of any surfactant. The stable suspensions were used to deposit micrometer-thick MLG/GNF films on glass substrates. Calculations of initial droplet size and of timescale of droplet evaporation are performed and possible thermophoretic effects on droplet deposition discussed as well. Coating glass substrates with a methacrylic acid–methyl methacrylate (MA) copolymer prior to the deposition significantly improved the adhesion of the nanomaterials to the substrate. With the MA coating, a substrate coverage of nearly 100% was achieved at 14-min spraying time for 0.05 wt% GNF and 0.1 wt% MLG suspensions. Raman spectra of the GNF and MLG films reveal that the films were made of MLG in which the individual graphene layers rotated from each other as in turbostratic graphene. This work provides a general approach to prepare graphene nanomaterial suspensions and to create films for a variety of applications. The spraying process applied in the current work is highly scalable and allows control of film characteristics through process parameters. Copyright 2015 American Association for Aerosol Research

Physicochemical Characterization of Aerosol Generated in the Gas Tungsten Arc Welding of Stainless Steel.

OBJECTIVES Exposure to stainless steel (SS) welding aerosol that contain toxic heavy metals, chromium (Cr), manganese (Mn), and nickel (Ni), has been associated with numerous adverse health effects. The gas tungsten arc welding (GTAW) is commonly applied to SS and produces high number concentration of substantially smaller particles compared with the other welding techniques, although the mass emission rate is low. Here, a field study in a workshop with the GTAW as principal welding technique was conducted to determine the physicochemical properties of the airborne particles and to improve the understanding of the hazard the SS welding aerosols pose to welders. METHODS Particle number concentration and number size distribution were measured near the breathing zone (50cm from the arc) and in the middle of the workshop with condensation particle counters and electrical mobility particle sizers, respectively. Particle morphology and chemical composition were studied using scanning and transmission electron microscopy and energy-dispersive X-ray spectroscopy. RESULTS In the middle of the workshop, the number size distribution was unimodal with the geometric mean diameter (GMD) of 46nm. Near the breathing zone the number size distribution was multimodal, and the GMDs of the modes were in the range of 10-30nm. Two different agglomerate types existed near the breathing zone. The first type consisted of iron oxide primary particles with size up to 40nm and variable amounts of Cr, Mn, and Ni replacing iron in the structure. The second type consisted of very small primary particles and contained increased proportion of Ni compared to the proportion of (Cr + Mn) than the first agglomerate type. CONCLUSIONS The alterations in the distribution of Ni between different welding aerosol particles have not been reported previously.

A Novel Porous Tube Reactor for Nanoparticle Synthesis with Simultaneous Gas-Phase Reaction and Dilution

A novel porous tube reactor that combines simultaneous reactions and continuous dilution in a single-stage gas-phase process was designed for nanoparticle synthesis. The design is based on the atmospheric pressure chemical vapor synthesis (APCVS) method. In comparison to the conventional hot wall chemical vapor synthesis reactor, the APCVS method offers an effective process for the synthesis of ultrafine metal particles with controlled oxidation. In this study, magnetic iron and maghemite were synthesized using iron pentacarbonyl as a precursor. Morphology, size, and magnetic properties of the synthesized nanoparticles were determined. The X-ray diffraction results show that the porous tube reactor produced nearly pure iron or maghemite nanoparticles with crystallite sizes of 24 and 29 nm, respectively. According to the scanning mobility particle sizer data, the geometric number mean diameter was 110 nm for iron and 150 nm for the maghemite agglomerates. The saturation magnetization value of iron was 150 emu/g and that of maghemite was 12 emu/g, measured with superconducting quantum interference device (SQUID) magnetometry. A computational fluid dynamics (CFD) simulation was used to model the temperature and flow fields and the decomposition of the precursor as well as the mixing of the precursor vapor and the reaction gas in the reactor. An in-house CFD model was used to predict the extent of nucleation, coagulation, sintering, and agglomeration of the iron nanoparticles. CFD simulations predicted a primary particle size of 36 nm and an agglomerate size of 134 nm for the iron nanoparticles, which agreed well with the experimental data. Copyright 2015 American Association for Aerosol Research