科研成果 by Type: 期刊论文

2018
Duan J, Qin M, Ouyang B, Fang W, Li X, Lu K, Tang K, Liang S, Meng F, Hu Z. Development of an incoherent broadband cavity-enhanced absorption spectrometer for in situ measurements of HONO and NO 2. Atmospheric Measurement Techniques. 2018;11(7).
Le Breton M *, Hallquist AM, Pathak RK, Simpson D, Wang YJ, Johansson J, Zheng J, Yang YD, Shang DJ, Wang HC, et al. Chlorine oxidation of VOCs at a semi-rural site in Beijing: significant chlorine liberation from ClNO 2 and subsequent gas-and particle-phase Cl–VOC production. Atmospheric Chemistry and Physics. 2018;18(17):13013-13030.
Tham YJ, Wang Z, Li Q, Wang W, Wang X, Lu K, Ma N, Yan C, Kecorius S, Wiedensohler A. Heterogeneous N2O5 uptake coefficient and production yield of ClNO2 in polluted northern China: roles of aerosol water content and chemical composition. Atmospheric Chemistry and Physics. 2018;18(17):13155-13171.
蒋美青, 陆克定, 苏榕, 谭照峰, 王红丽, 李莉, 伏晴艳, 翟崇治, 谭钦文, 岳玎利. 我国典型城市群 O3 污染成因和关键 VOCs 活性解析. 科学通报. 2018;63:1130.PKU 
Wang L, Wang X, Gu R, Wang H, Yao L, Wen L, Zhu F, Wang W, Xue L, Yang L, et al. Observations of fine particulate nitrated phenols in four sites in northern China: concentrations, source apportionment, and secondary formation. Atmospheric Chemistry and Physics [Internet]. 2018;18:4349–4359. 访问链接
Wang HC, Lu KD, Chen XR, Zhu QD, Wu ZJ, Wu YS, Sun K. Fast particulate nitrate formation via N2O5 uptake aloft in winter in Beijing. Atmos. Chem. Phys. [Internet]. 2018;(18):10483-10495. 访问链接Abstract
Particulate nitrate (pNO3-) is an important component of secondary aerosols in urban areas. Therefore, it is critical to explore its formation mechanism to assist with the planning of haze abatement strategies. Here we report vertical measurement of NOx and O3 by in-situ instruments on a movable carriage on a tower during a winter heavy-haze episode (December 18 to 20, 2016) in urban Beijing, China. Based on the box model simulation at different height, we found that pNO3- formation via N2O5 heterogeneous uptake was negligible at ground level due to N2O5 concentration of near zero controlling by high NO emission and NO concentration. In contrast, the contribution from N2O5 uptake was large at high altitudes (e.g., > 150 m), which was supported by the low total oxidant (NO2 + O3) level at high altitudes than that at ground level. Modeling results show the specific case that the nighttime integrated production of pNO3- for the high-altitude air mass above urban Beijing was estimated to be 50 μg m-3 and enhanced the surface-layer pNO3- the next morning by 28 μg m-3 through vertical mixing. Sensitivity tests suggested that the nocturnal NOx loss by NO3-N2O5 chemistry was maximized once the N2O5 uptake coefficient was over 2×10-3 on polluted days with Sa was 3000 μm2 cm-3 in wintertime. The case study provided a chance to highlight that pNO3- formation via N2O5 heterogeneous hydrolysis may be an important source of the particulate nitrate in the urban airshed during wintertime.
Wang HC, Lu KD, Guo S, Wu ZJ, Shang DJ, Tan ZF, Wang YJ, Le Breton M, Lou SR, Tang MJ, et al. Efficient N2O5uptake and NO3oxidation in the outflow of urban Beijing. Atmos. Chem. Phys. [Internet]. 2018;(18):9705-9721. 访问链接Abstract
Nocturnal reactive nitrogen compounds play an important role in regional air pollution. Here we present the measurements of dinitrogen pentoxide (N2O5) associated with nitryl chloride (ClNO2) and particulate nitrate (pNO3-) in a suburban site of Beijing in the summer of 2016. High levels of N2O5 and ClNO2 were observed in the outflow of the urban Beijing air masses, with 1-min average maxima of 937 pptv and 2900 pptv, respectively. The N2O5 uptake coefficients, γ, and ClNO2 yield, f, were experimentally determined from the observed parameters. The N2O5 uptake coefficient ranged from 0.012 to 0.055, with an average of 0.034 ± 0.018, which is in the upper range of previous field studies reported in North America and Europe but is a moderate value in the North China Plain (NCP), which reflects efficient N2O5 heterogeneous processes in Beijing. The ClNO2 yield exhibited high variability, with a range of 0.50 to unity and an average of 0.73 ± 0.25. The concentration of the nitrate radical (NO3) was calculated assuming that the thermal equilibrium between NO3 and N2O5 was maintained. In NOx-rich air masses, the oxidation of nocturnal biogenic volatile organic compounds (BVOCs) was dominated by NO3 rather than O3. The production rate of organic nitrate (ON) via NO3+BVOCs was significant, with an average of 0.10 ± 0.07 ppbv h-1. We highlight the importance of NO3 oxidation of VOCs in the formation of ON and subsequent secondary organic aerosols in summer in Beijing. 
