Analysis of China's PM2.5 and ozone coordinated control strategy based on the observation data from 2015 to 2020.

The coordinated control of PM2.5 and ozone has become the strategic goal of national air pollution control. Considering the gradual decline in PM2.5 concentration and the aggravation of ozone pollution, a better understanding of the coordinated control of PM2.5 and ozone is urgently needed. Here, we collected and sorted air pollutant data for 337 cities from 2015 to 2020 to explore the characteristics of PM2.5 and ozone pollution based on China's five major air pollution regions. The results show that it is necessary to continue to strengthen the emission reduction in PM2.5 and ozone precursors, and control NOx and VOCs while promoting a dramatic emission reduction in PM2.5. The primary method of curbing ozone pollution is to strengthen the emission control of VOCs, with a long-term strategy of achieving substantial emission reductions in NOx, because VOCs and NOx are also precursors to PM2.5; hence, their reductions also contribute to the reduction in PM2.5. Therefore, the implementation of a multipollutant emission reduction control strategy aimed at the prevention and control of PM2.5 and ozone pollution is the only means to realize the coordinated control of PM2.5 and ozone.

Validating HONO as an Intermediate Tracer of the External Cycling of Reactive Nitrogen in the Background Atmosphere.

In the urban atmosphere, nitrogen oxide (NOx═NO + NO2)-related reactions dominate the formation of nitrous acid (HONO). Here, we validated an external cycling route of HONO and NOx, i.e., formation of HONO resulting from precursors other than NOx, in the background atmosphere. A chemical budget closure experiment of HONO and NOx was conducted at a background site on the Tibetan Plateau and provided direct evidence of the external cycling. An external daytime HONO source of 100 pptv h-1 was determined. Both soil emissions and photolysis of nitrate on ambient surfaces constituted likely candidate mechanisms characterizing this external source. The external source dominated the chemical production of NOx with HONO as an intermediate tracer. The OH production was doubled as a result of the external cycling. A high HONO/NOx ratio (0.31 ± 0.06) during the daytime was deduced as a sufficient condition for the external cycling. Literature review suggested the prevalence of high HONO/NOx ratios in various background environments, e.g., polar regions, pristine mountains, and forests. Our analysis validates the prevalence of external cycling in general background atmosphere and highlights the promotional role of external cycling regarding the atmospheric oxidative capacity.

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust.

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.

A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling.

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO2 radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.

Impacts of synoptic circulation on surface ozone pollution in a coastal eco-city in Southeastern China during 2014-2019.

The coastal eco-city of Fuzhou in Southeastern China has experienced severe ozone (O3) episodes at times in recent years. In this study, three typical synoptic circulations types (CTs) that influenced more than 80% of O3 polluted days in Fuzhou during 2014-2019 were identified using a subjective approach. The characteristics of meteorological conditions linked to photochemical formation and transport of O3 under the three CTs were summarized. Comprehensive Air Quality Model with extensions was applied to simulate O3 episodes and to quantify O3 sources from different regions in Fuzhou. When Fuzhou was located to the west of a high-pressure system (classified as "East-ridge"), more warm southwesterly currents flowed to Fuzhou, and the effects of cross-regional transport from Guangdong province and high local production promoted the occurrence of O3 episodes. Under a uniform pressure field with a low-pressure system occurring to the east of Fuzhou (defined as "East-low"), stagnant weather conditions caused the strongest local production of O3 in the atmospheric boundary layer. Controlled by high-pressure systems over the mainland (categorized as "Inland-high"), northerly airflows enhanced the contribution of cross-regional transport to O3 in Fuzhou. The abnormal increases of the "East-ridge" and "Inland-high" were closely related to O3 pollution in Fuzhou in April and May 2018, resulting in the annual maximum number of O3 polluted days during recent years. Furthermore, the rising number of autumn O3 episodes in 2017-2019 was mainly related to the "Inland-high", indicating the aggravation of cross-regional transport and highlighting the necessity of enhanced regional collaboration and efforts in combating O3 pollution.

Humidity-Dependent Phase State of Gasoline Vehicle Emission-Related Aerosols.

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.

Assessing the Ratios of Formaldehyde and Glyoxal to NO2 as Indicators of O3-NOx-VOC Sensitivity.

