Resolving Atmospheric Oxygenated Organic Molecules in Urban Beijing Using Online Ultrahigh-Resolution Chemical Ionization Mass Spectrometry.

Gaseous oxygenated organic molecules (OOMs) are crucial precursors of atmospheric organic aerosols. OOMs in urban atmospheres have complex compositions, posing challenges to understanding their formation, evolution, and influences. In this study, we identify 2403 atmospheric gaseous OOMs in urban Beijing using online nitrate-based chemical ionization Orbitrap mass spectrometry based on one-year atmospheric measurements. We find that OOMs in urban atmospheres can be identified with higher accuracy and wider coverage, compared to previously used online mass spectrometry. With optimized OOM resolving capabilities, previous knowledge of OOMs in urban atmospheres can be expanded. First, clear homologous and oxygen-addition characteristics of the OOMs are revealed. Second, OOMs with lower concentrations or higher masses are identified and characterized with high confidence, e.g., OOMs with masses above 350 Da. In particular, dimers of OOMs (e.g., C20H32O8-15N2), crucial species for organic nucleation, are identified. During four seasons, nitrogen-containing OOMs dominate the total concentration of OOMs, and OOMs are mainly from aromatic and aliphatic oxidation. Additionally, radicals with similar composition as OOMs, intermediates for OOM formation, are identified with clear diurnal variation, e.g., CnH2n-5O6 radicals (n = 8-10) and CmH2m-4NO9 radicals (m = 9-10), peak during the daytime and nighttime, respectively, previously having scarce measurement evidence in urban atmospheres.

Combined solar power and storage as cost-competitive and grid-compatible supply for China's future carbon-neutral electricity system.

As the world's largest CO2 emitter, China's ability to decarbonize its energy system strongly affects the prospect of achieving the 1.5 °C limit in global, average surface-temperature rise. Understanding technically feasible, cost-competitive, and grid-compatible solar photovoltaic (PV) power potentials spatiotemporally is critical for China's future energy pathway. This study develops an integrated model to evaluate the spatiotemporal evolution of the technology-economic-grid PV potentials in China during 2020 to 2060 under the assumption of continued cost degression in line with the trends of the past decade. The model considers the spatialized technical constraints, up-to-date economic parameters, and dynamic hourly interactions with the power grid. In contrast to the PV production of 0.26 PWh in 2020, results suggest that China's technical potential will increase from 99.2 PWh in 2020 to 146.1 PWh in 2060 along with technical advances, and the national average power price could decrease from 4.9 to 0.4 US cents/kWh during the same period. About 78.6% (79.7 PWh) of China's technical potential will realize price parity to coal-fired power in 2021, with price parity achieved nationwide by 2023. The cost advantage of solar PV allows for coupling with storage to generate cost-competitive and grid-compatible electricity. The combined systems potentially could supply 7.2 PWh of grid-compatible electricity in 2060 to meet 43.2% of the country's electricity demand at a price below 2.5 US cents/kWh. The findings highlight a crucial energy transition point, not only for China but for other countries, at which combined solar power and storage systems become a cheaper alternative to coal-fired electricity and a more grid-compatible option.

Drivers of Increasing Ozone during the Two Phases of Clean Air Actions in China 2013-2020.

In response to the severe air pollution issue, the Chinese government implemented two phases (Phase I, 2013-2017; Phase II, 2018-2020) of clean air actions since 2013, resulting in a significant decline in fine particles (PM2.5) during 2013-2020, while the warm-season (April-September) mean maximum daily 8 h average ozone (MDA8 O3) increased by 2.6 µg m-3 yr-1 in China during the same period. Here, we derived the drivers behind the rising O3 concentrations during the two phases of clean air actions by using a bottom-up emission inventory, a regional chemical transport model, and a multiple linear regression model. We found that both meteorological variations (3.6 µg m-3) and anthropogenic emissions (6.7 µg m-3) contributed to the growth of MDA8 O3 from 2013 to 2020, with the changes in anthropogenic emissions playing a more important role. The anthropogenic contributions to the O3 rise during 2017-2020 (1.2 µg m-3) were much lower than that in 2013-2017 (5.2 µg m-3). The lack of volatile organic compound (VOC) control and the decline in nitrogen oxides (NOx) emissions were responsible for the O3 increase in 2013-2017 due to VOC-limited regimes in most urban areas, while the synergistic control of VOC and NOx in Phase II initially worked to mitigate O3 pollution during 2018-2020, although its effectiveness was offset by the penalty of PM2.5 decline. Future mitigation efforts should pay more attention to the simultaneous control of VOC and NOx to improve O3 air quality.

