Dark NO2 Reduction on a Graphene Surface with Implications for Soot Aging and HONO Formation.

Soot, primarily composed of elemental carbon (EC) and organic carbon (OC), is ubiquitous in PM2.5. In the atmosphere, the heterogeneous interaction between NO2 and soot is not only an important pathway driving soot aging but also of central importance to nitrous acid (HONO) formation. It is commonly believed that the surface redox reaction between reductive OC and NO2 dominates the night aging of soot and the conversion of NO2 to HONO. However, completely differing from the currently popular explanation, we find here that the redox reaction between EC and NO2 can also drive the conversion of NO2 to HONO during soot aging. By combining in situ experiments with density functional theory (DFT) calculations, we proposed that the surface carbon vacancy defects on graphite/graphene-like EC should be a type of potential primary adsorption and reactive sites inducing the heterogeneous reduction of NO2. We suggested a new mechanism that NO2 is reduced to form HONO on surface vacancy defects through the splitting of H2O molecules, and the carbon atoms adjacent to surface vacancy are simultaneously oxidized to form hydroxyl-functionalized EC. This novel finding provides insights into the chemical mechanism driving the NO2-to-HONO conversion and rapid soot aging, which expands our knowledge of the heterogeneous chemistry of soot in the atmosphere.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br-) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br-, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton-electron transfer process at the air-water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br- and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm-2 ⋅ s-1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br- activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br- activation. Our findings highlight the crucial role of the proton-electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br- by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.

Clonal hematopoiesis of indeterminate potential in patients with immunoglobulin light-chain AL amyloidosis.

ABSTRACT: Immunoglobulin light-chain (AL) amyloidosis is characterized by the deposition of misfolded monoclonal free light chains, with cardiac complications accounting for patient mortality. Clonal hematopoiesis of indeterminate potential (CHIP) has been associated with worse cardiovascular outcomes in the general population. Its significance in AL amyloidosis remains unclear. We collected clinical information and outcome data on 76 patients with a diagnosis of AL amyloidosis who underwent deep targeted sequencing for myeloid neoplasia-associated mutations between April 2018 and August 2023. Variant allele frequency was set at 2% to call CHIP-associated mutations. CHIP mutations were present in patients with AL amyloidosis at a higher frequency compared with age-matched control individuals. Sixteen patients (21%) had at least 1 CHIP mutation. DNMT3A was the most frequent mutation (7/16; 44%). Compared with patients without CHIP, patients with CHIP had a higher prevalence of t(11;14) translocation (69% vs 25%, respectively; P = .004). Furthermore, among patients with renal involvement, those with CHIP had a lower Palladini renal stage (P = .001). At a median follow-up of 32.5 months, the presence of CHIP was not associated with worse overall survival or major organ dysfunction progression-free survival. Larger studies and longer follow-up are needed to better define the impact of CHIP in patients with AL amyloidosis.

Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols.

We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 µg·h-1 at 72% RH and 1.33 × 10-4 µg·h-1 at 81% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.

Nonlinear effect of NOx concentration decrease on secondary aerosol formation in the Beijing-Tianjin-Hebei region: Evidence from smog chamber experiments and field observations.

During the COVID-19 lockdown in the Beijing-Tianjin-Hebei (BTH) region in China, large decrease in nitrogen oxides (NOx) emissions, especially in the transportation sector, could not avoid the occurrence of heavy PM2.5 pollution where nitrate dominated the PM2.5 mass increase. To experimentally reveal the effect of NOx control on the formation of PM2.5 secondary components (nitrate in particular), photochemical simulation experiments of mixed volatile organic compounds (VOCs) under various NOx concentrations with smog chamber were performed. The proportions of gaseous precursors in the control experiment were comparable to ambient conditions typically observed in the BTH region. Under relatively constant VOCs concentrations, when the initial NOx concentration was reduced to 40% of that in the control experiment (labelled as NOx,0), the particle mass concentration was not significantly reduced, but when the initial NOx concentration decreased to 20 % of NOx,0, the mass concentration of particles as well as nitrate and organics showed a sudden decrease. A "critical point" where the mass concentration of secondary aerosol started to decline as the initial NOx concentration decreased, located at 0.2-0.4 NOx,0 (or 0.18-0.44 NO2,0) in smog chamber experiments. The oxidation capacity and solar radiation intensity played key roles in the mass concentration and compositions of the formed particles. In field observations in the BTH region in the autumn and winter seasons, the "critical point" exist at 0.15-0.34 NO2,0, which coincided mostly with the laboratory simulation results. Our results suggest that a reduction of NOx emission by >60% could lead to significant reductions of secondary aerosol formation, which can be an effective way to further alleviate PM2.5 pollution in the BTH region.

