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The chemical composition of PM 10 and non-overlapping PM 2.5 was studied at the summit of Mt. Chacaltaya (5380 m a.s.l., lat. - 16.346950°, long. - 68.128250°) providing a unique long-term record spanning from December 2011 to March 2020. The chemical composition of aerosol at the Chacaltaya Global Atmosphere Watch (GAW) site is representative of the regional background, seasonally affected by biomass burning practices and by nearby anthropogenic emissions from the metropolitan area of La Paz–El Alto. Concentration levels are clearly influenced by seasons with minima occurring during the wet season (December to March) and maxima occurring during the dry and transition seasons (April to November). Ions, total carbon (EC + OC), and saccharide interquartile ranges for concentrations are 558–1785, 384–1120, and 4.3–25.5 ng m -3 for bulk PM 10 and 917–2308, 519–1175, and 3.9–24.1 ng m -3 for PM 2.5 , respectively, with most of the aerosol seemingly present in the PM 2.5 fraction. Such concentrations are overall lower compared to other high-altitude stations around the globe but higher than Amazonian remote sites (except for OC). For PM 10 , there is dominance of insoluble mineral matter (33 %–56 % of the mass), organic matter (7 %–34 %), and secondary inorganic aerosol (15 %–26 %). Chemical composition profiles were identified for different origins: EC, NO 3- , NH 4+ , glucose, and C 2 O 42- for the nearby urban and rural areas; OC, EC, NO 3- , K + , acetate, formate, levoglucosan, and some F - and Br - for biomass burning; MeSO 3- , Na + , Mg 2+ , K + , and Ca 2+ for aged marine emissions from the Pacific Ocean; arabitol, mannitol, and glucose for biogenic emissions; Na + , Ca 2+ , Mg 2+ , and K + for soil dust; and SO 42- , F - , and some Cl - for volcanism. Regional biomass burning practices influence the soluble fraction of the aerosol between June and November. The organic fraction is present all year round and has both anthropogenic (biomass burning and other combustion sources) and natural (primary and secondary biogenic emissions) origins, with the OC/EC mass ratio being practically constant all year round (10.5 ± 5.7, IQR 8.1–13.3). Peruvian volcanism has dominated the SO 42- concentration since 2014, though it presents strong temporal variability due to the intermittence of the sources and seasonal changes in the transport patterns. These measurements represent some of the first long-term observations of aerosol chemical composition at a continental high-altitude site in the tropical Southern Hemisphere. [ABSTRACT FROM AUTHOR]

New particle formation (NPF) is a major source of aerosol particles and cloud condensation nuclei in the troposphere, playing an important role in both air quality and climate. Frequent NPF events have been observed in heavily polluted urban environments, contributing to the aerosol number concentration by a significant amount. The Po Valley region in northern Italy has been characterized as a hotspot for high aerosol loadings and frequent NPF events in southern Europe. However, the mechanisms of NPF and growth in this region are not completely understood. In this study, we conducted a continuous 2-month measurement campaign with state-of-the-art instruments to elucidate the NPF and growth mechanisms in northern Italy. Our results demonstrate that frequent NPF events (66 % of all days during the measurement campaign) are primarily driven by abundant sulfuric acid (8.5×106 cm -3) and basic molecules in this area. In contrast, oxygenated organic molecules from the atmospheric oxidation of volatile organic compounds (VOCs) appear to play a minor role in the initial cluster formation but contribute significantly to the consecutive growth process. Regarding alkaline molecules, amines are insufficient to stabilize all sulfuric acid clusters in the Po Valley. Ion cluster measurements and kinetic models suggest that ammonia (10 ppb) must therefore also play a role in the nucleation process. Generally, the high formation rates of sub-2 nm particles (87 cm -3 s -1) and nucleation-mode growth rates (5.1 nm h -1) as well as the relatively low condensational sink (8.9×10-3 s -1) will result in a high survival probability for newly formed particles, making NPF crucial for the springtime aerosol number budget. Our results also indicate that reducing key pollutants, such as SO 2 , amine and NH 3 , could help to substantially decrease the particle number concentrations in the Po Valley region. [ABSTRACT FROM AUTHOR]

