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The Arctic region is undergoing considerable changes and is warming at a rate three to four times as fast as the rest of the world. Aerosols, which can originate from natural or anthropogenic sources, both of which can be locally emitted or long-range transported, play a crucial role in the Arctic radiative balance by directly absorbing or scattering incoming solar radiation or indirectly by changing cloud properties and modulating cloud formation mechanisms. Here, we investigate the sources of anthropogenic and natural aerosols in the central Arctic Ocean, using data collected during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition with a high-resolution time-of-flight aerosol mass spectrometer. Using positive matrix factorization on the organic fraction of aerosols during spring and summertime (March – July), we identified six distinct chemical sources of organic aerosols (OA): a hydrocarbon-like factor, a Haze factor, two factors related to two extreme events of warm and moist air mass intrusions (WAMI) in mid-April, an Arctic oxygenated factor, and a Marine factor. We also describe the geographical origin of these factors, inferred from a potential source contribution function applied on 3-hourly back-trajectories. Together, these results suggest that OA from Eurasian anthropogenic origin (including the two extreme WAMI events in mid-April) dominate the central Arctic OA budget until at least the month of May, where episodic spikes in naturally-sourced marine OA, originating from the Fram Strait marginal ice-zone start to become important through June and July. We also highlight a hitherto unreported highly-oxygenated organic factor, whose temporal variability is closely related to that of particulate ammonium (maximum concentration in May) and whose geographical origin, in the Canadian archipelagoes, could indicate a co-emission mechanism of organic aerosols and ammonia from Arctic seabird colonies.

Understanding the mercury cycle in the Arctic is important due to the harmful bioaccumulation of its toxic form, methylmercury, in wildlife and ultimately Arctic residents. Gaseous elemental mercury (Hg(0)) is relatively well-mixed across the northern hemisphere atmosphere due to its long atmospheric lifetime. Hg(0) can be oxidized, especially in the Arctic spring during halogen-driven depletion events. The resulting gaseous oxidized mercury (Hg(II)) is relatively quickly deposited onto snow, either directly or via condensing onto particles, forming particulate mercury (PHg). It is generally understood that a large fraction of the deposited Hg(II) and PHg is photoreduced to Hg(0) and re-emitted to the atmosphere. However, mercury remaining in the snowpack till melt can become bioavailable through entering the ocean.There is a severe lack of Hg(II) and PHg observations in the central Arctic, particularly over sea ice, limiting our understanding of the mercury cycle in that region and inhibiting us from quantifying mercury budgets in all environmental compartments and particularly where it unfolds its harmful neurotoxic effects. Moreover, most of the observational efforts aiming at creating process understanding focused on spring during mercury depletion events or the snow melt period, leaving large knowledge gaps for fall and winter.Here, we show atmospheric observations of PHg during MOSAiC, measured with an aerosol mass spectrometer in fall and spring over the central Arctic pack ice. In both seasons, PHg concentrations correlate strongly with wind speed and chloride, suggesting a mechanical (wind-driven) process behind atmospheric PHg related partly to blowing snow. In addition, there are significant differences between fall and spring observations (e.g. no atmospheric mercury depletion events in fall), suggesting that various processes are at play.This wind-driven process has hitherto not been reported and is different from observations at land-based stations as well as previous measurements over sea ice that ascribed the formation of PHg to adsorption of Hg(II) onto pre-existing aerosols or diamond dust rather than aerosolization from the snow pack. We hypothesize, based on snow chemical analyzes and literature, that the elevated halide content in snow on sea ice creates complexes of PHg, which are much harder to photoreduce than Hg(II), leading to a larger PHg content in snow. These processes of forming PHg and wind-driven aerosolization have implications for the mercury content of snow and the distances over which PHg is re-deposited after atmospheric transport given that the lifetime of PHg is about one order of magnitude larger than that of Hg(II) in the atmosphere.

While the importance of bromine chemistry for the Arctic surface ozone budget is well documented, the effect of iodine chemistry has received less attention. Here we present observations performed as part of the ship-based Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition, where halogen oxides were measured during the sunlit period from March to October 2020. Ozone shows drastic loss during the boreal spring (March, April and May), when near-complete depletion is regularly observed, highlighting that ozone depletion in the central Arctic is widespread. The drastic ozone depletion coincides with ‘bromine explosion’ episodes, when bromine oxide (BrO) reaches values as high as 14.8±0.8pptv. In contrast, observations of IO show the presence of active iodine chemistry on most days during the whole sunlit period (including boreal spring, summer and autumn), presenting elevated levels of IO (usually between 0.2 and 1 pptv) that peak during spring (2.9±0.3 pptv). We find that chemical reactions between iodine and ozone are the second highest contributor to ozone loss over the study period, after ozone photolysis-initiated loss and ahead of bromine.

Sea salt aerosols play a critical role in aerosol-radiation and aerosol-cloud interactions. Salty blowing snow has been hypothesized as an important source of sea salt aerosol in polar regions. The snow over sea ice can become salty by upward brine migration or deposition of sea spray produced from leads or transported from the ice edge. Wind-driven resuspension and sublimation of the snow is hypothesized to leave salty aerosol particles behind. Our understanding of aerosol emissions from blowing snow is based mainly on modeling studies, and direct observations to validate this process are sparse. The year-long Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition, with its integrated measurements and sampling of frequent winter storms, is well suited to enhance our understanding of coupled Arctic system processes. Here, we focus on the impact of blowing snow and high wind speed events on aerosol number concentrations, size distributions, optical properties and cloud condensation nuclei (CCN) concentrations. Total aerosol number concentrations were significantly enhanced during high-wind speed periods, also concurrent with increased scattering aerosol coefficients and CCN concentrations. We further present a process-based characterization of the blowing snow events during MOSAiC and identify the influence of environmental variables on aerosol emissions. Our observations provide new insights into wind-driven aerosol in the central Arctic and may help to validate modelling studies and inform parameterization improvement particularly with respect to aerosol direct and indirect radiative forcing.

