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2021 Vol. 38, No. 7

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Editorial Notes
Preface to the Special Issue on Atmospheric Oxidation Capacity, Ozone, and PM2.5 Pollution: Quantification Methods, Formation Mechanisms, Simulation, and Control
Yuesi WANG, Zirui LIU
2021, 38(7): 1051-1052. doi: 10.1007/s00376-021-1001-6
Abstract:
Review
Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation
Li XU, Lin DU, Narcisse T. TSONA, Maofa GE
2021, 38(7): 1053-1084. doi: 10.1007/s00376-020-0284-3
Abstract:
Anthropogenic emissions alter biogenic secondary organic aerosol (SOA) formation from naturally emitted volatile organic compounds (BVOCs). We review the major laboratory and field findings with regard to effects of anthropogenic pollutants (NOx, anthropogenic aerosols, SO2, NH3) on biogenic SOA formation. NOx participate in BVOC oxidation through changing the radical chemistry and oxidation capacity, leading to a complex SOA composition and yield sensitivity towards NOx level for different or even specific hydrocarbon precursors. Anthropogenic aerosols act as an important intermedium for gas–particle partitioning and particle-phase reactions, processes of which are influenced by the particle phase state, acidity, water content and thus associated with biogenic SOA mass accumulation. SO2 modifies biogenic SOA formation mainly through sulfuric acid formation and accompanies new particle formation and acid-catalyzed heterogeneous reactions. Some new SO2-involved mechanisms for organosulfate formation have also been proposed. NH3/amines, as the most prevalent base species in the atmosphere, influence biogenic SOA composition and modify the optical properties of SOA. The response of SOA formation behavior to these anthropogenic pollutants varies among different BVOCs precursors. Investigations on anthropogenic–biogenic interactions in some areas of China that are simultaneously influenced by anthropogenic and biogenic emissions are summarized. Based on this review, some recommendations are made for a more accurate assessment of controllable biogenic SOA formation and its contribution to the total SOA budget. This study also highlights the importance of controlling anthropogenic pollutant emissions with effective pollutant mitigation policies to reduce regional and global biogenic SOA formation.
Spatial and Temporal Distributions and Sources of Anthropogenic NMVOCs in the Atmosphere of China: A Review
Fanglin WANG, Wei DU, Shaojun LV, Zhijian DING, Gehui WANG
2021, 38(7): 1085-1100. doi: 10.1007/s00376-021-0317-6
Abstract:
As the key precursors of O3, anthropogenic non-methane volatile organic compounds (NMVOCs) have been studied intensively. This paper performed a meta-analysis on the spatial and temporal variations of NMVOCs, their roles in photochemical reactions, and their sources in China, based on published research. The results showed that both non-methane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) in China have higher mixing ratios in the eastern developed cities compared to those in the central and western areas. Alkanes are the most abundant NMHCs species in all reported sites while formaldehyde is the most abundant among the OVOCs. OVOCs have the highest mixing ratios in summer and the lowest in winter, which is opposite to NMHCs. Among all NMVOCs, the top eight species account for 50%−70% of the total ozone formation potential (OFP) with different compositions and contributions in different areas. In devolved regions, OFP-NMHCs are the highest in winter while OFP-OVOCs are the highest in summer. Based on positive matrix factorization (PMF) analysis, vehicle exhaust, industrial emissions, and solvent usage in China are the main sources for NMHCs. However, the emission trend analysis showed that solvent usage and industrial emissions will exceed vehicle exhaust and become the two major sources of NMVOCs in near future. Based on the meta-analysis conducted in this work, we believe that the spatio-temporal variations and oxidation mechanisms of atmospheric OVOCs, as well as generating a higher spatial resolution of emission inventories of NMVOCs represent an area for future studies on NMVOCs in China.
