Atmospheric peroxyacetyl nitrate (PAN) and ozone (O₃) are two typical indicators for photochemical pollution that have adverse effects on the ecosystem and human health. Observation networks for these pollutants have been expanding in developed regions of China, such as North China Plain (NCP) and Pearl River Delta (PRD), but are sparse in Yangtze River Delta (YRD), meaning their concentration and influencing factors remain poorly understood. Here, we performed a one-year measurement of atmospheric PAN, O₃, particulate matter with aerodynamic diameter smaller than 2.5 μm (PM₂.₅), nitrogen oxides (NOₓ), carbon monoxide (CO), and meteorological parameters from December 2016 to November 2017 in Shanghai. Overall, high hourly maximum PAN and O₃ were found to be 7.0 and 185 ppbv in summer, 6.2 and 146 ppbv in autumn, 5.8 and 137 ppbv in spring, and 6.0 and 76.7 ppbv in winter, respectively. Continental air masses probably carried atmospheric pollutants to the sampling site, while frequent maritime winds brought in less polluted air masses. Furthermore, positive correlations (R: 0.72–0.85) between PAN and O₃ were found in summer, indicating a predominant role of photochemistry in their formation. Unlike in summer, weak or no correlations between PAN and O₃ were featured during the other seasons, especially in winter, due to their different loss pathways. Unexpectedly, positive correlations between PAN and PM₂.₅ were found in all seasons. During summer, moderate correlation could be attributed to the strong photochemistry acting as a common driver in the formation of secondary aerosols and PAN. During winter, high PM₂.₅ might promote PAN production through HONO production, hence resulting in a good positive correlation. Additionally, the loss of PAN by thermal decomposition (TPAN) only accounted for a small fraction (ca. 1%) of the total (PAN + TPAN) during a typical winter episode, while it significantly reached 14.4 ppbv (71.1% of the total) in summer.

Traffic source–dominated volatile organic compound (VOC) samples were collected during four time-intervals in a day (Ⅰ: 7:30–10:30, Ⅱ: 11:00–14:00, Ⅲ: 16:30–19:30, and Ⅳ: 20:00–23:00) in a tunnel in summer, 2019, in Xi’an, China. The total measured VOC (TVOC) in periods Ⅰ and Ⅲ (rush hours, 107.2 ± 8.2 parts per billion by volume [ppbv]) was 1.8 times that in periods Ⅱ and Ⅳ (non-rush hours, 58.6 ± 13.8 ppbv), consistent with the variation in vehicle numbers in the tunnel. The considerably elevated ethane and ethylbenzene levels could have been attributed to emissions from compressed natural gas vehicles and the rapid development of methanol-fueled taxis in Xi’an in 2019. The mixing ratios of benzene, toluene, ethylbenzene, and xylenes (BTEX) contributed 9.4%–12.7% to TVOCs, and the contributions were nearly 40% higher in periods Ⅰ and Ⅲ than in Ⅱ and Ⅳ, indicating that BTEX levels were strongly affected by vehicle emissions. The indicators of motor vehicle emission, namely ethylene, propylene, toluene, m/p-xylenes, o-xylene, and propane, contributed to more than half of the ozone formation potential in this study. The noncarcinogenic risks of VOCs in this study were within the international safety standard, whereas the carcinogenic risks exceeded the standard by 2.3–4.6 times, suggesting that carcinogenic risks were more serious than noncarcinogenic risks. VOCs presented 2.2 and 1.4 times noncarcinogenic and carcinogenic risks during rush hours than during non-rush hours, respectively. Notably, the carcinogenic risk in period Ⅳ was comparable with that in period Ⅲ; however, the vehicle numbers and VOC mixing ratios were the lowest at night, which may have attributed to the increasing number and proportion of methanol M100-fueled vehicles in the tunnel. Therefore, VOCs emitted by new energy vehicles should also be seriously considered while evaluating fossil fuel vehicle emissions.

