Trimethylamine from Subtropical Forests Rival Total Farmland Emissions in China.

Many types of living plants release gaseous trimethylamine (TMA), making it a potentially important contributor to new particle formation (NPF) in remote areas. However, a panoramic view of the importance of forest biogenic TMA at the regional scale is lacking. Here, we pioneered nationwide mobile measurements of TMA across a transect of contiguous farmland in eastern China and a transect of subtropical forests in southern China. In contrast to the farmland route, TMA concentrations measured during the subtropical forest route correlated significantly with isoprene, suggesting potential TMA emissions from leaves. Our high time-resolved concentrations obtained from a weak photo-oxidizing atmosphere reflected freshly emitted TMA, indicating the highest emission intensity from irrigated dryland (set as the baseline of 10), followed by paddy field (7.1), subtropical evergreen forests (5.9), and subtropical broadleaf and mixed forests (4.3). Extrapolating their proportions roughly to China, subtropical forests alone, which constitute half of the total forest area, account for nearly 70% of the TMA emissions from the nation's total farmland. Our estimates, despite the uncertainties, take the first step toward large-scale assessment of forest biogenic amines, highlighting the need for observational and modeling studies to consider this hitherto overlooked source of TMA.

Understanding the spatial and seasonal variation of the ground-level ozone in Southeast China with an interpretable machine learning and multi-source remote sensing.

Ground-level ozone (O3) pollution poses significant threats to both human health and air quality. This study uses ground observations and satellite retrievals to explore the spatiotemporal characteristics of ground-level O3 in Zhejiang Province, China. We created data-driven machine learning models that include meteorological, geographical and atmospheric parameters from multi-source remote sensing products, achieving good performance (Pearson's r of 0.81) in explaining regional O3 dynamics. Analyses revealed the crucial roles of temperature, relative humidity, total column O3, and the distributions and interactions of precursor (volatile organic compounds and nitrogen oxides) in driving the varied O3 patterns observed in Zhejiang. Furthermore, the interpretable modeling quantified multifactor interactions that sustain high O3 levels in spring and autumn, suppress O3 levels in summer, and inhibit O3 formation in winter. This work demonstrates the value of a combined approach using satellite and machine learning as an effective novel tool for regional air quality assessment and control.

Direct emissions of particulate glyoxal and methylglyoxal from biomass burning and coal combustion.

Glyoxal (Gly) and methylglyoxal (Mgly) are key precursors globally for secondary organic aerosol (SOA) formation. These two species were often thought to be formed in the atmosphere via photochemical oxidation of organics from biogenic and anthropogenic origins, although few studies have shown their direct emissions. In this study, we report direct emissions of particulate Gly and Mgly from different residential fuels typically used in north China. The emission ratios (ERs) and emission factors (EFs) of particulate Gly and Mgly for biomass burning were approximate 5-fold and 7-fold higher than those for coal combustion, respectively. The large variances in emissions of Gly and Mgly could be attributed to the different combustion processes, which influenced by the fuel types and combustion conditions. The averaged ERs and EFs of particulate Gly and Mgly were about one order of magnitude lower than their gaseous counterparts due to the low Henry's law constant, which was also consistent with the low particle-to-gas ratio of Gly (0.04) and Mgly (0.02). Our results suggest that the direct emissions of Gly and Mgly from emission sources should be considered when estimating the formation of SOA from Gly and Mgly.

Polycyclic aromatic hydrocarbons from cooking emissions.

Air pollution studies have often overlooked the contribution from cooking to the particle-bound polycyclic aromatic hydrocarbons (PAHs) in the ambient environment, despite cooking emissions have been identified as an important source of organic aerosol in most urban areas, known as the cooking-like organic aerosol factor (i.e., COA). In this study, a Long-Time-of-Flight (LToF) soot particle aerosol mass spectrometer (SP-AMS) was deployed to evaluate the impact of cooking emissions on outdoor particle-bound PAHs levels during a summer campaign in 2019 in Xi'an China. Combined with the robust receptor model, cooking emission was found to be the major source of ambient PAHs, on average, accounting for 90% of PAHs, 9 times higher than traffic (10%). The ambient cooking PAH profile was well correlated (r2 of 0.87) with that for frying oil fume, suggesting cooking oil was the major source of PAHs instead of the food being cooked. We further evaluated the health risk associated with the cooking PAHs and estimated the cooking PAH levels in some of the major cities in the world where COA factor has been reported. The results show the particle-bound PAHs from cooking can be an important source of ambient PAHs in most Chinese cities. The findings from this study hold important implications for public health and are informing for policymakers.

