Rising Alkali-to-Acid Ratios in the Atmosphere May Correspond to Increased Aerosol Acidity.

Aerosol acidity (or pH) is one central parameter in determining the health, climate, and ecological effects of aerosols. While it is traditionally assumed that the long-term aerosol pH levels are determined by the relative abundances of atmospheric alkaline to acidic substances (referred to as RC/A hereinafter), we observed contrasting pH─RC/A trends at different sites globally, i.e., rising alkali-to-acid ratios in the atmosphere may unexpectedly lead to increased aerosol acidity. Here, we examined this apparently counterintuitive phenomenon using the multiphase buffer theory. We show that the aerosol water content (AWC) set a pH "baseline" as the peak buffer pH, while the RC/A and particle-phase chemical compositions determine the deviation of pH from this baseline within the buffer ranges. Therefore, contrasting long-term pH trends may emerge when RC/A increases while the AWC or nitrate fraction decreases, or vice versa. Our results provided a theoretical framework for a quantitative understanding of the response of aerosol pH to variations in SO2, NOx versus NH3, and dust emissions, offering broad applications in studies on aerosol pH and the associated environmental and health effects.

The Significant Role of New Particle Composition and Morphology on the HNO3-Driven Growth of Particles down to Sub-10 nm.

New particle formation and growth greatly influence air quality and the global climate. Recent CERN Cosmics Leaving OUtdoor Droplets (CLOUD) chamber experiments proposed that in cold urban atmospheres with highly supersaturated HNO3 and NH3, newly formed sub-10 nm nanoparticles can grow rapidly (up to 1000 nm h-1). Here, we present direct observational evidence that in winter Beijing with persistent highly supersaturated HNO3 and NH3, nitrate contributed less than ∼14% of the 8-40 nm nanoparticle composition, and overall growth rates were only ∼0.8-5 nm h-1. To explain the observed growth rates and particulate nitrate fraction, the effective mass accommodation coefficient of HNO3 (αHNO3) on the nanoparticles in urban Beijing needs to be 2-4 orders of magnitude lower than those in the CLOUD chamber. We propose that the inefficient uptake of HNO3 on nanoparticles is mainly due to the much higher particulate organic fraction and lower relative humidity in urban Beijing. To quantitatively reproduce the observed growth, we show that an inhomogeneous "inorganic core-organic shell" nanoparticle morphology might exist for nanoparticles in Beijing. This study emphasized that growth for nanoparticles down to sub-10 nm was largely influenced by their composition, which was previously ignored and should be considered in future studies on nanoparticle growth.

Role of Carbon Dioxide, Ammonia, and Organic Acids in Buffering Atmospheric Acidity: The Distinct Contribution in Clouds and Aerosols.

Acidity is one central parameter in atmospheric multiphase reactions, influencing aerosol formation and its effects on climate, health, and ecosystems. Weak acids and bases, mainly CO2, NH3, and organic acids, are long considered to play a role in regulating atmospheric acidity. However, unlike strong acids and bases, their importance and influencing mechanisms in a given aerosol or cloud droplet system remain to be clarified. Here, we investigate this issue with new insights provided by recent advances in the field, in particular, the multiphase buffer theory. We show that, in general, aerosol acidity is primarily buffered by NH3, with a negligible contribution from CO2 and a potential contribution from organic acids under certain conditions. For fogs, clouds, and rains, CO2, organic acids, and NH3 may all provide certain buffering under higher pH levels (pH > ∼4). Despite the 104to 107 lower abundance of NH3 and organic weak acids, their buffering effect can still be comparable to that of CO2. This is because the cloud pH is at the very far end of the CO2 multiphase buffering range. This Perspective highlights the need for more comprehensive field observations under different conditions and further studies in the interactions among organic acids, acidity, and cloud chemistry.

Vehicular Ammonia Emissions Significantly Contribute to Urban PM2.5 Pollution in Two Chinese Megacities.

Ammonia (NH3) plays a vital role in the formation of fine particulate matter (PM2.5). Prior studies have primarily focused on the control of agricultural NH3 emissions, the dominant source of anthropogenic NH3 emissions. The air quality impact from vehicular NH3 emissions, which could be particularly important in urban areas, has not been adequately evaluated. We developed high-resolution vehicular NH3 emission inventories for Beijing and Shanghai based on detailed link-level traffic profiles and conducted atmospheric simulations of ambient PM2.5 concentrations contributed by vehicular NH3 emissions. We found that vehicular NH3 emissions shared high proportions among total anthropogenic NH3 emissions in the urban areas of Beijing (86%) and Shanghai (45%), where vehicular NH3 was primarily emitted by gasoline vehicles. Local vehicular NH3 emissions could be responsible for approximately 3% of urban PM2.5 concentrations during wintertime, and the contributions could be much higher during polluted periods (∼3 µg m-3). We also showed that controlling vehicular NH3 emissions will be effective and feasible to alleviate urban PM2.5 pollution for megacities in the near future.

