Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity.

Hydroxymethanesulfonate (HMS) has been found to be an abundant organosulfur aerosol compound in the Beijing-Tianjin-Hebei (BTH) region with a measured maximum daily mean concentration of up to 10 µg per cubic meter in winter. However, the production medium of HMS in aerosols is controversial, and it is unknown whether chemical transport models are able to capture the variations of HMS during individual haze events. In this work, we modify the parametrization of HMS chemistry in the nested-grid GEOS-Chem chemical transport model, whose simulations provide a good account of the field measurements during winter haze episodes. We find the contribution of the aqueous aerosol pathway to total HMS is about 36% in winter in Beijing, due primarily to the enhancement effect of the ionic strength on the rate constants of the reaction between dissolved formaldehyde and sulfite. Our simulations suggest that the HMS-to-inorganic sulfate ratio will increase from the baseline of 7% to 13% in the near future, given the ambitious clean air and climate mitigation policies for the BTH region. The more rapid reductions in emissions of SO2 and NOx compared to NH3 alter the atmospheric acidity, which is a critical factor leading to the rising importance of HMS in particulate sulfur species.

Adhesive surface-enhanced Raman scattering Cu-Au nanoassembly for the sensitive analysis of particulate matter.

Surface-enhanced Raman scattering (SERS) has been used in atmospheric aerosol detection as it enables the high-resolution analysis of particulate matter. However, its use in the detection of historical samples without damaging the sampling membrane while achieving effective transfer and the high-sensitivity analysis of particulate matter from sample films remains challenging. In this study, a new type of SERS tape was developed, consisting of Au nanoparticles (NPs) on an adhesive double-sided Cu film (DCu). The enhanced electromagnetic field generated by the coupled resonance of the local surface plasmon resonances of AuNPs and DCu led to an enhanced SERS signal with an experimental enhancement factor of 107. The AuNPs were semi-embedded and distributed on the substrate, and the viscous DCu layer was exposed, enabling particle transfer. The substrates exhibited good uniformity and favorable reproducibility with relative standard deviations of 13.53% and 9.74% respectively, and the substrates could be stored for 180 days with no signs of signal weakening. The application of the substrates was demonstrated by the extraction and detection of malachite green and ammonium salt particulate matter. The results demonstrated that SERS substrates based on AuNPs and DCu are highly promising in real-world environmental particle monitoring and detection.

Classification and sources of extremely severe sandstorms mixed with haze pollution in Beijing.

Air quality has significantly improved in China; however, new challenges emerge when dust weather is combined with haze pollution during spring in northern China. On March 15, 2021, an extremely severe sandstorm occurred in Beijing, with hourly maximum PM10 and PM2.5 concentrations reaching 5267.7 µg m-3 and 963.9 µg m-3, respectively. Continuous sandstorm events usually lead to complicated pollution status in spring. Three pollution types were identified disregarding the time sequence throughout March. The secondary formation type was dominant, with high ratios of PM2.5/PM10 (mean 74%) and PM1/PM2.5 (mean 52%). This suggests that secondary transformations are the primary cause of heavy pollution, even during the dry seasons. Sandstorm type resulted in dramatic PM10 levels, with a noticeable decrease in PM2.5/PM10 levels (27%), although PM2.5 levels remain high. The transitional pollution type was distinguished by an independent increase in PM10 levels, although PM2.5 and PM1 levels differed from the PM10 levels. Throughout March, the sulfur oxidation rate varied considerably, with high levels during most periods (mean 0.52). A strong correlation indicated that relative humidity was the primary variable promoting the formation of secondary sulfate. Sandstorms promote heterogeneous reactions by providing abundant reaction surfaces from mineral particles, therefore aggravating secondary pollution. The sandstorm air mass from the northwest passing through the sand sources of Mongolia carried not only crustal matter but also organic components, such as bioaerosols, resulting in a sharp increase in the organic carbon in PM2.5.

Spectroscopic and compositional profiles of dissolved organic matters in urban snow from 2019 to 2021: Focusing on pollution features identification.

