Search

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

In the lower troposphere, rapid collisions between ions and trace gases result in the transfer of positive charge to the highest proton affinity species and negative charge to the lowest proton affinity species. Measurements of the chemical composition of ambient ions thus provide direct insight into the most acidic and basic trace gases and their ion–molecule clusters – compounds thought to be important for new particle formation and growth. We deployed an atmospheric pressure interface time-of-flight mass spectrometer (APi-ToF) to measure ambient ion chemical composition during the 2016 Holistic Interactions of Shallow Clouds, Aerosols, and Land Ecosystems (HI-SCALE) campaign at the United States Department of Energy Atmospheric Radiation Measurement facility in the Southern Great Plains (SGP), an agricultural region. Cations and anions were measured for alternating periods of ∼ 24 h over 1 month. We use binned positive matrix factorization (binPMF) and generalized Kendrick analysis (GKA) to obtain information about the chemical formulas and temporal variation in ionic composition without the need for averaging over a long timescale or a priori high-resolution peak fitting. Negative ions consist of strong acids including sulfuric and nitric acid, organosulfates, and clusters of NO3- with highly oxygenated organic molecules (HOMs) derived from monoterpene (MT) and sesquiterpene (SQT) oxidation. Organonitrates derived from SQTs account for most of the HOM signal. Combined with the diel profiles and back trajectory analysis, these results suggest that NO3 radical chemistry is active at this site. SQT oxidation products likely contribute to particle growth at the SGP site. The positive ions consist of bases including alkyl pyridines and amines and a series of high-mass species. Nearly all the positive ions contained only one nitrogen atom and in general support ammonia and amines as being the dominant bases that could participate in new particle formation. Overall, this work demonstrates how APi-ToF measurements combined with binPMF analysis can provide insight into the temporal evolution of compounds important for new particle formation and growth.

The biogeochemistry of rapidly retreating Andean glaciers is poorly understood, and Ecuadorian glacier dissolved organic matter (DOM) composition is unknown. This study examined molecular composition and carbon isotopes of DOM from supraglacial and outflow streams (n = 5 and 14, respectively) across five ice capped volcanoes in Ecuador. Compositional metrics were paired with streamwater isotope analyses (delta O-18) to assess if outflow DOM composition was associated with regional precipitation gradients and thus an atmospheric origin of glacier DOM. Ecuadorian glacier outflows exported ancient, biolabile dissolved organic carbon (DOC), and DOM contained a high relative abundance (RA) of aliphatic and peptide-like compounds (>= 27%RA). Outflows were consistently more depleted in Delta C-14-DOC (i.e., older) compared to supraglacial streams (mean -195.2 and -61.3 parts per thousand respectively), perhaps due to integration of spatially heterogenous and variably aged DOM pools across the supraglacial environment, or incorporation of aged subglacial OM as runoff was routed to the outflow. Across Ecuador, Delta C-14-DOC enrichment was associated with decreased aromaticity of DOM, due to increased contributions of organic matter (OM) from microbial processes or atmospheric deposition of recently fixed and subsequently degraded OM (e.g., biomass burning byproducts). There was a regional gradient between glacier outflow DOM composition and streamwater delta O-18, suggesting covariation between regional precipitation gradients and the DOM exported from glacier outflows. Ultimately, this highlights that atmospheric deposition may exert a control on glacier outflow DOM composition, suggesting regional air circulation patterns and precipitation sources in part determine the origins and quality of OM exported from glacier environments., Plain Language Summary The composition of Ecuadorian glacier dissolved organic matter (DOM) is unknown, despite its potential importance for downstream carbon cycling. Here, regional variability in the source, composition, and age of DOM in glacier surface and outflow streams was explored to identify drivers of variability in DOM composition across Ecuadorian glaciers. Ecuadorian glacier outflows exported aged material (2,730-910 yBP), that was available for microbial metabolism, and hence was associated with a DOM pool enriched in simple, energy-rich compounds. Nonetheless, regionally, dissolved organic carbon (DOC) in glacier outflows was older than in studied surface streams, perhaps indicating integration of compositionally diverse surface sources, or potentially aged organic matter (OM) from beneath the glaciers, in transit to the outflow. Across Ecuador, the age and molecular composition of DOM covaried, demonstrating changing contributions of compositional diverse and variably aged OM sources to the glaciers. Regionally, a fraction of this variation was likely driven by atmospheric deposition to glacier surfaces. Given the rapid retreat of tropical glaciers and dearth of DOM compositional studies, future work must further constrain the origins of atmospheric deposition, since it may impact the quality of DOM exported to downstream ecosystems, potentially impacting its fate.

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

Enceladus, an icy moon of Saturn, possesses an internal water ocean and jets expelling ocean material into space. Cassini investigations indicated that the subsurface ocean could be a habitable environment having a complex interaction with the rocky core. Further investigation of the composition of the plume formed by the jets is necessary to fully understand the ocean, its potential habitability, and what it tells us about Enceladus' origin. Moonraker has been proposed as an ESA M-class mission designed to orbit Saturn and perform multiple flybys of Enceladus, focusing on traversals of the plume. The proposed Moonraker mission consists of an ESA-provided platform, with strong heritage from JUICE and Mars Sample Return, and carrying a suite of instruments dedicated to plume and surface analysis. The nominal Moonraker mission has a duration of 13.5 years. It includes a 23-flyby segment with 189 days allocated for the science phase, and can be expanded with additional segments if resources allow. The mission concept consists in investigating: i) the habitability conditions of present-day Enceladus and its internal ocean, ii) the mechanisms at play for the communication between the internal ocean and the surface of the South Polar Terrain, and iii) the formation conditions of the moon. Moonraker, thanks to state-of-the-art instruments representing a significant improvement over Cassini's payload, would quantify the abundance of key species in the plume, isotopic ratios, and physical parameters of the plume and the surface. Such a mission would pave the way for a possible future landed mission., Accepted for publication in The Planetary Science Journal

Polycyclic aromatic hydrocarbons (PAHs) are considered priority hazardous substances due to their carcinogenic activity and risk to public health. Strict regulations are in place limiting their release into the environment, but enforcement is hampered by a lack of adequate field-testing procedure, instead relying on sending samples to centralised analytical facilities. Reliably monitoring levels of PAHs in the field is a challenge, owing to the lack of field-deployable analytical methods able to separate, identify, and quantify the complex mixtures in which PAHs are typically observed. Here, we report the development of a hand-portable system based on high-performance liquid chromatography incorporating a spectrally wide absorption detector, capable of fingerprinting PAHs based on their characteristic spectral absorption profiles: identifying 100% of the 24 PAHs tested, including full coverage of the United States Environmental Protection Agency priority pollutant list. We report unsupervised methods to exploit these new capabilities for feature detection and identification, robust enough to detect and classify co-eluting and hidden peaks. Identification is fully independent of their characteristic retention times, mitigating matrix effects which can preclude reliable determination of these analytes in challenging samples. We anticipate the platform to enable more sophisticated analytical measurements, supporting real-time decision making in the field. Portable liquid chromatography instruments enable a myriad of applications in field research. Here a handportable system incorporating a broadband absorption detector is used to separate and classify polycyclic aromatic hydrocarbons from environmental water samples based solely on spectral fingerprinting.