Aerosol pH and Ion Activities of HSO4- and SO42- in Supersaturated Single Droplets.

Accurate determination of acidity (pH) and ion activities in aqueous droplets is a major experimental and theoretical challenge for understanding and simulating atmospheric multiphase chemistry. Here, we develop a ratiometric Raman spectroscopy method to measure the equilibrium concentration of sulfate (SO42-) and bisulfate (HSO4-) in single microdroplets levitated by aerosol optical tweezers. This approach enables determination of ion activities and pH in aqueous sodium bisulfate droplets under highly supersaturated conditions. The experimental results were compared against aerosol thermodynamic model calculations in terms of simulating aerosol ion concentrations, ion activity coefficients, and pH. We found that the Extended Aerosol Inorganics Model (E-AIM) can well reproduce the experimental results. The alternative model ISORROPIA, however, exhibits substantial deviations in SO42- and HSO4- concentrations and up to a full unit of aerosol pH under acidic conditions, mainly due to discrepancies in simulating ion activity coefficients of SO42--HSO4- equilibrium. Globally, this may cause an average deviation of ISORROPIA from E-AIM by 25 and 65% in predicting SO42- and HSO4- concentrations, respectively. Our results show that it is important to determine aerosol pH and ion activities in the investigation of sulfate formation and related aqueous phase chemistry.

Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain (McFAN): integrated analysis and intensive winter campaign 2018.

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. The Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain (McFAN) investigated the physicochemical mechanisms leading to haze formation with a focus on the contributions of multiphase processes in aerosols and fogs. We integrated observations on multiple platforms with regional and box model simulations to identify and characterize the key oxidation processes producing sulfate, nitrate and secondary organic aerosols. An outdoor twin-chamber system was deployed to conduct kinetic experiments under real atmospheric conditions in comparison to literature kinetic data from laboratory studies. The experiments were spanning multiple years since 2017 and an intensive field campaign was performed in the winter of 2018. The location of the site minimizes fast transition between clean and polluted air masses, and regimes representative for the North China Plain were observed at the measurement location in Gucheng near Beijing. The consecutive multi-year experiments document recent trends of PM2.5 pollution and corresponding changes of aerosol physical and chemical properties, enabling in-depth investigations of established and newly proposed chemical mechanisms of haze formation. This study is mainly focusing on the data obtained from the winter campaign 2018. To investigate multiphase chemistry, the results are presented and discussed by means of three characteristic cases: low humidity, high humidity and fog. We find a strong relative humidity dependence of aerosol chemical compositions, suggesting an important role of multiphase chemistry. Compared with the low humidity period, both PM1 and PM2.5 show higher mass fraction of secondary inorganic aerosols (SIA, mainly as nitrate, sulfate and ammonium) and secondary organic aerosols (SOA) during high humidity and fog episodes. The changes in aerosol composition further influence aerosol physical properties, e.g., with higher aerosol hygroscopicity parameter κ and single scattering albedo SSA under high humidity and fog cases. The campaign-averaged aerosol pH is 5.1 ± 0.9, of which the variation is mainly driven by the aerosol water content (AWC) concentrations. Overall, the McFAN experiment provides new evidence of the key role of multiphase reactions in regulating aerosol chemical composition and physical properties in polluted regions.

Episode-Based Evolution Pattern Analysis of Haze Pollution: Method Development and Results from Beijing, China.

Haze episodes occurred in Beijing repeatedly in 2013, resulting in 189 polluted days. These episodes differed in terms of sources, formation processes, and chemical composition and thus required different control policies. Therefore, an overview of the similarities and differences among these episodes is needed. For this purpose, we conducted one-year online observations and developed a program that can simultaneously divide haze episodes and identify their shapes. A total of 73 episodes were identified, and their shapes were linked with synoptic conditions. Pure-haze events dominated in wintertime, whereas mixed haze-dust (PM2.5/PM10 < 60%) and mixed haze-fog (Aerosol Water/PM2.5 ∼ 0.3) events dominated in spring and summer-autumn, respectively. For all types, increase of ratio of PM2.5 in PM10 was typically achieved before PM2.5 reached ∼150 µg/m(3). In all PM2.5 species observed, organic matter (OM) was always the most abundant component (18-60%), but it was rarely the driving factor: its relative contribution usually decreased as the pollution level increased. The only OM-driven episode observed was associated with intensive biomass-burning activities. In comparison, haze evolution generally coincided with increasing sulfur and nitrogen oxidation ratios (SOR and NOR), indicating the enhanced production of secondary inorganic species. Applicability of these conclusions required further tests with simultaneously multisite observations.

