Secondary Formation of Atmospheric Brown Carbon in China Haze: Implication for an Enhancing Role of Ammonia.

Optical characteristics and molecular compositions of brown carbon (BrC) were investigated during winter 2019 at a rural site of China with a focus on nitro-aromatic compounds (NACs) and imidazoles (IMs). The abundance of gaseous nitrophenols relative to CO during the campaign maximized at noontime, being similar to O3, while the particulate NACs during the haze periods strongly correlated with toluene and NO2, suggesting that NACs in the region are largely formed from the gas-phase photooxidation. Strong correlations of particulate IMs in the dry haze periods with the mass ratio of EC/PM2.5 and the concentration of levoglucosan were observed, indicating that IMs during the dry events are largely derived from biomass burning emissions. However, an increase in IMs with the increasing aerosol liquid water content and pH was observed in the humid haze events, along with much lower abundances of levoglucosan and K+ relative to PM2.5, suggesting that IMs were mostly formed from aqueous reactions in the humid haze periods. These IMs exponentially increased with an increasing NH3 owing to an aqueous reaction of carbonyls with free ammonia. Our findings for the first time revealed an enhancing effect of ammonia on BrC formation in China, especially in humid haze periods.

Ammonia in urban atmosphere can be substantially reduced by vehicle emission control: A case study in Shanghai, China.

To investigate the impact of emission controls on ammonia (NH3) pollution in urban atmosphere, observation on NH3 (1 hr interval) was performed in Shanghai before, during and after the 2019 China International Import Expo (CIIE) event, along with measurements on inorganic ions, organic tracers and stable nitrogen isotope compositions of ammonium in PM2.5. NH3 during the CIIE period was 6.5±1.0 µg/m3, which is 41% and 32% lower than that before and after the event, respectively. Such a decrease was largely ascribed to the emission controls in nonagricultural sources, of which contribution for measured NH3 in control phase abated by ∼20% compared to that during uncontrol period. Molecular compositions of PAHs and hopanes further suggested a dominant role of the reduced vehicle emissions in the urban NH3 abatement during the CIIE period. Our results revealed that vehicle exhaust emission control is an effective way to mitigate NH3 pollution and improve air quality in Chinese urban areas.

Significant coal combustion contribution to water-soluble brown carbon during winter in Xingtai, China: Optical properties and sources.

To understand the characteristics of atmospheric brown carbon (BrC), daily PM2.5 samples in Xingtai, a small city in North China Plain (NCP), during the four seasons of 2018-2019, were collected and analyzed for optical properties and chemical compositions. The light absorption at 365 nm (absλ=365 nm) displayed a strong seasonal variation with the highest value in winter (29.0±14.3 M/m), which was 3.2∼5.4-fold of that in other seasons. A strong correlation of absλ=365 nm with benzo(b)fluoranthene (BbF) was only observed in winter, indicating that coal combustion was the major source for BrC in the season due to the enhanced domestic heating. The mass absorbing efficiency of BrC also exhibited a similar seasonal pattern, and was found to correlate linearly with the aerosol pH, suggesting a positive effect of aerosol acidity on the optical properties and formation of BrC in the city. Positive matrix factorization (PMF) analysis further showed that on a yearly basis the major source for BrC was biomass burning, which accounted for 34% of the total BrC, followed by secondary formation (26.7%), coal combustion (21.3%) and fugitive dust (18%). However, the contribution from coal combustion was remarkably enhanced in winter, accounting for ∼40% of the total. Our work revealed that more efforts of "shifting coal to clean energy" are necessary in rural areas and small cities in NCP in order to further mitigate PM2.5 pollution in China.

Gas-to-Aerosol Phase Partitioning of Atmospheric Water-Soluble Organic Compounds at a Rural Site in China: An Enhancing Effect of NH3 on SOA Formation.

