Yingnan Zhang

Likun Xue
email: xuelikun@sdu.edu.cn

Can Dong

Tao Wang

Abdelwahid Mellouki

Qingzhu Zhang

Wenxing Wang

Gaseous carbonyls in China's atmosphere: tempo-spatial distributions, sources, photochemical formation, and impact on air quality

Keywords: Carbonyls, Human health, Ozone, Photochemical formation, Secondary organic aerosol

Carbonyls are an important class of oxygenated volatile organic compounds that play a crucial role in tropospheric chemistry as intermediates in the formation of ozone (O3) and secondary organic aerosols. Over the last two decades, China's severe air pollution has led atmospheric chemists to devote substantial efforts to investigate the contribution of carbonyl compounds to the observed phenomena. This study reviews the major findings with regard to the gas-phase atmospheric chemistry of carbonyls in China, including their chemical compositions, temporal and spatial distributions, source apportionments, photochemical formation mechanisms, and impact on tropospheric oxidative capacity, air quality, and human health. Extremely high levels of carbonyls have frequently been observed in China's most rapidly developing regions, such as the North China Plain, the Yangtze River Delta, and the Pearl River Delta, but observational data from other regions are relatively scarce. Primary emissions and photochemical formation are major sources of carbonyls. Alkenes, aromatics, and isoprene have been identified as major precursors on a national scale. In addition, an increasing number of studies has focused on the effects of carbonyls on O3 formation, radical chemistry, the formation of secondary organic aerosols, and human health. The photolysis of oxygenated volatile organic compounds was recognized as a dominant pathway to ROx production, which further influences O3 formation, mainly via HO2+NO or RO2+NO. Dicarbonyls (such as glyoxal and methylglyoxal) make important contributions to secondary organic aerosol formation via irreversible uptake by aqueous particles. Indoor and outdoor carbonyls often pose a significant threat to human health. This review also includes recommendations from the perspective of emissions, observations, photochemical formation mechanisms, and the effects of carbonyls to guide future research and provide scientific support for the formulation of mitigation policies to address photochemical air pollution.

Introduction

Carbonyls are important members of the family of oxygenated volatile organic compounds (OVOCs), which have a significant influence on the formation of ozone (O3) and secondary organic aerosol (SOA) and hence play key roles in tropospheric chemistry [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Mellouki | Atmospheric chemistry of oxygenated volatile organic compounds: impacts on air quality and climate[END_REF][START_REF] Shen | Heterogeneous reactions of volatile organic compounds in the atmosphere[END_REF]and references therein). In recent decades, photochemical air pollution, characterized by high concentrations of O3 and other secondary contaminants, has become a major environmental concern in China due to its rapid urbanization and industrialization [START_REF] Xue | Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes[END_REF]Wang et al., 2017b;and references therein). Due to the significance of carbonyls in O3 formation, investigation of their pollution characteristics, sources, relationships with precursors, and impact on air quality is essential to better understand and control photochemical pollution.

Extensive studies have been conducted in the United States and Europe to investigate the pollution characteristics and formation mechanisms of photochemical smog since the mid-20th century. In contrast, only in the last three decades has China realized the severity of its photochemical air pollution, and finding solutions to photochemical pollution problems has become a top priority. Most studies have focused on the characteristics and formation mechanisms of surface O3 because it is regarded as the principal constituent of photochemical smog (Wang et al., 2017b;and references therein). In the lower troposphere, O3 is formed mainly via photochemical reactions that involve volatile organic compounds (VOCs) and nitrogen oxides (NOx) [START_REF] Atkinson | Atmospheric chemistry of VOCs and NOx[END_REF][START_REF] Atkinson | Atmospheric degradation of volatile organic compounds[END_REF]. Among these precursors, the pollution characteristics of hydrocarbons have rapidly attracted considerable attention because of their complexity and our poor understanding of them. More and more studies have focused on the sources and photochemistry of VOCs (e.g., [START_REF] Guo | Regional and local contributions to ambient non-methane volatile organic compounds at a polluted rural/coastal site in Pearl River Delta, China[END_REF]Guo et al., 2004b;[START_REF] Xue | Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory[END_REF]. In particular, carbonyls have been dissected from VOCs as a research hotspot due to their great reactivity and important contributions to the formation of O3 and aerosols.

Despite its late start, China has made some promising progress in gaseous carbonyls research. In particular, in the last 20 years, several field observations have been carried out across China, and more than 25 carbonyl species have been monitored. Basic information on major carbonyls is provided in Table 1. The collected data show that various aspects of carbonyls have been investigated. Analyses of the temporal and spatial distributions of carbonyls have been widely performed [START_REF] Cheng | Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong[END_REF][START_REF] Dai | Seasonal and diurnal variations of mono-and di-carbonyls in Xi'an[END_REF][START_REF] Guo | Seasonal and diurnal characteristics of atmospheric carbonyls in Nanning, China[END_REF]Ho et al., 2014a;[START_REF] Ho | Spatiotemporal distribution of carbonyl compounds in China[END_REF]Ho et al., 2002;Lui et al., 2017a;Lui et al., 2017c;[START_REF] Pang | Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China[END_REF][START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF], but few studies have focused on the sources or photochemical mechanisms of carbonyls, or their influence on atmospheric chemistry, air quality, and human health [START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF][START_REF] Liu | Source identification of reactive hydrocarbons and oxygenated VOCs in the summertime in Beijing[END_REF]Wang et al., 2017a;[START_REF] Xue | Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode[END_REF][START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF], so these aspects are relatively poorly understood. In addition, most studies have focused on the characteristics of gaseous carbonyls; observational data on high-molecular weight carbonyls are relatively scarce. High-molecular weight carbonyls are semivolatile and largely partitioned into the particle phase, and their gas-phase concentrations are generally very low. This review article focuses on the most abundant gas-phase carbonyl compounds. Considering recent advances and the underlined needs, a critical review of the atmospheric chemistry of gaseous carbonyls in China's prevailing conditions is timely.

Brief review of atmospheric chemistry of carbonyls

Carbonyls are organic molecules that contain at least a carbonyl group (C=O), and mainly include aldehydes and ketones. The chemical fates of carbonyls in the atmosphere are determined in large part by their structures and physical properties. For a given carbon number, carbonyls usually have lower vapor pressure than the corresponding parent alkanes, indicating the more polar nature of carbonyls. In addition, most carbonyls have low Henry's law constants, below 10 3 M atm -1 , so their physical removal (including wet and dry deposition) is not important [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF][START_REF] Mellouki | Atmospheric chemistry of oxygenated volatile organic compounds: impacts on air quality and climate[END_REF]. Notable exceptions, including glyoxal (GLY) and methylglyoxal (MGLY), are extremely water-soluble and can easily hydrate and polymerize even at low humidity, hence contributing to SOA formation [START_REF] Shen | Heterogeneous reactions of volatile organic compounds in the atmosphere[END_REF]and references therein). Owing to their distinctive structures and physical properties, carbonyls play an active role in tropospheric chemistry.

Figure 1 illustrates the major atmospheric chemical processes of carbonyls, including their sources and sinks. The sources of carbonyl species in the troposphere are classified as primary or secondary. Carbonyls can be emitted directly from sources such as vehicular emissions, biomass burning, industrial activities, and biogenic emissions [START_REF] Guenther | The Model of Emissions of Gases and Aerosols from Nature version 2[END_REF][START_REF] Ho | Real-world emission factors of fifteen carbonyl compounds measured in a Hong Kong tunnel[END_REF][START_REF] Ma | Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer[END_REF][START_REF] Mason | Complex effects arising in smoke plume simulations due to inclusion of direct emissions of oxygenated organic species from biomass combustion[END_REF][START_REF] Zhang | On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China[END_REF]. Secondary carbonyls are formed via the photochemical oxidation of VOCs, mainly via RO+O2 reactions [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF]. Specifically, in the presence of sunlight, the OH-initiated degradation of VOCs leads to the production of alkyl peroxy radicals (RO2), which then rapidly oxidize NO into NO2 and form RO radicals [START_REF] Atkinson | Atmospheric degradation of volatile organic compounds[END_REF][START_REF] Seco | Short-chain oxygenated VOCs: Emission and uptake by plants and atmospheric sources, sinks, and concentrations[END_REF]. Carbonyls can then be formed by reactions of RO+O2. From the perspective of sources, OVOCs are important intermediate products that are formed during radical recycling circles. OVOCs also play significant roles in the radical-initiation processes because the photolysis of OVOCs presents a significant primary source of radicals in the atmosphere [START_REF] Xue | Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode[END_REF].

