Toxicity of particles derived from combustion of Ethiopian traditional biomass fuels in human bronchial and macrophage-like cells.

The combustion of traditional fuels in low-income countries, including those in sub-Saharan Africa, leads to extensive indoor particle exposure. Yet, the related health consequences in this context are understudied. This study aimed to evaluate the in vitro toxicity of combustion-derived particles relevant for Sub-Saharan household environments. Particles (< 2.5 µm) were collected using a high-volume sampler during combustion of traditional Ethiopian biomass fuels: cow dung, eucalyptus wood and eucalyptus charcoal. Diesel exhaust particles (DEP, NIST 2975) served as reference particles. The highest levels of particle-bound polycyclic aromatic hydrocarbons (PAHs) were found in wood (3219 ng/mg), followed by dung (618 ng/mg), charcoal (136 ng/mg) and DEP (118 ng/mg) (GC-MS). BEAS-2B bronchial epithelial cells and THP-1 derived macrophages were exposed to particle suspensions (1-150 µg/mL) for 24 h. All particles induced concentration-dependent genotoxicity (comet assay) but no pro-inflammatory cytokine release in epithelial cells, whereas dung and wood particles also induced concentration-dependent cytotoxicity (Alamar Blue). Only wood particles induced concentration-dependent cytotoxicity and genotoxicity in macrophage-like cells, while dung particles were unique at increasing secretion of pro-inflammatory cytokines (IL-6, IL-8, TNF-α). In summary, particles derived from combustion of less energy dense fuels like dung and wood had a higher PAH content and were more cytotoxic in epithelial cells. In addition, the least energy dense and cheapest fuel, dung, also induced pro-inflammatory effects in macrophage-like cells. These findings highlight the influence of fuel type on the toxic profile of the emitted particles and warrant further research to understand and mitigate health effects of indoor air pollution.

Compositional tuning of gas-phase synthesized Pd-Cu nanoparticles.

Bimetallic nanoparticles have gained significant attention in catalysis as potential alternatives to expensive catalysts based on noble metals. In this study, we investigate the compositional tuning of Pd-Cu bimetallic nanoparticles using a physical synthesis method called spark ablation. By utilizing pure and alloyed electrodes in different configurations, we demonstrate the ability to tailor the chemical composition of nanoparticles within the range of approximately 80 : 20 at% to 40 : 60 at% (Pd : Cu), measured using X-ray fluorescence (XRF) and transmission electron microscopy energy dispersive X-ray spectroscopy (TEM-EDXS). Time-resolved XRF measurements revealed a shift in composition throughout the ablation process, potentially influenced by material transfer between electrodes. Powder X-ray diffraction confirmed the predominantly fcc phase of the nanoparticles while high-resolution TEM and scanning TEM-EDXS confirmed the mixing of Pd and Cu within individual nanoparticles. X-ray photoelectron and absorption spectroscopy were used to analyze the outermost atomic layers of the nanoparticles, which is highly important for catalytic applications. Such comprehensive analyses offer insights into the formation and structure of bimetallic nanoparticles and pave the way for the development of efficient and affordable catalysts for various applications.

Missed Evaporation from Atmospherically Relevant Inorganic Mixtures Confounds Experimental Aerosol Studies.

Sea salt aerosol particles are highly abundant in the atmosphere and play important roles in the global radiative balance. After influence from continental air, they are typically composed of Na+, Cl-, NH4+, and SO42- and organics. Analogous particle systems are often studied in laboratory settings by atomizing and drying particles from a solution. Here, we present evidence that such laboratory studies may be consistently biased in that they neglect losses of solutes to the gas phase. We present experimental evidence from a hygroscopic tandem differential mobility analyzer and an aerosol mass spectrometer, further supported by thermodynamic modeling. We show that, at normally prevailing laboratory aerosol mass concentrations, for mixtures of NaCl and (NH4)2SO4, a significant portion of the Cl- and NH4+ ions are lost to the gas phase, in some cases, leaving mainly Na2SO4 in the dry particles. Not considering losses of solutes to the gas phase during experimental studies will likely result in misinterpretation of the data. One example of such data is that from particle water uptake experiments. This may bias the explanatory models constructed from the data and introduce errors inte predictions made by air quality or climate models.

Influence of Airborne Particles' Chemical Composition on SVOC Uptake from PVC Flooring-Time-Resolved Analysis with Aerosol Mass Spectrometry.

We sampled ammonium sulfate particles and indoor particles of outdoor origin through a small chamber covered with polyvinyl chloride flooring. We measured the uptake of semivolatile organic compounds (SVOCs) by the airborne particles in real time. The particles acquired SVOC mass fractions up to 10%. The phthalate ester (di(2-ethylhexyl)phthalate) (DEHP), a known endocrine disruptor, contributed by approximately half of the sorbed SVOC mass. The indoor particles acquired a higher DEHP fraction than laboratory-generated ammonium sulfate aerosol. We attribute this increased uptake to absorption by organic matter present in the indoor particles. Using a thermodenuder to remove volatile components, predominantly organics, reduced the SVOC uptake. Positive matrix factorization applied to the organic mass spectra suggests that hydrocarbon-like organic aerosol (typically fresh traffic exhaust) sorbs DEHP more efficiently than aged organic aerosol. The SVOC uptake is one of the processes that modify outdoor pollution particles after they penetrate buildings, where the majority of exposure occurs. Particles from indoor sources, typically dominated by organic matter, will undergo such processes as well. Aerosol mass spectrometry improves the time resolution of experimental investigations into these processes and enables experiments with lower, relevant particle concentrations. Additionally, particle size-resolved results are readily obtained.