Several studies have investigated new particle formation (NPF) events from various sites ranging from pristine locations, including forest sites, to urban areas. However, there is still a dearth of studies investigating NPF processes and subsequent aerosol growth in coastal yet semi-urban sites, where the tropospheric layer is a concoction of biogenic and anthropogenic gases and particles. The investigation of factors leading to NPF becomes extremely complex due to the highly dynamic meteorological conditions at the coastline especially when combined with both continental and oceanic weather conditions. Herein, we engage in a comprehensive study of particle number size distributions and aerosol-forming precursor vapors at the coastal semi-urban site in Helsinki, Finland. The measurement period, 25 June–18 August 2019, was timed with the recurring cyanobacterial summer bloom in the Baltic Sea region and coastal regions of Finland. Our study recorded several regional/local NPF and aerosol burst events during this period. Although the overall anthropogenic influence on sulfuric acid (SA) concentrations was low during the measurement period, we observed that the regional or local NPF events, characterized by SA concentrations on the order of 107 molec.cm-3, occurred mostly when the air mass traveled over the land areas. Interestingly, when the air mass traveled over the Baltic Sea, an area enriched with algae and cyanobacterial blooms, high iodic acid (IA) concentration coincided with an aerosol burst or a spike event at the measurement site. Further, SA-rich bursts were seen when the air mass traveled over the Gulf of Bothnia, enriched with cyanobacterial blooms. The two most important factors affecting aerosol precursor vapor concentrations, and thus the aerosol formation, were speculated to be (1) the type of phytoplankton species and intensity of bloom present in the coastal regions of Finland and the Baltic Sea and (2) the wind direction. During the events, most of the growth of sub-3 nm particles was probably due to SA, rather than IA or methane sulfonic acid (MSA); however much of the particle growth remained unexplained indicative of the strong role of organics in the growth of particles, especially in the 3–7 nm particle size range. Further studies are needed to explore the role of organics in NPF events and the potential influence of cyanobacterial blooms in coastal locations.

Near-surface mercury and ozone depletion events occur in the lowest part of the atmosphere during Arctic spring. Mercury depletion is the first step in a process that transforms long-lived elemental mercury to more reactive forms within the Arctic that are deposited to the cryosphere, ocean, and other surfaces, which can ultimately get integrated into the Arctic food web. Depletion of both mercury and ozone occur due to the presence of reactive halogen radicals that are released from snow, ice, and aerosols. In this work, we added a detailed description of the Arctic atmospheric mercury cycle to our recently published version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem 4.3.3) that includes Arctic bromine and chlorine chemistry and activation/recycling on snow and aerosols. The major advantage of our modelling approach is the online calculation of bromine concentrations and emission/recycling that is required to simulate the hourly and daily variability of Arctic mercury depletion. We used this model to study coupling between reactive cycling of mercury, ozone, and bromine during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) spring season in 2020 and evaluated results compared to land-based, ship-based, and remote sensing observations. The model predicts that elemental mercury oxidation is driven largely by bromine chemistry and that particulate mercury is the major form of oxidized mercury. The model predicts that the majority (74%) of oxidized mercury deposited to land-based snow is re-emitted to the atmosphere as gaseous elemental mercury, while a minor fraction (4%) of oxidized mercury that is deposited to sea ice is re-emitted during spring. Our work demonstrates that hourly differences in bromine/ozone chemistry in the atmosphere must be considered to capture the springtime Arctic mercury cycle, including its integration into the cryosphere and ocean.

Dry deposition to the surface is one of the main removal pathways of tropospheric ozone (O3). We quantified for the first time the impact of O3 deposition to the Arctic sea ice on the planetary boundary layer (PBL) O3 concentration and budget using year-round flux and concentration observations from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) campaign and simulations with a single-column atmospheric chemistry and meteorological model (SCM). Based on eddy-covariance O3 surface flux observations, we find a median surface resistance on the order of 20,000 s m−1, resulting in a dry deposition velocity of approximately 0.005 cm s−1. This surface resistance is up to an order of magnitude larger than traditionally used values in many atmospheric chemistry and transport models. The SCM is able to accurately represent the yearly cycle, with maxima above 40 ppb in the winter and minima around 15 ppb at the end of summer. However, the observed springtime ozone depletion events are not captured by the SCM. In winter, the modelled PBL O3 budget is governed by dry deposition at the surface mostly compensated by downward turbulent transport of O3 towards the surface. Advection, which is accounted for implicitly by nudging to reanalysis data, poses a substantial, mostly negative, contribution to the simulated PBL O3 budget in summer. During episodes with low wind speed (

