Diesel soot aging in urban plumes within hours under cold dark and humid conditions.

Fresh and aged diesel soot particles have different impacts on climate and human health. While fresh diesel soot particles are highly aspherical and non-hygroscopic, aged particles are spherical and hygroscopic. Aging and its effect on water uptake also controls the dispersion of diesel soot in the atmosphere. Understanding the timescales on which diesel soot ages in the atmosphere is thus important, yet knowledge thereof is lacking. We show that under cold, dark and humid conditions the atmospheric transformation from fresh to aged soot occurs on a timescale of less than five hours. Under dry conditions in the laboratory, diesel soot transformation is much less efficient. While photochemistry drives soot aging, our data show it is not always a limiting factor. Field observations together with aerosol process model simulations show that the rapid ambient diesel soot aging in urban plumes is caused by coupled ammonium nitrate formation and water uptake.

Evolution of In-Cylinder Diesel Engine Soot and Emission Characteristics Investigated with Online Aerosol Mass Spectrometry.

To design diesel engines with low environmental impact, it is important to link health and climate-relevant soot (black carbon) emission characteristics to specific combustion conditions. The in-cylinder evolution of soot properties over the combustion cycle and as a function of exhaust gas recirculation (EGR) was investigated in a modern heavy-duty diesel engine. A novel combination of a fast gas-sampling valve and a soot particle aerosol mass spectrometer (SP-AMS) enabled online measurements of the in-cylinder soot chemistry. The results show that EGR reduced the soot formation rate. However, the late cycle soot oxidation rate (soot removal) was reduced even more, and the net effect was increased soot emissions. EGR resulted in an accumulation of polycyclic aromatic hydrocarbons (PAHs) during combustion, and led to increased PAH emissions. We show that mass spectral and optical signatures of the in-cylinder soot and associated low volatility organics change dramatically from the soot formation dominated phase to the soot oxidation dominated phase. These signatures include a class of fullerene carbon clusters that we hypothesize represent less graphitized, C5-containing fullerenic (high tortuosity or curved) soot nanostructures arising from decreased combustion temperatures and increased premixing of air and fuel with EGR. Altered soot properties are of key importance when designing emission control strategies such as diesel particulate filters and when introducing novel biofuels.

Validation of an air-liquid interface toxicological set-up using Cu, Pd, and Ag well-characterized nanostructured aggregates and spheres.

ABSTRACT: Systems for studying the toxicity of metal aggregates on the airways are normally not suited for evaluating the effects of individual particle characteristics. This study validates a set-up for toxicological studies of metal aggregates using an air-liquid interface approach. The set-up used a spark discharge generator capable of generating aerosol metal aggregate particles and sintered near spheres. The set-up also contained an exposure chamber, The Nano Aerosol Chamber for In Vitro Toxicity (NACIVT). The system facilitates online characterization capabilities of mass mobility, mass concentration, and number size distribution to determine the exposure. By dilution, the desired exposure level was controlled. Primary and cancerous airway cells were exposed to copper (Cu), palladium (Pd), and silver (Ag) aggregates, 50-150 nm in median diameter. The aggregates were composed of primary particles <10 nm in diameter. For Cu and Pd, an exposure of sintered aerosol particles was also produced. The doses of the particles were expressed as particle numbers, masses, and surface areas. For the Cu, Pd, and Ag aerosol particles, a range of mass surface concentrations on the air-liquid interface of 0.4-10.7, 0.9-46.6, and 0.1-1.4 µg/cm2, respectively, were achieved. Viability was measured by WST-1 assay, cytokines (Il-6, Il-8, TNF-a, MCP) by Luminex technology. Statistically significant effects and dose response on cytokine expression were observed for SAEC cells after exposure to Cu, Pd, or Ag particles. Also, a positive dose response was observed for SAEC viability after Cu exposure. For A549 cells, statistically significant effects on viability were observed after exposure to Cu and Pd particles. The set-up produced a stable flow of aerosol particles with an exposure and dose expressed in terms of number, mass, and surface area. Exposure-related effects on the airway cellular models could be asserted.

Impacts of Combustion Conditions and Photochemical Processing on the Light Absorption of Biomass Combustion Aerosol.

