Identifying Driving Factors of Atmospheric N2O5 with Machine Learning.

Dinitrogen pentoxide (N2O5) plays an essential role in tropospheric chemistry, serving as a nocturnal reservoir of reactive nitrogen and significantly promoting nitrate formations. However, identifying key environmental drivers of N2O5 formation remains challenging using traditional statistical methods, impeding effective emission control measures to mitigate NOx-induced air pollution. Here, we adopted machine learning assisted by steady-state analysis to elucidate the driving factors of N2O5 before and during the 2022 Winter Olympics (WO) in Beijing. Higher N2O5 concentrations were observed during the WO period compared to the Pre-Winter-Olympics (Pre-WO) period. The machine learning model accurately reproduced ambient N2O5 concentrations and showed that ozone (O3), nitrogen dioxide (NO2), and relative humidity (RH) were the most important driving factors of N2O5. Compared to the Pre-WO period, the variation in trace gases (i.e., NO2 and O3) along with the reduced N2O5 uptake coefficient was the main reason for higher N2O5 levels during the WO period. By predicting N2O5 under various control scenarios of NOx and calculating the nitrate formation potential from N2O5 uptake, we found that the progressive reduction of nitrogen oxides initially increases the nitrate formation potential before further decreasing it. The threshold of NOx was approximately 13 ppbv, below which NOx reduction effectively reduced the level of night-time nitrate formations. These results demonstrate the capacity of machine learning to provide insights into understanding atmospheric nitrogen chemistry and highlight the necessity of more stringent emission control of NOx to mitigate haze pollution.

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

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

Nitrate Radicals Suppress Biogenic New Particle Formation from Monoterpene Oxidation.

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.

Direct field evidence of autocatalytic iodine release from atmospheric aerosol.

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICl] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICl and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICl and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.

Health risks and sources of trace elements and black carbon in PM2.5 from 2019 to 2021 in Beijing.

A comprehensive health risk assessment of PM2.5 is meaningful to understand the current status and directions regarding further improving air quality from the perspective of human health. In this study, we evaluated the health risks of PM2.5 as well as highly toxic inorganic components, including heavy metals (HMs) and black carbon (BC) based on long-term observations in Beijing from 2019 to 2021. Our results showed that the relative risks of chronic obstructive pulmonary disease, lung cancer, acute lower respiratory tract infection, ischemic heart disease, and stroke decreased by 4.07%-9.30% in 2020 and 2.12%-6.70% in 2021 compared with 2019. However, they were still at high levels ranging from 1.26 to 1.77, in particular, stroke showed the highest value in 2021. Mn had the highest hazard quotient (HQ, from 2.18 to 2.56) for adults from 2019 to 2021, while Ni, Cr, Pb, As, and BC showed high carcinogenic risks (CR > 1.0×10-6) for adults. The HQ values of Mn and As and the CR values of Pb and As showed constant or slight upwards trends during our observations, which is in contrast to the downward trends of other HMs and PM2.5. Mn, Cr, and BC are crucial toxicants in PM2.5. A significant shrink of southern region sourcesof HMs and BCshrank suggests the increased importance of local sources. Industry, dust, and biomass burning are the major contributors to the non-carcinogenic risks, while traffic emissions and industry are the dominant contributors to the carcinogenic risks in Beijing.

Reactive Chlorine Species Advancing the Atmospheric Oxidation Capacities of Inland Urban Environments.

Chlorine (Cl) radicals from photolabile chlorine species are highly reactive and can affect the fate of air pollutants in the atmosphere. Although several campaigns have been conducted, typically in coastal environments, long-term observations of reactive chlorine species and their impacts on atmospheric oxidation capacities (AOCs) are lacking. Here, we report nearly full-year observations of Cl2 and ClNO2 levels in Beijing and evaluate their impacts on the AOC with a box model coupled with Cl chemistry. Cl radicals promote the circulation of OH-HO2-RO2 by accelerating the OH chain lengths by up to 12.6% on average, hence boosting the AOC, especially in the winter or spring. This promotion effect is nonlinearly dependent on the VOC and NOx concentrations, thus leading to a slight shift in ozone formation from a VOC-sensitive regime to a transition regime with seasonal differences. Given the ubiquitous reactive chlorines in polluted inland urban regions, the AOCs and the formation of secondary pollutants will be underestimated if the reactive chlorine species are neglected.