27 pages, 12 figures, supplement https://doi.org/10.5194/acp-23-389-2023.-- Data availability: All data sets used in this work that were obtained during the MOSAiC campaign will be made publicly available by 1 January 2023 via PANGAEA (https://www.pangaea.de/, last access: June 2022) or are already publicly available in the Department of Energy Atmospheric Radiation Measurement program (ARM) user facility data discovery tool (https://adc.arm.gov/discovery/#/, last access: March 2022). Data from the PANGAEA archive include the following. Meteorological observations from Polarstern: Schmithüsen, H.: Continuous meteorological surface measurement during POLARSTERN cruise PS122/1. Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Bremerhaven, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.935221, 2021a. Schmithüsen, H.: Continuous meteorological surface measurement during POLARSTERN cruise PS122/2. Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Bremerhaven, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.935222, 2021b. Schmithüsen, H.: Continuous meteorological surface measurement during POLARSTERN cruise PS122/3. Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Bremerhaven, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.935223, 2021c. Schmithüsen, H.: Continuous meteorological surface measurement during POLARSTERN cruise PS122/4. Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Bremerhaven, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.935224, 2021d. Schmithüsen, H.: Continuous meteorological surface measurement during POLARSTERN cruise PS122/5. Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Bremerhaven, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.935225, 2021e. Black carbon (BC): Heutte, B., Beck, I., Quéléver, L., Jokinen, T., Laurila, T., Dada, L., Schmale, J.: Equivalent black carbon concentration in 10 minutes time resolution, measured in the Swiss container during MOSAiC 2019/2020, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.952251, 2022. Particle number concentration (CPC3025): Beck, I., Quéléver, L., Laurila, T., Jokinen, T., and Schmale, J.: Continuous corrected particle number concentration data in 10 sec resolution, measured in the Swiss aerosol container during MOSAiC 2019/2020, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.941886, 2022b. The ARM data include the following: Kuang, C., Singh, A., and Howie, J.: Scanning mobility particle sizer (AOSSMPS), ARM [data set], https://doi.org/10.5439/1476898, 2022. Kuang, C., Salwen, C., Boyer, M., and Singh, A.: Condensation Particle Counter (AOSCPCF), ARM [data set], https://doi.org/10.5439/1046184, 2022. The land-based PNSD data: Alert: Personal communication from Tak Chan and Sangeeta Sharma, 2022 (for details, see Croft et al., 2016). Villum: Personal communication from Jakob Boyd Pernov, 2022 (for details, see Nguyen et al., 2016). Zeppelin: Personal communication from Peter Tunved, 2022 (for details, see Tunved et al., 2013). Tiksi: Personal communication from Eija Asmi, 2022 (for details, see Asmi et al., 2016). Utqiaġvik: Freud, E., Krejci, R., Tunved, P., Leaitch, W. R., Nguyen, Q. T., Massling, A., Skov, H., and Barrie, L.: Hourly mean homogenised (dry diameter range 20 to 500 nm) observations of aerosol number size distributions from station Barrow, 2007-09-20 to 2015-07-09, PANGAEA [data set], https://doi.org/10.1594/PANGAEA.877329, 2017b. The land-based BC data: Villum: Personal communications from Daniel Thomas, Jakob Klenø Nøjgaard, and Andreas Massling, 2022 (for details, see Thomas et al., 2022). NOAA Barrow Atmospheric Baseline Observatory (Utqiaġvik) during 2020: personal communication from Elisabeth Andrews, 2022 (for processing details, see Schmale et al., 2022). Gruvebadet. The PSAP data are accessible at the Italian Arctic Data Center operated by the National Research Council of Italy: https://data.iadc.cnr.it/erddap/tabledap/ebc_2010_2020.html (last access: December 2021, refer to Schmale et al., 2022, for additional details). All other BC data sets used in this work will be made publicly available on EBAS (http://ebas-data.nilu.no/, last access: December 2021, refer to Schmale et al., 2022, for additional details). The Arctic Oscillation (AO) data are publicly available from the NOAA and the National Weather Service: https://www.cpc.ncep.noaa.gov/products/precip/CWlink/daily_ao_index/ao.shtml (last access: June 2022). An archive of the FLEXPART model output and quick looks for the whole campaign can be found at https://img.univie.ac.at/webdata/mosaic (last access: March 2022), The Arctic environment is rapidly changing due to accelerated warming in the region. The warming trend is driving a decline in sea ice extent, which thereby enhances feedback loops in the surface energy budget in the Arctic. Arctic aerosols play an important role in the radiative balance and hence the climate response in the region, yet direct observations of aerosols over the Arctic Ocean are limited. In this study, we investigate the annual cycle in the aerosol particle number size distribution (PNSD), particle number concentration (PNC), and black carbon (BC) mass concentration in the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. This is the first continuous, year-long data set of aerosol PNSD ever collected over the sea ice in the central Arctic Ocean. We use a k-means cluster analysis, FLEXPART simulations, and inverse modeling to evaluate seasonal patterns and the influence of different source regions on the Arctic aerosol population. Furthermore, we compare the aerosol observations to land-based sites across the Arctic, using both long-term measurements and observations during the year of the MOSAiC expedition (2019–2020), to investigate interannual variability and to give context to the aerosol characteristics from within the central Arctic. Our analysis identifies that, overall, the central Arctic exhibits typical seasonal patterns of aerosols, including anthropogenic influence from Arctic haze in winter and secondary aerosol processes in summer. The seasonal pattern corresponds to the global radiation, surface air temperature, and timing of sea ice melting/freezing, which drive changes in transport patterns and secondary aerosol processes. In winter, the Norilsk region in Russia/Siberia was the dominant source of Arctic haze signals in the PNSD and BC observations, which contributed to higher accumulation-mode PNC and BC mass concentrations in the central Arctic than at land-based observatories. We also show that the wintertime Arctic Oscillation (AO) phenomenon, which was reported to achieve a record-breaking positive phase during January–March 2020, explains the unusual timing and magnitude of Arctic haze across the Arctic region compared to longer-term observations. In summer, the aerosol PNCs of the nucleation and Aitken modes are enhanced; however, concentrations were notably lower in the central Arctic over the ice pack than at land-based sites further south. The analysis presented herein provides a current snapshot of Arctic aerosol processes in an environment that is characterized by rapid changes, which will be crucial for improving climate model predictions, understanding link, This research has been supported by the Academy of Finland (grant no. 337552), Horizon 2020 (EMME-CARE, grant no. 856612), the US Department of Energy (grant no. DE-SC0022046), and the Swiss Polar Institute (grant no. 188478), With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

6 pags., 2 figs., Unlike bromine, the effect of iodine chemistry on the Arctic surface ozone budget is poorly constrained. We present ship-based measurements of halogen oxides in the high Arctic boundary layer from the sunlit period of March to October 2020 and show that iodine enhances springtime tropospheric ozone depletion. We find that chemical reactions between iodine and ozone are the second highest contributor to ozone loss over the study period, after ozone photolysis-initiated loss and ahead of bromine., This study received funding from the European Research Council Executive Agency under the European Union’s Horizon 2020 Research and Innovation Program (project ERC‐2016‐COG 726349 CLIMAHAL and ERC-2016-STG 714621 GASPARCON) and the European Commission via the EMME-CARE project and was supported by the Consejo Superior de Investigaciones Científicas of Spain. This work was supported by the European Union’s Horizon 2020 Research and Innovation Programme under grant agreement no. 856612 and the Academy of Finland (project no. 334514). The Indian Institute of Tropical Meteorology is funded by the Ministry of Earth Sciences, Government of India. Ozone, CO, CH4 and AMS measurements were funded by the Swiss National Science Foundation (grant 200021_188478), the Swiss Polar Institute and U.S. National Science Foundation grants 1914781 and 1807163. J.S. holds the Ingvar Kamprad chair for extreme environments research, sponsored by Ferring Pharmaceuticals. Data reported in this manuscript were produced as part of the international MOSAiC expedition with tag MOSAiC20192020, with activities supported by Polarstern expedition AWI-PS122_00. H.S. was funded by the European ERA-PLANET projects iGOSP and iCUPE (consortium agreement no. 689443 for both projects). We thank FORMAS and the Swedish Polar Research Secretariat for support. We gratefully acknowledge funding by the Deutsche Forschungsgemeinschaft (project no. 268020496 – TRR 172) within the Transregional Collaborative Research Center ‘ArctiC Amplification: Climate Relevant Atmospheric and SurfaCe Processes, and Feedback Mechanisms (AC)3’ in subproject C03. We thank I. Bourgeois (NOAA/CIRES) for providing the ATom NOx data.