The most important loss pathways of carbonyls are photolysis and reactions with OH radicals. As mentioned above, the photolysis of carbonyls has been shown to make an important contribution to the primary production of HO2 and RO2 radicals [START_REF] Jia | Oxidative Capacity and Radical Chemistry in a Semi-arid and Petrochemicalindustrialized City, Northwest China[END_REF][START_REF] Li | Oxidizing capacity of the rural atmosphere in Hong Kong, Southern China[END_REF]Liu et al., 2012a;[START_REF] Xue | Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode[END_REF][START_REF] Xue | Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory[END_REF]. These radicals then participate in the NOx chemical cycle, oxidizing NO to NO2 and thus affecting O3 formation [START_REF] Wang | Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model[END_REF]. The oxidation of carbonyls by OH forms an acyl peroxy radical (generally for aldehydes) or an alkyl peroxy radical (mainly for ketones), both of which then undergo radical recycling and termination as RO2. The heterogeneous loss of aqueous particles, which commonly occurs for dicarbonyls such as GLY and MGLY, also serves as an important sink of carbonyls [START_REF] Fu | Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols[END_REF][START_REF] Hu | Modeling biogenic and anthropogenic secondary organic aerosol in China[END_REF]Li et al., 2013a). When these two dicarbonyls are in contact with aqueous particles and cloud droplets, SOA is rapidly produced. Another loss pathway of carbonyls is reaction with O3/NO3, which is an important fate of unsaturated carbonyls. Studies have shown that the dominant sources and sinks may vary between regions and carbonyl species.

Field observations over China

Field studies of carbonyls began relatively late in China. Tables S1-S4 list the field observations collected from articles published between 2000 and 2018. Although these references may not be exhaustive, we believe that they are sufficiently comprehensive to reflect the situation of carbonyls pollution in China. The measurement campaigns have been concentrated in the rapidly developing regions of the North China Plain (NCP), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD). Extremely high levels of carbonyls, indicating severe carbonyls pollution, have been frequently observed (Figures 2a-d) due to the thriving industry and high population density. In contrast, limited efforts have been devoted to slow-developing areas.

In the late 1990s, measurement campaigns were conducted in urban Qingdao, a coastal city on the NCP. [START_REF] Tan | Analysis and concentration variability of carbonyl compounds in Qingdao atmosphere[END_REF] analyzed the seasonal variations in 11 aldehydes and ketones, explored their interrelationships, and qualitatively identified their sources. The increasing number of field studies conducted across China over the next 20 years identified more than 25 carbonyl species. Moreover, the number of field studies has drastically increased in the NCP and PRD regions since 2005, especially in 2008 for the purpose of controlling air pollution and preparing to host the Beijing Olympic Games. Note that these field observations were not limited to urban areas; they were conducted in various environments, including suburban, rural, mountain, and forest sites, to investigate the spatial distribution of carbonyls across China.

Carbonyls levels were generally higher in urban sites [START_REF] Cheng | Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong[END_REF]Lui et al., 2017c;Yuan et al., 2012a). In addition, some field observations were conducted to examine the influence of various meteorological factors (e.g., haze, a lack of haze, dust storms, wind, and wet precipitation) on carbonyls levels [START_REF] Duan | Characteristics of atmospheric carbonyls during haze days in Beijing, China[END_REF]Pang et al., 2009a;[START_REF] Zhang | The pollution levels of BTEX and carbonyls under haze and non-haze days in Beijing, China[END_REF].

Other aspects, such as emission factors, have also been investigated. For example, to measure the on-road vehicle emissions of carbonyls, [START_REF] Ho | Real-world emission factors of fifteen carbonyl compounds measured in a Hong Kong tunnel[END_REF] and [START_REF] Zhang | On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China[END_REF] carried out measurements in tunnels in Hong Kong and Guangzhou, respectively. However, such investigations are relatively scarce in China.

Tables S1-S4 also show the measurement methods and analysis techniques used in each observational campaign. The various techniques used to measure and analyze carbonyls can be classified into two categories: online and offline. Offline methods were especially widely adopted during the measurement campaigns conducted before 2006. For example, many studies used silica cartridges coated with 2,4-dinitrophenylhydrazine (DNPH) to collect air samples for high-performance liquid chromatography (HPLC) analysis [START_REF] Lü | Seasonal and diurnal variations of carbonyl compounds in the urban atmosphere of Guangzhou, China[END_REF][START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF][START_REF] Wang | Characteristics of carbonyls: concentrations and source strengths for indoor and outdoor residential microenvironments in China[END_REF]. Although the DNPH-HPLC method has been widely used, its limitations include poor sensitivity and a strong dependence on the relative humidity (Pang et al., 2011). Some alternative offline approaches have been also developed. [START_REF] Altemose | Aldehydes in relation to air pollution sources: A case study around the Beijing Olympics[END_REF] used dansylhydrazine to derivatize carbonyls followed by HPLC analysis. Several other derivatization agents such as O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine and pentafluorophenyl hydrazine have also been used to absorb carbonyls, followed by analysis with thermal desorption-gas chromatography-mass spectrometry (Ho andYu, 2002, 2004;[START_REF] Pang | Determination of airborne carbonyls via pentafluorophenylhydrazine derivatisation by GC-MS and its comparison with HPLC method[END_REF]. Szuleiko and Kim (2015) summarized commonly used derivatization agents and analytical methods for carbonyls analysis and indicated that DNPH-HPLC remains the most common choice among the offline methods mentioned above. Since 2006, differential optical absorption spectroscopy has been used to measure carbonyls [START_REF] Kawamura | Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai[END_REF][START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF][START_REF] Nan | Study on the daytime OH radical and implication for its relationship with fine particles over megacity of Shanghai, China[END_REF], and [START_REF] Kawamura | Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai[END_REF] compared the performances of multi-axis differential optical absorption spectroscopy and filter sampling-gas chromatography measurements. In addition, [START_REF] Shao | Volatile organic compounds measured in summer in Beijing and their role in ground-level ozone formation[END_REF] used gas chromatography-flame ionization detection-mass spectrometry (MS) to achieve the continuous monitoring of carbonyls in China at a high time resolution. Online methods such as proton transfer reaction-mass spectrometry (PTR-MS; including PTR-QMS, PTR-IT-MS, PTR-TOF-MS, PTR-TOF-CIMS, and PTR-ID-CIMS) were then successively applied [START_REF] Kanaya | Rates and regimes of photochemical ozone production over Central East China in June 2006: a box model analysis using comprehensive measurements of ozone precursors[END_REF][START_REF] Ma | Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer[END_REF][START_REF] Yuan | Protontransfer-reaction mass spectrometry: Applications in atmospheric sciences[END_REF][START_REF] Yuan | A high-resolution time-of-flight chemical ionization mass spectrometer utilizing hydronium ions (H3O + ToF-CIMS) for measurements of volatile organic compounds in the atmosphere[END_REF]. Detailed information on these online methods has been published elsewhere [START_REF] Chi | Determination of carbonyl compounds in the atmosphere by DNPH derivatization and LC-ESI-MS/MS detection[END_REF][START_REF] Cui | Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong: relative humidity and temperature dependence, and field intercomparisons[END_REF][START_REF] Ho | Determination of airborne carbonyls: Comparison of a thermal desorption/GC method with the standard DNPH/HPLC method[END_REF][START_REF] Inomata | Determination of formaldehyde mixing ratios in air with PTR-MS: laboratory experiments and field measurements[END_REF]Wang et al., 2014b).