Organic aerosol formation and aging processes in Beijing constrained by size-resolved measurements of radiocarbon and stable isotopic 13C.

This study investigates the sources and atmospheric processes of size-resolved carbonaceous aerosols in winter 2018 in urban Beijing, based on analysis of dual-carbon isotopes (i.e., radiocarbon and the stable isotope 13C). We found a size dependence of fossil source contributions to elemental carbon (EC), but no clear size dependence for organic carbon (OC). Comparable fossil source contributions to water-insoluble OC (WIOC; 55 ± 3%) and to water-soluble OC (WSOC; 54 ± 4%) highlight the importance of secondary aerosol formation, considering that fossil sources emit only small amounts of primary WSOC. OC concentrations increased during high PM2.5 pollution events, with increased fossil and non-fossil WSOC concentrating at larger particles (0.44-2.5 µm) than WIOC (0.25-2.5 µm), highlighting the aqueous-phase chemistry as an important pathway for OC production. The ratio of 13C/12C (expressed as δ13C) of total carbon (-27.0‰ to -23.3‰) fell in the range of anthropogenic aerosol, reflecting small biogenic influence. δ13C of OC increased with desorption temperature steps (200 °C, 350 °C and 650 °C). The strongly enriched δ13COC,650 (-26.9‰ to -20.3‰) and large mass fraction of OC650°C in total desorbed OC, both increasing with the increase of particle sizes, were caused by photochemical aging, especially during low and moderate PM2.5 pollution events, when regional, aged aerosol played an important role. During low pollution events, higher δ13COC,650 and WSOC/OC ratios reflect a larger contribution and more extensive chemical processing of aged aerosol. In contrast, relatively low δ13COC,200 (-27.2‰ to -25.7‰) suggests the influence of secondary OC formation on the more volatile OC desorbed at 200 °C. δ13COC,200 was similar for all particle sizes and for different pollution events, pointing to an internal mixture of local and aged regional OC. Our results show that the organic aerosol in Beijing arises from a mixture of various sources and complex formation processes, spanning local to regional scales. Particle sizes < 250 nm show strong contribution from local secondary OC formation, whereas refractory OC in particles around 1 µm shows strong evidence for regional aging processes. In summary, primary emission, secondary and aqueous-phase formation, and (photo-)chemical aging all need to be considered to understand organic aerosol in this region and their importance varies with particle size.

Large contribution from worship activities to the atmospheric soot particles in northwest China.

Worship activities like burning joss paper during the Chinese Hanyi festival is a common, traditional custom in northwest China. However, the pollutants of e.g., soot particles, released from joss paper burning and the corresponding impacts on urban air quality were poorly investigated, which can be a particular concern since these activities are conducted in an uncontrolled manner. In this study, a long time-of-flight (LToF) soot particle aerosol mass spectrometry (SP-AMS) was deployed to characterize the refractory black carbon (rBC) emitted from the joss paper burning, as well as crop residue, coal combustion, and traffic during the Hanyi Festival in mid-November 2020 in the northwestern city of Xi'an in China. Large difference (from <5% to >100%) in the fragmentation patterns (Cn+) for the measured rBC from different source emissions were found when compared to the reference Regal Black. Using the receptor model of positive matrix factorization (PMF) with the multilinear engine (ME-2) algorithm, the obtained rBC mass spectra were used as the anchoring profiles to evaluate the emission strengths of different source types to the atmospheric rBC. Our results show that the burning of joss paper accounted for up to 42% of the atmospheric rBC mass, higher than traffic (14-17%), crop residue (10-17%), coal (18-20%) during the Hanyi festival in northwest China. Moreover, we show that the overall air quality can be worsened due to the practice of uncontrolled burning of joss paper during the festival, which is not just confined to the people who do the burning. Although worship activities occur mainly during festival periods, the pollution events contributed by joss paper burning may pose an acute exposure risk for public health. This is particularly important since burning joss paper during worship activities is common in China and most Asian countries with similar traditions.