The Arctic environment is rapidly changing due to accelerated warming in the region. The warming trend is driving a decline in sea ice extent, which thereby enhances feedback loops in the surface energy budget in the Arctic. Arctic aerosols play an important role in the radiative balance, and hence the climate response, in the region; yet direct observations of aerosols over the Arctic Ocean are limited. In this study, we investigate the annual cycle in the aerosol particle number size distribution (PNSD), particle number concentration (PNC), and black carbon (BC) mass concentration in the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. This is the first continuous, year-long dataset of aerosol PNSD ever collected over the sea ice in the central Arctic Ocean. We use a k-means cluster analysis, FLEXPART simulations, and inverse modeling to evaluate seasonal patterns and the influence of different source regions on the Arctic aerosol population. Furthermore, we compare the aerosol observations to land-based sites across the Arctic, using both long-term measurements and observations during the year of the MOSAiC expedition (2019–2020), to investigate interannual variability and to give context to the aerosol characteristics from within the central Arctic. Our analysis identifies that, overall, the central Arctic exhibits typical seasonal patterns of aerosols, including anthropogenic influence from Arctic Haze in winter and secondary aerosol processes in summer. The seasonal pattern corresponds with the global radiation, surface air temperature, and the timing of sea ice melting/freezing, which drives changes in transport patterns and secondary aerosol processes. In winter, the Norilsk region in Russia/Siberia was the dominant source of Arctic Haze signal in the PNSD and BC observations, which contributed to higher accumulation mode PNC and BC mass concentration in the central Arctic than at land-based observatories. We also show that the wintertime Arctic Oscillation (AO) phenomenon, which was reported to achieve a record-breaking positive phase during January–March 2020, explains the unusual timing and magnitude of Arctic Haze across the Arctic region compared to longer-term observations. In summer, the PNC of nucleation and Aitken mode aerosol is enhanced, but concentrations were notably lower in the central Arctic over the ice pack than at land-based sites further south. The analysis presented herein provides a current snapshot of Arctic aerosol processes in an environment that is characterized by rapid changes, which will be crucial for improving climate model predictions, understanding linkages between different environmental processes, and investigating the impacts of climate change in future Arctic aerosol studies.

Understanding chemical processes leading to the formation of atmospheric aerosol particles is crucial to improve our capabilities in predicting the future climate. However, those mechanisms are still inadequately characterized, especially in polar regions. In this study, we report observations of neutral and charged aerosol precursor molecules and chemical cluster composition (qualitatively and quantitatively), as well as air ions and aerosol particle number concentrations and size distributions from the Marambio research station (64∘15′ S, 56∘38′ W), located north of the Antarctic Peninsula. We conducted measurements during the austral summer, between 15 January and 25 February 2018. The scope of this study is to characterize new particle formation (NPF) event parameters and connect our observations of gas-phase compounds with the formation of secondary aerosols to resolve the nucleation mechanisms at the molecular scale. NPF occurred on 40 % of measurement days. All NPF events were observed during days with high solar radiation, mostly with above-freezing temperatures and with low relative humidity. The averaged formation rate for 3 nm particles (J3) was 0.686 cm−3 s−1, and the average particle growth rate (GR3.8–12 nm) was 4.2 nm h−1. Analysis of neutral aerosol precursor molecules showed measurable concentrations of iodic acid (IA), sulfuric acid (SA), and methane sulfonic acid (MSA) throughout the entire measurement period with significant increase in MSA and SA concentrations during NPF events. We highlight SA as a key contributor to NPF processes, while IA and MSA likely only contribute to particle growth. Mechanistically, anion clusters containing ammonia and/or dimethylamine (DMA) and SA were identified, suggesting significant concentration of ammonia and DMA as well. Those species are likely contributing to NPF events since SA alone is not sufficient to explain observed nucleation rates. Here, we provide evidence of the marine origin of the measured chemical precursors and discuss their potential contribution to the aerosol phase.

Understanding chemical processes leading to the formation of atmospheric aerosol particles is crucial to improve our capabilities in predicting the future climate. However, those mechanisms are still inadequately characterized, especially in polar regions, which are typically representative of the pre-industrial era in climate models. In this study, we report observations of neutral and charged aerosol precursor molecules and chemical clusters composition (qualitatively and quantitatively), as well as air ions and aerosol particle number concentrations and size distributions from the Marambio research station (64°15'S–56°38'W), located North of the Antarctic Peninsula. We conducted measurements during the austral summer, between 15 January and 25 February 2018. The scope of this study is to characterize New Particle Formation (NPF) event parameters and connect our observations of gas phase compounds with the formation of secondary aerosols to resolve the nucleation mechanisms at the molecular scale. NPF occurred on 40% of measurement days (i.e., 13 NPF events were recorded during 35 days). All NPF events were observed during sunny days (i.e., sufficient radiation), mostly with above freezing temperatures and low relative humidity (RH < 80 %). The averaged formation rate for 3 nm particles (J3) was 0.686 cm−3 s−1 and the average particle growth rate (GR 3.8–12 nm) was 4.2 nm h−1. Analysis of neutral aerosol precursor molecules showed measurable concentrations of iodic acid (IA), sulfuric acid (SA) and methane sulfonic acid (MSA) throughout the entire measurement period with average concentrations of 5.17 × 105, 1.18 × 106, 2.06 × 105 molecules cm−3, respectively. MSA and SA concentrations significantly increased during NPF events. We highlight SA as a key contributor to NPF processes, while IA and MSA would likely only contribute to particle growth. Mechanistically, anion clusters of dimethylamine (DMA)-bisulfate (2SA) as well as numerous ammonium-(bi)sulfate clusters were identified, with the latter at mass-to-charge ratios (m/z) larger than 1000 Th. All of which suggests elevated concentration of both ammonia and amines in the atmosphere. Those species are likely contributing to NPF events since SA alone is not sufficient to explain observed nucleation rates. Here, we provide evidence of the marine origin of the measured chemical precursors and discuss their potential contribution to the aerosol phase. Our observations highlight the importance of the Antarctic Ocean, water, and ice ecosystems interacting with the land-fauna – the plausible sources of the principal precursor molecules hereby investigated – for secondary aerosol formation.