Snow owns stronger adsorption capacity for organic pollutants compared with rain. Huge amounts of anthropogenic dissolved organic matters (DOMs) in the atmosphere may enter the water environment with urban snow and increase water pollution risk. Extracting stable pollution features of urban snow is conducive to identifying the urban snow pollution from the water environment. Herein, we systematically explored the spectroscopic and compositional profiles of urban snow in Beijing from three snow events by multiple analytical tools and extracted stable pollution features of urban snow for the first time. Results showed that conventional pollutants with high concentration were detected in urban snow. The fluorescence signals of humic-like and some protein-like materials, the molecular weight distributions of chromophoric DOM at 254 nm and humic-like materials, and 172 kinds of lignin-like molecular formulas were extracted as stable features for urban snow. These stable features of urban snow laid the foundation for the identification of urban snow pollution and the analysis of the impact mechanisms of atmospheric pollution sources on the water environment.

Distinct diurnal chemical compositions and formation processes of individual organic-containing particles in Beijing winter.

Organic aerosols (OA) are major components of fine particulate matter, yet their formation mechanism remains unclear, especially in polluted environments. In this study, we investigated the diurnal chemical compositions and formation processes of OA in carbonaceous particles during winter in Beijing using aerosol time-of-flight mass spectrometry. We found that 84.5% of the measured carbonaceous particles underwent aging processes, characterized by larger diameter and more secondary species compared to fresh carbonaceous particles, and presented different chemical compositions of OA in the daytime and nighttime. During the day, under high O3 concentrations, organosulfates and oligomers existed in the aged carbonaceous particles, which were mixed with a higher signal of nitrate compared with sulfate. At night, under high relative humidity, distinct spectral signatures of hydroxymethanesulfonate and organic nitrogen compounds, and minor signals of other hydroxyalkylsulfonates and high molecular weight organic compounds were present in the aged carbonaceous particles, which were mixed with a higher signal of sulfate compared with nitrate. Our results indicated that photochemistry contributed to OA formation in the daytime, while aqueous chemistry played an important role in OA formation in the nighttime. The findings can help improve the performance of air quality and climate models on OA simulation.

Unbalanced emission reductions and adverse meteorological conditions facilitate the formation of secondary pollutants during the COVID-19 lockdown in Beijing.

During the coronavirus disease 2019 (COVID-19) lockdown in 2020, severe haze pollution occurred in the North China Plain despite the significant reduction in anthropogenic emissions, providing a natural experiment to explore the response of haze pollution to the reduction of human activities. Here, we study the characteristics and causes of haze pollution during the COVID-19 outbreak based on comprehensive field measurements in Beijing during January and February 2020. After excluding the Spring Festival period affected by fireworks activities, we found the ozone concentrations and the proportion of sulfate and nitrate in PM2.5 increased during the COVID-19 lockdown compared with the period before the lockdown, and sulfate played a more important role. Heterogeneous chemistry and photochemistry dominate the formation of sulfate and nitrate during the whole campaign, respectively, and the heterogeneous formation of nitrate at night was enhanced during the lockdown. The coeffects of more reductions in NOx than VOCs, weakened titration of NO, and increased temperature during the lockdown led to the increase in ozone concentrations, thereby promoting atmospheric oxidation capacity and photochemistry. In addition, the increase in relative humidity during the lockdown facilitated heterogeneous chemistry. Our results indicate that unbalanced emission reductions and adverse meteorological conditions induce the formation of secondary pollutants during the COVID-19 lockdown haze, and the formulation of effective coordinated emission-reduction control measures for PM2.5 and ozone pollution is needed in the future, especially the balanced control of NOx and VOCs.

Constructing a Raman and surface-enhanced Raman scattering spectral reference library for fine-particle analysis.