Excretion of Urinary Metabolites of the Phthalate Esters DEP and DEHP in 16 Volunteers after Inhalation and Dermal Exposure.

Phthalate esters are suspected endocrine disruptors that are found in a wide range of applications. The aim of this study was to determine the excretion of urinary metabolites in 16 individuals after inhalation and/or dermal exposure to 100⁻300 µg/m³ of deuterium-labelled diethyl phthalate (D4-DEP) and bis(2-ethylhexyl) phthalate (D4-DEHP). Dermal exposure in this study represents a case with clean clothing acting as a barrier. After inhalation, D4-DEP and D4-DEHP metabolites were excreted rapidly, though inter-individual variation was high. D4-DEP excretion peaked 3.3 h (T½ of 2.1 h) after combined inhalation and dermal exposure, with total excreted metabolite levels ranging from 0.055 to 2.351 nmol/nmol/m³ (nmol of urinary metabolites per phthalates air concentration in (nmol/m³)). After dermal exposure to D4-DEP, metabolite excretion peaked 4.6 h (T½ of 2.7 h) after exposure, with excreted metabolite levels in between 0.017 and 0.223 nmol/nmol/m³. After combined inhalation and dermal exposure to D4-DEHP, the excretion of all five analysed metabolites peaked after 4.7 h on average (T½ of 4.8 h), and metabolite levels ranged from 0.072 to 1.105 nmol/nmol/m³ between participants. No dermal uptake of particle phase D4-DEHP was observed. In conclusion, the average excreted levels of metabolites after combined inhalation and dermal exposure to D4-DEP was three times higher than after combined exposure to D4-DEHP; and nine times higher than after dermal exposure of D4-DEP. This study was made possible due to the use of novel approaches, i.e., the use of labelled phthalate esters to avoid the background concentration, and innovative technique of phthalate generation, both in the particle and the gas phase.

Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates-A Human Exposure Study.

Phthalates are ubiquitous in indoor environments, which raises concern about their endocrine-disrupting properties. However, studies of human uptake from airborne exposure are limited. We studied the inhalation uptake and dermal uptake by air-to-skin transfer with clean clothing as a barrier of two deuterium-labeled airborne phthalates: particle-phase D4-DEHP (di(2-ethylhexyl)phthalate) and gas-phase D4-DEP (diethyl phthalate). Sixteen participants, wearing trousers and long-sleeved shirts, were under controlled conditions exposed to airborne phthalates in four exposure scenarios: dermal uptake alone and combined inhalation + dermal uptake of both phthalates. The results showed an average uptake of D4-DEHP by inhalation of 0.0014 ± 0.00088 (µg kg-1 bw)/(µg m-3)/h. No dermal uptake of D4-DEHP was observed during the 3 h exposure with clean clothing. The deposited dose of D4-DEHP accounted for 26% of the total inhaled D4-DEHP mass. For D4-DEP, the average uptake by inhalation + dermal was 0.0067 ± 0.0045 and 0.00073 ± 0.00051 (µg kg-1 bw)/(µg m-3)/h for dermal uptake. Urinary excretion factors of metabolites after inhalation were estimated to 0.69 for D4-DEHP and 0.50 for D4-DEP. Under the described settings, the main uptake of both phthalates was through inhalation. The results demonstrate the differences in uptake of gas and particles and highlight the importance of considering the deposited dose in particle uptake studies.

Effective density and mixing state of aerosol particles in a near-traffic urban environment.

In urban environments, airborne particles are continuously emitted, followed by atmospheric aging. Also, particles emitted elsewhere, transported by winds, contribute to the urban aerosol. We studied the effective density (mass-mobility relationship) and mixing state with respect to the density of particles in central Copenhagen, in wintertime. The results are related to particle origin, morphology, and aging. Using a differential mobility analyzer-aerosol particle mass analyzer (DMA-APM), we determined that particles in the diameter range of 50-400 nm were of two groups: porous soot aggregates and more dense particles. Both groups were present at each size in varying proportions. Two types of temporal variability in the relative number fraction of the two groups were found: soot correlated with intense traffic in a diel pattern and dense particles increased during episodes with long-range transport from polluted continental areas. The effective density of each group was relatively stable over time, especially of the soot aggregates, which had effective densities similar to those observed in laboratory studies of fresh diesel exhaust emissions. When heated to 300 °C, the soot aggregate volatile mass fraction was ∼10%. For the dense particles, the volatile mass fraction varied from ∼80% to nearly 100%.

Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.