Explicit diagnosis of the local ozone production rate and the ozone-NOx-VOC sensitivities

In the troposphere, ozone is a harmful gas compound to both human health and vegetation. Ozone is produced from the reaction of NO_x(@NO + NO_2) and VOCs(volatile organic compounds) with light. Due to the highly nonlinear relationships between ozone and its precursors, proper ozone mitigation relies on the knowledge of chemical mechanisms. In this study, an observation-based method is used to simulate ozone formation and elucidate its controlling factors for a rural site on the North China Plain. The instantaneous ozone production rate is calculated utilizing a box model using the dataset obtained from the Wangdu campaign. First, the model was operated in a time-dependent mode to calculate the ozone production rate at each time stamp. The calculated ozone formation rate showed a diurnal average maximum value of 17 ppbv/h(1-h diurnal averaged). The contribution of individual peroxy radicals to ozone production was analyzed. In addition, the functional dependence of calculated P(O_3) reveals that ozone production was in a NO_x-limited regime during the campaign. Furthermore, the missing peroxy radical source will further extend NO_x-limited conditions to earlier in the day, making NO_xlimitation dominate more of a day than the current chemical model predicts. Finally, a multiple scenarios mode,also known as EKMA(empirical kinetic modeling approach), was used to simulate the response of P(O_3) to the imaginary change in precursor concentrations. We found that ozone production was in the NO_x-limited region. However, the use of NO_2 measured by the molybdenum converter and/or the absence of a peroxy radical source in the current chemical model could over-emphasize the VOC-limited effect on ozone production.

Field measurement of the organic peroxy radicals by the low-pressure reactor plus laser-induced fluorescence spectroscopy

A low-pressure reactor(LPR) was developed for the measurement of ambient organic peroxy(RO2)radicals with the use of the laser-induced fluorescence(LIF) instrument.The reactor converts all the RO_(x)(=RO2+HO2+RO+OH) radicals into HO2 radicals.It can conduct different measurement modes through altering the reagent gases,achieving the speciated measurement of RO2 and RO2^#(RO2 radicals derived from the long-chain alkane,alkene and aromatic hydrocarbon).An example of field measurement results was given,with a maximum concentration of 1.88 × 10^(8) molecule/cm^(3) for RO2 and 1.18×10^(8) molecule/cm^(3) for RO2^(#).Also,this instrument quantifies the local ozone production rates directly,which can help to deduce the regional ozone control strategy from an experimental perspective.The new device can se rve as a potent tool for both the explo ration of frontier chemistry and the diagnosis of the control strategies.