In this study, we present and analyze the first continuous timeseries of relevant aerosol precursor vapors from the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. These precursor vapors include sulfuric acid (SA), methanesulfonic acid (MSA), and iodic acid (IA). We use FLEXPART simulations, inverse modeling, sulfur dioxide (SO2) mixing ratios, and chlorophyll-a (chl-a) observations to interpret the seasonal variability of the vapor concentrations and identify dominant sources. Our results show that both natural and anthropogenic sources are relevant for the concentrations of SA in the Arctic, but anthropogenic sources associated with Arctic haze are the most prevalent. MSA concentrations are an order of magnitude higher during polar day than during polar night due to seasonal changes in biological activity. Peak MSA concentrations were observed in May, which corresponds with the timing of the annual peak in chl-a concentrations north of 75°N. IA concentrations exhibit two distinct peaks during the year: a dominant peak in spring and a secondary peak in autumn, suggesting that seasonal IA concentrations depend on both solar radiation and sea ice conditions. In general, the seasonal cycles of SA, MSA, and IA in the central Arctic Ocean are related to sea ice conditions, and we expect that changes in the Arctic environment will affect the concentrations of these vapors in the future. The magnitude of these changes and the subsequent influence on aerosol processes remains uncertain, highlighting the need for continued observations of these precursor vapors in the Arctic. [ABSTRACT FROM AUTHOR]

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 the 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. Despite the challenging topography and ambient conditions around the station, the simple particle growth model used in the study was able to show that the detected vapors were sufficient to explain the observed particle growth, although some discrepancies were found between modeled and measured particle growth rates. This study, one of the first of such studies conducted on high altitude, gives insight on the key factors affecting the particle growth on the site and helps to improve the understanding of important factors on high-altitude sites and the atmosphere in general. Low-volatility organic compounds originating from multiple surrounding sources such as the Amazonia and La Paz metropolitan area were found to be the main contributor to the particle growth, covering on average 65 % of the simulated particle mass in particles with a diameter of 30 nm. In addition, sulfuric acid made a major contribution to the particle growth, covering at maximum 37 % of the simulated particle mass in 30 nm particles during periods when volcanic activity was detected on the area, compared to around 1 % contribution on days without volcanic activity. This suggests that volcanic emissions can greatly enhance the particle growth. [ABSTRACT FROM AUTHOR]

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 m 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. [ABSTRACT FROM AUTHOR]

Atmospheric new particle formation (NPF) and associated production of secondary particulate matter dominate aerosol particle number concentrations and submicron particle mass loadings in many environments globally. Our recent investigations show that atmospheric NPF produces a significant amount of particles on days when no clear NPF event has been observed/identified. Furthermore, it has been observed in different environments all around the world that growth rates of nucleation mode particles vary little, usually much less than the measured concentrations of condensable vapors. It has also been observed that the local clustering, which in many cases acts as a starting point of regional new particle formation (NPF), can be described with the formation of intermediate ions at the smallest sizes. These observations, together with a recently developed ranking method, lead us to propose a paradigm shift in atmospheric NPF investigations. In this opinion paper, we will summarize the traditional approach of describing atmospheric NPF and describe an alternative method, covering both particle formation and initial growth. The opportunities and remaining challenges offered by the new approach are discussed. [ABSTRACT FROM AUTHOR]

New particle formation (NPF) is a major source of aerosol particles and cloud condensation nuclei in the troposphere, playing an important role in both air quality and climate. Frequent NPF events have been observed in heavily polluted urban environments, contributing to the aerosol number concentration by a significant amount. The Po Valley region in northern Italy has been characterized as a hotspot for high aerosol loadings and frequent NPF events in Southern Europe. However, the mechanisms of NPF and growth in this region are not completely understood. In this study, we conducted a continuous 2-month measurement campaign with state-of-the-art instruments to elucidate the NPF and the growth mechanisms in Northern Italy. Our results show that abundant sulfuric acid, ammonia and amines from agricultural activities may be the dominant components driving the frequent NPF events (66 % of all days during the measurement campaign) in this area. In contrast, organics seem to have a smaller role in cluster formation but contribute to the consecutive growth process. According to ion cluster measurements and kinetic model results, dimethylamine is not sufficient to stabilize all of the sulfuric acid during springtime in the Po Valley, suggesting that other amines and ammonia can also be involved. Generally, the high formation rates of sub-2 nm particles (87 cm−3 s−1) and nucleation mode growth rates (5.1 nm h−1) together with the relatively low condensational sink (8.9 × 10−3 s−1) will result in a high survival probability of newly formed particles, making NPF crucial for the springtime aerosol number budget in the Po Valley region. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 (H 2 SO 4) 0–3⚫ HSO 4- , (HNO 3) 0–2⚫ NO 3- , SO 5- , (NH 3) 1–6⚫ (H 2 SO 4) 3–7⚫ HSO 4- , malonic-acid-derived, and CHO / CHON ⚫ (HSO 4- / NO 3-) 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. H 2 SO 4 –NH 3 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 SO 2 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

