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Abstract: In this paper, trace metals (As, Be, Cd, Cr, Hg Ni, Pb, Se and V) emission from the atmospheric entrained flow gasifier REGA at Karlsruhe Institute of Technology, Germany is presented. Elemental composition and metals concentration in glycol (model fuel) and straw char samples were determined. In order to achieve well defined and reproducible operating conditions, gasification experiments were carried out with glycol and slurry (straw char mixed with glycol) as fuel. Trace metals emission and distribution into particle and gas phase in syngas from gasification were measured according to US EPA method 29. During glycol gasification, metals concentration in syngas ranged from 0.1μg/Nm3 (V) to 4.6μg/Nm3 (Cr). In slurry gasification, metals concentration in syngas ranged from 2.4μg/Nm3 (Hg) to 53.2μg/Nm3 (Ni). Trace metals tend to volatilize more in reducing gasification environment. Tendency of metals to speciate into particle phase increased in slurry gasification than glycol gasification due to increased in particle concentration and unburned carbon content in syngas. The increase of particle and carbon content in syngas possessed strong influence in distribution behavior of As, Be and Pb, however, such influence was less for other metals studied. Mercury in syngas was speciated predominantly into elemental form followed by oxidized form whereas share of particle bond mercury was the least. [Copyright &y& Elsevier]

Abstract: The introduction of engineered nanostructured materials into a rapidly increasing number of industrial and consumer products will result in enhanced exposure to engineered nanoparticles. Workplace exposure has been identified as the most likely source of uncontrolled inhalation of engineered aerosolized nanoparticles, but release of engineered nanoparticles may occur at any stage of the lifecycle of (consumer) products. The dynamic development of nanomaterials with possibly unknown toxicological effects poses a challenge for the assessment of nanoparticle induced toxicity and safety. In this consensus document from a workshop on in-vitro cell systems for nanoparticle toxicity testing 1 [1] Workshop on ‘In-Vitro Exposure Studies for Toxicity Testing of Engineered Nanoparticles’ sponsored by the Association for Aerosol Research (GAeF), 5–6 September 2009, Karlsruhe, Germany. an overview is given of the main issues concerning exposure to airborne nanoparticles, lung physiology, biological mechanisms of (adverse) action, in-vitro cell exposure systems, realistic tissue doses, risk assessment and social aspects of nanotechnology. The workshop participants recognized the large potential of in-vitro cell exposure systems for reliable, high-throughput screening of nanoparticle toxicity. For the investigation of lung toxicity, a strong preference was expressed for air–liquid interface (ALI) cell exposure systems (rather than submerged cell exposure systems) as they more closely resemble in-vivo conditions in the lungs and they allow for unaltered and dosimetrically accurate delivery of aerosolized nanoparticles to the cells. An important aspect, which is frequently overlooked, is the comparison of typically used in-vitro dose levels with realistic in-vivo nanoparticle doses in the lung. If we consider average ambient urban exposure and occupational exposure at 5mg/m3 (maximum level allowed by Occupational Safety and Health Administration (OSHA)) as the boundaries of human exposure, the corresponding upper-limit range of nanoparticle flux delivered to the lung tissue is 3×10−5–5×10-3 μg/h/cm2 of lung tissue and 2–300particles/h/(epithelial) cell. This range can be easily matched and even exceeded by almost all currently available cell exposure systems. The consensus statement includes a set of recommendations for conducting in-vitro cell exposure studies with pulmonary cell systems and identifies urgent needs for future development. As these issues are crucial for the introduction of safe nanomaterials into the marketplace and the living environment, they deserve more attention and more interaction between biologists and aerosol scientists. The members of the workshop believe that further advances in in-vitro cell exposure studies would be greatly facilitated by a more active role of the aerosol scientists. The technical know-how for developing and running ALI in-vitro exposure systems is available in the aerosol community and at the same time biologists/toxicologists are required for proper assessment of the biological impact of nanoparticles. [Copyright &y& Elsevier]