Staggered-peak production is a mixed blessing in the control of particulate matter pollution.

Staggered-peak production (SP)-a measure to halt industrial production in the heating season-has been implemented in North China Plain to alleviate air pollution. We compared the variations of PM1 composition in Beijing during the SP period in the 2016 heating season (SPhs) with those in the normal production (NP) periods during the 2015 heating season (NPhs) and 2016 non-heating season (NPnhs) to investigate the effectiveness of SP. The PM1 mass concentration decreased from 70.0 ± 54.4 µg m-3 in NPhs to 53.0 ± 56.4 µg m-3 in SPhs, with prominent reductions in primary emissions. However, the fraction of nitrate during SPhs (20.2%) was roughly twice that during NPhs (12.7%) despite a large decrease of NOx, suggesting an efficient transformation of NOx to nitrate during the SP period. This is consistent with the increase of oxygenated organic aerosol (OOA), which almost doubled from NPhs (22.5%) to SPhs (43.0%) in the total organic aerosol (OA) fraction, highlighting efficient secondary formation during SP. The PM1 loading was similar between SPhs (53.0 ± 56.4 µg m-3) and NPnhs (50.7 ± 49.4 µg m-3), indicating a smaller difference in PM pollution between heating and non-heating seasons after the implementation of the SP measure. In addition, a machine learning technique was used to decouple the impact of meteorology on air pollutants. The deweathered results were comparable with the observed results, indicating that meteorological conditions did not have a large impact on the comparison results. Our study indicates that the SP policy is effective in reducing primary emissions but promotes the formation of secondary species.

Enhanced formation of secondary organic aerosol from photochemical oxidation during the COVID-19 lockdown in a background site in Northwest China.

The COVID-19 pandemic has drastically affected the economic and social activities, leading to large reductions in anthropogenic emissions on a global scale. Despite the reduction of primary emissions during the lockdown period, heavy haze pollution was observed unexpectedly in megacities in North and East China. In this study, we conducted online measurements of organic aerosol in a background site before and during the lockdown in Guanzhong basin, Northwest China. The oxygenated organic aerosol (OOA) increased from 24% of total OA (3.2 ± 1.6 µg m-3) before lockdown to 54% of total OA (4.5 ± 1.3 µg m-3) during lockdown, likely due to substantial decrease of NOx emissions during lockdown which resulted in large increase of O3 and thus atmospheric oxidizing capacity. OOA showed higher mass concentrations and fractional contributions during lockdown than before lockdown, and increased with the increase of Ox in both periods. In comparison, aqueous secondary organic aerosol (aqSOA) showed high mass concentrations and fractional contributions in both polluted periods before and during lockdown with the increase of aerosol liquid water content (ALWC). The increase of aqSOA under high ALWC conditions is very likely the reason of pollution events during lockdown. Combined with trajectory analysis, the absence of Guanzhong cluster in polluted period during lockdown may play a key role in the OA variations between two polluted periods. In addition, when comparing the clusters from the same transmission directions between before lockdown and during lockdown, the OA fractions showed similar variations during lockdown in all clusters, suggesting the OA variations are widespread in northwest China.

Measurement report of the change of PM2.5 composition during the COVID-19 lockdown in urban Xi'an: Enhanced secondary formation and oxidation.

Enhanced secondary aerosol formation was observed during the COVID-19 lockdown in Xi'an, especially for polluted episodes. More oxidized­oxygenated organic aerosol (MO-OOA) and sulfate showed the dominant enhancements, especially in large particle-mode. Meanwhile, relative humidity (RH) showed a positive promotion on the formation of sulfate and MO-OOA during the lockdown, but had no obvious correlation with less oxidized­oxygenated organic aerosol (LO-OOA) or nitrate. Organosulfurs (OS) displayed a higher contribution (~58%) than inorganic sulfate to total sulfate enhancement in the polluted episode during the lockdown. Although the total nitrate (TN) decreased during the lockdown ascribing to a larger reduction of inorganic nitrate, organic nitrate (ON) showed an obvious increase from pre-lockdown (0.5 ± 0.6 µg m-3 and 1 ± 2% of TN) to lockdown (5.3 ± 3.1 µg m-3 and 17 ± 9% of TN) in the polluted case (P < 0.05). In addition, RH also displayed a positive promotion on the formation of ON and OS, and the increases of both OS and ON were much efficient in the nighttime than in the daytime. These results suggest that higher RH and stagnant meteorology might facilitate the sulfate and MO-OOA enhancement, especially in the nighttime, which dominated the secondary aerosol enhancement in haze pollution during the lockdown.