Although offline methods have been widely used, they have some disadvantages. One disadvantage is that the length of the derivatization time makes it difficult to characterize the continuous evolution process of carbonyls. The application of online methods has achieved continuous online measurements of carbonyls in the atmosphere at the trace level. Nevertheless, some carbonyl species still cannot be detected with these novel methods [START_REF] Chen | Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model[END_REF][START_REF] Kawamura | Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai[END_REF][START_REF] Nan | Study on the daytime OH radical and implication for its relationship with fine particles over megacity of Shanghai, China[END_REF]Wang et al., 2014b). For example, PTR-MS can only detect species with a proton affinity greater than that of water and cannot distinguish isomeric/isobaric compounds [START_REF] Blake | Proton-transfer reaction mass spectrometry[END_REF][START_REF] Yuan | Protontransfer-reaction mass spectrometry: Applications in atmospheric sciences[END_REF]. Formaldehyde and acetaldehyde cannot be detected with online gas chromatography-MS because they do not produce unique ions in the MS [START_REF] Pang | Determination of airborne carbonyls via pentafluorophenylhydrazine derivatisation by GC-MS and its comparison with HPLC method[END_REF]. Further developments in measurement techniques for carbonyls are required to provide high-quality data and cover more species in future studies.

It is noteworthy to mention that most of these field observations were carried out by the research community and that carbonyls have not been listed as a target by the national air quality monitoring network. Very recently, Chinese government agencies have begun to attach greater importance to the measurement of carbonyls after realizing their significance in ozone pollution. In 2017, the Ministry of Ecology and Environment of the People's Republic of China issued a series of regulations to promote the development of OVOC measurement, including both manual and automatic monitoring (http://www.mee.gov.cn/). For example, some air quality monitoring stations in key regions and/or cities have been asked to perform routine measurements of 13 major carbonyls (see Table 1) with the same method (i.e., DNPH-HPLC and gas chromatography-flame ionization detection-MS), so a picture of nationwide carbonyls levels across China seems around the corner.

Chemical compositions and tempo-spatial distributions

Historical data show that formaldehyde (HCHO), acetaldehyde (CH3CHO), and acetone (CH3COCH3) are the three most abundant carbonyl species in field studies, but the most abundant species vary between sites. The contributions of these three species to the total observed carbonyl compounds generally exceed 70% (Guo et al., 2014a;[START_REF] Guo | Seasonal and diurnal characteristics of atmospheric carbonyls in Nanning, China[END_REF][START_REF] Yang | Carbonyl compounds at Mount Tai in the North China Plain: Characteristics, sources, and effects on ozone formation[END_REF]. In addition, the mixing ratios of two dicarbonyl compounds (i.e., GLY and MGLY) that are crucial players in the formation of O3 and SOA have also shown high concentration levels in China (Ho et al., 2014a;[START_REF] Rao | Carbonyl compounds over urban Beijing: Concentrations on haze and non-haze days and effects on radical chemistry[END_REF].

Figures 2a-d show the spatial distributions of major carbonyl species over China.

Carbonyls pollution is obviously much more severe in the NCP, YRD, and PRD regions than in other areas. Of these three severely polluted regions, the PRD has a slightly better carbonyls pollution situation. Within a given region, higher levels of carbonyls were usually observed at urban sites than at suburban and rural sites. Megacities such as Beijing, Shanghai, Guangzhou, and Hong Kong have severe carbonyls pollution. High levels of HCHO (exceeding 20 ppbv), CH3CHO (exceeding 10 ppbv), and CH3COCH3 (exceeding 6 ppbv) have been frequently observed in Beijing [START_REF] Altemose | Aldehydes in relation to air pollution sources: A case study around the Beijing Olympics[END_REF][START_REF] Duan | Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing[END_REF][START_REF] He | Chemical Characteristics and Sources of Atmospheric Carbonyls during the 2014 Beijing APEC[END_REF][START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF]. Observational data for carbonyls other than the top three carbonyl species are relatively limited because they have high reactivities and low concentration levels. Nevertheless, observational data for propionaldehyde (C2H5CHO), butyraldehyde (C3H7CHO), GLY, and MGLY have also been collected. The spatial distributions of these four carbonyl species differ slightly from those of the three abundant species. In addition to the NCP, YRD, and PRD regions, Taiwan also showed elevated levels of C2H5CHO (>1 ppbv) and C3H7CHO (>2 ppbv) [START_REF] Huang | Characteristics of carbonyl compounds in ambient air of Shanghai, China[END_REF][START_REF] Lü | Seasonal and diurnal variations of carbonyl compounds in the urban atmosphere of Guangzhou, China[END_REF][START_REF] Lü | Carbonyl compounds in the ambient air of hazy days and clear days in Guangzhou, China[END_REF][START_REF] Shi | Measurement of Carbonyl Compounds in Ambient Air of Tianjin City and Bohai Sea[END_REF]Wang et al., 2010a). Figures 3a-b show that GLY and MGLY in limited studies were found to exhibit high levels in Beijing and Xi'an (>0.3 ppbv and >1 ppbv for GLY and MGLY, respectively) (Ho et al., 2014a;[START_REF] Rao | Carbonyl compounds over urban Beijing: Concentrations on haze and non-haze days and effects on radical chemistry[END_REF]. GLY generally has a greater concentration than MGLY due to its longer lifespan (2.9 vs. 1.6 h) [START_REF] Fu | Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols[END_REF]. [START_REF] Dai | Seasonal and diurnal variations of mono-and di-carbonyls in Xi'an[END_REF] reported similar data in which the GLY concentrations were higher than those of MGLY in Xi'an in winter. However, at the same site, MGLY exhibited higher levels than GLY during summer, which may be attributed to seasonal variations in the sources of dicarbonyls.

The status of carbonyls pollution in China is less optimal than that of other countries. For example, levels of major carbonyl species (HCHO+CH3CHO+CH3COCH3) exceeding 20 ppbv have frequently been observed in Beijing (e.g., [START_REF] Duan | Characteristics of atmospheric carbonyls during haze days in Beijing, China[END_REF][START_REF] Duan | Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing[END_REF][START_REF] He | Chemical Characteristics and Sources of Atmospheric Carbonyls during the 2014 Beijing APEC[END_REF][START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF][START_REF] Rao | Carbonyl compounds over urban Beijing: Concentrations on haze and non-haze days and effects on radical chemistry[END_REF][START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF], on par with those of Los Angeles (19.2 ppbv in 2008-2010) [START_REF] Warneke | Multiyear trends in volatile organic compounds in Los Angeles, California: Five decades of decreasing emissions[END_REF] and Campeche, Mexico (37.1 ppbv in the summer of 2004) [START_REF] Cerón | Diurnal and seasonal trends in carbonyl levels in a semiurban coastal site in the Gulf of Campeche, Mexico[END_REF], which have experienced the world's most serious photochemical pollution.

