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Air ions are the key components for a series of atmospheric physicochemical interactions, such as ion-catalyzed reactions, ion-molecule reactions, and ion-induced new particle formation (NPF). They also control atmospheric electrical properties with effects on global climate. We performed molecular-level measurements of cluster ions at the high-altitude research station Chacaltaya (CHC; 5240 m a.s.l.), located in the Bolivian Andes, from January to May 2018 using an atmospheric-pressure-interface time-of-flight mass spectrometer. The negative ions mainly consisted of (H2SO4)0–3⚫HSO4-, (HNO3)0–2⚫NO3-, SO5-, (NH3)1–6⚫(H2SO4)3–7⚫HSO4-, malonic-acid-derived, and CHO / CHON⚫(HSO4- / NO3-) cluster ions. Their temporal variability exhibited distinct diurnal and seasonal patterns due to the changes in the corresponding neutral species' molecular properties (such as electron affinity and proton affinity) and concentrations resulting from the air masses arriving at CHC from different source regions. The positive ions were mainly composed of protonated amines and organic cluster ions but exhibited no clear diurnal variation. H2SO4–NH3 cluster ions likely contributed to the NPF process, particularly during the wet-to-dry transition period and the dry season, when CHC was more impacted by air masses originating from source regions with elevated SO2 emissions. Our study provides new insights into the chemical composition of atmospheric cluster ions and their role in new particle formation in the high-altitude mountain environment of the Bolivian Andes.

New particle formation (NPF) in the tropical free troposphere (FT) is a globally important source of cloud condensation nuclei, affecting cloud properties and climate. Oxidized organic molecules (OOMs) produced from biogenic volatile organic compounds are believed to contribute to aerosol formation in the tropical FT, but without direct chemical observations. We performed in-situ molecular-level OOMs measurements at the Bolivian station Chacaltaya at 5240 meters above sea level, on the western edge of Amazonia. For the first time, we demonstrate the presence of OOMs, mainly with 4-5 carbon atoms, in both gas-phase and particle-phase (in terms of mass contribution) measurements in tropical FT air from Amazonia. These observations, combined with air mass history analyses, indicate that the observed OOMs are linked to isoprene emitted from the rainforests hundreds of kilometers away. Based on particle-phase measurements, we find that these compounds can contribute to NPF, at least the growth of newly formed nanoparticles, in the tropical FT on a continental scale. Thus, our study is a fundamental and significant step in understanding the aerosol formation process in the tropical FT.

Early growth of atmospheric particles is essential for their survival and ability to participate in cloud formation. Many different atmospheric vapors contribute to the growth, but even the main contributors still remain poorly identified in many environments, such as high-altitude sites. Based on measured organic vapor and sulfuric acid concentrations under ambient conditions, particle growth during new particle formation events was simulated and compared with the measured particle size distribution at Chacaltaya Global Atmosphere Watch station in Bolivia (5240 m a.s.l.) during April and May 2018, as a part of the SALTENA (Southern Hemisphere high-ALTitude Experiment on particle Nucleation and growth) campaign . The simulations showed that the detected vapors were sufficient to explain the observed particle growth, although some discrepancies were found between modelled and measured particle growth rates. This study gives an insight on the key factors affecting the particle growth on the site. Low volatile organic compounds were found to be the main contributor to the particle growth, covering on average 65 % of simulated particle mass in particle with diameter of 40 nm In addition, sulfuric acid had a major contribution to the particle growth, covering at maximum 39 % of simulated particle mass in 40 nm particle during periods when volcanic activity was detected on the area, suggesting that volcanic emissions can greatly enhance the particle growth.

Dimethyl sulfide (DMS) is the primary natural contributor to the atmospheric sulfur burden. Observations concerning the fate of DMS oxidation products after long-range transport in the remote free troposphere are, however, sparse. Here we present quantitative chemical ionization mass spectrometric measurements of DMS and its oxidation products sulfuric acid (H2SO4), methanesulfonic acid (MSA), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), methanesulfinic acid (MSIA), methyl thioformate (MTF), methanesulfenic acid (MSEA, CH3SOH), and a compound of the likely structure CH3S(O)2OOH in the gas phase, as well as measurements of the sulfate and methanesulfonate aerosol mass fractions. The measurements were performed at the Global Atmosphere Watch (GAW) station Chacaltaya in the Bolivian Andes located at 5240 m above sea level (a.s.l.). DMS and DMS oxidation products are brought to the Andean high-altitude station by Pacific air masses during the dry season after convective lifting over the remote Pacific ocean to 6000–8000 m a.s.l. and subsequent long-range transport in the free troposphere (FT). Most of the DMS reaching the station is already converted to the rather unreactive sulfur reservoirs DMSO2 in the gas phase and methanesulfonate (MS−) in the particle phase, which carried nearly equal amounts of sulfur to the station. The particulate sulfate at Chacaltaya is however dominated by regional volcanic emissions during the time of the measurement and not significantly affected by the marine air masses. In one of the FT events, even some DMS was observed next to reactive intermediates such as methyl thioformate, dimethylsulfoxide, and methanesulfinic acid. Also for this event, back trajectory calculations show that the air masses came from above the ocean (distance >330 km) with no local surface contacts. This study demonstrates the potential impact of marine DMS emissions on the availability of sulfur-containing vapors in the remote free troposphere far away from the ocean.

