HOx radical chemistry in oxidation flow reactors with low-pressure mercury lamps systematically examined by modeling

摘要

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 O-3 since OH is formed from O-3 photolysis, while OFR185 does not since O-2 can be photolyzed to produce O-3, 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 O-3 (e.g., 70 ppm), as a larger primary OH source from O-3, 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 O-3, OH suppression can reach 2 orders of magnitude. For a typical input of 7 ppm O-3 (OHRO3 D = 10 s(-1)), 10-fold OH suppression is observed at OHRext similar to 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 O-3, O-2, and H2O and reactions of OH and HO2 with themselves or with some abundant species, i.e., O-3 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.