A novel wet electrostatic precipitator is designed for control of fine aerosol from humid effluent gases. It operates on the principle of unipolar particle charging in a dc corona discharge in a high-velocity (> 20 m/s) ionizing stage and aerosol precipitation in the low-velocity (< 3 m/s) collection stage under the field of the particle's own space charge. The high gas velocity in the ionizing section diminishes the corona suppression at high particle number concentrations of H2SO4 and HCl aerosol. [ABSTRACT FROM AUTHOR]

A novel electrostatic collector CAROLA (Corona Aerosol Abscheider) for gas cleaning from submicrometer particles is described. The CAROLA concept is based on particle charging by corona discharge and subsequent particle removal in the grounded part of the collector. CAROLA collectors for fine oil mists and for fly ash were tested. The influence of the operation conditions on corona discharge was studied. It is shown that the CAROLA electrostatic collectors have high fractional removal efficiencies (>98% for particles >1 μm and 95%-98% for particles with sizes 0.3-1 μm), low operating voltages (10-20 kV), and low pressure drop (<200 Pa). The collection of charged particles without external electric field and the compact design provide a cost-effective solution for the removal of submicrometer particles from industrial off gases. [ABSTRACT FROM AUTHOR]

A central challenge for the safe design of nanomaterials (NMs) is the inherent variability of NM properties, both as produced and as they interact with and evolve in, their surroundings. This has led to uncertainty in the literature regarding whether the biological and toxicological effects reported for NMs are related to specific NM properties themselves, or rather to the presence of impurities or physical effects such as agglomeration of particles. Thus, there is a strong need for systematic evaluation of the synthesis and processing parameters that lead to potential variability of different NM batches and the reproducible production of commonly utilized NMs. The work described here represents over three years of effort across 14 European laboratories to assess the reproducibility of nanoparticle properties produced by the same and modified synthesis routes for four of the OECD priority NMs (silica dioxide, zinc oxide, cerium dioxide and titanium dioxide) as well as amine-modified polystyrene NMs, which are frequently employed as positive controls for nanotoxicity studies. For 46 different batches of the selected NMs, all physicochemical descriptors as prioritized by the OECD have been fully characterized. The study represents the most complete assessment of NMs batch-to-batch variability performed to date and provides numerous important insights into the potential sources of variability of NMs and how these might be reduced. [ABSTRACT FROM AUTHOR]

The applied surface dose is a key parameter for the measurement of toxic effects of airborne particles by air liquid interface exposure of human lung cells. Besides online measurement of the deposited particle mass by quartz crystal microbalance frequently other dose metrics such as particle size distribution, surface and agglomeration state are required. These particle properties and their spatial distribution can be determined by digital processing of micrographs obtained by transmission electron microscopy (TEM). Here, we report the development and characterization of a novel holder for film coated TEM copper grids, which allows for sampling under identical geometric and ambient conditions as in a cell culture chamber. The sample holder avoids artefacts by reliable grounding of the grids and improves handling of the grids to prevent damage of the sensitive film. This sample holder is applied during exposure experiments with titanium dioxide nanoparticles. The measured dose of 0.2 µg/cm² corresponds well to the mass loading signal of the quartz crystal microbalance. Additionally, the spatial distribution of particles on the sampling surface shows a good homogeneity of deposition. This novel sampling method allows verifying other dosimetry methods and gives additional information about particle properties and homogeneity of the dose. [ABSTRACT FROM AUTHOR]