Insights into the Peroxide-Bicyclic Intermediate Pathway of Aromatic Photooxidation: Experimental Yields and NOx-Dependency of Ring-Opening and Ring-Retaining Products.

Aromatic hydrocarbons are important contributors to the formation of ozone and secondary organic aerosols in urban environments. The different parallel pathways in aromatic oxidation, however, remain inadequately understood. Here, we investigated the production yields and chemical distributions of gas-phase tracer products during the photooxidation of alkylbenzenes at atmospheric OH levels with NOx present using high-resolution mass spectrometers. The peroxide-bicyclic intermediate pathway emerged as the major pathway in aromatic oxidation, accounting for 52.1 ± 12.6%, 66.1 ± 16.6%, and 81.4 ± 24.3% of the total OH oxidation of toluene, m-xylene, and 1,3,5-trimethylbenzene, respectively. Notably, the yields of bicyclic nitrates produced from the reactions of bicyclic peroxy radicals (BPRs) with NO were considerably lower (3-5 times) than what the current mechanism predicted. Alongside traditional ring-opening products formed through the bicyclic pathway (dicarbonyls and furanones), we identified a significant proportion of carbonyl olefinic acids generated via the 1,5-aldehydic H-shift occurring in subsequent reactions of BPRs + NO, contributing 4-7% of the carbon flow in aromatic oxidation. Moreover, the observed NOx-dependencies of ring-opening and ring-retaining product yields provide insights into the competitive nature of reactions involving BPRs with NO, HO2, and RO2, which determine the refined product distributions and offer an explanation for the discrepancies between the experimental and model-based results.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 µg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Characterizing dry mass and volume changes in human multiple myeloma cells upon treatment with proteotoxic and genotoxic drugs.

Multiple myeloma (MM) is a cancer of terminally differentiated plasma cells. MM remains incurable, but overall survival of patients has progressively increased over the past two decades largely due to novel agents such as proteasome inhibitors (PI) and the immunomodulatory agents. While these therapies are highly effective, MM patients can be de novo resistant and acquired resistance with prolonged treatment is inevitable. There is growing interest in early, accurate identification of responsive versus non-responsive patients; however, limited sample availability and need for rapid assays are limiting factors. Here, we test dry mass and volume as label-free biomarkers to monitor early response of MM cells to treatment with bortezomib, doxorubicin, and ultraviolet light. For the dry mass measurement, we use two types of phase-sensitive optical microscopy techniques: digital holographic tomography and computationally enhanced quantitative phase microscopy. We show that human MM cell lines (RPMI8226, MM.1S, KMS20, and AMO1) increase dry mass upon bortezomib treatment. This dry mass increase after bortezomib treatment occurs as early as 1 h for sensitive cells and 4 h for all tested cells. We further confirm this observation using primary multiple myeloma cells derived from patients and show that a correlation exists between increase in dry mass and sensitivity to bortezomib, supporting the use of dry mass as a biomarker. The volume measurement using Coulter counter shows a more complex behavior; RPMI8226 cells increase the volume at an early stage of apoptosis, but MM.1S cells show the volume decrease typically observed with apoptotic cells. Altogether, this cell study presents complex kinetics of dry mass and volume at an early stage of apoptosis, which may serve as a basis for the detection and treatment of MM cells.

Synergistic Effects of SO2 and NH3 Coexistence on SOA Formation from Gasoline Evaporative Emissions.

Vehicular evaporative emissions make an increasing contribution to anthropogenic sources of volatile organic compounds (VOCs), thus contributing to secondary organic aerosol (SOA) formation. However, few studies have been conducted on SOA formation from vehicle evaporative VOCs under complex pollution conditions with the coexistence of NOx, SO2, and NH3. In this study, the synergistic effects of SO2 and NH3 on SOA formation from gasoline evaporative VOCs with NOx were examined using a 30 m3 smog chamber with the aid of a series of mass spectrometers. Compared with the systems involving SO2 or NH3 alone, SO2 and NH3 coexistence had a greater promotion effect on SOA formation, which was larger than the cumulative effect of the two promotions alone. Meanwhile, contrasting effects of SO2 on the oxidation state (OSc) of SOA in the presence or absence of NH3 were observed, and SO2 could further increase the OSc with the coexistence of NH3. The latter was attributed to the synergistic effects of SO2 and NH3 coexistence on SOA formation, wherein N-S-O adducts can be formed from the reaction of SO2 with N-heterocycles generated in the presence of NH3. Our study contributes to the understanding of SOA formation from vehicle evaporative VOCs under highly complex pollution conditions and its atmospheric implications.