International audience; With the Arctic rapidly changing, the needs to observe, understand, and model the changes are essential. To support these needs, an annual cycle of observations of atmospheric properties, processes, and interactions were made while drifting with the sea ice across the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition from October 2019 to September 2020. An international team designed and implemented the comprehensive program to document and characterize all aspects of the Arctic atmospheric system in unprecedented detail, using a variety of approaches, and across multiple scales. These measurements were coordinated with other observational teams to explore cross-cutting and coupled interactions with the Arctic Ocean, sea ice, and ecosystem through a variety of physical and biogeochemical processes. This overview outlines the breadth and complexity of the atmospheric research program, which was organized into 4 subgroups: atmospheric state, clouds and precipitation, gases and aerosols, and energy budgets. Atmospheric variability over the annual cycle revealed important influences from a persistent large-scale winter circulation pattern, leading to some storms with pressure and winds that were outside the interquartile range of past conditions suggested by long-term reanalysis. Similarly, the MOSAiC location was warmer and wetter in summer than the reanalysis climatology, in part due to its close proximity to the sea ice edge. The comprehensiveness of the observational program for characterizing and analyzing atmospheric phenomena is demonstrated via a winter case study examining air mass transitions and a summer case study examining vertical atmospheric evolution. Overall, the MOSAiC atmospheric program successfully met its objectives and was the most comprehensive atmospheric measurement program to date conducted over the Arctic sea ice. The obtained data will support a broad range of coupled-system scientific research and provide an important foundation for advancing multiscale modeling capabilities in the Arctic.

Aerosol particles form in the atmosphere via the clustering of certain atmospheric vapors. After growing into larger particles by the condensation of low-volatility gases, they can affect the Earth's climate by scattering light and acting as cloud condensation nuclei (CCN). Observations of low-volatility aerosol precursor gases have been reported around the world, but longer-term measurement series and any Arctic data sets showing seasonal variation are close to nonexistent. Here, we present ∼7 months of aerosol precursor gas measurements performed with a nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer. We deployed our measurements ∼150 km north of the Arctic Circle at the SMEAR I (Station for Measuring Ecosystem–Atmosphere Relations) continental Finnish subarctic field station, located in the Värriö strict nature reserve. We report concentration measurements of the most common compounds related to new particle formation (NPF): sulfuric acid (SA), methane sulfonic acid (MSA), iodic acid (IA) and the total concentration of highly oxygenated organic molecules (HOMs). At this remote measurement site, SA originates from both anthropogenic and biological sources and has a clear diurnal cycle but no significant seasonal variation. MSA shows a more distinct seasonal cycle, with concentrations peaking in the summer. Of the measured compounds, IA concentrations are the most stable throughout the measurement period, except in April during which time the concentration of IA is significantly higher than during the rest of the year. Otherwise, IA has almost identical daily maximum concentrations in spring, summer and autumn, and on NPF event or non-event days. HOMs are abundant during the summer months and low in the autumn months. Due to their low autumn concentrations and high correlation with ambient air temperature, we suggest that most HOMs are products of biogenic emissions, most probably monoterpene oxidation products. NPF events at SMEAR I happen under relatively low-temperature (1–8 ∘C) conditions, with a fast temperature rise in the early morning hours as well as lower and decreasing relative humidity (RH, 55 % vs. 80 %) during NPF days compared with non-event days. NPF days have clearly higher global irradiance values (∼450 m−2 vs. ∼200 m−2) and about 10 ppbv higher ozone concentrations than non-event days. During NPF days, we have, on average, higher SA concentrations, peaking at noon; higher MSA concentrations in the afternoon; and slightly higher IA concentration than during non-event days. In summary, these are the first long-term measurements of aerosol-forming vapors from SMEAR I in the subarctic region, and the results of this work will help develop an understanding of atmospheric chemical processes and aerosol formation in the rapidly changing Arctic.

Measurements of aerosol particles and clusters smaller than 3 nm in diameter are performed by many groups in order to detect recently formed or emitted nanoparticles and for studying the formation and early growth processes of aerosol particles. The Airmodus nano-Condensation Nucleus Counter (nCNC), consisting of a Particle Size Magnifier (PSM) and a Condensation Particle Counter (CPC) is a versatile tool to detect aerosol particles and clusters as small as ca. 1 nm in mobility diameter. It offers several different operation modes: fixed mode to measure the total particle number concentration with a fixed, but adjustable lower cut-off size and stepping and scanning modes for retrieving size-resolved information of ca. 1–4 nm particles. The size analysis is based on changing the supersaturation of the working fluid (diethylene glycol) inside the instrument, which changes the lowest detectable size. Here we present a standard operating procedure (SOP) for setting up, calibrating and operating the instrument for atmospheric field measurements. We will also present recommendations for data monitoring and analysis, and discuss some of the uncertainties related to the measurements. This procedure is the first step in harmonizing the use of the PSM/nCNC for atmospheric field measurements of sub-3 nm clusters and particles. Measurements of aerosol particles and clusters smaller than 3 nm in diameter are performed by many groups in order to detect recently formed or emitted nanoparticles and for studying the formation and early growth processes of aerosol particles. The Airmodus nano-Condensation Nucleus Counter (nCNC), consisting of a Particle Size Magnifier (PSM) and a Condensation Particle Counter (CPC) is a versatile tool to detect aerosol particles and clusters as small as ca. 1 nm in mobility diameter. It offers several different operation modes: fixed mode to measure the total particle number concentration with a fixed, but adjustable lower cut-off size and stepping and scanning modes for retrieving size-resolved information of ca. 1–4 nm particles. The size analysis is based on changing the supersaturation of the working fluid (diethylene glycol) inside the instrument, which changes the lowest detectable size. Here we present a standard operating procedure (SOP) for setting up, calibrating and operating the instrument for atmospheric field measurements. We will also present recommendations for data monitoring and analysis, and discuss some of the uncertainties related to the measurements. This procedure is the first step in harmonizing the use of the PSM/nCNC for atmospheric field measurements of sub-3 nm clusters and particles.