• OMICs analysis reveals a strong impact of the gas phase of wood smoke. • CMAP indicates DPC agents as drivers of OMICs response. • Carbonyls were identified as DPC agents and key pollutants triggering DNA damage and stress signalling. Epidemiological studies identified air pollution as one of the prime causes for human morbidity and mortality, due to harmful effects mainly on the cardiovascular and respiratory systems. Damage to the lung leads to several severe diseases such as fibrosis, chronic obstructive pulmonary disease and cancer. Noxious environmental aerosols are comprised of a gas and particulate phase representing highly complex chemical mixtures composed of myriads of compounds. Although some critical pollutants, foremost particulate matter (PM), could be linked to adverse health effects, a comprehensive understanding of relevant biological mechanisms and detrimental aerosol constituents is still lacking. Here, we employed a systems toxicology approach focusing on wood combustion, an important source for air pollution, and demonstrate a key role of the gas phase, specifically carbonyls, in driving adverse effects. Transcriptional profiling and biochemical analysis of human lung cells exposed at the air–liquid-interface determined DNA damage and stress response, as well as perturbation of cellular metabolism, as major key events. Connectivity mapping revealed a high similarity of gene expression signatures induced by wood smoke and agents prompting DNA-protein crosslinks (DPCs). Indeed, various gaseous aldehydes were detected in wood smoke, which promote DPCs, initiate similar genomic responses and are responsible for DNA damage provoked by wood smoke. Hence, systems toxicology enables the discovery of critical constituents of complex mixtures i.e. aerosols and highlights the role of carbonyls on top of particulate matter as an important health hazard. [ABSTRACT FROM AUTHOR]

Indoor air pollution is associated with increased morbidity and mortality. Specifically, the health impact of emissions from domestic burning of biomass and coal is most relevant and is estimated to contribute to over 4 million premature deaths per year worldwide. Wood is the main fuel source for biomass combustion and the shift towards renewable energy sources will further increase emissions from wood combustion even in developed countries. However, little is known about the constituents of wood smoke and biological mechanisms that are responsible for adverse health effects. We exposed A549 lung epithelial cells to collected wood smoke particles and found an increase in cellular reactive oxygen species as well as a response to bioavailable polycyclic aromatic hydrocarbons. In contrast, cell vitality and regulation of the pro-inflammatory cytokine interleukin-8 were not affected. Using a candidate approach, we could recapitulate WSP toxicity by the combined actions of its constituents soot, metals and PAHs. The soot fraction and metals were found to be the most important factors for ROS formation, whereas the PAH response can be mimicked by the model PAH benzo[a]pyrene. Strikingly, PAHs adsorbed to WSPs were even more potent in activating target gene expression than B[a]P individually applied in suspension. As PAHs initiate multiple adverse outcome pathways and are prominent carcinogens, their role as key pollutants in wood smoke and its health effects warrants further investigation. The presented results suggest that each of the investigated constituents soot, metals and PAHs are major contributors to WSP toxicity. Mitigation strategies to prevent adverse health effects of wood combustion should therefore not only aim at reducing the emitted soot and PAHs but also the metal content, through the use of more efficient combustion appliances, and particle precipitation techniques, respectively. [ABSTRACT FROM AUTHOR]

Exposure to air pollution resulting from fossil fuel combustion has been linked to multiple short-term and long term health effects. In a previous study, exposure of lung epithelial cells to engine exhaust from heavy fuel oil (HFO) and diesel fuel (DF), two of the main fuels used in marine engines, led to an increased regulation of several pathways associated with adverse cellular effects, including pro-inflammatory pathways. In addition, DF exhaust exposure was shown to have a wider response on multiple cellular regulatory levels compared to HFO emissions, suggesting a potentially higher toxicity of DF emissions over HFO. In order to further understand these effects, as well as to validate these findings in another cell line, we investigated macrophages under the same conditions as a more inflammation-relevant model. An air-liquid interface aerosol exposure system was used to provide a more biologically relevant exposure system compared to submerged experiments, with cells exposed to either the complete aerosol (particle and gas phase), or the gas phase only (with particles filtered out). Data from cytotoxicity assays were integrated with metabolomics and proteomics analyses, including stable isotope-assisted metabolomics, in order to uncover pathways affected by combustion aerosol exposure in macrophages. Through this approach, we determined differing phenotypic effects associated with the different components of aerosol. The particle phase of diluted combustion aerosols was found to induce increased cell death in macrophages, while the gas phase was found more to affect the metabolic profile. In particular, a higher cytotoxicity of DF aerosol emission was observed in relation to the HFO aerosol. Furthermore, macrophage exposure to the gas phase of HFO leads to an induction of a pro-inflammatory metabolic and proteomic phenotype. These results validate the effects found in lung epithelial cells, confirming the role of inflammation and cellular stress in the response to combustion aerosols. [ABSTRACT FROM AUTHOR]