Four year-round observation campaigns are carefully selected to elucidate the seasonal variations in carbonyls in various regions [START_REF] Huang | Characteristics of carbonyl compounds in ambient air of Shanghai, China[END_REF][START_REF] Lü | Seasonal and diurnal variations of carbonyl compounds in the urban atmosphere of Guangzhou, China[END_REF]Lui et al., 2017c;[START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF]. These four measurements were conducted in urban areas of Beijing (from November 2004 to October 2005), Shanghai (from January to October 2007), Guangzhou (from January to November 2005), and Hong Kong (from January to December 2013), respectively. These studies were chosen to obtain a comprehensive understanding of the severe carbonyls pollution characteristics in typical fast-developing regions of China. Although a time gap separates these four observation campaigns, we believe that it should have little effect on the seasonal variations of carbonyls. Figure 4 shows that HCHO and CH3CHO were significantly more abundant in summer than in winter in Beijing, Shanghai, and Guangzhou. This difference can be explained by the stronger photochemical activities in summer and was confirmed with 13 C isotope evidence by [START_REF] Guo | 13 C isotope evidence for photochemical production of atmospheric formaldehyde, acetaldehyde, and acetone pollutants in Guangzhou[END_REF]. In Hong Kong, both HCHO and CH3CHO exhibited their maximum levels in autumn, and similar levels were seen in summer and winter. The reason for this distinct seasonal pattern is that Hong Kong is frequently influenced by clean marine air masses under prevailing southerly or southeasterly winds in summer, which alleviates carbonyls pollution to some degree. Autumn is the most photochemically polluted season in Hong Kong due to the regional transport of continental air masses from mainland China via the winter monsoon and the sunny weather at low latitudes (Wang et al., 2009b). Another exception is the seasonal pattern in Xiamen, where higher levels of both HCHO and CH3CHO were found in winter than in summer, which may be attributed to the stronger sea-land breeze circulation during summer [START_REF] Ho | Spatiotemporal distribution of carbonyl compounds in China[END_REF].

The diurnal patterns in carbonyls levels have been also examined. [START_REF] Liu | Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games: observation and modeling implications[END_REF] reported the diurnal patterns of several carbonyl species measured at PKU in urban Beijing in July 2008. Levels of HCHO, CH3CHO, and CH3COCH3 peaked at noon after a daytime buildup, following the trend of O3, thus indicating the significance of secondary production during the day. These carbonyl species then reached another peak in early evening, which may be attributed to primary vehicle emissions. At Mount Tai, [START_REF] Yang | Carbonyl compounds at Mount Tai in the North China Plain: Characteristics, sources, and effects on ozone formation[END_REF] observed an evening peak in carbonyls that could be ascribed to regional transport. In addition, diurnal variations in carbonyls in some studies are not clear-cut [START_REF] Cheng | Diurnal and seasonal trends of carbonyl compounds in roadside, urban, and suburban environment of Hong Kong[END_REF]Guo et al., 2014a;[START_REF] Guo | Seasonal and diurnal characteristics of atmospheric carbonyls in Nanning, China[END_REF][START_REF] Huang | Characteristics of carbonyl compounds in ambient air of Shanghai, China[END_REF][START_REF] Lü | Seasonal and diurnal variations of carbonyl compounds in the urban atmosphere of Guangzhou, China[END_REF][START_REF] Rao | Carbonyl compounds over urban Beijing: Concentrations on haze and non-haze days and effects on radical chemistry[END_REF]Yuan et al., 2012b). In general, the mixing ratios of carbonyls are related to many factors, including their sources (both primary emissions and secondary formation), sinks, regional transport, and meteorological conditions.

Seasonal variations and diurnal patterns roughly reflect the influences of these factors on the ambient carbonyls levels.

Source apportionment

The sources of carbonyls are rather complex. Several methods have been used to diagnose or quantify the major sources of ambient carbonyls, and detailed information on these methods can be found in the Supplementary Materials. Here, we focus on the major findings of the source apportionment studies in a few regions.

North China Plain

Many studies have attempted to identify the principal sources of carbonyls and quantify their contributions to ambient carbonyls levels in the NCP. Although various methods have been used, source apportionment results have consistently demonstrated the dominance of the secondary formation of carbonyls in summer. For example, [START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF] conducted an intensive measurement campaign from November 2004 to October 2005 in urban Beijing and found a strong correlation between carbonyls and O3 in summer. In addition, the calculated C1/C2 ratios exhibited the highest average values (e.g., 1.94) in summer, which suggests the importance of photo-oxidation of biogenic hydrocarbons. Later, during the summer of 2014, [START_REF] Yang | Carbonyl compounds at Mount Tai in the North China Plain: Characteristics, sources, and effects on ozone formation[END_REF] used the multilinear regression method and found that secondary formation made the largest contribution to the carbonyls level (except CH3COCH3) at Mount Tai, a regional site in the central NCP. [START_REF] Liu | Source identification of reactive hydrocarbons and oxygenated VOCs in the summertime in Beijing[END_REF] used the photochemical age-based parameterization method and found that nearly half of the CH3CHO, C2H5CHO, and C3H7CHO in urban Beijing were attributed to secondary anthropogenic sources, whereas the measured alcohols (CH3OH and C2H5OH) and ketones (CH3COCH3 and CH3COC2H5 [methyl ethyl ketone]) were mainly from primary sources. Secondary formation usually made a larger contribution to reactive aldehydes than to inert alcohols and ketones. This conclusion was also confirmed by Yuan et al. (2012b), who also reported that biogenic VOCs accounted for a large part (36%) of HCHO formation at PKU in urban Beijing. In contrast, [START_REF] Chen | Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model[END_REF] identified a much lower contribution of biogenic sources to HCHO at the same site based on the results of a positive matrix factorization model. The cause of this discrepancy may be that the biogenic sources identified by the positive matrix factorization model represented relatively fresh emissions, whereas secondary formation from biogenic sources was also considered by Yuan et al. (2012b).

In comparison, carbonyls were reported to come mainly from primary anthropogenic emissions in winter, when the photochemistry is relatively weak [START_REF] Ho | Spatiotemporal distribution of carbonyl compounds in China[END_REF][START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF]. In winter 2004, [START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF] found a significant correlation between carbonyls and CO, an anthropogenic emission tracer, over urban Beijing, thus suggesting the importance of anthropogenic emissions (especially vehicular emissions) to carbonyls levels. Furthermore, the results of principal component analysis showed that gasoline and diesel engine exhausts are the principal components of vehicle emissions, which make an important contribution to ambient carbonyls [START_REF] Rao | Carbonyl compounds over urban Beijing: Concentrations on haze and non-haze days and effects on radical chemistry[END_REF]. However, [START_REF] Chen | Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model[END_REF] found that secondary formation dominated carbonyls sources not only in summer (with a contribution of 46.0%), but also in winter (with a contribution of 51.2%). In addition, coal burning for heat during winter was identified as an important component of primary anthropogenic emissions [START_REF] Chen | Understanding primary and secondary sources of ambient carbonyl compounds in Beijing using the PMF model[END_REF].

Yangtze River Delta

Source apportionment studies in the YRD region are relatively limited compared to those in the NCP and PRD regions. In the YRD region, primary emissions were identified as important sources of carbonyls in spring and autumn. [START_REF] Huang | Ambient Levels of Carbonyl Compounds in Shanghai, China[END_REF] reported that the ambient carbonyls in urban Shanghai in April 2008 were dominated by vehicle emissions during the day and industrial emissions at night. The importance of industrial emissions was also confirmed by [START_REF] Ma | Detection of formaldehyde emissions from an industrial zone in the Yangtze River Delta region of China using a proton transfer reaction ion-drift chemical ionization mass spectrometer[END_REF], who used a multilinear regression approach to show that industrial activities made the largest contribution (59%) to HCHO in April 2015 in an industrial zone of Zhejiang province. In contrast, [START_REF] Wang | Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China[END_REF] used the same method and found that industrial emissions made a relatively smaller contribution (19%) to HCHO at a rural site in Nanjing, Jiangsu province; CH3CHO and CH3COCH3 dominated (>50%). These results prove the variability of carbonyls sources in various parts of the YRD region. One point in common is that the contribution of photochemical formation to carbonyls was relatively low in both studies due to weaker photochemical reactions during spring and autumn in the YRD region.