Characteristics and sources of hourly elements in PM10 and PM2.5 during wintertime in Beijing.

Characteristics and sources of ambient particle elements in urban Beijing were studied by hourly observations in two size fractions (PM10 and PM2.5) during November and December 2017 using an online multi-element analyzer. The reconstructed oxide concentrations of 24 elements (from Al to Pb) comprise an appreciable fraction of PM10 and PM2.5, accounting for 37% and 17%, respectively on average. We demonstrate the benefit of using high-time-resolution chemical speciation data in achieving robust source apportionment of the total elemental PM10 (PM10el) and elemental PM2.5 (PM2.5el) mass using positive matrix factorization (PMF). Biomass burning, coal combustion, secondary sulfate, industry, non-exhaust traffic and dust were identified in both size fractions (with varying relative concentrations), which accounted on average for 4%, 12%, 5%, 2%, 14%, and 63%, respectively to the total PM10el, and 14%, 35%, 21%, 6%, 12% and 12%, respectively to the total PM2.5el. Biomass burning and coal combustion exhibited higher concentrations during haze episodes of the heating season. In contrast, secondary sulfate and industry contributed more to haze episodes during the non-heating season. The fractional contribution of dust was mostly high during clean days, while the fractional non-exhaust traffic emission contribution was similar throughout the measurement period. The non-exhaust traffic emissions contributed locally, while the remaining sources were dominated by neighboring areas. Furthermore, trajectory analysis showed that the origin of the industrial sources roughly agreed with the locations of the main point sources. Overall, this work provides detailed information on the characteristics of the elements during different haze events during heating and non-heating seasons.

The formation and evolution of secondary organic aerosol during summer in Xi'an: Aqueous phase processing in fog-rain days.

Secondary organic aerosol (SOA) is an important contributor to organic aerosol (OA), however, the model simulations of SOA concentrations and oxidation states remain significant uncertainties because of inadequate cognition of its formation and aging chemistry. In this study, SOA formation and evolution processes during summer in Xi'an were investigated, based on high-resolution online measurements of non-refractory PM2.5 (NR-PM2.5) species and OA source apportionment using positive matrix factorization. The results showed that the total SOA, including less oxidized-oxygenated OA (LO-OOA), more oxidized-oxygenated OA (MO-OOA), and aqueous-phase-processed oxygenated OA (aq-OOA), on average constituted 69% of OA, and 43% of NR-PM2.5, suggesting the high atmospheric oxidation capacity and the dominance of SOA during summer in Xi'an. Photochemical oxidation processes dominated the summertime SOA formation both during non-fog-rain days and fog-rain days, which were responsible for the formation of both LO-OOA and MO-OOA. Consistently, LO-OOA and MO-OOA in total contributed 59% to OA during non-fog-rain days and 56% to OA during fog-rain days, respectively. On the contrary, aq-OOA was mainly observed during fog-rain days, which increased dramatically from 2% of OA during non-fog-rain days to 19% of OA during fog-rain days with the mass concentration increasing accordingly from 0.3 µg m-3 to 2.5 µg m-3. Episodic analyses further highlighted the persistently high RH period with high aerosol liquid water content (ALWC) was the driving factor of aq-OOA formation, and high Ox condition could further enhance its formation. Meanwhile, air masses from east and southeast were much favorable for the formation of long-time fog-rain days, which facilitated aq-OOA production during summer in Xi'an.

Cobalt decorated nitrogen-doped carbon bowls as efficient electrocatalysts for the oxygen reduction reaction.

Cobalt decorated nitrogen-doped carbon bowls (Co@NCB) have been successfully constructed by impregnating bowl-like resin particles with cobalt salt followed by annealing. The cobalt exists in the following two forms in the obtained Co@NCB: Co nanoparticles and CoN4. The Co@NCB outperforms the commercial Pt/C in the oxygen reduction reaction in terms of half-wave potential and stability. When Co@NCB is applied in zinc-air batteries, a high open-circuit voltage, excellent power density, and satisfactory stability are achieved.

