Browsing by Subject "AEROSOL"

Sort by: Order: Results:

Now showing items 1-20 of 46
  • Sokhi, Ranjeet S.; Singh, Vikas; Querol, Xavier; Finardi, Sandro; Targino, Admir Creso; Andrade, Maria de Fatima; Pavlovic, Radenko; Garland, Rebecca M.; Massague, Jordi; Kong, Shaofei; Baklanov, Alexander; Ren, Lu; Tarasova, Oksana; Carmichael, Greg; Peuch, Vincent-Henri; Anand, Vrinda; Arbilla, Graciela; Badali, Kaitlin; Beig, Gufran; Carlos Belalcazar, Luis; Bolignano, Andrea; Brimblecombe, Peter; Camacho, Patricia; Casallas, Alejandro; Charland, Jean-Pierre; Choi, Jason; Chourdakis, Eleftherios; Coll, Isabelle; Collins, Marty; Cyrys, Josef; da Silva, Cleyton Martins; Di Giosa, Alessandro Domenico; Di Leo, Anna; Ferro, Camilo; Gavidia-Calderon, Mario; Gayen, Amiya; Ginzburg, Alexander; Godefroy, Fabrice; Alexandra Gonzalez, Yuri; Guevara-Luna, Marco; Haque, Sk Mafizul; Havenga, Henno; Herod, Dennis; Horrak, Urmas; Hussein, Tareq; Ibarra, Sergio; Jaimes, Monica; Kaasik, Marko; Kousa, Anu; Kukkonen, Jaakko; Kulmala, Markku; Kuula, Joel; Petäjä, Tuukka (2021)
    This global study, which has been coordinated by the World Meteorological Organization Global Atmospheric Watch (WMO/GAW) programme, aims to understand the behaviour of key air pollutant species during the COVID-19 pandemic period of exceptionally low emissions across the globe. We investigated the effects of the differences in both emissions and regional and local meteorology in 2020 compared with the period 2015-2019. By adopting a globally consistent approach, this comprehensive observational analysis focuses on changes in air quality in and around cities across the globe for the following air pollutants PM2.5, PM10, PMC (coarse fraction of PM), NO2, SO2, NOx, CO, O-3 and the total gaseous oxidant (O-X = NO2 + O-3) during the pre-lockdown, partial lockdown, full lockdown and two relaxation periods spanning from January to September 2020. The analysis is based on in situ ground-based air quality observations at over 540 traffic, background and rural stations, from 63 cities and covering 25 countries over seven geographical regions of the world. Anomalies in the air pollutant concentrations (increases or decreases during 2020 periods compared to equivalent 2015-2019 periods) were calculated and the possible effects of meteorological conditions were analysed by computing anomalies from ERA5 reanalyses and local observations for these periods. We observed a positive correlation between the reductions in NO2 and NOx concentrations and peoples' mobility for most cities. A correlation between PMC and mobility changes was also seen for some Asian and South American cities. A clear signal was not observed for other pollutants, suggesting that sources besides vehicular emissions also substantially contributed to the change in air quality. As a global and regional overview of the changes in ambient concentrations of key air quality species, we observed decreases of up to about 70% in mean NO2 and between 30% and 40% in mean PM2.5 concentrations over 2020 full lockdown compared to the same period in 2015-2019. However, PM2.5 exhibited complex signals, even within the same region, with increases in some Spanish cities, attributed mainly to the long-range transport of African dust and/or biomass burning (corroborated with the analysis of NO2/CO ratio). Some Chinese cities showed similar increases in PM2.5 during the lockdown periods, but in this case, it was likely due to secondary PM formation. Changes in O-3 concentrations were highly heterogeneous, with no overall change or small increases (as in the case of Europe), and positive anomalies of 25% and 30% in East Asia and South America, respectively, with Colombia showing the largest positive anomaly of similar to 70%. The SO2 anomalies were negative for 2020 compared to 2015-2019 (between similar to 25 to 60%) for all regions. For CO, negative anomalies were observed for all regions with the largest decrease for South America of up to similar to 40%. The NO2/CO ratio indicated that specific sites (such as those in Spanish cities) were affected by biomass burning plumes, which outweighed the NO2 decrease due to the general reduction in mobility (ratio of similar to 60%). Analysis of the total oxidant (OX = NO2 + O-3) showed that primary NO2 emissions at urban locations were greater than the O-3 production, whereas at background sites, O-X was mostly driven by the regional contributions rather than local NO2 and O-3 concentrations. The present study clearly highlights the importance of meteorology and episodic contributions (e.g., from dust, domestic, agricultural biomass burning and crop fertilizing) when analysing air quality in and around cities even during large emissions reductions. There is still the need to better understand how the chemical responses of secondary pollutants to emission change under complex meteorological conditions, along with climate change and socio-economic drivers may affect future air quality. The implications for regional and global policies are also significant, as our study clearly indicates that PM2.5 concentrations would not likely meet the World Health Organization guidelines in many parts of the world, despite the drastic reductions in mobility. Consequently, revisions of air quality regulation (e.g., the Gothenburg Protocol) with more ambitious targets that are specific to the different regions of the world may well be required.