Partitioning gaseous water-soluble organic compounds (WSOC) to the aerosol phase is a major formation pathway of atmospheric secondary organic aerosols (SOA). However, the fundamental mechanism of the WSOC-partitioning process remains elusive. By simultaneous measurements of both gas-phase WSOC (WSOCg) and aerosol-phase WSOC (WSOCp) and formic and acetic acids at a rural site in the Yangtze River Delta (YRD) region of China during winter 2019, we showed that WSOCg during the campaign dominantly partitioned to the organic phase in the dry period (relative humidity (RH) < 80%) but to aerosol liquid water (ALW) in the humid period (RH > 80%), suggesting two distinct SOA formation processes in the region. In the dry period, temperature was the driving factor for the uptake of WSOCg. In contrast, in the humid period, the factors controlling WSOCg absorption were ALW content and pH, both of which were significantly elevated by NH3 through the formation of NH4NO3 and neutralization with organic acids. Additionally, we found that the relative abundances of WSOCp and NH4NO3 showed a strong linear correlation throughout China with a spatial distribution consistent with that of NH3, further indicating a key role of NH3 in WSOCp formation at a national scale. Since WSOCp constitutes the major part of SOA, such a promoting effect of NH3 on SOA production by elevating ALW formation and WSOCg partitioning suggests that emission control of NH3 is necessary for mitigating haze pollution, especially SOA, in China.

Spatial and Temporal Distributions and Sources of Anthropogenic NMVOCs in the Atmosphere of China: A Review.

As the key precursors of O3, anthropogenic non-methane volatile organic compounds (NMVOCs) have been studied intensively. This paper performed a meta-analysis on the spatial and temporal variations of NMVOCs, their roles in photochemical reactions, and their sources in China, based on published research. The results showed that both non-methane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs) in China have higher mixing ratios in the eastern developed cities compared to those in the central and western areas. Alkanes are the most abundant NMHCs species in all reported sites while formaldehyde is the most abundant among the OVOCs. OVOCs have the highest mixing ratios in summer and the lowest in winter, which is opposite to NMHCs. Among all NMVOCs, the top eight species account for 50%-70% of the total ozone formation potential (OFP) with different compositions and contributions in different areas. In devolved regions, OFP-NMHCs are the highest in winter while OFP-OVOCs are the highest in summer. Based on positive matrix factorization (PMF) analysis, vehicle exhaust, industrial emissions, and solvent usage in China are the main sources for NMHCs. However, the emission trend analysis showed that solvent usage and industrial emissions will exceed vehicle exhaust and become the two major sources of NMVOCs in near future. Based on the meta-analysis conducted in this work, we believe that the spatio-temporal variations and oxidation mechanisms of atmospheric OVOCs, as well as generating a higher spatial resolution of emission inventories of NMVOCs represent an area for future studies on NMVOCs in China.

Efficient Heterogeneous Formation of Ammonium Nitrate on the Saline Mineral Particle Surface in the Atmosphere of East Asia during Dust Storm Periods.

To understand the chemical evolution of dust in the current East Asian atmosphere, the chemistry of PM2.5 and size-resolved aerosols in Shanghai, China, during the 2019 dust storm event was investigated. Our results showed that concentrations of SO42- in the city during the event highly correlated with Ca2+ and Na+ due to the direct emissions of CaSO4 and Na2SO4 from the upwind deserts. In contrast, during the event, NO3- linearly correlated with NH4+ at a molar ratio close to 1:1, and both almost entirely stayed in coarse particles, suggesting they accumulated on the dust surface as NH4NO3. Based on the field observations and laboratory smog chamber simulations, we found that NO2 and O3 in Shanghai during the dust period reacted to form N2O5, which subsequently hydrolyzed into HNO3 on the surface of saline mineral dusts (e.g., CaSO4 and Na2SO4) and was further neutralized by NH3 as NH4NO3. The relative abundances of NO3- and NH4+ in Shanghai during the dust event were notably higher than those a decade ago, indicating that this heterogeneous formation of NH4NO3 on dust was enhanced by the abundantly coexisting NOx, O3, and NH3 in the current East Asian atmosphere, which should be considered in future modeling studies.

Dexmedetomidine attenuates spinal cord ischemia-reperfusion injury through both anti-inflammation and anti-apoptosis mechanisms in rabbits.