Molecular Understanding of the Enhancement in Organic Aerosol Mass at High Relative Humidity.

The mechanistic pathway by which high relative humidity (RH) affects gas-particle partitioning remains poorly understood, although many studies report increased secondary organic aerosol (SOA) yields at high RH. Here, we use real-time, molecular measurements of both the gas and particle phase to provide a mechanistic understanding of the effect of RH on the partitioning of biogenic oxidized organic molecules (from α-pinene and isoprene) at low temperatures (243 and 263 K) at the CLOUD chamber at CERN. We observe increases in SOA mass of 45 and 85% with increasing RH from 10-20 to 60-80% at 243 and 263 K, respectively, and attribute it to the increased partitioning of semi-volatile compounds. At 263 K, we measure an increase of a factor 2-4 in the concentration of C10H16O2-3, while the particle-phase concentrations of low-volatility species, such as C10H16O6-8, remain almost constant. This results in a substantial shift in the chemical composition and volatility distribution toward less oxygenated and more volatile species at higher RH (e.g., at 263 K, O/C ratio = 0.55 and 0.40, at RH = 10 and 80%, respectively). By modeling particle growth using an aerosol growth model, which accounts for kinetic limitations, we can explain the enhancement in the semi-volatile fraction through the complementary effect of decreased compound activity and increased bulk-phase diffusivity. Our results highlight the importance of particle water content as a diluting agent and a plasticizer for organic aerosol growth.

Nontarget Screening Exhibits a Seasonal Cycle of PM2.5 Organic Aerosol Composition in Beijing.

The molecular composition of atmospheric particulate matter (PM) in the urban environment is complex, and it remains a challenge to identify its sources and formation pathways. Here, we report the seasonal variation of the molecular composition of organic aerosols (OA), based on 172 PM2.5 filter samples collected in Beijing, China, from February 2018 to March 2019. We applied a hierarchical cluster analysis (HCA) on a large nontarget-screening data set and found a strong seasonal difference in the OA chemical composition. Molecular fingerprints of the major compound clusters exhibit a unique molecular pattern in the Van Krevelen-space. We found that summer OA in Beijing features a higher degree of oxidation and a higher proportion of organosulfates (OSs) in comparison to OA during wintertime, which exhibits a high contribution from (nitro-)aromatic compounds. OSs appeared with a high intensity in summer-haze conditions, indicating the importance of anthropogenic enhancement of secondary OA in summer Beijing. Furthermore, we quantified the contribution of the four main compound clusters to total OA using surrogate standards. With this approach, we are able to explain a small fraction of the OA (∼11-14%) monitored by the Time-of-Flight Aerosol Chemical Speciation Monitor (ToF-ACSM). However, we observe a strong correlation between the sum of the quantified clusters and OA measured by the ToF-ACSM, indicating that the identified clusters represent the major variability of OA seasonal cycles. This study highlights the potential of using nontarget screening in combination with HCA for gaining a better understanding of the molecular composition and the origin of OA in the urban environment.

Insufficient Condensable Organic Vapors Lead to Slow Growth of New Particles in an Urban Environment.