Original Paper
Characteristics of Chemical Speciation in PM1 in Six Representative Regions in China
Kaixu BAI, Can WU, Jianjun LI, Ke LI, Jianping GUO, Gehui WANG
2021, 38(7): 1101-1114. doi: 10.1007/s00376-020-0224-2
Abstract:
A better knowledge of aerosol properties is of great significance for elucidating the complex mechanisms behind frequently occurring haze pollution events. In this study, we examine the temporal and spatial variations in both PM1 and its major chemical constituents using three-year field measurements that were collected in six representative regions in China between 2012 and 2014. Our results show that both PM1 and its chemical compositions varied significantly in space and time, with high PM1 loadings mainly observed in the winter. By comparing chemical constituents between clean and polluted episodes, we find that the elevated PM1 mass concentration during pollution events should be largely attributable to significant increases in organic matter (OM) and inorganic aerosols like sulfate, nitrate, and ammonium (SNA), indicative of the critical role of primary emissions and secondary aerosols in elevating PM1 pollution levels. The ratios of PM1/PM2.5 are found to be generally high in Shanghai and Guangzhou, while relatively low ratios are seen in Xi’an and Chengdu, indicating anthropogenic emissions were more likely to accumulate in forms of finer particles. With respect to the relative importance of chemical components and meteorological factors quantified via statistical modeling practices, we find that primary emissions and secondary aerosols were the two leading factors contributing to PM1 variations, though meteorological factors also played important roles in regulating the dispersion of atmospheric PM.
Characterization of Organic Aerosol at a Rural Site in the North China Plain Region: Sources, Volatility and Organonitrates
Qiao ZHU, Li-Ming CAO, Meng-Xue TANG, Xiao-Feng HUANG, Eri SAIKAWA, Ling-Yan HE
2021, 38(7): 1115-1127. doi: 10.1007/s00376-020-0127-2
Abstract:
The North China Plain (NCP) is a region that experiences serious aerosol pollution. A number of studies have focused on aerosol pollution in urban areas in the NCP region; however, research on characterizing aerosols in rural NCP areas is comparatively limited. In this study, we deployed a TD-HR-AMS (thermodenuder high-resolution aerosol mass spectrometer) system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols (PM1). The average PM1 mass concentration was 51.2 ± 48.0 μg m−3 and organic aerosol (OA) contributed most (35.4%) to PM1. Positive matrix factorization (PMF) analysis of OA measurements identified four OA factors, including hydrocarbon-like OA (HOA, accounting for 18.4%), biomass burning OA (BBOA, 29.4%), less-oxidized oxygenated OA (LO-OOA, 30.8%) and more-oxidized oxygenated OA (MO-OOA, 21.4%). The volatility sequence of the OA factors was HOA > BBOA > LO-OOA > MO-OOA, consistent with their oxygen-to-carbon (O:C) ratios. Additionally, the mean concentration of organonitrates (ON) was 1.48−3.39 μg m−3, contributing 8.1%–19% of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement. Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA. Also, volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas.
Particulate Amines in the Background Atmosphere of the Yangtze River Delta, China: Concentration, Size Distribution, and Sources
Wei DU, Xinpei WANG, Fengqin YANG, Kaixu BAI, Can WU, Shijie LIU, Fanglin WANG, Shaojun LV, Yubao CHEN, Jinze WANG, Wenliang LIU, Lujun WANG, Xiaoyong CHEN, Gehui WANG
2021, 38(7): 1128-1140. doi: 10.1007/s00376-021-0274-0
Abstract:
Amines are important for new particle formation and subsequent growth in the atmosphere. Consequently, the processes involved are receiving more attention in recent years. Here, we conduct a field observation in order to investigate the atmospheric particulate amines at a background site in the Yangtze River Delta (YRD) during the summer of 2018. Four amines in PM2.5, i.e., methylamine (MA), dimethylamine (DMA), diethylamine (DEA), and trimethylamine (TMA), were collected, twice daily and analyzed. During the campaign, our measurements found the concentrations of MA, DMA, DEA, and TMA of 15.0 ± 15.0, 6.3 ± 6.9, 20.4 ± 30.1, and 4.0 ± 5.9 ng m–3, respectively, and the four amines correlated well with each other. The concentration of amines appear to be independent of whether they were collected during the day or night. Both MA and DMA exhibited a bimodal size distribution that had peaks at 0.67 and 1.1 μm, suggesting amines preferably distribute on submicron particles. Boundary layer height (BLH), relative humidity, and pH of aerosols were found have a negative relationship with amines, while aerosol liquid water content (ALWC) was found to have a positive relationship with amines. The PMF (positive matrix factorization) source apportionment results showed that the main source of amines in Chongming Island was of anthropogenic origin such as industrial and biomass emission, followed by marine sources including sea salt and marine biogenic sources. Given that the YRD region is still suffering from complex atmospheric pollution and that the knowledge on aerosol amines is still limited, more field studies are in urgent need for a better understanding of the pollution characteristics of amines.