Transboundary health impacts of transported global air pollution and international trade.

Millions of people die every year from diseases caused by exposure to outdoor air pollution. Some studies have estimated premature mortality related to local sources of air pollution, but local air quality can also be affected by atmospheric transport of pollution from distant sources. International trade is contributing to the globalization of emission and pollution as a result of the production of goods (and their associated emissions) in one region for consumption in another region. The effects of international trade on air pollutant emissions, air quality and health have been investigated regionally, but a combined, global assessment of the health impacts related to international trade and the transport of atmospheric air pollution is lacking. Here we combine four global models to estimate premature mortality caused by fine particulate matter (PM2.5) pollution as a result of atmospheric transport and the production and consumption of goods and services in different world regions. We find that, of the 3.45 million premature deaths related to PM2.5 pollution in 2007 worldwide, about 12 per cent (411,100 deaths) were related to air pollutants emitted in a region of the world other than that in which the death occurred, and about 22 per cent (762,400 deaths) were associated with goods and services produced in one region for consumption in another. For example, PM2.5 pollution produced in China in 2007 is linked to more than 64,800 premature deaths in regions other than China, including more than 3,100 premature deaths in western Europe and the USA; on the other hand, consumption in western Europe and the USA is linked to more than 108,600 premature deaths in China. Our results reveal that the transboundary health impacts of PM2.5 pollution associated with international trade are greater than those associated with long-distance atmospheric pollutant transport.

A review and evaluation of nonroad diesel mobile machinery emission control in China.

China's emission control for nonroad diesel mobile machinery (NDMM) must deal with a fast increase in stock as well as regulations that are two decades behind those for on-road vehicles. This study provides the first large-scale review and evaluation of China's NDMM policies, along with emission measurements and an investigation on diesel fuel quality. The sulfur contents of the investigated diesel declined from 430 ppm (median value) in 2011 to 6-8 ppm during the 2017-2018 period. The emission control of NOx and PM greatly improved with the shift from the China II to China IV standards, as demonstrated by engine tests and field NOx measurements. However, the NOx emission factors for non-type-approved engines were approximately twice the limits of the China II standards. Emission compliance based on bench tests was not sufficient to control actual emissions because the field-measured NOx emission factors of all machinery ranged from 24% to 225% greater than the respective emission limits for the engines. These circumstances adversely affected the effectiveness of the regulations and policies for China's emission control of NDMM. Nevertheless, the policies on new and in-use NDMM, as well as diesel fuel quality, prevented NOx and PM emissions amounting to 4.4 Tg and 297.8 Gg during the period 2008-2017, respectively. The emission management strategy contributed to enhancing the international competitiveness of China's NDMM industries by promoting advanced technologies. For effective NDMM emission control in the future, portable testing and noncontact remote supervision should be strengthened; also, the issue of noncompliant diesel should be addressed through rigorous control measures and financial penalties.

Tracking PM2.5 and O3 Pollution and the Related Health Burden in China 2013-2020.