The aim was to identify relationships between combustion conditions, particle characteristics, and optical properties of fresh and photochemically processed emissions from biomass combustion. The combustion conditions included nominal and high burn rate operation and individual combustion phases from a conventional wood stove. Low temperature pyrolysis upon fuel addition resulted in "tar-ball" type particles dominated by organic aerosol with an absorption Ångström exponent (AAE) of 2.5-2.7 and estimated Brown Carbon contributions of 50-70% to absorption at the climate relevant aethalometer-wavelength (520 nm). High temperature combustion during the intermediate (flaming) phase was dominated by soot agglomerates with AAE 1.0-1.2 and 85-100% of absorption at 520 nm attributed to Black Carbon. Intense photochemical processing of high burn rate flaming combustion emissions in an oxidation flow reactor led to strong formation of Secondary Organic Aerosol, with no or weak absorption. PM1 mass emission factors (mg/kg) of fresh emissions were about an order of magnitude higher for low temperature pyrolysis compared to high temperature combustion. However, emission factors describing the absorption cross section emitted per kg of fuel consumed (m(2)/kg) were of similar magnitude at 520 nm for the diverse combustion conditions investigated in this study. These results provide a link between biomass combustion conditions, emitted particle types, and their optical properties in fresh and processed plumes which can be of value for source apportionment and balanced mitigation of biomass combustion emissions from a climate and health perspective.

Particulate PAH emissions from residential biomass combustion: time-resolved analysis with aerosol mass spectrometry.

Time-resolved emissions of particulate polycyclic aromatic hydrocarbons (PAHs) and total organic particulate matter (OA) from a wood log stove and an adjusted pellet stove were investigated with high-resolution time-of-flight aerosol mass spectrometry (AMS). The highest OA emissions were found during the addition of log wood on glowing embers, that is, slow burning pyrolysis conditions. These emissions contained about 1% PAHs (of OA). The highest PAH emissions were found during fast burning under hot air starved combustion conditions, in both stoves. In the latter case, PAHs contributed up to 40% of OA, likely due to thermal degradation of other condensable species. The distribution of PAHs was also shifted toward larger molecules in these emissions. AMS signals attributed to PAHs were found at molecular weights up to 600 Da. The vacuum aerodynamic size distribution was found to be bimodal with a smaller mode (Dva ∼ 200 nm) dominating under hot air starved combustion and a larger sized mode dominating under slow burning pyrolysis (Dva ∼ 600 nm). Simultaneous reduction of PAHs, OA and total particulate matter from residential biomass combustion may prove to be a challenge for environmental legislation efforts as these classes of emissions are elevated at different combustion conditions.

Thorium exposure during tungsten inert gas welding with thoriated tungsten electrodes.

The exposure to 232Th from TIG welding with thoriated electrodes has been determined at five different workshops. Welding with both alternating and direct current was investigated. The exposure levels of 232Th were generally below 10 mBq m(-3) in the breathing zone of the welders. Two samples from AC welding showed significant higher exposure levels, probably due to maladjustment of the TIG welding power source. Samples of the respirable fraction of 232Th from grinding thoriated electrodes were also collected showing exposure levels of 5 mBq m(-3) or lower. A dose estimate has been made for two scenarios, one realistic and one with conservative assumptions, showing that the annual committed effective dose from inhalation of 232Th, 230Th, 228Th and 228Ra, for a full-time TIG welder, in the realistic case is below 0.3 mSv and with conservative assumptions around 1 mSv or lower. The contribution from grinding electrodes was lower, 10 microSv or lower in the realistic case and 63 microSv or lower based on conservative assumptions. The study does not exclude occurrence of higher exposure levels under welding conditions different from those prevailing in this study.

Terrestrial gastropod hosts of Parelaphostrongylus tenuis at the National Zoological Park's Conservation and Research Center, Virginia.

Terrestrial gastropods at the National Zoological Park's Conservation and Research Center (CRC) near Front Royal, Virginia, were surveyed from June 1985 to May 1986, to assess their role in transmission of the meningeal worm, Parelaphostrongylus tenuis. A total of 670 gastropods representing 9 families and 18 species was collected. The slug Deroceras laeve accounted for 50.4% of the specimens collected. Parelaphostrongylus tenuis infections were found in 15 gastropods (2.2% prevalence) representing 5 species; 5 of the infected gastropods were D. laeve. New host records for this nematode are Ventridens collisella and Philomycus carolinianus. Infected gastropods were recovered from June through October 1985 and in May 1986. All 6 sampling locations yielded infected gastropods, suggesting this parasite is widely distributed at the CRC, and is therefore likely to continue to pose a serious threat to exotic ungulates maintained there for conservation and research purposes.