High-quality data of atmospheric mercury (Hg) is rare for South America, especially for its tropical part. In consequence, mercury dynamics are still highly uncertain in this region, a significant deficiency, as South America appears to play a major role in the global budget of this toxic pollutant. To address this issue, we performed nearly two years (July 2014-February 2016) of continuous high resolution total gaseous mercury (TGM) measurements at the Chacaltaya (CHC) mountain site in the Bolivian Andes, which is subject to a diverse mix of air masses coming predominantly from the Altiplano and the Amazon rainforest. For the first eleven months of measurements, we obtained a mean TGM concentration of 0.89±0.01 ng m-3, in good agreement with the sparse amount of data available from the continent. For the remaining nine months, we obtained a significantly higher TGM concentration of 1.34±0.01 ng m-3, a difference which we tentatively attribute to the strong "El Niño" event of 2015-2016. Based on HYSPLIT back-trajectories and clustering techniques, we show that lower mean TGM concentrations were linked to either westerly Altiplanic air masses or those originating from the lowlands to the south-east of CHC. Elevated TGM concentrations were related to northerly air masses of Amazonian or southerly air masses of Altiplanic origin, the former possibly linked to artisanal and small scale gold mining (ASGM), while the latter might be explained by volcanic activity. We observed a marked seasonal pattern, with low TGM concentrations in the dry season (austral winter), rising concentrations during biomass burning (BB) season, and highest concentrations at the beginning of the wet season (austral summer). With the help of simultaneously sampled equivalent black carbon (eBC) and carbon monoxide (CO) data, we use the clearly BB influenced signal during BB season (August to October) to derive a mean TGM/CO emission ratio of (2.3±0.6)· 10-7 ppbvTGM ppbvCO-1, which could be used to constrain South American BB emissions. Through the link with in-situ measured CO2 and remotely sensed solar-induced fluorescence (SIF) as proxies for vegetation activity, we detect signs of a vegetation sink effect in Amazonian air masses and derive a "best guess" TGM/CO2 uptake ratio of 0.058±0.017 (ng m-3)TGM ppmCO2-1. Finally, significantly higher Hg concentrations in western Altiplanic air masses during the wet season as compared to the dry season point towards the modulation of atmospheric Hg by the Eastern Pacific Ocean. [ABSTRACT FROM AUTHOR]

The Station for Measuring Ecosystem Atmosphere Relations (SMEAR) II is a unique station in the world due to the wide range of long-term measurements tracking the Earth-atmosphere interface. In this study, we characterize the composition of organic aerosol (OA) at SMEAR II by quantifying its driving constituents. We utilize a multi-year data set of OA mass spectra measured in situ with an Aerosol Chemical Speciation Monitor (ACSM) at the station. To our knowledge, this mass spectral time series is the longest of its kind published to date, and its detailed analysis required development of a new methodology. To this purpose, we developed an efficient and robust data analysis framework utilizing machine learning tools. These included unsupervised feature extraction and classification stages to manage and process the large amounts of data. The extensive chemometric analysis was conducted with a combination of Positive Matrix Factorization (PMF), rolling window analysis, bootstrapping, K-Means clustering, data weighting and diagnostics based algorithmic choice-making, among others. This combination of statistical tools provided a data driven analysis methodology to achieve robust solutions with minimal subjectivity. [ABSTRACT FROM AUTHOR]

The Station for Measuring Ecosystem Atmosphere Relations (SMEAR) II is well known among atmospheric scientists due to the immense amount of observational data it provides of the earth-atmosphere interface. Moreover, SMEAR II plays an important role in large European research infrastructures, enabling the large scientific community to tackle climate and air pollution related questions, utilising the high-quality long-term data sets recorded at the site. So far, the well-documented site was missing the description of the seasonal variation of aerosol chemical composition that is crucial for understanding the complex biogeochemical and -physical processes governing the forest ecosystem. Here, we report the sub-micron aerosol chemical composition and its variability utilising data measured between 2012 and 2018 using an Aerosol Chemical Speciation Monitor (ACSM). We observed a bimodal seasonal trend in the sub-micron aerosol concentration culminating in February (2.7, 1.6, 5.1 μg m-3 for median, 25th, 75th percentiles, respectively) and July (4.2, 2.2, and 5.7 μg m-3 for median, 25th, 75th percentiles, respectively). The wintertime maximum was linked to an enhanced presence of inorganic aerosol species (ca. 50 %) whereas the summertime maximum (ca. 80 % organics) to biogenic secondary organic aerosol (SOA) formation. During the exceptionally hot Julys of 2014 and 2018, the organic aerosol concentrations were up to 70 % higher than the 7-year July mean. The projected increase of heat wave frequency over Finland will most likely influence the loading and chemical composition of aerosol particles in the future. Our findings suggest strong influence of meteorological conditions such as radiation, ambient temperature, wind speed and direction on aerosol chemical composition. To our understanding, this is the longest time series reported describing the aerosol chemical composition measured online in the boreal region, but the continuous monitoring will be maintained also in the future. [ABSTRACT FROM AUTHOR]