Tan ZF, Rohrer F, Lu KD, Ma XF, Bohn B, Broch S, Dong HB, Fuchs H, Gkatzelis G, Hofzumahaus A, et al. Wintertime photochemistry in Beijing: Observations of ROx radical concentrations in the North China Plain during the BEST-ONE campaign. Atmos. Chem. Phys. [Internet]. 2018. 访问链接Abstract
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, kOH 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 2.4×106cm−3 in severely polluted air (kOH~27s−1) to 3.6×106cm−3 in relatively clean air (kOH~5s−1). These values are nearly two-fold larger than OH concentrations observed in previous winter campaign 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 ROxradicals. 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 underestimated 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 NOxregime. 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.
Le Breton M, Wang YJ, Hallquist M, Pathak RK, Zheng J, Yang Y, Shang D, Glasius M, Bannan TJ, Liu Q, et al. Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS. Atmospheric Chemistry and Physics [Internet]. 2018;18:10355–10371. 访问链接
Tan ZF, Lu KD, Jiang MQ, Su R, Dong HB, Zeng LM, Xie SD, Tan QW, Zhang YH. Exploring ozone pollution in Chengdu, southwestern China: A case study from radical chemistry to O3-VOC-NOx sensitivity. Science of the Total Environment [Internet]. 2018;(636):775-786. 访问链接Abstract
We present the in-situ measurements in Chengdu, a major city in south west of China, in September 2016. The concentrations of ozone and its precursor were measured at four sites. Although the campaign was conducted in early autumn, up to 100 ppbv (parts per billion by volume) daily maximum ozone was often observed at all sites. The observed ozone concentrations showed good agreement at all sites, which implied that ozone pollution is a regional issue in Chengdu. To better understand the ozone formation in Chengdu, an observation based model is used in this study to calculate the ROx radical concentrations (ROx = OH + HO2 + RO2) and ozone production rate (P(O3)). The model predicts OH daily maximum is in the range of 4–8 × 106 molecules cm−3 , and HO2 and RO2 are in the range of 3–6 × 108 molecules cm−3 . The modelled radical concentrations show a distinct difference between ozone pollution and attainment period. The relative incremental reactivity (RIR) results demonstrate that anthropogenic VOCs reduction is the most efficient way to mitigate ozone pollution at all sites, of which alkenes dominate >50% of the ozone production. Empirical kinetic modelling approach shows that three out of four sites are under the VOC-limited regime, while Pengzhou is in a transition regime due to the local petrochemical industry. The ozone budget analysis showed that the local ozone production driven by the photochemical process is important to the accumulation of ozone concentrations.
Su R, Lu KD, Yu JY, Tan ZF, Jiang MQ, Li J, Xie SD, Wu YS, Zeng LM, Zhai CZ, et al. Exploration of the formation mechanism and source attribution of ambient ozone in Chongqing with an observation-based model. Science China-Earth SciencesScience China-Earth SciencesScience China-Earth Sciences. 2018;61:23-32.Abstract
An intensive field campaign was conducted in Chongqing during the summer of 2015 to explore the formation mechanisms of ozone pollution. The sources of ozone, the local production rates, and the controlling factors, as well as key species of volatile organic compounds (VOCs), were quantified by integrating a local ozone budget analysis, calculations of the relative incremental reactivity, and an empirical kinetic model approach. It was found that the potential for rapid local ozone formation exists in Chongqing. During ozone pollution episodes, the ozone production rates were found to be high at the upwind station Nan Quan, the urban station Chao Zhan, and the downwind station Jin-Yun Shan. The average local ozone production rate was 30x10(-9) V/V h(-1) and the daily integration of the produced ozone was greater than 180x10(-9) V/V. High ozone concentrations were associated with urban and downwind air masses. At most sites, the local ozone production was VOC-limited and the key species were aromatics and alkene, which originated mainly from vehicles and solvent usage. In addition, the air masses at the northwestern rural sites were NO (x) -limited and the local ozone production rates were significantly higher during the pollution episodes due to the increased NO (x) concentrations. In summary, the ozone abatement strategies of Chongqing should be focused on the mitigation of VOCs. Nevertheless, a reduction in NO (x) is also beneficial for reducing the regional ozone peak values in Chongqing and the surrounding areas.