BACKGROUND: Dexmedetomidine (Dex) can improve neuronal viability and protect the spinal cord from ischemia-reperfusion (I/R) injury, but the underlying mechanisms are not fully understood. This study investigated the effects of dexmedetomidine on the toll-like receptor 4 (TLR4)-mediated nuclear factor κB (NF-κB) inflammatory system and caspase-3 dependent apoptosis induced by spinal cord ischemia-reperfusion injury. METHODS: Twenty-four rabbits were divided into three groups: I/R, Dex (10 µg/kg/h prior to ischemia until reperfusion), and Sham. Abdominal aortic occlusion was carried out for 30 min in the I/R and Dex groups. Hindlimb motor function was assessed using the Tarlov scoring system for gait evaluation. Motor neuron survival and apoptosis in the ventral grey matter were assessed by haematoxylin-eosin staining and terminal deoxynucleotidyl transferase-mediated dUTP biotin nick end labelling staining. The expression and localisation of ionised calcium-binding adaptor molecule 1, TLR4, NF-κB and caspase-3 were assessed by immunoreactivity analysis. The levels of interleukin 1ß and tumour necrosis factor α were assessed using enzyme-linked immunosorbent assays. RESULTS: Perioperative treatment with dexmedetomidine was associated with a significant preservation of locomotor function following spinal cord ischemia-reperfusion injury with increased neuronal survival in the spinal cord compared to control. In addition, dexmedetomidine suppressed microglial activation, inhibited the TLR4-mediated NF-κB signalling pathway, and inhibited the caspase-3 dependent apoptosis. CONCLUSIONS: Dexmedetomidine confers neuroprotection against spinal cord ischemia-reperfusion injury through suppression of spinal cord inflammation and neuronal apoptosis. A reduction in microglial activation and inhibition of both the TLR4-mediated NF-κB signalling pathway and caspase-3 dependent apoptosis are implicated.

Atmospheric brown carbon in China haze is dominated by secondary formation.

Brown carbon (BrC) is a class of light-absorbing organic aerosols (OA) and has significant influence on atmospheric radiative forcing. However, the current limited understanding of the physicochemical properties of BrC restricts the accurate evaluation of its environmental effects. Here the optical characteristics and chemical composition of BrC during wintertime in the Yangtze River Delta (YRD) region, China were measured by using high-resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectrometry. Our results showed that BrC in PM2.5 during the campaign was dominated by water-soluble organics, which consist of less oxidized oxygenated OA (LO-OOA), more oxidized oxygenated OA (MO-OOA), fossil fuel OA (FFOA) and biomass burning OA (BBOA). MO-OOA and BBOA were the strongest light absorbing BrC at 365 nm (Abs365), followed by LO-OOA and FFOA with a mass absorption coefficient (MAC) being 0.74 ± 0.04, 0.73 ± 0.03, 0.48 ± 0.04 and 0.39 ± 0.06 m2 g-1 during the campaign, respectively. In the low relative humidity (RH < 80 %) haze periods Abs365 of LO-OOA contributed to 44 % of the total light absorption at 365 nm, followed by MO-OOA (31 %), FFOA (21 %) and BBOA (4 %). In contrast, in the high-RH (RH > 80 %) haze periods Abs365 was dominated by MO-OOA, which accounted for 62 % of the total Abs365, followed by LO-OOA (17 %), BBOA (13 %) and FFOA (8 %). Chemical composition analysis further showed that LO-OOA and MO-OOA are produced from gas-phase photooxidation of VOCs and aerosol aqueous reactions, respectively, in which ammonia significantly enhanced the formation and light absorption of BrC in the high RH haze period. On average, >75 % of the total Abs365nm in the YRD region during the haze events was contributed by LO-OOA and MO-OOA, suggesting that atmospheric BrC in China haze periods is predominantly formed by secondary reactions.

Investigation into the differences and relationships between gasSOA and aqSOA in winter haze pollution on Chongming Island, Shanghai, based on VOCs observation.

