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Volatile organic compounds (VOCs) are key precursors of ozone and particulate matter, which are the two dominant air pollutants in urban environments. However, compositions and sources of VOCs in urban air aloft have rarely been reported so far. To address this matter, highly time-resolved measurements of VOCs were made by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at a 450 m platform on the Canton Tower in Guangzhou, China. A combination of in situ measurements and modeling techniques was used to characterize variations in and sources of VOCs. Five sources were identified from positive matrix factorization (PMF) analysis, namely daytime mixed (e.g., biogenic emissions and secondary formation), visitor-related (e.g., human breath, cooking, and volatilization of ethanol-containing products), vehicular–industrial, regional transport, and volatile chemical product (VCP) (i.e., volatilization of personal care products), contributing on average to 21 %, 30 %, 28 %, 10 %, and 11 % of total VOC (TVOC) mixing ratios, respectively. We observe that contributions of the visitor-related source, mainly composed of ethanol, followed with the variation in visitor numbers on the tower well. The VCP-dominated source only had an average contribution of ∼5.7 ppb during the campaign, accounting for a small fraction (11 %) of TVOC mixing ratios but a large fraction (22 %) of the total OH reactivity. However, large fractions of reactive VOC species, e.g., monoterpenes (49 %), were attributed to the VCP-dominated source, indicating important contributions of VCPs to ambient concentrations of these species in urban environments. Vertical profiles of air pollutants (namely NOx, ozone, Ox, and PM2.5), measured at 5, 118, 168, and 488 m, exhibited more evident gradients at night than in the daytime owing to the stronger stability of the nocturnal boundary layer. Mixing ratios of VOC species during the nighttime generally decreased with time when the 450 m platform was located in the nocturnal residual layer and markedly increased when impacted by emissions at ground level. The results in this study demonstrated composition characteristics and sources of VOCs in urban air aloft, which could provide valuable implications in making strategies for control of VOCs and secondary air pollutants.

Ambient nitrate has been of increasing concern in PM2.5, while there are still large uncertainties in quantifying the formation of nitrate aerosol. The formation pathways of nitrate aerosol at an urban site and a suburban site in the Pearl River Delta (PRD) are investigated using an observation-constrained box model. Throughout the campaigns, aerosol pollution episodes were constantly accompanied with the increase in nitrate concentrations and fractions at both urban and suburban sites. The simulations demonstrate that chemical reactions in the daytime and at night both contributed significantly to formation of nitrate in the boundary layer at the two sites. However, nighttime reactions predominantly occurred aloft in the residual layer at the urban site, and downward transport from the residual layer in the morning is an important source (53 %) for surface nitrate at the urban site, whereas similar amounts of nitrate were produced in the nocturnal boundary layer and residual layer at the suburban site, which results in little downward transport of nitrate from the residual layer to the ground at the suburban site. We show that nitrate formation was in the volatile-organic-compound-limited (VOC-limited) regime at the urban site, and in the transition regime at the suburban site, identical to the response of ozone at both sites. The reduction of VOC emissions can be an efficient approach to mitigate nitrate in both urban and suburban areas through influencing hydroxyl radical (OH) and N2O5 production, which will also be beneficial for the synergistic control of regional ozone pollution. The results highlight that the relative importance of nitrate formation pathways and ozone can be site-specific, and the quantitative understanding of various pathways of nitrate formation will provide insights for developing nitrate and ozone mitigation strategies.

Nitrous acid (HONO) is an important photochemical precursor to hydroxyl radicals particularly in an urban atmosphere, yet its primary emission and secondary production are often poorly constrained. Here, we measured HONO and nitrogen oxides (NOx) at both the inlet and the outlet in a busy urban tunnel (>30 000 vehicles per day) in south China. Multiple linear regression revealed that 73.9% of the inlet-outlet incremental HONO concentration was explained by NO2 surface conversion, while the rest was directly emitted from vehicles with an average HONO/NOx ratio of 1.31 ± 0.87%, which was higher than that from previous tunnel studies. The uptake coefficient of NO2, γ(NO2), on the tunnel surfaces was calculated to be (7.01 ± 0.02) × 10-5, much higher than that widely used in models. As tunnel surfaces are typical of urban surfaces in the wall and road materials, the dominance of HONO from surface reactions in the poorly lit urban tunnel demonstrated the importance of NO2 conversion on urban surfaces, instead of NO2 conversion on the aerosol surface, for both daytime and night-time HONO even in polluted ambient air. The higher γ(NO2) on urban surfaces and the elevated HONO/NOx ratio from this study can help explain the missing HONO sources in urban areas.

