Browsing by Subject "SOURCE APPORTIONMENT"

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  • Qi, Lu; Vogel, Alexander L.; Esmaeilirad, Sepideh; Cao, Liming; Zheng, Jing; Jaffrezo, Jean-Luc; Fermo, Paola; Kasper-Giebl, Anne; Dällenbach, Kaspar; Chen, Mindong; Ge, Xinlei; Baltensperger, Urs; Prevot, Andre S. H.; Slowik, Jay G. (2020)
    The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which limit chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24 h filter samples collected approximately every fourth day throughout 2013 at an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABB(EESI) and MABB(EESI), respectively), cigarette-smoke-related organic aerosol, primary biological organic aerosol, biogenic secondary organic aerosol, and a summer mixed oxygenated organic aerosol factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species of two distinct populations: one with low H : C and high O : C and the other with high H : C and low O : C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The cigarette-smoke-related factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m/z.
  • Bressi, M.; Cavalli, F.; Putaud, J.P.; Fröhlich, R.; Petit, J.-E.; Aas, W.; Äijälä, M.; Alastuey, A.; Allan, J.D.; Aurela, M.; Berico, M.; Bougiatioti, A.; Bukowiecki, N.; Canonaco, F.; Crenn, V.; Dusanter, S.; Ehn, Mikael; Elsasser, M.; Flentje, H.; Graf, P.; Green, D.C.; Heikkinen, Liine; Hermann, H.; Holzinger, R.; Hueglin, C.; Keernik, H.; Kiendler-Scharr, A.; Kubelová, L.; Lunder, C.; Maasikmets, M.; Makeš, O.; Malaguti, A.; Mihalopoulos, N.; Nicolas, J.B.; O'Dowd, C.; Ovadnevaite, J.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Schlag, P.; Schwarz, J.; Sciare, J.; Slowik, J.; Sosedova, Y.; Stavroulas, I.; Teinemaa, E.; Via, M.; Vodička, P.; Williams, P.I.; Wiedensohler, A.; Young, D.E.; Zhang, S.; Favez, O.; Minguillón, M.C.; Prevot, A.S.H. (2021)
    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 degrees N and 10 degrees W - 26 degrees 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 midlatitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (mu g/m(3)) 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 mu g/m(3) at half of the sites.
  • Cavalli, F.; Alastuey, A.; Areskoug, H.; Ceburnis, D.; Cech, J.; Genberg, J.; Harrison, R. M.; Jaffrezo, J. L.; Kiss, G.; Laj, P.; Mihalopoulos, N.; Perez, N.; Quincey, P.; Schwarz, J.; Sellegri, K.; Spindler, G.; Swietlicki, E.; Theodosi, C.; Yttri, K. E.; Aas, W.; Putaud, J. P. (2016)
    Although particulate organic and elemental carbon (OC and EC) are important constituents of the suspended atmospheric particulate matter (PM), measurements of OC and EC are much less common and More uncertain than measurements of e.g. the ionic components of PM. In the framework of atmospheric research infrastructures supported by the European Union, actions have been undertaken to determine and mitigate sampling artefacts, and assess the comparability of OC and EC data obtained in a network of 10 atmospheric observatories across Europe. Positive sampling artefacts (from 0:4 to 2.8 mu g C/m(3)) and analytical discrepancies (between -50% and +40% for the EC/TC ratio) have been taken into account to generate a robust data set, from which we established the phenomenology of carbonaceous aerosols at regional background sites in Europe. Across the network, TC and EC annual average concentrations range from 0.4 to 9 mu g C/m(3), and from 0.1 to 2 mu g C/m(3), respectively. TC/PM10 annual mean ratios range from 0.11 at a Mediterranean site to 0.34 at the most polluted continental site, and TC/PM2.5 ratios are slightly greater at all sites (0.15-0.42). EC/TC annual mean ratios range from 0.10 to 0.22, and do not depend much on PM concentration levels, especially in winter. Seasonal variations in PM and TC concentrations, and in TC/PM and EC/TC ratios, differ across the network, which can be explained by seasonal changes in PM source contributions at some sites. (C) 2016 The Authors. Published by Elsevier Ltd.
  • 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.