Based on the exposure data sets from the Tracking Air Pollution in China (TAP, http://tapdata.org.cn/), we characterized the spatiotemporal variations in PM2.5 and O3 exposures and quantified the long- and short-term exposure related premature deaths during 2013-2020 with respect to the two-stage clean air actions (2013-2017 and 2018-2020). We find a 48% decrease in national PM2.5 exposure during 2013-2020, although the decrease rate has slowed after 2017. At the same time, O3 pollution worsened, with the average April-September O3 exposure increased by 17%. The improved air quality led to 308 thousand and 16 thousand avoided long- and short-term exposure related deaths, respectively, in 2020 compared to the 2013 level, which was majorly attributed to the reduction in ambient PM2.5 concentration. It is also noticed that with smaller PM2.5 reduction, the avoided long-term exposure associated deaths in 2017-2020 (13%) was greater than that in 2013-2017 (9%), because the exposure-response curve is nonlinear. As a result of the efforts in reducing PM2.5-polluted days with the daily average PM2.5 higher than 75 µg/m3 and the considerable increase in O3-polluted days with the daily maximum 8 h average O3 higher than 160 µg/m3, deaths attributable to the short-term O3 exposure were greater than those due to PM2.5 exposure since 2018. Future air quality improvement strategies for the coordinated control of PM2.5 and O3 are urgently needed.

Comprehensive Assessment for the Impacts of S/IVOC Emissions from Mobile Sources on SOA Formation in China.

Semivolatile/intermediate-volatility organic compounds (S/IVOCs) from mobile sources are essential SOA contributors. However, few studies have comprehensively evaluated the SOA contributions of S/IVOCs by simultaneously comparing different parameterization schemes. This study used three SOA schemes in the CMAQ model with a measurement-based emission inventory to quantify the mobile source S/IVOC-induced SOA (MS-SI-SOA) for 2018 in China. Among different SOA schemes, SOA predicted by the 2D-VBS scheme was in the best agreement with observations, but there were still large deviations in a few regions. Three SOA schemes showed the peak value of annual average MS-SI-SOA was up to 0.6 ± 0.3 µg/m3. High concentrations of MS-SI-SOA were detected in autumn, while the notable relative contribution of MS-SI-SOA to total SOA was predicted in the coastal areas in summer, with a regional average contribution up to 20 ± 10% in Shanghai. MS-SI-SOA concentrations varied by up to 2 times among three SOA schemes, mainly due to the discrepancy in SOA precursor emissions and chemical reactions, suggesting that the differences between SOA schemes should also be considered in modeling studies. These findings identify the hotspot areas and periods for MS-SI-SOA, highlighting the importance of S/IVOC emission control in the future upgrading of emission standards.

Primary nature of brown carbon absorption in a frigid atmosphere with strong haze chemistry.

Severe haze hovered over Harbin during the heating season of 2019-2020, making it one of the ten most polluted Chinese cities in January of 2020. Here we focused on the optical properties and sources of brown carbon (BrC) during the extreme atmospheric pollution periods. Enhanced formation of secondary BrC (BrCsec) was evident as relative humidity (RH) became higher, accompanied with a decrease of ozone but concurrent increases of aerosol water content and secondary inorganic aerosols. These features were generally similar to the characteristics of haze chemistry observed during winter haze events in the North China Plain, and indicated that heterogeneous reactions involving aerosol water might be at play in the formation of BrCsec, despite the low temperatures in Harbin. Although BrCsec accounted for a substantial fraction of brown carbon mass, its contribution to BrC absorption was much smaller (6 vs. 28%), pointing to a lower mass absorption efficiency (MAE) of BrCsec compared to primary BrC. In addition, emissions of biomass burning BrC (BrCBB) were inferred to increase with increasing RH, coinciding with a large drop of temperature. Since both the less absorbing BrCsec and the more absorbing BrCBB increased as RH became higher, the MAE of total BrC were largely unchanged throughout the measurement period. This study unfolded the contrast in the source apportionment results of BrC mass and absorption, and could have implications for the simulation of radiative forcing by brown carbon.

Impacts of climate change on future air quality and human health in China.