Atmospheric new particle formation significantly affects global climate and air quality after newly formed particles grow above ∼50 nm. In polluted urban atmospheres with 1-3 orders of magnitude higher new particle formation rates than those in clean atmospheres, particle growth rates are comparable or even lower for reasons that were previously unclear. Here, we address the slow growth in urban Beijing with advanced measurements of the size-resolved molecular composition of nanoparticles using the thermal desorption chemical ionization mass spectrometer and the gas precursors using the nitrate CI-APi-ToF. A particle growth model combining condensational growth and particle-phase acid-base chemistry was developed to explore the growth mechanisms. The composition of 8-40 nm particles during new particle formation events in urban Beijing is dominated by organics (∼80%) and sulfate (∼13%), and the remainder is from base compounds, nitrate, and chloride. With the increase in particle sizes, the fraction of sulfate decreases, while that of the slow-desorbed organics, organic acids, and nitrate increases. The simulated size-resolved composition and growth rates are consistent with the measured results in most cases, and they both indicate that the condensational growth of organic vapors and H2SO4 is the major growth pathway and the particle-phase acid-base reactions play a minor role. In comparison to the high concentrations of gaseous sulfuric acid and amines that cause high formation rates, the concentration of condensable organic vapors is comparably lower under the high NOx levels, while those of the relatively high-volatility nitrogen-containing oxidation products are higher. The insufficient condensable organic vapors lead to slow growth, which further causes low survival of the newly formed particles in urban environments. Thus, the low growth rates, to some extent, counteract the impact of the high formation rates on air quality and global climate in urban environments.

A New Type of Quartz Smog Chamber: Design and Characterization.

Since the 1960s, many indoor and outdoor smog chambers have been developed worldwide. However, most of them are made of Teflon films, which have relatively high background contaminations due to the wall effect. We developed the world's first medium-size quartz chamber (10 m3), which is jointed with 32 pieces of 5 mm thick polished quartz glasses and a stainless-steel frame. Characterizations show that this chamber exhibits excellent performance in terms of relative humidity (RH) (2-80%) and temperature (15-30 ± 1 °C) control, mixing efficiency of the reactants (6-8 min), light transmittance (>90% above 290 nm), and wall loss of pollutants. The wall loss rates of the gas-phase pollutants are on the order of 10-4 min-1 at 298 K under dry conditions. It is 0.08 h-1 for 100-500 nm particles, significantly lower than those of Teflon chambers. The photolysis rate of NO2 (JNO2) is automatically adjustable to simulate the diurnal variation of solar irradiation from 0 to 0.40 min-1. The inner surface of the chamber can be repeatedly washed with deionized water, resulting in low background contaminations. Both experiments (toluene-NOx and α-pinene-ozone systems) and box model demonstrate that this new quartz chamber can provide high-quality data for investigating SOA and O3 formation in the atmosphere.

Observation and Source Apportionment of Atmospheric Alkaline Gases in Urban Beijing.

Alkaline gases, including NH3, C1-3-amines, C1-3-amides, and C1-3-imines, were measured in situ using a water cluster-CIMS in urban Beijing during the wintertime of 2018, with a campaign average of 2.8 ± 2.0 ppbv, 5.2 ± 4.3, 101.1 ± 94.5, and 5.2 ± 5.4 pptv, respectively. Source apportionment analysis constrained by emission profiles of in-use motor vehicles was performed using a SoFi-PMF software package, and five emission sources were identified as gasoline-powered vehicles (GV), diesel-powered vehicles (DV), septic system emission (SS), soil emission (SE), and combustion-related sources (CS). SS was the dominant NH3 source (60.0%), followed by DV (18.6%), SE (13.1%), CS (4.3%), and GV (4.0%). GV and DV were responsible for 69.9 and 85.2% of C1- and C2-amines emissions, respectively. Most of the C3-amines were emitted from nonmotor vehicular sources (SS = 61.3%; SE = 17.8%; CS = 9.1%). DV accounted for 71.9 and 34.1% of C1- and C2-amides emissions, respectively. CS was mainly comprised of amides and imines, likely originating from the pyrolysis of nitrogen-containing compounds. Our results suggested that motor vehicle exhausts can not only contribute to criteria air pollutants emission but also promote new particle formation, which has not been well recognized and considered in current regulations. Urban residential septic system was the predominant contributor to background NH3. Enhanced NH3 emissions from soil and combustion-related sources were the major cause of PM2.5 buildup during the haze events. Combustion-related sources, together with motor vehicles, were responsible for most of the observed amides and imines and may be of public health concern within the vicinity of these sources.

Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation.

Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce.

Molecular Composition of Oxygenated Organic Molecules and Their Contributions to Organic Aerosol in Beijing.

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26-39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation.

Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3.