  • Hussein, Tareq; Juwhari, Hassan; Al Kuisi, Mustafa; Alkattan, Hamza; Lahlouh, Bashar; Al-Hunaiti, Afnan (2018)
    In this study, we analyzed the concentrations of accumulation and coarse modes measured during November 2013–July 2017 at an urban background site in Amman, Jordan. The concentrations showed distinct seasonal variations with high concentrations with a monthly average higher than 100 cm−3 and 1.5 cm−3, respectively, for accumulation and coarse modes during the winter and low concentrations with a monthly average less than 40 cm−3 and 1–1.5 cm−3, respectively, for accumulation and coarse modes during the summer. Sand and dust storms (SDS) affected the coarse mode during the early spring whereas local dust re-suspension affected them during the autumn. The gravimetric analysis confirmed the seasonal variation of the calculated particulate mass concentration but suggested that the assumption of spherical particles and unit density is not always proper. The ATR-FTIR analysis of selected filters revealed that aerosols in the background atmosphere of Amman are a mixture of locally emitted (fossil fuel combustion) and local/regional dust. Based on the 24-h average of the calculated PM10, the pollution standard index (PSI) revealed that about 81% of the days were either good or moderate air quality conditions. About 71% of the days were below the 24-h PM10 limit value according to the Jordanian air quality standards (120 μg m−3).
  • Crenn, V.; Sciare, J.; Croteau, P. L.; Verlhac, S.; Froehlich, R.; Belis, C. A.; Aas, W.; Äijälä, M.; Alastuey, A.; Artinano, B.; Baisnee, D.; Bonnaire, N.; Bressi, M.; Canagaratna, M.; Canonaco, F.; Carbone, C.; Cavalli, F.; Coz, E.; Cubison, M. J.; Esser-Gietl, J. K.; Green, D. C.; Gros, V.; Heikkinen, L.; Herrmann, H.; Lunder, C.; Minguillon, M. C.; Mocnik, G.; O'Dowd, C. D.; Ovadnevaite, J.; Petit, J. -E.; Petralia, E.; Poulain, L.; Priestman, M.; Riffault, V.; Ripoll, A.; Sarda-Esteve, R.; Slowik, J. G.; Setyan, A.; Wiedensohler, A.; Baltensperger, U.; Prevot, A. S. H.; Jayne, J. T.; Favez, O. (2015)
    As part of the European ACTRIS project, the first large Quadrupole Aerosol Chemical Speciation Monitor (Q-ACSM) intercomparison study was conducted in the region of Paris for 3 weeks during the late-fall-early-winter period (November-December 2013). The first week was dedicated to the tuning and calibration of each instrument, whereas the second and third were dedicated to side-by-side comparison in ambient conditions with co-located instruments providing independent information on submicron aerosol optical, physical, and chemical properties. Near real-time measurements of the major chemical species (organic matter, sulfate, nitrate, ammonium, and chloride) in the non-refractory submicron aerosols (NR-PM1) were obtained here from 13 Q-ACSM. The results show that these instruments can produce highly comparable and robust measurements of the NR-PM1 total mass and its major components. Taking the median of the 13 Q-ACSM as a reference for this study, strong correlations (r(2) > 0.9) were observed systematically for each individual Q-ACSM across all chemical families except for chloride for which three Q-ACSMs showing weak correlations partly due to the very low concentrations during the study. Reproducibility expanded uncertainties of Q-ACSM concentration measurements were determined using appropriate methodologies defined by the International Standard Organization (ISO 17025, 1999) and were found to be 9, 15, 19, 28, and 36% for NR-PM1, nitrate, organic matter, sulfate, and ammonium, respectively. However, discrepancies were observed in the relative concentrations of the constituent mass fragments for each chemical component. In particular, significant differences were observed for the organic fragment at mass-to-charge ratio 44, which is a key parameter describing the oxidation state of organic aerosol. Following this first major intercomparison exercise of a large number of Q-ACSMs, detailed intercomparison results are presented, along with a discussion of some recommendations about best calibration practices, standardized data processing, and data treatment.