Key factors in epidemiological exposure and insights for environmental management: Evidence from meta-analysis.

In recent years, the precision of exposure assessment methods has been rapidly improved and more widely adopted in epidemiological studies. However, such methodological advancement has introduced additional heterogeneity among studies. The precision of exposure assessment has become a potential confounding factors in meta-analyses, whose impacts on effect calculation remain unclear. To explore, we conducted a meta-analysis to integrate the long- and short-term exposure effects of PM2.5, NO2, and O3 on all-cause, cardiovascular, and respiratory mortality in the Chinese population. Literature was identified through Web of Science, PubMed, Scopus, and China National Knowledge Infrastructure before August 28, 2023. Sub-group analyses were performed to quantify the impact of exposure assessment precisions and pollution levels on the estimated risk. Studies achieving merely city-level resolution and population exposure are classified as using traditional assessment methods, while those achieving sub-kilometer simulations and individual exposure are considered finer assessment methods. Using finer assessment methods, the RR (under 10 µg/m3 increment, with 95% confidence intervals) for long-term NO2 exposure to all-cause mortality was 1.13 (1.05-1.23), significantly higher (p-value = 0.01) than the traditional assessment result of 1.02 (1.00-1.03). Similar trends were observed for long-term PM2.5 and short-term NO2 exposure. A decrease in short-term PM2.5 levels led to an increase in the RR for all-cause and cardiovascular mortality, from 1.0035 (1.0016-1.0053) and 1.0051 (1.0021-1.0081) to 1.0055 (1.0035-1.0075) and 1.0086 (1.0061-1.0111), with weak between-group significance (p-value = 0.13 and 0.09), respectively. Based on the quantitative analysis and literature information, we summarized four key factors influencing exposure assessment precision under a conceptualized framework: pollution simulation resolution, subject granularity, micro-environment classification, and pollution levels. Our meta-analysis highlighted the urgency to improve pollution simulation resolution, and we provide insights for researchers, policy-makers and the public. By integrating the most up-to-date epidemiological research, our study has the potential to provide systematic evidence and motivation for environmental management.

China's public health initiatives for climate change adaptation.

China's health gains over the past decades face potential reversals if climate change adaptation is not prioritized. China's temperature rise surpasses the global average due to urban heat islands and ecological changes, and demands urgent actions to safeguard public health. Effective adaptation need to consider China's urbanization trends, underlying non-communicable diseases, an aging population, and future pandemic threats. Climate change adaptation initiatives and strategies include urban green space, healthy indoor environments, spatial planning for cities, advance location-specific early warning systems for extreme weather events, and a holistic approach for linking carbon neutrality to health co-benefits. Innovation and technology uptake is a crucial opportunity. China's successful climate adaptation can foster international collaboration regionally and beyond.

Revisiting the Key Driving Processes of the Decadal Trend of Aerosol Acidity in the U.S.

Acidity is one essential parameter in determining the aqueous phase physical and chemical processes in the atmosphere and strongly influences the climate, ecological, and health effects of aerosols. Traditionally, aerosol acidity is thought to increase with emissions of atmospheric acidic substances (SO2, NOx, etc.) and decrease with that of alkaline ones (NH3, dust, etc.). However, decade-long observations in southeastern U.S. seem to disagree with this hypothesis: while the emissions of NH3 versus SO2 enhanced by over three times, the predicted aerosol acidity is stable, and the observed particle-phase ammonium-to-sulfate ratio is even decreasing. Here, we investigated into this issue with the recently proposed multiphase buffer theory. We show that historically, there is a transition in the dominant drivers of aerosol acidity in this region. Under the ammonia-poor conditions before ∼2008, the acidity is governed by HSO4 -/SO4 2- buffering and the water self-buffering effect. Under the ammonia-rich conditions after ∼2008, aerosol acidity is mainly buffered by NH4 +/NH3. Buffering from the organic acids is negligible in the investigated period. In addition, the observed decrease in ammonium-to-sulfate ratio is due to the increased importance of non-volatile cations, especially after ∼2014. We predict that until ∼2050, the aerosols will remain in the ammonia-buffered regime, and the nitrate will remain largely (>98%) in the gas phase in southeastern U.S.

New particle formation in the remote marine boundary layer.