Impacts of Aerosol−Radiation Interactions on the Wintertime Particulate Pollution under Different Synoptic Patterns in the Guanzhong Basin, China
Naifang BEI, Xia LI, Qiyuan WANG, Suixin LIU, Jiarui WU, Jiayi LIANG, Lang LIU, Ruonan WANG, Guohui LI
2021, 38(7): 1141-1152. doi: 10.1007/s00376-020-0329-7
Abstract:
The effects of aerosol–radiation interactions (ARI) are not only important for regional and global climate, but they can also drive particulate matter (PM) pollution. In this study, the ARI contribution to the near-surface fine PM (PM2.5) concentrations in the Guanzhong Basin (GZB) is evaluated under four unfavorable synoptic patterns, including “north-low”, “transition”, “southeast-trough”, and “inland-high”, based on WRF-Chem model simulations of a persistent heavy PM pollution episode in January 2019. Simulations show that ARI consistently decreases both solar radiation reaching down to the surface (SWDOWN) and surface temperature (TSFC), which then reduces wind speed, induces sinking motion, and influences cloud formation in the GZB. However, large differences under the four synoptic patterns still exist. The average reductions of SWDOWN and daytime TSFC in the GZB range from 15.2% and 1.04°C in the case of the “transition” pattern to 26.7% and 1.69°C in the case of the “north-low” pattern, respectively. Furthermore, ARI suppresses the development of the planetary boundary layer (PBL), with the decrease of PBL height (PBLH) varying from 18.7% in the case of the “transition” pattern to 32.0% in the case of the “north-low” pattern. The increase of daytime near-surface PM2.5 in the GZB due to ARI is 12.0%, 8.1%, 9.5%, and 9.7% under the four synoptic patterns, respectively. Ensemble analyses also reveal that when near-surface PM2.5 concentrations are low, ARI tends to lower PM2.5 concentrations with decreased PBLH, which is caused by enhanced divergence or a transition from divergence to convergence in an area. ARI contributes 15%–25% toward the near-surface PM2.5 concentrations during the severe PM pollution period under the four synoptic patterns.
Analysis of the Effect of Optical Properties of Black Carbon on Ozone in an Urban Environment at the Yangtze River Delta, China
Junlin AN, Huan LV, Min XUE, Zefeng ZHANG, Bo HU, Junxiu WANG, Bin ZHU
2021, 38(7): 1153-1164. doi: 10.1007/s00376-021-0367-9
Abstract:
Black carbon (BC) reduces the photolysis coefficient by absorbing solar radiation, thereby affecting the concentration of ozone (O3) near the ground. The influence of BC on O3 has thus received much attention. In this study, Mie scattering and the tropospheric Ultraviolet and Visible radiation model are used to analyze the effect of BC optical properties on radiation. Combined with data of O3 precursors in Nanjing in 2014, an EKMA curve is drawn, and the variations in O3 concentration are further investigated using a zero-dimensional box mechanism model (NCAR MM). When O3 precursors are unchanged, radiation and O3 show a highly similar tendency in response to changing BC optical properties (R=0.997). With the increase of modal radius, the attenuation of fresh BC to radiation and O3 first trends upward before decreasing. In the mixing process, the attenuation of BC to radiation and O3 presents an upward tendency with the increase of relative humidity but decreases rapidly before increasing slowly with increasing thickness of coating. In addition, mass concentration is another major factor. When the BC to PM2.5 ratio increases to 5% in Nanjing, the radiation decreases by approximately 0.13%–3.71% while O3 decreases by approximately 8.13%–13.11%. The radiative effect of BC not only reduces O3 concentration but also changes the EKMA curve. Compared with the NOx control area, radiation has a significant influence on the VOCs control area. When aerosol optical depth (AOD) increases by 17.15%, the NOx to VOCs ratio decreases by 8.27%, and part of the original NOx control area is transferred to the VOCs control area.