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.

Gaseous hydrochloric (HCl) and hydrobromic acid (HBr) are vital halogen species that play essential roles in tropospheric physicochemical processes. Yet, the majority of the current studies on these halogen species were conducted in marine or coastal areas. Detection and source identification of HCl and HBr in inland urban areas remain scarce, thus limiting the full understanding of halogen chemistry and potential atmospheric impacts in the environments with limited influence from the marine sources. Here, both gaseous HCl and HBr were concurrently measured in urban Beijing, China, during winter and early spring of 2019. We observed significant HCl and HBr concentrations ranging from a minimum value at 1 × 108 molecules cm−3 (4 ppt) and 4 × 107 molecules cm−3 (1 ppt) up to 6 × 109 molecules cm−3 (222 ppt) and 1 × 109 molecules cm−3 (37 ppt), respectively. The HCl and HBr concentrations are enhanced along with the increase of atmospheric temperature, UVB and levels of gaseous HNO3. Based on the air mass analysis and high correlations of HCl and HBr with the burning indicators (HCN and HCNO), gaseous HCl and HBr are found to be related to anthropogenic burning aerosols. The gas–particle partitioning may also play a dominant role in the elevated daytime HCl and HBr. During the daytime, the reactions of HCl and HBr with OH radicals lead to significant production of atomic Cl and Br, up to 2 × 104 molecules cm−3 s−1 and 8 × 104 molecules cm−3 s−1, respectively. The production rate of atomic Br (via HBr + OH) is 2–3 times higher than that of atomic Cl (via HCl + OH), highlighting the potential importance of bromine chemistry in the urban area. On polluted days, the production rates of atomic Cl and Br are faster than those on clean days. Furthermore, our observations of elevated HCl and HBr may suggest an important recycling pathway of halogen species in inland megacities and may provide a plausible explanation for the widespread halogen chemistry, which could affect the atmospheric oxidation in China.

The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (ΣANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.

Secondary organic aerosol (SOA) is known to impact both climate and air quality, yet molecular-level composition measurements remain challenging, hampering our understanding of SOA formation and evolution. Here, we reveal the importance of underestimated reaction pathways for the (trans)formation of SOA from monoterpenes, one of the largest SOA precursors globally. Utilizing mass spectrometric techniques to achieve a comprehensive characterization of molecular-level changes in the SOA, we were able to link the appearance of high-molecular weight (HMW) organic molecules to the concentration and level of neutralization of particulate sulfate. Interestingly, this oligomerization coincided with a decrease of highly oxygenated molecules (HOMs). Our findings highlight the role of particle-phase processing, and the underestimated importance of sulfate aerosol for monoterpene-SOA formation. The observations of these processes directly in the atmosphere reveal the need to account for the formation of HMW oligomers to fully understand the physicochemical properties of organic aerosol. Sulfate aerosols produced by industrial activities provide a key substrate for the formation of secondary organic aerosols (SOA) hundreds of km away. An international research group led by Matthieu Riva, now at the Universite de Lyon, applied detailed field observations and atmospheric transport modeling to show that SOA are produced when sulfate aerosols interact with monoterpenes — a volatile organic compound emitted by forests. Specifically, along the atmospheric transport pathway from the Russian pollution source to the research station in Finland, oxidized monoterpenes condensed onto sulfate particles, forming SOA. The team used laboratory experiments to confirm a powerful influence of sulfate levels on SOA formation. The research extends prior work showing similar pathways for isoprene-related SOA formation, and cements the importance of SOA formation through multiphase chemistry across of range of biogenically-derived atmospheric compounds.

Gaseous hydrochloric (HCl) and hydrobromic acid (HBr) are vital halogen species that play essential roles in tropospheric physicochemical processes. Yet, majority of the current studies on these halogen species were conducted in marine or coastal areas. Detection and source identification of HCl and HBr in inland urban areas (especially megacities) remain scarce, thus, limiting the full understanding of halogen chemistry and potential atmospheric impacts in the environments with limited influence from the marine sources. Here, both gaseous HCl and HBr were concurrently measured by Chemical Ionization-Atmospheric Pressure interface-Long Time Of Flight-Mass Spectrometer (CI-APi-LTOF-MS) in urban Beijing, China at the BUCT station (39.94° N, 116.30° E) during winter and early spring of 2019. We observed significant HCl and HBr concentrations ranged from a minimum value at 1.3×108 cm-3 and 4.3×107 cm-3 up to 5.9×109 cm-3 and 1.2×109 cm-3, respectively. The HCl and HBr concentrations are enhanced along with the increase of atmospheric temperature, UVB, and levels of gaseous HNO3. Based on the air mass analysis and high correlations of HCl and HBr with the burning indicators (HCN and HCNO), the gaseous HCl and HBr are found to be related to anthropogenic burning aerosols. The gas-aerosol partitioning may also play a dominant role in the elevated daytime HCl and HBr. During the daytime, the reaction of HCl and HBr with OH radicals lead to significant production of atomic Cl and Br, up to 1.7×104 cm-3 s-1and 7.9×104 cm-3 s-1, respectively. The production rate of atomic Br (via HBr + OH) are 2-3 times higher than that of atomic Cl (via HCl + OH), highlighting the potential importance of bromine chemistry in the urban area. Furthermore, our observations of elevated HCl and HBr may suggest an important recycling pathway of halogen species in inland megacities, and may provide a plausible explanation for the widespread of halogen chemistry, which could affect the atmospheric oxidation in China.

