Glyoxal (GLY) and methylglyoxal (MGLY), as tracers of oxidation of volatile organic compounds (VOCs), play an important role in atmospheric chemistry. In this work, the concentrations of these two aldehydes were simultaneously measured online at a regional site in Jiangsu Province (China) during the 2018 EXPLORE-YRD campaign. The maximum measured concentration of GLY and MGLY was 0.47 and 6.68 ppb, respectively. As the campaign site was surrounded by farmland and the observations were recorded during harvest, significant enhancements to the concentration of GLY and MGLY were found owing to agricultural biomass burning. While the enhancement of MGLY relative to CO (0.0059 ± 0.0012) was found to be consistent with previous study, the corresponding enhancement ratios of GLY were lower (0.0003 ± 0.0001). The possibility of using the ratios between formaldehyde (HCHO), GLY, and MGLY concentrations as indicators of reactive VOC composition was investigated. Based on measured data and model simulation results, we found that the MGLY to HCHO ratio was sensitive to VOC precursors and reasonably well correlated with the reactivity of aromatics.

Formaldehyde (HCHO) is the most abundant atmospheric carbonyl compound and plays an important role in the troposphere. However, HCHO detection via traditional incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) is limited by short optical path lengths and weak light intensity. Thus, a new light-emitting diode (LED)-based IBBCEAS was developed herein to measure HCHO in ambient air. Two LEDs (325 and 340 nm) coupled by a Y-type fiber bundle were used as an IBBCEAS light source, which provided both high light intensity and a wide spectral fitting range. The reflectivity of the two cavity mirrors used herein was 0.99965 (1 - reflectivity = 350 ppm loss) at 350 nm, which corresponded with an effective optical path length of 2.15 km within a 0.84 m cavity. At an integration time of 30 s, the measurement precision (1 sigma) for HCHO was 380 parts per trillion volume (pptv), and the corresponding uncertainty was 8.3%. The instrument was successfully deployed for the first time in a field campaign and delivered results that correlated well with those of a commercial wet-chemical instrument based on Hantzsch fluorimetry (R2 = 0.769). The combined light source based on a Y-type fiber bundle overcomes the difficulty of measuring ambient HCHO via IBBCEAS in near-ultraviolet range, which may extend IBBCEAS technology to measure other atmospheric trace gases with high precision.

Formaldehyde (HCHO) is one of the most important intermediate products of atmospheric photochemical reactions and is also a radical source that promotes ozone formation. Given its high solubility, HCHO is likely to exist in particulate form. In this work, gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were separated and collected by a rotating wet annular denude (RWAD) and an aerosol growth chamber–coil aerosol cooler (AC). The collected HCHO from the RWAD and AC are measured by two online Hantzsch method-based formaldehyde analyzers. The comprehensive campaign was held in the Yangtze River Delta of China from 15 May to 18 June 2018, which is during the harvest season. Several biomass burning events were identified by using acetonitrile as a tracer. During the period influenced by biomass burning, the mixing ratios of HCHOg and HCHOp were respectively 122% and 231% higher than those during other time periods. The enhancement ratio of HCHOg to acetonitrile obtained from this work generally agrees with those from the existing literature. Biomass burning contributed 14.8% to HCHOg, but the abundant freshly discharged precursors it emitted greatly promoted the secondary production of HCHOg. We suggest that the high concentration of HCHOp during the biomass burning period was from uptake of HCHOg by aerosols during their transportation; the liquid state particles are conducive to HCHOg uptake. High relative humidity, a low particle rebound fraction f, as well as low temperatures may result in higher uptake coefficient values.

Naphthalene (Nap) and methylnaphthalene (MN) are the most abundant polycyclic aromatic hydrocarbons (PAHs) in atmosphere and have been proposed to be important precursors of anthropogenic secondary organic aerosol (SOA) derived from laboratory chamber experiments. In this study, atmospheric Nap/MN and their gas-phase photooxidation products were quantified by a Proton Transfer Reaction-Quadrupole interface Time-of-Flight Mass Spectrometer (PTR-QiTOF) during the 2016 winter in Beijing. Phthalic anhydride, a late generation product from Nap under high-NOx conditions, appeared to be more prominent than 2-formylcinnamaldehyde (early generation product), possibly due to more sufficient oxidation during the haze. 1,2-Phthalic acid (1,2-PhA), the hydrated form of phthalic anhydride, was capable of partitioning into aerosol phase and served as a tracer to explore the contribution of Nap to ambient SOA. The measured fraction in particle phase (Fp) of 1,2-PhA averaged at 73 ± 13% with OA mass loadings of 52.5–87.8 μg/m3, lower than the value predicted by the absorptive partitioning model (100%). Using tracer product-based and precursor consumption-based methods, 2-ring PAHs (Nap and MN) were estimated to produce 14.9% (an upper limit) of the SOA formed in the afternoon during the wintertime haze, suggesting a comparable contribution of Nap and MN with monocyclic-aromatics on urban SOA formation.