One way to form aerosol particles is the condensation of oxidized atmospheric trace gases, such as sulfuric acid (SA) into small molecular clusters. After growing to larger particles by condensation of low volatile gases, they can affect the planets climate directly by scattering light and indirectly by acting as cloud condensation nuclei. Observations of low-volatility aerosol precursor gases have been reported around the world but long-term measurement series and Arctic data sets showing seasonal variation are close to non-existent. In here, we present ~7 months of aerosol precursor gas measurements performed with the nitrate based chemical ionization mass spectrometer (CI-APi-TOF). We deployed our measurements ~250 km above the Arctic Circle at the Finnish sub-Arctic field station, SMEAR I in Värriö. We report concentration measurements of the most common new particle formation related compounds; sulfuric acid, methanesulfonic acid (MSA), iodic acid (IA) and highly oxygenated organic compounds, HOMs. At this remote measurement site, surrounded by a strict nature preserve, that gets occasional pollution from a Russian city of Murmansk, SA is originated both from anthropogenic and biological sources and has a clear diurnal cycle but no significant seasonal variation, while MSA as an oxidation product of purely biogenic sources is showing a more distinct seasonal cycle. Iodic acid concentrations are the most stable throughout the measurement period, showing almost identical peak concentrations for spring, summer and autumn. HOMs are abundant during the summer months and due to their high correlation with ambient air temperature, we suggest that most of HOMs are products of monoterpene oxidation. New particle formation events at SMEAR I happen under relatively low temperatures, low relative humidity, high ozone concentration, high SA concentration in the morning and high MSA concentrations in the afternoon. The role of HOMs in aerosol formation will be discussed. All together, these are the first long term measurements of aerosol forming precursor from the sub-arctic region helping us to understand atmospheric chemical processes and aerosol formation in the rapidly changing Arctic.

Aerosols can originate from different sources and undergo various formation pathways. New Particle formation (NPF) events occur when precursor vapors nucleate and vapors with low volatility condense on the critical nuclei enabling them to grow to cloud condensation nuclei (CCN) relevant sizes. As CCN, these aerosols affect the occurrence of clouds and their lifetime on local, regional and global level. Many studies have investigated new particle formation events from various sites ranging from urban areas, boreal forests to pristine locations; however, there is still a dearth of studies investigating coastal new particle formation, which is a complex phenomenon due to the dynamic and ever-changing atmospheric conditions at the coast. A comprehensive study of particle number distributions and aerosol forming precursor vapors was carried out in a coastal capital city of Finland, Helsinki, during the summer of 2019. The experimental setup comprising of a nitrate-based chemical ionization atmospheric pressure interface time of flight mass spectrometer (CI-APi-TOF), a neutral cluster-air ion spectrometer (NAIS) and a particle size magnifier (PSM) were housed in and around the SMEAR III station in Kumpula Science campus. SMEAR III is a unique site situated in a semi-urban yet coastal location. The period of experiment coincided with the cyanobacterial bloom in the coastal areas of Finland and in the Baltic Sea region. Our study recorded several regional NPF and aerosol burst events during this period. High concentrations of sulfuric acid was found to be associated with the regional NPF events whereas increasing iodic acid concentrations was mostly associated with the initiation of burst events. The sources of sulfuric acid and iodic acid has been carefully evaluated in this study.

In the high Arctic, the climate is warming faster than in the lower latitudes due to the Arctic amplification. Sea ice is melting and permafrost is thawing, and the scarce vegetation of the Arctic is changing rapidly. All these varying conditions will have an impact on possible emission sources of aerosol precursor gases, thus affecting the New Particle Formation (NPF) in the Arctic atmosphere, of which we still know very little. It is important to study the NPF events, which parameters affect the aerosol phase and how these newly formed aerosols can grow into cloud condensation nuclei sizes. Only then, it is possible to understand how climate change is affecting the aerosol population, clouds and regional climate of the pristine Arctic. The role of the precursor gases like Sulphuric Acid (SA), Iodic Acid (IA), Methane Sulphonic Acid (MSA) and Highly Oxygenated organic Molecules (HOM) in NPF in boreal and urban environments has been explored to a great extent. However, the role of these precursor gases in NPF events in remote locations - devoid of pollution sources and the vegetation - is still ambiguous. Therefore, it is crucial to conduct long-term measurements to study the composition and concentrations of aerosol precursors molecules, nanoparticles and air ions in remote and climatically fragile place like Ny-Ålesund in the Arctic. This research location is not only a natural pristine laboratory to understand the atmospheric processes but also acts as a climate mirror reflecting the most drastic changes happening in the atmosphere and cryosphere. In this study, we aim to enhance the understanding of the role of aerosol precursor gases in new particle formation in Ny-Ålesund, Svalbard. We have studied aerosol particle formation now for almost three years in the Ny-Ålesund research village in Svalbard (78° 55' 24.7368'' N, 11° 54' 35.6220'' E.) with the Neutral cluster and Air Ion Spectrometer (NAIS) measuring ~1-40 nm particles and ions. We have conducted measurements with a Chemical Ionization Atmospheric Pressure interface Time Of Flight (CI-APi-TOF) mass spectrometer to understand the chemical composition of organic precursors vapours and abundance of inorganic aerosol precursor gases such as SA, MSA and IA. Additionally, we have studied the emission and composition of volatile organic compounds on the site during summer-time. In this study, we report the time series concentrations of the most common aerosol precursor gases like SA, MSA, IA and HOM from the period 28.6.-25.7.2019, which are responsible for the initiation and/or growth of particles. The variability in the concentrations of these vapours is compared between NPF event and non-event days. The study explores also the role of meteorological parameters like wind speed, wind direction, temperature and humidity on NPF processes.