  • Lihavainen, H.; Alghamdi, M. A.; Hyvärinen, A.; Hussein, T.; Neitola, Kimmo; Khoder, M.; Abdelmaksoud, A. S.; Al-Jeelani, H.; Shabbaj, I. I.; Almehmadi, F. M. (2017)
    To derive the comprehensive aerosol in situ characteristics at a rural background area in Saudi Arabia, an aerosol measurements station was established to Hada Al Sham, 60 km east from the Red Sea and the city of Jeddah. The present sturdy describes the observational data from February 2013 to February 2015 of scattering and absorption coefficients, Angstrom exponents and single scattering albedo over the measurement period. The average scattering and absorption coefficients at wavelength 525 nm were 109 +/- 71 Min(-1) (mean +/- SD, at STP conditions) and 15 +/- 17 Mm(-1) (at STP conditions), respectively. As expected, the scattering coefficient was dominated by large desert dust particles with low Angstrom scattering exponent, 0.49 +/- 0.62. Especially from February to June the Angstrom scattering exponent was clearly lower (0.23) and scattering coefficients higher (124 Mm(-1)) than total averages because of the dust outbreak season. Aerosol optical properties had clear diurnal cycle. The lowest scattering and absorption coefficients and aerosol optical depths were observed around noon. The observed diurnal variation is caused by wind direction and speed, during night time very calm easterly winds are dominating whereas during daytime the stronger westerly winds are dominating (sea breeze). Positive Matrix Factorization mathematical tool was applied to the scattering and absorption coefficients and PM2.5 and coarse mode (PM10-PM2.5) mass concentrations to identify source characteristics. Three different factors with clearly different properties were found; anthropogenic, BC source and desert dust. Mass absorption efficiencies for BC source and desert dust factors were, 6.0 m(2) g(-1) and 0.4 m(2) g(-1), respectively, and mass scattering efficiencies for anthropogenic (sulphate) and desert dust, 2.5 m(2) g(-1) and 0.8 m(2) g(-1), respectively.
  • Dall'Osto, M.; Ceburnis, D.; Martucci, G.; Bialek, J.; Dupuy, R.; Jennings, S. G.; Berresheim, H.; Wenger, J.; Healy, R.; Facchini, M. C.; Rinaldi, M.; Giulianelli, L.; Finessi, E.; Worsnop, Douglas; Ehn, Mikael; Mikkilä, Jyri; Kulmala, Markku; O'Dowd, C. D. (2010)
  • Rantala, Pekka; Järvi, Leena; Taipale, Risto; Laurila, Terhi K.; Patokoski, Johanna; Kajos, Maija K.; Kurppa, Mona; Haapanala, Sami; Siivola, Erkki; Petäjä, Tuukka; Ruuskanen, Taina M.; Rinne, Janne (2016)
    We measured volatile organic compounds (VOCs), carbon dioxide (CO2) and carbon monoxide (CO) at an urban background site near the city centre of Helsinki, Finland, northern Europe. The VOC and CO2 measurements were obtained between January 2013 and September 2014 whereas for CO a shorter measurement campaign in April-May 2014 was conducted. Both anthropogenic and biogenic sources were identified for VOCs in the study. Strong correlations between VOC fluxes and CO fluxes and traffic rates indicated anthropogenic source of many VOCs. The VOC with the highest emission rate to the atmosphere was methanol, which originated mostly from traffic and other anthropogenic sources. The traffic was also a major source for aromatic compounds in all seasons whereas isoprene was mostly emitted from biogenic sources during summer. Some amount of traffic-related isoprene emissions were detected during other seasons but this might have also been an instrumental contamination from cycloalkane products. Generally, the observed VOC fluxes were found to be small in comparison with previous urban VOC flux studies. However, the differences were probably caused by lower anthropogenic activities as the CO2 fluxes were also relatively small at the site.
  • Nielsen, Ingeborg E.; Skov, Henrik; Massling, Andreas; Eriksson, Axel C.; Dall'Osto, Manuel; Junninen, Heikki; Sarnela, Nina; Lange, Robert; Collier, Sonya; Zhang, Qi; Cappa, Christopher D.; Nøjgaard, Jacob K. (2019)
    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 degrees 36' 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 mu g m(-3) in February, March and April, respectively, to 1.2 mu g m(-3) in May. Particulate sulfate (SO42-) 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 mu g m(-3). In March and April, rBC averaged 0.1 mu g m(-3) while decreasing to 0.02 mu g m(-3) 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 SO42-, 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.