In recent years, air pollution has caused more than 1 million deaths per year in China, making it a major focus of public health efforts. However, future climate change may exacerbate such human health impacts by increasing the frequency and duration of weather conditions that enhance air pollution exposure. Here, we use a combination of climate, air quality, and epidemiological models to assess future air pollution deaths in a changing climate under Representative Concentration Pathway 4.5 (RCP4.5). We find that, assuming pollution emissions and population are held constant at current levels, climate change would adversely affect future air quality for >85% of China's population (∼55% of land area) by the middle of the century, and would increase by 3% and 4% the population-weighted average concentrations of fine particulate matter (PM2.5) and ozone, respectively. As a result, we estimate an additional 12,100 and 8,900 Chinese (95% confidence interval: 10,300 to 13,800 and 2,300 to 14,700, respectively) will die per year from PM2.5 and ozone exposure, respectively. The important underlying climate mechanisms are changes in extreme conditions such as atmospheric stagnation and heat waves (contributing 39% and 6%, respectively, to the increase in mortality). Additionally, greater vulnerability of China's aging population will further increase the estimated deaths from PM2.5 and ozone in 2050 by factors of 1 and 3, respectively. Our results indicate that climate change and more intense extremes are likely to increase the risk of severe pollution events in China. Managing air quality in China in a changing climate will thus become more challenging.

Drivers of improved PM2.5 air quality in China from 2013 to 2017.

From 2013 to 2017, with the implementation of the toughest-ever clean air policy in China, significant declines in fine particle (PM2.5) concentrations occurred nationwide. Here we estimate the drivers of the improved PM2.5 air quality and the associated health benefits in China from 2013 to 2017 based on a measure-specific integrated evaluation approach, which combines a bottom-up emission inventory, a chemical transport model, and epidemiological exposure-response functions. The estimated national population-weighted annual mean PM2.5 concentrations decreased from 61.8 (95%CI: 53.3-70.0) to 42.0 µg/m3 (95% CI: 35.7-48.6) in 5 y, with dominant contributions from anthropogenic emission abatements. Although interannual meteorological variations could significantly alter PM2.5 concentrations, the corresponding effects on the 5-y trends were relatively small. The measure-by-measure evaluation indicated that strengthening industrial emission standards (power plants and emission-intensive industrial sectors), upgrades on industrial boilers, phasing out outdated industrial capacities, and promoting clean fuels in the residential sector were major effective measures in reducing PM2.5 pollution and health burdens. These measures were estimated to contribute to 6.6- (95% CI: 5.9-7.1), 4.4- (95% CI: 3.8-4.9), 2.8- (95% CI: 2.5-3.0), and 2.2- (95% CI: 2.0-2.5) µg/m3 declines in the national PM2.5 concentration in 2017, respectively, and further reduced PM2.5-attributable excess deaths by 0.37 million (95% CI: 0.35-0.39), or 92% of the total avoided deaths. Our study confirms the effectiveness of China's recent clean air actions, and the measure-by-measure evaluation provides insights into future clean air policy making in China and in other developing and polluting countries.

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.

Air quality and health benefits of China's current and upcoming clean air policies.

China is currently in a crucial stage of air pollution control and has intensive clean air policies. Past strict policies have demonstrated remarkable effectiveness in emission control and fine particulate matter (PM2.5) pollution mitigation; however, it is not clear what the continuous benefits of current policies are for the future. Here, we summarize China's currently implemented, released, and upcoming clean air policies and estimate the air quality and health benefits of the implementation of these policies until 2030. We found that China's current and upcoming clean air policies could reduce major pollutant emissions by 14.3-70.5% under continued socio-economic growth from 2010 to 2030. These policies could decrease the national population-weighted PM2.5 concentrations from 61.6 µg m-3 in 2010 to 26.4 µg m-3 in 2030 (57.2% reduction). These air quality improvements will ensure that over 80% of the population lives in areas with PM2.5 levels below the current annual PM2.5 air quality standard (i.e., 35 µg m-3) and will avoid 95.0 (95% CI, 76.3, 104.2) thousand premature deaths in 2030. We also point out several inadequacies of current clean air policies, suggesting that more ambitious control actions are needed to better protect public health with an increasing ageing population. Our findings could provide quantitative insights that can be used to better address air pollution issues in China and other developing countries.

Tracking Air Pollution in China: Near Real-Time PM2.5 Retrievals from Multisource Data Fusion.