A system based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) has been developed for simultaneous measurement of nitrogen dioxide (NO2), glyoxal (GLY), and methylglyoxal (MGLY). In this system, the measured light absorption at around 460 nm is spectrally resolved. The concentration of absorbers is determined from a multicomponent fit. At an integration time of 100 s, the measurement sensitivity (2 sigma) for NO2, GLY, and MGLY is 18, 30, and 100 ppt, respectively. The measurement uncertainty, which mainly originates from path length calibration, sampling loss, and uncertainty of absorption cross sections is estimated to be 8% for NO2, 8% for GLY, and 16% for MGLY. When deploying the instrument during field observations, we found significant influence of NO2 on the spectra fitting for retrieving GLY and MGLY concentrations, which is caused by the fact that NO2 has a higher absorption cross section and higher ambient concentration. In order to minimize such an effect, a NO2 photolytic convertor (NPC), which removes sampled NO2 at an efficiency of 76 %, was integrated on the IBBCEAS system. Since sampled GLY and MGLY are mostly (>= 95 %) conserved after passing through the NPC, the quality of the spectra fitting and the measurement accuracy of ambient GLY and MGLY under NO2-rich environments could be improved.

As nitrous acid (HONO) photolysis is an important source of hydroxyl radical (OH), apportionment of the ambient HONO sources is necessary to better understand atmospheric oxidation. Based on the data HONO-related species and various parameters measured during the one–month campaign at Wangdu (a rural site in North China plain) in summer 2014, a box model was adopted with input of current literature parametrizations for various HONO sources (nitrogen dioxide heterogeneous conversion, photoenhanced conversion, photolysis of adsorbed nitric acid and particulate nitrate, acid displacement, and soil emission) to reveal the relative importance of each source at the rural site. The simulation results reproduced the observed HONO production rates during noontime in general but with large uncertainty from both the production and destruction terms. NO2 photoenhanced conversion and photolysis of particulate nitrate were found to be the two major mechanisms with large potential of HONO formation but the associated uncertainty may reduce their importance to be nearly negligible. Soil nitrite was found to be an important HONO source during fertilization periods, accounted for (80 ± 6)% of simulation HONO during noontime. For some episodes of the biomass burning, only the NO2 heterogeneous conversion to HONO was promoted significantly. In summary, the study of the HONO budget is still far from closed, which would require a significant effort on both the accurate measurement of HONO and the determination of related kinetic parameters for its production pathways.

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.

Since 1971, it has been known that the atmospheric free radicals play a pivotal role in maintaining the oxidizing power of the troposphere. The existence of the oxidizing power is an important feature of the troposphere to remove primary air pollutants emitted from human beings as well as those from the biosphere. Nevertheless, serious secondary air-pollution incidents can take place due to fast oxidation of the primary pollutants. Elucidating the atmospheric free-radical chemistry is a demanding task in the field of atmospheric chemistry worldwide, which includes two kinds of work: first, the setup of reliable radical detection systems; second, integrated field studies that enable closure studies on the sources and sinks of targeted radicals such as OH and NO3. In this review, we try to review the Chinese efforts to explore the atmospheric free-radical chemistry in such chemical complex environments and the possible link of this fast gas-phase oxidation with the fast formation of secondary air pollution in the city-cluster areas in China.

Glyoxal (GLY) acts as a key contributor to tropospheric ozone production and secondary organic aerosol (SOA) formation on local to regional scales. The detection of GLY provides useful indicators of fast photochemistry occurring in the lower troposphere. The fast and sensitive detection of GLY is thus important, while traditional chemical ionization such as the proton-transfer reaction (PTR) is extremely limited by the poor detection limit and extensive fragmentation. To address these limitations, electron attachment reaction (EAR) ionization was applied to detect GLY. The generation of parent anions (GLY–) without fragmentation was observed, and cryogenic photoelectron imaging spectroscopy further characterized the structure of GLY–. The detection limit was estimated to be as low as (52 ± 1) pptv (parts per trillion by volume) with 1 min measurements. Other components in ambient air, such as water, carbon dioxide, and trace gases (acetone, propanal, etc.) have no effect on the detection of GLY. The EAR ionization is more promising than PTR ionization in detecting GLY. The detection of GLY in ambient air by the EAR ionization has been demonstrated.