Pearl River Delta

Severe photochemical smog episodes are frequently observed in the PRD region during autumn because of its distinct meteorological conditions. Intensive measurement campaigns were conducted from September to November 2010 at a mountain site (TMS) and an urban site (TW) in Hong Kong (Guo et al., 2013;[START_REF] Ling | Formaldehyde and acetaldehyde at different elevations in mountainous areas in Hong Kong[END_REF]. The positive matrix factorization model results were similar at these two sites. Secondary formation (including in-situ photochemical production and the transport of secondary products) was identified as the major contributor to HCHO (>50%) and CH3CHO (>45%). Meanwhile, secondary formation and vehicle emissions made the greatest contribution (>65%) to the ambient CH3COCH3 level.

These findings indicate the importance of photochemical formation. In addition, carbonyls were more likely to be primary emissions in urban areas than in rural areas, as confirmed by Lui et al. (2017c). In addition to autumn, [START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF] showed strong photochemical activities in summer, but the prevailing southerly and southeasterly winds from the oceans alleviated carbonyls pollution during summer, whereas the northeasterly winds in autumn aggravated the pollution. Wang et al. (2017a) investigated the source category contributions to HCHO in different seasons. They used the photochemical age-based parameterization method and found that the contributions of biogenic sources (including both primary and secondary biogenic sources) to HCHO were much higher during summer (41%) and autumn (39%) than during spring (26%) and winter (28%). In contrast, the contributions of primary anthropogenic emissions during spring (20%) and winter (18%) were double those during summer (9%) and autumn (9%). Some studies also identified primary emissions as important sources of carbonyls [START_REF] Feng | Ambient levels of carbonyl compounds and their sources in Guangzhou, China[END_REF]Guo et al., 2004a;Ho et al., 2002;[START_REF] Lü | Carbonyl compounds in the ambient air of hazy days and clear days in Guangzhou, China[END_REF][START_REF] Yuan | Biomass burning contributions to ambient VOCs species at a receptor site in the Pearl River Delta (PRD), China[END_REF], so the emission profiles of vehicular emissions and biomass burning were investigated in the PRD region. Two tunnel tests were successively conducted in Hong Kong and Guangzhou [START_REF] Ho | Real-world emission factors of fifteen carbonyl compounds measured in a Hong Kong tunnel[END_REF][START_REF] Zhang | On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China[END_REF]. [START_REF] Ho | Real-world emission factors of fifteen carbonyl compounds measured in a Hong Kong tunnel[END_REF] reported a range of 21.7 to 68.9 mg veh -1 km -1 of emission factors of a combination of 15 monocarbonyls. Furthermore, HCHO presented the highest emission factor throughout the sampling period, followed by CH3CHO and CH3COCH3 [START_REF] Ho | Carbonyl emissions from vehicular exhausts sources in Hong Kong[END_REF].

Higher emission factors of carbonyls were observed in summer than in winter, partly due to the higher temperature. [START_REF] Zhang | On-road vehicle emissions of glyoxal and methylglyoxal from tunnel tests in urban Guangzhou, China[END_REF] reported average emission factors of 1.18 and 0.52 mg veh -1 km -1 for GLY and MGLY, respectively. The higher emission factor of GLY usually accompanies a higher proportion of gasoline vehicles, whereas a higher proportion of diesel vehicles was responsible for the higher emission factors of monocarbonyls and MGLY. In addition, biomass burning was also found to exert a significant influence on ambient carbonyls in specific circumstances. [START_REF] Wang | The contributions of biomass burning to primary and secondary organics: A case study in Pearl River Delta (PRD), China[END_REF] suggested that biomass burning could serve as a primary source of OVOCs and promote the production of secondary OVOCs by emitting their precursors. [START_REF] Yuan | Biomass burning contributions to ambient VOCs species at a receptor site in the Pearl River Delta (PRD), China[END_REF] reported an enhancement of 10% to 18% of OVOCs during biomass burning plumes at a receptor site in the PRD region. [START_REF] Yuan | VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China[END_REF] and [START_REF] Mo | Compilation of a source profile database for hydrocarbon and OVOC emissions in China[END_REF] both reported that OVOC emissions were significantly underestimated in the current emission inventory, possibly due to the poor understanding of the emission characteristics of nonvehicle primary sources. In addition to anthropogenic emissions, some studies have reported biogenic emissions of carbonyls. In China, the total biogenic VOC emissions were reported to range from 35 to 50 Tg/y from 1981 to 2003, among which the contributions of OVOCs ranged from 30% to 40% [START_REF] Li | Historical variations of biogenic volatile organic compound emission inventories in China, 1981-2003[END_REF]. Moreover, [START_REF] Guenther | The Model of Emissions of Gases and Aerosols from Nature version 2[END_REF] identified CH3COCH3 (43.7 Tg/y), CH3CHO (20.7 Tg/y), and HCHO (5.0 Tg/y) as the three most abundant primary biogenic carbonyl species on a global scale. However, great uncertainty remains in the evaluation of biogenic carbonyls emissions.

As discussed above, secondary formation generally dominated the carbonyls sources in China, but the importance of the contributions from primary emissions should not be overlooked. However, current knowledge of carbonyls sources remains far from sufficient to provide scientific support for carbonyls abatement strategies. First, the means to accurately characterize primary emissions (both anthropogenic and biogenic) is a major work underway and is urgently needed to aid in compiling the current emission inventories. Second, the photochemical formation mechanisms of some reactive carbonyl species remain poorly understood, so more relevant studies are needed.

Photochemical formation mechanisms

The source apportionment results elucidate the necessity to comprehensively understand the secondary formation mechanisms of carbonyls. The methods commonly used to investigate the photochemical formation mechanisms of carbonyls are based on chemical models.

Investigations have included monocarbonyls, among others. Important dicarbonyls such as GLY and MGLY are also involved. Below we summarize the major findings regarding the photochemical formation mechanisms of monocarbonyls and dicarbonyls.

Monocarbonyls

In China, the photochemical formation mechanisms of monocarbonyls such as HCHO, CH3CHO, CH3COCH3, and CH3COC2H5 have been investigated with an observation-based box model coupled with chemical mechanisms. Previous studies showed that models could well reproduce the diurnal variations and concentrations of secondary products such as O3, HCHO, and GLY (Li et al., 2014;[START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF]. Li et al. (2014) and [START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF] conducted field observations in the PRD region in July 2006 at a semirural site (BG) and an urban site (GPEMC), respectively, and further refined the secondary formation pathways of HCHO. Li et al. (2014) found that isoprene oxidation contributed most to the secondarily formed HCHO (43%), followed by oxidation of anthropogenic alkenes (29%), aromatics (15%), and alkanes (13%). In contrast, [START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF] showed that alkenes (including isoprene) made an overwhelming contribution (77%) to the photochemical production of HCHO, followed by aromatics (20%) and alkanes (3%).

Trans-2-butene was identified as the largest contributor (16%) of the individual VOC precursors, whereas isoprene made a smaller contribution (9.6%). The differences between the results of Li et al. (2014) and [START_REF] Ling | Sources of formaldehyde and their contributions to photochemical O3 formation at an urban site in the Pearl River Delta, southern China[END_REF] are likely the result of differences in the chemical compositions of first-generation VOC precursors between urban and rural areas. The photochemical formation mechanism of CH3COCH3 differs greatly from that of HCHO. Guo et al. (2013) used the observation-based box model to investigate the photochemical precursors of CH3COCH3 from September to November 2010 at a mountain site (TMS) and an urban site (TW) in Hong Kong. C3-C6 alkanes were found to be the largest contributor to the secondary formation of CH3COCH3 at both sites, making an average contribution of 28.7% at TMS and 54.5% at TW. This result is also consistent with that of [START_REF] Jacob | Atmospheric budget of acetone[END_REF], who confirmed the oxidation of C3-C5 isoalkanes as a dominant source of the in situ formation of CH3COCH3 in the northern hemisphere. The contributions of C2-C3 alkenes to secondarily formed CH3COCH3 were comparable at the two sites (20.0% at TMS and 16.1% at TW). Furthermore, the most important of all measured VOC precursors was identified to be i-butene at TMS and i-butane at TW, with the two compounds contributing 20% and 30%, respectively.