Vertical Evolution of Boundary Layer Volatile Organic Compounds in Summer over the North China Plain and the Differences with Winter
Shuang WU, Guiqian TANG, Yinghong WANG, Rong MAI, Dan YAO, Yanyu KANG, Qinglu WANG, Yuesi WANG
2021, 38(7): 1165-1176. doi: 10.1007/s00376-020-0254-9
Abstract:
The vertical observation of volatile organic compounds (VOCs) is an important means to clarify the mechanisms of ozone formation. To explore the vertical evolution of VOCs in summer, a field campaign using a tethered balloon during summer photochemical pollution was conducted in Shijiazhuang from 8 June to 3 July 2019. A total of 192 samples were collected, 23 vertical profiles were obtained, and the concentrations of 87 VOCs were measured. The range of the total VOC concentration was 41–48 ppbv below 600 m. It then slightly increased above 600 m, and rose to 58 ± 52 ppbv at 1000 m. The proportion of alkanes increased with height, while the proportions of alkenes, halohydrocarbons and acetylene decreased. The proportion of aromatics remained almost unchanged. A comparison with the results of a winter field campaign during 8–16 January 2019 showed that the concentrations of all VOCs in winter except for halohydrocarbons were more than twice those in summer. Alkanes accounted for the same proportion in winter and summer. Alkenes, aromatics, and acetylene accounted for higher proportions in winter, while halohydrocarbons accounted for a higher proportion in summer. There were five VOC sources in the vertical direction. The proportions of gasoline vehicular emissions + industrial sources and coal burning were higher in winter. The proportions of biogenic sources + long-range transport, solvent usage, and diesel vehicular emissions were higher in summer. From the surface to 1000 m, the proportion of gasoline vehicular emissions + industrial sources gradually increased.
Vertical Profiles of Volatile Organic Compounds in Suburban Shanghai
Yuhan LIU, Hongli WANG, Shengao JING, Ming ZHOU, Shenrong LOU, Kun QU, Wanyi QIU, Qian WANG, Shule LI, Yaqin GAO, Yusi LIU, Xiaobing LI, Zhong-Ren PENG, Junhui CHEN, Keding LU
2021, 38(7): 1177-1187. doi: 10.1007/s00376-021-0126-y
Abstract:
As Volatile Organic Compounds (VOCs) are one of the precursors of ozone, their distribution and variable concentrations are highly related to local ozone pollution control. In this study, we obtained vertical profiles of VOCs in Shanghai’s Jinshan district on 8 September and 9 September in 2016 to investigate their distribution and impact on local atmospheric oxidation in the near surface layer. Vertical samples were collected from heights between 50 m and 400 m by summa canisters using an unmanned aerial vehicle (UAV). Concentrations of VOCs (VOCs refers to the 52 species measured in this study) varied minimally below 200 m, and decreased by 21.2% from 100 m to 400 m. The concentrations of VOCs above 200 m decreased significantly in comparison to those below 200 m. The proportions of alkanes and aromatics increased from 55.2% and 30.5% to 57.3% and 33.0%, respectively. Additionally, the proportion of alkenes decreased from 13.2% to 8.4%. Toluene and m/p-xylene were the key species in the formation of SOA and ozone. Principal component analysis (PCA) revealed that the VOCs measured in this study mainly originated from industrial emissions.
Evaluation and Evolution of MAX-DOAS-observed Vertical NO2 Profiles in Urban Beijing
Yanyu KANG, Guiqian TANG, Qihua LI, Baoxian LIU, Jianfeng CAO, Qihou HU, Yuesi WANG
2021, 38(7): 1188-1196. doi: 10.1007/s00376-021-0370-1
Abstract:
Multiaxis differential absorption spectroscopy (MAX-DOAS) is a newly developed advanced vertical profile detection method, but the vertical nitrogen dioxide (NO2) profiles measured by MAX-DOAS have not yet been fully verified. In this study, we perform MAX-DOAS and tower gradient observations to simultaneously acquire tropospheric NO2 observations in the Beijing urban area from 1 April to 31 May 2019. The average values of the tropospheric NO2 vertical column densities measured by MAX-DOAS and the tropospheric monitoring instrument are 15.8 × 1015 and 12.4 × 1015 molecules cm−2, respectively, and the correlation coefficient R reaches 0.87. The MAX-DOAS measurements are highly consistent with the tower-based in situ measurements, and the correlation coefficients R from the ground to the upper air are 0.89 (60 m), 0.87 (160 m), and 0.76 (280 m). MAX-DOAS accurately measures the trend of NO2 vertical profile changes, although a large underestimation occurs by a factor of two. By analyzing the NO2 vertical profile, the NO2 concentration reveals an exponential decrease with height. The NO2 vertical profile also coincides with the evolution of the boundary layer height. The study shows that the NO2 over Beijing mainly originates from local sources and occurs in the boundary layer, and its vertical evolution pattern has an important guiding significance to better understand nitrate production and ozone pollution.