A field campaign was conducted from November to December 2017 at the campus of Peking University (PKU) to investigate the formation mechanism of the winter air pollution in Beijing with the measurement of hydroxyl and hydroperoxyl radical (OH and HO2) with the support from comprehensive observation of trace gases compounds. The extent of air pollution depends on meteorological conditions. The daily maximum OH radical concentrations are on average 2.0 × 106 cm−3 and 1.5 × 106 cm−3 during the clean and polluted episodes, respectively. The daily maximum HO2 radical concentrations are on average 0.4 × 108 cm−3 and 0.3 × 108 cm−3 during the clean and polluted episodes, respectively (diurnal averaged for one hour bin). A box model based on RACM2-LIM1 mechanism can reproduce the OH concentrations but underestimate the HO2 concentrations by 50% during the clean episode. The OH and HO2 concentrations are underestimated by 50% and 12 folds during the polluted episode, respectively. Strong dependence on nitric oxide (NO) concentration is found for both observed and modeled HO2 concentrations, with the modeled HO2 decreasing more rapidly than observed HO2, leading to severe HO2 underestimation at higher NO concentrations. The OH reactivity is calculated from measured and modeled species and inorganic compounds (carbon monoxide (CO), NO, and nitrogen dioxide (NO2)) make up 69%–76% of the calculated OH reactivity. The photochemical oxidation rate denoted by the OH loss rate increases by 3 times from the clean to polluted episodes, indicating the strong oxidation capacity in polluted conditions. The comparison between measurements at PKU site and a suburban site from one previous study shows that chemical conditions are similar in both urban and suburban areas. Hence, the strong oxidation capacity and its potential contribution to the pollution bursts are relatively homogeneous over the whole Beijing city and its surrounding areas.

During the period 2012-2015, photolysis frequencies were measured at the Peking University site (PKUERS), a site representative of Beijing. We present a study of the effects of aerosols on two key photolysis frequencies, j((OD)-D-1) and j(NO2). Both j((OD)-D-1) and j(NO2) display significant dependence on aerosol optical depth (AOD; 380 nm) with a non-linear negative correlation. With the increase in AOD, the slopes of photolysis frequencies vs. AOD decrease, which indicates that the capacity of aerosols to reduce the actinic flux decreases with AOD. The absolute values of slopes are equal to 4.2-6.9x10(-6) and 3.4x10(-3) s(-1) per AOD unit for j((OD)-D-1) and j(NO2) respectively at a solar zenith angle (SZA) of 60 degrees and AOD smaller than 0.7, both of which are larger than those observed in a similar, previous study in the Mediterranean. This indicates that the aerosols in Beijing have a stronger extinction effect on actinic flux than absorptive dust aerosols in the Mediterranean. Since the photolysis frequencies strongly depended on the AOD and the SZA, we established a parametric equation to quantitatively evaluate the effect of aerosols on photolysis frequencies in Beijing. According to the parametric equation, aerosols lead to a decrease in seasonal mean j(NO2) by 24% and 30% for summer and winter, respectively, and a corresponding decrease in seasonal mean j((OD)-D-1) by 27% and 33 %, respectively, compared to an aerosol-free atmosphere (AOD = 0). Based on an observation campaign in August 2012, we used a photochemical box model to simulate the ozone production rate (P(O-3)). The simulation results shows that the monthly mean daytime net ozone production rate is reduced by up to 25% due to the light extinction of aerosols. Through further in-depth analysis, it was found that particulate matter concentra-tions maintain a high level under the condition of high concentrations of ozone precursors (volatile organic compounds, VOCs, and NOx), which inhibits the production of ozone to a large extent. This phenomenon implies a negative feedback mechanism in the atmospheric environment of Beijing.

芳香烃是城市地区人为源排放的重要挥发性有机物, 其光化学氧化与臭氧和细颗粒物的生成密切相关. 本研究以SAPHIR烟雾箱实验测得的甲苯光化学氧化反应数据为基础, 基于盒子模型搭载MCM3.3.1、SAPRC07、RACM2以及CB06机理对不同机理中的甲苯氧化机制进行比较. 结果表明, 四种机理均可较好地模拟甲苯光化学氧化过程中O3和OH自由基浓度以及OH总反应活性(kOH)的变化, 但是高估了PAN的浓度且低估了HCHO和HO2自由基的浓度. 本研究通过调整PAN、HCHO生成过程中重要的氧化中间态物种CH3CO3反应途径的分支比例, 并增加RO2和HO2反应再生OH的循环机制, 使模型模拟PAN、HCHO以及HO2自由基的结果得以改进, 表明未来对关键氧化中间态物种的准确测量将有助于对现有光化学反应机理的验证与更新.