Nowadays, the emission source and formation mechanism of fine particulate nitrate (pNO

Despite the large reduction in anthropogenic activities due to the outbreak of COVID-19, air quality in China has witnessed little improvement and featured great regional disparities. Here, by combining observational data and simulations, this work aims to understand the diverse air quality response in two city clusters, Yangtze River Delta region (YRD) and Pearl River Delta region (PRD), China. Though there was a noticeable drop in primary pollutants in both the regions, differently, the maximum daily 8 h average ozone (O3) soared by 20.6–76.8% in YRD but decreased by 15.5–28.1% in PRD. In YRD, nitrogen oxide (NOx) reductions enhanced O3 accumulation and hence increased secondary aerosol formation. Such an increment in secondary organic and inorganic aerosols under stationary weather reached up to 36.4 and 10.2%, respectively, which was further intensified by regional transport. PRD was quite the opposite. The emission reductions benefited PRD air quality, while regional transport corresponded to an increase of 17.3 and 9.3% in secondary organic and inorganic aerosols, respectively. Apart from meteorology, the discrepancy in O3–VOCs–NOx relationships determined the different O3 responses, indicating that future emission control shall be regionally specific, instead of one-size-fits-all cut. Overall, the importance of regionally coordinated and balanced control strategy for multiple pollutants is highly emphasized.

Ozone (O

Vehicle emissions are an important source of nitrated aromatic compounds (NACs) in particulate size smaller 2.5 μm (PM

Ammonia (NH

Nitrous acid (HONO) is an important photochemical precursor to hydroxyl radicals particularly in an urban atmosphere, yet its primary emission and secondary production are often poorly constrained. Here, we measured HONO and nitrogen oxides (NO

The real-time detection of the mixing states of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs in ambient particles is of great significance for analyzing the source, aging process, and health effects of PAHs and nitro-PAHs; yet there is still few effective technology to achieve this type of detection. In this study, 11 types of PAH and nitro-PAH standard samples were analyzed using a high performance-single particle aerosol mass spectrometer (HP-SPAMS) in lab studies. The identification principles 'parent ions' and 'mass-to-charge (m/z) = 77' of each compound were obtained in this study. It was found that different laser energies did not affect the identification of the parent ions. The comparative experiments of ambient atmospheric particles, cooking and biomass burning emitted particles with and without the addition of PAHs were conducted and ruled out the interferences from primary and secondary organics on the identification of PAHs. Besides, the reliability of the characteristic ions extraction method was evaluated through the comparative study of similarity algorithm and deep learning algorithm. In addition, the real PAH-containing particles from vehicle exhaust emissions and ambient particles were also analyzed. This study improves the ability of single particle mass spectrometry technology to detect PAHs and nitro-PAHs, and HP-SPAMS was superior to SPAMS for detecting single particles containing PAHs and nitro-PAHs. This study provides support for subsequent ambient observations to identify the characteristic spectrum of single particles containing PAHs and nitro-PAHs.

Measurements of vertical distribution of volatile organic compounds (VOCs) have attracted wide attentions, which could help to understand atmospheric oxidation mechanism and provide implications for VOC control. This study measured the non-methane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) simultaneously for the first time at three different heights, namely ground, 118 m and 488 m, in the Canton Tower located in the urban core of the Pearl River Delta (PRD). The results show that NMHCs decreased while some OVOC species such as formaldehyde and acetaldehyde increased with increasing height. It was mainly attributed to the dilution and chemical loss of NMHCs but secondary production of OVOCs during vertical transport. Ratio analysis and receptor modeling indicate that vehicle exhausts (47%) and fuel evaporation (39%) were major sources of the total NMHCs. Interestingly, industry contributed much more at 118 m, probably affected by organic gas discharge from the high chimney of industrial factories. The chemical reactivities in terms of OH radical loss rate (LOH), ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) were lowest at 118 m, smaller than those influenced by high fresh NMHC emissions at ground and strong formation of secondary species (e.g. OVOCs) at 488 m. OH exposure estimated by isoprene and m,p-xylene/ethylbenzene was different depending on their time scale of vertical turbulent mixing and chemical loss. OVOC species measured at different heights were positively correlated with Ox (R = 0.48–0.87), indicating that OVOCs were largely contributed by secondary formation in photochemical process. The tower measurements of NMHCs and OVOCs provided a unique opportunity to investigate the VOC distribution and chemical behaviors, which could give important information for understanding O3 and PM2.5 pollution mechanism in the PRD region with fast developing urban setting and substantially changing air quality.