Marine low clouds play an important role in the climate system, and their properties are sensitive to cloud condensation nuclei concentrations. While new particle formation represents a major source of cloud condensation nuclei globally, the prevailing view is that new particle formation rarely occurs in remote marine boundary layer over open oceans. Here we present evidence of the regular and frequent occurrence of new particle formation in the upper part of remote marine boundary layer following cold front passages. The new particle formation is facilitated by a combination of efficient removal of existing particles by precipitation, cold air temperatures, vertical transport of reactive gases from the ocean surface, and high actinic fluxes in a broken cloud field. The newly formed particles subsequently grow and contribute substantially to cloud condensation nuclei in the remote marine boundary layer and thereby impact marine low clouds.

Multiphase buffer theory explains contrasts in atmospheric aerosol acidity.

Aerosol acidity largely regulates the chemistry of atmospheric particles, and resolving the drivers of aerosol pH is key to understanding their environmental effects. We find that an individual buffering agent can adopt different buffer pH values in aerosols and that aerosol pH levels in populated continental regions are widely buffered by the conjugate acid-base pair NH4 +/NH3 (ammonium/ammonia). We propose a multiphase buffer theory to explain these large shifts of buffer pH, and we show that aerosol water content and mass concentration play a more important role in determining aerosol pH in ammonia-buffered regions than variations in particle chemical composition. Our results imply that aerosol pH and atmospheric multiphase chemistry are strongly affected by the pervasive human influence on ammonia emissions and the nitrogen cycle in the Anthropocene.

Integration of field observation and air quality modeling to characterize Beijing aerosol in different seasons.

Fine particulate matter (PM2.5) pollution in Beijing was investigated based on field observation and air quality modeling. Measurement results showed that when using elemental carbon (EC) as the reference component, concurrent increases were observed in the relative abundances of sulfate, nitrate, organic carbon (OC) and water-soluble organic carbon (WSOC) when RH exceeded ∼65% during winter. The observed increases could not be explained by variations of primary biomass burning emissions, instead they likely pointed to heterogeneous chemistry and presumably indicated that formation of secondary inorganic and organic aerosols might be related during winter haze events in Beijing. Large gaps were found in winter when comparing the observational and modeling results. In summer, RH exhibited little influence on the observed sulfate/EC, OC/EC or WSOC/EC, and the observed and modeled results were in general comparable for the concentrations of sulfate, EC and OC. This study suggests that distinct yet poorly-understood atmospheric chemistry may be at play in China's winter haze events, and it could be a substantial challenge to properly incorporate the related mechanisms into air quality models.

Long-range transported North American wildfire aerosols observed in marine boundary layer of eastern North Atlantic.

Wildfire is a major source of biomass burning aerosols, which greatly impact Earth climate. Tree species in North America (NA) boreal forests can support high-intensity crown fires, resulting in elevated injection height and longer lifetime (on the order of months) of the wildfire aerosols. Given the long lifetime, the properties of aged NA wildfire aerosols are required to understand and quantify their effects on radiation and climate. Here we present comprehensive characterization of climatically relevant properties, including optical properties and cloud condensation nuclei (CCN) activities of aged NA wildfire aerosols, emitted from the record-breaking Canadian wildfires in August 2017. Despite the extreme injection height of ~12 km, some of the wildfire plumes descended into the marine boundary layer in the eastern North Atlantic over a period of ~2 weeks, owing to the dry intrusions behind mid-latitude cyclones. The aged wildfire aerosols have high single scattering albedos at 529 nm (ω529; 0.92-0.95) while low absorption Ångström exponents (Åabs) at 464 nm/648 nm (0.7-0.9). In comparison, Åabs of fresh/slightly aged ones are typically 1.4-3.5. This low Åabs indicates a nearly complete loss of brown carbon, likely due to bleaching and/or evaporation, during the long-range transport. The nearly complete loss suggests that on global average, direct radiative forcing of BrC may be minor. Combining Mie calculations and the measured aerosol hygroscopicity, volatility and size distributions, we show that the high ω529 and low Åabs values are best explained by an external mixture of non-absorbing organic particles and absorbing particles of large BC cores (>~110 nm diameter) with thick non-absorbing coatings. The accelerated descent of the wildfire plume also led to strong increase of CCN concentration at the supersaturation levels representative of marine low clouds. The hygroscopicity parameter, κCCN, of the aged wildfire aerosols varies from 0.2 to 0.4, substantially lower than that of background marine boundary layer aerosols. However, the high fraction of particles with large diameter (i.e., within accumulation size ranges, ~100-250 nm) compensates for the low values of κ, and as a result, the aged NA wildfire aerosols contribute more efficiently to CCN population. These results provide direct evidence that the long-range transported NA wildfires can strongly influence CCN concentration in remote marine boundary layer, therefore the radiative properties of marine low clouds. Given the expected increases of NA wildfire intensity and frequency and regular occurrence of dry intrusion following mid-latitude cyclones, the influence of NA wildfire aerosols on CCN and clouds in remote marine environment need to be further examined.