Air pollution has altered the Earth's radiation balance, disturbed the ecosystem, and increased human morbidity and mortality. Accordingly, a full-coverage high-resolution air pollutant data set with timely updates and historical long-term records is essential to support both research and environmental management. Here, for the first time, we develop a near real-time air pollutant database known as Tracking Air Pollution in China (TAP, http://tapdata.org.cn/) that combines information from multiple data sources, including ground observations, satellite aerosol optical depth (AOD), operational chemical transport model simulations, and other ancillary data such as meteorological fields, land use data, population, and elevation. Daily full-coverage PM2.5 data at a spatial resolution of 10 km is our first near real-time product. The TAP PM2.5 is estimated based on a two-stage machine learning model coupled with the synthetic minority oversampling technique and a tree-based gap-filling method. Our model has an averaged out-of-bag cross-validation R2 of 0.83 for different years, which is comparable to those of other studies, but improves its performance at high pollution levels and fills the gaps in missing AOD on daily scale. The full coverage and near real-time updates of the daily PM2.5 data allow us to track the day-to-day variations in PM2.5 concentrations over China in a timely manner. The long-term records of PM2.5 data since 2000 will also support policy assessments and health impact studies. The TAP PM2.5 data are publicly available through our website for sharing with the research and policy communities.

Reduced carbon emission estimates from fossil fuel combustion and cement production in China.

Nearly three-quarters of the growth in global carbon emissions from the burning of fossil fuels and cement production between 2010 and 2012 occurred in China. Yet estimates of Chinese emissions remain subject to large uncertainty; inventories of China's total fossil fuel carbon emissions in 2008 differ by 0.3 gigatonnes of carbon, or 15 per cent. The primary sources of this uncertainty are conflicting estimates of energy consumption and emission factors, the latter being uncertain because of very few actual measurements representative of the mix of Chinese fuels. Here we re-evaluate China's carbon emissions using updated and harmonized energy consumption and clinker production data and two new and comprehensive sets of measured emission factors for Chinese coal. We find that total energy consumption in China was 10 per cent higher in 2000-2012 than the value reported by China's national statistics, that emission factors for Chinese coal are on average 40 per cent lower than the default values recommended by the Intergovernmental Panel on Climate Change, and that emissions from China's cement production are 45 per cent less than recent estimates. Altogether, our revised estimate of China's CO2 emissions from fossil fuel combustion and cement production is 2.49 gigatonnes of carbon (2 standard deviations = ±7.3 per cent) in 2013, which is 14 per cent lower than the emissions reported by other prominent inventories. Over the full period 2000 to 2013, our revised estimates are 2.9 gigatonnes of carbon less than previous estimates of China's cumulative carbon emissions. Our findings suggest that overestimation of China's emissions in 2000-2013 may be larger than China's estimated total forest sink in 1990-2007 (2.66 gigatonnes of carbon) or China's land carbon sink in 2000-2009 (2.6 gigatonnes of carbon).

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.

Variation characteristics of fine particulate matter and its components in diesel vehicle emission plumes.

A rapid reaction occurs near the exhaust nozzle when vehicle emissions contact the air. Twenty diesel vehicles were studied using a new multipoint sampling system that is suitable for studying the exhaust plume near the exhaust nozzle. The variation characteristics of fine particle matter (PM2.5) and its components in diesel vehicle exhaust plumes were analyzed. The PM2.5 emissions gradually increased with increasing distance from the nozzle in the plume. Elemental carbon emissions remained basically unchanged, organic carbon and total carbon (TC) increased with increasing distance. The concentrations of SO42-, NO3- and NH4+ (SNA) directly emitted by the vehicles were very low but increased rapidly in the exhaust plume. The selective catalytic reduction (SCR) reduced 42.7% TC, 40% NO3- emissions, but increased 104% SO42- and 36% NH4+ emissions, respectively. In summary, the SCR reduced 29% primary PM2.5 emissions for the tested diesel vehicles. The NH4NO3 particle formation maybe more important in the plume, and there maybe other forms of formation of NH4+ (eg. NH4Cl). The generation of secondary organic carbon (SOC) plays a leading role in the generation of secondary PM2.5. The SCR enhanced the formation of SOC and SNA in the plume, but comprehensive analysis shows that the SCR more enhanced the SNA formation in the plume, which is mainly new particles formation process. The inconsistency between secondary organic aerosol (SOA) and primary organic aerosol definitions is one of the important reasons for the difference between SOA simulation and observation.