The toxic effects of lead on human health and the environment have long been a focus of research. To explore sources of lead in Guangzhou, China, we investigated atmospheric lead-containing particles (LCPs) during wintertime using a single particle aerosol mass spectrometer (SPAMS). Based on mass spectral features, LCPs were classified into eight major particle types, including Pb-Cl and Pb-Cl-Li (coal combustion and waste incineration), Pb-Cl-EC and Pb-Cl-OC (diesel trucks and coal combustion), Pb-Cl-Fe (iron and steel industry), Pb-Cl-AlSi (dust), Pb-Sec (secondary formation), and Pb-Cl-Zn (industrial process); these sources (in parentheses) were identified by comparing atmospheric LCP mass spectra with authentic Pb emission source mass spectra. Sampling periods with LCP number fractions (NFs) more than three times the average LCP NF (APF = 4.35%) and below the APF were defined as high LCP NF periods (HLFPs: H1, H3, and H5) and low LCP NF APF periods (LLFPs: L2 and L4), respectively. Diurnal patterns and high Pb-Sec content during LLFPs indicate that photochemical activity and heterogeneous reactions may have controlled Pb-Sec particle formation. The inverse Pb-Cl and Pb-Sec particle diurnal trends during LLFPs suggest the replacement of Cl by sulfate and nitrate. On average over the five periods, ~ 76% of the LCPs likely arose from coal combustion and/or waste incineration, which were dominant sources during all five periods, followed by diesel trucks during LLFPs and iron- and steel-related sources during HLFPs; HLFP LCPs arose mainly from primary emissions. These results can be used to more efficiently control Pb emission sources and prevent harm to human and environmental health from Pb toxicity.

With changing numbers, compositions, emission standards and fuel quality of on-road vehicles, it is imperative to accordingly characterize and update vehicular emissions of carbonaceous aerosols for better understanding their health and climatic effects. In this study, a 7-day field campaign was conducted in 2019 in a busy urban tunnel (>30,000 vehicles day-1) in south China with filter-based aerosol samples collected every 2 h at both the inlet and the outlet for measuring carbonaceous aerosols and their light absorbing properties. Observed fleet average emission factor (EF) of total carbon (TC) was 13.4 ± 8.3 mg veh-1 km-1, and 17.4 ± 11.3 mg veh-1 km-1 if electric and LPG-driven vehicles were excluded; and fleet average EF of organic carbon (OC) and elemental carbon (EC) was 8.5 ± 6.6 and 4.9 ± 2.6 mg veh-1 km-1 (11.0 ± 8.8 and 6.3 ± 3.6 mg veh-1 km-1 if excluding electric and LPG vehicles), respectively. Regression analysis revealed an average TC-EF of 319.8 mg veh-1 km-1 for diesel vehicles and 2.1 mg veh-1 km-1 for gasoline vehicles, and although diesel vehicles only shared ~4% in the fleet compositions, they still dominate on-road vehicular carbonaceous aerosol emissions due to their over 150 times higher average TC-EF than gasoline vehicles. Filter-based light absorption measurement demonstrated that on average brown carbon (BrC) could account for 19.1% of the total carbonaceous light absorption at 405 nm, and the average mass absorption efficiency of EC at 635 nm and that of OC at 405 nm were 5.2 m2 g-1 C and 1.0 m2 g-1 C, respectively.