Fine particles associated with haze pollution threaten the health of over 400 million people in China. Owing to excellent non-destructive fingerprint recognition characteristics, Raman and surface-enhanced Raman scattering (SERS) are often used to analyze the composition of fine particles to determine their physical and chemical properties as well as reaction mechanisms. However, there is no comprehensive Raman spectral library of fine particles. Furthermore, various studies that used SERS for fine-particle composition analysis showed that the uniqueness of the SERS substrates and different excitation wavelengths can produce a different spectrum for the same fine-particle component. To overcome this limitation, we conducted SERS experiments with a portable Raman spectrometer using two common SERS substrates (silver (Ag) foil and gold nanoparticles (Au NPs)) and a 785 nm laser. Herein, we introduced three main particle component types (sulfate-nitrate-ammonium (SNA), organic material, and soot) with a total of 39 chemical substances. We scanned the solid Raman, liquid Raman, and SERS spectra of these substances and constructed a fine-particle reference library containing 105 spectra. Spectral results indicated that for soot and SNA, the differences in characteristic peaks mainly originated from the solid-liquid phase transition; Ag foil had little effect on this difference, while the Au NPs caused a significant red shift in the peak positions of polycyclic aromatic hydrocarbons. Moreover, with various characteristic peak positions in the three types of spectra, we could quickly and correctly distinguish substances. We hope that this spectral library will aid in the future identification of fine particles.

Large contribution of non-priority PAHs in atmospheric fine particles: Insights from time-resolved measurement and nontarget analysis.

Polycyclic aromatic hydrocarbons (PAHs), detrimental to human health, are key components contributing to the carcinogenicity of fine particles. The 16 priority PAHs listed by the United States Environment Protection Agency have been studied extensively. However, other than them, there is a large diversity of PAH species, whose atmospheric concentrations, risks, and variations remain elusive. Here, we carried out a time-resolved nontarget measurement in atmospheric PM2.5 using an improved comprehensive two-dimensional gas chromatography mass spectrometry. The measurement conducted during a 5-day pollution episode at an urban site of Beijing with a time resolution of 2 h. The nontarget analysis of time-resolved chromatographic data was performed for screening PAHs. A total number of 85 PAHs were identified and quantified. We found that other than 16 EPA PAHs, other screened PAHs contributed 43.3% of the total PAH mass concentration and 40.8% poential health risks. Dynamic variations of mass concentrations and their potential health risks of the screened PAHs were captured during a short-term heavy pollution episode, during which the instantaneous PAHs concentrations were much higher than their average concentrations. This study shows the potential for application of nontarget analysis for online comprehensive two-dimensional gas chromatography mass spectrometry and highlights the importance of time-resolved measurement of PAHs in PM2.5 and attention on extended PAHs species other than 16 EPA PAHs.

Dynamic variations of phthalate esters in PM2.5 during a pollution episode.

Phthalate esters (PAEs) as hazardous air pollutants can be easily released during the life cycle of plastic products. In this study, a thermal desorption aerosol comprehensive two-dimensional gas chromatography mass spectrometer coupled with a dual-trap was developed and used to measure the hourly-resolved PAEs characteristics in atmospheric PM2.5 at an urban site. Dimethyl phthalate (DMP), diethyl (DEP), dibutyl (DnBP), benzyl butyl (BBP), di(2-ethylhexyl) (DEHP), and di-n-octyl phthalate (DnOP) in PM2.5 were analyzed. The most abundant compounds were DEHP and DMP, followed by DnBP and DEP. The mass concentrations of the detected PAEs are comparable to those at other urban sites measured using offline methods with a lower time resolution. The concentrations of PAEs showed intense change with the variation of PM2.5 mass concentration. The proportion of DEHP increased while that of DMP decreased with the increase in PM2.5 pollution. Positive correlations between PAEs and PM2.5, organic carbon, and elemental carbon were observed, while PAEs had negative correlation with the ambient temperature. Our observation provides evidences on understanding the volatile and semi-volatile PAEs in the ambient aerosols.

Characterization of haze pollution in Zibo, China: Temporal series, secondary species formation, and PMx distribution.