Significance Recycling of reactive iodine from heterogeneous processes on sea-salt aerosol was hypothesized over two decades ago to play an important role in the atmospheric cleansing capacity. However, the understanding of this mechanism has been limited to laboratory studies and has not been confirmed in the atmosphere until now. We present atmospheric measurement of gas-phase iodine interhalogen species and show that their production via heterogeneous processing on marine aerosols is remarkably fast. These observations reveal that the atmospheric recycling of atomic iodine through photolysis of iodine interhalogen species is more efficient than previously thought, which is ultimately expected to lead to higher ozone loss and faster new particle formation in the marine environment., 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.

The role of new particle formation (NPF) events and their contribution to haze formation through subsequent growth in polluted megacities is still controversial. To improve the understanding of the sources, meteorological conditions, and chemistry behind air pollution, we performed simultaneous measurements of aerosol composition and particle number size distributions at ground level and at 260 m in central Beijing, China, during a total of 4 months in 2015–2017. Our measurements show a pronounced decoupling of gas-to-particle conversion between the two heights, leading to different haze processes in terms of particle size distributions and chemical compositions. The development of haze was initiated by the growth of freshly formed particles at both heights, whereas the more severe haze at ground level was connected directly to local primary particles and gaseous precursors leading to higher particle growth rates. The particle growth creates a feedback loop, in which a further development of haze increases the atmospheric stability, which in turn strengthens the persisting apparent decoupling between the two heights and increases the severity of haze at ground level. Moreover, we complemented our field observations with model analyses, which suggest that the growth of NPF-originated particles accounted up to ∼60% of the accumulation mode particles in the Beijing–Tianjin–Hebei area during haze conditions. The results suggest that a reduction in anthropogenic gaseous precursors, suppressing particle growth, is a critical step for alleviating haze although the number concentration of freshly formed particles (3–40 nm) via NPF does not reduce after emission controls.

Pyruvic acid (CH3C(O)C(O)OH, 2-oxopropanoic acid) is an organic acid of biogenic origin that plays a crucial role in plant metabolism, is present in tropospheric air in both gas-phase and aerosol-phase, and is implicated in the formation of secondary organic aerosols (SOAs). Up to now, only a few field studies have reported mixing ratios of gas-phase pyruvic acid, and its tropospheric sources and sinks are poorly constrained. We present the first measurements of gas-phase pyruvic acid in the boreal forest as part of the IBAIRN (Influence of Biosphere–Atmosphere Interactions on the Reactive Nitrogen budget) field campaign in Hyytiälä, Finland, in September 2016. The mean pyruvic acid mixing ratio during IBAIRN was 96 pptv, with a maximum value of 327 pptv. From our measurements we estimated the overall pyruvic acid source strength and quantified the contributions of isoprene oxidation and direct emissions from vegetation in this monoterpene-dominated forested environment. Further, we discuss the relevance of gas-phase pyruvic acid for atmospheric chemistry by investigating the impact of its photolysis on acetaldehyde and peroxy radical production rates. Our results show that, based on our present understanding of its photochemistry, pyruvic acid is an important source of acetaldehyde in the boreal environment, exceeding ethane and propane oxidation by factors of ∼10 and ∼20. Pyruvic acid (CH3C(O)C(O)OH, 2-oxopropanoic acid) is an organic acid of biogenic origin that plays a crucial role in plant metabolism, is present in tropospheric air in both gas-phase and aerosol-phase, and is implicated in the formation of secondary organic aerosols (SOAs). Up to now, only a few field studies have reported mixing ratios of gas-phase pyruvic acid, and its tropospheric sources and sinks are poorly constrained. We present the first measurements of gas-phase pyruvic acid in the boreal forest as part of the IBAIRN (Influence of Biosphere-Atmosphere Interactions on the Reactive Nitrogen budget) field campaign in Hyytiala, Finland, in September 2016. The mean pyruvic acid mixing ratio during IBAIRN was 96 pptv, with a maximum value of 327 pptv. From our measurements we estimated the overall pyruvic acid source strength and quantified the contributions of isoprene oxidation and direct emissions from vegetation in this monoterpene-dominated forested environment. Further, we discuss the relevance of gas-phase pyruvic acid for atmospheric chemistry by investigating the impact of its photolysis on acetaldehyde and peroxy radical production rates. Our results show that, based on our present understanding of its photochemistry, pyruvic acid is an important source of acetaldehyde in the boreal environment, exceeding ethane and propane oxidation by factors of similar to 10 and similar to 20.