羟基自由基(·OH)总反应性(kOH)是大气中所有·OH反应物的浓度与其·OH反应速率常数乘积的总和,对kOH的直接测量有助于识别未知的·OH反应物种及提升·OH收支分析的准确度.因此,本研究建立了一套基于激光光解-激光诱导荧光技术的kOH在线测量系统(LP-LIF),利用紫外脉冲激光在流动管内光解臭氧产生·OH,采用激光诱导荧光技术实时测量其与采样进入流动管的活性气体反应而导致的·OH浓度衰减,通过对该衰减进行指数拟合得到采样气的kOH.经实验室测试,LP-LIF系统对kOH的测量灵敏度为1.2 s^-1,时间分辨率5 min.应用该系统对2018年秋季深圳地区的大气kOH进行为期1个月的连续测量,结合同步观测的·OH反应物浓度数据发现,kOH观测值在10~30 s^-1之间,主要来自一氧化碳(14%)、氮氧化物(26%)和一次排放的挥发性有机物(24%).此外,由未测量的·OH反应物贡献的kOH平均约23%,且在夜间和早晚高峰时段贡献较高,推测其主要来自溶剂涂料、石化工业及LPG机动车排放.

Gaseous nitrous acid (HONO) is an important source of OH radicals in the troposphere. However, its source, especially that during daytime hours remains unclear. We present an instrument for simultaneous unambiguous measurements of HONO and NO2 with high time resolution based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). To achieve robust performance and system stability under different environment conditions, the current IBBCEAS instrument has been developed with significant improvements in terms of efficient sampling as well as resistance against vibration and temperature change, and the IBBCEAS instrument also has low power consumption and a compact design that can be easily deployed on different platforms powered by a high-capacity lithium ion battery. The effective cavity length of the IBBCEAS was determined using the absorption of O-2-O-2 to account for the "shortening" effect caused by the mirror purge flows. The wall loss for HONO was estimated to be 2.0% via a HONO standard generator. Measurement precisions (2 sigma) for HONO and NO2 are about 180 and 340 ppt in 30 s, respectively. A field inter-comparison was carried out at a rural suburban site in Wangdu, Hebei Province, China. The concentrations of HONO and NO2 measured by IBBCEAS were compared with a long optical path absorption photometer (LOPAP) and a NOx analyzer (Thermo Fisher Electron Model 42i), and the results showed very good agreement, with correlation coefficients (R-2) of HONO and NO2 being similar to 0.89 and similar to 0.95, respectively; in addition, vehicle deployments were also tested to enable mobile measurements of HONO and NO2, demonstrating the promising potential of using IBBCEAS for in situ, sensitive, accurate and fast simultaneous measurements of HONO and NO2 in the future.

The first wintertime in situ measurements of hydroxyl (OH), hydroperoxy (HO2) and organic peroxy (RO2) radicals (ROx = OH + HO2 + RO2) in combination with observations of total reactivity of OH radicals, k(OH) in Beijing are presented. The field campaign "Beijing winter finE particle STudy - Oxidation, Nucleation and light Extinctions" (BEST-ONE) was conducted at the suburban site Huairou near Beijing from January to March 2016. It aimed to understand oxidative capacity during wintertime and to elucidate the secondary pollutants' formation mechanism in the North China Plain (NCP). OH radical concentrations at noontime ranged from 2.4 x 10(6) cm(-3) in severely polluted air (k(OH) similar to 27s 1 / to 3.6 x 10(6) cm(-3) in relatively clean air (k(OH) similar to 5 s(-1)). These values are nearly 2-fold larger than OH concentrations observed in previous winter campaigns in Birmingham, Tokyo, and New York City. During this campaign, the total primary production rate of ROx radicals was dominated by the photolysis of nitrous acid accounting for 46% of the identified primary production pathways for ROx radicals. Other important radical sources were alkene ozonolysis (28 %) and photolysis of oxygenated organic compounds (24 %). A box model was used to simulate the OH, HO2 and RO2 concentrations based on the observations of their long-lived precursors. The model was capable of reproducing the observed diurnal variation of the OH and peroxy radicals during clean days with a factor of 1.5. However, it largely un-derestimated HO2 and RO2 concentrations by factors up to 5 during pollution episodes. The HO2 and RO2 observed-to-modeled ratios increased with increasing NO concentrations, indicating a deficit in our understanding of the gas-phase chemistry in the high NOx regime. The OH concentrations observed in the presence of large OH reactivities indicate that atmospheric trace gas oxidation by photochemical processes can be highly effective even during wintertime, thereby facilitating the vigorous formation of secondary pollutants.