The Arctic is a unique region featuring many environmental variations from a season to another. For example, sea ice is highly dynamic, with varying thickness and homogeneity, ultimately leading to open sea with a boost of biological activity during the warmest month. This, in turn, affects the emissions of gas-phase chemicals, potentially impacting New Particle Formation (NPF) and subsequent aerosol growth.Several chemical vapors such as sulfuric acid (SA) and methane sulfonic acid (MSA) are known to possibly contribute to NPF and/or particle growth. Additionally, halogenated compounds, such as iodic acid, have recently revealed to be important for the formation of aerosol particles, especially in coastal and Arctic sites.Few studies exist regarding direct measurements of iodic acid in the high Arctic, and none of them report multi-seasonal continuous observations - especially during the polar-night when the extremely low temperatures and the absence of solar radiation would likely prohibit any synthesis of such chemical species.Here, we present our observations of iodine-containing vapors, principally iodic acid, as the result of continuous on-line measurements with the Nitrate based Chemical Ionization Atmospheric Pressure interface Time Of Flight Mass Spectrometer (NO3-CI-APi-TOF-MS) during the whole Multidisciplinary Drifting Observatory of the Study of Arctic Climate (MOSAiC) expedition. In this study we combine and examine iodic acid multi-seasonal concentration time series in the central Arctic. In short, we aim at characterizing the observed iodic acid with the central Arctic environmental conditions (e.g., meteorological conditions, sea ice features and trace gases) and the linkage to NPF and particle growth.

The Arctic aerosol and trace gas regime features strong seasonal differences. The haze season in winter is dominated by long-range transported mid-latitude anthropogenic emissions, while the cleaner summer season is characterized by more local and natural trace gas and aerosol sources. Aerosols and trace gases have been shown to be important for the Arctic radiative balance, inducing an overall net positive radiative forcing through direct radiation interactions.Aerosols and trace gases are fundamentally different between seasons in terms of chemical composition and microphysical properties. In winter, accumulation mode particles - with a concentration between 100 and 300 cm-3- composed mainly of sulfate, sodium and organics occur, and trace gases relevant for aerosol formation have very low concentrations. In summer, the aerosol number concentration is highly variable reaching from a few to thousands per cubic centimeter, in case of new particle formation. Their size distribution contains nucleation, Aitken and accumulation modes. Trace gases become more abundant, particularly in the marginal ice zone where marine microbial activity emits dimethylsulfide, which leads to the formation of the trace gases sulfuric acid and methanesulfonic acid, which in turn form secondary aerosol mass.The transition seasons, i.e. spring and autumn, have been studied much less in terms of aerosol and trace gas chemical and microphysical properties in the past , except for ozone depletion events in spring where halogenated trace gases are predominantly involved. The transition between the two aerosol regimes is relatively short. Focusing on spring, the season is characterized by the arrival of warmer and moister air masses from the south, which transport different aerosols and trace gases up north. Cloud formation and precipitation en route have a strong impact on the aerosol number concentrations and size distribution, as well as on the chemical composition due to heterogeneous chemistry in cloud droplets.Here, we present first results from observations of warm air mass intrusions reaching the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in mid-April 2020. The period before arrival was characterized by persistent northerly winds, hence aged and dry Arctic air masses, where a very stable accumulation mode composed of sulfate and organics with traces of halogens was measured. With the arrival of southerly air masses, the size distribution started featuring several modes, which increased and decreased in diameter and concentration. Moreover, the chemical composition was significantly changed, featuring methanesulfonic acid from algal blooms in the north Atlantic.

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.

11 pags., 4 figs., New particle formation in the Arctic atmosphere is an important source of aerosol particles. Understanding the processes of Arctic secondary aerosol formation is crucial due to their significant impact on cloud properties and therefore Arctic amplification. We observed the molecular formation of new particles from low-volatility vapors at two Arctic sites with differing surroundings. In Svalbard, sulfuric acid (SA) and methane sulfonic acid (MSA) contribute to the formation of secondary aerosol and to some extent to cloud condensation nuclei (CCN). This occurs via ion-induced nucleation of SA and NH and subsequent growth by mainly SA and MSA condensation during springtime and highly oxygenated organic molecules during summertime. By contrast, in an ice-covered region around Villum, we observed new particle formation driven by iodic acid but its concentration was insufficient to grow nucleated particles to CCN sizes. Our results provide new insight about sources and precursors of Arctic secondary aerosol particles., The authors acknowledge European Research Council (GASPARCON, Grant no. 714621 and COALA, Grant no. 638703), Academy of Finland (Project nos. 296628, 306853, 317380, 316114, and 320094), INTERACT, European Regional Development Fund (project MOBTT42), Austrian Science Fund (FWF, Project J3951-N36), the European Union's Horizon 2020 Research and Innovation Program (Grant no. 689443) via project iCUPE (Integrative and Comprehensive Understanding on Polar Environments) and Project ERC-2016- COG 726349 CLIMAHAL, National Research Foundation (NRF) of the Ministry of Science, ICT and Future Planning (NRF-2018R1A2A1A19019281), Knut-and-Alice-Wallenberg Foundation within the Arctic Climate Across Scales (Project No. \,2016.0024), the Swedish EPA's (Naturvårdsverket) Environmental monitoring program (Miljöövervakning), the Swedish Research Council FORMAS (Project "Interplay between water, clouds and Aerosols in the Arctic," \# 2016-01427), Climate Change Tower – Integrated Project of the National Research Council of Italy and the National Interest Project by the Italian Minister of Education, University and Research (PRIN2007 and PRIN2009). The authors thank Department of Earth System Sciences and Technologies for the Environment, Department of Earth Sciences and Technology of the Environment of CNR and the doctoral program in atmospheric sciences at the University of Helsinki for financial support. Aarhus University acknowledge financial support from Danish Ministry of Environment and food and Ministry of Climate, Energy and Utilities by means of DANCEA.

