Links between the optical properties and chemical compositions of brown carbon (BrC) are poorly understood because of the complexity of BrC chromophores. We conducted field studies simultaneously at both vehicle-influenced site and biomass burning-affected site in China in polluted winter. The chemical compositions and light absorption values of functionalized aromatic compounds, including phenyl aldehyde, phenyl acid, and nitroaromatic compounds, were measured. P-phthalic acid, nitrophenols and nitrocatechols were dominant BrC species, accounting for over 50% of the concentration of identified chromophores. Nitrophenols and nitrocatechols contributed more than 50% of the identified BrC absorbance between 300 and 400 nm. Oxidation of biomass burning-related products (e.g., pyrocatechol and methylcatechols) and anthropogenic volatile organic compounds (e.g., benzene and toluene) generated similar BrC chromophores, implying that these functionalized aromatic compounds play an important role in both environments. Compared with the biomass burning-affected site (22%), functionalized aromatic compounds at vehicle-influenced site accounted for a higher percentage of BrC absorption (25%). This research improves our understanding of the links between optical properties and composition of BrC, and the difference between BrC chromophores from BB-influenced area and vehicle-affected area under polluted atmospheric conditions. © 2021 Elsevier B.V.

Particulate PAHs are of significant concern due to their carcinogenic and mutagenic properties. In order to investigate the characteristics and sources of particulate PAHs during heavy pollution episodes, PM2.5 samples were collected in Beijing and Dezhou in the North China Plain from November 17th, 2018 to January 19th, 2019. 26 species of PAHs in PM2.5 during six heavy pollution episodes were measured by gas chromatography-mass spectrometer (GC-MS). The results showed that: (1) The total concentration of PAHs during six heavy pollution episodes ranged from 62 to 191 ng/m3 in Dezhou, and from 61 to 129 ng/m3 in Beijing. (2) The ratios of ∑26PAHs/PM2.5 were higher in Beijing, although PM2.5 concentrations were lower. (3) The dominant components of PAHs were benzo[b]fluoranthene, benzo[a]pyrene (Bap), benzo[a]anthracene, methyl-fluoranthene and retene, accounting for about 50% of ∑26PAHs. (4) The diagnostic ratios indicated vehicle exhaust, coal combustion and biomass burning were the main sources of PAHs at both sites. A more obvious influence of biomass burning in Dezhou was found via a tracer-based approach and using the ratio of PAHs to levoglucosan in fresh biomass burning aerosols. (5) The Bap toxic equivalent concentrations (TEQ) were 6.5-17.2 ng/m3, with higher values in Dezhou than those in Beijing. The BaP concentration ranged from 5.2 to 13.1 ng/m3 and exceeded BaP standard (24 h average: 2.5 ng/m3) in China (Ambient Air Quality Standard, GB 3095-2012), indicating a potential hazardous effect on human health. The studies have shown that both sites have similar distribution characteristics and sources, while the enrichment ratios of ∑26PAHs/PM2.5 in Beijing were higher. PAHs emission control needs to be further strengthened to reduce the risk of human exposure to heavy pollution episodes and the PM2.5 pollution levels. © 2021, Editorial Board, Research of Environmental Sciences. All right reserved.

