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We developed incremental reactivity (IR) scales for 116 volatile organic compounds (VOCs) in a Chinese megacity (Guangzhou) and elucidated their application in calculating the ozone (O3) formation potential (OFP) in China. Two sets of model inputs (emission-based and observation-based) were designed to localize the IR scales in Guangzhou using the Master Chemical Mechanism (MCM) box model and were also compared with those of the US. The two inputs differed in how primary pollutant inputs in the model were derived, with one based on emission data and the other based on observed pollutant levels, but the maximum incremental reactivity (MIR) scales derived from them were fairly similar. The IR scales showed a strong dependence on the chemical mechanism (MCM vs. Statewide Air Pollution Research Center), and a higher consistency was found in IR scales between China and the US using a similar chemical mechanism. With a given chemical mechanism, the MIR scale for most VOCs showed a relatively small dependence on environmental conditions. However, when the NOx availability decreased, the IR scales became more sensitive to environmental conditions and the discrepancy between the IR scales obtained from emission-based and observation-based inputs increased, thereby implying the necessity to localize IR scales over mixed-limited or NOx -limited areas. This study provides recommendations for the application of IR scales, which has great significance for VOC control in China and other countries suffering from serious O3 air pollution. [ABSTRACT FROM AUTHOR]

Limiting fuel sulfur content (FSC) is a widely adopted approach for reducing ship emissions of sulfur dioxide (SO2) and particulate matter (PM), particularly in emission control areas (ECAs), but its impact on the emissions of volatile organic compounds (VOCs) is still not well understood. In this study, emissions from ships at berth in Guangzhou, southern China, were characterized before and after the implementation of the fuel switch policy (IFSP) with an FSC limit of 0.5 % in the Pearl River Delta ECA (ECA-PRD). After IFSP, the emission factors (EFs) of SO2 and PM 2.5 for the coastal vessels decreased by 78 % and 56 % on average, respectively; however, the EFs of the VOCs were 1807±1746 mg kg -1 , approximately 15 times that of 118±56.1 mg kg -1 before IFSP. This dramatic increase in the emissions of the VOCs might have been largely due to the replacement of high-sulfur residual fuel oil with low-sulfur diesel or heavy oils, which are typically richer in short-chain hydrocarbons. Moreover, reactive alkenes surpassed alkanes to become the dominant group among the VOCs, and low-carbon-number VOCs, such as ethylene, propene and isobutane, became the dominant species after IFSP. As a result of the largely elevated EFs of the reactive alkenes and aromatics after IFSP, the emitted VOCs per kilogram of fuel burned had nearly 29 times greater ozone formation potential (OFP) and approximately 2 times greater secondary organic aerosol formation potential (SOAFP) than those before IFSP. Unlike the coastal vessels, the river vessels in the region used diesel fuels consistently and were not affected by the fuel switch policy, but the EFs of their VOCs were 90 % greater than those of the coastal vessels after IFSP, with approximately 120 % greater fuel-based OFP and 70 %–140 % greater SOAFP. The results from this study suggest that while the fuel switch policy could effectively reduce SO2 and PM emissions, and thus help control PM 2.5 pollution, it will also lead to greater emissions of reactive VOCs, which may threaten ozone pollution control in harbor cities. This change for coastal or ocean-going vessels, in addition to the large amounts of reactive VOCs from the river vessels, raises regulatory concerns for ship emissions of reactive VOCs. [ABSTRACT FROM AUTHOR]

