Abstract
Abstract. Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH ∼ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ∼ −0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OSC ∼ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to higher ages where OA loss dominates. The mass added at low-to-intermediate ages is due primarily to condensation of oxidized species, not heterogeneous oxidation. The OA decrease at high photochemical ages is dominated by heterogeneous oxidation followed by fragmentation/evaporation. A comparison of urban SOA formation in this study with a similar study of vehicle SOA in a tunnel suggests the importance of vehicle emissions for urban SOA. Pre-2007 SOA models underpredict SOA formation by an order of magnitude, while a more recent model performs better but overpredicts at higher ages. These results demonstrate the value of the reactor as a tool for in situ evaluation of the SOA formation potential and OA evolution from ambient air.
Highlights
Atmospheric aerosols are the most uncertain aspect of climate radiative forcing (Myhre et al, 2013) and have negative impacts on human health (Pope et al, 2002) and visibility (Watson, 2002)
By combining results from the ambient aerosol and aged ambient aerosol measurements, we provide a stronger test of current secondary Organic aerosol (OA) (SOA) models, since they can be compared with data from a much wider range of photochemical ages
The ambient aerosol during the first third (30 May– 3 June 2010) of the measurement period is characterized by OA dominance, while the remaining two-thirds of the period (3–11 June 2010) is characterized by high concentrations of OA and nitrate, moderate sulfate and ammonium, and low chloride, with a marked diurnal cycle
Summary
Atmospheric aerosols are the most uncertain aspect of climate radiative forcing (Myhre et al, 2013) and have negative impacts on human health (Pope et al, 2002) and visibility (Watson, 2002). SOA concentrations are typically underestimated by over an order of magnitude when pre-2007 models are applied in urban regions (Volkamer et al, 2006; de Gouw and Jimenez, 2009; Hodzic et al, 2010; Morino et al, 2014; Hayes et al, 2015) These “traditional” models treated SOA formation as partitioning of semivolatile products from gas-phase oxidation of VOCs, using aerosol yields and saturation concentrations from older environmental chamber studies. S/IVOCs have been identified as additional precursors that were not considered in traditional models (Robinson et al, 2007) These updated approaches have been applied to several urban data sets, leading to better closure between measured and modeled bulk OA, but have resulted in other problems such as several-fold overpredictions of SOA at long aging times (> 1 day; Dzepina et al, 2011; Hayes et al, 2015; Zhang et al, 2015) or SOA that is much too volatile compared to observations (Dzepina et al, 2011). Targeted field studies in urban areas, with sufficient constraints and with novel approaches for focused investigation of SOA formation, are essential for continued model testing and improvement
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