To investigate the formation of secondary organic aerosol (SOA) under current atmospheric conditions, we conducted a field observation of SOA precursors in the downwind region of the Yangtze River Delta (YRD) in winter 2019 using a variety of offline and online instruments. During the entire observation period, the averaged fine particulate SOA was 7.9 ± 2.3 µg m-3, with precursor concentrations of 31 ± 11 ppbv for the measured volatile organic compounds (VOCs) and 16 ± 12 ppbv for NOx. Compared to those on the clean days, SOA on the haze days increased by a factor of 1.6, while the VOC and NOx increased by a factor of 1.3 and 2.0, respectively. Aerosol liquid water content (ALWC) and oxygenated VOCs (OVOCs, including acetaldehyde, formic acid, acetone, acetic acid, methyl ethyl ketone, and methylglyoxal) relationships suggested that the gasSOA and aqSOA occurred simultaneously on Chongming Island in winter. The gasSOA was primarily formed by the oxidation of aromatics and NOx at low RH (RH < 80%) conditions. In contrast, the aqSOA was formed under higher RH (RH > 80%) conditions via a combination of daytime photochemical aqueous phase processes of water-soluble OVOCs and nocturnal dark aqueous phase processes of primary emissions from biomass. The inversed higher mass ratio of NACs to (benzene + toluene) and nitrogen oxidation ratio (NOR) in the daytime during the gasSOA-dominated haze periods indicated that gasSOA could be transformed to aqSOA at high NOx levels. Our results also suggested the importance of NOx and VOC reduction measures in directly mitigating gasSOA and indirectly mitigating aqSOA during winter haze pollution.

Increasing role of phenolic oxidative branch in daytime oxidation process of aromatics in Chinese haze period.

To understand the photooxidation mechanisms of aromatic compounds in the NOx-rich atmosphere, gaseous aromatics and their oxidization products (i.e., methyl glyoxal (MGLY), and nitrated phenols (NPs) including nitrophenols (NPhs) and methylnitrophenols (MNPs)) were measured with a 1-h time resolution on Chongming Island, a downwind region of the Yangtze River Delta (YRD) metropolitans of China in winter 2019 by using a proton-transfer-reaction mass spectrometer (PTR-MS). During the entire observation period, concentrations of the measured VOCs were 9.6 ± 7.1 ppbv for aromatics, 118 ± 59 pptv for MGLY, 36 ± 10 pptv for NPhs, and 9.3 ± 2.8 pptv for MNPs, respectively. Secondary NPs (SNPs) accounted for only 19-24 % of the total nitrated phenols during the clean and transition periods but increased to 44 % of the total on the hazy days. Moreover, the daytime mixing ratios of SNPs increased along with an increasing NO2 concentration during the clean and transition periods, but in the haze period the daytime SNPs first increased along with the increasing NO2 levels and then increased much more sharply when NO2 was >25 ppbv. Such highly proportional and sharply increased daytime SNPs in the haze period indicated an enhanced phenolic oxidation under the high NOx conditions. In addition, the lack of correlations between aromatics and MGLY, increased MGLYaro (MGLY produced by aromatics), and sharply increased ΔSNPs / Δ(benzene + toluene) further suggested that such an increasing role of the phenolic oxidative branch in the daytime oxidation process of aromatics during the YRD haze period was caused by the strong atmospheric oxidation capacity and the high level of NOx.

Insights into high concentrations of particle-bound imidazoles in the background atmosphere of southern China: Potential sources and influencing factors.

Imidazoles are important constituents in atmospheric brown carbon and have gained increasing attention in the past decade. Although imidazoles have been studied widely in laboratories, the sparse field observations severely limit the understanding of imidazole's abundance and sources in the atmosphere. In this study, we measured particle-bound imidazoles and their precursors at a background forest site in the Nanling Mountains of southern China. The average concentration of imidazoles (4.17 ± 3.76 ng/m3) was found to be significantly higher than other background sites worldwide. Further analyses revealed that a majority of imidazoles (59.1%) at the site originated from secondary formation through reactions of dicarbonyls (e.g., glyoxal and methylglyoxal) and reduced nitrogen species, with relatively minor contributions from regional transport (32.8%) and biomass burning (8.1%). In addition, the key factors influencing secondary formation of imidazoles, such as relative humidity, water-soluble inorganic ions, and pH, were analyzed. Our results indicated that the secondary formation of imidazoles can be greatly enhanced under high humidity conditions, particularly during fog events. Overall, this study offers valuable insights into potential sources and influencing factors of ambient imidazoles in background atmospheres.

Rapid sulfate formation from synergetic oxidation of SO2 by O3 and NO2 under ammonia-rich conditions: Implications for the explosive growth of atmospheric PM2.5 during haze events in China.