Intense and frequent new particle formation (NPF) events have been observed in polluted urban environments, yet the dominant mechanisms are still under debate. To understand the key species and governing processes of NPF in polluted urban environments, we conducted comprehensive measurements in downtown Beijing during January–March, 2018. We performed detailed analyses on sulfuric acid cluster composition and budget, as well as the chemical and physical properties of oxidized organic molecules (OOMs). Our results demonstrate that the fast clustering of sulfuric acid (H2SO4) and base molecules triggered the NPF events, and OOMs further helped grow the newly formed particles toward climate- and health-relevant sizes. This synergistic role of H2SO4, base species, and OOMs in NPF is likely representative of polluted urban environments where abundant H2SO4 and base species usually co-exist, and OOMs are with moderately low volatility when produced under high NOx concentrations. publishedVersion

To quantify the contribution of new particle formation (NPF) to ultrafine particle number and CCN budgets, one has to understand the mechanisms that govern NPF in different environments and its temporal extent. Here, we study NPF in Cyprus, an Eastern Mediterranean country located at the crossroads of three continents. We performed one-year continuous measurements of aerosol particles down to ~ 1 nm in diameter, for the first time in the Eastern Mediterranean and Middle East (EMME) region. These measurements were complemented with trace gas data, meteorological variables and retroplume analysis. We show that NPF is a very frequent phenomenon at this site and has higher frequencies of occurrence during spring and autumn. NPF events were both of local and regional origin, and the local events occurred frequently during the month with the lowest NPF frequency. Some NPF events exhibited multiple onsets, while others exhibited particle apparent shrinkage in size. Additionally, NPF events were observed during the night-time and during episodes of high desert dust loadings. Particle formation rates and growth rates were comparable to those in urban environments, although our site is a rural one. Meteorological variables and trace gases played a role in explaining the intra-monthly variability of NPF events, but did not explain why summer month had the least NPF frequency. Similarly, pre-existing aerosol loading did not explain the observed seasonality. The month with the least NPF frequency were associated with higher H2SO4 concentrations but lower NOx concentration, which is an indicator of anthropogenic influence. Air masses arriving from the Middle East were not observed during these month, which could suggest that precursor vapors important for nucleation and growth are transported to our site from the Middle East. Further comprehensive measurements of precursor vapors are required to prove this hypothesis.

Trace iodine vapours have a significant impact on atmospheric chemistry, influencing catalytic ozone destruction and the HOx / NOx cycles. Oxidized iodine species also form aerosols in coastal and polar regions (O’Dowd et al, 2002), playing a direct role in Earth’s radiation balance. It was recently shown that iodic acid (HIO3) has a significant impact on coastal new particle formation processes (Sipilä et al., 2016). However, neutral HIO3 molecules have only been measured in two sites (Sipilä et al., 2016).In this study, a global observation of HIO3 has been carried out in ten sites around the globe, including city sites, Arctic and Antarctica sites, a remote island site, a coastal site and a boreal forest site. While the existence of HIO3 is unambiguously revealed in all of the sites, its concentration varies significantly among them. Dedicated laboratory experiments are required to examine the particle formation rates from iodine-containing species to be able to predict their global importance in particle formation, and further, in cloud condensation nuclei formation. O’Dowd, C. D. et al. Marine aerosol formation from biogenic iodine emissions. Nature 417, 632–6 (2002)Sipilä, M. et al. Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3. Nature 537, 532–534 (2016).

Sulphuric acid has been shown to be a key driver for new particle formation and subsequent growth in various environments mainly due to its low volatility. However, direct measurements of gas-phase sulphuric acid are oftentimes not available, and the current sulphuric acid proxies cannot predict for example its nighttime concentrations or result in significant discrepancies with measured values. Here, we define the sources and sinks of sulphuric acid in different environments and derive a new physical proxy for sulphuric acid to be utilized in locations and during periods when it is not measured. We used H2SO4 measurements from four different locations: Hyytiälä, Finland; Agia Marina, Cyprus; Budapest, Hungary; and Beijing, China, representing semi-pristine boreal forest, rural environment in the Mediterranean area, urban environment and heavily polluted megacity, respectively. The new proxy takes into account the formation of sulphuric acid from SO2 via OH oxidation and other oxidation pathways, specifically that via stabilized Criegee Intermediates. The sulphuric acid sinks included in the proxy are its condensation sink (CS) and atmospheric clustering starting from H2SO4 dimer formation. Indeed, we found that the observed sulphuric acid concentration can be explained by the proposed sources and sinks with similar coefficients in the four contrasting environments where we have tested it. Thus, the new proxy is a more flexible and an important improvement of previous proxies. Following the recommendations in the manuscript, a proxy for a specific location can be derived.

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.

Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere., Secondary organic aerosols are important contributors to the Earth's radiation budget, however questions remain about their formation from highly-oxidized precursors. Here the authors show that the daytime reaction of hydroxyl radicals with α- and β-pinene is a greater source of highly-oxidized products than previously assumed.

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. publishedVersion

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.

Dimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20 nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1–1.3 for a 2 nm particle and DMA gas-phase mi...

We present the first observation of airborne organic and inorganic arsenic cations, detected in real time within the boreal forest in Hyytiala, Finland, and over nearby Lake Kuivajarvi. The technique of atmospheric-pressure interface time-of-flight mass spectrometry provides online, in situ monitoring as well as chemical information about the arsenic species, identified as protonated trimethylarsine oxide (AsC3H10O+) and AsO(H2O)n+ clusters (n = 0–4). Quantum chemical calculations confirm that the proposed cations are stable under atmospheric conditions. Our most remarkable discovery is that minimal arsenic appeared during spring 2011 until after the ground began to thaw, triggering a sharp increase in airborne arsenic levels as snowmelt flooded the soil with water and stimulated microbial activity. These findings reveal that volatile arsenic species, detected here as atmospheric ions, link the biogeochemical cycling of arsenic through air, soil, water, and living organisms.