Low-molecular-weight dicarboxylic acids, which are important components of secondary organic aerosols, have been extensively studied in recent years. Many studies have focused on ground-level observations and literature reports on the vertical distribution of the organic aerosols within the urban boundary layer are limited. In this study, the vertical profiles of dicarboxylic acids and related organic compounds (DCRCs) in PM

During the COVID-19 lockdown, ambient ozone levels are widely reported to show much smaller decreases or even dramatical increases under substantially reduced precursor NOx levels, yet changes in ambient precursor volatile organic compounds (VOCs) have been scarcely reported during the COVID-19 lockdown, which is an opportunity to examine the impacts of dramatically changing anthropogenic emissions on ambient VOC levels in megacities where ozone formation is largely VOC-limited. In this study, ambient VOCs were monitored online at an urban site in Guangzhou in the Pearl River Delta region before, during, and after the COVID-19 lockdown. The average total mixing ratios of VOCs became 19.1% lower during the lockdown than before, and those of alkanes, alkenes and aromatics decreased by 19.0%, 24.8% and 38.2%, respectively. The levels of light alkanes (C6) decreased by only 13.0%, while those of higher alkanes (C ≥ 6) decreased by 67.8% during the lockdown. Disappeared peak VOC levels in morning rush hours and the drop in toluene to benzene ratios during the lockdown suggested significant reductions in vehicle exhaust and industrial solvent emissions. Source apportioning by positive matrix factorization model revealed that reductions in industrial emissions, diesel exhaust (on-road diesel vehicles and off-road diesel engines) and gasoline-related emissions could account for 48.9%, 42.2% and 8.8%, respectively, of the decreased VOC levels during the lockdown. Moreover, the reduction in industrial emissions could explain 56.0% and 70.0% of the reductions in ambient levels of reactive alkenes and aromatics, respectively. An average increase in O

Vehicle emission is an important source of ammonia (NH3) in urban areas. To better address the role of vehicle emission in urban NH3 sources, the emission factor of NH3 (NH3-EF) from vehicles running on roads under real-world conditions (on-road vehicles) needs to update accordingly with the increasingly tightened vehicle emission standards. In this study, laser-absorption based measurements of NH3 were conducted during a six-day campaign in 2019 at a busy urban tunnel with a daily traffic flow of nearly 40,000 vehicles in south China’s Pearl River Delta (PRD) region. The NH3-EF was measured to be 16.6 ± 6.3 mg km−1 for the on-road vehicle fleets and 19.0 ± 7.2 mg km−1 for non-electric vehicles, with an NH3 to CO2 ratio of 0.27 ± 0.09 ppbv ppmv−1. Multiple linear regression revealed that the average NH3-EFs for gasoline vehicles (GVs), liquefied petroleum gas vehicles, and heavy-duty diesel vehicles (HDVs) were 18.8, 15.6, and 44.2 mg km−1, respectively. While NH3 emissions from GVs were greatly reduced with enhanced performance of engines and catalytic devices to meet stricter emission standards, the application of urea selective catalytic reduction (SCR) in HDVs makes their NH3 emission an emerging concern. Based on results from this study, HDVs may contribute over 11% of the vehicular NH3 emissions, although they only share ∼4% by vehicle numbers in China. With the updated NH3-EFs, NH3 emission from on-road vehicles was estimated to be 9 Gg yr−1 in the PRD region in 2019, contributing only 5% of total NH3 emissions in the region, but still might be a dominant NH3 source in the urban centers with little agricultural activity.

Volatile organic compounds (VOCs) play a crucial role in modulating air pollution by ozone and fine particles, particularly in urban areas. While in recent years short-term intervention actions for better air quality during big events in China did present good opportunities to examine the effectiveness of control measures in reducing anthropogenic VOCs emission, it is highly challenging to interpret the real effect of a specific control measure based on field monitoring data when a cocktail of control measures were adopted. Here we took the air quality intervention actions during the 16th Asian Games (AG) in Guangzhou as a case study to explore the impact of short-term multiple measures on VOCs reduction. The average mass concentrations of VOCs decreased by 52-68% during the AG. These percentages could not reflect emission reduction rates as the concentration might be also heavily impacted by dispersion conditions. Diagnostic ratios, such as methyl tert-butyl ether to carbon monoxide (MTBE/CO) and i-pentane/CO, decreased by over 60% during the AG, suggesting a substantial reduction in gasoline related emissions. A method linking emission reduction rates of two sources with their contribution percentages before and during the AG by using a receptor model was further formulated. With the available reduction rate of 34% for vehicular exhaust obtained during the traffic restriction drill in our previous study, VOCs emissions from gasoline evaporation and solvent use reduced by 45.7% and 13.6% during the AG, respectively. Total VOCs emissions decreased by 25.3% on average during the AG, and the emission control of vehicular exhaust, oil evaporation, and solvent use accounted for 17.0%, 6.3% and 2.0% of total VOCs emission reduction, respectively. This study presented an observed-based method with diagnostic/quantitative approaches to single out the effectiveness of each control measures in reducing VOCs emissions.