Traffic restriction (TR) is a widely adopted control measure in case of heavy air pollution particularly in urban areas, yet it is hard to evaluate the effect of TR on reducing VOC emissions based on monitoring data since ambient VOC mixing ratios are influenced not only by source emissions but also by meteorological conditions and atmospheric degradation. Here we collected air samples for analysis of VOCs before, during and after a TR drill carried out in Guangzhou in September 2010 at both a roadside and a rooftop (∼50 m above the ground) site. TR measures mainly included the “odd-even license” rule and banning high-emitting “yellow label” vehicles. The mixing ratios of non-methane hydrocarbons (NMHCs) did not show significant changes at the roadside site with total NMHCs of 39.0 ± 11.8 ppbv during non-TR period and 39.1 ± 14.8 ppbv during TR period, whereas total NMHCs decreased from 30.4 ± 14.3 ppbv during the non-TR period to 22.1 ± 10.6 ppbv during the TR period at rooftop site. However, the ratios of methyl tert-butyl ether (MTBE), benzene and toluene against carbon monoxide (MTBE/CO, T/CO and B/CO) at the both sampling sites dropped significantly. The ratios of toluene to benzene (T/B) instead increased significantly. Changes in these ratios all consistently indicated reduced input from traffic emissions particularly gasoline vehicles. Source attribution by positive matrix factorization (PMF) confirmed that during the TR period gasoline vehicles contributed less VOCs in percentages while industrial sources, biomass burning and LPG shared larger percentages. Assuming that emissions from industrial sources remained unchanged during the TR and non-TR periods, we further used the PMF-retrieved contribution percentages to deduce the reduction rate of traffic-related VOC emissions, and obtained a reduction rate of 31% based on monitoring data at the roadside site and of 34% based on the monitoring data at the rooftop site. Considering VOC emissions from all sources in Guangzhou city, the TR control measures adopted could reduce VOC up to 15%. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) have attracted an increasing concern in China's megacities. However, rare information is available on the spatial and seasonal variations of inhalation cancer risk (ICR) due to PAH exposure and their relations to specific sources. In this study, year-round PM 2.5 samples were collected from 2013 to 2014 by high-volume samplers at four sites (one urban, two rural and one roadside station) in Guangzhou in the highly industrialized and densely populated Pearl River Delta (PRD) region and analyzed for 26 polycyclic aromatic hydrocarbons (PAHs) together with molecular tracers including levoglucosan, hopanes and elemental carbon. Higher molecular weight PAHs (5-ring or above) accounted for 64.3–87.5% of total PAHs. Estimated annual averages of benzo( a )pyrene-equivalent carcinogenic potency (BaP eq ) were 1.37, 2.31 and 1.56 ng/m 3 at urban SZ, rural JL and rural WQS, respectively, much higher than that at the roadside station YJ in an urban street canyon. ICR of PAHs in wintertime reached 2.2 × 10 −4 , nearly 3 times that in summer; and cancer risk of PAHs was surprisingly higher at the rural site than at other sites. Source contributions by positive matrix factorization (PMF) in the aid of molecular tracers revealed that overall coal combustion and biomass burning altogether contributed 73.8% of total PAHs and 85.2% of BaP eq , and particularly in winter biomass burning became the most significant source of total PAHs and BaP eq (51.8% and 52.5%), followed by coal combustion (32.0% and 39.1%) and vehicle emission (16.2% and 8.4%). The findings of this work suggest that even in China's megacities like Guangzhou, limiting biomass burning may benefit PAHs pollution control and cancer risk reduction. [ABSTRACT FROM AUTHOR]

Ozone (O 3) pollution has emerged as a major air quality issue in China. Here we emphasize the great challenges in controlling O 3 pollution by analyzing the recent experience of the Pearl River Delta (PRD) in southern China in reducing the autumn O 3 peaks. Despite significant reductions in the concentration of O 3 precursors, i.e., nitrogen oxides (NO x) and volatile organic compounds (VOCs), regional O 3 pollution in the PRD was largely worse in autumn 2019 than in autumn 2018. We found that the supra-regional and regional background concentrations of O 3 increased significantly in the PRD in autumn 2019 due to increased concentrations of O 3 in the vast surrounding areas. We also observed slight increases in the concentrations of PRD-regionally and Guangzhou-locally produced O 3. A chemical box-model analysis confirmed a slight increase in the in-situ production of O 3 and revealed that increased biogenic VOCs (BVOCs) and decreased NO x levels negated the effect of significant decrease in the anthropogenic VOCs. Taken together, these aspects exacerbated O 3 pollution in the PRD region in autumn 2019 relative to autumn 2018. The findings from this study highlight the strong interactions of O 3 pollution over multiple regions and the need for collaborative inter-regional efforts to control O 3 pollution. The experience of PRD also underlines the key role of BVOCs and the importance of science-based strategies to decrease VOCs and NO x. [Display omitted] • The O 3 pollution in the PRD exacerbated despite large reductions of VOCs and NO x in autumn 2019. • Increased regional-background and local production exacerbated O 3 pollution. • Increased BVOC and decreased NO x negated the effects of AVOC reductions. [ABSTRACT FROM AUTHOR]

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 (NO 2), 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. NO 2 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. • Vertical distribution of NO 2 , HCHO and aerosol were derived by MAX-DOAS. • High resolution tropospheric ozone profiles were observed by LIDAR. • Validations were performed using in-situ and off-line data at Canton Tower. • As high as 300 μg/m3 ozone was observed at Guangzhou during the campaign. [ABSTRACT FROM AUTHOR]