Clouds are made of droplets that arise from the activation of suitable aerosol particles (termed cloud condensation nuclei, CCN). In the activation process, water vapor saturation ratio exceeds a critial ratio enabling CCN runaway-growth to cloud droplet sizes. The number concentration of cloud droplets (CDNC) is highly dependent on the aerosol population properties (size distribution and composition), relative humidity, and the vertical wind component. While the activation of CCN consisting of non-volatile particulate matter is fairly well understood, the same process involving semi-volatile organic vapors (SVOCs) has received less attention despite their significant presence in ambient air. A recent cloud parcel modeling study shows substanial CDNC enhancement due to SVOC condensation (Topping et al., 2013). Surprisingly, the topic has not been widely investigated nor the results replicated with other cloud parcel models (CPM). Thus, in the current study we seek to quantify the CDNC enhancement by SVOC condensation using a recently developed CPM framework (Lowe et al., 2020, in prep.). Moreover, the CPM initialization is performed, for the first time, with state-of-the art measurement data including measured SVOC data for multiple airmass types.Here, the CPM, which uses spectral microphysics for the simulation of CCN activation and hydrometeor growth, also includes a SVOC condensation equation analogous to those of water vapor. Equilibrium initialization of the SVOC volatility basis set (VBS) partitioning coefficients is performed iteratively, and constrained by the organic to inorganic ratio in the particle phase determined by ambient measurements performed at the Chacaltaya Global Atmospheric Watch (GAW) Station located at 5240 m a.s.l. in the Bolivian Andes, in spring 2018. The uniquely comprehensive data set recorded, which tracks all of the relevant aerosol population characteristics in near real-time, reveals a high degree of variability in aerosol composition, size distribution and loading depending on the air mass origin. Lagrangian backward simulations during the measurement period at Chacaltaya GAW reveal at least 18 significantly different airmass origins (Aliaga et al., 2020, in prep.). Such variability served multiple model initialization scenarios for individual case studies. We will show a suite of CDNC enhancements by SVOC condensation under different initialization scenarios actualized in data recorded at Chacaltaya GAW Station, including airmasses originating from the Amazon (biomass burning and biogenic VOCs), Andean plateau (volcanic activity), and La Paz/El Alto metropolitan areas (anthropogenic emissions).References:Topping, D., Connolly, P. and McFiggans, G., 2013. Cloud droplet number enhanced by co-condensation of organic vapours. Nature Geoscience, 6(6), p.443.

A significant fraction (>50%) of cloud condensation nuclei (CCN) in the atmosphere arises from new particle formation (Dunne et al., 2016). While particle nucleation has been observed almost everywhere in the atmosphere, the mechanisms governing this process are still poorly understood and subject of on-going research. For example, it is still largely unknown which components participate in new-particle formation. Laboratory experiments and quantum chemical calculations have identified potential candidates that may play a role, including sulphuric acid, ions, ammonia, amines and highly oxygenated organic molecules (Kirkby et al., 2011; Almeida et al., 2013; Bianchi et al., 2016; Bianchi et al., 2019).Here we present observations of the formation and growth of newly formed particles measured during intense volcano activities.The measurements were conducted at Chacaltaya mountain station (5240 m a.s.l.) in Bolivia. The station is located on top of the Cordillera Real. It has air masses coming from the Amazon forest, La Paz and the Bolivian altiplano.With the Chemical Ionization Atmospheric Pressure interface Time-Of-Light mass spectrometers (CI-APi-TOF) we measured H2SO4, the APi-TOF retrieved the chemical composition of positive and negative ions. Ion and particle size distributions were measured with the NAIS (Neutral cluster and Air Ion Spectrometer) and the SMPS (Scanning Mobility Particle Sizer), respectively. The PSM (Particle Sizer Magnifier) measured particles with a cut off that varied from 1-4 nm. Finally, with the ACSM (Aerosol Chemical Speciation Monitor) and the FIGAERO (Filter Inlet for Gases and AEROsols) we retrieved the aerosol chemical composition. Besides this set of instruments, other parameters were measured at the Chacaltaya GAW station.During the intensive measurement campaign, air masses coming directly from volcano eruptions were detected by all our instruments. We were therefore able to determine the gas and particle chemical composition of the air mass. In addition to that, we observed several NPF events triggered by air masses coming from volcanic emissions. With this set of instruments, we were able to retrieve the chemical composition of the vapours leading to the formation of new particles. It was found that all the nucleation event observed during the volcano activity were triggered by sulphuric acid and ammonia. In the presentation we will show more details on the chemical and physical mechanism behind this process. Almeida, J., et al., (2013) Nature 502, 359-363.Bianchi, F., et al., (2016) Science 6289, 1109-1112.Bianchi, F., et al., (2019) Chemical Review 119, 3472−3509Dunne et al., (2016) Science 354, 1119-1124.Kirkby, J., et al., (2011) Nature 476, (7361), 429-433.