ATP Hydrolysis Determines Cold Tolerance by Regulating Available Energy for Glutathione Synthesis in Rice Seedling Plants.

BACKGROUND: Glutathione (GSH) is important for plants to resist abiotic stress, and a large amount of energy is required in the process. However, it is not clear how the energy status affects the accumulation of GSH in plants under cold stress. RESULTS: Two rice pure lines, Zhongzao39 (ZZ39) and its recombinant inbred line 82 (RIL82) were subjected to cold stress for 48 h. Under cold stress, RIL82 suffered more damages than ZZ39 plants, in which higher increases in APX activity and GSH content were showed in the latter than the former compared with their respective controls. This indicated that GSH was mainly responsible for the different cold tolerance between these two rice plants. Interestingly, under cold stress, greater increases in contents of carbohydrate, NAD(H), NADP(H) and ATP as well as the expression levels of GSH1 and GSH2 were showed in RIL82 than ZZ39 plants. In contrast, ATPase content in RIL82 plants was adversely inhibited by cold stress while it increased significantly in ZZ39 plants. This indicated that cold stress reduced the accumulation of GSH in RIL82 plants mainly due to the inhibition on ATP hydrolysis rather than energy deficit. CONCLUSION: We inferred that the energy status determined by ATP hydrolysis involved in regulating the cold tolerance of plants by controlling GSH synthesis.

Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China.

Fine-particle pollution associated with winter haze threatens the health of more than 400 million people in the North China Plain. Sulfate is a major component of fine haze particles. Record sulfate concentrations of up to ~300 µg m-3 were observed during the January 2013 winter haze event in Beijing. State-of-the-art air quality models that rely on sulfate production mechanisms requiring photochemical oxidants cannot predict these high levels because of the weak photochemistry activity during haze events. We find that the missing source of sulfate and particulate matter can be explained by reactive nitrogen chemistry in aerosol water. The aerosol water serves as a reactor, where the alkaline aerosol components trap SO2, which is oxidized by NO2 to form sulfate, whereby high reaction rates are sustained by the high neutralizing capacity of the atmosphere in northern China. This mechanism is self-amplifying because higher aerosol mass concentration corresponds to higher aerosol water content, leading to faster sulfate production and more severe haze pollution.

Measurement of humic-like substances in aerosols: a review.

Aerosol-phase humic-like substances (HULIS) have received increasingly attention due to their universal ambient presence, active participation in atmospheric chemistry and important environmental and health effects. In last decade, intensive field works have promoted development of quantification and analysis method, unearthed spatio-temporal variation, and proved evidence for source identification of HULIS. These important developments were summarized in this review to provide a global perspective of HULIS. The diverse operational HULIS definitions were gradually focused onto several versions. Although found globally in Europe, Asia, Australasia and North America, HULIS are far more typical in continental and near-ground aerosols. HULIS concentrations varied from <1 µg/m(3) to >13 µg/m(3), with their carbon fraction making up 9%-72% of water soluble organic carbon. Dominant HULIS source was suggested as secondary processes and biomass burning, with the detailed formation pathways suggested and verified in laboratory works.

[Effect of permeabilization on sulfate reduction activity of Desulfovibrio vulgaris Hildenborough cells in the presence of different electron donors].

The Desulfovibrio vulgaris Hildenborough (DvH) cells permeabilized with ethanol were used as biocatalysts to enhance hydrogenotrophic sulfate conversion. The effect of permeabilization extent of DvH cells on sulfate reduction was studied in the presence of different electron donors. When hydrogen was used as an electron donor, the highest level of sulfate reduction activity attained in cells treated with 10% ethanol (V/V), followed by 15% -ethanol treated cells. Furthermore, sulfate reduction activity markedly decreased when the ethanol concentration exceeded 15%. However, when lactate was used as the electron donor, the optimum ethanol concentration of the permeabilizing reagent was 20%, followed by 15% and 10%. Even when ethanol concentration reached 25%, DvH cells remained their partial activity with lactate. In a word, sulfate reduction activity of DvH cells responded differently in the presence of different donors. This was because the oxidation process of H2 and lactate occurred at different positions in DvH cells, and consequently intracellular electron transport pathway differed. To ensure the integrity of the electron transport chain between the donor and the accepter was a key factor for determining the permeabilization extent and for the application of cell permeabilization technology.