The determination of both stable nitrogen (δ¹⁵N–NO₃⁻) and stable oxygen (δ¹⁸O–NO₃⁻) isotopic signatures of nitrate in PM₂.₅ has shown potential for an approach of assessing the sources and oxidation pathways of atmospheric NOx (NO+NO₂). In the present study, daily PM₂.₅ samples were collected in the megacity of Beijing, China during the winter of 2017–2018, and this new approach was used to reveal the origin and oxidation pathways of atmospheric NOx. Specifically, the potential of field δ¹⁵N–NO₃⁻ signatures for determining the NOx oxidation chemistry was explored. Positive correlations between δ¹⁸O–NO₃⁻ and δ¹⁵N–NO₃⁻ were observed (with R² between 0.51 and 0.66, p < 0.01), and the underlying environmental significance was discussed. The results showed that the pathway-specific contributions to NO₃⁻ formation were approximately 45.3% from the OH pathway, 46.5% from N₂O₅ hydrolysis, and 8.2% from the NO₃+HC channel based on the δ¹⁸O-δ¹⁵N space of NO₃⁻. The overall nitrogen isotopic fractionation factor (εN) from NOx to NO₃⁻ on a daily scale, under winter conditions, was approximately +16.1‰±1.8‰ (consistent with previous reports). Two independent approaches were used to simulate the daily and monthly ambient NOx mixtures (δ¹⁵N-NOx), respectively. Results indicated that the monthly mean values of δ¹⁵N-NOx compared well based on the two approaches, with values of −5.5‰ ± 2.6‰, −2.7‰ ± 1.9‰, and −3.2‰ ± 2.2‰ for November, December, and January (2017–2018), respectively. The uncertainty was in the order of 5%, 5‰ and 5.2‰ for the pathway-specific contributions, the εN, and δ¹⁵N-NOx, respectively. Results also indicated that vehicular exhaust was the key contributor to the wintertime atmospheric NOx in Beijing (2017–2018). Our advanced isotopic perspective will support the future assessment of the origin and oxidation of urban atmospheric NOx.

This research apportioned size-resolved particulate matter (PM) contributions in a megacity in northern China based on a full year of measurements of both inorganic and organic markers. Ions, elements, carbon fractions, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), hopanes and steranes in 9 p.m. size fractions were analyzed. High molecular weight PAHs concentrated in fine PM, while most other organic compounds showed two peaks. Both two-way and three-way receptor models were used for source apportionment of PM in different size ranges. The three-way receptor model gave a clearer separation of factors than the two-way model, because it uses a combination of chemical composition and size distributions, so that factors with similar composition but distinct size distributions (like more mature and less mature coal combustion) can be resolved. The three-way model resolved six primary and three secondary factors. Gasoline vehicles and coal and biomass combustion, nitrate and high relative humidity related secondary aerosol, and resuspended dust and diesel vehicles (exhaust and non-exhaust) are the top two contributors to pseudo-ultrafine (<0.43 μm), fine (0.43–2.1 μm) and coarse mode (>2.1 μm) PM, respectively. Mass concentration of PM from coal and biomass combustion, industrial emissions, and diesel vehicle sources showed a bimodal size distribution, but gasoline vehicles and resuspended dust exhibited a peak in the fine and coarse mode, separately. Mass concentration of sulphate, nitrate and secondary organic aerosol exhibited a bimodal distribution and were correlated with temperature, indicating strong photochemical processing and repartitioning. High relative humidity related secondary aerosol was strongly associated with size shifts of PM, NO₃⁻ and SO₄²⁻ from the usual 0.43–0.65 μm to 1.1–2.1 μm. Our results demonstrated the dominance of primary combustion sources in the <0.43 μm particle mass, in contrast to that of secondary aerosol in fine particle mass, and dust in coarse particle mass in the Northern China megacity.