We present the variability of aerosol particle optical properties measured at the global Atmosphere Watch (GAW) station Chacaltaya (5240 m a.s.l.). The in-situ mountain site is ideally located to study regional impacts of the densely populated urban area of La Paz/El Alto, and the intensive activity in the Amazonian basin. Four year measurements allow to study aerosol particle properties for distinct atmospheric conditions as stable and turbulent layers, different airmass origins, as well as for wet and dry seasons, including biomass-burning influenced periods. The absorption, scattering and extinction coefficients (median annual values of 0.74, 12.14 and 12.96 Mm-1 respectively) show a clear seasonal variation with low values during the wet season (0.57, 7.94 and 8.68 Mm-1 respectively) and higher values during the dry season (0.80, 11.23 and 14.51 Mm-1 respectively). These parameters also show a pronounced diurnal variation (maximum during daytime, minimum during night-time, as a result of the dynamic and convective effects of leading to lower atmospheric layers reaching the site during daytime. Retrieved intensive optical properties are significantly different from one season to the other, showing the influence of different sources of aerosols according to the season. Both intensive and extensive optical properties of aerosols were found to be different among the different atmospheric layers. The particle light absorption, scattering and extinction coefficients are in average 1.94, 1.49 and 1.55 times higher, respectively, in the turbulent layer compared to the stable layer. We observe that the difference is highest during the wet season and lowest during the dry season. Using wavelength dependence of aerosol particle optical properties, we discriminated contributions from natural (mainly mineral dust) and anthropogenic (mainly biomass-burning and urban transport or industries) emissions according to seasons and tropospheric layers. The main sources influencing measurements at CHC are arising from the urban area of La Paz/El Alto, and regional biomass-burning from the Amazonian basin. Results show a 28 % to 80 % increase of the extinction coefficients during the biomass-burning season with respect to the dry season, which is observed in both tropospheric layers. From this analyse, long-term observations at CHC provides the first direct evidence of the impact of emissions in the Amazonian basin on atmospheric optical properties far away from their sources, all the way to the stable layer. [ABSTRACT FROM AUTHOR]

High altitude stations are often emphasized as free tropospheric measuring sites but they remain influenced by atmospheric boundary layer (ABL) air masses due to convective transport processes. The local and meso-scale topographical features around the station are involved in the convective boundary layer development and in the formation of thermally induced winds leading to ABL air lifting. The station altitude is not a sufficient parameter to characterize the ABL influence. Topography data from the global digital elevation model GTopo30 were used to calculate 5 parameters for 46 high altitude stations situated in five continents. The geometric mean of these 5 parameters determines a topography based index called ABL-TopoIndex which can be used to rank the high altitude stations as a function of the ABL influence. To construct the ABL-TopoIndex, we rely on the criteria that the ABL influence will be low if the station is one of the highest points in the mountainous massif, if there is a large altitude difference between the station and the valleys or plateaus, if the slopes around the station are steep, and finally if the drainage basin for air convection is small. All stations on volcanic islands exhibit a low ABL-TopoIndex whereas stations in the Himalaya and the Tibetan Plateau have high ABL-TopoIndex values. Spearman's rank correlation between aerosol optical properties and number concentration from 28 stations and the ABL-TopoIndex, the altitude and the latitude are used to validate this topographical approach. Statistically significant (s.s.) correlations are found between the 5 and 50 percentiles of all aerosol parameters and the ABL-TopoIndex whereas no s.s. correlation is found with the station altitude. The diurnal cycles of aerosol parameters seem to be best explained by the station latitude although a s.s. correlation is found between the amplitude of the diurnal cycles of the absorption coefficient and the ABL-TopoIndex. Finally, the main flow paths for air convection were calculated for various ABL heights. [ABSTRACT FROM AUTHOR]

Pure biogenic new particle formation (NPF) induced by highly oxygenated organic molecules (HOMs) could be an important mechanism for pre-industrial aerosol formation. However, it has not been unambiguously confirmed in the ambient due to the scarcity of truly pristine continental locations in the present-day atmosphere or the lack of chemical characterization of NPF precursors. Here, we report ambient observations of pure biogenic HOM-driven NPF over a peatland in southern Finland. Meteorological decoupling processes formed an "air pocket" (i.e., a very shallow surface layer) at night and favored NPF initiated entirely by biogenic HOM from this peatland, whose atmospheric environment closely resembles that of the pre-industrial era. Our study sheds light on pre-industrial aerosol formation, which represents the baseline for estimating the impact of present and future aerosol on climate, as well as on future NPF, the features of which may revert toward pre-industrial-like conditions due to air pollution mitigation. [ABSTRACT FROM AUTHOR]