Seasonal variations in the sources of organic aerosol in Xi'an, Northwest China: The importance of biomass burning and secondary formation.

The Guanzhong basin is a part of the three top priority regions in China's blue sky action as of 2019. Understanding the chemical composition, sources, and atmospheric process of aerosol in this region is therefore imperative for improving air quality. In this study, we present, for the first time, the seasonal variations of organic aerosol (OA) in Xi'an, the largest city in the Guanzhong basin. Biomass burning OA (BBOA) and oxidized OA (OOA) contributed >50% of OA in both autumn and winter. The average concentrations of BBOA in autumn (14.8 ± 5.1 µg m-3) and winter (11.6 ± 6.8 µg m-3) were similar. The fractional contribution of BBOA to total OA, however, decreased from 31.9% in autumn to 15.3% in winter, because of enhanced contributions from other sources in winter. The OOA fraction in OA increased largely from 20.9% in autumn to 34.9% in winter, likely due to enhanced emissions of precursors and stagnant meteorological conditions which facilitate the accumulation and secondary formation. A large increase in OOA concentration was observed during polluted days, by a factor of ~4 in autumn and ~6 in winter compared to clean days. In both seasons, OOA formation was most likely dominated by photochemical oxidation when aerosol liquid water content was <30 µg m-3 or by aqueous-phase processes when Ox was <35 ppb. A higher concentration of BBOA was observed for air masses circulated within the Guanzhong basin (16.5-18.1 µg m-3), compared to air masses from Northwest and West (10.9-14.5 µg m-3). Furthermore, compared with OA fraction in non-refractory PM1 in other regions of China, BBOA (17-19%) and coal combustion OA (10-20%) were major emission sources in the Guanzhong Basin and the BTH region, respectively, whereas OOA (10-34%) was an important source in all studied regions.

Characterization and health risk assessment of airborne pollutants in commercial restaurants in northwestern China: Under a low ventilation condition in wintertime.

Impacts on indoor air quality of dining areas from cooking activities were investigated in eight categories of commercial restaurants including Szechwan Hotpot, Hunan, Shaanxi Noodle, Chinese Barbecue, Chinese Vegetarian, Korean Barbecue, Italian, and Indian, in Northwestern China during December 2011 to January 2012. Chemical characterization and health risk assessment for airborne carbonyls, and particulate-bound polycyclic aromatic hydrocarbons (PAHs) and heavy metals were conducted under low ventilation conditions in wintertime. The highest total quantified carbonyls (Σcarbonyls) concentration of 313.6µgm-3 was found in the Chinese Barbecue, followed by the Szechwan Hotpot (222.6µgm-3) and Indian (221.9µgm-3) restaurants. However, the highest Σcarbonyls per capita was found at the Indian restaurant (4500µgcapita-1), suggesting that cooking methods such as stir-fly and bake for spices ingredients released more carbonyls from thermal cooking processes. Formaldehyde, acetaldehyde, and acetone were the three most abundant species, totally accounting for >60% of mass concentrations of the Σcarbonyls. Phenanthrene, chrysene, and benzo[a]anthracene were the three most abundant PAHs. Low molecular weight fraction (ΣPAHs≤178) had the highest contributions accounting for 40.6%-65.7%, much greater than their heaver counterparts. Diagnostic PAHs ratios suggest that cooking fuel and environmental tobacco smoke (ETS) contribute to the indoor PAHs profiles. Lead was the most abundant heavy metal in all sampled restaurants. High quantity of nickel was also found in samples due to the emissions from stainless-steel made kitchen utensils and cookware and ETS. Cancer risk assessments on the toxic substances demonstrate that the working environment of dining areas were hazard to health. Formation of reactive organic species (ROS) from the cooking activities was evidenced by measurement of hydroxyl radical (OH) formed from simulating particulate matter (PM) react with surrogate lung fluid. The highest OH concentration of 294.4ngm-3 was detected in Chinese Barbecue. In addition, the elevation of the concentrations of PM and OH after non-dining periods implies that the significance of formation of oxidizing-active species indoor at poor ventilation environments.