Photocatalytic Oxidation of NO2 on TiO2 : Evidence of a New Source of N2 O5.

N2 O5 is an important intermediate in the atmospheric nitrogen cycle. Using a flow tube reactor, N2 O5 was found to be released from the TiO2 surface during the photocatalytic oxidation of NO2 , revealing a previously unreported source of N2 O5 . The rate of N2 O5 release from TiO2 was dependent on the initial NO2 concentration, relative humidity, O2 /N2 ratio, and irradiation intensity. Experimental evidence and quantum chemical calculations showed that NO2 can react with the surface hydroxyl groups and the generated electron holes on the TiO2 , followed by combining with another NO2 molecule to form N2 O5 . The latter was physisorbed on TiO2 and had a low adsorption energy of -0.13 eV. Box model simulations indicated that the new source of N2 O5 released from TiO2 can increase the daytime N2 O5 concentration by up to 20 % in urban areas if abundant TiO2 -containing materials and high NOx concentrations were present. This joint experimental/theoretical study not only demonstrates a new chemical mechanism for N2 O5 formation but also has important implications for air quality in urban areas.

[Research Progress of SOA Formation from Anthropogenic VOCs Under Complex Pollution Condition].

Although the air quality in China has been greatly improved in recent years, the air pollution remains severe. The annual mean PM2.5 concentrations have not met the second grade of the National Ambient Air Quality Standards in China and are still much higher than the guideline value of the World Health Organization. Thus, the PM2.5 concentration needs to be further reduced. Secondary organic aerosol (SOA) is an important component of PM2.5 and has an important impact on air quality, global climate change, and human health. Therefore, understanding the formation mechanism of SOA is an important basis to control SOA and further reduce PM2.5. As an important precursor of SOA, volatile organic compounds (VOCs) can be oxidized by oxidants such as ·OH, NO3[KG-*2/3]·, Cl·, and O3 to generate low volatile organic compounds and further to form SOA through gas-particle partitioning, homogeneous nucleation, aqueous phase reaction, and heterogeneous reaction processes. The formation of SOA can be affected by many factors, such as the types and initial concentrations of VOCs, VOCs/NOx ratios, relative humidity (RH), temperature (T), seed aerosols, oxidants, aqueous phase process, and photochemical process. The observed SOA concentration is always underestimated by air quality models because a comprehensive understanding of the complexity of SOA chemical composition and formation mechanisms is still lacking, especially that under the highly complex air pollution conditions in China. Therefore, the formation mechanism and influencing factors of SOA under highly complex air pollution conditions have become an important concern in the field of atmospheric sciences. Recently, much laboratory work has focused on the formation of SOA under complex conditions. The research progress of SOA formation from different anthropogenic VOCs are reviewed here, and the methods used and the impact of different influencing factors on SOA formation are introduced. Finally, the key scientific issues that exist in the research of the SOA mechanism at present are put forward, and the future research direction is projected.

Insight into the Mechanism and Kinetics of the Heterogeneous Reaction between SO2 and NO2 on Diesel Black Carbon under Light Irradiation.

The heterogeneous oxidation of SO2 by NO2 has been extensively proposed as an important pathway of sulfate production during haze events in China. However, the kinetics and mechanism of oxidation of SO2 by NO2 on the surface of complex particles remain poorly understood. Here, we systematically explore the mechanism and kinetics of the reaction between SO2 and NO2 on diesel black carbon (DBC) under light irradiation. The experimental results prove that DBC photochemistry can not only significantly promote the heterogeneous reduction of NO2 to produce HONO via transferring photoinduced electrons but also indirectly promote OH radical formation. These reduction products of NO2 as well as NO2 itself greatly promote the heterogeneous oxidation of SO2 on DBC. NO2 oxidation, HONO oxidation, and the surface photo-oxidation process are proven to be three major surface oxidation pathways of SO2. The kinetics results indicate that the surface photooxidation pathway accounts for the majority of the total SO2 uptake (∼63%), followed by the HONO oxidation pathway (∼27%) and direct oxidation by NO2 (∼10%). This work highlights the significant synergistic roles of DBC, NO2, and light irradiation in enhancing the atmospheric oxidation capacity and promoting the heterogeneous formation of sulfate.