A source-oriented Community Multiscale Air Quality model was used to quantify the contributions of different sources to ground-level fine particulate matter (PM2.5) and ozone (O3) over the Yangtze River Delta (YRD) region during the EXPLORE-YRD (EXPeriment on the eLucidation of the atmospheric Oxidation capacity and aerosol foRmation, and their Effects in the Yangtze River Delta) campaign (17 May to June 17, 2018). O3 formation in most urban areas of YRD is attributed to volatile organic compounds (VOCs) (81.1%, 78.5%, 60.2%, and 55.1% in Shanghai, Nanjing, Hefei, and Hangzhou, respectively), but is affected more by nitrogen oxides (NOx) in suburban and rural areas. Industry and transportation are the two major sources of O3 and PM2.5. In addition to the two sources, NOx produced owing to power generation, and VOC emissions from biogenic sources are important source of O3. Industry contributes the most to the total mass of PM2.5 in the YRD during the study period (9–25 μg/m3), followed by transportation (2–7 μg/m3). Industry, residential emissions, and transportation are the major sources of primary organic carbon and elemental carbon, whereas industry, transportation, and power generation account for most of the sulphate (SO2− 4) and nitrate (NO− 3) in the YRD. Agriculture is the most dominant source of ammonium emissions (NH+ 4). In Shanghai, Nanjing, Hefei, and Taizhou, secondary organic aerosol (SOA) are mainly contributed by industrial emissions. However, in Hangzhou, biogenic emissions contribute more than 40% of SOA. During all types of pollution episodes, industry and transportation are generally the two greatest sources of O3 and PM2.5 in YRD. The contribution of industry is higher during high PM2.5 pollution episodes, whereas biogenic and open burning contributions are more important during high O3 episodes. Overall, anthropogenic sources dominate the formation of O3 and PM2.5 pollution in the YRD, whereas biogenic emissions contribute significantly to O3 attributable to VOC emissions (O3_VOCs) accounting for 9–20% in urban areas of the YRD. © 2021 Elsevier Ltd

Severe haze pollution occurs frequently in the winter over the Beijing-Tianjin-Hebei (BTH) region (China), exerting profound impacts on air quality, visibility, and human health. The Chinese Government has taken strict mitigation actions since 2013 and has achieved a significant reduction in the annual mean PM2.5 concentration over this region. However, the level of secondary aerosols during heavy haze episodes showed little decrease during this period. During heavy haze episodes, the concentrations of secondary aerosol components, including sulfate, nitrate and secondary organics, in aerosol particles increase sharply, acting as the main contributors to aerosol pollution. To achieve effective control of particle pollution in the BTH region, the precise and complete secondary aerosol formation mechanisms have been investigated, and advances have been made about the mechanisms of gas phase reaction, nucleation and heterogeneous reactions in forming secondary aerosols. This paper reviews the research progress in aerosol chemistry during haze pollution episodes in the BTH region, lays out the challenges in haze formation studies, and provides implications and directions for future research. [Figure not available: see fulltext.]. © 2020, Higher Education Press.

Nitro-aromatic compounds (NACs) were measured hourly at a rural site in China during wintertime to monitor the changes due to local and regional impacts of biomass burning (BB). Concurrent and continuous measurements of the concentrations of 16 NACs in the gas and particle phases were performed with a time-of-flight chemical ionization mass spectrometer (CIMS) equipped with a Filter Inlet for Gases and AEROsols (FIGAERO) unit using iodide as the reagent ion. NACs accounted for <2% of the mass concentration of organic matter (OM) and total particulate matter (PM), but the total particle mass concentrations of these compounds can reach as high as 1000 ngm-3 (299 ngm-3 avg), suggesting that they may contribute significantly to the radiative forcing effects of atmospheric particles. Levels of gas-phase NACs were highest during the daytime (15:00-16:00 local time, LT), with a smaller nighttime peak around 20:00 LT. Box-model simulations showed that this occurred because the rate of NAC production from gas-phase sources exceeded the rate of loss, which occurred mainly via the OH reaction and to a lesser degree via photolysis. Data gathered during extended periods with high contributions from primary BB sources (resulting in 40 %-60% increases in NAC concentrations) were used to characterize individual NACs with respect to gas-particle partitioning and the contributions of regional secondary processes (i.e. photochemical smog). On days without extensive BB, secondary formation was the dominant source of NACs, and NAC levels correlated strongly with the ambient ozone concentration. Analyses of individual NACs in the regionally aged plumes sampled on these days allowed precursors such as phenol and catechol to be linked to their NAC derivatives (i.e. nitrophenol and nitrocatechol). Correlation analysis using the high time resolution data and box-model simulation results constrained the relationships between these compounds and demonstrated the contribution of secondary formation processes. Furthermore, 13 of 16 NACS were classified according to primary or secondary formation process. Primary emission was the dominant source (accounting for 60 %- 70% of the measured concentrations) of 5 of the 16 studied NACs, but secondary formation was also a significant source. Photochemical smog thus has important effects on brown carbon levels even during wintertime periods dominated by primary air pollution in rural China. © Author(s) 2021.