Wu ZJ, Wang Y, Tan TY, Zhu YS, Li MR, Shang DJ, Wang HC, Lu KD, Guo S, Zeng LM, et al. Aerosol Liquid Water Driven by Anthropogenic Inorganic Salts: Implying Its Key Role in Haze Formation over the North China Plain. Environmental Science & Technology Letters. 2018;5:160-166.Abstract
This study reveals aerosol liquid water content (ALWC) in PM2.5 ranged from 2% up to 74%, and the associated secondary inorganic fraction rose from 24% to 55%, while ambient relative humidity (RH) increased from 15% to 83% in the atmosphere over Beijing. Unexpectedly, the secondary inorganic fraction in PM2.5 increased with an increase in the ambient RH, which is a meteorological parameter independent of anthropogenic activities, indicating the presence of a feedback mechanism driven by Henry's law and thermodynamic equilibrium. During haze episodes, simultaneously elevated RH levels and anthropogenic secondary inorganic mass concentrations resulted in an abundant ALWC. The condensed water could act as an efficient medium for multiphase reactions, thereby facilitating the transformation of reactive gaseous pollutants into particles and accelerating the formation of heavy haze. ALWC was well correlated with the mass concentrations of both nitrate and sulfate, indicating both nitrate and sulfate salts play key roles in determining ALWC. Coincident with a significant reduction in SO2 emissions throughout China, nitrates will become a dominant anthropogenic inorganic salt driving ALWC. Thus, the abundance of ALWC and its effects on the aerosol chemistry and climate should be reconsidered.
Li ZY, Zhu R, Xie PH, Wang HC, Lu KD, Wang D. Intercomparison of in situ CRDS and CEAS for measurements of atmospheric N2O5 in Beijing, China. Science of the Total Environment. 2018;613:131-139.Abstract
Dinitrogen pentoxide (N2O5) is one of the basic trace gases which plays a key role in nighttime atmosphere. An intercomparison and validation of different N2O5 measurement methods is important for determining the true accuracy of these methods. Cavity ring down spectroscopy (CRDS) and cavity enhanced absorption spectrometer (CEAS) were used to measure N2O5 at the campus of the University of Chinese Academy of Sciences (UCAS) from February 21, 2016 to March 4, 2016. The detection limits were 1.6 ppt (1 sigma) at 30 s intervals for the CEAS instrument and 3.9 ppt (1 sigma) at 10 s time resolution for the CRDS instrument respectively. In this study, a comparison of the 1 min observations from the two instruments was presented. The two data sets showed a good agreement within their uncertainties, with an absolute shift of 15.6 ppt, slope of 0.94 and a correlation coefficient R-2 = 0.97. In general, the difference between the CRDS and CEAS instruments for N2O5 measurement can be explained by their combined measurement uncertainties. However, high relative humidity (> 60%) and high PM2.5 concentration (> 200 mu g/m(3)) may contribute to the discrepancies. The excellent agreement between the measurement by the CRDS and CEAS instruments demonstrates the capability of the two instruments for accurately measuring N2O5 with high sensitivity. (C) 2017 Elsevier B.V. All rights reserved.
2017
Liu Y, Lu K, Ma Y, Yang X, Zhang W, Wu Y, Peng JF, Shuai S, Hu M, Zhang Y. Direct emission of nitrous acid (HONO) from gasoline cars in China determined by vehicle chassis dynamometer experiments. ATMOSPHERIC ENVIRONMENT. 2017;169:89-96.Abstract
HONO plays a key role in atmospheric chemistry, and while its importance is well-known, the sources of HONO are still not completely understood. As a component of ambient HONO sources, direct emission from vehicles is an area that should be extensively studied. In this study, we determined the HONO emission index for typical gasoline vehicles in the car population of China through a chassis dynamometer with different types of engines (PFI/GDI), starting conditions (cold/warm) and running styles (Beijing cycle). Emission ratios of HONO to nitrogen oxide (NOx) for the Chinese gasoline cars are determined to be in the range of (0.03-0.42) % and an averaged value is about 0.18%, which are comparable to those reported in the few studies available in Europe, the United States and Japan for gasoline cars while smaller for those of the diesel cars. The atmospheric impact of the direct HONO emission from gasoline cars was analyzed for a typical urban site in Beijing, significant contributions of the direct emission toward the HONO budget were found during morning rush hours or twilight conditions to be 8-12%. (C) 2017 Published by Elsevier Ltd.