Mutations in the alternative complement pathway in multiple myeloma patients with carfilzomib-induced thrombotic microangiopathy.

Thrombotic microangiopathy (TMA) has been reported to occur in multiple myeloma (MM) patients in association with treatment with carfilzomib, an irreversible proteasome inhibitor (PI). The hallmark of TMA is vascular endothelial damage leading to microangiopathic hemolytic anemia, platelet consumption, fibrin deposition and small-vessel thrombosis with resultant tissue ischemia. The molecular mechanisms underlying carfilzomib-associated TMA are not known. Germline mutations in the complement alternative pathway have been recently shown to portend increased risk for the development of atypical hemolytic uremic syndrome (aHUS) and TMA in the setting of allogeneic stem cell transplant in pediatric patients. We hypothesized that germline mutations in the complement alternative pathway may similarly predispose MM patients to carfilzomib-associated TMA. We identified 10 MM patients with a clinical diagnosis of TMA in the context of carfilzomib treatment and assessed for the presence of germline mutations in the complement alternative pathway. Ten, matched MM patients exposed to carfilzomib but without clinical TMA were used as negative controls. We identified a frequency of deletions in the complement Factor H genes 3 and 1 (delCFHR3-CFHR1) and genes 1 and 4 (delCFHR1-CFHR4) in MM patients with carfilzomib-associated TMA that was higher as compared to the general population and matched controls. Our data suggest that complement alternative pathway dysregulation may confer susceptibility to vascular endothelial injury in MM patients and predispose to development of carfilzomib-associated TMA. Larger, retrospective studies are needed to evaluate whether screening for complement mutations may be indicated to properly counsel patients about TMA risk with carfilzomib use.

Titanium Dioxide Promotes New Particle Formation: A Smog Chamber Study.

TiO2 is a widely used material in building coatings. Many studies have revealed that TiO2 promotes the heterogeneous oxidation of SO2 and the subsequent sulfate formation. However, whether and how much TiO2 contributes to the gaseous H2SO4 and subsequent new particle formation (NPF) still remains unclear. Herein, we used a 1 m3 quartz smog chamber to investigate NPF in the presence of TiO2. The experimental results indicated that TiO2 could greatly promote NPF. The increases in particle formation rate (J) and growth rate due to the presence of TiO2 were quantified, and the promotion effect was attributed to the production of gaseous H2SO4. The promotion effect of TiO2 on SO2 oxidation and subsequent NPF decreased gradually due to the formation of surface sulfate but did not disappear completely, instead partly recovering after washing with water. Moreover, the promotion effect of TiO2 on NPF was observed regardless of differences in RH, and the most significant promotion effect of TiO2 associated with the strongest NPF occurred at an RH of 20%. Based on the experimental evidence, the environmental impact of TiO2 on gaseous H2SO4 and particle pollution in urban areas was estimated.

Formation mechanisms and atmospheric implications of summertime nitrous acid (HONO) during clean, ozone pollution and double high-level PM2.5 and O3 pollution periods in Beijing.

Nitrous acid (HONO) is a key precursor of the hydroxyl radicals (OH) and has a significant impact on air quality. Nowadays, the source of HONO is still controversial due to its complex formation mechanisms, which is widely explored in extensive field and laboratory studies. In this study, the pollution characteristics and source contribution of HONO under different air quality conditions in summer in Beijing were analyzed. The observation periods were classified as three typical periods: clean, ozone pollution, and double high pollution (co-occurrence of high PM2.5 and O3 concentrations). The average concentrations of observed HONO were 0.38 ± 0.35 ppb, 0.21 ± 0.18 ppb, 0.26 ± 0.20 ppb and 0.54 ± 0.45 ppb during the whole, clean, ozone and double high periods, respectively. The elevated HONO levels at night were attributed to vehicle emissions and the RH-dependent heterogeneous conversion of NO2 to HONO. The average emission ratio (HONO/NOx) was 0.85 % ± 0.38 %, and the mean value of calculated nocturnal NO2 to HONO conversion frequency was 0.0076 ± 0.0031 h-1. Based on daytime HONO budget analysis, the largest potential source of HONO was the homogeneous reaction of NO and OH (0.33 and 0.34 ppb h-1), followed by the unknown source (0.11 and 0.21 ppb h-1) during clean and ozone periods, while the unknown source (0.49 ppb h-1) played the predominant role during double high period. The unknown sources of HONO could be attributed to the photo-enhanced heterogeneous conversion of NO2 and the photolysis of particulate nitrate. Furthermore, the photolysis of ozone (0.17, 0.34 and 0.44 ppb h-1) was the major contributor to primary OH during three typical periods. HONO photolysis contributed considerable amounts of primary OH (0.32 ppb h-1) during double high period. These results are helpful to further understand the linkage between HONO and air quality variation.