Ozone (O3) pollution has a negative effect on the public health and crop yields. Accurate diagnosis of O3 production sensitivity and targeted reduction of O3 precursors [i.e., nitrogen oxides (NOx) or volatile organic compounds (VOCs)] are effective for mitigating O3 pollution. This study assesses the indicative roles of the surface formaldehyde-to-NO2 ratio (FNR) and glyoxal-to-NO2 ratio (GNR) on surface O3-NOx-VOC sensitivity based on a meta-analysis consisting of multiple field observations and model simulations. Thresholds of the FNR and GNR are determined using the relationship between the relative change of the O3 production rate and the two indicators, which are 0.55 ± 0.16 and 1.0 ± 0.3 for the FNR and 0.009 ± 0.003 and 0.024 ± 0.007 for the GNR. The sensitivity analysis indicated that the surface FNR is likely to be affected by formaldehyde primary sources under certain conditions, whereas the GNR might not be. As glyoxal measurements are becoming increasingly available, using the FNR and GNR together as O3 sensitivity indicators has broad potential applications.

Chemical Production of Oxygenated Volatile Organic Compounds Strongly Enhances Boundary-Layer Oxidation Chemistry and Ozone Production.

Photolysis of oxygenated volatile organic compounds (OVOCs) produces a primary source of free radicals, including OH and inorganic and organic peroxy radicals (HO2 and RO2), consequently increasing photochemical ozone production. The amplification of radical cycling through OVOC photolysis provides an important positive feedback mechanism to accelerate ozone production. The large production of OVOCs near the surface helps promote photochemistry in the whole boundary layer. This amplifier effect is most significant in regions with high nitrogen oxides (NOx) and VOC concentrations such as Wangdu, China. Using a 1-D model with comprehensive observations at Wangdu and the Master Chemical Mechanism (MCM), we find that OVOC photolysis is the largest free-radical source in the boundary layer (46%). The condensed chemistry mechanism we used severely underestimates the OVOC amplifier effect in the boundary layer, resulting in a lower ozone production rate sensitivity to NOx emissions. Due to this underestimation, the model-simulated threshold NOx emission value, below which ozone production decreases with NOx emission decrease, is biased low by 24%. The underestimated OVOC amplifier effect in a condensed mechanism implies a low bias in the current 3-D model-estimated efficacy of NOx emission reduction on controlling ozone in polluted urban and suburban regions of China.

Secondary Production of Gaseous Nitrated Phenols in Polluted Urban Environments.

Nitrated phenols (NPs) are important atmospheric pollutants that affect air quality, radiation, and health. The recent development of the time-of-flight chemical ionization mass spectrometer (ToF-CIMS) allows quantitative online measurements of NPs for a better understanding of their sources and environmental impacts. Herein, we deployed nitrate ions as reagent ions in the ToF-CIMS and quantified six classes of gaseous NPs in Beijing. The concentrations of NPs are in the range of 1 to 520 ng m-3. Nitrophenol (NPh) has the greatest mean concentration. Dinitrophenol (DNP) shows the greatest haze-to-clean concentration ratio, which may be associated with aqueous production. The high concentrations and distinct diurnal profiles of NPs indicate a strong secondary formation to overweigh losses, driven by high emissions of precursors, strong oxidative capacity, and high NOx levels. The budget analysis on the basis of our measurements and box-model calculations suggest a minor role of the photolysis of NPs (<1 ppb h-1) in producing OH radicals. NPs therefore cannot explain the underestimated OH production in urban environments. Discrepancies between these results and the laboratory measurements of the NP photolysis rates indicate the need for further studies aimed at understanding the production and losses of NPs in polluted urban environments.

More Significant Impacts From New Particle Formation on Haze Formation During COVID-19 Lockdown.

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, >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.

DGAT1 inhibitors protect pancreatic ß-cells from palmitic acid-induced apoptosis.

Previous studies demonstrated that prolonged exposure to elevated levels of free fatty acids (FFA), especially saturated fatty acids, could lead to pancreatic ß-cell apoptosis, which plays an important role in the progression of type 2 diabetes (T2D). Diacylglycerol acyltransferase 1 (DGAT1), an enzyme that catalyzes the final step of triglyceride (TG) synthesis, has been reported as a novel target for the treatment of multiple metabolic diseases. In this study we evaluated the potential beneficial effects of DGAT1 inhibitors on pancreatic ß-cells, and further verified their antidiabetic effects in db/db mice. We showed that DGAT1 inhibitors (4a and LCQ908) at the concentration of 1 µM significantly ameliorated palmitic acid (PA)-induced apoptosis in MIN6 pancreatic ß-cells and primary cultured mouse islets; oral administration of a DGAT1 inhibitor (4a) (100 mg/kg) for 4 weeks significantly reduced the apoptosis of pancreatic islets in db/db mice. Meanwhile, 4a administration significantly decreased fasting blood glucose and TG levels, and improved glucose tolerance and insulin tolerance in db/db mice. Furthermore, we revealed that pretreatment with 4a (1 µM) significantly alleviated PA-induced intracellular lipid accumulation, endoplasmic reticulum (ER) stress, and proinflammatory responses in MIN6 cells, which might contribute to the protective effects of DGAT1 inhibitors on pancreatic ß-cells. These findings provided a better understanding of the antidiabetic effects of DGAT1 inhibitors.

