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Hydroxyl (OH) and peroxy radicals (HO2 and RO2) were measured in the Pearl River Delta, which is one of the most polluted areas in China, in autumn 2014. The radical observations were complemented by measurements of OH reactivity (inverse OH lifetime) and a comprehensive set of trace gases including carbon monoxide (CO), nitrogen oxides (NOx=NO , NO2) and volatile organic compounds (VOCs). OH reactivity was in the range from 15 to 80 s-1 , of which about 50 % was unexplained by the measured OH reactants. In the 3 weeks of the campaign, maximum median radical concentrations were 4.5×106 cm-3 for OH at noon and 3×108 and 2.0×108 cm-3 for HO2 and RO2 , respectively, in the early afternoon. The completeness of the daytime radical measurements made it possible to carry out experimental budget analyses for all radicals (OH, HO2 , and RO2) and their sum (ROx). The maximum loss rates for OH, HO2 , and RO2 reached values between 10 and 15 ppbvh-1 during the daytime. The largest fraction of this can be attributed to radical interconversion reactions while the real loss rate of ROx remained below 3 ppbvh-1. Within experimental uncertainties, the destruction rates of HO2 and the sum of OH, HO2 , and RO2 are balanced by their respective production rates. In case of RO2 , the budget could be closed by attributing the missing OH reactivity to unmeasured VOCs. Thus, the presumption of the existence of unmeasured VOCs is supported by RO2 measurements. Although the closure of the RO2 budget is greatly improved by the additional unmeasured VOCs, a significant imbalance in the afternoon remains, indicating a missing RO2 sink. In case of OH, the destruction in the morning is compensated by the quantified OH sources from photolysis (HONO and O3), ozonolysis of alkenes, and OH recycling (HO2+NO). In the afternoon, however, the OH budget indicates a missing OH source of 4 to 6 ppbvh-1. The diurnal variation of the missing OH source shows a similar pattern to that of the missing RO2 sink so that both largely compensate each other in the ROx budget. These observations suggest the existence of a chemical mechanism that converts RO2 to OH without the involvement of NO, increasing the RO2 loss rate during the daytime from 5.3 to 7.4 ppbvh-1 on average. The photochemical net ozone production rate calculated from the reaction of HO2 and RO2 with NO yields a daily integrated amount of 102 ppbv ozone, with daily integrated ROx primary sources being 22 ppbv in this campaign. The produced ozone can be attributed to the oxidation of measured (18 %) and unmeasured (60 %) hydrocarbons, formaldehyde (14 %), and CO (8 %). An even larger integrated net ozone production of 140 ppbv would be calculated from the oxidation rate of VOCs with OH if HO2 and all RO2 radicals react with NO. However, the unknown RO2 loss (evident in the RO2 budget) causes 30 ppbv less ozone production than would be expected from the VOC oxidation rate. [ABSTRACT FROM AUTHOR]

The oxidation of nitric oxide to nitrogen dioxide by hydroperoxy (HO 2 ) and organic peroxy radicals (RO 2 ) is responsible for the chemical net ozone production in the troposphere and for the regeneration of hydroxyl radicals, the most important oxidant in the atmosphere. In Summer 2014, a field campaign was conducted in the North China Plain, where increasingly severe ozone pollution has been experienced in the last years. Chemical conditions in the campaign were representative for this area. Radical and trace gas concentrations were measured, allowing for calculating the turnover rates of gas-phase radical reactions. Therefore, the importance of heterogeneous HO 2 uptake on aerosol could be experimentally determined. HO 2 uptake could have suppressed ozone formation at that time because of the competition with gas-phase reactions that produce ozone. The successful reduction of the aerosol load in the North China Plain in the last years could have led to a significant decrease of HO 2 loss on particles, so that ozone-forming reactions could have gained importance in the last years. However, the analysis of the measured radical budget in this campaign shows that HO 2 aerosol uptake did not impact radical chemistry for chemical conditions in 2014. Therefore, reduced HO 2 uptake on aerosol since then is likely not the reason for the increasing number of ozone pollution events in the North China Plain, contradicting conclusions made from model calculations reported in the literature.

Compound specific carbon isotopic measurements (δ 13 C) of levoglucosan were carried out for ambient aerosol sampled during an intensive biomass burning period at different sites in Guangdong province, China. The δ 13 C of ambient levoglucosan was found to be noticeably heavier than the average δ 13 C of levoglucosan found in source C3-plant-combustion samples. To estimate the photochemical age of sampled ambient levoglucosan, back trajectory analyses were done. The origin and pathways of the probed air masses were determined, using the Lagrangian-particle-dispersion-model FLEXPART and ECMWF meteorological data. On the other hand, the isotopic hydrocarbon clock concept was applied to relate the changes in the field-measured stable carbon isotopic composition to the extent of chemical processing during transport. Comparison of the photochemical age derived using these two independent approaches shows on average good agreement, despite a substantial scatter of the individual data pairs. These analyses demonstrate that the degree of oxidative aging of particulate levoglucosan can be quantified by combining laboratory KIE studies, observed δ 13 C at the source and in the field, as well as back trajectory analyses. In this study, the chemical loss of levoglucosan was found to exceed 50% in one-fifth of the analyzed samples. Consequently, the use of levoglucosan as a stable molecular tracer may underestimate the contribution of biomass burning to air pollution.