Three-Year Observations of Ozone Columns over Polar Vortex Edge Area above West Antarctica
Yuanyuan QIAN, Yuhan LUO, Fuqi SI, Taiping YANG, Dongshang YANG
2021, 38(7): 1197-1208. doi: 10.1007/s00376-021-0243-7
Abstract:
Ozone vertical column densities (VCDs) were retrieved by Zenith Scattered Light-Differential Optical Absorption Spectroscopy (ZSL-DOAS) from January 2017 to February 2020 over Fildes Peninsula, West Antarctica (62.22°S, 58.96°W). Each year, ozone VCDs started to decline around July with a comparable gradient around 1.4 Dobson Units (DU) per day, then dropped to their lowest levels in September and October, when ozone holes appeared (less than 220 DU). Daily mean values of retrieved ozone VCDs were compared with Ozone Monitoring Instrument (OMI) and Global Ozone Monitoring Experiment 2 (GOME-2) satellite observations and the Modern-Era Retrospective analysis for Research and Applications Version 2 (MERRA-2) reanalysis dataset, with correlation coefficients (R2) of 0.86, 0.94, and 0.90, respectively. To better understand the causes of ozone depletion, the retrieved ozone VCDs, temperature, and potential vorticity (PV) at certain altitudes were analyzed. The profiles of ozone and PV were positively correlated during their fluctuations, which indicates that the polar vortex has a strong influence on stratospheric ozone depletion during Antarctic spring. Located at the edge of polar vortex, the observed data will provide a basis for further analysis and prediction of the inter-annual variations of stratospheric ozone in the future.
ROx Budgets and O3 Formation during Summertime at Xianghe Suburban Site in the North China Plain
Min XUE, Jianzhong MA, Guiqian TANG, Shengrui TONG, Bo HU, Xinran ZHANG, Xinru LI, Yuesi WANG
2021, 38(7): 1209-1222. doi: 10.1007/s00376-021-0327-4
Abstract:
Photochemical smog characterized by high concentrations of ozone (O3) is a serious air pollution issue in the North China Plain (NCP) region, especially in summer and autumn. For this study, measurements of O3, nitrogen oxides (NOx), volatile organic compounds (VOCs), carbon monoxide (CO), nitrous acid (HONO), and a number of key physical parameters were taken at a suburban site, Xianghe, in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O3 formation and find an optimal way to control O3 pollution. Here, the radical chemistry and O3 photochemical budget based on measurement data from 1−23 July using a chemical box model is investigated. The daytime (0600−1800 LST) average production rate of the primary radicals referred to as ROx (OH + HO2 + RO2) is 3.9 ppbv h−1. HONO photolysis is the largest primary ROx source (41%). Reaction of NO2 + OH is the largest contributor to radical termination (41%), followed by reactions of RO2 + NO2 (26%). The average diurnal maximum O3 production and loss rates are 32.9 ppbv h−1 and 4.3 ppbv h−1, respectively. Sensitivity tests without the HONO constraint lead to decreases in daytime average primary ROx production by 55% and O3 photochemical production by 42%, highlighting the importance of accurate HONO measurements when quantifying the ROx budget and O3 photochemical production. Considering heterogeneous reactions of trace gases and radicals on aerosols, aerosol uptake of HO2 contributes 11% to ROx sink, and the daytime average O3 photochemical production decreases by 14%. The O3-NOx-VOCs sensitivity shows that the O3 production at Xianghe during the investigation period is mainly controlled by VOCs.