Sensitive Detection of Ambient Formaldehyde by Incoherent Broadband Cavity Enhanced Absorption Spectroscopy.

Formaldehyde (HCHO) is the most abundant atmospheric carbonyl compound and plays an important role in the troposphere. However, HCHO detection via traditional incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) is limited by short optical path lengths and weak light intensity. Thus, a new light-emitting diode (LED)-based IBBCEAS was developed herein to measure HCHO in ambient air. Two LEDs (325 and 340 nm) coupled by a Y-type fiber bundle were used as an IBBCEAS light source, which provided both high light intensity and a wide spectral fitting range. The reflectivity of the two cavity mirrors used herein was 0.99965 (1 - reflectivity = 350 ppm loss) at 350 nm, which corresponded with an effective optical path length of 2.15 km within a 0.84 m cavity. At an integration time of 30 s, the measurement precision (1σ) for HCHO was 380 parts per trillion volume (pptv), and the corresponding uncertainty was 8.3%. The instrument was successfully deployed for the first time in a field campaign and delivered results that correlated well with those of a commercial wet-chemical instrument based on Hantzsch fluorimetry (R2 = 0.769). The combined light source based on a Y-type fiber bundle overcomes the difficulty of measuring ambient HCHO via IBBCEAS in near-ultraviolet range, which may extend IBBCEAS technology to measure other atmospheric trace gases with high precision.

Profiling Aerosol Liquid Water Content Using a Polarization Lidar.

Aerosol liquid water content (ALWC) plays fundamental roles in atmospheric radiation and chemical processes. However, there is little information about ALWC vertical distribution due to the lack of sufficient measurement. In this study, a novel method to retrieve ALWC using a polarization lidar is proposed. By analyzing lidar measurement combined with in situ chemical composition measurements at the surface, the particle linear depolarization ratio δp is found to be well correlated with the liquid water mass fraction. The method is built upon a valid relationship between δp and the ratio of ALWC to the particle backscatter coefficient. ALWC can be retrieved with a relative error of 30% with this method. A case study shows that the ALWC in upper levels of the boundary layer may be different from that at the ground, suggesting the importance of measuring ALWC vertical profiles during haze episodes. The study proves that polarization lidars have the potential to retrieve vertical distributions of ALWC which will benefit studies on haze formation.

No Evidence for a Significant Impact of Heterogeneous Chemistry on Radical Concentrations in the North China Plain in 2014.

The oxidation of nitric oxide to nitrogen dioxide by hydroperoxy (HO2) and organic peroxy radicals (RO2) is responsible for the chemical net ozone production in the troposphere and for the regeneration of hydroxyl radicals, the most important oxidant in the atmosphere. In Summer 2014, a field campaign was conducted in the North China Plain, where increasingly severe ozone pollution has been experienced in the last years. Chemical conditions in the campaign were representative for this area. Radical and trace gas concentrations were measured, allowing for calculating the turnover rates of gas-phase radical reactions. Therefore, the importance of heterogeneous HO2 uptake on aerosol could be experimentally determined. HO2 uptake could have suppressed ozone formation at that time because of the competition with gas-phase reactions that produce ozone. The successful reduction of the aerosol load in the North China Plain in the last years could have led to a significant decrease of HO2 loss on particles, so that ozone-forming reactions could have gained importance in the last years. However, the analysis of the measured radical budget in this campaign shows that HO2 aerosol uptake did not impact radical chemistry for chemical conditions in 2014. Therefore, reduced HO2 uptake on aerosol since then is likely not the reason for the increasing number of ozone pollution events in the North China Plain, contradicting conclusions made from model calculations reported in the literature.

Field Determination of Nitrate Formation Pathway in Winter Beijing.

Particulate nitrate (pNO3-) has often been found to be the major component of fine particles in urban air-sheds in China, the United States, and Europe during winter haze episodes in recent years. However, there is a lack of knowledge regarding the experimentally determined contribution of different chemical pathways to the formation of pNO3-. Here, for the first time, we combine ground and tall-tower observations to quantify the chemical formation of pNO3- using observationally constrained model approach based on direct observations of OH and N2O5 for the urban air-shed. We find that the gas-phase oxidation pathway (OH+NO2) during the daytime is the dominant channel over the nocturnal uptake of N2O5 during pollution episodes, with percentages of 74% in urban areas and 76% in suburban areas. This is quite different from previous studies in some regions of the US, in which the uptake of N2O5 was concluded to account for a larger contribution in winter. These results indicate that the driving factor of nitrate pollution in Beijing and different regions of the US is different, as are the mitigation strategies for particulate nitrate.