The occurrence of new particle formation (NPF) events detected in a coastal agricultural site, at Qvidja, in Southwestern Finland, was investigated using the data measured with a nitrate ion-based chemical-ionization atmospheric-pressure-interface time-of-flight (CI-APi-TOF) mass spectrometer. The binned positive matrix factorization method (binPMF) was applied to the measured spectra. It resulted in eight factors describing the time series of ambient gas and cluster composition at Qvidja during spring 2019. The most interesting factors related to the observed NPF events were the two factors with the highest mass-to-charge ratios, numbered 7 and 8, both having profiles with patterns of highly oxygenated organic molecules with one nitrogen atom. It was observed that factor 7 had elevated intensities during the NPF events. A variable with an even better connection to the observed NPF events is fF7, which denotes the fraction of the total spectra within the studied mass-to-charge ratio range between 169 and 450 Th being in a form of factor 7. Values of fF7 higher than 0.50±0.05 were observed during the NPF events, of which durations also correlated with the duration of fF7 exceeding this critical value. It was also observed that factor 8 acts like a precursor for factor 7 with solar radiation and that the formation of factor 8 is associated with ozone levels.

Aerosols and their interaction with clouds constitute the largest uncertainty in estimating the radiative forcing affecting the climate system. Secondary aerosol formation is responsible for a large fraction of the cloud condensation nuclei in the global atmosphere. Wetlands are important to the budgets of methane and carbon dioxide, but the potential role of wetlands in aerosol formation has not been investigated. Here we use direct atmospheric sampling at the Siikaneva wetland in Finland to investigate the emission of methane and volatile organic compounds, and subsequently formed atmospheric clusters and aerosols. We find that terpenes initiate stronger atmospheric new particle formation than is typically observed over boreal forests and that, in addition to large emissions of methane which cause a warming effect, wetlands also have a cooling effect through emissions of these terpenes. We suggest that new wetlands produced by melting permafrost need to be taken into consideration as sources of secondary aerosol particles when estimating the role of increasing wetland extent in future climate change. Boreal wetlands emit terpenes which initiate atmospheric new particle formation to an even greater degree than is usually seen over boreal forests, according to direct measurements of volatile organic compounds from a Finnish wetland.

Particulate matter from biomass burning emissions affects air quality, ecosystems and climate; however, quantifying these effects requires that the connection between primary emissions and secondary aerosol production is firmly established. We performed atmospheric simulation chamber experiments on the chemical oxidation of residential biomass burning emissions under dark conditions. Biomass burning organic aerosol was found to age under dark conditions, with its oxygen to carbon ratio increasing by 7-34% and producing 1-38 μg m-3 of secondary organic aerosol (5-80% increase over the fresh organic aerosol) after 30 min of exposure to NO3 radicals in the chamber (corresponding to 1-3 h of exposure to typical nighttime NO3 radical concentrations in an urban environment). The average mass concentration of SOA formed under dark oxidation conditions was comparable to the mass concentration formed after 3 h (equivalent to 7-10 h of ambient exposure) under ultraviolet lights (6 μg m-3 or a 47% increase over the emitted organic aerosol concentration). The dark aging experiments showed a substantial increase in secondary nitrate aerosol (0.12-3.8 μg m-3), 46-100% of which is in the form of organic nitrates. The biomass burning aerosol pH remained practically constant at 2.8 throughout the experiment. This value promotes inorganic nitrate partitioning to the particulate phase, potentially contributing to the buildup of nitrate aerosol in the boundary layer and enhancing long range transport. These results suggest that oxidation through reactions with the NO3 radical is an additional secondary aerosol formation pathway in biomass burning emission plumes that should be accounted for in atmospheric chemical-transport models., Kodros, J. K., Kaltsonoudis, C., Paglione, M., Florou, K., Jorga, S., Vasilakopoulou, C., Cirtog, M., Cazaunau, M., Picquet-Varrault, B., Nenes, A. and Pandis, S. N.: Secondary aerosol formation during the dark oxidation of residential biomass burning emissions, Environ. Sci. Atmos., 2, 1221–1236, doi:10.1039/D2EA00031H, 2022.

The Po Valley (Italy) is a well-known air quality hotspot characterized by particulate matter (PM) levels well above the limit set by the European Air Quality Directive and by the World Health Organization, especially during the colder season. In the framework of Emilia-Romagna regional project “Supersito”, the southern Po Valley submicron aerosol chemical composition was characterized by means of high-resolution aerosol mass spectroscopy (HR-AMS) with the specific aim of organic aerosol (OA) characterization and source apportionment. Eight intensive observation periods (IOPs) were carried out over 4 years (from 2011 to 2014) at two different sites (Bologna, BO, urban background, and San Pietro Capofiume, SPC, rural background), to characterize the spatial variability and seasonality of the OA sources, with a special focus on the cold season. On the multi-year basis of the study, the AMS observations show that OA accounts for averages of 45±8 % (ranging from 33 % to 58 %) and 46±7 % (ranging from 36 % to 50 %) of the total non-refractory submicron particle mass (PM1-NR) at the urban and rural sites, respectively. Primary organic aerosol (POA) comprises biomass burning (23±13 % of OA) and fossil fuel (12±7 %) contributions with a marked seasonality in concentration. As expected, the biomass burning contribution to POA is more significant at the rural site (urban / rural concentration ratio of 0.67), but it is also an important source of POA at the urban site during the cold season, with contributions ranging from 14 % to 38 % of the total OA mass. Secondary organic aerosol (SOA) contributes to OA mass to a much larger extent than POA at both sites throughout the year (69±16 % and 83±16 % at the urban and rural sites, respectively), with important implications for public health. Within the secondary fraction of OA, the measurements highlight the importance of biomass burning aging products during the cold season, even at the urban background site. This biomass burning SOA fraction represents 14 %–44 % of the total OA mass in the cold season, indicating that in this region a major contribution of combustion sources to PM mass is mediated by environmental conditions and atmospheric reactivity. Among the environmental factors controlling the formation of SOA in the Po Valley, the availability of liquid water in the aerosol was shown to play a key role in the cold season. We estimate that the organic fraction originating from aqueous reactions of biomass burning products (“bb-aqSOA”) represents 21 % (14 %–28 %) and 25 % (14 %–35 %) of the total OA mass and 44 % (32 %–56 %) and 61 % (21 %–100 %) of the SOA mass at the urban and rural sites, respectively.