Highly oxygenated organic molecules (HOMs) from atmospheric oxidation of alpha-pinene can irreversibly condense to particles and contribute to secondary organic aerosol (SOA) formation. Recently, the formation of nitryl chloride (ClNO2) from heterogeneous reactions, followed by its subsequent photolysis, is suggested to be an important source of chlorine atoms in many parts of the atmosphere. However, the oxidation of monoterpenes such as alpha-pinene by chlorine atoms has received very little attention, and the ability of this reaction to form HOMs is completely unstudied. Here, chamber experiments were conducted with alpha-pinene and chlorine under low- and high-nitrogen-oxide (NOx, NOx=NO+NO2) conditions. A nitrate-based CI-APi-ToF (chemical ionization–atmospheric pressure interface–time of flight) mass spectrometer was used to measure HOM products. Clear distributions of monomers with 9–10 carbon atoms and dimers with 18–20 carbon atoms were observed under low-NOx conditions. With increased concentration of NOx within the chamber, the formation of dimers was suppressed due to the reactions of peroxy radicals with NO. We estimated the HOM yields from chlorine-initiated oxidation of alpha-pinene under low-NOx conditions to be around 1.8 %, though with a substantial uncertainty range (0.8 %–4 %) due to lack of suitable calibration methods. Corresponding yields at high NOx could not be determined because of concurrent ozonolysis reactions. Our study demonstrates that also the oxidation of alpha-pinene by chlorine atoms and yield low-volatility organic compounds.

Sulfur trioxide (SO3) is a crucial compound for atmospheric sulfuric acid (H2SO4) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO3 is mainly produced from the photo-oxidation of SO2 by OH radicals. However, the sources of SO3 during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-offlight) mass spectrometer to detect atmospheric SO3 and H2SO4. Our results show the level of SO3 was higher during the winter than during the summer, with high SO3 levels observed especially during the early morning (similar to 05:00 to similar to 08:30) and night (similar to 18:00 to similar to 05:00 the next day). On the basis of analysis of SO2, NOx, black carbon, traffic flow, and atmospheric ions, we suggest SO3 could be formed from the catalytic oxidation of SO2 on the surface of traffic-related black carbon. This previously unidentified SO3 source results in significant H2SO4 formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO3 and formulating policies to mitigate secondary particle formation in Chinese megacities.

NOx is important for particle growth as it can participate in HOM formation and alter the HOM volatility distribution., Atmospheric new-particle formation (NPF) affects climate by contributing to a large fraction of the cloud condensation nuclei (CCN). Highly oxygenated organic molecules (HOMs) drive the early particle growth and therefore substantially influence the survival of newly formed particles to CCN. Nitrogen oxide (NOx) is known to suppress the NPF driven by HOMs, but the underlying mechanism remains largely unclear. Here, we examine the response of particle growth to the changes of HOM formation caused by NOx. We show that NOx suppresses particle growth in general, but the suppression is rather nonuniform and size dependent, which can be quantitatively explained by the shifted HOM volatility after adding NOx. By illustrating how NOx affects the early growth of new particles, a critical step of CCN formation, our results help provide a refined assessment of the potential climatic effects caused by the diverse changes of NOx level in forest regions around the globe.

With the recent developments in mass spectrometry, combined with the strengths of factor analysis techniques, our understanding of atmospheric oxidation chemistry has improved significantly. The typical approach for using techniques like positive matrix factorization (PMF) is to input all measured data for the factorization in order to separate contributions from different sources and/or processes to the total measured signal. However, while this is a valid approach for assigning the total signal to factors, we have identified several cases where useful information can be lost if solely using this approach. For example, gaseous molecules emitted from the same source can show different temporal behaviors due to differing loss terms, like condensation at different rates due to different molecular masses. This conflicts with one of PMF's basic assumptions of constant factor profiles. In addition, some ranges of a mass spectrum may contain useful information, despite contributing only minimal fraction to the total signal, in which case they are unlikely to have a significant impact on the factorization result. Finally, certain mass ranges may contain molecules formed via pathways not available to molecules in other mass ranges, e.g. dimeric species versus monomeric species. In this study, we attempted to address these challenges by dividing mass spectra into sub-ranges and applying the newly developed binPMF method to these ranges separately. We utilized a dataset from a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer as an example. We compare the results from these three different ranges, each corresponding to molecules of different volatilities, with binPMF results from the combined range. Separate analysis showed clear benefits in dividing factors for molecules of different volatilities more accurately, in resolving different chemical processes from different ranges, and in giving a chance for high-molecular-weight molecules with low signal intensities to be used to distinguish dimeric species with different formation pathways. In addition, daytime dimer formation (diurnal peak around noon) was identified, which may contribute to NPF in Hyytiälä. Also, dimers from NO3 oxidation were separated by the sub-range binPMF, which would not be identified otherwise. We recommend PMF users to try running their analyses on selected sub-ranges in order to further explore their datasets.