A Comprehensive Model Test of the HONO Sources Constrained to Field Measurements at Rural North China Plain.

As nitrous acid (HONO) photolysis is an important source of hydroxyl radical (OH), apportionment of the ambient HONO sources is necessary to better understand atmospheric oxidation. Based on the data HONO-related species and various parameters measured during the one-month campaign at Wangdu (a rural site in North China plain) in summer 2014, a box model was adopted with input of current literature parametrizations for various HONO sources (nitrogen dioxide heterogeneous conversion, photoenhanced conversion, photolysis of adsorbed nitric acid and particulate nitrate, acid displacement, and soil emission) to reveal the relative importance of each source at the rural site. The simulation results reproduced the observed HONO production rates during noontime in general but with large uncertainty from both the production and destruction terms. NO2 photoenhanced conversion and photolysis of particulate nitrate were found to be the two major mechanisms with large potential of HONO formation but the associated uncertainty may reduce their importance to be nearly negligible. Soil nitrite was found to be an important HONO source during fertilization periods, accounted for (80 ± 6)% of simulation HONO during noontime. For some episodes of the biomass burning, only the NO2 heterogeneous conversion to HONO was promoted significantly. In summary, the study of the HONO budget is still far from closed, which would require a significant effort on both the accurate measurement of HONO and the determination of related kinetic parameters for its production pathways.

Fast Photochemistry in Wintertime Haze: Consequences for Pollution Mitigation Strategies.

In contrast to summer smog, the contribution of photochemistry to the formation of winter haze in northern mid-to-high latitude is generally assumed to be minor due to reduced solar UV and water vapor concentrations. Our comprehensive observations of atmospheric radicals and relevant parameters during several haze events in winter 2016 Beijing, however, reveal surprisingly high hydroxyl radical oxidation rates up to 15 ppbv/h, which is comparable to the high values reported in summer photochemical smog and is two to three times larger than those determined in previous observations during winter in Birmingham (Heard et al. Geophys. Res. Lett. 2004, 31, (18)), Tokyo (Kanaya et al. J. Geophys. Res.: Atmos. 2007, 112, (D21)), and New York (Ren et al. Atmos. Environ. 2006, 40, 252-263). The active photochemistry facilitates the production of secondary pollutants. It is mainly initiated by the photolysis of nitrous acid and ozonolysis of olefins and maintained by an extremely efficiently radical cycling process driven by nitric oxide. This boosted radical recycling generates fast photochemical ozone production rates that are again comparable to those during summer photochemical smog. The formation of ozone, however, is currently masked by its efficient chemical removal by nitrogen oxides contributing to the high level of wintertime particles. The future emission regulations, such as the reduction of nitrogen oxide emissions, therefore are facing the challenge of reducing haze and avoiding an increase in ozone pollution at the same time. Efficient control strategies to mitigate winter haze in Beijing may require measures similar as implemented to avoid photochemical smog in summer.

Markedly enhanced absorption and direct radiative forcing of black carbon under polluted urban environments.

Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using a novel environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. Our findings indicate that BC under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

Persistent sulfate formation from London Fog to Chinese haze.

Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

Characteristics and formation mechanism of regional haze episodes in the Pearl River Delta of China.

To investigate the characteristics and the specific mechanism of continuous haze, comprehensive measurements were conducted from 15 October to 19 November in the Atmospheric Environment Monitoring Super-Station in Heshan of Guangdong province. Five haze episodes occurred in October and November 2014 in the Pearl River Delta (PRD) region. The meteorological parameters, gas data, chemical compositions, and optical parameters of the aerosols were obtained. Among these events, the second haze episode, with the highest concentration of PM2.5 of 187.51µg/m3, was the most severe. NO3- was always higher than SO42-, which indicated that motor vehicles played an important role in the haze, even though the oxidation rate from SO2 to SO42- was faster than that of NOX to NO3-. The difference between the hourly averages of Na+ and K+ during the haze episode and clean days was small, implying that straw combustion and sea salt had no significant effect on the occurrence of haze, and the backward trajectories of the air masses also conformed with this result. The air pollutants were difficult to disperse because of the significant decrease in the planetary boundary layer (PBL) height. Relative humidity played a crucial role in the formation of haze by leading to hygroscopic growth of the diameter of aerosols.