The phase states of primarily emitted and secondarily formed aerosols from gasoline vehicle exhausts were investigated by quantifying the particle rebound fraction (f). The rebound behaviors of gasoline vehicle emission-related aerosols varied with engines, fuel types, and photochemical aging time, showing distinguished differences from biogenic secondary organic aerosols. The nonliquid-to-liquid phase transition of primary aerosols emitted from port fuel injection (PFI) and gasoline direct injection (GDI) vehicles started at a relative humidity (RH) = 50 and 60%, and liquefaction was accomplished at 60 and 70%, respectively. The RH at which f declined to 0.5 decreased from 70 to 65% for the PFI case with 92# fuel, corresponding to the photochemical aging time from 0.37 to 4.62 days. For the GDI case, such RH enhanced from 60 to 65%. Our results can be used to imply the phase state of traffic-related aerosols and further understand their roles in urban atmospheric chemistry. Taking Beijing, China, as an example, traffic-related aerosols were mainly nonliquid during winter with the majority ambient RH below 50%, whereas they were mostly liquid during the morning rush hour of summer, and traffic-related secondary aerosols fluctuated between nonliquid and liquid during the daytime and tended to be liquid at night with increased ambient RH. © 2020 American Chemical Society.

In the present work, we performed chassis dynamometer experiments to investigate the emissions and secondary organic aerosol (SOA) formation potential of intermediate-volatility organic compounds (IVOCs) from an on-road Chinese gasoline vehicle. High IVOC emission factors (EFs) and distinct volatility distribution were recognized. The IVOC EFs for the China V vehicle ranged from 12.1 to 226.3 mg per kilogram fuel, with a median value of 83.7 mg per kilogram fuel, which was higher than that from US vehicles. Besides, a large discrepancy in volatility distribution and chemical composition of IVOCs from Chinese gasoline vehicle exhaust was discovered, with larger contributions of B14-B16 compounds (retention time bins corresponding to C14-C16 n-alkanes) and a higher percentage of n-alkanes. Further we investigated the possible reasons that influence the IVOC EFs and volatility distribution and found that fuel type, starting mode, operating cycles and acceleration rates did have an impact on the IVOC EF. When using E10 (ethanol volume ratio of 10 %, v=v) as fuel, the IVOC EF of the tested vehicle was lower than that using commercial China standard V fuel. The average IVOC-to-THC (total hydrocarbon) ratios for gasoline-fueled and E10-fueled gasoline vehicles were 0:07 ± 0:01 and 0:11 ± 0:02, respectively. Cold-start operation had higher IVOC EFs than hot-start operation. The China Light-Duty Vehicle Test Cycle (CLTC) produced 70 % higher IVOCs than those from the Worldwide Harmonized Light Vehicles Test Cycle (WLTC). We found that the tested vehicle emitted more IVOCs at lower acceleration rates, which leads to high EFs under CLTC. The only factor that may influence the volatility distribution and compound composition is the engine aftertreatment system, which has compound and volatility selectivity in exhaust purification. These distinct characteristics in EFs and volatility may result in higher SOA formation potential in China. Using published yield data and a surrogate equivalent method, we estimated SOA formation under different OA (organic aerosol) loading and NOx conditions. Results showed that under low-and high-NOx conditions at different OA loadings, IVOCs contributed more than 80 % of the predicted SOA. Furthermore, we built up a parameterization method to simply estimate the vehicular SOA based on our bottomup measurement of VOCs (volatile organic compounds) and IVOCs, which would provide another dimension of information when considering the vehicular contribution to the ambient OA. Our results indicate that vehicular IVOCs contribute significantly to SOA, implying the importance of reducing IVOCs when making air pollution controlling policies in urban areas of China. © 2021 Author(s).

During the COVID-19 lockdown in 2020, large-scale industrial and transportation emissions were reduced, but high PM2.5 concentration still occurred. This study investigated the variation of particle number size distribution during the lockdown, and analyzed the characteristics of new particle formation (NPF) events and its potential impact on haze formation. Through measurement conducted in urban Beijing during the first 3 months of 2020, and comparison with year-over-year data, the decrease of primary Aitken-mode particles was observed. However, frequencies, formation rates and growth rates of NPF events remained stable between 2020 and 2019 in the same period. As a result, &gt;25 nm particles produced by NPF events, would play a more important role in serving as the haze formation “seeds” compared to those produced by primary emissions. This finding emphasizes the significance on the understanding of NPF mechanisms when making pollution mitigation policy in the future. © 2021. The Authors.

