Nighttime HOx chemistry was investigated in two ground-based field campaigns (PRIDE-PRD2006 and CAREBEIJING2006) in summer 2006 in China by comparison of measured and modeled concentration data of OH and HO2. The measurement sites were located in a rural environment in the Pearl River Delta (PRD) under urban influence and in a suburban area close to Beijing, respectively. In both locations, significant nighttime concentrations of radicals were observed under conditions with high total OH reactivities of about 40-50 s(-1) in PRD and 25 s(-1) near Beijing. For OH, the nocturnal concentrations were within the range of (0.5-3) x 10(6) cm(-3), implying a significant nighttime oxidation rate of pollutants on the order of several ppb per hour. The measured nighttime concentration of HO2 was about (0.2-5) x 10(8) cm(-3), containing a significant, model-estimated contribution from RO2 as an interference. A chemical box model based on an established chemical mechanism is capable of reproducing the measured nighttime values of the measured peroxy radicals and k(OH), but underestimates in both field campaigns the observed OH by about 1 order of magnitude. Sensitivity studies with the box model demonstrate that the OH discrepancy between measured and modeled nighttime OH can be resolved, if an additional ROx production process (about 1 ppb h(-1)) and additional recycling (RO2 -> HO2 -> OH) with an efficiency equivalent to 1 ppb NO is assumed. The additional recycling mechanism was also needed to reproduce the OH observations at the same locations during daytime for conditions with NO mixing ratios below 1 ppb. This could be an indication that the same missing process operates at day and night. In principle, the required primary ROx source can be explained by ozonolysis of terpenoids, which react faster with ozone than with OH in the nighttime atmosphere. However, the amount of these highly reactive biogenic volatile organic compounds (VOCs) would require a strong local source, for which there is no direct evidence. A more likely explanation for an additional ROx source is the vertical downward transport of radical reservoir species in the stable nocturnal boundary layer. Using a simplified one-dimensional two-box model, it can be shown that ground-based NO emissions could generate a large vertical gradient causing a downward flux of peroxy acetic nitrate (PAN) and peroxymethacryloyl nitrate (MPAN). The downward transport and the following thermal decomposition of these compounds can produce up to 0.3 ppb h(-1) radicals in the atmospheric layer near the ground. Although this rate is not sufficient to explain the complete OH discrepancy, it indicates the potentially important role of vertical transport in the lower nighttime atmosphere.

Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene(1-8). Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed(5,9-11). Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain(12-14). Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations(9-11). Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.

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) x 10(6) 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((OD)-D-1) 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 Muller (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 Muller (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.

We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1-5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH + NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of approximate to 200 ppt indicate the existence of a daytime source higher than the OH + NO -> HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (P-M) was calculated to be 0.77 ppb h(-1) on average. This value compares well to previous measurements in other environments. Our analysis of P-M provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation.

Researches on HO(x) radical chemistry would provide theoretical support for understanding the global climate change and regional air pollution control. At present stage, comprehensive field campaign including HO(x) radial measurements is one of the critical approaches to advance it. However, due to the very short lifetime and extremely low concentration of HO(x) in the atmosphere, direct measurement of HO(x) radical is one of most challenged works in atmospheric chemistry. This paper reviews the direct measurement techniques of the HO(x) radical, summarizes the observed dynamics range of its concentrations, introduces the current schematic diagram of the HO(x) radical chemistry and the important contributions from previous field studies, and discusses the main scientific questions that need further researches. Besides, the progress of the HO(x) radical chemistry in China is reviewed, and several potentially important research directions are pointed out.

For CareBeijing-2006, two sites were established in urban and suburban regions of Beijing in summer 2006. Observations of O(3) and its precursors together with meteorological parameters at both sites are presented. Gross ozone production rate P(O(3)) and sensitivity to nitric oxides (NO(x)) and volatile organic compounds (VOCs) were investigated using an observation-based photochemical box model (OBM). P(O(3)) varied from nearly zero to 120 and 50 ppb h(-1) for urban and suburban sites, respectively. These rates were greater than the accumulation rates of the observed oxidant (O(3) + NO(2)) concentrations. The O(3) episodes typically appeared under southerly wind conditions with high P(O(3)), especially at the urban site. Sensitivity studies with and without measured nitrous acid (HONO) as a model constraint suggested that the estimated P(O(3)) at both sites was strongly enhanced by radical production from HONO photolysis. Both NO(x)- and VOC-sensitive chemistries existed over time scales from hours to days at the two sites. The variation in O(3)-sensitive chemistry was relatively well explained by the ratio of the average daytime total VOC reactivity (k(TVOC)) to NO, with the transition chemistry corresponding to a k(TVOC)/NO value of 2-4 s(-1) ppb(-1). Pronounced diurnal variations in the O(3) production regime were found. In the morning, conditions were always strongly VOC-limited, while in the afternoon, conditions were variable for different days and different sites. The model-calculated results were tested by measurements of H(2)O(2), HNO(3), total OH reactivity, and HO(x) radicals. The OBM was generally capable of correctly simulating the levels of P(O(3)), although it might tend to overpredict the VOC-sensitive chemistry.