In the NCP region, the relationships between monocarbonyls and their precursors were also investigated using box models. As mentioned above, many observation campaigns were carried out in 2008 to improve air quality and prepare for the Beijing Olympic Games. During that period, two intensive measurements conducted from July to August 2008 were selected for comparison. These two measurements were carried out by [START_REF] Liu | Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games: observation and modeling implications[END_REF] in the PKU and by [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF] at the Chinese Research Academy of Environmental Sciences (both in urban areas). These two studies investigated the photochemical formation mechanisms of carbonyls from different perspectives. [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF] identified five major pathways responsible for the formation of secondary HCHO and CH3CHO: OVOC photolysis, O3+OVOCs, OH+OVOCs, radical propagation reactions, and RO+O2 reactions. Of these, RO+O2 reactions made the largest contribution to the in situ formation of HCHO (~85%) and CH3CHO (~70%).

One point that must be clarified is that the target carbonyls were excluded from the OVOC precursors mentioned above. As for the first-generation VOC precursors, the further refinement of the RO+O2 formation routes suggested that anthropogenic alkenes played an important role in the production of RO (~30%). [START_REF] Liu | Impact of pollution controls in Beijing on atmospheric oxygenated volatile organic compounds (OVOCs) during the 2008 Olympic Games: observation and modeling implications[END_REF] investigated the photochemical formation mechanisms of carbonyls from the perspective of precursors and showed that anthropogenic alkenes made the largest contribution to the photochemical formation of HCHO (54%), CH3CHO (91%), and CH3COCH3 (60%), whereas alkanes were predominantly responsible for the in situ formation of CH3COC2H5 (>95%). As for individual VOC precursors, the oxidation of isoprene made the largest contribution (30%) to secondary HCHO. In addition, the loss rates of HCHO were governed both by reactions with OH and by photolysis, whereas CH3CHO losses were dominated by reactions with OH [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF]. Such studies of the detailed photochemical processes of carbonyls remain limited in other regions, and more efforts are needed.

Dicarbonyls

The photochemical formation mechanisms of GLY and MGLY have also been investigated [START_REF] Miller | Hotspot of glyoxal over the Pearl River delta seen from the OMI satellite instrument: implications for emissions of aromatic hydrocarbons[END_REF]Liu et al., 2012b;[START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF]. [START_REF] Fu | Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols[END_REF] conducted a detailed simulation based on a global three-dimensional model (GEOS-Chem) and found that isoprene dominated the secondary formation of GLY and MGLY on a global scale, whereas acetylene and acetone were the second most important precursors for GLY and MGLY, respectively. However, the photochemical formation mechanisms of GLY and MGLY in China differ significantly from those on a global scale. Liu et al. (2012b) quantified the missing source of GLY in China by comparing the vertical column densities observed by SCIAMACHY and those simulated by a three-dimensional regional chemical transport model. Inverse modeling was then applied to calculate the emission adjustment for each grid, and the results showed a substantial underestimation of aromatics emissions (by a factor of 4 to 10) in the VOC emission inventories over China, which well explained the missing source of GLY. Later, [START_REF] Miller | Hotspot of glyoxal over the Pearl River delta seen from the OMI satellite instrument: implications for emissions of aromatic hydrocarbons[END_REF] identified the PRD region as a hotspot of GLY based on satellite observations from the Ozone Monitoring Instrument. In contrast with the results of Liu et al. (2012b), they found good agreement between the observed GLY enhancements and the current VOC emission inventories. The difference in the results was attributed to the combined effects of bias in the satellite data and underestimation of GLY production from aromatics oxidation. Based on MCM v3.2 (Master Chemical Mechanism, a nearly-explicit chemical mechanism), the aromatics emitted by industrial sources were determined as a dominant contributor to GLY formation in the PRD region [START_REF] Miller | Hotspot of glyoxal over the Pearl River delta seen from the OMI satellite instrument: implications for emissions of aromatic hydrocarbons[END_REF]. [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF] investigated the photochemical formation mechanisms of GLY and MGLY in urban Beijing. RO+O2 and OH+OVOCs reactions were identified as the dominant formation pathways for both GLY and MGLY. Furthermore, aromatics made the largest contribution of all first-generation VOC precursors to the formation of GLY (>43%) and MGLY (39%). The dominant first-generation VOC precursors responsible for secondarily formed GLY and MGLY in Beijing are similar to those identified in the PRD region (i.e., aromatics).

Overall, some progress has been made in gaining a better understanding of the photochemical formation mechanisms of carbonyls in China. Nonetheless, most studies have focused on the identification of important precursors; the detailed photochemical processes of carbonyls have not been fully addressed. Moreover, most work has been concentrated in the NCP and PRD regions, with few studies considering other regions of China. More work is needed to further unravel the detailed formation mechanisms of carbonyls with a wider spatial coverage in China.

Effects of carbonyls on atmospheric chemistry, air quality, and human health 7.1 Atmospheric oxidative capacity and radicals

OVOCs play crucial roles in radical chemistry. First, they exert a significant influence on radical initiation reactions. As mentioned in Section 2, OVOC photolysis is acknowledged as a major primary source of ROx radicals. [START_REF] Xue | Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode[END_REF] used box modeling analysis to quantify the radical budget of a prolonged severe photochemical smog episode in Hong Kong and found that OVOC photolysis (except for HCHO photolysis) made an overwhelming contribution (47%) to daytime primary ROx production. Moreover, the photolysis of HCHO was an important source of HO2. The dominance of OVOC photolysis to RO2+HO2 production was also found in many other areas, such as Beijing, Lanzhou, and Waliguan (see Table 2 and references therein). Despite this similarity, RO2+HO2 production from OVOC photolysis was much more efficient in polluted urban areas than in rural or remote areas.

OVOCs also play an important role in radical recycling cycles, which further influence the atmospheric oxidizing capacity. Generally, OH is the largest contributor to the atmospheric oxidizing capacity. Some studies have calculated the OH reactivity to track the contributions of various VOC groups to OH oxidation. Table 2 summarizes the related studies of OH reactivity in China. In the PRD region, [START_REF] Lou | Atmospheric OH reactivities in the Pearl River Delta-China in summer 2006: measurement and model results[END_REF] compared the measured and calculated OH reactivity and found a discrepancy of a factor of ~2. Further examination suggested that the missing reactivity was attributed to a lack of measurement data for OVOCs (mainly aldehydes and ketones), suggesting the significant contributions of carbonyls to OH reactivity. Yuan et al. (2012a) calculated that that OH reactivity was dominated by OVOCs. The dominance of OVOCs to OH reactivity in the PRD region was also confirmed by [START_REF] Xue | Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode[END_REF] and [START_REF] Li | Oxidizing capacity of the rural atmosphere in Hong Kong, Southern China[END_REF] based on model simulations. In the NCP region, [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF] and [START_REF] Fuchs | OH reactivity at a rural site (Wangdu) in the North China Plain: contributions from OH reactants and experimental OH budget[END_REF] reported the dominant contributions of OVOCs to OH reactivity. Of all OVOC species, HCHO and CH3CHO were identified as the largest contributors to OH reactivity [START_REF] Duan | Characteristics of atmospheric carbonyls during haze days in Beijing, China[END_REF][START_REF] Fuchs | OH reactivity at a rural site (Wangdu) in the North China Plain: contributions from OH reactants and experimental OH budget[END_REF][START_REF] Shao | Volatile organic compounds measured in summer in Beijing and their role in ground-level ozone formation[END_REF][START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF]. In addition, OVOCs (especially carbonyls) usually dominated OH reactivity in rural areas, whereas alkenes tended to dominate OH reactivity in urban areas. Overall, OVOCs not only behaved as a predominant radical source via photolysis but also as a major contributor to the atmospheric oxidizing capacity via OH-initiated degradation.