To investigate the composition, variation, and sources of nitrated phenols (NPs) in the winter of Beijing, gas-phase NPs were measured by a chemical ionization long time-of-flight mass spectrometer (CI-LToF-MS). A box model was applied to simulate the secondary formation process of NPs. In addition, the primary sources of NPs were resolved by a non-negative matrix factorization (NMF) model. Our results showed that secondary formation contributed 38 %, 9 %, 5 %, 17 %, and almost 100% of the nitrophenol (NP), methyl-nitrophenol (MNP), dinitrophenol (DNP), methyl-dinitrophenol (MDNP or DNOC), and dimethyl-nitrophenol (DMNP) concentrations. The phenol-OH reaction was the predominant loss pathway (46.7 %) during the heavy pollution episode, which produced the phenoxy radical (C6H5O). The phenoxy radical consequently reacted with NO2 and produced nitrophenol. By estimating the primarily emitted phenol from the ratio of phenol=CO from freshly emitted vehicle exhaust, this study proposed that oxidation of primary phenol contributes much more nitrophenol (37 %) than that from benzene oxidation (< 1 %) in the winter of Beijing. The latter pathway was widely used in models and might lead to great uncertainties. The source apportionment results by NMF indicated the importance of combustion sources (> 50 %) to the gas-phase NPs. The industry source contributed 30% and 9% to DNP and MDNP, respectively, which was non-negligible. The concentration weighted trajectory (CWT) analysis demonstrated that regional transport from provinces that surround the Yellow and Bohai seas contributed more primary NPs to Beijing. Both primary sources and secondary formation at either local or regional scale should be considered when making control policies of NPs. © 2021 Kai Song et al.

The variations in physicochemical properties of airborne particles collected during a typical transition from haze to dust were investigated using single particle analysis with transmission and scanning electron microscopes combined with online measurement of chemical compositions of airborne particles in Beijing in February 2013. The transition was divided into three phases based on the weather condition. During haze pollution (Phase 1), gaseous and particle pollutants enhanced gradually. Results from single particle analysis showed that more coatings and more anthropogenic elements (e.g., S) appeared on the surface of fine and coarse particles, which was probably caused by efficient aqueous-phase reactions under high humidity (70%) condition. Phase 2 was dust intrusion episode. PM10 reached over 1000 μg m−3. Larger fractions of mineral particles and bare-like soot particles were observed in fine particles, while the fraction of secondary particles with coatings decreased. The proportion of black carbon in submicron particles also increased. Photochemical oxidation in gas phase likely dominated in secondary formation under high O3 concentration. After the dust episode (Phase 3), secondary formation enhanced obviously. Soot aged quickly and had a larger mode of 0.45 μm than the other phases. The size modes of airborne fine particles during Phases 1 and 3 were 0.35 μm, which were a bit larger than that during Phase 2 (0.24 μm). These results indicate that dust plumes accompanied with strong wind brought mineral particles in both fine and coarse modes and freshly emitted particles with smaller sizes, and swept away pre-presence air pollutants. This study could provide detailed information on the physicochemical properties of airborne particles during typical severe pollution processes in a short time. Such short-term change should be taken into account in order to more accurately assess the environmental, climatic and health-related effects of airborne particles. © 2020 Elsevier B.V.