Homogeneous nucleation and subsequent cluster growth leads to the formation of new aerosol particles in the atmosphere. The nucleation of sulfuric acid and organic vapours is thought to be responsible for the formation of new particles over continents, whereas iodine oxide vapours have been implicated in particle formation over coastal regions. The molecular clustering pathways that are involved in atmospheric particle formation have been elucidated in controlled laboratory studies of chemically simple systems, but direct molecular-level observations of nucleation in atmospheric field conditions that involve sulfuric acid, organic or iodine oxide vapours have yet to be reported. Here we present field data from Mace Head, Ireland, and supporting data from northern Greenland and Queen Maud Land, Antarctica, that enable us to identify the molecular steps involved in new particle formation in an iodine-rich, coastal atmospheric environment. We find that the formation and initial growth process is almost exclusively driven by iodine oxoacids and iodine oxide vapours, with average oxygen-to-iodine ratios of 2.4 found in the clusters. On the basis of this high ratio, together with the high concentrations of iodic acid (HIO3) observed, we suggest that cluster formation primarily proceeds by sequential addition of HIO3, followed by intracluster restructuring to I2O5 and recycling of water either in the atmosphere or on dehydration. Our study provides ambient atmospheric molecular-level observations of nucleation, supporting the previously suggested role of iodine-containing species in the formation of new aerosol particles, and identifies the key nucleating compound.

Amazon boundary layer aerosol concentration sustained by vertical transport during rainfall.

The nucleation of atmospheric vapours is an important source of new aerosol particles that can subsequently grow to form cloud condensation nuclei in the atmosphere. Most field studies of atmospheric aerosols over continents are influenced by atmospheric vapours of anthropogenic origin (for example, ref. 2) and, in consequence, aerosol processes in pristine, terrestrial environments remain poorly understood. The Amazon rainforest is one of the few continental regions where aerosol particles and their precursors can be studied under near-natural conditions, but the origin of small aerosol particles that grow into cloud condensation nuclei in the Amazon boundary layer remains unclear. Here we present aircraft- and ground-based measurements under clean conditions during the wet season in the central Amazon basin. We find that high concentrations of small aerosol particles (with diameters of less than 50 nanometres) in the lower free troposphere are transported from the free troposphere into the boundary layer during precipitation events by strong convective downdrafts and weaker downward motions in the trailing stratiform region. This rapid vertical transport can help to maintain the population of particles in the pristine Amazon boundary layer, and may therefore influence cloud properties and climate under natural conditions.

Deposition potential of 0.003-10 µm ambient particles in the humidified human respiratory tract: Contribution of new particle formation events in Beijing.

Ultrafine particles (UFPs) usually explosive growth during new particle formation (NPF) events. However, the risk of exposure to UFPs on NPF days has been ignored due to the prevalence of mass-based air quality standards. In this study, the daily deposited doses, i.e., the daily deposited particle number dose (DPNd), mass dose (DPMd), and surface area dose (DPSd), of ambient particles in the human respiratory tract in Beijing were evaluated based on the particle number size distribution (3 nm-10 µm) from June 2018 to May 2019 utilizing a Multiple-Path Particle Dosimetry Model (MPPD) after the hygroscopic growth of particles in the respiratory tract had been accounted for. Our observations showed a high frequency (72.6%) of NPF on excellent air quality days, with daily mean PM2.5 concentrations less than 35 µg m-3. The daily DPNd on excellent air quality days was comparable with that on polluted days, although the DPMd on excellent air quality days was as low as 15.6% of that on polluted days. The DPNd on NPF days was ~1.3 times that on non-NPF days. The DPNd in respiratory tract regions decreased in the order: tracheobronchial (TB) > pulmonary (PUL) > extrathoracic (ET) on NPF days, while it was PUL > TB > ET on non-NPF days. The number of deposited nucleation mode particles, which were deposited mainly in the TB region (45%), was 2 times higher on NPF days than that on non-NPF days. Our results demonstrated that the deposition potential due to UFPs in terms of particle number concentrations is high in Beijing regardless of the aerosol mass concentration. More toxicological studies related to UFPs on NPF days, especially those targeting tracheobronchial and pulmonary impairment, are required in the future.