Extremely high levels of atmospheric sulfate aerosols have still frequently occurred in China especially in winter haze periods and often been underestimated by models due to some missing formation mechanisms. Here we investigated the heterogeneous reaction dynamics of SO2 oxidation by the abundantly co-existing O3 and NO2 in the urban atmosphere of China by using a laboratory smog chamber simulation technique. Our results showed that with an increase of NH3 concentrations from 0.05 ppm to 1.5 ppm, SO2 oxidation by O3 can be greatly promoted and lead to an exponential increase of diameter growth factor (GF) of particles in the chamber from 1.29 to 1.98 for NaCl seeds and from 1.20 to 1.60 for (NH4)2SO4 seeds, along with an increasing uptake coefficient (γ) of SO2 from 4.47 × 10-5 to 1.52 × 10-4 on NaCl seeds and from 2.32 × 10-5 to 5.74 × 10-5 on (NH4)2SO4 seeds, respectively. The heterogeneous production of sulfate from oxidation of SO2 under NH3-rich conditions by O3 and NO2 mixture in the chamber was 2.0-3.5 times the sum of sulfate from SO2 oxidations by O3 and NO2, suggesting a strongly synergetic effect of the mixed oxidants on the heterogeneous oxidation of SO2, which can cause rapid formation of (NH4)2SO4 and NH4NO3 and is responsible for the explosive growth of PM2.5 in the winter haze period of China. Our chamber results further showed that such synergetic process is only efficient under NH3-rich conditions, clearly indicating that the combined controls on O3, NOx and NH3 are necessary for further mitigating the PM2.5 pollution in China.

Important contribution of N2O5 hydrolysis to the daytime nitrate in Xi'an, China during haze periods: Isotopic analysis and WRF-Chem model simulation.

Nitrate, as one of the major components of tropospheric aerosols, plays a crucial role in winter haze formation. While, the formation mechanism of the high production of nitrate in Chinese megacities is still not fully understood. To quantify the contributions of major formation pathways to nitrate, airborne particles in Xi'an, inland China during the winter of 2017 were measured and analyzed for the water-soluble ions and stable nitrogen/oxygen isotope compositions of nitrate in PM2.5, followed by a WRF-Chem model simulation. The oxygen isotopic results indicated that N2O5 hydrolysis was an important formation pathway for the daytime nitrate in the haze episodes. The model simulation further revealed that N2O5 hydrolysis contribution increased from 8.2% to 20.5% of the total nitrate over 14:00-16:00 p.m., clearly showing that N2O5 formation followed by a heterogeneous hydrolysis to nitrate can effectively proceed in daytime under the abundantly co-existing O3, NO2 and NH3 conditions.

The safety of tai chi: A meta-analysis of adverse events in randomized controlled trials.

OBJECTIVES: To review current publications to examine safety of tai chi (TC). DESIGN: Cochrane Library, EBSCO host and MEDLINE/PubMed were searched for randomized controlled trials (RCTs) including TC as the core intervention and reporting adverse events (AEs). Data were extracted considering active vs. inactive control group comparisons and presence of an AE monitoring protocol. Meta-analyses were conducted for overall results as well as control group and reporting specific conditions. RESULTS: In 256 RCTs of TC, 24 met eligibility criteria (1794 participants) and were assessed using the Cochrane Risk of Bias tool. The frequency of non-serious, serious and intervention-related AEs were not found to be significantly different between TC and inactive or active control conditions. In studies with an AE monitoring protocol, more non-serious adverse events (RD = 0.05; 95% CI: 0.00, 0.10; P = 0.05) were reported for TC compared to inactive interventions. Given the higher overall AE risks related to studies of participants with heart failure, additional analyses examined this set separately. More serious AEs were found for inactive interventions compared with TC in studies with heart failure participants (RD = -0.11; 95% CI: -0.20, -0.03; P = 0.01). CONCLUSION: Findings indicate that TC does not result in more AEs than active and inactive control conditions, and produces fewer AEs than inactive control conditions for heart failure patients.

Elevated levels of glyoxal and methylglyoxal at a remote mountain site in southern China: Prompt in-situ formation combined with strong regional transport.