An online field observation was conducted in Zibo, China from September 1, 2018 to February 28, 2019, covering autumn and winter. Within the investigation period, the mean mass concentrations of PM1, PM2.5, and PM10 were 49.3, 86.1, and 136.5 µg m-3, respectively. OA (organic aerosol) was the most dominant species in PM2.5 (39.7 %), followed by NO3- (26.3 %) and SO42- (17.0 %), indicating the importance of secondary species on PM2.5. Increase of particles were always accompanied increasing relative humidity (RH), slow wind, and increasing precursors, contributing the secondary transition. SO42- was more susceptible to RH, indicating the dominant role of heterogeneous processes in its secondary formation. As RH increased, its strengthening effect on SO42- increased as well. Photochemistry was the main contributor to the secondary formation of NO3-. The morning and evening rush hours determined the peak of absolute NO3- throughout the day. By classifying particles into three bins, we found that smaller particles were the biggest contributors (larger PM1/PM2.5) of slight pollution (35 < PM2.5<115 µg m-3). When severe haze occurred, PM2.5 contributed more than particles of other sizes (PM1 or PM10). Secondary species contributed more to particles within 2.5 µm but less to larger particles. PM1/PM2.5 was high from 9:00 to 15:00, indicating the strong effect of photochemistry on smaller particles. In comparison, larger particles favored more humid conditions. NO3- preferentially existed in larger particles because the hygroscopicity of preexisting species (SO42- and NO3-) promoted partitioning. SO42- appeared a stable diurnal variation, replying its stable contribution to particles of different sizes.

Improving the representation of HONO chemistry in CMAQ and examining its impact on haze over China.

We compare Community Multiscale Air Quality (CMAQ) model predictions with measured nitrous acid (HONO) concentrations in Beijing, China for December 2015. The model with the existing HONO chemistry in CMAQ severely under-estimates the observed HONO concentrations with a normalized mean bias of -97%. We revise the HONO chemistry in the model by implementing six additional heterogeneous reactions in the model: reaction of nitrogen dioxide (NO2) on ground surfaces, reaction of NO2 on aerosol surfaces, reaction of NO2 on soot surfaces, photolysis of aerosol nitrate, nitric acid displacement reaction, and hydrochloric acid displacement reaction. The model with the revised chemistry substantially increases HONO predictions and improves the comparison with observed data with a normalized mean bias of -5%. The photolysis of HONO enhances day-time hydroxyl radical by almost a factor of two. The enhanced hydroxyl radical concentrations compare favourably with observed data and produce additional sulfate via the reaction with sulfur dioxide, aerosol nitrate via the reaction with nitrogen dioxide, and secondary organic aerosols via the reactions with volatile organic compounds. The additional sulfate stemming from revised HONO chemistry improves the comparison with observed concentration; however, it does not close the gap between model prediction and the observation during polluted days.

Investigating the effect of sources and meteorological conditions on wintertime haze formation in Northeast China: A case study in Harbin.

Heavy haze pollution has occurred frequently in the past few years in Northeast China during winters, which was distinct from other regions in China because of the particular meteorological conditions. In this study, we analyzed the temporal variation, source appointment, and influencing factors of PM2.5 from December 1, 2018 to February 28, 2019 in Harbin. The results showed obvious differences between the non-haze and haze periods. The source appointment based on a single-particle aerosol mass spectrometer showed that coal combustion, vehicle emissions, biomass burning, and secondary inorganic aerosols (SIAs) were the major contributors of PM2.5. It is interesting that from the non-haze to the haze period, contributions of coal combustion and SIAs increased (from 20.2% to 27.3%, and from 17.3% to 18.9%, respectively) while other sources decreased or increased little. It indicated the primary pollutants from heating supply were the most important contributor to haze formation due to the low temperature. Furthermore, from levels I (0 < PM2.5 ≤ 75 µg m-3) to III (115 < PM2.5 ≤ 150 µg m-3), SIAs increased from 15.3% to 19.4% (increased 4.1%), while coal combustion from 23.7% to 27.1% and increased 3.4%. It implied clearly that SIAs played a comparable role in the early stage of the evolution of haze episode as that of coal combustion. Combining data on prevailing winds and results of potential source contribution function indicated that PM2.5 during the haze period was primarily influenced by the air masses originating from the southwestern areas via regional transport. A positive correlation was observed between relative humidity (RH) and haze pollution when RH ≥ 60%, indicating that hygroscopic growth may be the principal factor promoting secondary formation. CAPSULE: Coal combustion was the most important source in Harbin due to the low temperature, and secondary aerosols promoted the early stage of the haze evolution.