Yang YD, Shao M, Kessel S, Li Y, Lu KD, Lu SH, Williams J, Zhang YH, Zeng LM, Noelscher AC, et al. How the OH reactivity affects the ozone production efficiency: case studies in Beijing and Heshan, China. Atmospheric Chemistry and PhysicsAtmospheric Chemistry and PhysicsAtmospheric Chemistry and Physics. 2017;17:7127-7142.Abstract
Total OH reactivity measurements were conducted on the Peking University campus (Beijing) in August 2013 and in Heshan (Guangdong province) from October to November 2014. The daily median OH reactivity was 20 +/- 11 s(-1) in Beijing and 31 +/- 20 s(-1) in Heshan, respectively. The data in Beijing showed a distinct diurnal pattern with the maxima over 27 s(-1) in the early morning and minima below 16 s(-1) in the afternoon. The diurnal pattern in Heshan was not as evident as in Beijing. Missing reactivity, defined as the difference between measured and calculated OH reactivity, was observed at both sites, with 21% missing reactivity in Beijing and 32% missing reactivity in Heshan. Unmeasured primary species, such as branched alkenes, could contribute to missing reactivity in Beijing, especially during morning rush hours. An observation-based model with the RACM2 (Regional Atmospheric Chemical Mechanism version 2) was used to understand the daytime missing reactivity in Beijing by adding unmeasured oxygenated volatile organic compounds and simulated intermediates of the degradation from primary volatile organic compounds (VOCs). However, the model could not find a convincing explanation for the missing reactivity in Heshan, where the ambient air was found to be more aged, and the missing reactivity was presumably attributed to oxidized species, such as unmeasured aldehydes, acids and dicarbonyls. The ozone production efficiency was 21% higher in Beijing and 30% higher in Heshan when the model was constrained by the measured reactivity, compared to the calculations with measured and modeled species included, indicating the importance of quantifying the OH reactivity for better understanding ozone chemistry.
Wu ZJ, Ma N, Gross J, Kecorius S, Lu KD, Shang DJ, Wang Y, Wu YS, Zeng LM, Hu M, et al. Thermodynamic properties of nanoparticles during new particle formation events in the atmosphere of North China Plain. Atmospheric ResearchAtmospheric Research. 2017;188:55-63.Abstract
To better understand the sources, formation, and the transport of air pollutants over North China Plain (NCP), a four-week intensive campaign during summertime in 2014 was conducted in a central NCP rural site. In this study, particle hygroscopicity and volatility measurements were focused to characterize the thermodynamic properties of nanoparticles and gain insight into chemical composition of nanoparticles during the new particle formation (NPF) events. The water-soluble fractions of 30 and 50 nm newly formed particles were respectively 0.64 +/- 0.06 and 0.61 +/- 0.06, indicating that the water-soluble chemical compounds, most likely ammonium sulfate, dominated the condensational growth of newly formed particles over the NCP. Due to containing higher water-soluble fraction, nanoparticles can be activated as cloud condensation nuclei (CCN) at lower supersaturation in the atmosphere of NCP in contrast to cleaner environments, such as Melpitz (Central European background) and Hyytiala (boreal forest) during the NPF events. Our observations showed that the NPF and subsequent growth significantly resulted in an enhancement in CCN number concentration. The ranges of enhancement factors of CCN number concentration for supersaturation (SS) = 0.2, 0.4, 0.8% were respectively 1.9-7.0, 2.7-8.4, and 3.6-10.1. After being heated to 300 degrees C, the shrink factors for 30 and 50 nm particles were respectively 0.35 and 038. This indicated that non-volatile compounds could be produced during the growth process of newly formed particles. (C) 2017 Elsevier B.V. All rights reserved.