  • Äijälä, Mikko; Dällenbach, Kaspar; Canonaco, Francesco; Heikkinen, Liine; Junninen, Heikki; Petäjä, Tuukka; Kulmala, Markku; Prevot, Andre S. H.; Ehn, Mikael (2019)
    The interactions between organic and inorganic aerosol chemical components are integral to understanding and modelling climate and health-relevant aerosol physicochemical properties, such as volatility, hygroscopicity, light scattering and toxicity. This study presents a synthesis analysis for eight data sets, of non-refractory aerosol composition, measured at a boreal forest site. The measurements, performed with an aerosol mass spectrometer, cover in total around 9 months over the course of 3 years. In our statistical analysis, we use the complete organic and inorganic unit-resolution mass spectra, as opposed to the more common approach of only including the organic fraction. The analysis is based on iterative, combined use of (1) data reduction, (2) classification and (3) scaling tools, producing a data-driven chemical mass balance type of model capable of describing site-specific aerosol composition. The receptor model we constructed was able to explain 83 +/- 8% of variation in data, which increased to 96 +/- 3% when signals from low signal-to-noise variables were not considered. The resulting interpretation of an extensive set of aerosol mass spectrometric data infers seven distinct aerosol chemical components for a rural boreal forest site: ammonium sulfate (35 +/- 7% of mass), low and semi-volatile oxidised organic aerosols (27 +/- 8% and 12 +/- 7 %), biomass burning organic aerosol (11 +/- 7 %), a nitrate-containing organic aerosol type (7 +/- 2 %), ammonium nitrate (5 +/- 2 %), and hydrocarbon-like organic aerosol (3 +/- 1 %). Some of the additionally observed, rare outlier aerosol types likely emerge due to surface ionisation effects and likely represent amine compounds from an unknown source and alkaline metals from emissions of a nearby district heating plant. Compared to traditional, ionbalance-based inorganics apportionment schemes for aerosol mass spectrometer data, our statistics-based method provides an improved, more robust approach, yielding readily useful information for the modelling of submicron atmospheric aerosols physical and chemical properties. The results also shed light on the division between organic and inorganic aerosol types and dynamics of salt formation in aerosol. Equally importantly, the combined methodology exemplifies an iterative analysis, using consequent analysis steps by a combination of statistical methods. Such an approach offers new ways to home in on physicochemically sensible solutions with minimal need for a priori information or analyst interference. We therefore suggest that similar statisticsbased approaches offer significant potential for un- or semi-supervised machine-learning applications in future analyses of aerosol mass spectrometric data.
  • Schmale, Julia; Henning, Silvia; Henzing, Bas; Keskinen, Helmi; Sellegri, Karine; Ovadnevaite, Jurgita; Bougiatioti, Aikaterini; Kalivitis, Nikos; Stavroulas, Lasonas; Jefferson, Anne; Park, Minsu; Schlag, Patrick; Kristensson, Adam; Iwamotol, Yoko; Pringle, Kirsty; Reddington, Carly; Aalto, Pasi; Äijälä, Mikko; Baltensperger, Urs; Bialek, Jakub; Birmili, Wolfram; Bukowiecki, Nicolas; Ehn, Mikael; Fjaeraa, Ann Mari; Fiebig, Markus; Frank, Goran; Frohlich, Roman; Frumau, Arnoud; Furuyals, Masaki; Hammerl', Emanuel; Heikkinen, Liine; Herrmann, Erik; Holzinger, Rupert; Hyonols, Hiroyuki; Kanakidoug, Maria; Kiendler-Scharr, Astrid; Kinouchi, Kento; Kos, Gerard; Kulmala, Markku; Mihalopoulos, Nikolaos; Motos, Ghislain; Nenes, Athanasios; O'Dowd, Colin; Paramonov, Mikhail; Petäjä, Tuukka; Picard, David; Poulain, Laurent; Prevot, Andre Stephan Henry; Slowik, Jay; Sonntag, Andre; Swietlicki, Erik; Svenningsson, Birgitta; Tsurumaru, Hiroshi; Wiedensohler, Alfred; Wittbom, Cerina; Ogren, John A.; Matsuki, Atsushi; Yum, Seong Soo; Myhre, Cathrine Lund; Carslaw, Ken; Stratmann, Frank; Gysel, Martin (2017)
    Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.
