Characterization and dark oxidation of the emissions of a pellet stove.

Pellet combustion in residential heating stoves has increased globally during the last decade. Despite their high combustion efficiency, the widespread use of pellet stoves is expected to adversely impact air quality. The atmospheric aging of pellet emissions has received even less attention, focusing mainly on daytime conditions, while the degree to which pellet emissions undergo night-time aging as well as the role of relative humidity remain poorly understood. In this study, environmental simulation chamber experiments were performed to characterize the fresh and aged organic aerosol (OA) emitted by a pellet stove. The fresh pellet stove PM1 (particulate matter with an aerodynamic diameter less than 1 µm) emissions consisted mainly of OA (93 ± 4%, mean ± standard deviation) and black carbon (5 ± 3%). The primary OA (POA) oxygen-to-carbon ratio (O : C) was 0.58 ± 0.04, higher than that of fresh logwood emissions. The fresh OA at a concentration of 70 µg m-3 (after dilution and equilibration in the chamber) consisted of semi-volatile (68%), low and extremely low volatility (16%) and intermediate-volatility (16%) compounds. The oxidation of pellet emissions under dark conditions was investigated by injecting nitrogen dioxide (NO2) and ozone (O3) into the chamber, at different (10-80%) relative humidity (RH) levels. In all dark aging experiments secondary organic aerosol (SOA) formation was observed, increasing the OA levels after a few hours of exposure to NO3 radicals. The change in the aerosol composition and the extent of oxidation depended on RH. For low RH, the SOA mass formed was up to 30% of the initial OA, accompanied by a moderate change in both O : C levels (7-8% increase) and the OA spectrum. Aging under higher RH conditions (60-80%) led to a more oxygenated aerosol (increase in O : C of 11-18%), but only a minor (1-10%) increase in OA mass. The increase in O : C at high RH indicates the importance of heterogeneous aqueous reactions in this system, that oxidize the original OA with a relatively small net change in the OA mass. These results show that the OA in pellet emissions can chemically evolve under low photochemical activity (e.g. the wintertime period) with important enhancement in SOA mass under certain conditions.

Secondary aerosol formation during the dark oxidation of residential biomass burning emissions.

Particulate matter from biomass burning emissions affects air quality, ecosystems and climate; however, quantifying these effects requires that the connection between primary emissions and secondary aerosol production is firmly established. We performed atmospheric simulation chamber experiments on the chemical oxidation of residential biomass burning emissions under dark conditions. Biomass burning organic aerosol was found to age under dark conditions, with its oxygen-to-carbon ratio increasing by 7-34% and producing 1-38 µg m-3 of secondary organic aerosol (5-80% increase over the fresh organic aerosol) after 30 min of exposure to NO3 radicals in the chamber (corresponding to 1-3 h of exposure to typical nighttime NO3 radical concentrations in an urban environment). The average mass concentration of SOA formed under dark-oxidation conditions was comparable to the mass concentration formed after 3 h (equivalent to 7-10 h of ambient exposure) under ultraviolet lights (6 µg m-3 or a 47% increase over the emitted organic aerosol concentration). The dark-aging experiments showed a substantial increase in secondary nitrate aerosol (0.12-3.8 µg m-3), 46-100% of which is in the form of organic nitrates. The biomass burning aerosol pH remained practically constant at 2.8 throughout the experiment. This value promotes inorganic nitrate partitioning to the particulate phase, potentially contributing to the buildup of nitrate aerosol in the boundary layer and enhancing long-range transport. These results suggest that oxidation through reactions with the NO3 radical is an additional secondary aerosol formation pathway in biomass burning emission plumes that should be accounted for in atmospheric chemical-transport models.

A Method for the Measurement of the Water Solubility Distribution of Atmospheric Organic Aerosols.