Tang MJ, Huang X, Lu KD, Ge MF, Li YJ, Cheng P, Zhu T, Ding AJ, Zhang YH, Gligorovski S, et al. Heterogeneous reactions of mineral dust aerosol: implications for tropospheric oxidation capacity. Atmospheric Chemistry and PhysicsAtmospheric Chemistry and PhysicsAtmospheric Chemistry and Physics. 2017;17:11727-11777.Abstract
Heterogeneous reactions of mineral dust aerosol with trace gases in the atmosphere could directly and indirectly affect tropospheric oxidation capacity, in addition to aerosol composition and physicochemical properties. In this article we provide a comprehensive and critical review of laboratory studies of heterogeneous uptake of OH, NO3, O-3, and their directly related species as well (including HO2, H2O2, HCHO, HONO, and N2O5) by mineral dust particles. The atmospheric importance of heterogeneous uptake as sinks for these species is assessed (i) by comparing their lifetimes with respect to heterogeneous reactions with mineral dust to lifetimes with respect to other major loss processes and (ii) by discussing relevant field and modeling studies. We have also outlined major open questions and challenges in laboratory studies of heterogeneous uptake by mineral dust and discussed research strategies to address them in order to better understand the effects of heterogeneous reactions with mineral dust on tropospheric oxidation capacity.
Tan ZF, Fuchs H, Lu KD, Hofzumahaus A, Bohn B, Broch S, Dong HB, Gomm S, Haseler R, He LY, et al. Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO2 and RO2 radicals. Atmospheric Chemistry and PhysicsAtmospheric Chemistry and Physics. 2017;17:663-690.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) 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.
Ma YF, Lu KD, Chou CCK, Li XQ, Zhang YH. Strong deviations from the NO-NO2-O-3 photostationary state in the Pearl River Delta: Indications of active peroxy radical and chlorine radical chemistry. Atmospheric EnvironmentAtmospheric Environment. 2017;163:22-34.Abstract
Simultaneous measurements of meteorological data, trace gases, and volatile organic compounds were made in two regional sites, viz. Backgarden and Kaiping, in the Pearl River Delta (PRD) during summer and autumn, respectively. The strong deviations from the NO-NO2-O-3 Photostationary State, quantified by the leighton ratios, are carefully deduced through a comprehensive data set consist of the high-quality measurements of NO, NO2, O-3 and JNoz as well as the peroxy radical measurements. This is the first report of the Leighton ratio in China, with relatively high recorded values of 2.3 +/- 0.4 (Backgarden) and 3.1 +/- 1.4 (Kaiping), suggesting a strongly oxidising atmosphere in the PRD, typical of the ozone pollution season. A sensitivity analysis using a zero-dimensional chemical box model based on the regional atmospheric chemistry mechanism, version 2 (RACM2) constrained by the experimental measurements, indicated that peroxy radicals account for 70 (Backgarden) and 66% (Kaiping) of the observed positive deviations from the NOx photostationary state (characterized by a Leighton ratio of 1) on average. We consider that the remaining deviations result from neglecting the effects of chlorine chemistry, so We introduced a Cl chemistry module into RACM2, and the modelled results for Cl were as follows: 4.7 x 10(-4) pptv in Backgarden and 1.3 x 10(-3) pptv in Kaiping; these results are lower than the CI concentration derived from the NOx photostationary state. More work is required to confirm the role of additional peroxy radical sources at both high and low NOx regimes, as well as that of the halogen radicals, in perturbing the NO-NOx-O-3 cycle, which would significantly enhance trace gas removal and photochemical ozone production. (C) 2017 Elsevier Ltd. All rights reserved.
Liu XX, Qu H, Huey LG, Wang YH, Sjostedt S, Zeng LM, Lu KD, Wu YS, Ho M, Shao M, et al. High Levels of Daytime Molecular Chlorine and Nitryl Chloride at a Rural Site on the North China Plain. Environmental Science & TechnologyEnvironmental Science & TechnologyEnviron Sci Technol. 2017;51:9588-9595.Abstract
Molecular chlorine (Cl-2) and nitryl chloride (GINO(2)) concentrations were measured using chemical ionization mass spectrometry at a rural site over the North China Plain during June 2014. High levels of daytime Cl-2 up to similar to 450 pptv were observed. The average diurnal Cl-2 mixing ratios showed a maximum around noon at pptv. ClNO2 exhibited a strong diurnal variation with early morning maxima reaching ppbv levels and afternoon minima sustained above 60 pptv. A moderate correlation (R-2 = 0.31) between Cl-2 and sulfur dioxide was observed, perhaps indicating a role for power plant emissions in the generation of the observed chlorine. We also observed a strong correlation (R-2 = 0.83) between daytime (10:00-20:00) Cl-2 and ClNO2, which implies that both of them were formed from a similar mechanism. In addition, Cl-2 production is likely associated with a photochemical mechanism as Cl-2 concentrations varied with ozone (O-3) levels. The impact of Cl-2 and ClNO2 as Cl atom sources is investigated using a photochemical box model. We estimated that the produced Cl atoms oxidized slightly more alkanes than OH radicals and enhanced the daily concentrations of peroxy radicals by 15% and the O-3 production rate by 19%.

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