  • Heikkinen, Liine; Äijälä, Mikko; Dällenbach, Kaspar; Chen, Gang; Garmash, Olga; Aliaga, Diego; Graeffe, Frans; Räty, Meri; Luoma, Krista; Aalto, Pasi; Kulmala, Markku; Petäjä, Tuukka; Worsnop, Douglas; Ehn, Mikael (2021)
    The Station for Measuring Ecosystem-Atmosphere Relations (SMEAR) II, located within the boreal forest of Finland, is a unique station in the world due to the wide range of long-term measurements tracking the Earth-atmosphere interface. In this study, we characterize the composition of organic aerosol (OA) at SMEAR II by quantifying its driving constituents. We utilize a multi-year data set of OA mass spectra measured in situ with an Aerosol Chemical Speciation Monitor (ACSM) at the station. To our knowledge, this mass spectral time series is the longest of its kind published to date. Similarly to other previously reported efforts in OA source apportionment from multi-seasonal or multi-annual data sets, we approached the OA characterization challenge through positive matrix factorization (PMF) using a rolling window approach. However, the existing methods for extracting minor OA components were found to be insufficient for our rather remote site. To overcome this issue, we tested a new statistical analysis framework. This included unsupervised feature extraction and classification stages to explore a large number of unconstrained PMF runs conducted on the measured OA mass spectra. Anchored by these results, we finally constructed a relaxed chemical mass balance (CMB) run that resolved different OA components from our observations. The presented combination of statistical tools provided a data-driven analysis methodology, which in our case achieved robust solutions with minimal subjectivity. Following the extensive statistical analyses, we were able to divide the 2012-2019 SMEAR II OA data (mass concentration interquartile range (IQR): 0.7, 1.3, and 2.6 mu gm(-3)) into three sub-categories - low-volatility oxygenated OA (LV-OOA), semi-volatile oxygenated OA (SV-OOA), and primary OA (POA) - proving that the tested methodology was able to provide results consistent with literature. LV-OOA was the most dominant OA type (organic mass fraction IQR: 49 %, 62 %, and 73 %). The seasonal cycle of LV-OOA was bimodal, with peaks both in summer and in February. We associated the wintertime LV-OOA with anthropogenic sources and assumed biogenic influence in LV-OOA formation in summer. Through a brief trajectory analysis, we estimated summertime natural LV-OOA formation of tens of ngm 3 h 1 over the boreal forest. SV-OOA was the second highest contributor to OA mass (organic mass fraction IQR: 19 %, 31 %, and 43 %). Due to SV-OOA's clear peak in summer, we estimate biogenic processes as the main drivers in its formation. Unlike for LV-OOA, the highest SV-OOA concentrations were detected in stable summertime nocturnal surface layers. Two nearby sawmills also played a significant role in SV-OOA production as also exemplified by previous studies at SMEAR II. POA, taken as a mix of two different OA types reported previously, hydrocarbon-like OA (HOA) and biomass burning OA (BBOA), made up a minimal OA mass fraction (IQR: 2 %, 6 %, and 13 %). Notably, the quantification of POA at SMEAR II using ACSM data was not possible following existing rolling PMF methodologies. Both POA organic mass fraction and mass concentration peaked in winter. Its appearance at SMEAR II was linked to strong southerly winds. Similar wind direction and speed dependence was not observed among other OA types. The high wind speeds probably enabled the POA transport to SMEAR II from faraway sources in a relatively fresh state. In the event of slower wind speeds, POA likely evaporated and/or aged into oxidized organic aerosol before detection. The POA organic mass fraction was significantly lower than reported by aerosol mass spectrometer (AMS) measurements 2 to 4 years prior to the ACSM measurements. While the co-located long-term measurements of black carbon supported the hypothesis of higher POA loadings prior to year 2012, it is also possible that short-term (POA) pollution plumes were averaged out due to the slow time resolution of the ACSM combined with the further 3 h data averaging needed to ensure good signal-to-noise ratios (SNRs). Despite the length of the ACSM data set, we did not focus on quantifying long-term trends of POA (nor other components) due to the high sensitivity of OA composition to meteorological anomalies, the occurrence of which is likely not normally distributed over the 8-year measurement period. Due to the unique and realistic seasonal cycles and meteorology dependences of the independent OA subtypes complemented by the reasonably low degree of unexplained OA variability, we believe that the presented data analysis approach performs well. Therefore, we hope that these results encourage also other researchers possessing several-yearlong time series of similar data to tackle the data analysis via similar semi- or unsupervised machine-learning approaches. This way the presented method could be further optimized and its usability explored and evaluated also in other environments.
