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Oxidized Organic Aerosol (OOA), a major component of fine atmospheric particles, impacts climate and human health. Previous experiments and atmospheric models emphasize the importance of nocturnal OOA formation from NO 3 · oxidation of biogenic VOCs. This seasonal study extends the understanding by showing that nocturnal oxidation of biomass-burning emissions can account for up to half of total OOA production in fall and winter. It is the first to distinguish nocturnal OOA characteristics from daytime OOA across all seasons using bulk aerosol measurements. Summer observations of nocturnal OOA align well with regional chemistry transport model predictions, but discrepancies in other seasons reveal a common model deficiency in representing biomass-burning emissions and their nocturnal oxidation. This study underscores the significance of near-ground nocturnal OOA production, proposes a method to differentiate it using bulk aerosol measurements, and suggests model optimization strategies. These findings enhance the understanding and prediction of nighttime OOA formation., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2024.)

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.

In contrast to summer smog, the contribution of photochemistry to the formation of winter haze in northern mid-to-high latitude is generally assumed to be minor due to reduced solar UV and water vapor concentrations. Our comprehensive observations of atmospheric radicals and relevant parameters during several haze events in winter 2016 Beijing, however, reveal surprisingly high hydroxyl radical oxidation rates up to 15 ppbv/h, which is comparable to the high values reported in summer photochemical smog and is two to three times larger than those determined in previous observations during winter in Birmingham (Heard et al. Geophys. Res. Lett. 2004, 31, (18)), Tokyo (Kanaya et al. J. Geophys. Res.: Atmos. 2007, 112, (D21)), and New York (Ren et al. Atmos. Environ. 2006, 40, 252-263). The active photochemistry facilitates the production of secondary pollutants. It is mainly initiated by the photolysis of nitrous acid and ozonolysis of olefins and maintained by an extremely efficiently radical cycling process driven by nitric oxide. This boosted radical recycling generates fast photochemical ozone production rates that are again comparable to those during summer photochemical smog. The formation of ozone, however, is currently masked by its efficient chemical removal by nitrogen oxides contributing to the high level of wintertime particles. The future emission regulations, such as the reduction of nitrogen oxide emissions, therefore are facing the challenge of reducing haze and avoiding an increase in ozone pollution at the same time. Efficient control strategies to mitigate winter haze in Beijing may require measures similar as implemented to avoid photochemical smog in summer.

Ye et al. have determined a maximum nitrous acid (HONO) yield of 3% for the reaction HO2·H2O + NO2, which is much lower than the yield used in our work. This finding, however, does not affect our main result that HONO in the investigated Po Valley region is mainly from a gas-phase source that consumes nitrogen oxides., (Copyright © 2015, American Association for the Advancement of Science.)

Gaseous nitrous acid (HONO) is an important precursor of tropospheric hydroxyl radicals (OH). OH is responsible for atmospheric self-cleansing and controls the concentrations of greenhouse gases like methane and ozone. Due to lack of measurements, vertical distributions of HONO and its sources in the troposphere remain unclear. Here, we present a set of observations of HONO and its budget made onboard a Zeppelin airship. In a sunlit layer separated from Earth's surface processes by temperature inversion, we found high HONO concentrations providing evidence for a strong gas-phase source of HONO consuming nitrogen oxides and potentially hydrogen oxide radicals. The observed properties of this production process suggest that the generally assumed impact of HONO on the abundance of OH in the troposphere is substantially overestimated.

The degradation of trace gases and pollutants in the troposphere is dominated by their reaction with hydroxyl radicals (OH). The importance of OH rests on its high reactivity, its ubiquitous photochemical production in the sunlit atmosphere, and most importantly on its regeneration in the oxidation chain of the trace gases. In the current understanding, the recycling of OH proceeds through HO2 reacting with NO, thereby forming ozone. A recent field campaign in the Pearl River Delta, China, quantified tropospheric OH and HO2 concentrations and turnover rates by direct measurements. We report that concentrations of OH were three to five times greater than expected, and we propose the existence of a pathway for the regeneration of OH independent of NO, which amplifies the degradation of pollutants without producing ozone.

A new method (ROxLIF) for the measurement of atmospheric peroxy radicals (HO(2) and RO(2)) was developed using a two-step chemical conversion scheme and laser-induced fluorescence (LIF) for radical detection. Ambient air is sampled into a differentially pumped flow reactor, in which atmospheric RO(x) radicals (=RO(2)+RO+HO(2)+OH) are chemically converted to HO(2) by a large excess of NO and CO at reduced pressures (ROx mode). When only CO is added as a reagent, the sum of atmospheric HO(2)+OH is converted to HO(2) (HOx mode). At the reactor outlet, part of the air flow is transferred into a low-pressure detection chamber, where the HO(2) is further converted by reaction with NO to OH, which is then detected with high sensitivity by LIF at 308 nm. The ROxLIF technique has been implemented in an existing LIF instrument that is also capable of measuring atmospheric OH. From the concurrent measurements of RO(x), HO(x) and OH, concentrations of HO(2) and RO(2) can be determined. The system is calibrated using the quantitative photolysis of water vapor at 185 nm as a radical source. Addition of CO or hydrocarbons to the calibration gas yields well-defined concentrations of HO(2) or RO(2), respectively, providing an estimated accuracy for the calibration of about 20%. The ROxLIF technique is extremely sensitive and has detection limits (signal-to-noise ratio=2) of about 0.1 pptv of HO(2) or RO(2) at a time resolution of 1 min. The paper describes the technique and its calibration, discusses the chemistry in the conversion reactor and possible interferences, and gives an example of ambient air measurements to demonstrate the performance of the new technique.