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.

Abstract. Total atmospheric OH reactivities (k OH ) have been measured as reciprocal OH lifetimes by a newly developed instrument at a rural site in the densely populated Pearl River Delta (PRD) in Southern China in summer 2006. The deployed technique, LP-LIF, uses laser flash photolysis (LP) for artificial OH generation and laser-induced fluorescence (LIF) to measure the time-dependent OH decay in samples of ambient air. The reactivities observed at PRD covered a range from 10 s −1 to 120 s −1 , indicating a large load of chemical reactants. On average, k OH exhibited a pronounced diurnal profile with a mean maximum value of 50 s −1 at daybreak and a mean minimum value of 20 s −1 at noon. The comparison of reactivities calculated from measured trace gases with measured k OH reveals a missing reactivity of about a factor of 2 at day and night. The reactivity explained by measured trace gases was dominated by anthropogenic pollutants (e.g., CO, NO x , light alkenes and aromatic hydrocarbons) at night, while it was strongly influenced by local, biogenic emissions of isoprene during the day. Box model calculations initialized by measured parameters reproduce the observed OH reactivity well and suggest that the missing reactivity is contributed by unmeasured, secondary chemistry products (mainly aldehydes and ketones) that were photochemically formed by hydrocarbon oxidation. Overall, k OH was dominated by organic compounds, which had a maximum contribution of 85% in the afternoon. The paper demonstrates the usefulness of direct reactivity measurements, emphasizes the Correspondence to: A. Hofzumahaus (a.hofzumahaus@fz-juelich.de) need for direct measurements of oxygenated organic compounds in atmospheric chemistry studies, and discusses uncertainties of the modelling of OVOC reactivities.

Abstract. Ambient OH and HO2 concentrations were measured by laser induced fluorescence (LIF) during the PRIDE-PRD2006 (Program of Regional Integrated Experiments of Air Quality over the Pearl River Delta, 2006) campaign at a rural site downwind of the megacity of Guangzhou in Southern China. The observed OH concentrations reached daily peak values of (15–26) × 106 cm−3 which are among the highest values so far reported for urban and suburban areas. The observed OH shows a consistent high correlation with j(O1D) over a broad range of NOx conditions. The correlation cannot be reproduced by model simulations, indicating that OH stabilizing processes are missing in current models. The observed OH exhibited a weak dependence on NOx in contrast to model predictions. While modelled and measured OH agree well at NO mixing ratios above 1 ppb, a continuously increasing underprediction of the observed OH is found towards lower NO concentrations, reaching a factor of 8 at 0.02 ppb NO. A dependence of the modelled-to-measured OH ratio on isoprene cannot be concluded from the PRD data. However, the magnitude of the ratio fits into the isoprene dependent trend that was reported from other campaigns in forested regions. Hofzumahaus et al. (2009) proposed an unknown OH recycling process without NO, in order to explain the high OH levels at PRD in the presence of high VOC reactivity and low NO. Taking a recently discovered interference in the LIF measurement of HO2 into account, the need for an additional HO2 → OH recycling process persists, but the required source strength may be up to 20% larger than previously determined. Recently postulated isoprene mechanisms by Lelieveld et al. (2008) and Peeters and Müller (2010) lead to significant enhancements of OH expected for PRD, but an underprediction of the observed OH by a factor of two remains at low NO (0.1–0.2 ppb). If the photolysis of hydroperoxy aldehydes from isoprene is as efficient as proposed by Peeters and Müller (2010), the corresponding OH formation at PRD would be more important than the primary OH production from ozone and HONO. While the new isoprene mechanisms need to be confirmed by laboratory experiments, there is probably need for other, so far unidentified chemical processes to explain entirely the high OH levels observed in Southern China.

The most important chemical cleaning agent of the atmosphere is the hydroxyl radical, OH. It determines the oxidizing power of the atmosphere, and thereby controls the removal of nearly all gaseous atmospheric pollutants. The atmospheric supply of OH is limited, however, and could be overcome by consumption due to increasing pollution and climate change, with detrimental feedback effects. To date, the high variability of OH concentrations has prevented the use of local observations to monitor possible trends in the concentration of this species. Here we present and analyse long-term measurements of atmospheric OH concentrations, which were taken between 1999 and 2003 at the Meteorological Observatory Hohenpeissenberg in southern Germany. We find that the concentration of OH can be described by a surprisingly linear dependence on solar ultraviolet radiation throughout the measurement period, despite the fact that OH concentrations are influenced by thousands of reactants. A detailed numerical model of atmospheric reactions and measured trace gas concentrations indicates that the observed correlation results from compensations between individual processes affecting OH, but that a full understanding of these interactions may not be possible on the basis of our current knowledge of atmospheric chemistry. As a consequence of the stable relationship between OH concentrations and ultraviolet radiation that we observe, we infer that there is no long-term trend in the level of OH in the Hohenpeissenberg data set.

Abstract. A comprehensive field campaign was carried out in summer 2014 in Wangdu, located in the North China Plain. A month of continuous OH, HO2 and RO2 measurements was achieved. Observations of radicals by the laser-induced fluorescence (LIF) technique revealed daily maximum concentrations between (5–15)  × 106 cm−3, (3–14)  × 108 cm−3 and (3–15)  × 108 cm−3 for OH, HO2 and RO2, respectively. Measured OH reactivities (inverse OH lifetime) were 10 to 20 s−1 during daytime. The chemical box model RACM 2, including the Leuven isoprene mechanism (LIM), was used to interpret the observed radical concentrations. As in previous field campaigns in China, modeled and measured OH concentrations agree for NO mixing ratios higher than 1 ppbv, but systematic discrepancies are observed in the afternoon for NO mixing ratios of less than 300 pptv (the model–measurement ratio is between 1.4 and 2 in this case). If additional OH recycling equivalent to 100 pptv NO is assumed, the model is capable of reproducing the observed OH, HO2 and RO2 concentrations for conditions of high volatile organic compound (VOC) and low NOx concentrations. For HO2, good agreement is found between modeled and observed concentrations during day and night. In the case of RO2, the agreement between model calculations and measurements is good in the late afternoon when NO concentrations are below 0.3 ppbv. A significant model underprediction of RO2 by a factor of 3 to 5 is found in the morning at NO concentrations higher than 1 ppbv, which can be explained by a missing RO2 source of 2 ppbv h−1. As a consequence, the model underpredicts the photochemical net ozone production by 20 ppbv per day, which is a significant portion of the daily integrated ozone production (110 ppbv) derived from the measured HO2 and RO2. The additional RO2 production from the photolysis of ClNO2 and missing reactivity can explain about 10 % and 20 % of the discrepancy, respectively. The underprediction of the photochemical ozone production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.