Surface-enhanced Raman scattering for mixing state characterization of individual fine particles during a haze episode in Beijing, China.

The nondestructive characterization of the mixing state of individual fine particles using the traditional single particle analysis technique remains a challenge. In this study, fine particles were collected during haze events under different pollution levels from September 5 to 11 2017 in Beijing, China. A nondestructive surface-enhanced Raman scattering (SERS) technique was employed to investigate the morphology, chemical composition, and mixing state of the multiple components in the individual fine particles. Optical image and SERS spectral analysis results show that soot existing in the form of opaque material was predominant during clear periods (PM2.5 ≤ 75 µg/m3). During polluted periods (PM2.5 > 75 µg/m3), opaque particles mixed with transparent particles (nitrates and sulfates) were generally observed. Direct classical least squares analysis further identified the relative abundances of the three major components of the single particles: soot (69.18%), nitrates (28.71%), and sulfates (2.11%). A negative correlation was observed between the abundance of soot and the mass concentration of PM2.5. Furthermore, mapping analysis revealed that on hazy days, PM2.5 existed as a core-shell structure with soot surrounded by nitrates and sulfates. This mixing state analysis method for individual PM2.5 particles provides information regarding chemical composition and haze formation mechanisms, and has the potential to facilitate the formulation of haze prevention and control policies.

Stronger secondary pollution processes despite decrease in gaseous precursors: A comparative analysis of summer 2020 and 2019 in Beijing.

To control the spread of COVID-19, China implemented a series of lockdowns, limiting various offline interactions. This provided an opportunity to study the response of air quality to emissions control. By comparing the characteristics of pollution in the summers of 2019 and 2020, we found a significant decrease in gaseous pollutants in 2020. However, particle pollution in the summer of 2020 was more severe; PM2.5 levels increased from 35.8 to 44.7 µg m-3, and PM10 increased from 51.4 to 69.0 µg m-3 from 2019 to 2020. The higher PM10 was caused by two sandstorm events on May 11 and June 3, 2020, while the higher PM2.5 was the result of enhanced secondary formation processes indicated by the higher sulfate oxidation rate (SOR) and nitrate oxidation rate (NOR) in 2020. Higher SOR and NOR were attributed mainly to higher relative humidity and stronger oxidizing capacity. Analysis of PMx distribution showed that severe haze occurred when particles within Bin2 (size ranging 1-2.5 µm) dominated. SO42-(1/2.5) and SO42-(2.5/10) remained stable under different periods at 0.5 and 0.8, respectively, indicating that SO42- existed mainly in smaller particles. Decreases in NO3-(1/2.5) and increases in NO3-(2.5/10) from clean to polluted conditions, similar to the variations in PMx distribution, suggest that NO3- played a role in the worsening of pollution. O3 concentrations were higher in 2020 (108.6 µg m-3) than in 2019 (96.8 µg m-3). Marked decreases in fresh NO alleviated the titration of O3. Furthermore, the oxidation reaction of NO2 that produces NO3- was dominant over the photochemical reaction of NO2 that produces O3, making NO2 less important for O3 pollution. In comparison, a lower VOC/NOx ratio (less than 10) meant that Beijing is a VOC-limited area; this indicates that in order to alleviate O3 pollution in Beijing, emissions of VOCs should be controlled.

Characteristics and seasonal variations of high-molecular-weight oligomers in urban haze aerosols.

Organic aerosols (OA) undergo sophisticated physiochemical processes in the atmosphere, playing a crucial role in extreme haze formations over the Northern China Plain. However, current understandings of the detailed composition and formation pathways are limited. In this study, high-molecular weight (HMW) species were observed in samples collected year-round in urban Beijing, especially in autumn and winter, during 2016-2017. The positive-ion-mode mass spectra of matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) showed that higher signal intensities were obtained in the mass-to-charge (m/z) ranges of 200-500 and 800-900, with repetitive mass difference patterns of m/z 12, 14, 16, and 18. This provided sound evidence that high-molecular-weight oligomers were generated as haze episodes became exacerbated. These oligomer signal intensities were enhanced in the presence of high relative humidity, aerosol water content, and PM2.5 (particles with an aerodynamic diameter ≤ 2.5 µm) mass, proving that the multiphase reaction processes play a fundamental role in haze formation in Beijing. Our study can form a basis for improved air pollution mitigation measures aimed at OA to improve health outcomes.