Ancient martian organic matter is likely to take the form of kerogen-like recalcitrant macromolecular organic matter (MOM), existing in close association with reactive mineral surfaces, especially iron oxides. Detecting and identifying a biological origin for martian MOM will therefore be of utmost importance for life detection efforts at Mars. We show that Type I and Type IV kerogens provide effective analogues for putative martian MOM of biological and abiological (meteoric) provenances respectively. We analyse the pyrolytic breakdown products when these kerogens are mixed with mineral matrices highly relevant for the search for life on Mars. We demonstrate that, using traditional thermal techniques as generally used by the Sample Analysis at Mars and Mars Organic Molecule Analyser instruments, even the breakdown products of highly recalcitrant MOM are transformed during analysis in the presence of reactive mineral surfaces, particularly iron. Analytical transformation reduces the diagnostic ability of this technique, as detected transformation products of both biological and abiological MOM may be identical (low molecular weight gas phases and benzene) and indistinguishable. The severity of transformational effects increased through: calcite < kaolinite < haematite < nontronite < magnetite < goethite. Due to their representation of various habitable aqueous environments and the preservation potential of organic matter by iron, it is not advisable to completely avoid iron-rich strata. We conclude that haematite-rich localities, with evidence of extensive aqueous alteration of originally reducing phases, such as the Vera Rubin Ridge, may be relatively promising targets for identifying martian biologically-sourced MOM.

Residential biomass burning for heating purposes is an important source of air pollutants during winter. Here we test the hypothesis that significant secondary organic aerosol production can take place even during winter nights through oxidation of the emitted organic vapors by the nitrate (NO3) radical produced during the reaction of ozone and nitrogen oxides. We use a mobile dual smog chamber system which allows the study of chemical aging of ambient air against a control reference. Ambient urban air sampled during a wintertime campaign during nighttime periods with high concentrations of biomass burning emissions was used as the starting point for the aging experiments. Biomass burning organic aerosol (OA) was, on average, 70 % of the total OA at the beginning of our experiments. Ozone was added in the perturbed chamber to simulate mixing with background air (and subsequent NO3 radical production and aging), while the second chamber was used as a reference. Following the injection of ozone, rapid OA formation was observed in all experiments, leading to increases in the OA concentration by 20 %–70 %. The oxygen-to-carbon ratio of the OA increased on average by 50 %, and the mass spectra of the produced OA was quite similar to the oxidized OA mass spectra reported during winter in urban areas. Furthermore, good correlation was found for the OA mass spectra between the ambient-derived emissions in this study and the nocturnal aged laboratory-derived biomass burning emissions from previous work. Concentrations of NO3 radicals as high as 25 ppt (parts per trillion) were measured in the perturbed chamber, with an accompanying production of 0.1–3.2 µg m−3 of organic nitrate in the aerosol phase. Organic nitrate represented approximately 10 % of the mass of the secondary OA formed. These results strongly indicate that the OA in biomass burning plumes can chemically evolve rapidly even during wintertime periods with low photochemical activity.

We collected 1 year of aerosol chemical speciation monitor (ACSM) data in Magadino, a village located in the south of the Swiss Alpine region, one of Switzerland's most polluted areas. We analysed the mass spectra of organic aerosol (OA) by positive matrix factorisation (PMF) using Source Finder Professional (SoFi Pro) to retrieve the origins of OA. Therein, we deployed a rolling algorithm, which is closer to the measurement, to account for the temporal changes in the source profiles. As the first-ever application of rolling PMF with multilinear engine (ME-2) analysis on a yearlong dataset that was collected from a rural site, we resolved two primary OA factors (traffic-related hydrocarbon-like OA (HOA) and biomass burning OA (BBOA)), one mass-to-charge ratio (m/z) 58-related OA (58-OA) factor, a less oxidised oxygenated OA (LO-OOA) factor, and a more oxidised oxygenated OA (MO-OOA) factor. HOA showed stable contributions to the total OA through the whole year ranging from 8.1 % to 10.1 %, while the contribution of BBOA showed an apparent seasonal variation with a range of 8.3 %–27.4 % (highest during winter, lowest during summer) and a yearly average of 17.1 %. OOA (sum of LO-OOA and MO-OOA) contributed 71.6 % of the OA mass, varying from 62.5 % (in winter) to 78 % (in spring and summer). The 58-OA factor mainly contained nitrogen-related variables which appeared to be pronounced only after the filament switched. However, since the contribution of this factor was insignificant (2.1 %), we did not attempt to interpolate its potential source in this work. The uncertainties (σ) for the modelled OA factors (i.e. rotational uncertainty and statistical variability in the sources) varied from ±4 % (58-OA) to a maximum of ±40 % (LO-OOA). Considering that BBOA and LO-OOA (showing influences of biomass burning in winter) had significant contributions to the total OA mass, we suggest reducing and controlling biomass-burning-related residential heating as a mitigation strategy for better air quality and lower PM levels in this region or similar locations. In Appendix A, we conduct a head-to-head comparison between the conventional seasonal PMF analysis and the rolling mechanism. We find similar or slightly improved results in terms of mass concentrations, correlations with external tracers, and factor profiles of the constrained POA factors. The rolling results show smaller scaled residuals and enhanced correlations between OOA factors and corresponding inorganic salts compared to those of the seasonal solutions, which was most likely because the rolling PMF analysis can capture the temporal variations in the oxidation processes for OOA components. Specifically, the time-dependent factor profiles of MO-OOA and LO-OOA can well explain the temporal viabilities of two main ions for OOA factors, m/z 44 (CO+2) and m/z 43 (mostly C2H3O+). Therefore, this rolling PMF analysis provides a more realistic source apportionment (SA) solution with time-dependent OA sources. The rolling results also show good agreement with offline Aerodyne aerosol mass spectrometer (AMS) SA results from filter samples, except for in winter. The latter discrepancy is likely because the online measurement can capture the fast oxidation processes of biomass burning sources, in contrast to the 24 h filter samples. This study demonstrates the strengths of the rolling mechanism, provides a comprehensive criterion list for ACSM users to obtain reproducible SA results, and is a role model for similar analyses of such worldwide available data., Atmospheric Chemistry and Physics, 21 (19), ISSN:1680-7375, ISSN:1680-7367