We assessed the contribution of transboundary air pollutants (TAPs) transported from China to Tokyo using the Pb₍₀.₅<Dₚ < ₁₎/Cu₍₂.₅<Dₚ < ₁₀₎ index. We conducted intensive observations over four seasons during 2014–2015 and analyzed ionic components and thirteen elements in size-segregated aerosols collected at the top of a 30-m-high tower in a hilly forested area of the Field Museum Tamakyuryo (FM Tama), in a western suburb of Tokyo. In order to evaluate if the Pb₍₀.₅<Dₚ < ₁₎/Cu₍₂.₅<Dₚ < ₁₀₎ ratio can be applied in Tokyo as the megacity, the annual average concentration of Pb at Cape Hedo, Kumamoto city, on the west side of Japan, was higher than that of Pb at Tokyo, on the east side; this result indicates that TAPs affect western Japan more than eastern Japan. We inferred the main source of Cu to be braking abrasion from cars at local scale on the basis of its enrichment factor and size distribution. From the Pb₍₀.₅<Dₚ < ₁₎/Cu₍₂.₅<Dₚ < ₁₀₎ ratio and sulfate concentration, we inferred that the highest contribution of TAPs to the total mass concentration in Tokyo occurred in spring, when TAPs accounted for 55%, 72%, and 53% of the total mass concentration in the 0.1 < Dp < 0.5, 0.5 < Dp < 1, and 1 < Dp < 2.5 fractions, respectively. These results can contribute to assessment of TAPs in Tokyo.

Organophosphate esters (OPEs) are ubiquitous contaminants in the environment, whereas their atmospheric processes and fate are poorly understood. The present study revealed the spatial heterogeneity and seasonal variations of traditional and novel OPEs in PM₂.₅ (particulate matter with diameters < 2.5 μm) across a megacity (including residential areas and potential source sites) in South China. Potential influencing factors on the contamination levels of OPEs were addressed. The total concentrations of 11 traditional OPEs ranging from 262 to 42,194 pg/m³ (median = 1872 pg/m³) were substantially higher than those of 10 novel OPEs (33.5–3835 pg/m³, median = 318 pg/m³). Significant spatial and temporal variations in the concentrations of most OPEs were observed. The overall district-specific contamination levels in this city showed dependence on the secondary industry sector for non-predominant OPEs and on the tertiary industry for predominant OPEs. The seasonal variations of the OPE concentrations suggest difference in their sources or influence of meteorological conditions. The correlations between the individual OPEs in PM₂.₅ are determined largely by either their applications or physicochemical properties (in particular vapor pressure). The correlations between OPE concentrations and each meteorological factor (temperature, relative humidity, wind speed, and surface solar radiation) were inconsistent (positive and negative). Wind speed had the greatest effect on the OPE levels; While most OPEs bound to PM₂.₅ were not efficiently scavenged by below-cloud rainfall. The results suggest that atmospheric half-life and Henry’s Law Constant of OPEs are also determining factors for the wind speed and rainfall influence, respectively. However, mechanisms underlying the influence of meteorological conditions on atmospheric OPEs still need further research.

While local anthropogenic emission sources contribute largely to deteriorate metro air quality, long range transport can also play a significant role in influencing levels of pollutants, particularly carbon monoxide (CO) that has a relatively long life span. A nationwide lockdown of two months imposed across India amid COVID-19 led to a dramatic decline in major sources of emissions except for household, mainly from cooking. This initially led to declined levels of CO in two of the largest megacities of India, Delhi and Mumbai under stable weather conditions, followed by a distinctly different variability under the influence of prevailing mesoscale circulation. We hereby trace the sources of CO from local emissions to transport pathways and interpret the observed variability in CO using the interactive WRF-Chem model and back trajectory analysis. For this purpose, COVID-19 emission inventory of CO has been estimated. Model results indicate a significant contribution from externally generated CO in Delhi from surrounding regions and an unusual peak on 17th May amid lockdown due to long range transport from the source region of biofuel emissions in central India. However, the oceanic winds played a larger role in keeping CO levels in check in a coastal megacity Mumbai which otherwise has high CO emissions from household sources due to a larger share of urban slums. Keeping track of evolving carbon-intensive pathways can help inform government responses to the COVID-19 pandemic to prioritize controls of emissions sources.