O 3 formation

The worsening O3 pollution situation has caused wide public concern, and many studies have investigated O3-precursor relationships (e.g., [START_REF] Duan | Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing[END_REF][START_REF] Tan | Exploring ozone pollution in Chengdu, southwestern China: A case study from radical chemistry to O3-VOC-NOx sensitivity[END_REF]Wang et al., 2018;[START_REF] Xue | Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes[END_REF][START_REF] Xue | Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory[END_REF]. However, most studies have focused on hydrocarbons; relatively limited attention has been paid to the contributions of OVOCs to O3.

A close relationship has been assumed to exist between O3 and OVOCs because high levels of O3 and OVOCs are often monitored concurrently during photochemical pollution episodes [START_REF] Wang | Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model[END_REF][START_REF] Yang | Carbonyl compounds at Mount Tai in the North China Plain: Characteristics, sources, and effects on ozone formation[END_REF]. A clear understanding of the role played by carbonyls during O3 formation is essential for air pollution control.

Based on the PBM-MCM model, [START_REF] Wang | Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model[END_REF] found that HCHO photolysis dominated HO2 formation and that HO2 then further oxidizes NO to NO2, facilitating the formation of O3. Some studies evaluated the O3-precursor relationships based upon O3 formation potential (OFP) calculations and model sensitivity tests. Yuan et al. (2012a) calculated the OFP of various VOC groups measured in the PRD region and found that aromatics made the largest contribution to the OFP at most urban sites, whereas carbonyls usually dominated the OFP in rural areas. In contrast, [START_REF] Duan | Concentration, sources and ozone formation potential of volatile organic compounds (VOCs) during ozone episode in Beijing[END_REF] found that carbonyls dominated the OFP (40%) at an urban site in Beijing. This discrepancy reveals the different formation regimes of O3 in various regions of China. However, one common conclusion is that of the carbonyl species, HCHO and CH3CHO usually exhibited the highest OFP due to their relatively high reactivity and abundance. Some studies were based on model-calculated relative incremental reactivity. [START_REF] Yang | Observations and explicit modeling of summertime carbonyl formation in Beijing: Identification of key precursor species and their impact on atmospheric oxidation chemistry[END_REF] identified carbonyls as the most sensitive precursors responsible for O3 formation in Beijing. [START_REF] Wang | Surface O3 photochemistry over the South China Sea: Application of a near-explicit chemical mechanism box model[END_REF] calculated the relative incremental reactivity values for each VOC precursor to O3 production over the South China Sea. They showed that HCHO exhibited the highest relative incremental reactivity value on both episode days and non-episode days (Here, the episode days refer to days with maximum hourly average O3 value exceeding 100 ppbv [China's Grade II Standard]). Cutting carbonyls emissions would be an effective way to alleviate O3 pollution in these regions.

The studies mentioned above have demonstrated that carbonyls make important contributions to O3 formation. These findings are useful for the formulation of effective ozone pollution control strategies. However, most of these studies have focused on the sensitivity of O3 formation to the bulk of carbonyls, to which secondary formation contributed a large proportion. Control policies can only reduce primary emissions. Thus, more efforts are needed to better quantify the contributions of primary carbonyl species to O3 formation in China.

SOA formation

Heterogeneous reactions are an important sink of carbonyls and an important source of SOA. As previously mentioned, GLY and MGLY usually exhibit high levels in China. These two small dicarbonyls have relatively high reactivity and water solubility [START_REF] Shen | Heterogeneous reactions of volatile organic compounds in the atmosphere[END_REF] and references therein). They can easily hydrate and polymerize even at low humidity. This distinct feature makes GLY and MGLY important contributors to SOA formation. [START_REF] Fu | Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols[END_REF] added the known sources and sinks of GLY and MGLY to the GEOS-Chem model and found that the yield of global SOA increased by 38%, thus indicating their significant contributions to SOA formation on a global scale.

Investigations of the relationships between carbonyls and SOA formation in China are relatively limited. [START_REF] Yuan | VOC emissions, evolutions and contributions to SOA formation at a receptor site in eastern China[END_REF] reported a discrepancy between measured and calculated SOA and attributed it partly to the lack of measurement data for GLY. Li et al. (2013a) improved the representation of the gas-phase and aqueous-phase chemistry of dicarbonyls (GLY and MGLY) in the community multiscale air quality (CMAQ) modeling system to simulate SOA levels over the PRD region and made comparisons with observations. The simulated average SOA concentration was in better agreement with the observed mean SOA concentration after the improvement. Furthermore, dicarbonyls were found to make a large contribution (~53%) to the simulated surface SOA formation, mainly via irreversible uptake by aqueous particles, whereas the contributions of dicarbonyls to SOA via gas-phase reactions can be negligible (Li et al., 2013a). This finding was consistent with that of [START_REF] Hu | Modeling biogenic and anthropogenic secondary organic aerosol in China[END_REF], who used the CMAQ model to study the tempo-spatial distribution of SOA in China and found that the reactive surface uptake of GLY and MGLY was an important formation pathway for SOA, with respective contributions of 14% to 25% and 23% to 28%. Some laboratory experiments have also investigated the roles of monocarbonyls in SOA formation. The heterogeneous reactions of carbonyls can occur on various aerosol surfaces, including mineral particles, sea salt, and soot particles. Therefore, some laboratory studies have provided reliable uptake coefficients and identified the reaction products under various conditions [START_REF] Shen | Heterogeneous reactions of volatile organic compounds in the atmosphere[END_REF]and references therein). Some studies have also attempted to quantify the contributions of some monocarbonyls to SOA formation. For example, assuming the partition efficiency of both oxalic and malonic acid to be 100%, the aqueous OH-oxidation of methacrolein and methyl vinyl ketone was reported to make maximum contributions of 8.8% and 23.8% to SOA formation, respectively, after a 7-h reaction [START_REF] Zhang | Laboratory simulation for the aqueous OH-oxidation of methyl vinyl ketone and methacrolein: significance to the in-cloud SOA production[END_REF]. However, the detailed formation mechanisms of SOA from carbonyls across China remain unclear and warrant further investigation.

Human health

The World Health Organization has classified several carbonyl species (e.g., HCHO and CH3CHO) as toxic air pollutants and even human carcinogens. In the last two decades, the Chinese government has issued a series of standards to regulate indoor exposure to toxic carbonyl species, but few focused on outdoor carbonyls. Indoor carbonyls often exhibit high levels, and some even exceed the national standard [START_REF] Huang | Characteristics and health impacts of VOCs and carbonyls associated with residential cooking activities in Hong Kong[END_REF][START_REF] Lü | Levels and health risk of carbonyl compounds in air of the library in Guangzhou, South China[END_REF]Lui et al., 2017b;[START_REF] Wang | Characteristics of carbonyls: concentrations and source strengths for indoor and outdoor residential microenvironments in China[END_REF][START_REF] Weng | Levels and health risks of carbonyl compounds in selected public places in Hangzhou, China[END_REF]. Therefore, studies have been conducted to investigate the detrimental effects of both indoor and outdoor carbonyls on human health in China.