  • Hong, Juan; Äijälä, Mikko; Häme, Silja A. K.; Hao, Liqing; Duplissy, Jonathan; Heikkinen, Liine M.; Nie, Wei; Mikkilä, Jyri; Kulmala, Markku; Prisle, Nonne L.; Virtanen, Annele; Ehn, Mikael; Paasonen, Pauli; Worsnop, Douglas R.; Riipinen, Ilona; Petäjä, Tuukka; Kerminen, Veli-Matti (2017)
    The volatility distribution of secondary organic aerosols that formed and had undergone aging - i. e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase - was characterized in a boreal forest environment of Hyytiala, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40% of the organics in particles were semi-volatile, 34% were low-volatility organics and 26% were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (Delta H-VAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol(-1) were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m/z 43 (f43) and m/z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when Delta H-VAP D 80 kJ mol(-1) was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16% (R-2)of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.
  • Wu, Kai; Yang, Xianyu; Chen, Dean; Gu, Shan; Lu, Yaqiong; Jiang, Qi; Wang, Kun; Ou, Yihan; Qian, Yan; Shao, Ping; Lu, Shihua (2020)
    Biogenic volatile organic compounds (BVOC) play an important role in global environmental chemistry and climate. In the present work, biogenic emissions from China in 2017 were estimated based on the Model of Emissions of Gases and Aerosols from Nature (MEGAN). The effects of BVOC emissions on ozone and secondary organic aerosol (SOA) formation were investigated using the WRF-CMAQ modeling system. Three parallel scenarios were developed to assess the impact of BVOC emissions on China's ozone and SOA formation in July 2017. Biogenic emissions were estimated at 23.54 Tg/yr, with a peak in the summer and decreasing from southern to northern China. The high BVOC emissions across eastern and southwestern China increased the surface ozone levels, particularly in the BTH (Beijing-Tianjin-Hebei), SCB (Sichuan Basin), YRD (Yangtze River Delta) and central PRD (Pearl River Delta) regions, with increases of up to 47 μg m−3 due to the sensitivity of VOC-limited urban areas. In summer, most SOA concentrations formed over China are from biogenic sources (national average of 70%). And SOA concentrations in YRD and SCB regions are generally higher than other regions. Excluding anthropogenic emissions while keeping biogenic emissions unchanged results that SOA concentrations reduce by 60% over China, which indicates that anthropogenic emissions can interact with biogenic emissions then facilitate biogenic SOA formation. It is suggested that controlling anthropogenic emissions would result in reduction of both anthropogenic and biogenic SOA.
  • Hellen, Heidi; Kangas, Leena; Kousa, Anu; Vestenius, Mika; Teinila, Kimmo; Karppinen, Ari; Kukkonen, Jaakko; Niemi, Jarkko V. (2017)
    Even though emission inventories indicate that wood combustion is a major source of polycyclic aromatic hydrocarbons (PAHs), estimating its impacts on PAH concentration in ambient air remains challenging. In this study the effect of local small-scale wood combustion on the benzo[a] pyrene (BaP) concentrations in ambient air in the Helsinki metropolitan area in Finland is evaluated, using ambient air measurements, emission estimates, and dispersion modeling. The measurements were conducted at 12 different locations during the period from 2007 to 2015. The spatial distributions of annual average BaP concentrations originating from wood combustion were predicted for four of those years: 2008, 2011, 2013, and 2014. According to both the measurements and the dispersion modeling, the European Union target value for the annual average BaP concentrations (1 ngm(-3) ) was clearly exceeded in certain suburban detached-house areas. However, in most of the other urban areas, including the center of Helsinki, the concentrations were below the target value. The measured BaP concentrations highly correlated with the measured levoglucosan concentrations in the suburban detached-house areas. In street canyons, the measured concentrations of BaP were at the same level as those in the urban background, clearly lower than those in suburban detached-house areas. The predicted annual average concentrations matched with the measured concentrations fairly well. Both the measurements and the modeling clearly indicated that wood combustion was the main local source of ambient air BaP in the Helsinki metropolitan area.