In this work, we analyzed freshly emitted particles from ship exhaust in the Guangzhou port region before and after the implementation of a clean fuel policy. We used a single particle aerosol mass spectrometer (SPAMS) to measure the changes in the chemical compositions of single particles and evaluate the role of V as a tracer for ship emissions. Particles from high sulfur fuel (SF) oil (HS) combustion ships consisted of 54.8% elemental carbon-vanadium-sulfate (EC-V-S) and 25.0% vanadium-sulfate (V-S) particles, while particles from low SF oil (LS) combustion ships were composed of 38.7% organic carbon-sulfate (OC-S) and 28.6% elemental and organic carbon (ECOC) particles. The sulfate-containing particles exhibited a moderate decrease from 95% in HS emissions to 78% in LS emissions, which still suggests the dominant role of sulfate in LS emissions after the implementation of a clean fuel policy. The V-containing particles showed a sharp decrease from 67% in HS emissions to 14% in LS emissions along with the decrease in the relative peak area (RPA) of V, suggesting a remarkable reduction in V in ship exhaust. The count of V-containing particles in urban Guangzhou in June 2017 was generally ten times lower than that in June 2016, which was in accordance with the sharp decrease in V-containing particles in LS emissions rather than in HS emissions. Despite the decrease in V in source-oriented ship emitted particles, the ubiquitous distribution of V in particles from lower SF combustion ships suggests V is still effective as a tracer of ship emissions in port regions after the implementation of the clean fuel policy. Furthermore, the particles from LS emissions were investigated in comparison to those from gasoline vehicles (GV), diesel vehicles (DV) and coal combustion (CC) sources to better resolve ship-related particles in port regions.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km-1 in 2014 against that of 194, 129, and 160 mg km-1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km-1; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km-1; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km-1, respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km-1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km-1. While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km-1 in 2004 to 449 ± 40 mg km-1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 103 mg km-1 in 2004 to 1.10 × 103 mg km-1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km-1 in 2004 to 25 mg km-1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards.

Low-molecular-weight dicarboxylic acids, which are important components of secondary organic aerosols, have been extensively studied in recent years. Many studies have focused on ground-level observations and literature reports on the vertical distribution of the organic aerosols within the urban boundary layer are limited. In this study, the vertical profiles of dicarboxylic acids and related organic compounds (DCRCs) in PM2.5 were investigated at altitudinal levels (ground level and 488 m above the ground level) at the Canton Tower in Guangzhou, southern China, to elucidate their primary sources and secondary formation processes. The concentrations of DCRCs at ground level were generally higher than those at 488 m. Oxalic acid (C2) was the most abundant species, followed by succinic acid (C4) and malonic acid (C3) at both heights. The higher ratio of DCRCs-bound carbon to organic carbon (i.e., DCRCs-C/OC) at 488 m (4.8 ± 1.2%) relative to that at ground level (2.7 ± 0.5%) indicated a higher degree of aerosol aging at 488 m. The abundance of C2 was increased and the conversion of C4 to C3 was enhanced due to the photochemical oxidation of its homologues during long-range transport periods. The increase in C2 was associated with in-cloud processes during pollution periods. Principal component analysis showed that DCRCs were mainly derived from atmospheric secondary processing and biomass burning was also an important source of long-chain carboxylic acids during autumn in Guangzhou. Our results illustrate that secondary processing and biomass burning play prominent roles in controlling the abundance of DCRCs. Furthermore, DCRCs are affected by air masses from regional areas, oxidation of their precursors via vertical transport and in-cloud processes.

