Abstract. An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydroatmosphere interactions of Energy, Aerosols, Carbon, H 2 O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m −3 when LVOC fate corrected) compared to daytime (average 0.9 µg m −3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 4.4 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. To our knowledge this is the first time that this has been shown when comparing VOC concentrations with SOA formation measured at the same time, rather than comparing measurements made at different times. An SOA yield of 18-58 % from those compounds can explain the observed SOA formation. S/IVOCs were the only pool of gas-phase carbon that was large enough to explain the observed SOA formation. This work suggests that these typically unmeasured gases play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. These measurements help clarify the magnitu...

Abstract. Oxidation flow reactors (OFRs) using OH produced from low-pressure Hg lamps at 254 nm (OFR254) or both 185 and 254 nm (OFR185) are commonly used in atmospheric chemistry and other fields. OFR254 requires the addition of externally formed O3 since OH is formed from O3 photolysis, while OFR185 does not since O2 can be photolyzed to produce O3, and OH can also be formed from H2O photolysis. In this study, we use a plug-flow kinetic model to investigate OFR properties under a very wide range of conditions applicable to both field and laboratory studies. We show that the radical chemistry in OFRs can be characterized as a function of UV light intensity, H2O concentration, and total external OH reactivity (OHRext, e.g., from volatile organic compounds (VOCs), NOx, and SO2). OH exposure is decreased by added external OH reactivity. OFR185 is especially sensitive to this effect at low UV intensity due to low primary OH production. OFR254 can be more resilient against OH suppression at high injected O3 (e.g., 70 ppm), as a larger primary OH source from O3, as well as enhanced recycling of HO2 to OH, make external perturbations to the radical chemistry less significant. However if the external OH reactivity in OFR254 is much larger than OH reactivity from injected O3, OH suppression can reach 2 orders of magnitude. For a typical input of 7 ppm O3 (OHRO3 = 10 s−1), 10-fold OH suppression is observed at OHRext ~ 100 s−1, which is similar or lower than used in many laboratory studies. The range of modeled OH suppression for literature experiments is consistent with the measured values except for those with isoprene. The finding on OH suppression may have important implications for the interpretation of past laboratory studies, as applying OHexp measurements acquired under different conditions could lead to over a 1-order-of-magnitude error in the estimated OHexp. The uncertainties of key model outputs due to uncertainty in all rate constants and absorption cross-sections in the model are within ±25 % for OH exposure and within ±60 % for other parameters. These uncertainties are small relative to the dynamic range of outputs. Uncertainty analysis shows that most of the uncertainty is contributed by photolysis rates of O3, O2, and H2O and reactions of OH and HO2 with themselves or with some abundant species, i.e., O3 and H2O2. OHexp calculated from direct integration and estimated from SO2 decay in the model with laminar and measured residence time distributions (RTDs) are generally within a factor of 2 from the plug-flow OHexp. However, in the models with RTDs, OHexp estimated from SO2 is systematically lower than directly integrated OHexp in the case of significant SO2 consumption. We thus recommended using OHexp estimated from the decay of the species under study when possible, to obtain the most appropriate information on photochemical aging in the OFR. Using HOx-recycling vs. destructive external OH reactivity only leads to small changes in OHexp under most conditions. Changing the identity (rate constant) of external OH reactants can result in substantial changes in OHexp due to different reductions in OH suppression as the reactant is consumed. We also report two equations for estimating OH exposure in OFR254. We find that the equation estimating OHexp from measured O3 consumption performs better than an alternative equation that does not use it, and thus recommend measuring both input and output O3 concentrations in OFR254 experiments. This study contributes to establishing a firm and systematic understanding of the gas-phase HOx and Ox chemistry in these reactors, and enables better experiment planning and interpretation as well as improved design of future reactors.

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.