Highly oxygenated organic molecules (HOMs) from atmospheric oxidation of alpha-pinene can irreversibly condense to particles and contribute to secondary organic aerosol (SOA) formation. Recently, the formation of nitryl chloride (ClNO2) from heterogeneous reactions, followed by its subsequent photolysis is suggested to be an important source of chlorine atoms in many parts of the atmosphere. However, the oxidation of monoterpenes such as alpha-pinene by chlorine atoms has received very little attention, and the ability of this reaction to form HOM is completely unstudied. Here, chamber experiments were conducted with alpha-pinene and chlorine under low and high nitrogen oxide (NOx) conditions. A NO3-based CI-APi-TOF was used to measure HOM products. Clear distributions of monomers with 9–10 carbon atoms and dimers with 18–20 carbon atoms were observed under low NOx conditions. With increased concentration of NOx within the chamber, the formation of dimers was suppressed due to the reactions of peroxy radicals with NO. We estimated the HOM yields from chlorine-initiated oxidation of alpha-pinene under low-NOx conditions to be around 1.8 %, though with a substantial uncertainty range (0.8–4 %) due to lack of suitable calibration methods. Corresponding yields at high NOx could not be determined because of concurrent ozonolysis reactions. Our study demonstrates that chlorine atoms also initiated oxidation of alpha-pinene and yields low volatility organic compounds.

Pyruvic acid, CH3C(O)C(O)OH, is an organic acid of biogenic origin that plays a crucial role in plant metabolism, is present in tropospheric air in both gas-phase and aerosol-phase and is implicated in the formation of secondary organic aerosols (SOA). Up to now, only a few field studies have reported mixing ratios of gas-phase pyruvic acid and its tropospheric sources and sinks are poorly constrained. We present the first gas-phase measurements of pyruvic acid in the boreal forest as part of the IBAIRN (Influence of Biosphere–Atmosphere Interactions on the Reactive Nitrogen budget) field campaign in Hyytiälä, Finland, in September 2016. The mean pyruvic acid mixing ratio during IBAIRN was 96 pptv, with a maximum value of 327 pptv. From our measurements we derived the overall pyruvic acid source strength and quantified the contributions of isoprene oxidation and direct emissions from vegetation in this monoterpene-dominated, forested environment. Further, we discuss the relevance of gas-phase pyruvic acid for atmospheric chemistry by investigating the impact of its photolysis on acetaldehyde and peroxy radical production rates. Our results show that, based on our present understanding of its photo-chemistry, pyruvic acid is an important source of acetaldehyde in the boreal environment, exceeding ethane/propane oxidation by factors of ~ 10 and ~ 20.

Nitrate radical (NO3) and dinitrogen pentoxide (N2O5) play crucial roles in the nocturnal atmosphere. To quantify their impacts, we deployed a thermal-dissociation chemical ionization mass spectrometry (TD-CIMS), to measure their concentration, as well as ClNO2 at a coastal background site in the southern of China during the late autumn of 2012. Moderate levels of NO3, N2O5 and high concentration of ClNO2 were observed during the study period, indicating active NOx-O-3 chemistry in the region. Distinct features of NO3, N2O5 and ClNO2 mixing ratios were observed in different airmasses. Further analysis revealed that the N2O5 heterogeneous reaction was the dominant loss of N2O5 and NO3, which showed higher loss rate compared to that in other coastal sites. Especially, the N2O5 loss rates could reach up to 0.0139 s(-1) when airmasses went across the sea. The fast heterogeneous loss of N2O5 led to rapid NOx loss which could be comparable to the daytime process through NO2 oxidization by OH, and on the other hand, to rapid nitrate aerosol formation. In summary, our results revealed that the N2O5 hydrolysis could play significant roles in regulating the air quality by reducing NOx but forming nitrate aerosols. (C) 2019 Published by Elsevier B.V.

The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain-termination in atmospheric photo-oxidation cycles. The low volatility alkyl nitrates formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3-reactivity and the mixing ratio of total alkyl nitrates in the Finnish boreal forest enabled assessment of the relative importance of NO3−, O3− and OH-initiated formation of alkyl-nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3, during the day. The lifetimes of the gas-phase ANs formed in this environment were of the order of 2 hours implying that the lifetime of NOx is strongly controlled by biogenic emissions from the forest. As the organic nitrates are lost to the particle phase and via dry-deposition to foliar surfaces, the overall result is transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.