Is reducing new particle formation a plausible solution to mitigate particulate air pollution in Beijing and other Chinese megacities?

Atmospheric gas-to-particle conversion is a crucial or even dominant contributor to haze formation in Chinese megacities in terms of aerosol number, surface area and mass. Based on our comprehensive observations in Beijing during 15 January 2018-31 March 2019, we are able to show that 80-90% of the aerosol mass (PM2.5) was formed via atmospheric reactions during the haze days and over 65% of the number concentration of haze particles resulted from new particle formation (NPF). Furthermore, the haze formation was faster when the subsequent growth of newly formed particles was enhanced. Our findings suggest that in practice almost all present-day haze episodes originate from NPF, mainly since the direct emission of primary particles in Beijing has considerably decreased during recent years. We also show that reducing the subsequent growth rate of freshly formed particles by a factor of 3-5 would delay the buildup of haze episodes by 1-3 days. Actually, this delay would decrease the length of each haze episode, so that the number of annual haze days could be approximately halved. Such improvement in air quality can be achieved with targeted reduction of gas-phase precursors for NPF, mainly dimethyl amine and ammonia, and further reductions of SO2 emissions. Furthermore, reduction of anthropogenic organic and inorganic precursor emissions would slow down the growth rate of newly-formed particles and consequently reduce the haze formation.

Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol.

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Contribution of Atmospheric Oxygenated Organic Compounds to Particle Growth in an Urban Environment.

Gas-phase oxygenated organic molecules (OOMs) can contribute substantially to the growth of newly formed particles. However, the characteristics of OOMs and their contributions to particle growth rate are not well understood in urban areas, which have complex anthropogenic emissions and atmospheric conditions. We performed long-term measurement of gas-phase OOMs in urban Beijing during 2018-2019 using nitrate-based chemical ionization mass spectrometry. OOM concentrations showed clear seasonal variations, with the highest in the summer and the lowest in the winter. Correspondingly, calculated particle growth rates due to OOM condensation were highest in summer, followed by spring, autumn, and winter. One prominent feature of OOMs in this urban environment was a high fraction (∼75%) of nitrogen-containing OOMs. These nitrogen-containing OOMs contributed only 50-60% of the total growth rate led by OOM condensation, owing to their slightly higher volatility than non-nitrate OOMs. By comparing the calculated condensation growth rates and the observed particle growth rates, we showed that sulfuric acid and its clusters are the main contributors to the growth of sub-3 nm particles, with OOMs significantly promoting the growth of 3-25 nm particles. In wintertime Beijing, however, there are missing contributors to the growth of particles above 3 nm, which remain to be further investigated.

Acid-Base Clusters during Atmospheric New Particle Formation in Urban Beijing.

Molecular clustering is the initial step of atmospheric new particle formation (NPF) that generates numerous secondary particles. Using two online mass spectrometers with and without a chemical ionization inlet, we characterized the neutral clusters and the naturally charged ion clusters during NPF periods in urban Beijing. In ion clusters, we observed pure sulfuric acid (SA) clusters, SA-amine clusters, SA-ammonia (NH3) clusters, and SA-amine-NH3 clusters. However, only SA clusters and SA-amine clusters were observed in the neutral form. Meanwhile, oxygenated organic molecule (OOM) clusters charged by a nitrate ion and a bisulfate ion were observed in ion clusters. Acid-base clusters correlate well with the occurrence of sub-3 nm particles, whereas OOM clusters do not. Moreover, with the increasing cluster size, amine fractions in ion acid-base clusters decrease, while NH3 fractions increase. This variation results from the reduced stability differences between SA-amine clusters and SA-NH3 clusters, which is supported by both quantum chemistry calculations and chamber experiments. The lower average number of dimethylamine (DMA) molecules in atmospheric ion clusters than the saturated value from controlled SA-DMA nucleation experiments suggests that there is insufficient DMA in urban Beijing to fully stabilize large SA clusters, and therefore, other basic molecules such as NH3 play an important role.