  • Zhang, Yanjun; Peräkylä, Otso; Yan, Chao; Heikkinen, Liine; Äijälä, Mikko; Dällenbach, Kaspar; Zha, Qiaozhi; Riva, Matthieu; Garmash, Olga; Junninen, Heikki; Paatero, Pentti; Worsnop, Douglas; Ehn, Mikael (2019)
    Recent advancements in atmospheric mass spectrometry provide huge amounts of new information but at the same time present considerable challenges for the data analysts. High-resolution (HR) peak identification and separation can be effort- and time-consuming yet still tricky and inaccurate due to the complexity of overlapping peaks, especially at larger mass-to-charge ratios. This study presents a simple and novel method, mass spectral binning combined with positive matrix factorization (binPMF), to address these problems. Different from unit mass resolution (UMR) analysis or HR peak fitting, which represent the routine data analysis approaches for mass spectrometry datasets, binPMF divides the mass spectra into small bins and takes advantage of the positive matrix factorization's (PMF) strength in separating different sources or processes based on different temporal patterns. In this study, we applied the novel approach to both ambient and synthetic datasets to evaluate its performance. It not only succeeded in separating overlapping ions but was found to be sensitive to subtle variations as well. Being fast and reliable, binPMF has no requirement for a priori peak information and can save much time and effort from conventional HR peak fitting, while still utilizing nearly the full potential of HR mass spectra. In addition, we identify several future improvements and applications for binPMF and believe it will become a powerful approach in the data analysis of mass spectra.
  • Krieger, Ulrich K.; Siegrist, Franziska; Marcolli, Claudia; Emanuelsson, Eva U.; Gobel, Freya M.; Bilde, Merete; Marsh, Aleksandra; Reid, Jonathan P.; Huisman, Andrew J.; Riipinen, Ilona; Hyttinen, Noora; Myllys, Nanna; Kurten, Theo; Bannan, Thomas; Percival, Carl J.; Topping, David (2018)
    To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H-(O-CH2-CH2)(n)-OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10(-7) to 5 x 10(-2) Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures.
  • Pusfitasari, Eka Dian; Ruiz-Jimenez, Jose; Heiskanen, Ilmari; Jussila, Matti; Hartonen, Kari; Riekkola, Marja-Liisa (2022)
    A wide variety of nitrogen-containing compounds are present in the environment, which contributes to air pollution and new particle formation, for example. These eventually affect human health and the climate. With all this consideration, there is a growing interest in the development of efficient and reliable methods to determine these compounds in the atmosphere. In this study, titanium hydrogen phosphate-modified Mobil Composition of Matter No. 41 was used as sorbent material for in-tube extraction (ITEX) sampling system, to selectively collect nitrogen-containing compounds from natural air samples. The effect of sampling accessories, based on adsorbent coatings (with Tenax-GR as an adsorbent material) and polytetrafluoroethylene filters, was studied to improve the selectivity of the sampling system and to remove particles. Aerial drone with miniaturized air sampling system was employed for the reliable collection of nitrogen-containing compounds in both gas phase and aerosol particles. A total of 170 air samples were collected in July 2020 at the SMEAR II station, Finland to evaluate nitrogen-containing compounds diurnal patterns and vertical profiles (0.25, 5, 50, and 150 m). More than twenty nitrogen-containing compounds, such as aliphatic amines, imines, imidazoles, and pyridines, were identified, quantified or semi-quantified. The average concentrations of detected aliphatic amines at the altitude of 50 m were up to 40.4 ng m−3 (dimethylamine) in gas phase and 128 ng m−3 (ethylamine) in aerosol particles. Among nitrogen-containing compounds detected, pyridine gave the highest average concentration of 746 ng m−3 in gas phase and 644 ng m−3 in particle phase.