Source-Receptor Relationship Revealed by the Halted Traffic and Aggravated Haze in Beijing during the COVID-19 Lockdown.

The COVID-19 outbreak greatly limited human activities and reduced primary emissions particularly from urban on-road vehicles but coincided with Beijing experiencing "pandemic haze," raising the public concerns about the effectiveness of imposed traffic policies to improve the air quality. This paper explores the relationship between local vehicle emissions and the winter haze in Beijing before and during the COVID-19 lockdown based on an integrated analysis framework, which combines a real-time on-road emission inventory, in situ air quality observations, and a localized numerical modeling system. We found that traffic emissions decreased substantially during the COVID-19 pandemic, but its imbalanced emission abatement of NOx (76%, 125.3 Mg/day) and volatile organic compounds (VOCs, 53%, 52.9 Mg/day) led to a significant rise of atmospheric oxidants in urban areas, resulting in a modest increase in secondary aerosols due to inadequate precursors, which still offset reduced primary emissions. Moreover, the enhanced oxidizing capacity in the surrounding regions greatly increased the secondary particles with relatively abundant precursors, which was transported into Beijing and mainly responsible for the aggravated haze pollution. We recommend that mitigation policies should focus on accelerating VOC emission reduction and synchronously controlling regional sources to release the benefits of local traffic emission control.

Intermediate-Volatility Organic Compound Emissions from Nonroad Construction Machinery under Different Operation Modes.

Intermediate-volatility organic compounds (IVOCs) have been found as important sources for secondary organic aerosol (SOA) formation. IVOC emissions from nonroad construction machineries (NRCMs), including two road rollers and three motor graders, were characterized under three operation modes using an improved portable emission measurement system. The fuel-based IVOC emission factors (EFs) of NRCMs varied from 245.85 to 1802.19 mg/kg·fuel, which were comparable at magnitudes to the reported results of an ocean-going ship and on-road diesel vehicles without filters. The discrepancy of IVOC EFs is significant within different operation modes. IVOC EFs under the idling mode were 1.24-3.28 times higher than those under moving/working modes. Unspeciated b-alkanes and cyclic compounds, which were the unresolved components in IVOCs at the molecular level, accounted for approximately 91% of total IVOCs from NRCMs. The SOA production potential analysis shows that IVOCs dominated SOA formation of NRCMs. Our results demonstrate that IVOC emissions from NRCMs are non-negligible. Thus, an accurate estimation of their IVOC emissions would benefit the understanding of SOA formation in the urban atmosphere.

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.

Physicochemical analysis of individual atmospheric fine particles based on effective surface-enhanced Raman spectroscopy.

Fine particles associated with haze pollution threaten the health of more than 400 million people in China. It is therefore of great importance to thoroughly investigate and understand their composition. To determine the physicochemical properties in atmospheric fine particles at the micrometer level, we described a sensitive and feasible surface-enhanced Raman scattering (SERS) method using Ag foil as a substrate. This novel method enhanced the Raman signal intensities up to 10,000 a.u. for ν(NO3-) in fine particles. The SERS effect of Ag foil was further studied experimentally and theoretically and found to have an enhancement factor of the order of ~104. Size-fractionated real particle samples with aerodynamic diameters of 0.4-2.5 µm were successfully collected on a heavy haze day, allowing ready observation of morphology and identification of chemical components, such as soot, nitrates, and sulfates. These results suggest that the Ag-foil-based SERS technique can be effectively used to determine the microscopic characteristics of individual fine particles, which will help to understand haze formation mechanisms and formulate governance policies.