Atmospheric aerosol formation from biogenic vapors is strongly affected by air pollutants, like NOx, SO2, and NH3., A major fraction of atmospheric aerosol particles, which affect both air quality and climate, form from gaseous precursors in the atmosphere. Highly oxygenated organic molecules (HOMs), formed by oxidation of biogenic volatile organic compounds, are known to participate in particle formation and growth. However, it is not well understood how they interact with atmospheric pollutants, such as nitrogen oxides (NOx) and sulfur oxides (SOx) from fossil fuel combustion, as well as ammonia (NH3) from livestock and fertilizers. Here, we show how NOx suppresses particle formation, while HOMs, sulfuric acid, and NH3 have a synergistic enhancing effect on particle formation. We postulate a novel mechanism, involving HOMs, sulfuric acid, and ammonia, which is able to closely reproduce observations of particle formation and growth in daytime boreal forest and similar environments. The findings elucidate the complex interactions between biogenic and anthropogenic vapors in the atmospheric aerosol system.

Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5-laden air at the high-elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well-processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5–16% at the ozone peak or 11–41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground-level ozone and haze.

Nighttime reactions of nitrogen oxides influence ozone, volatile organic compounds, and aerosol and are thus important to the understanding of regional air quality. Despite large emissions and rapid recent growth of nitrogen oxide concentrations, there are few studies of nighttime chemistry in China. Here we present measurements of nighttime nitrogen oxides, NO3 and N2O5, from a coastal mountaintop site in Hong Kong adjacent to the megacities of the Pearl River Delta region. This is the first study of nighttime chemistry from a site within the residual layer in China. Key findings include the following. First, highly concentrated urban NOx outflow from the Pearl River Delta region was sampled infrequently at night, with N2O5 mixing ratios up to 8 ppbv (1 min average) or 12 ppbv (1 s average) in nighttime aged air masses. Second, the average N2O5 uptake coefficient was determined from a best fit to the available steady state lifetime data as γ(N2O5) = 0.014 ± 0.007. Although this determination is uncertain due to the difficulty of separating N2O5 losses from those of NO3, this value is in the range of previous residual layer determinations of N2O5 uptake coefficients in polluted air in North America. Third, there was a significant contribution of biogenic hydrocarbons to NO3 loss inferred from canister samples taken during daytime. Finally, daytime N2O5 mixing ratios were in accord with their predicted photochemical steady state. Heterogeneous uptake of N2O5 in fog is determined to be an important production mechanism for soluble nitrate, even during daytime.

The detailed formation mechanism of increased number of haze events in China is still not very clear. Here, we found that reduced surface visibility and an increase in satellite derived columnar concentration of inorganic precursor concentrations are connected with each other. Typically higher inorganic mass fractions lead to increased aerosol water uptake and light scattering ability in elevated relative humidity. Satellite observation of aerosol precursors of NO2 and SO2 showed increased concentrations during study period. Our in-situ measurement of aerosol chemical composition in Beijing also confirmed increased contribution of inorganic aerosol fraction as a function of increased particle pollution level. Our investigations demonstrate that the increased inorganic fraction in the aerosol particles is a key component in the frequently occurring haze days during studying period, and particularly the reduction of nitrate, sulfate and their precursor gases would contribute towards better air quality in China.

On the ability of biogenic vapors to initiate ion-induced cluster formation in the boreal forest., A substantial fraction of aerosols, which affect air quality and climate, is formed from gaseous precursors. Highly oxygenated organic molecules (HOMs) are essential to grow the newly formed particles and have been evidenced to initiate ion-induced nucleation in chamber experiments in the absence of sulfuric acid. We investigate this phenomenon in the real atmosphere using an extensive set of state-of-the-art ion and mass spectrometers deployed in a boreal forest environment. We show that within a few hours around sunset, HOMs resulting from the oxidation of monoterpenes are capable of forming and growing ion clusters even under low sulfuric acid levels. In these conditions, we hypothesize that the lack of photochemistry and essential vapors prevents the organic clusters from growing past 6 nm. However, this phenomenon might have been a major source of particles in the preindustrial atmosphere and might also contribute to particle formation in the future and consequently affect the climate.

New particle formation (NPF) provides a large source of atmospheric aerosols, which affect the climate and human health. Ion-induce nucleation (IIN) has been discovered as an important pathway of forming particles within recent chamber studies, however, atmospheric investigation remains incomplete. For this study, we investigated the air anion compositions in the boreal forest in Southern Finland for 3 consecutive springs, with a special focus on H2SO4-NH3 anion clusters. We found that the ratio between the concentrations of highly oxygenated organic molecules (HOMs) and H2SO4 controlled the appearance of H2SO4-NH3 clusters (#S > 3): All such clusters were observed when [HOM] / [H2SO4] was smaller than 30. The number of H2SO4 molecules in the largest observable cluster correlated with the probability of ion-induced nucleation (IIN) occurrence, which reached almost 100 % when the largest observable cluster contained 6 or more H2SO4 molecules. During selected cases when the time evolution of H2SO4-NH3 clusters could be tracked, the calculated ion growth rates exhibited a good agreement across measurement methods and cluster (particle) sizes. In these cases, H2SO4-NH3 clusters alone could explain ion growth up to 3 nm (mobility diameter). IIN events also occurred in the absence of H2SO4-NH3, implying that also other NPF mechanisms prevail at this site, most likely involving HOMs. It seems that H2SO4 and HOMs both affect the occurrence of an IIN event, but their ratio ([HOMs] / [H2SO4]) defines the primary mechanism of the event. Since that ratio is strongly influenced by solar radiation and temperature, IIN mechanism ought to vary depending on conditions and seasons.