  • Liebmann, Jonathan; Sobanski, Nicolas; Schuladen, Jan; Karu, Einar; Hellen, Heidi; Hakola, Hannele; Zha, Qiaozhi; Ehn, Mikael; Riva, Matthieu; Heikkinen, Liine; Williams, Jonathan; Fischer, Horst; Lelieyeld, Jos; Crowley, John N. (2019)
    The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (6 ANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O-3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49% of the local production rate of ANs, with contributions of 21 %, 18% and 12% for NO3, OH and O-3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.
  • Sipilä, M.; Sarnela, N.; Jokinen, T.; Junninen, H.; Hakala, J.; Rissanen, M. P.; Praplan, A.; Simon, M.; Kürten, A.; Bianchi, F.; Dommen, J.; Curtius, J.; Petäjä, T.; Worsnop, D.R. (2015)
    Atmospheric amines may play a crucial role in formation of new aerosol particles via nucleation with sulfuric acid. Recent studies have revealed that concentrations below 1 pptV can significantly promote nucleation of sulfuric acid particles. While sulfuric acid detection is relatively straightforward, no amine measurements to date have been able to reach the critical sub-pptV concentration range and atmospheric amine concentrations are in general poorly characterized. In this work we present a proof-of-concept of an instrument capable of detecting dimethyl amine (DMA) with concentrations even down to 70 ppqV (parts per quadrillion, 0.07 pptV) for a 15 min integration time. Detection of ammonia and amines other than dimethyl amine is discussed. We also report results from the first ambient measurements performed in spring 2013 at a boreal forest site. While minute signals above the signal-to-noise ratio that could be attributed to trimethyl or propyl amine were observed, DMA concentration never exceeded the detection threshold of ambient measurements (150 ppqV), thereby questioning, though not excluding, the role of DMA in nucleation at this location.
  • Wiedensohler, A.; Andrade, M.; Weinhold, K.; Müller, T.; Birmili, W.; Velarde, F.; Moreno, Adam; Forno, R.; Sanchez, M. F.; Laj, P.; Ginot, P.; Whiteman, D. N.; Krejci, R.; Sellegri, K.; Reichler, T. (2018)
    Urban development, growing industrialization, and increasing demand for mobility have led to elevated levels of air pollution in many large cities in Latin America, where air quality standards and WHO guidelines are frequently exceeded. The conurbation of the metropolitan area of La Paz/El Alto is one of the fastest growing urban settlements in South America with the particularity of being located in a very complex terrain at a high altitude. As many large cities or metropolitan areas, the metropolitan area of La Paz/El Alto and the Altiplano region are facing air quality deterioration. Long-term measurement data of the equivalent black carbon (eBC) mass concentrations and particle number size distributions (PNSD) from the Global Atmosphere Watch Observatory Chacaltaya (CHC; 5240 m a.s.l., above sea level) indicated a systematic transport of particle matter from the metropolitan area of La Paz/El Alto to this high altitude station and subsequently to the lower free troposphere. To better understand the sources and the transport mechanisms, we conducted eBC and PNSDs measurements during an intensive campaign at two locations in the urban area of La Paz/El Alto from September to November 2012. While the airport of El Alto site (4040 m a.s.l.) can be seen as representative of the urban and Altiplano background, the road site located in Central La Paz (3590 m a.s.l.) is representative for heavy traffic-dominated conditions. Peaks of eBC mass concentrations up to 5 mu g m(-3) were observed at the El Alto background site in the early morning and evening, while minimum values were detected in the early afternoon, mainly due to thermal convection and change of the planetary boundary layer height. The traffic-related eBC mass concentrations at the road site reached maximum values of 10-20 mu g m(-3). A complete traffic ban on the specific Bolivian Day of Census (November 21, 2012) led to a decrease of eBC below 1 mu g m(-3) at the road site for the entire day. Compared to the day before and after, particle number concentrations decreased by a factor between 5 and 25 over the particle size range from 10 to 800 nm, while the submicrometer particle mass concentration dropped by approximately 80%. These results indicate that traffic is the dominating source of BC and particulate air pollution in the metropolitan area of La Paz/El Alto. In general, the diurnal cycle of eBC mass concentration at the Chacaltaya observatory is anti-correlated to the observations at the El Alto background site. This pattern indicates that the traffic-related particulate matter, including BC, is transported to higher altitudes with the developing of the boundary layer during daytime. The metropolitan area of La Paz/El Alto seems to be a significant source for BC of the regional lower free troposphere. From there, BC can be transported over long distances and exert impact on climate and composition of remote southern hemisphere.