Mixed and intensive haze pollution during the transition period between autumn and winter in Beijing, China.

In the Northern China Plain (NCP), extreme haze events with high concentrations of fine particles occur frequently during the winter but rarely occur in autumn. In this study, we present a synthetic analysis of particulate constituents during the historically polluted transition period of autumn-winter in 2018, revealing that mixed-type haze episodes are the result of regional transport, homogeneous/heterogeneous conversion, and sandstorm influences. The hydrolysis process of N2O5 at higher relative humidity levels (>70%), which feature an enhanced nitrate oxidation ratio (0.30-0.70) and NO3- concentration (>60 µg m-3), was the driving factor for high PM2.5 mass concentrations during the observation periods. The long-distance transport of sandstorms, characterized by decreasing PM2.5/PM10 ratios (<30%) from the north/northwest, is the most important factor for the explosive growth of PM10 concentration. These results can help us gain a comprehensive understanding of haze formation and highlight the importance of nitrate chemistry in the aqueous phase. The results suggest that persistent NOx emission reduction measures must be made to better achieve air quality standards in Beijing and the NCP region.

Characteristics and formation mechanisms of winter haze in Changzhou, a highly polluted industrial city in the Yangtze River Delta, China.

Changzhou, an industrial city in the Yangtze River Delta, has been experiencing serious haze pollution, particularly in winter. However, studies pertaining to the haze in Changzhou are very limited, which makes it difficult to understand the characteristics and formation of winter haze in this area, and develop effective control measures. In this study, we carried out continuous online observation of particulate matter, chemical components, and meteorology in Changzhou in February 2017. Our results showed that haze pollution occurred frequently in Changzhou winter and exhibited two patterns: dry haze with low relative humidity (RH) and wet haze with high RH. Water-soluble inorganic ions (SO42-, NO3-, and NH4+) accounted for ∼52.2% of the PM2.5 mass, of which sulfate was dominant in wet haze periods while nitrate was dominant in other periods. With the deterioration of haze pollution, the proportion of nitrate in PM2.5 increased, while sulfate proportion increased under wet haze and decreased under dry haze. Dry haze and wet haze appeared under slow north wind and south wind, respectively, and strong north wind or sea breeze scavenged pollution. We found that formation of nitrate occurred rapidly in daytime with high concentrations of odd oxygen (Ox = O3 + NO2), whereas formation of sulfate occurred rapidly during nighttime with high RH, indicating that photochemistry and heterogeneous reaction were the major formation mechanisms for nitrate and sulfate, respectively. Through the cluster analysis of 36-h backward trajectories, five sources of air masses from three directions were identified. High PM2.5 concentrations (84.1 µg m-3 on average) usually occurred under the influence of two clusters (46%) from the northwest, indicating that regional transport from northern China aggravated the winter haze pollution in Changzhou. Emission reduction, particularly the mobile sources, and regional joint prevention and control can help to mitigate the winter haze in Changzhou.

Air pollution characteristics and their relationship with emissions and meteorology in the Yangtze River Delta region during 2014-2016.