Although nitrous acid (HONO) plays an important role in the chemistry of polluted atmospheres, its atmospheric abundances and sources are still not well understood. This paper reports ambient measurements of HONO taken over four select months in different seasons at a suburban site in Hong Kong. The data were analyzed to elucidate the seasonal characteristics, emission ratios and rates of heterogeneous production. The monthly averaged HONO concentrations ranged from 0.35 ± 0.30 ppbv in late spring (May) to 0.93 ± 0.67 ppbv in late autumn (November). The similar variation patterns of HONO, NOx, and traffic flow from midnight to rush hours suggest that the HONO concentration was strongly influenced by vehicle emissions. The emission ratios (HONO/NOx) were derived from an analysis of 21 fresh plumes (NO/NOx > 0.80), with the range of 0.5–1.6%. The large variability in the emission ratios is attributed to the reaction of NO2 on black carbon (BC) emitted from vehicles, based on a strong correlation between the HONO/NOx and concurrently measured BC. The mean conversion rate of NO2 to HONO on ground surface during nighttime estimated on nine select days was 0.52 × 10−2 h−1, which is relatively low compared with other reported values. This paper highlights a large variability in vehicle emission ratios and heterogeneous conversions of NO2 at ground surface. Photochemical models must consider this variability to better simulate the primary sources of HONO and subsequent photochemistry in the lower part of the troposphere.

Atmospheric oxidizing capacity (AOC), dominated by the hydroxyl radical (OH), is an important index of the self-cleaning capacity of atmosphere and plays a vital role in the tropospheric chemistry. To better understand the key processes governing the chemistry of rural atmosphere of southern China, we analyzed the oxidation capacity and radical chemistry at a regional background site in Hong Kong from 23 August to 22 December 2012, which covered the summer, autumn and winter seasons. A chemical box model built on the latest Master Chemical Mechanism (v3.3) was used to elucidate the OH reactivity and sources of ROX radicals (ROX=OH+HO2+RO2). The AOC showed a clear seasonal pattern with stronger intensity in late summer compared to autumn and winter. Reactions with NO2 (30%) and oxygenated volatile organic compounds (OVOCs) (31%) together dominated the OH loss in summer, while reactions with CO (38% in autumn and 39% in winter) and OVOCs (34% in autumn and 25% in winter) made larger contributions in autumn and winter. Photolysis of O3 (36%-47%) presented the major ROX source during all three seasons. The second largest ROx source was HONO photolysis (25%) in summer compared to HCHO photolysis in autumn (20%) and winter (21%). Besides, photolysis of other OVOCs was another important primary source of ROx radicals with average contributions of 14%, 13% and 20% for the summer, autumn and winter cases, respectively. Overall, the present study evaluates the oxidizing capacity of the rural atmosphere of South China and elucidates the varying characteristics of photochemical processes in different air masses.

Recent studies have revealed potentially important effects of additional source(s) of hydroxyl radicals on the atmosphere’s oxidative capacity and, in turn, the production of secondary air pollutants. In this paper, we give an overview of our recent efforts in investigating the sources and effects of nitrous acid (HONO) on ozone and some secondary aerosols in southern China by combining field measurements and model simulations. Beginning in 2011, a series of field measurements of HONO were conducted at five sites, with diverse land use and different effects of emission sources. We observed the seasonal characteristics, emission ratios, heterogeneous production, and made simulations with a chemical transport model for the photochemical effects of HONO. The key findings are as follows. The derived emission ratios from vehicles exhibited wide variability and were mostly higher than the more uniform value of 0.8% reported in the literature. Larger nocturnal heterogeneous conversion rates of NO2 to HONO were observed when air masses were passing over sea surfaces, compared with land surfaces. Widely reported daytime sources of HONO also exist in Hong Kong. Moreover, the revised WRF-Chem model with comprehensive HONO sources significantly improved the simulations of the observed HONO, which enhanced regional hydroxyl radicals, O3, and PM2.5 by 10–20, 8–15, and 10–15% over urban areas in the Pearl River Delta region, respectively. Our studies highlight the importance of considering HONO sources when simulating secondary pollutants in polluted atmospheres.

Nitrous acid (HONO) plays important roles in tropospheric chemistry, but its source(s) are not completely understood. Here we analyze measurements of HONO, nitrogen dioxide (NO2), and related parameters at a coastal site in Hong Kong during September–December 2012. The nocturnal NO2-to-HONO conversion rates were estimated in air masses passing over land and sea surfaces. The conversion rates in the “sea cases” (3.17–3.36 × 10−2 h−1) were significantly higher than those in the “land cases” in our study (1.20–1.30 × 10−2 h−1) and in previous studies by others. These results suggest that air-sea interactions may be a significant source of atmospheric HONO and need to be considered in chemical transport models.