  • Acton, W. Joe F.; Schallhart, Simon; Langford, Ben; Valach, Amy; Rantala, Pekka; Fares, Silvano; Carriero, Giulia; Tillmann, Ralf; Tomlinson, Sam J.; Dragosits, Ulrike; Gianelle, Damiano; Hewitt, C. Nicholas; Nemitz, Eiko (2016)
    This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4aEuro-m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketoneaEuro-+aEuro-methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9aEuro-mgaEuro-m(-2)aEuro-h(-1). Mixing ratios, recorded 4aEuro-m above the canopy, were dominated by methanol with a mean value of 6.2aEuro-ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7aEuro-mgaEuro-m(-2)aEuro-h(-1) was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC-MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.
  • Booyens, Wanda; Van Zyl, Pieter G.; Beukes, Johan P.; Ruiz-Jimenez, Jose; Kopperi, Matias; Riekkola, Marja-Liisa; Vakkari, Ville; Josipovic, Miroslav; Kulmala, Markku; Laakso, Lauri (2019)
    Although atmospheric organic N compounds are considered to be important, especially in new particle formation and their contribution to brown carbon, these species are not that well understood. This can be partially attributed to their chemical complexity. Therefore, the aim of this study was to assess the characteristics of organic N compounds utilising comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GCxGC-TOFMS) in aerosol samples that were collected at a savanna-grassland background region and to determine the possible sources. 135 atmospheric organic N compounds were tentatively characterised and semi-quantified, which included amines, nitriles, amides, urea, pyridine derivatives, amino acids, nitro-and nitroso compounds, imines, cyanates and isocyanates, and azo compounds. Amines contributed to 51% of the semi-quantified concentrations, while nitriles, pyridine derivatives, and amides comprised 20%, 11%, and 8%, respectively, of the semi-quantified concentrations. Amines, nitriles, amides, and pyridine derivatives concentrations were higher during the dry season, which were attributed to meteorology and open biomass burning. Anthropogenic sources impacting air masses measured at Welgegund, as well as regional agricultural activities, were considered as the major sources of amines, while the regional influence of household combustion was most likely the main source of nitriles, amides, and pyridine derivatives. The other organic N species were most likely related to the influence of local and regional agricultural activities.
  • Cai, Runlong; Attoui, Michel; Jiang, Jingkun; Korhonen, Frans; Hao, Jiming; Petäjä, Tuukka; Kangasluoma, Juha (2018)
    Classifying sub-3 nm particles effectively with relatively high penetration efficiencies and sizing resolutions is important for atmospheric new particle formation studies. A high-resolution supercritical differential mobility analyzer (half-mini DMA) was recently improved to classify aerosols at a sheath flow rate less than 100 L/min. In this study, we characterized the transfer functions, the penetration efficiencies, and the sizing resolution of the new half-mini DMA at the aerosol flow rate of 2.5-10 L/min and the sheath flow rate of 25-250 L/min using tetra-alkyl ammonium ions and tungsten oxide particles. The transfer functions of the new half-mini DMA at an aerosol flow rate lower than 5 L/min and a sheath flow rate lower than 150 L/min agree well with predictions using a theoretical diffusing transfer function. The penetration efficiencies can be approximated using an empirical formula. When classifying 1.48 nm molecular ions at an aerosol-to-sheath flow ratio of 5/50 L/min, the penetration efficiency, the sizing resolution, and the multiplicative broadening factor of the new half-mini DMA are 0.18, 6.8, and 1.11, respectively. Compared to other sub-3 nm DMAs applied in atmospheric measurements (e.g. the mini-cyDMA, the TSI DMA 3086, the TSI nanoDMA 3085, and the Grimm S-DMA), the new half-mini DMA characterized in this study is able to classify particles at higher aerosol and sheath flow rates, leading to a higher sizing resolution at the same aerosol-to-sheath flow ratio. Accordingly, the new half-mini DMA can reduce the uncertainties in atmospheric new particle formation measurement if coupled with an aerosol detector that could work at the corresponding high aerosol flow rate. (c) 2018 American Association for Aerosol Research
  • Frege, Carla; Bianchi, Federico; Molteni, Ugo; Trostl, Jasmin; Junninen, Heikki; Henne, Stephan; Sipilä, Mikko; Herrmann, Erik; Rossi, Michel J.; Kulmala, Markku; Hoyle, Christopher R.; Baltensperger, Urs; Dommen, Josef (2017)
    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.