Acid deposition has been regarded as a serious factor in the deteriorative water environment and ecosystems. Despite the powerful acid emission control measures have been implemented by the Chinese government, many areas (especially Southeast China) are still suffering from acid deposition. The chemical and isotopic (δ³⁴S and ⁸⁷Sr/⁸⁶Sr) compositions of rainwater in Hangzhou, a typical megacity in Southeast China with serious acid rain problem, for one year were studied with the aim to better constrain potential sources and explore the causes of rainwater acidification. Most rainwater samples were acidic, with a VWM pH value of 4.65. SO₄²⁻ was the dominant anion and the main acid ion in rainwater. Sulfur isotope and the quantity equilibrium model revealed that sea salt, crustal, biogenic, and anthropogenic sulfur represented 2.3%, 0.1%, 16.7%, and 80.8% of the SO₄²⁻ source in rainwater, respectively. The back trajectory and strontium isotopes indicated that the base cations (BCs) in rainwater originated mainly from anthropogenic sources. The relatively low neutralizing capacity caused by limited BCs input and emission control measures undermines some efforts to reduce rainwater acidity. This case study demonstrated that a valuable tool to probe the source of acid rain and unravel the mechanism of rainwater acidification can be provided by multiple lines of evidence, including rainwater chemical compositions, stable sulfur isotopes, and stable strontium isotopes.

To prevent the spread of the COVID-19 epidemic, the Chinese megacity Wuhan has taken emergent lockdown measures starting on January 23, 2020. This provided a natural experiment to investigate the response of air quality to such emission reductions. Here, we decoupled the influence of meteorological and non-meteorological factors on main air pollutants using generalized additive models (GAMs), driven by data from the China National Environmental Monitoring Center (CNEMC) network. During the lockdown period (Jan. 23 – Apr. 8, 2020), PM₂.₅, PM₁₀, NO₂, SO₂, and CO concentrations decreased significantly by 45 %, 49 %, 56 %, 39 %, and 18 % compared with the corresponding period in 2015–2019, with contributions by S(meteos) of 15 %, 17 %, 13 %, 10 %, and 6 %. This indicates an emission reduction of NOₓ at least 43 %. However, O₃ increased by 43 % with a contribution by S(meteos) of 6 %. In spite of the reduced volatile organic compound (VOC) emissions by 30 % during the strict lockdown period (Jan. 23 – Feb. 14, 2020), which likely reduced the production of O₃, O₃ concentrations increased due to a weakening of the titration effect of NO. Our results suggest that conventional emission reduction (NOₓ reduction only) measures may not be sufficient to reduce (or even lead to an increase of) surface O₃ concentrations, even if reaching the limit, and VOC-specific measures should also be taken.

Anthropogenic activities experienced a pause due to the nationwide lockdown, imposed to contain the rapid spread of COVID-19 in the third week of March 2020. The impacts of suspension of industrial activities, vehicular transport and other businesses for three months (25 March-30 June) on the environmental settings of Chennai, a coastal megacity was assessed. A significant reduction in the key urban air pollutants [PM₂.₅ (66.5%), PM₁₀ (39.5%), NO₂ (94.1%), CO (29%), O₃ (45.3%)] was recorded as an immediate consequence of the reduced anthropogenic activities. Comparison of water quality of an urban river Adyar, between pre-lockdown and lockdown, showed a substantial drop in the dissolved inorganic N (47%) and suspended particulate matter (41%) during the latter period. During the pandemic, biomedical wastes in India showed an overall surge of 17%, which were predominantly plastic. FTIR-ATR analysis confirmed the polymers such as polypropylene (25.4%) and polyester (15.4%) in the personal protective equipment.