With rapid economic growth and urbanization, the Yangtze River Delta (YRD) region in China has experienced serious air pollution challenges. In this study, we analyzed the air pollution characteristics and their relationship with emissions and meteorology in the YRD region during 2014-2016. In recent years, the concentrations of all air pollutants, except O3, decreased. Spatially, the PM2.5, PM10, SO2, and CO concentrations were higher in the northern YRD region, and NO2 and O3 were higher in the central YRD region. Based on the number of non-attainment days (i.e., days with air quality index greater than 100), PM2.5 was the largest contributor to air pollution in the YRD region, followed by O3, PM10, and NO2. However, particulate matter pollution has declined gradually, while O3 pollution worsened. Meteorological conditions mainly influenced day-to-day variations in pollutant concentrations. PM2.5 concentration was inversely related to wind speed, while O3 concentration was positively correlated with temperature and negatively correlated with relative humidity. The air quality improvement in recent years was mainly attributed to emission reductions. During 2014-2016, PM2.5, PM10, SO2, NOx, CO, NH3, and volatile organic compound (VOC) emissions in the YRD region were reduced by 26.3%, 29.2%, 32.4%, 8.1%, 15.9%, 4.5%, and 0.3%, respectively. Regional transport also contributed to the air pollution. During regional haze periods, pollutants from North China and East China aggravated the pollution in the YRD region. Our findings suggest that emission reduction and regional joint prevention and control helped to improve the air quality in the YRD region.

Parameterization of heterogeneous reaction of SO2 to sulfate on dust with coexistence of NH3 and NO2 under different humidity conditions.

Sulfate plays an important role in atmospheric haze in China, which has received considerable attention in recent years. Various types of parameterization methods and heterogeneous oxidation rates of SO2 have been used in previous studies. However, properly representing heterogeneous sulfate formation in air quality models remains a big challenge. In this study, we quantified the heterogeneous oxidation reaction using experimental results that approximate the haze conditions in China. Firstly, a series of experiments were conducted to investigate the heterogeneous uptake of SO2 with different relative humidity (RH) levels and the presence of NH3 and NO2 on natural dust surfaces. Then the uptake coefficients for heterogeneous oxidation of SO2 to sulfate at different RH under NH3 and NO2coexistence were parameterized based on the experimental results and implemented in the Community Multiscale Air Quality modeling system (CMAQ). Simulation results suggested that this new parameterization improved model performance by 6.6% in the simulation of wintertime sulfate concentrations for Beijing. The simulated maximum growth rate of SO4 2- during a heavy pollution period increased from 0.97 µg m-3 h-1 to 10.11 µg m-3 h-1. The heterogeneous oxidation of SO2 in the presence of NH3 contributed up to 23% of the sulfate concentration during heavy pollution periods.

Biotoxicity of water-soluble species in PM2.5 using Chlorella.

China has been faced with severe haze pollution, which is hazardous to human health. Among the air pollutants, PM2.5 (particles with an aerodynamic diameter ≤ 2.5 µm) is the most dangerous because of its toxicity and impact on human health and ecosystems. However, there has been limited research on PM2.5 particle toxicity. In the present study, we collected daily PM2.5 samples from January 1 to March 31, 2018 and selected samples to extract water-soluble species, including SO42-, NO3-, WSOC, and NH4+. These samples represented clean, good, slight, moderate, and heavy pollution days. After extraction using an ultrasonic method, PM2.5 solutions were obtained. We used Chlorella as the test algae and studied the content of chlorophyll a, as well as the variation in fluorescence when they were placed into the PM2.5 extraction solution, and their submicroscopic structure was analyzed using transmission electron microscopy (TEM). The results showed that when the air quality was relatively clean and good (PM2.5 concentration ≤ 75 µg m-3), the PM2.5 extraction solutions had no inhibiting effects on Chlorella, whereas when the air quality was polluted (PM2.5 concentration > 75 µg m-3) and heavily polluted (PM2.5 concentration > 150 µg m-3), with increasing PM2.5 concentrations and exposure time, the chlorophyll a content in Chlorella decreased. Moreover, the maximum photochemical quantum yield (Fv/Fm) of Chlorella obviously decreased, indicating chlorophyll inhibition during polluted days with increasing PM2.5 concentrations. The effects on the chlorophyll fluorescence parameters were also obvious, leading to an increase of energy dissipated per unit reaction center (DIo/RC), suggesting that Chlorella could survive when exposed to PM2.5 solutions, whereas the physiological activities were significantly inhibited. The TEM analysis showed that there were few effects on Chlorella cell microstructure during clean days, whereas plasmolysis occurred during light- and medium-polluted days. With increasing pollution levels, plasmolysis became more and more apparent, until the organelles inside the cells were thoroughly destroyed and most of the parts could not be recognized.