Similarities and differences in the submicron atmospheric aerosol chemical composition are analyzed from a unique set of measurements performed at 21 sites across Europe for at least one year. These sites are located between 35 and 62°N and 10° W – 26°E, and represent various types of settings (remote, coastal, rural, industrial, urban). Measurements were all carried out on-line with a 30-min time resolution using mass spectroscopy based instruments known as Aerosol Chemical Speciation Monitors (ACSM) and Aerosol Mass Spectrometers (AMS) and following common measurement guidelines. Data regarding organics, sulfate, nitrate and ammonium concentrations, as well as the sum of them called non-refractory submicron aerosol mass concentration ([NR-PM1]) are discussed. NR-PM1 concentrations generally increase from remote to urban sites. They are mostly larger in the mid-latitude band than in southern and northern Europe. On average, organics account for the major part (36–64%) of NR-PM1 followed by sulfate (12–44%) and nitrate (6–35%). The annual mean chemical composition of NR-PM1 at rural (or regional background) sites and urban background sites are very similar. Considering rural and regional background sites only, nitrate contribution is higher and sulfate contribution is lower in mid-latitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (μg/m³) of one or more components of NR-PM1 can be observed at all sites, as well as in the chemical composition of NR-PM1 (%) at most sites. Significant diel cycles in the contribution to [NR-PM1] of organics, sulfate, and nitrate can be observed at a majority of sites both in winter and summer. Early morning minima in organics in concomitance with maxima in nitrate are common features at regional and urban background sites. Daily variations are much smaller at a number of coastal and rural sites. Looking at NR-PM1 chemical composition as a function of NR-PM1 mass concentration reveals that although organics account for the major fraction of NR-PM1 at all concentration levels at most sites, nitrate contribution generally increases with NR-PM1 mass concentration and predominates when NR-PM1 mass concentrations exceed 40 μg/m³ at half of the sites., This study was partially supported by the European Union's projects ACTRIS (EU FP7-262254) and ACTRIS-2 (EU Horizon 2020–654109). COST Action CA16109 COLOSSAL, Chemical On-Line cOmpoSition and Source Apportionment of fine aerosoL, is acknowledged. The ACSM observations at Birkenes was funded by the Norwegian Ministry of Climate and Environment Strategic Institute Program. IDAEA-CSIC (3 datasets: BCN, MSA, MSY) was partially supported by the Spanish Ministry of Economy and Competitiveness and FEDER funds under the PRISMA project (CGL 2012-39623-C02-1). The London measurements were supported by the UK National Research Council through the ClearfLo project and a PhD studentship (grant refs. NE/H008136/1 and NE/I528142/1) and the Department of Environment, Food and Rural Affairs (DEFRA). ECPL personel, namely Nikolaos Mihalopoulos, Aikaterini Bougiatioti and Iasonas Stavroulas acknowledge support by the project “Panhellenic infrastructure for atmospheric composition and climate change, PANACEA” (MIS 5021516) which is implemented under the Action “Reinforcement of the Research and Innovation Infrastructure”, funded by the Operational Programme” Competitiveness, Entrepreneurship and Innovation” (NSRF 2014–2020) and co-financed by Greece and the European Union (European Regional Development Fund). IMT Lille Douai acknowledges financial support from the CaPPA (Chemical and Physical Properties of the Atmosphere) project funded by the French National Research Agency (ANR) through the PIA (Programme d'Investissement d'Avenir) under contract ANR-11-LABX-0005-01, and two CPER projects funded by the French Ministry of Higher Education and Research, the CNRS, the Regional Council “Hauts-de-France” and the European Regional Development Fund (ERDF): Climibio, and IRENI (additionally financed by the Communauté Urbaine de Dunkerque). S. Zhang thanks IMT Lille Douai and the Regional Council “Hauts-de-France” for her PhD grant. Prague co-authors would like to acknowledge a Czech MEYS's project under INTER-EXCELENCE INTERCOST program under grant agreement LTC18068 and from European Regional Development Fund-Project under the grant ACTRIS-CZ RI (CZ.02.1.01/0.0/0.0/16_013/0001315). EPA Ireland, Department of Communications, Climate Action and Environment (DCCAE) and the European Union's Seventh Framework Programme (FP7/2007–2013) project BACCHUS under grant agreement n_603445 are acknowledged for research support at Mace Head. The physical measurements were also funded by the German Ultrafine Aerosol Network GUAN, which was jointly established with help of the German Federal Environment Ministry (BMU) grants F&E 370343200 (German title: “Erfassung der Zahl feiner und ultrafeiner Partikel in der Auβenluft”), 2008–2010, and F&E 371143232 (German title: “Trendanalysen gesundheitsgefährdender Fein-und Ultrafeinstaubfraktionen unter Nutzung der im German Ultrafine Aerosol Network (GUAN) ermittelten Immissionsdaten durch Fortführung und Interpretation der Messreihen”) 2012–2014. We also acknowledge the WCCAP (World Calibration Center for Aerosol Physics) as part of the WMO-GAW program. The WCCAP is base-funded by the German Federal Environmental Agency (Umweltbundesamt), Germany. Support by the European Regional Development Funds (EFRE – Europe funds Saxony) is gratefully acknowledged. Atmospheric measurements performed in Corsica is part of the ChArMEx project supported by CNRS-INSU, ADEME, Météo-France and CEA in the framework of the multidisciplinary programme MISTRALS (Mediterranean Integrated Studies aT Regional And Local Scales; http://mistrals-home.org/, last access: June 10, 2020). Final data processing of these measurements has been supported by the EMME-CARE (Eastern Mediterranean and Middle East Climate and Atmosphere Research Center) which has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No. 856612 and the Cyprus Government. The measurements in Switzerland were supported by the Federal Office for the Environment. We thank the International Foundation High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG) for the opportunity to perform experiments on the Jungfraujoch.

Isoprene (2-methyl-1, 3-butadiene) is a nonmethane volatile organic compound (VOC) with the largest global emission and high reactivity. The oxidation of isoprene is crucial to atmospheric photochemistry and contributes significantly to the global formation of secondary organic aerosol. Here, we conducted comprehensive observations in polluted megacities of Nanjing and Shanghai during summer of 2018. We identified multiple functionalized isoprene oxidation products, of which 72% and 88% of the total mole concentration were nitrogen-containing species with the dominant compound being C5 dihydroxyl dinitrate (C5H10N2O8). We calculated the volatility using the group-contribution method and estimated the particle-phase concentration by equilibrium gas/particle partitioning. The results showed that the multifunctional products derived from isoprene oxidation can contribute to 2.6% of the total organic aerosol mass (0.28 +/- 0.27 mu g/m(3)), highlighting the potential importance of isoprene oxidation in polluted regions.