Carbonyls play a vital role in atmospheric photochemistry. Vehicle emission is among most important primary emission sources of carbonyls in urban areas, yet knowledge is quite scarce about real-world emissions of carbonyls with the changing on-road vehicle fleets. In this study, emissions of carbonyls were characterized based on tests in a busy urban tunnel in south China. Emission factor (EF) of carbonyls was measured to be 9.89 ± 0.65 mg km−1 on average, in which formaldehyde alone shared 53.1% with an EF of 5.25 ± 0.35 mg km−1, followed by acetaldehyde with an EF of 1.47 ± 0.13 mg km−1. Glyoxal and methylglyoxal showed identical EFs of 0.18 ± 0.02 mg km−1. Multiple linear regression retrieved total carbonyl EFs of 5.68, 47.71 and 35.09 mg km−1 and ozone formation potentials (OFPs) of 38.4, 329.3, and 242.4 mg km−1 for gasoline, diesel and liquefied petroleum gas vehicles (LPGVs), respectively. The unexpectedly high carbonyl emissions from LPGVs were largely attributed to the lack of after-treatment systems or the inefficiency of the after-treatment systems. Among vehicle-emitted non-methane hydrocarbons and carbonyls, carbonyls could contribute ~20% of the total OFPs while they only accounted for 7.1% of the total mass.

Volatile organic compounds (VOCs) were monitored online at three photochemical assessment monitoring stations (MDS, WQS and HGS) in the Pearl River Delta region during the summer of 2016. Measured levels of VOCs at the MDS, WQS and HGS sites were 34.78, 8.54 and 8.47 ppbv, respectively, with aromatics and alkenes as major ozone precursors and aromatics as major precursors to secondary organic aerosol (SOA). The positive matrix factorization (PMF) model revealed that VOCs at the sites mainly came from vehicle exhaust, petrochemical industry, and solvent use. Vehicle exhaust and industrial processes losses contributed most to ozone formation potentials (OFP) of VOCs, while industrial processes losses contributed most to SOA formation potentials of VOCs. Potential source contribution function (PSCF) analysis revealed a north-south distribution for source regions of aromatics occurring at MDS with emission sources in Guangzhou mainly centered in the Guangzhou central districts, and source regions of aromatics at WQS showed an east-west distribution across Huizhou, Dongguan and east of Guangzhou, while that at HGS showed a south-north distribution across Guangzhou, Foshan, Zhaoqing and Yangjiang. This study demonstrates that multi-point high time resolution data can help resolve emission sources and locate emission areas of important ozone and SOA precursors.

Accurate estimation of speciated emissions of volatile organic compounds (VOCs) is challenging due to the complexity of both species and sources. Evaluation of the bottom-up emission inventory (EI) by atmospheric observation is needed to better understand the VOC emissions and then to control air pollutions caused by VOCs. This study conducts vertical measurements of VOCs between November 3 and 11, 2018 at the Canton Tower in the urban core of Pearl River Delta (PRD), China. A mixed layer gradient (MLG) technique is applied to the tower observation data to derive emission fluxes for individual VOC. The results show that the measured VOCs concentrations at ground level were always higher than those at the heights of 118 m and 488 m. Obvious vertical gradients of concentrations were found for VOC species, such as benzene, toluene and isoprene. The emission flux was estimated to be largest for propane (3.29 mg m−2 h−1), followed by toluene (2.55 mg m−2 h−1), isoprene (2.24 mg m−2 h−1), n-butane (2.10 mg m−2 h−1) and iso-pentane (1.73 mg m−2 h−1). The total VOC emission fluxes were around 3 times larger than those in the EI, suggesting 1.5–2 times underestimations of ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) by current EI. Substantial underestimations (3–20 times) were found for C2-C5 alkanes by current EI. Due to unmeasured input parameters, limited sample size and short sampling period, there are still large uncertainties (40%–117%) in the estimated emission fluxes for individual species. Whereas, this study shows that the tower observation and emission estimation using MLG method could provide useful information for better understanding vertical distributions and emission fluxes of VOCs, and pioneer in assessing the existing emission inventories at species-level and hour-level.