Smog Chamber Study on the Role of NOx in SOA and O3 Formation from Aromatic Hydrocarbons.

China is facing dual pressures to reduce both PM2.5 and O3 pollution, the crucial precursors of which are NOx and VOCs. In our study, the role of NOx in both secondary organic aerosol (SOA, the important constituent of PM2.5) and O3 formation was examined in our 30 m3 indoor smog chamber. As revealed in the present study, the NOx level can obviously affect the OH concentration and volatility distribution of gas-phase oxidation products and thus O3 and SOA formation. Reducing the NOx concentration to the NOx-sensitive regime can inhibit O3 formation (by 42%), resulting in the reduction of oxidation capacity, which suppresses the SOA formation (by 45%) by inhibiting the formation of O- and N-containing gas-phase oxidation products with low volatility. The contribution of these oxidation products to the formation of SOA was also estimated, and the results could substantially support the trend of SOA yield with NOx at different VOC levels. The atmospheric implications of NOx in the coordinated control of PM2.5 and O3 are also discussed.

Diesel soot photooxidation enhances the heterogeneous formation of H2SO4.

Both field observation and experimental simulation have implied that black carbon or soot plays a remarkable role in the catalytic oxidation of SO2 for the formation of atmospheric sulfate. However, the catalytic mechanism remains ambiguous, especially that under light irradiation. Here we systematically investigate the heterogeneous conversion of SO2 on diesel soot or black carbon (DBC) under light irradiation. The experimental results show that the presence of DBC under light irradiation can significantly promote the heterogeneous conversion of SO2 to H2SO4, mainly through the heterogeneous reaction between SO2 and photo-induced OH radicals. The detected photo-chemical behaviors on DBC suggest that OH radical formation is closely related to the abstraction and transfer of electrons in DBC and the formation of reactive superoxide radical (•O2-) as an intermediate. Our results extend the known sources of atmospheric H2SO4 and provide insight into the internal photochemical oxidation mechanism of SO2 on DBC.

Dramatic decrease of secondary organic aerosol formation potential in Beijing: Important contribution from reduction of coal combustion emission.

Secondary organic aerosol (SOA) formation originating from the emission of anthropogenic volatile organic compounds (VOCs) makes a significant contribution to fine particulate matter (PM2.5) pollution in urban areas. Investigation on the SOA formation potential (SOAFP) can help us understand the contribution of different sources to SOA formation. To characterize the SOAFP of ambient air from anthropogenic VOCs in the urban area of Beijing, field observation was implemented using a twin oxidation flow reactor (Twin-OFRs) system in the winters of 2016 and 2017. Compared to the winter of 2016, the seasonal-average SOAFP in the winter of 2017 was found to decrease by about 74% (18.6 to 4.9 µg/m3), which is more than that of PM1 (59%, 48.7 to 20.2 µg/m3), PM2.5 (61%, 114.4 to 44.8 µg/m3) and CO (57%, 2.1 to 0.9 mg/m3) that mainly comes from the combustion of fossil fuels, suggesting complex affecting factors on SOAFP. The results of wind decomposition mathematical modeling showed that anthropogenic factors and favorable meteorological conditions both contributed significantly to the decrease in SOAFP. The reduction of emissions from scatter coal combustion, which is the key VOCs source for SOAFP, is probably the most important anthropogenic factor affecting SOAFP. In the winter of 2016, the ratio of benzene to toluene is 1.45 that was close to 1.54 representing coal combustion emission; however, it decreased dramatically to 1.05 in the winter of 2017, suggesting considerable reduction of VOC emissions from scatter coal combustion in the latter year due to the coal-to-gas transition in Beijing and surrounding regions. The SOAFP measured in this study considers all ambient VOCs that can react with OH radical, providing another representative method for estimating it. These results could be beneficial to understanding the factors driving SOAFP and its contribution to PM2.5, especially in regions with high-intensity anthropogenic emissions. Synopsis: This study reported the sharp decline of secondary organic aerosol formation potential (SOAFP) between two consecutive winters in Beijing and analyzed the reasons.