Цель работы: расширение класса систем с идеальной пространственно-временной фокусировкой путем Ð¸Ñ Ð¿Ð¾Ð³Ñ€ÑƒÐ¶ÐµÐ½Ð¸Ñ в однородное магнитное поле Задачи, решаемые в работе: создание ÐºÐ¾Ð¼Ð¿ÑŒÑŽÑ‚ÐµÑ€Ð½Ñ‹Ñ Ð¼Ð¾Ð´ÐµÐ»ÐµÐ¹ полей и частиц, Ð½Ð°Ñ Ð¾Ð´ÑÑ‰Ð¸Ñ ÑÑ в Ð½Ð¸Ñ , написание размерной теории к полям, анализ результатов моделирования и проверка его с согласованием с написанной теорией Показана теоретически, а также подтверждена в ÐºÐ¾Ð¼Ð¿ÑŒÑŽÑ‚ÐµÑ€Ð½Ñ‹Ñ Ð¼Ð¾Ð´ÐµÐ»ÑÑ Ð²Ð¾Ð·Ð¼Ð¾Ð¶Ð½Ð¾ÑÑ‚Ð¸ идеальной фокусировки для Ð¸ÑÑÐ»ÐµÐ´ÑƒÐµÐ¼Ñ‹Ñ ÑÐ¸ÑÑ‚ÐµÐ¼ при наличии магнитного поля. Область применения результатов – масс-спектрометрия., The meaning of this work was to expand class of systems with perfect time space focusing by adding a constant homogeneous magnetic field. In this work we created a computer model of the fields and particles and explored it for presence of perfect time and space focusing. As a result, we found conditions for perfect time and space focusing in these systems which can be used to create or modify mass-spectrometers.

The volatility distribution of the organic compounds present in secondary organic aerosol (SOA) at different conditions is a key quantity that has to be captured in order to describe SOA dynamics accurately. The development of the Filter Inlet for Gases and AEROsols (FIGAERO) and its coupling to a chemical ionization mass spectrometer (CIMS; collectively FIGAERO-CIMS) has enabled near-simultaneous sampling of the gas and particle phases of SOA through thermal desorption of the particles. The thermal desorption data have been recently shown to be interpretable as a volatility distribution with the use of the positive matrix factorization (PMF) method. Similarly, volatility distributions can be inferred from isothermal particle evaporation experiments when the particle size change measurements are analyzed with process-modeling techniques. In this study, we compare the volatility distributions that are retrieved from FIGAERO-CIMS and particle size change measurements during isothermal particle evaporation with process-modeling techniques. We compare the volatility distributions at two different relative humidities (RHs) and two oxidation conditions. In high-RH conditions, where particles are in a liquid state, we show that the volatility distributions derived via the two ways are similar within a reasonable assumption of uncertainty in the effective saturation mass concentrations that are derived from FIGAERO-CIMS data. In dry conditions, we demonstrate that the volatility distributions are comparable in one oxidation condition, and in the other oxidation condition, the volatility distribution derived from the PMF analysis shows considerably more high-volatility matter than the volatility distribution inferred from particle size change measurements. We also show that the Vogel-Tammann-Fulcher equation together with a recent glass transition temperature parametrization for organic compounds and PMF-derived volatility distribution estimates are consistent with the observed isothermal evaporation under dry conditions within the reported uncertainties. We conclude that the FIGAERO-CIMS measurements analyzed with the PMF method are a promising method for inferring the volatility distribution of organic compounds, but care has to be taken when the PMF factors are analyzed. Future process-modeling studies about SOA dynamics and properties could benefit from simultaneous FIGAERO-CIMS measurements.

The ways in which marine biological activity affects climate, by modifying aerosol properties, are not completely understood, causing high uncertainties in climate predictions. In this work, in situ measurements of aerosol chemical composition, particle number size distribution, cloud condensation nuclei (CCN), and ice-nucleating particle (INP) number concentrations are combined with high-resolution sea surface chlorophyll-a concentration (CHL) and back-trajectory data to elucidate the relationship between oceanic biological activity and marine aerosol. The measurements were performed during an intensive field campaign conducted in late summer (August–September) 2015 at the Mace Head Research Station (MHD). At the short time scale (1–2months) of the experiment, we observed a clear dependency of the main aerosol physicochemical and cloud-relevant properties on the patterns of biological activity, in specific oceanic regions with a delayed response of about 1–3weeks. The oceanic region comprised between 47°–57°N and 14°–30°W was identified as the main source of biogenic aerosols during the campaign, with hints of some minor influence of waters up to the Greenland coast. These spatial and temporal relationships demonstrate that the marine biota influences aerosol properties under a variety of features up to the most cloud-relevant properties. Such dependency of aerosol properties with oceanic biological activity was previously reported over the North Atlantic Ocean only for multiyear data sets, where the correlation may be enhanced by coincident seasonalities. A better knowledge of these short time scale interactions may lead to a significant improvement in understanding the ocean-atmosphere-cloud system, with important impacts on climate science.

The deep bedrock surroundings are an analog for extraterrestrial habitats for life. In this study, we investigated microbial life within anoxic ultradeep boreholes in Precambrian bedrock, including the adaptation to environmental conditions and lifestyle of these organisms. Samples were collected from Pyh&auml, salmi mine environment in central Finland and from geothermal drilling wells in Otaniemi, Espoo, in southern Finland. Microbial communities inhabiting the up to 4.4 km deep bedrock were characterized with phylogenetic marker gene (16S rRNA genes and fungal ITS region) amplicon and DNA and cDNA metagenomic sequencing. Functional marker genes (dsrB, mcrA, narG) were quantified with qPCR. Results showed that although crystalline bedrock provides very limited substrates for life, the microbial communities are diverse. Gammaproteobacterial phylotypes were most dominant in both studied sites. Alkanindiges -affiliating OTU was dominating in Pyh&auml, salmi fluids, while different depths of Otaniemi samples were dominated by Pseudomonas. One of the most common OTUs detected from Otaniemi could only be classified to phylum level, highlighting the uncharacterized nature of the deep biosphere in bedrock. Chemoheterotrophy, fermentation and nitrogen cycling are potentially significant metabolisms in these ultradeep environments. To conclude, this study provides information on microbial ecology of low biomass, carbon-depleted and energy-deprived deep subsurface environment. This information is useful in the prospect of finding life in other planetary bodies.