Simulated Sensitivity of Ozone Generation to Precursors in Beijing during a High O3 Episode
Meng CUI, Xingqin AN, Li XING, Guohui LI, Guiqian TANG, Jianjun HE, Xin LONG, Shuman ZHAO
2021, 38(7): 1223-1237. doi: 10.1007/s00376-021-0270-4
Abstract:
This study uses the WRF-Chem model combined with the empirical kinetic modeling method (EKMA curve) to study the compound pollution event in Beijing that happened in 13−23 May 2017. Sensitivity tests are conducted to analyze ozone sensitivity to its precursors, and to develop emission reduction measures. The results suggest that the model can accurately simulate the compound pollution process of photochemistry and haze. When VOCs and NOx were reduced by the same proportion, the effect of O3 reduction at peak time was more obvious, and the effect during daytime was more significant than at night. The degree of change in ozone was peak time > daytime average. When reducing or increasing the ratio of precursors by 25% at the same time, the effect of reducing 25% VOCs on the average ozone concentration reduction was most significant. The degree of change in ozone decreased with increasing altitude, the location of the ozone maximum change shifted westward, and its range narrowed. As the altitude increases, the VOCs-limited zone decreases, VOCs sensitivity decreases, NOx sensitivity increases. The controlled area changed from near-surface VOCs-limited to high-altitude NOx-limited. Upon examining the EKMA curve, we have found that suburban and urban are sensitive to VOCs. The sensitivity tests indicate that when VOCs in suburban are reduced about 60%, the O3-1h concentration could reach the standard, and when VOCs of the urban decreased by about 50%, the O3-1h concentration could reach the standard. Thus, these findings could provide references for the control of compound air pollution in Beijing.
Smog Chamber Study on the Ozone Formation Potential of Acetaldehyde
Hailiang ZHANG, Yongfu XU, Long JIA, Min XU
2021, 38(7): 1238-1251. doi: 10.1007/s00376-021-0407-5
Abstract:
Acetaldehyde is one of the important VOC species of O3 precursors in the atmospheric environment. The influences of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the formation of O3 are studied in smog chamber experiments, and the MCM v3.3.1 mechanism of acetaldehyde is modified based on the experimental results. In low-RH conditions (RH = 11.6%±1.1%), the O3 concentration at 6 h increases first and then decreases with the increase of RCN, and the RCN at the inflection point of O3 concentrations is 3.2. In high-RH experiments (RH = 78.8%±1.0%), variation of the O3 concentration at 6 h with RCN is similar to that in low-RH experiments, but the RCN at the inflection point is 2.8. RH has no significant effect on the O3 concentrations under low RCN (< 3), whereas it has a negative effect under high RCN (> 3). Compared with the experimental results, original MCM v3.3.1 greatly underestimates the O3 concentrations. Addition of both the photolysis process of peroxyacetyl nitrate and the photolysis process of HNO3 on the reactor surface into the original MCM can reduce the difference between the simulated O3 concentrations and the experimental results at 6 h from 24%−35% and 17%−49% to 6%−26% and 10%−42% under low- and high-RH conditions, respectively. The maximum incremental reactivity (MIR) of acetaldehyde simulated with the modified MCM is 4.0 ppb ppb−1 without considering the effect of other VOCs.
Photooxidation of Methacrolein in Fe(III)-Oxalate Aqueous System and Its Atmospheric Implication
Yu WANG, Jie ZHAO, Huihui LIU, Yuan LI, Wenbo DONG, Yanlin WU
2021, 38(7): 1252-1263. doi: 10.1007/s00376-021-0415-5
Abstract:
Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex (Fe(III)-Ox). The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation. Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively, information about the oxidation of volatile organic compounds (VOC), specifically the potential for Secondary Organic Aerosol (SOA) formation in the Fe(III)-Ox system, is lacking. In this study, a ubiquitous VOC methacrolein (MACR) is chosen as a model VOC, and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions. The effects of oxalate concentration, Fe(III) concentration, MACR concentration, and pH on the oxidation of MACR are studied in detail. Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III). The oxidation rate of MACR also accelerates with increasing concentration of oxalate. The effect of Fe(III) is found to be more complicated. The oxidation rate of MACR first increases and then decreases with increasing Fe(III) concentration. The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration. The production of ferrous and hydrogen peroxide, pH, and aqueous absorbance are monitored throughout the reaction process. The quenching experiments verify that ·OH and \begin{document}$\rm{O}_{\small 2}^{\overline {\,\cdot\,}} $\end{document} are both responsible for the oxidation of MACR. MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight, which contributes to the yield of SOA. These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.