In vitro toxicity testing of airborne particles usually takes place in multi-well plates, where the cells are exposed to a suspension of particles in cell culture medium. Due to the artefacts caused by particle collection and preparation of suspensions, the air–liquid interface (ALI) exposure is challenging this conventional exposure technique to become the method of choice. The ALI technique allows for direct sampling of an aerosol and exposure of cell cultures to airborne particles. At the same time, it reflects the physiological conditions in the lung to a greater extent. So far, the available ALI systems have mostly been laboratory set-ups of the single components. Here, we present a mobile and complete system providing all process technology required for cell exposure experiments at dynamic aerosol sources. The system is controlled by a human machine interface (HMI) with standard routines for experiments and internal testing to assure reproducibility. It also provides documentation of the exposure experiment regarding process parameters and measured doses. The performance of this system is evaluated using fluorescein-sodium dosimetry, which is also used to determine the factor of dose enhancement by optional electrostatic deposition. The application of the system is shown for two different technical aerosol sources: wood smoke particles emitted by a household log wood stove and emissions from a ship diesel engine. After exposure of lung cells, cytotoxicity and gene regulation on a genome-wide scale were analysed. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Abstract: We developed a fluid dynamic model to predict the size and material dependent particle deposition efficiencies for a commercial available exposure chamber. Validated by measurements with SiO2 and polystyrene particle standards between 29nm and we obtained a parameterization of the particle deposition efficiency for a specific set of practically relevant flow, pressure and temperature conditions that can be used for accurate dose calculations at these conditions. Furthermore, the model predicts that a significant impact on the deposition efficiency due to the fractal-like structure of nanoparticle agglomerates is expected for cluster sizes beyond 200nm mobility equivalent diameter. For the commercially available gravitation–diffusion based exposure chamber investigated here at one specific flow rate, the results indicate that deposition rates of particles smaller than 100nm are too low in order to deposit mass doses that are equivalent to typical cytotoxic LOAELs determined in submerged experiments within reasonable times. [Copyright &y& Elsevier]

Abstract: A particle mass spectrometer has been used to investigate the formation of electrically charged species and soot particles in laminar premixed flames. The mass range was from 600–6×105 amu and extends from high molecular hydrocarbons to soot particles of 10nm diameter. The flames were stabilized on cooled porous plate burners. Acetylene/oxygen flames were investigated at low pressure (30mbar), and ethylene/air flames were investigated at atmospheric pressure. Soot particles could only be detected in flames showing yellow luminosity, i.e. above the critical C/O-ratio for soot formation. Both positively and negatively charged particles were found, the positive charge dominating in the low pressure acetylene/oxygen flames, the negative charge dominating in the atmospheric ethylene/air flames. With the assumption of spherical shape and constant density, the mass spectra were converted to size spectra. Usually, they show a multiple peak structure which is somewhat difficult to interpret. There are indications that particles may carry multiple (1–2) charges, and also that particles of different types may coexist beside polyaromatic and polyhedral species in the early stage of particle inception. [Copyright &y& Elsevier]