Данная работа посвящена разработке и калибровке измерительной системы, позволяющей обучать испытателей определять интенсивность запаха одорированного природного газа. Задачи, которые решались в ходе исследования: 1. Изучение особенностей измерения интенсивности запаха газа 2. Разработка измерительной системы для обучения испытателей 3. Калибровка разработанной системы Работа проведена на базе лаборатории в ФГУП «ВНИИМ им. Д.И. Менделеева», где было расположено оборудование для создания измерительной системы. Были изучены методы измерения интенсивности запаха, в результате чего был сделан выбор в пользу метода с использованием ольфактометра. В качестве ольфактометра использовался Scentroid SM100. Была разработана и собрана установка, в основе которой SM100. Также была разработана методика калибровки данного ольфактометра по этилмеркаптану, содержащемуся в одорированном природном газе. В результате был проведен анализ результатов калибровки и выявлено соответствие стандарту концентраций этилмеркаптана., This work is devoted to the development and calibration of a measuring system that allows educating smellers to determine the odor intensity of odorized natural gas. The research set the following goals: 1. The study of the features of measuring the intensity of the smell of gas 2. Development of a measuring system for training smellers 3. Calibration of the developed system The work was carried out on the basis of a laboratory in The D.I. Mendeleev All-Russian Institute for Metrology (VNIIM) where the equipment was located to create a measuring system. Methods for measuring odor intensity were studied, as a result of which a choice was made in favor of the method using an olfactometer. The Scentroid SM100 was used as an olfactometer. An installation based on the SM100 was developed and assembled. A method was also developed for calibrating this olfactometer using ethyl mercaptan contained in odorized natural gas. As a result, an analysis of the calibration results was carried out and compliance with the standard for ethyl mercaptan concentrations was revealed.

Sulfuric 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 sulfuric acid are oftentimes not available, and the current sulfuric 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 sulfuric acid in different environments and derive a new physical proxy for sulfuric 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 sulfuric acid from SO2 via OH oxidation and other oxidation pathways, specifically via stabilized Criegee intermediates. The sulfuric 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 sulfuric 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 over previous proxies. Following the recommendations in this paper, a proxy for a specific location can be derived.

Ions enhance the formation rate of atmospheric aerosol particles, which play an important role in Earth’s radiative balance. Ion-induced nucleation involves the stepwise accretion of neutral monomers onto a molecular cluster containing an ion, which helps to stabilize the cluster against evaporation. Although theoretical frameworks exist to calculate the collision rate coefficients between neutral molecules and ions, they need to be experimentally confirmed, ideally under atmospherically relevant conditions of around 1000 ion pairs cm−3. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we have measured the collision rate coefficients between neutral iodic acid (HIO3) monomers and charged iodic acid molecular clusters containing up to 11 iodine atoms. Three methods were analytically derived to calculate ion-polar molecule collision rate coefficients. After evaluation with a kinetic model, the 50% appearance time method is found to be the most robust. The measured collision rate coefficient, averaged over all iodine clusters, is (2.4 ± 0.8)×10−9 cm3 s−1, which is close to the expectation from the surface charge capture theory.

Evaporation of sulfuric acid from particles can be important in the atmospheres of Earth and Venus. However, the equilibrium constant for the dissociation of H2SO4 to bisulfate ions, which is the one of the fundamental parameters controlling the evaporation of sulfur particles, is not well constrained. In this study we explore the volatility of sulfate particles at very low relative humidity. We measured the evaporation of sulfur particles versus temperature and relative humidity in the CLOUD chamber at CERN. We modelled the observed sulfur particle shrinkage with the ADCHAM model. Based on our model results, we conclude that the sulfur particle shrinkage is mainly governed by H2SO4 and potentially to some extent by SO3 evaporation. We found that the equilibrium constants for the dissociation of H2SO4 to HSO4−(KH2SO4) and the dehydration of H2SO4 to SO3 (xKSO3) are KH2SO4 = 2–4 × 109 mol kg−1 and xKSO3 ≥ 1.4 × 1010 at 288.8 ± 5 K.

The article presents the results of operation of ion source with Penning discharge developed in the IAP of NAS of Ukraine to produce doubly charged helium ions He2+ beam and to increase the energy of accelerated ions up to 3.2 MeV. This energy is necessary for ERDA channel when measuring hydrogen concentration in the structural materials used in nuclear engineering. The ion source parameters are the following: discharge voltage is 6 kV, discharge current is 0.8 - 1.2 mA, the current of singly charged helium ions He+ 24 μA, the current of doubly charged helium ions He2+ 0.5 μA.

The ion composition at high altitude (3454 m a.s.l.) was measured with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) during a period of 9 months, from August 2013 to April 2014. The negative mass spectra were dominated by the ions of sulfuric, nitric, malonic, and methanesulfonic acid (MSA) as well as SO5−. The most prominent positive ion peaks were from amines. The other cations were mainly organic compounds clustered with a nitrogen-containing ion, which could be either NH4+ or an aminium. Occasionally the positive spectra were characterized by groups of compounds each differing by a methylene group. In the negative spectrum, sulfuric acid was always observed during clear sky conditions following the diurnal cycle of solar irradiation. On many occasions we also saw a high signal of sulfuric acid during nighttime when clusters up to the tetramer were observed. A plausible reason for these events could be evaporation from particles at low relative humidity. A remarkably strong correlation between the signals of SO5− and CH3SO3− was observed for the full measurement period. The presence of these two ions during both the day and the night suggests a non-photochemical channel of formation which is possibly linked to halogen chemistry. Halogenated species, especially Br− and IO3−, were frequently observed in air masses that originated mainly from the Atlantic Ocean and occasionally from continental areas based on back trajectory analyses. We found I2O5 clustered with an ion, a species that was proposed from laboratory and modeling studies. All halogenated ions exhibited an unexpected diurnal behavior with low values during daytime. New particle formation (NPF) events were observed and characterized by (1) highly oxygenated molecules (HOMs) and low sulfuric acid or (2) ammonia–sulfuric acid clusters. We present characteristic spectra for each of these two event types based on 26 nucleation episodes. The mass spectrum of the ammonia–sulfuric acid nucleation event compares very well with laboratory measurements reported from the CLOUD chamber. A source receptor analysis indicates that NPF events at the Jungfraujoch take place within a restricted period of time of 24–48 h after air masses have had contact with the boundary layer. This time frame appears to be crucial to reach an optimal oxidation state and concentration of organic molecules necessary to facilitate nucleation.

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 (HOMs) are important contributors to secondary organic aerosol (SOA) and new-particle formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOCs), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during α-pinene ozonolysis experiments performed at three different temperatures, 20, 0 and -15 ĝC, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb α-pinene and 100 ppb ozone), decreased considerably at lower temperature, with molar yields dropping by around a factor of 50 when experiments were performed at 0 ĝC, compared to 20 ĝC. At -15 ĝC, the HOM signals were already close to the detection limit of the nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOMs. Surprisingly, comparing spectra measured at 0 and 20 ĝC, ratios between HOMs of different oxidation levels, e.g., the typical HOM products C10H14O7, C10H14O9, and C10H14O11, changed considerably less than the total HOM yields. More oxidized species have undergone more isomerization steps; yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is that the primary rate-limiting steps forming these HOMs occur before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e., typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant to the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, both the magnitude and complexity of this effect clearly deserve more consideration in future studies in order to estimate the ultimate role of HOMs on SOA and NPF under different atmospheric conditions.