Reducing emissions of methane (CH4) in developed regions and urban areas is a practical way to curb the unexpected surge in global CH4 levels in recent decades. Traffic emissions are among the important anthropogenic CH4 emission sources in megacities, yet CH4 emissions from on-road vehicles are less characterized and not well addressed. Based on tunnel tests in an urban tunnel in south China, a real-world emission factor (EF) of CH4 was measured to be 0.26 ± 0.03 g·km−1 (mean ±95% C.I.) for on-road vehicle fleet which including gasoline vehicles, diesel vehicles, and liquefied petroleum gas vehicles, with an average CH4/CO2 mass ratio of 40.6E-5 g·g−1, and CH4 could account for 1.3% of vehicle CO2-equivalent emissions. Using the measured CH4/CO2 ratio and available automobile CO2 emission estimates, traffic CH4 emissions in 2014 could have reached 333 Gg and represented 0.6% of total anthropogenic CH4 emissions in China, approximately four times the previous reported value of 79 Gg. Our results indicate that improving energy efficiency would have co-benefits for reducing traffic emissions of CH4, as observed EFs of CH4 are positively correlated with that of CO2, and over 90% of traffic CH4 emissions in China could be avoided if the traffic CH4/CO2 ratio can be an order of magnitude lower as previously observed in a tunnel in Switzerland.

Unresolved complex mixture (UCM) accounts for a substantial fraction of particulate organic matters and plays an important role in forming secondary organic aerosol (SOA), yet their abundance, sources and atmospheric processes are not well understood. In this study, filter-based ambient PM2.5 samples were collected concourrently at an urban site and a rural site in the Pearl River Delta (PRD) region, south China, to characterize semi-volatile UCM. Dust, urban tunnel exhaust, ship exhaust and biomass burning samples were also collected to characterize UCM from typical primary emission sources. No obvious UCM humps were found in total ion chromatograms (TIC) of the PM2.5 samples collected during July–October, while the determined UCM reached 6.51 ± 4.92 μg/m3 at the urban site and 6.75 ± 4.78 μg/m3 at the rural site during November–May, accounting for ~9% of PM2.5 mass at both sites. The missing UCM humps in the hot months were due to much large fraction of these semi-volatiles partitioning to gas phase and their much faster atmospheric oxidation. In addition, the lower organic matter (OM) was also a non-negligible factor contributing to less particulate UCM in summer. Five major sources for PM2.5-bound UCM were identified by positive matrix factorization (PMF) involving organic and inorganic molecular source tracers. Vehicle exhaust accounted for 44.4% and 30.3% of UCM at the urban and the rural site, respectively. Biomass burning contributed more to UCM at the rural site (28.0%) than at the urban site (19.2%). Ship emission was found to contribute substantially to UCM (28.9% at the urban and 17.3% at the rural site) in the PRD harbor megacity. Coal combustion and dust altogether contributed much less at the urban site (7.5%) than at the rural site (24.4%).

As the development of megacities, combined air pollution has been of increasing concern in China, which is composed by primary pollution, such as Nitrogen dioxide (NO2), and the followed secondary pollution under certain meteorology circumstances and high concentration of precursors, such as tropospheric ozone, formaldehyde (HCHO) and fine particles. During PRIDE-GBA 2018 Campaign (Particles, Radicals, Intermediates from oxiDation of primary Emissions in Great Bay Area), we performed the high resolution vertical observations of pollution gases and aerosol, which are significant but scarce indexes in studying the mechanisms of tropospheric pollution, using remote sensing techniques. NO2 and HCHO column densities and vertical profiles are reconstructed from data of multi-axis differential optical absorption spectroscopy (MAX-DOAS). Tropospheric ozone profile and aerosol extinction are retrieved by the differential absorption light detection and ranging (LIDAR) system. In order to verifying the accuracy, we evaluated the consistency and reliability of MAX-DOAS and LIDAR measurements. The results showed reasonable agreement with in-situ and off-line observations at Canton Tower. A typical combined pollution process from Sep 29 to Oct 10 was analyzed in detail. More than 200 μg/m3 tropospheric ozone in this case was considered from the anthropogenic sources, including industry, power plant, residential and transportation. The high emission from local industry and polluted air transport from northeast brought the main precursors of this pollution process. The photochemical formation of tropospheric ozone was turned into a VOC-limited regime on polluted days.