A method for the measurement of the water solubility distribution of atmospheric organic aerosols is presented. This method is based on the extraction of organic aerosols collected on filters, using different amounts of water and measurement of the corresponding water-soluble organic carbon concentration. The solubility distribution is then estimated using the solubility basis set. The method was applied on both ambient and source-specific aerosols. Approximately 60% of the atmospheric urban organic aerosol analyzed had water solubility higher than 0.6 g L-1. Around 10% of the fresh cooking organic aerosol had water solubility higher than 10 g L-1, while 80% of the total fresh cooking organic aerosol had solubility lower than 0.1 g L-1. The ambient measurements suggested that the solubility distributions are roughly consistent with the positive matrix factorization analysis results determined during the analysis of the high-resolution time-of-flight aerosol mass spectrometry data. Most of the oxidized organic aerosol appears to have water solubility above 0.6 g L-1, while the hydrocarbon-like organic aerosol and cooking organic aerosol have water solubility less than 0.002 and 0.1 g L-1, respectively. The biomass burning organic aerosol seems to have mostly intermediate solubility in water, between 0.04 and 0.6 g L-1. The proposed approach can quantify the solubility distribution in the 0.002-15 g L-1 range. Future extension of the method to higher solubility ranges would be useful for capturing the complete solubility range for atmospheric cloud condensation studies (0.1-100 g L-1).

Water soluble reactive phosphate (SRP) in atmospheric particles over East Mediterranean: The importance of dust and biomass burning events.

The importance of dust and biomass burning episodes on the atmospheric concentration of water-soluble reactive phosphate (SRP) was determined in the eastern Mediterranean. SRP was measured with a new rapid real-time automated analytical system with a time resolution of a few minutes per sample and with an extremely low detection limit. The average atmospheric concentration of SRP during the sampling campaign was estimated at 0.35 ± 0.25 (median 0.30) nmol P m-3. The maximum concentration of SRP (3.08 nmol P m-3) was recorded during an intense dust episode, and was almost ten times higher than the campaign average, confirming that Saharan dust was an important primary source of bioavailable P to the eastern Mediterranean, especially during the spring period when 60% of the events occurred. Predicted increases in the frequency and intensity of dust storms in the area will enhance the role of the atmosphere as a source of bioavailable P for the Mediterranean marine ecosystem. During the warm period, when Northerly winds prevailed, biomass burning processes contributed significantly to soluble phosphorus delivered from atmospheric sources to the eastern Mediterranean. These inputs during warm periods are especially important for the Eastern Mediterranean, where biological productivity is strongly limited by nutrient availability.

Rapid dark aging of biomass burning as an overlooked source of oxidized organic aerosol.

Oxidized organic aerosol (OOA) is a major component of ambient particulate matter, substantially impacting climate, human health, and ecosystems. OOA is readily produced in the presence of sunlight, and requires days of photooxidation to reach the levels observed in the atmosphere. High concentrations of OOA are thus expected in the summer; however, our current mechanistic understanding fails to explain elevated OOA during wintertime periods of low photochemical activity that coincide with periods of intense biomass burning. As a result, atmospheric models underpredict OOA concentrations by a factor of 3 to 5. Here we show that fresh emissions from biomass burning exposed to NO2 and O3 (precursors to the NO3 radical) rapidly form OOA in the laboratory over a few hours and without any sunlight. The extent of oxidation is sensitive to relative humidity. The resulting OOA chemical composition is consistent with the observed OOA in field studies in major urban areas. Additionally, this dark chemical processing leads to significant enhancements in secondary nitrate aerosol, of which 50 to 60% is estimated to be organic. Simulations that include this understanding of dark chemical processing show that over 70% of organic aerosol from biomass burning is substantially influenced by dark oxidation. This rapid and extensive dark oxidation elevates the importance of nocturnal chemistry and biomass burning as a global source of OOA.

Urban particulate matter pollution: a tale of five cities.

Five case studies (Athens and Paris in Europe, Pittsburgh and Los Angeles in the United States, and Mexico City in Central America) are used to gain insights into the changing levels, sources, and role of atmospheric chemical processes in air quality in large urban areas as they develop technologically. Fine particulate matter is the focus of our analysis. In all cases reductions of emissions by industrial and transportation sources have resulted in significant improvements in air quality during the last few decades. However, these changes have resulted in the increasing importance of secondary particulate matter (PM) which dominates over primary in most cases. At the same time, long range transport of secondary PM from sources located hundreds of kilometres from the cities is becoming a bigger contributor to the urban PM levels in all seasons. "Non-traditional" sources including cooking, and residential and agricultural biomass burning contribute an increasing fraction of the now reduced fine PM levels. Atmospheric chemistry is found to change the chemical signatures of a number of these sources relatively fast both during the day and night, complicating the corresponding source apportionment.