  • Riva, M.; Ehn, M.; Li, D.; Tomaz, S.; Bourgain, F.; Perrier, S.; George, C. (2019)
    While acknowledged as key components in the formation of new particles in the atmosphere, the accurate characterization of gaseous (highly) oxygenated organic compounds remains challenging and requires analytical developments. Earlier studies have successfully used the nitrate ion (NO3) based chemical ionization (CI) coupled to atmospheric pressure interface time-of-flight mass spectrometry (CI-APi-TOF) for monitoring these compounds. Despite many breakthroughs in recent years, the CI-APi-TOF has many limitations, preventing for instance the unambiguous ion identification of overlapping peaks. To tackle this analytical challenge, we developed a CI interface coupled to an ultrahigh-resolution Orbitrap mass spectrometer (CI-Orbitrap). We show that the CI-Orbitrap has similar sensitivity and selectivity as the CI-APi-TOF, but with over an order of magnitude higher mass resolving power (up to 140 000). Equally importantly, the CI-Orbitrap allows tandem mass spectrometry, providing the possibility for structural elucidation of the highly oxygenated organic molecules (HOM). As a proof of concept, we characterized HOM formed during the ozonolysis of two biogenic compounds (alpha-pinene and limonene), under different environmental conditions in a flow reactor. The CI-Orbitrap exhibited high sensitivity to both HOM and radical species, while easily separating ions of different elemental composition in cases where the more common TOF applications would not have been able to distinguish all ions. Our tandem mass spectrometry analyses revealed distinct fingerprint spectra for all the studied HOM. Overall, the CI-Orbitrap is an extremely promising instrument, and it provides a much-needed extension to ongoing research on HOM, with potential to impact also many other fields within atmospheric chemistry.
  • Lopez-Hilfiker, Felipe D.; Iyer, Siddharth; Mohr, Claudia; Lee, Ben H.; D'Ambro, Emma L.; Kurten, Theo; Thornton, Joel A. (2016)
    The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion-molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion-molecule reaction time, which is strongly influenced by mixing and ion losses in the ion-molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.
  • Paasonen, Pauli; Kupiainen, Kaarle; Klimont, Zbigniew; Visschedijk, Antoon; van der Gon, Hugo A. C. Denier; Amann, Markus (2016)
    Atmospheric aerosol particle number concentrations impact our climate and health in ways different from those of aerosol mass concentrations. However, the global, current and future anthropogenic particle number emissions and their size distributions are so far poorly known. In this article, we present the implementation of particle number emission factors and the related size distributions in the GAINS (Greenhouse Gas-Air Pollution Interactions and Synergies) model. This implementation allows for global estimates of particle number emissions under different future scenarios, consistent with emissions of other pollutants and greenhouse gases. In addition to determining the general particulate number emissions, we also describe a method to estimate the number size distributions of the emitted black carbon particles. The first results show that the sources dominating the particle number emissions are different to those dominating the mass emissions. The major global number source is road traffic, followed by residential combustion of biofuels and coal (especially in China, India and Africa), coke production (Russia and China), and industrial combustion and processes. The size distributions of emitted particles differ across the world, depending on the main sources: in regions dominated by traffic and industry, the number size distribution of emissions peaks in diameters range from 20 to 50 nm, whereas in regions with intensive biofuel combustion and/or agricultural waste burning, the emissions of particles with diameters around 100 nm are dominant. In the baseline (current legislation) scenario, the particle number emissions in Europe, Northern and Southern Americas, Australia, and China decrease until 2030, whereas especially for India, a strong increase is estimated. The results of this study provide input for modelling of the future changes in aerosol-cloud interactions as well as particle number related adverse health effects, e.g. in response to tightening emission regulations. However, there are significant uncertainties in these current emission estimates and the key actions for decreasing the uncertainties are pointed out.
  • Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Zotter, Peter; Prevot, Andre S. H.; Xu, Lu; Ng, Nga L.; Herndon, Scott C.; Williams, Leah R.; Franklin, Jonathan P.; Zahniser, Mark S.; Worsnop, Douglas R.; Knighton, W. Berk; Aiken, Allison C.; Gorkowski, Kyle J.; Dubey, Manvendra K.; Allan, James D.; Thornton, Joel A. (2013)
  • Fung, Pak Lun; Zaidan, Martha Arbayani; Surakhi, Ola; Tarkoma, Sasu; Petäjä, Tuukka; Hussein, Tareq (2021)
    In air quality research, often only size-integrated particle mass concentrations as indicators of aerosol particles are considered. However, the mass concentrations do not provide sufficient information to convey the full story of fractionated size distribution, in which the particles of different diameters (Dp) are able to deposit differently on respiratory system and cause various harm. Aerosol size distribution measurements rely on a variety of techniques to classify the aerosol size and measure the size distribution. From the raw data the ambient size distribution is determined utilising a suite of inversion algorithms. However, the inversion problem is quite often ill-posed and challenging to solve. Due to the instrumental insufficiency and inversion limitations, imputation methods for fractionated particle size distribution are of great significance to fill the missing gaps or negative values. The study at hand involves a merged particle size distribution, from a scanning mobility particle sizer (NanoSMPS) and an optical particle sizer (OPS) covering the aerosol size distributions from 0.01 to 0.42 µm (electrical mobility equivalent size) and 0.3 to 10 µm (optical equivalent size) and meteorological parameters collected at an urban background region in Amman, Jordan, in the period of 1 August 2016–31 July 2017. We develop and evaluate feed-forward neural network (FFNN) approaches to estimate number concentrations at particular size bin with (1) meteorological parameters, (2) number concentration at other size bins and (3) both of the above as input variables. Two layers with 10–15 neurons are found to be the optimal option. Worse performance is observed at the lower edge (0.01<Dp<0.02 µm), the mid-range region (0.15<Dp<0.5 µm) and the upper edge (6<Dp<10 µm). For the edges at both ends, the number of neighbouring size bins is limited, and the detection efficiency by the corresponding instruments is lower compared to the other size bins. A distinct performance drop over the overlapping mid-range region is due to the deficiency of a merging algorithm. Another plausible reason for the poorer performance for finer particles is that they are more effectively removed from the atmosphere compared to the coarser particles so that the relationships between the input variables and the small particles are more dynamic. An observable overestimation is also found in the early morning for ultrafine particles followed by a distinct underestimation before midday. In the winter, due to a possible sensor drift and interference artefacts, the estimation performance is not as good as the other seasons. The FFNN approach by meteorological parameters using 5 min data (R2= 0.22–0.58) shows poorer results than data with longer time resolution (R2= 0.66–0.77). The FFNN approach using the number concentration at the other size bins can serve as an alternative way to replace negative numbers in the size distribution raw dataset thanks to its high accuracy and reliability (R2= 0.97–1). This negative-number filling approach can maintain a symmetric distribution of errors and complement the existing ill-posed built-in algorithm in particle sizer instruments.
  • Simon, Mario; Heinritzi, Martin; Herzog, Stephan; Leiminger, Markus; Bianchi, Federico; Praplan, Arnaud; Dommen, Josef; Curtius, Joachim; Kuerten, Andreas (2016)
    Amines are potentially important for atmospheric new particle formation, but their concentrations are usually low with typical mixing ratios in the pptv range or even smaller. Therefore, the demand for highly sensitive gas-phase amine measurements has emerged in the last several years. Nitrate chemical ionization mass spectrometry (CIMS) is routinely used for the measurement of gas-phase sulfuric acid in the sub-pptv range. Furthermore, extremely low volatile organic compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine (DMA, (CH3)(2)NH) using the NO3-center dot(HNO3)(1-2)center dot(DMA) cluster ion signal. Calibration measurements were made at the CLOUD chamber during two different measurement campaigns. Good linearity between 0 and similar to 120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38% RH.