The dicarbonyls glyoxal (Gly) and methylglyoxal (Mgly) are key tracers for the oxidation of volatile organic compounds (VOCs) in the atmosphere, but their atmospheric chemistry in remote forest environments is not well understood. A study was carried out during Jul. 31-Nov. 5 of 2016 at the summit of Mt. Tianjing (1690 m.a.s.l.), a remote mountaintop site in southern China, to measure the levels of Gly and Mgly and explore their sources and fate. During the study period, the average mixing ratios of Gly and Mgly were 509 ±â€¯31 pptv and 340 ±â€¯32 pptv, respectively, with the Gly/Mgly ratios averaging 1.8 ±â€¯0.2. Both the dicarbonyl concentrations and the Gly/Mgly ratios were significantly higher than those observed in other background sites. Production yield calculations and meteorological data analysis indicate that high levels of Gly and Mgly observed at the study site were largely a combined result of rapid in-situ formation and regional transport by prevailing winds. On average, in-situ formation from precursors is estimated to account for 67% of the observed Mgly and about 9% of the observed Gly. There were significant changes in Gly and Mgly mixing ratios among different time periods when air masses from different source regions dominated, indicating contribution of regional transport to the observed dicarbonyl mixing ratios at the study site. Biogenic emissions in eastern China and anthropogenic emissions in the Pearl River Delta region were the two main sources responsible for the dicarbonyls observed at the site during most of the sampling period, but large-scale biomass burning in central China was also important in the late autumn, as supported by a backward trajectory analysis of fire spot data and the identification of biomass burning tracers. This study provides insights into the background atmospheric chemistry and the impact of biogenic and anthropogenic sources on the dicarbonyls speciation.

BMI, leisure-time physical activity, and physical fitness in adults in China: results from a series of national surveys, 2000-14.

BACKGROUND: Obesity, physical inactivity, and reduced physical fitness contribute to the rising burden of chronic diseases in China. We investigated these factors in Chinese adults over a 14-year period (2000-14) using data from randomised national surveys. METHODS: We did four national surveys in 2000, 2005, 2010, and 2014 among Chinese adults aged 20-59 years. We used BMI to assess underweight (<18·5 kg/m(2)), overweight (≥23·0 to <27·5 kg/m(2)), and obesity (≥27·5 kg/m(2)). Central obesity was defined as a waist circumference greater than 90 cm in men and greater than 85 cm in women. We assessed leisure-time physical activity (LTPA) by whether or not participants had completed the recommended minimum 150 min of moderate or 75 min of vigorous exercise per week. Indices for assessment of physical fitness were forced vital capacity, resting heart rate, hand grip strength, sit and reach distance, and time standing on one leg. FINDINGS: 151 656 (78%) of 193 440 adults responded to the survey in 2000, 163 386 (84%) in 2005, 154 931 (80%) in 2010, and 146 703 (76%) in 2014. The prevalence of obesity increased from 8·6% in 2000, to 10·3% in 2005, 12·2% in 2010, and 12·9% in 2014 (estimated increase 0·32% per year, 95% CI 0·30-0·33; p<0·0001). The equivalent estimates were 37·4%, 39·2%, 40·7%, and 41·2% for overweight (estimated increase 0·27% per year, 95% CI 0·25-0·30; p<0·0001) and 13·9%, 18·3%, 22·1%, and 24·9% for central obesity (estimated increase 0·78% per year, 0·76-0·80; p<0·0001). The prevalence of overweight, obesity, and central obesity increased with age (all p<0·0001) and was higher in men than in women (all p<0·0001). We noted a simultaneous decrease in the prevalence of underweight (estimated decrease of 0·06% per year, 95% CI 0·04-0·07; p<0·0001). The proportion of adults meeting the minimum LTPA recommendation increased over time (17·2% in 2000, 18·1% in 2005, and 22·8% in 2014), with the estimated prevalence change per year being 0·33% (95% CI 0·24-0·42; p<0·0001) for underweight people, 0·50% (0·47-0·53; p<0·0001) for normal-weight people, 0·37% (0·34-0·40; p<0·0001) for overweight people, and 0·06% (0·00-0·13; p=0·044) for obese people. We noted deteriorations over time in all measures of physical fitness in normal-weight adults (all p<0·0001), apart from resting heart rate (p=0·69). INTERPRETATION: Despite increased participation in LTPA, we noted increases in overweight or obesity and a decrease in physical fitness in Chinese adults. Continued nationwide interventions are needed to promote physical activity and other healthy lifestyle behaviours in China. FUNDING: National Physical Fitness Surveillance Center and Ministry of Science and Technology of the People's Republic of China.