Hydroxyl (OH) radical reactivity (k(OH)) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Julich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection < 1 s(-1) at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactivity method (CRM) has a higher limit of detection of 2 s(-1) at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flow-tube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (< 15 s(-1)) and low NO (< 5 ppbv) conditions.

In 2014, a large, comprehensive field campaign was conducted in the densely populated North China Plain. The measurement site was located in a botanic garden close to the small town Wangdu, without major industry but influenced by regional transportation of air pollution. The loss rate coefficient of atmospheric hydroxyl radicals (OH) was quantified by direct measurements of the OH reactivity. Values ranged between 10 and 20 s(-1) for most of the daytime. Highest values were reached in the late night with maximum values of around 40 s(-1). OH reactants mainly originated from anthropogenic activities as indicated (1) by a good correlation between measured OH reactivity and carbon monoxide (linear correlation coefficient R-2 = 0 : 33) and (2) by a high contribution of nitrogen oxide species to the OH reactivity (up to 30% in the morning). Total OH reactivity was measured by a laser flash photolysis-laser-induced fluorescence instrument (LP-LIF). Measured values can be explained well by measured trace gas concentrations including organic compounds, oxygenated organic compounds, CO and nitrogen oxides. Significant, unexplained OH reactivity was only observed during nights, when biomass burning of agricultural waste occurred on surrounding fields. OH reactivity measurements also allow investigating the chemical OH budget. During this campaign, the OH destruction rate calculated from measured OH reactivity and measured OH concentration was balanced by the sum of OH production from ozone and nitrous acid photolysis and OH regeneration from hydroperoxy radicals within the uncertainty of measurements. However, a tendency for higher OH destruction compared to OH production at lower concentrations of nitric oxide is also observed, consistent with previous findings in field campaigns in China.

Besides isoprene, monoterpenes are the non-methane volatile organic compounds (VOCs) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber). One focus of this study is on the OH budget in the degradation process. Therefore, the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC β-pinene, its main oxidation products, acetone and nopinone and photolysis frequencies. All experiments were carried out under low-NO conditions ( ≤  300 ppt) and at atmospheric β-pinene concentrations ( ≤  5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism (MCM) 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of 2, whereas the total OH reactivity was slightly overestimated because the model predicted a nopinone mixing ratio which was 3 times higher than measured. A new, theory-derived, first-generation product distribution by Vereecken and Peeters (2012) was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless, the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2. Although the mechanism of additional HO2 formation could not be resolved, our model studies suggest that an activated alkoxy radical intermediate proposed in the model of Vereecken and Peeters (2012) generates HO2 in a new pathway, whose importance has been underestimated so far. The proposed reaction path involves unimolecular rearrangement and decomposition reactions and photolysis of dicarbonyl products, yielding additional HO2 and CO. Further experiments and quantum chemical calculations have to be made to completely unravel the pathway of HO2 formation.

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) x 10(6) cm(-3), (3-14) x 10(8) cm(-3) and (3-15) x 10(8) 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 ppbvh(-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.

The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) is important to understanding the formation of particulate nitrate (pNO(3)(-)). Measurements of N2O5 in the surface layer taken at an urban site in Beijing are presented here. N2O5 was observed with large day-to-day variability. High N2O5 concentrations were determined during pollution episodes with the co-presence of large aerosol loads. The maximum value was 1.3 ppbv (5 s average), associated with an air mass characterized by a high level of O-3. N2O5 uptake coefficients were estimated to be in the range of 0.025-0.072 using the steady-state lifetime method. As a consequence, the nocturnal pNO(3)(-) formation potential by N2O5 heterogeneous uptake was calculated to be 24-85 mu g m(-3) per night and, on average, 57 mu g m(-3) during days with pollution. This was comparable to or even higher than that formed by the partitioning of HNO3. The results highlight that N2O5 heterogeneous hydrolysis is vital in pNO(3)(-) formation in Beijing.