The electron-beam (EB) degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes: BTEX) in groundwater strip gas, which in the present work has been modeled by the introduction of the desired aromatic(s) to a stream of air or another gas, such as oxygen, is initiated essentially by the addition of [sup ...]OH radicals to the aromatic ring, giving rise to hydroxycyclohexadienyl radicals, which form the corresponding peroxyl radicals upon addition of oxygen. As studied in some detail with benzene as a BTEX representative, various reactions of these lead to numerous oxidation products in a cascade of reactions, including the decomposition of products under the prevailing conditions of high turnover of the initial aromatic. Importantly, hydroxycyclohexadienylperoxyl radical formation is partly reversible, and the reactions of the hydroxycyclohexadienyl radicals, which thus have a significant presence in these systems, must therefore also be taken into consideration. In the gas phase, in contrast to the aqueous phase (see Part 1), the reactions of the hydroxycyclohexadienyl radicals lead to oligomeric products that appear to contribute, in addition to ionic clusters, to nucleation for the aerosols observed. Various nitrated products, among them nitrophenols, are observed when air is used for the stripping. However, these studies did not clear the pilot plant stage, since BTEX degradation using a bioreactor carried out in parallel was so successful that the EB technology was judged to be noncompetitive. As for the latter, expensive equipment consisting of a stripper, the EB machine, and an aerosol precipitator would be required. The condensed aerosols are biorefractory and would require further treatment for detoxification. [ABSTRACT FROM AUTHOR]

Extensive production and use of nanomaterials (NMs), such as titanium dioxide (TiO2), raises concern regarding their potential adverse effects to humans. While considerable efforts have been made to assess the safety of TiO2 NMs using in vitro and in vivo studies, results obtained to date are unreliable, possibly due to the dynamic agglomeration behavior of TiO2 NMs. Moreover, agglomerates are of prime importance in occupational exposure scenarios, but their toxicological relevance remains poorly understood. Therefore, the aim of this study was to investigate the potential pulmonary effects induced by TiO2 agglomerates of different sizes at the air–liquid interface (ALI), which is more realistic in terms of inhalation exposure, and compare it to results previously obtained under submerged conditions. A nano-TiO2 (17 nm) and a non-nano TiO2 (117 nm) was selected for this study. Stable stock dispersions of small agglomerates and their respective larger counterparts of each TiO2 particles were prepared, and human bronchial epithelial (HBE) cells were exposed to different doses of aerosolized TiO2 agglomerates at the ALI. At the end of 4h exposure, cytotoxicity, glutathione depletion, and DNA damage were evaluated. Our results indicate that dose deposition and the toxic potential in HBE cells are influenced by agglomeration and exposure via the ALI induces different cellular responses than in submerged systems. We conclude that the agglomeration state is crucial in the assessment of pulmonary effects of NMs. [ABSTRACT FROM AUTHOR]

Reliable and predictive in vitro assays for hazard assessments of manufactured nanomaterials (MNMs) are still limited. Specifically, exposure systems which more realistically recapitulate the physiological conditions in the lung are needed to predict pulmonary toxicity. To this end, air-liquid interface (ALI) systems have been developed in recent years which might be better suited than conventional submerged exposure assays. However, there is still a need for rigorous side-by-side comparisons of the results obtained with the two different exposure methods considering numerous parameters, such as different MNMs, cell culture models and read outs. In this study, human A549 lung epithelial cells and differentiated THP-1 macrophages were exposed under submerged conditions to two abundant types of MNMs i.e., ceria and titania nanoparticles (NPs). Membrane integrity, metabolic activity as well as pro-inflammatory responses were recorded. For comparison, A549 monocultures were also exposed at the ALI to the same MNMs. In the case of titania NPs, genotoxicity was also investigated. In general, cells were more sensitive at the ALI compared to under classical submerged conditions. Whereas ceria NPs triggered only moderate effects, titania NPs clearly initiated cytotoxicity, pro-inflammatory gene expression and genotoxicity. Interestingly, low doses of NPs deposited at the ALI were sufficient to drive adverse outcomes, as also documented in rodent experiments. Therefore, further development of ALI systems seems promising to refine, reduce or even replace acute pulmonary toxicity studies in animals. [ABSTRACT FROM AUTHOR]