The impact of aerosols on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated products, generated from the gas-phase oxidation of volatile organic compounds (VOCs), to aerosol formation. Indeed, atmospheric gaseous chemical processes yield thousands of (highly) oxygenated species, spanning a wide range of chemical formulas, functional groups and, consequently, volatilities. While recent mass spectrometric developments have allowed extensive on-line detection of a myriad of oxygenated organic species, playing a central role in atmospheric chemistry, the detailed quantification and characterization of this diverse group of compounds remains extremely challenging. To address this challenge, we evaluated the capability of current state-of-the-art mass spectrometers equipped with different chemical ionization sources to detect the oxidation products formed from α-Pinene ozonolysis under various conditions. Five different mass spectrometers were deployed simultaneously for a chamber study. Two chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate and amine reagent ion chemistries and an iodide chemical ionization time-of-flight mass spectrometer (TOF-CIMS) were used. Additionally, a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF 8000) and a new “vocus” PTR-TOF were also deployed. In the current study, we compared around 1000 different compounds between each of the five instruments, with the aim of determining which oxygenated VOCs (OVOCs) the different methods were sensitive to and identifying regions where two or more instruments were able to detect species with similar molecular formulae. We utilized a large variability in conditions (including different VOCs, ozone, NOx and OH scavenger concentrations) in our newly constructed atmospheric simulation chamber for a comprehensive correlation analysis between all instruments. This analysis, combined with estimated concentrations for identified molecules in each instrument, yielded both expected and surprising results. As anticipated based on earlier studies, the PTR instruments were the only ones able to measure the precursor VOC, the iodide TOF-CIMS efficiently detected many semi-volatile organic compounds (SVOCs) with three to five oxygen atoms, and the nitrate CI-APi-TOF was mainly sensitive to highly oxygenated organic (O > 5) molecules (HOMs). In addition, the vocus showed good agreement with the iodide TOF-CIMS for the SVOC, including a range of organonitrates. The amine CI-APi-TOF agreed well with the nitrate CI-APi-TOF for HOM dimers. However, the loadings in our experiments caused the amine reagent ion to be considerably depleted, causing nonlinear responses for monomers. This study explores and highlights both benefits and limitations of currently available chemical ionization mass spectrometry instrumentation for characterizing the wide variety of OVOCs in the atmosphere. While specifically shown for the case of α-Pinene ozonolysis, we expect our general findings to also be valid for a wide range of other VOC–oxidant systems. As discussed in this study, no single instrument configuration can be deemed better or worse than the others, as the optimal instrument for a particular study ultimately depends on the specific target of the study.

Chemical characteristics and the sources of submicron particles (

18 pages, 4 figures, 2 tables, supplement https://doi.org/10.5194/acp-19-10239-2019-supplement, There are limited measurements of the chemical composition, abundance and sources of atmospheric particles in the High Arctic To address this, we report 93 d of soot particle aerosol mass spectrometer (SP-AMS) data collected from 20 February to 23 May 2015 at Villum Research Station (VRS) in northern Greenland (81?360 N). During this period, we observed the Arctic haze phenomenon with elevated PM1 concentrations ranging from an average of 2.3, 2.3 and 3.3 μg m in February, March and April, respectively, to 1.2 μg m in May. Particulate sulfate (SO2 4-) accounted for 66 % of the non-refractory PM1 with the highest concentration until the end of April and decreasing in May. The second most abundant species was organic aerosol (OA) (24 %). Both OA and PM1, estimated from the sum of all collected species, showed a marked decrease throughout May in accordance with the polar front moving north, together with changes in aerosol removal processes. The highest refractory black carbon (rBC) concentrations were found in the first month of the campaign, averaging 0.2 μg m. In March and April, rBC averaged 0.1 μg m while decreasing to 0.02 μg m in May. Positive matrix factorization (PMF) of the OA mass spectra yielded three factors: (1) a hydrocarbon-like organic aerosol (HOA) factor, which was dominated by primary aerosols and accounted for 12 % of OA mass, (2) an Arctic haze organic aerosol (AOA) factor and (3) a more oxygenated marine organic aerosol (MOA) factor. AOA dominated until mid-April (64 %-81 % of OA), while being nearly absent from the end of May and correlated significantly with SO2-4, suggesting the main part of that factor is secondary OA. The MOA emerged late at the end of March, where it increased with solar radiation and reduced sea ice extent and dominated OA for the rest of the campaign until the end of May (24 %-74 % of OA), while AOA was nearly absent. The highest O=C ratio (0.95) and S=C ratio (0.011) was found for MOA. Our data support the current understanding that Arctic aerosols are highly influenced by secondary aerosol formation and receives an important contribution from marine emissions during Arctic spring in remote High Arctic areas. In view of a changing Arctic climate with changing sea-ice extent, biogenic processes and corresponding source strengths, highly time-resolved data are needed in order to elucidate the components dominating aerosol concentrations and enhance the understanding of the processes taking place, This research has been financially supported by the Danish Environmental Protection Agency and Danish Energy Agency with means from the MIKA/DANCEA funds for environmental support to the Arctic Region (project nos. MST-113-0079, 2016-3025, MST-112-00298) and the Danish Council for In dependent Research (project NUMEN, grant no. DFF-FTP-4005-00485B).

It is generally assumed that isoprene-derived secondary organic aerosol (SOA) precursors are mainly formed from the secondary reactions of intermediate products with OH radicals in the gas phase and multiphase oxidation in particles. In this paper, we predicted a theoretical mechanism for the primary formation of highly oxygenated molecules (HOM) in the gas phase through successive intramolecular H-shifts and O-2 addition in the specific Z-delta isomer of hydroxyl-peroxy radicals and alkoxy radicals. The position of O-2 addition is different from that in forming hydroperoxy aldehydes. The prediction was further supported experimentally by successfully identifying a few highly oxidized peroxy radicals and closed-shell products such as C5H9O7,9, C5H10O6,7,8, and C4H8O5 in a flow reactor by chemical ionization mass spectrometry at air pressure. These HOM products could serve as important precursors to isoprene-derived SOA. Further modeling studies on the effect of NO concentration suggested that HOM formation could account for up to, similar to 11% of the branching ratio (similar to 9% from the 4-OH channel and similar to 2% from the 1-OH channel) in the reaction of isoprene with OH when the lifetimes of peroxy radicals due to bimolecular reactions are similar to 100 s, which is typical in forest regions.