  • Hansel, Armin; Scholz, Wiebke; Mentler, Bernhard; Fischer, Lukas; Bernd, Torsten (2018)
    The performance of the novel ammonium chemical ionization time of flight mass spectrometer (NH4+-CI3-TOF) utilizing NH4+ adduct ion chemistry to measure first generation oxidized product molecules (OMs) as well as highly oxidized organic molecules (HOMs) was investigated for the first time. The gas-phase ozonolysis of cyclohexene served as a first test system. Experiments have been carried out in the TROPOS free-jet flow system at close to atmospheric conditions. Product ion signals were simultaneously observed by the NH4+-CI3-TOF and the acetate chemical ionization atmospheric pressure interface time of flight mass spectrometer (acetate-CI-APITOF). Both instruments are in remarkable good agreement within a factor of two for HOMs. For OMs not containing an OOH group the acetate technique can considerably underestimate OM concentrations by 2-3 orders of magnitude. First steps of cyclohexene ozonolysis generate ten different main products, detected with the ammonium-CI3-TOF, comprising 93% of observed OMs. The remaining 7% are distributed over several minor products that can be attributed to HOMs, predominately to highly oxidized RO2 radicals. Summing up, observed ammonium-CI3-TOF products yield 5.6 x le molecules cm" in excellent agreement with the amount of reacted cyclohexene of 4.5 x 10(9) molecules cm(-3) for reactant concentrations of [O-3] = 2.25 x 10(12) molecules cm(-3) and [cyclohexene] = 2.0 x 10(12) molecules cm(-3) and a reaction time of 7.9 s. NH4+ adduct ion chemistry is a promising CIMS technology for achieving carbon-closure due to the unique opportunity for complete detection of the whole product distribution including also peroxy radicals, and consequently, for a much better understanding of oxidation processes.
  • Quéléver, Lauriane L. J.; Kristensen, Kasper; Jensen, Louise Normann; Rosati, Bernadette; Teiwes, Ricky; Dällenbach, Kaspar; Peräkylä, Otso; Roldin, Pontus; Bossi, Rossana; Pedersen, Henrik B.; Glasius, Marianne; Bilde, Merete; Ehn, Mikael (2019)
    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 a -pinene ozonolysis experiments performed at three different temperatures, 20, 0 and - 15 degrees C, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb alpha-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 degrees C, compared to 20 degrees C. At -15 degrees C, 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 degrees C, 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.
  • Szukalska, Marta; Szyfter, Krzysztof; Florek, Ewa; Rodrigo, Juan P.; Rinaldo, Alessandra; Mäkitie, Antti A.; Strojan, Primoz; Takes, Robert P.; Suarez, Carlos; Saba, Nabil F.; Braakhuis, Boudewijn J. M.; Ferlito, Alfio (2020)
    Simple Summary The risk of developing cancer is always higher for tobacco smokers than for non-smokers. Electronic cigarettes (e-cigarettes) have become increasingly popular in the last decade and are considered less harmful than traditional tobacco products, due to the lower content of toxic and carcinogenic compounds. However, this is still a controversial issue. This paper contains a review of previous reports on the composition of e-cigarettes and their impact on the pathogenesis and risk of head and neck cancer (HNC). The authors reviewed articles on both toxic and carcinogenic compounds contained in e-cigarettes and their molecular and health effects on the upper respiratory tract in comparison to traditional tobacco cigarettes. In conclusion, the studies discussed in the review strongly suggest that more long-term studies are needed to better address the safety of e-cigarettes. E-cigarettes have become increasingly popular in the last decade and are considered less harmful than traditional tobacco products due to the lower content of toxic and carcinogenic compounds. However, this is still a controversial issue. This paper contains a review of previous reports on the composition of e-cigarettes and their impact on the pathogenesis and risk of head and neck cancer (HNC). The objective of the review was to compare the molecular and health effects of e-cigarette use in relation to the effects of traditional cigarette smoking in the upper respiratory tract, and to assess the safety and effect of e-cigarettes on HNC risk. A review for English language articles published until 31 August 2020 was made, using a PubMed (including MEDLINE), CINAHL Plus, Embase, Cochrane Library and Web of Science data. The authors reviewed articles on both toxic and carcinogenic compounds contained in e-cigarettes and their molecular and health effects on the upper respiratory tract in comparison to tobacco cigarettes. The risk of developing head and neck squamous cell carcinoma (HNSCC) remains lower in users of e-cigarettes compared with tobacco smokers. However, more long-term studies are needed to better address the safety of e-cigarettes.