The Sichuan Basin is one of the regions suffering from severe haze pollution in southwest China. However, the secondary aerosol formation in this region is poorly understood. In this study, the chemical compositions of PM2.5 and molecular compositions of water-soluble organics in wintertime Sichuan were measured to investigate the aerosol sources and formation under typical high relative humidity (RH) conditions. Strong correlations between PM2.5, carbonaceous aerosols and K+ suggested the influence of biomass burning. The impacts of biomass burning were also supported by the dominance of primarily emitted reduced/less oxidized nitrogen-containing organics as well as the high peak intensities of secondarily formed nitrocatechols and methyl-nitrocatechols. High humidity (average RH = 80%) and aerosol liquid water (ALW) in Sichuan facilitated the secondary formation of sulfate, nitrate, and secondary organic aerosols (SOA). The average sulfate oxidation ratio and nitrogen oxidation ratio in Sichuan were 2.5 and 3.1 times of those in winter Beijing (average RH = 27%). This suggested higher potentials of SO2 and NOx to form sulfate and nitrate under high-RH conditions. The abundant aqueous-SOA formation in Sichuan was supported by the dominance of organosulfates (OSs) and nitrooxy-OSs in mass spectra of water-soluble organics, while the OSs in winter Beijing were quite limited. The more abundant OS formation in Sichuan was attributed to the much higher RH, ALW, aerosol acidity, and sulfate, which favored the acidic sulfate-catalyzed aqueous-phase reactions for OS formation. Higher concentrations of biogenic volatile organic compounds were additional reasons for the more abundant OSs in Sichuan than in Beijing. © 2021. American Geophysical Union. All Rights Reserved.

The EXPeriment on the eLucidation of the atmospheric Oxidation capacity and aerosol foRmation and their Effects in the Yangtze River Delta (EXPLORE-YRD) campaign was carried out between May and June 2018 at a regional site in Taizhou, China. The EXPLORE-YRD campaign helped construct a detailed air quality model to understand the formation of O3 and PM2.5 further, identify the key sources of elevated air pollution events, and design efficient emission control strategies to reduce O3 and PM2.5 pollution in YRD. In this study, we predicted the air quality during the EXPLORE-YRD campaign using the Weather Research and Forecasting/Community Multiscale Air Quality modelling system (WRF/CMAQ) and evaluated model performance on O3 and PM2.5 concentrations and compositions. Air quality was predicted using two sets of reanalysis data—NCEP Final (FNL) Operational Global Analysis and ECMWF Reanalysis v5.0 (ERA5)—and three horizontal resolutions of 36, 12, and 4 km. The results showed that PM2.5 concentration was generally under-predicted using both the FNL and ERA5 data. ERA5 yielded slightly higher PM2.5 predictions during the EXPLORE-YRD campaign. Both reanalysis data sets under-predicted the high PM2.5 pollution processes on 29–30 May 2018, indicating that reanalysis data is not essential for under-predicting extreme PM2.5 pollution processes. The performance of O3 was similar in both the reanalysis data sets, because O3 is mostly sensitive to temperature predictions and FNL and ERA5 yielded similar temperature results. Although the average performance of PM2.5 and O3 predictions yielded by FNL and ERA5 was similar, large differences were observed in certain locations on specific days (e.g. in Hangzhou between 29 May and June 6, 2018 and in Hefei on 1–3 June 2018). Therefore, the choice of reanalysis data could be an important factor affecting the predictions of PM2.5 and O3, depending on locations and episodes. Comparable results were obtained using predictions with different horizontal resolutions, indicating that grid resolution was not crucial for determining the model performance of both PM2.5 and O3 during the campaign. © 2020 Elsevier Ltd

To investigate the effects of biomass burning and photochemical oxidation on the black carbon (BC) mixing state and light absorption, a tandem centrifugal particle mass analyzer (CPMA) and single-particle soot photometer (SP2) system was used to measure ambient fine particulate BC during EXPLORE-YRD 2018 campaign (EXPeriment on the eLucidation of the atmospheric Oxidation capacity and aerosol foRmation, and their Effects in Yangtze River Delta). The mass ratio (MR) of the non-BC coating to BC core, a morphology-independent parameter to quantify the mixing state of BC-containing aerosols, is derived. Two types of periods were identified, namely non-significant biomass-burning period (NB), and enhanced biomass burning period (EB). The MR was higher during EB (2.3 ± 0.5), compared with during the NB (2.0 ± 0.5). MR showed bimodal diurnal variation with peaks in the early morning and early afternoon, mainly due to the biomass burning and photochemical processes, respectively. The light-absorbing enhancement ranged from 1.0 to 1.19 when MR was from 1.4 to 3.4. The relationship of rBC mixing state and its optical properties was parameterized, which can further be used in the regional model. © 2021 The Author(s)