Based on numerous experimental studies and historical data, [START_REF] Cogliano | Meeting report: summary of IARC monographs on formaldehyde, 2-butoxyethanol, and 1-tert-butoxy-2-propanol[END_REF] confirmed the carcinogenicity (e.g., nasopharyngeal cancer, leukemia, and sinonasal cancer) of HCHO in humans and animals. The acute and chronic toxicity effects of HCHO apart from carcinogenicity were also investigated [START_REF] Cogliano | Meeting report: summary of IARC monographs on formaldehyde, 2-butoxyethanol, and 1-tert-butoxy-2-propanol[END_REF][START_REF] Tang | Formaldehyde in China: production, consumption, exposure levels, and health effects[END_REF]and references therein). Such laboratory studies of other carbonyl species are very scarce in China, and more investigations are urgently needed. In addition, few studies have focused on personal exposure levels and risk assessments. For example, [START_REF] Ho | Spatiotemporal distribution of carbonyl compounds in China[END_REF] conducted field studies in nine

Chinese cities and assessed the potential health risks of HCHO and CH3CHO using a simple risk-calculation model. High cumulative cancer risks were found in summer in all cities except for Xiamen, a coastal city in southeast China. Furthermore, the highest risk was observed at Chengdu in summer and Wuhan in winter. High exposure and health risks of HCHO and CH3CHO were also found in public places in Hangzhou and Shanghai [START_REF] Feng | Characteristics and personal exposures of carbonyl compounds in the subway stations and in-subway trains of Shanghai, China[END_REF][START_REF] Weng | Levels and health risks of carbonyl compounds in selected public places in Hangzhou, China[END_REF]. In addition, Ho et al. (2014b), [START_REF] Huang | Characteristics and health impacts of VOCs and carbonyls associated with residential cooking activities in Hong Kong[END_REF][START_REF] Lü | Levels and health risk of carbonyl compounds in air of the library in Guangzhou, South China[END_REF] investigated the health risks of indoor carbonyls at a university in Xiamen, two residential kitchens in Hong Kong, and a library in Guangzhou, respectively. Each identified HCHO exposure as a valid occupational health and safety concern. Furthermore, [START_REF] Tang | Formaldehyde in China: production, consumption, exposure levels, and health effects[END_REF] elucidated the indoor and outdoor exposure levels and health effects of HCHO across China in detail. Overall, these limited results revealed the high risk of exposure to carbonyls in China. More studies of the health impact of carbonyls are needed, and essential measures to protect human health should be taken.

Summary and outlook

Significant progress has been achieved in the last 20 years in the study of ambient carbonyls in China's atmosphere. A number of field observations have been conducted at various surface sites across China. The results have revealed the severity and tempo-spatial variations of carbonyls pollution in China. Photochemical formation was identified as the dominant source of ambient carbonyls, but primary emissions also made important contributions in specific circumstances. Alkenes, aromatics, and isoprene usually dominated the secondary formation of carbonyls. Carbonyls are acknowledged as important precursors of O3 and SOA. For O3, carbonyls usually dominate the OFP in rural areas, and for SOA, dicarbonyls such as GLY and MGLY make important contributions to SOA formation, mainly via irreversible uptake by aqueous particles. In addition, few studies have revealed the high exposure and health risk of both indoor and outdoor carbonyls in China.

Despite the abovementioned progress, more efforts are still needed to gain a thorough understanding of the role of carbonyls in tropospheric chemistry, O3 and SOA formation, and human health. The following directions are recommended for future study.

(1) The current field observations remain far from sufficient to comprehensively reflect the carbonyls pollution situation across China. Although high-molecular weight carbonyls play a significant role in aerosol formation, the observational data available are very scarce because they are largely partitioned into the particle phase and thus exhibit low gas-phase concentrations. More studies should be conducted to investigate the characteristics of high-molecular weight carbonyls. Furthermore, the vertical distribution profiles for gaseous carbonyls remain unclear. In addition, most ground observations have been concentrated in fast-developing regions, such as the NCP, YRD, and PRD. It is strongly suggested that more field studies be conducted on other overpopulated and fast-developing regions. This suggestion also applies to other more reactive carbonyl species that should receive more attention.

(2) The emission patterns of primary sources (especially the non-vehicle primary sources) remain poorly understood. The combined efforts of the research community and government agencies are needed to accurately characterize the primary emissions and develop a national species-specific carbonyls emission inventory in China.

(3) Most studies have focused on identifying dominant precursors; little attention has been paid to the detailed photochemical formation processes of carbonyls. To some extent, such an investigation is impeded by the accurate representation of chemical mechanisms of carbonyls in models, which is still considered a difficulty in current research. We recommend that more laboratory experiments be conducted to update the chemical mechanisms that can be incorporated into models to better identify dominant precursors and investigate the detailed photochemical formation mechanisms of carbonyls. It can also help to precisely quantify the contributions of isoprene and other important biogenic VOCs to carbonyls.

(4) Due to the limitations of observation techniques, few studies have focused on the effects of carbonyls on O3 and SOA. Ways of better dissecting the contributions of primary and secondary carbonyls to O3 and better understanding the formation mechanisms of SOA from carbonyls remain significant challenges that require further investigation. In addition, research and control policy making should attach equal importance to indoor and outdoor exposure to carbonyls.

Figure 1 .

 1 Figure 1. Major chemical processes of OVOCs in the atmosphere. The red and blue lines indicate the initiation and recycling pathways of radicals. The dotted lines indicate chemical processes in which OVOCs directly involved.

Figure 2a .

 2a Figure 2a. Spatial distributions of HCHO levels (ppbv) in China. Urban, suburban, rural sites are marked as circles, triangles and squares, respectively. The observation data are taken from

Figure 2c .

 2c Figure 2c. The same to Figure 2a but for C2H5CHO.

Figure 2d .

 2d Figure 2d. The same to Figure 2a but for C3H7CHO.

Figure 3a .

 3a Figure 3a. Spatial distributions of GLY and MGLY levels (ppbv) in China in summer. The observation data are taken from Ho et al. (2014a), Ho et al. (2015), Kawamura et al. (2013), Lui et al. (2017a), and Rao et al. (2016).

Figure 3b .

 3b Figure 3b. The same to Figure 3a but for data in winter.

  -HPLC; Online: GC-MS/FID, PTR-MS, PTR-TOF-CIMS, PTR-TOF-MS;

Table 1 .

 1 Summary of basic information of major carbonyl species that have ever been observed in China.

Table 2 .

 2 Summary of studies of radical source and OH reactivity in China.

	Site	Measurement period	Type	Dominant primary source of OH	Dominant contributor to OH reactivity	Dominant primary source of HO2	Dominant primary source of RO2	Reference
	a CRAES, Beijing	Jul.-Aug. 2008	Urban	O3 photolysis	OVOCs	OVOCs photolysis	OVOCs photolysis	Yang et al. (2018)
	a PKU, Beijing	Aug. 2005	Urban	-	Alkenes	-	-	Shao et al. (2009)

Acknowledgements

This work was funded by the National Natural Science Foundation of China (41675118, 91544213), the National Key Research and Development Program of China (2016YFC0200500), the Qilu Youth Talent Program of Shandong University, the Jiangsu Collaborative Innovation Center for Climate Change, and the Taishan Scholars (ts201712003).

Hong Kong, respectively. The observation data are taken from [START_REF] Huang | Characteristics of carbonyl compounds in ambient air of Shanghai, China[END_REF], [START_REF] Lü | Seasonal and diurnal variations of carbonyl compounds in the urban atmosphere of Guangzhou, China[END_REF], Lui et al. (2017c), and [START_REF] Pang | Seasonal and diurnal variations of carbonyl compounds in Beijing ambient air[END_REF]. The kOH values were under conditions of 298 K and 1 bar; the kOH values and photolysis frequencies are taken from [START_REF] Calvert | The Mechanisms of Atmospheric Oxidation of the Oxygenates[END_REF] and [START_REF] Mellouki | Atmospheric chemistry of oxygenated volatile organic compounds: impacts on air quality and climate[END_REF].