The gas-particle partitioning of primary organic aerosol (POA) emissions from a diesel engine and the combustion of hard- and soft-woods in a stove was investigated by isothermally diluting them in a smog chamber or by passing them through a thermodenuder and measuring the extent of evaporation. The experiments were conducted at atmospherically relevant conditions: low concentrations and small temperature perturbations. The partitioning of the POA emissions from both sources varied continuously with changing concentration and temperature. Although the POA emissions are semivolatile, they do not completely evaporate at typical atmospheric conditions. The overall partitioning characteristics of diesel and wood smoke POA are similar, with wood smoke being somewhat less volatile than the diesel exhaust. The gas-particle partitioning of aerosols formed from flash-vaporized engine lubricating oil was also studied; diesel POA is somewhat more volatile than the oil aerosol. The experimental data from the dilution- and thermodenuder-based techniques were fit using absorptive partitioning theory to derive a volatility distribution of the POA emissions from each source. These distributions are suitable for use in chemical transport models that simulate POA concentrations.

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[1] This paper discusses the reversibility of gas-particle partitioning in secondary organic aerosol (SOA) formed from a-pinene ozonolysis in a smog chamber. Previously, phase partitioning has been studied quantitatively via SOA production experiments and qualitatively by perturbing temperature and observing particle evaporation. In this work, two methods were used to isothermally dilute the SOA: an external dilution sampler and an in-chamber technique. Dilution caused some evaporation of SOA, but repartitioning took place on a time scale of tens of minutes to hours -consistent with an uptake coefficient on the order of 0.001 -0.01. However, given sufficient time, a-pinene SOA repartitions reversibly based on comparisons with data from conventional SOA yield experiments. Further, aerosol mass spectrometer (AMS) data indicate that the composition of SOA varies with partitioning. These results suggest that oligomerization observed in high-concentration laboratory experiments may be a reversible process and underscore the complexity of the kinetics of formation and evaporation of SOA. Citation: Grieshop, A. P., N. M. Donahue, and A. L.Robinson (2007), Is the gas-particle partitioning in alpha-pinene secondary organic aerosol reversible?, Geophys. Res. Lett., 34, L14810,

Emissions from traditional cooking practices in low- and middle-income countries have detrimental health and climate effects; cleaner-burning cookstoves may provide “co-benefits”. Here we assess this potential via in-home measurements of fuel-use and emissions and real-time optical properties of pollutants from traditional and alternative cookstoves in rural Malawi. Alternative cookstove models were distributed by existing initiatives and include a low-cost ceramic model, two forced-draft cookstoves (FDCS; Philips HD4012LS and ACE-1), and three institutional cookstoves. Among household cookstoves, emission factors (EF; g (kg wood)−1) were lowest for the Philips, with statistically significant reductions relative to baseline of 45% and 47% for fine particulate matter (PM2.5) and carbon monoxide (CO), respectively. The Philips was the only cookstove tested that showed significant reductions in elemental carbon (EC) emission rate. Estimated health and climate cobenefits of alternative cookstoves were smaller than predicted from laboratory tests due to the effects of real-world conditions including fuel variability and nonideal operation. For example, estimated daily PM intake and field-measurement-based global warming commitment (GWC) for the Philips FDCS were a factor of 8.6 and 2.8 times higher, respectively, than those based on lab measurements. In-field measurements provide an assessment of alternative cookstoves under real-world conditions and as such likely provide more realistic estimates of their potential health and climate benefits than laboratory tests.

Atmospheric transformations determine the contribution of emissions from combustion systems to fine particulate matter (PM) mass. For example, combustion systems emit vapors that condense onto existing particles or form new particles as the emissions are cooled and diluted. Upon entering the atmosphere, emissions are exposed to atmospheric oxidants and sunlight, which causes them to evolve chemically and physically, generating secondary PM. This review discusses these transformations, focusing on organic PM. Organic PM emissions are semi-volatile at atmospheric conditions and thus their partitioning varies continuously with changing temperature and concentration. Because organics contribute a large portion of the PM mass emitted by most combustion sources, these emissions cannot be represented using a traditional, static emission factor. Instead, knowledge of the volatility distribution of emissions is required to explicitly account for changes in gas-particle partitioning. This requires updating how PM emissions from combustion systems are measured and simulated from combustion systems. Secondary PM production often greatly exceeds the direct or primary PM emissions; therefore, secondary PM must be included in any assessment of the contribution of combustion systems to ambient PM concentrations. Low-volatility organic vapors emitted by combustion systems appear to be very important secondary PM precursors that are poorly accounted for in inventories and models. The review concludes by discussing the implications that the dynamic nature of these PM emissions have on source testing for emission inventory development and regulatory purposes. This discussion highlights important linkages between primary and secondary PM, which could lead to simplified certification test procedures while capturing the emission components that contribute most to atmospheric PM mass. IMPLICATIONSEmissions from combustion systems such as motor vehicles are a major source of atmospheric fine PM. Quantifying the contribution of these emissions to atmospheric PM requires a bridge in the gap between the tailpipe, where emission measurements are made, and the atmosphere, where the emissions are transformed and ultimately delivered to a receptor, whether measured, deposited, or inhaled. This review describes these transformations and discusses their implications for the measurement, simulation, and regulation of emissions from combustion systems. There are important linkages between primary and secondary PM, which could lead to improved test procedures.