The formation of biogenic secondary organic aerosols (BSOAs) in forest environments is potentially important to cloud formation via changes of the cloud condensation nuclei (CCN) activity of aerosols. In this study, the CCN activation of submicrometer aerosols and their chemical compositions and size distributions were measured at a midlatitude forest site in Japan during the summer of 2014 to assess the hygroscopicity of the organic aerosols and their contributions to the local CCN concentrations. The mean number concentrations of the condensation nuclei and CCN at supersaturation (SS) conditions of 0.11-0.80% were 1,238 and 166-740cm(-3), respectively. Organic aerosols and sulfate dominated the submicrometer aerosol mass concentrations. The particle hygroscopicity increased with increases in particle diameters. The hygroscopicity parameter for the organics, (org), was positively correlated with the atomic O to C ratio. The product of (org) and the volume fraction of OA was 0.12, accounting for 38% of the water uptake by aerosol particles. The hygroscopicity parameter of the locally formed fresh BSOA was estimated to be 0.09. The contribution of OA to the CCN number concentration, which was assessed by subtracting the CCN concentration of the hypothetical inorganic aerosols from that of the ambient aerosols, was 50-182cm(-3) for the SS range of 0.11-0.80%. The increase of the CCN number concentrations per 1-g/m(3) increase of the BSOA was 23-299cm(-3) at 0.11-0.80% SS. The contribution of the BSOA to the CCN number concentration can be enhanced by new particle formation. Plain Language Summary Some of the particles suspended in the atmosphere can absorb water vapors around them and act as nuclei to form cloud droplets. These particles are called cloud condensation nuclei (CCN), the quantification of which is important for climate forcing prediction. The ability of a particle to absorb water is referred to as hygroscopicity, which is governed by the chemical composition. Volatile organic vapors emitted by vegetation (i.e., biogenic volatile organic compound) after chemical reactions in the atmosphere can either condense onto existing particles or participate in the formation of new particles and thus change the aerosol chemical composition. The aerosol component originated from biogenic volatile organic compounds, named biogenic secondary organic aerosol (BSOA), is an important constituent of CCN on a global scale. However, the hygroscopicity of BSOA and its contribution to CCN are not understood well. We performed measurements of the hygroscopicity and chemical composition of aerosol particles in a forest in Japan. Based on the observation, we calculated the hygroscopicity of the BSOA formed in the forest and quantified the contribution of the BSOA to the CCN number concentrations. An enhancement of the contribution of BSOA to the CCN number concentrations by new particle formation is suggested, which is an important subject of future studies.

We present measurements of highly oxidized multifunctional molecules (HOMs) detected in the gas phase using a high-resolution time-of-flight chemical ionization mass spectrometer with nitrate reagent ion (NO_3– CIMS). The measurements took place during the 2013 Southern Oxidant and Aerosol Study (SOAS 2013) at a forest site in Alabama, where emissions were dominated by biogenic volatile organic compounds (BVOCs). Primary BVOC emissions were represented by isoprene mixed with various terpenes, making it a unique sampling location compared to previous NO_3– CIMS deployments in monoterpene-dominated environments. During SOAS 2013, the NO_3–CIMS detected HOMs with oxygen-to-carbon (O:C) ratios between 0.5 and 1.4 originating from both isoprene (C_5) and monoterpenes (C_(10)) as well as hundreds of additional HOMs with carbon numbers between C_3 and C_(20). We used positive matrix factorization (PMF) to deconvolve the complex data set and extract information about classes of HOMs with similar temporal trends. This analysis revealed three isoprene-dominated and three monoterpene-dominated PMF factors. We observed significant amounts of isoprene- and monoterpene-derived organic nitrates (ONs) in most factors. The abundant presence of ONs was consistent with previous studies that have highlighted the importance of NO_x-driven chemistry at the site. One of the isoprene-dominated factors had a strong correlation with SO_2 plumes likely advected from nearby coal-fired power plants and was dominated by an isoprene-derived ON (C_5H_(10)N_2O_8). These results indicate that anthropogenic emissions played a significant role in the formation of low-volatility compounds from BVOC emissions in the region.

A micro-engineered, skimmer-based vacuum interface has been demonstrated and used to investigate gas dynamics on a sub-millimeter length scale. The interface is fabricated as a stacked assembly of silicon dies, based on an anisotropically etched inlet orifice and a pyramidal skimmer cone formed in electroplated nickel. Expansion of gas into vacuum, interaction of a supersonic jet with the skimmer and transmission of a collimated beam into a second vacuum stage have all been imaged with a schlieren microscope. Using a glass-walled vacuum chamber, flow patterns upstream and fully downstream of the skimmer have been imaged together for the first time. At low first-stage pressures, the 150–200 µm tall skimmers cannot fully penetrate the shock arising from interaction of the jet with the back wall. However, as the pressure is increased, a multiple shock cell structure evolves, the jet narrows and transmission rises sharply. Eventually, a collimated beam is transmitted to the second stage. When the skimmer aperture is smaller than the source aperture, a series of distinct peaks is evident in a plot of transmission against first-stage pressure. Imaging shows that at each successive peak, the number of shock cells increases by one and the skimmer inlet is coincident with a node.

Particulate emissions from biomass burning can both alter the atmosphere's radiative balance and cause significant harm to human health. However, due to the large effect on emissions caused by even small alterations to the way in which a fuel burns, it is difficult to study particulate production of biomass combustion mechanistically and in a repeatable manner. In order to address this gap, in this study, small wood samples sourced from Cote D'Ivoire in West Africa were burned in a highly controlled laboratory environment. The shape and mass of samples, available airflow and surrounding thermal environment were carefully regulated. Organic aerosol and refractory black carbon emissions were measured in real time using an Aerosol Mass Spectrometer and a Single Particle Soot Photometer, respectively. This methodology produced remarkably repeatable results, allowing aerosol emissions to be mapped directly onto different phases of combustion. Emissions from pyrolysis were visible as a distinct phase before flaming was established. After flaming combustion was initiated, a black-carbon-dominant flame was observed during which very little organic aerosol was produced, followed by a period that was dominated by organic-carbon-producing smouldering combustion, despite the presence of residual flaming. During pyrolysis and smouldering, the two phases producing organic aerosol, distinct mass spectral signatures that correspond to previously reported variations in biofuel emissions measured in the atmosphere are found. Organic aerosol emission factors averaged over an entire combustion event were found to be representative of the time spent in the pyrolysis and smouldering phases, rather than reflecting a coupling between emissions and the mass loss of the sample. Further exploration of aerosol yields from similarly carefully controlled fires and a careful comparison with data from macroscopic fires and real-world emissions will help to deliver greater constraints on the variability of particulate emissions in atmospheric systems.