  • Dällenbach, Kaspar; Kourtchev, Ivan; Vogel, Alexander L.; Bruns, Emily A.; Jiang, Jianhui; Petäjä, Tuukka; Jaffrezo, Jean-Luc; Aksoyoglu, Sebnem; Kalberer, Markus; Baltensperger, Urs; El Haddad, Imad; Prevot, Andre S. H. (2019)
    This study presents the molecular composition of organic aerosol (OA) using ultra-high-resolution mass spectrometry (Orbitrap) at an urban site in Central Europe (Zurich, Switzerland). Specific source spectra were also analysed, including samples representative of woodburning emissions from Alpine valleys during wood-burning pollution episodes and smog chamber investigations of woodsmoke, as well as samples from Hyytiala, which were strongly influenced by biogenic secondary organic aerosol. While samples collected during winter in Alpine valleys have a molecular composition remarkably similar to fresh laboratory wood-burning emissions, winter samples from Zurich are influenced by more aged wood-burning emissions. In addition, other organic aerosol emissions or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiala and are predominantly impacted by oxygenated compounds with an H/C ratio of 1.5, indicating the importance of biogenic precursors for secondary organic aerosol (SOA) formation at this location (summertime Zurich - carbon number 7.6, O : C 0.7; Hyytiala - carbon number 10.5, O : C 0.57). We could explain the strong seasonality of the molecular composition at a typical European site by primary and aged wood-burning emissions and biogenic secondary organic aerosol formation during winter and summer, respectively. Results presented here likely explain the rather constant seasonal predominance of non-fossil organic carbon at European locations.
  • Saarikoski, S.; Timonen, H.; Carbone, S.; Kuuluvainen, H.; Niemi, J. V.; Kousa, A.; Rönkkö, T.; Worsnop, D.; Hillamo, R.; Pirjola, L. (2017)
    Detailed chemical characterization of exhaust particles from 23 individual city buses was performed in Helsinki, Finland. Investigated buses represented different technologies in terms of engines, exhaust after-treatment systems (e.g., diesel particulate filter, selective catalytic reduction, and three-way catalyst) and fuels (diesel, diesel-electric (hybrid), ethanol, and compressed natural gas). Regarding emission standards, the buses operated at EURO III, EURO IV, and EEV (enhanced environmentally friendly vehicle) emission levels. The chemical composition of exhaust particles was determined by using a soot particle aerosol mass spectrometer (SP-AMS). Based on the SP-AMS results, the bus emission particles were dominated by organics and refractory black carbon (rBC). The mass spectra of organics consisted mostly of hydrocarbon fragments (54-86% of total organics), the pattern of hydrocarbon fragments being rather similar regardless of the bus type. Regarding oxygenated organic fragments, ethanol-fueled buses had unique mass-to-charge ratios (m/z) of 45, 73, 87, and 89 (mass fragments of C2H5OC, C3H5O2+, C4H7O2+, and C4H9O2+, respectively) that were not detected for the other bus types at the same level. For rBC, there was a small difference in the ratio of C-4(+) and C-5(+) to C-3(+) for different bus types but also for the individual buses of the same type. In addition to organics and rBC, the presence of trace metals in the bus emission particles was investigated.
  • Heikkinen, Liine; Äijälä, Mikko; Riva, Matthieu; Luoma, Krista Hannele; Dällenbach, Kaspar; Aalto, Juho; Aalto, Pasi; Aliaga Badani, Diego Alonso; Aurela, Minna; Keskinen, Helmi-Marja; Makkonen, Ulla; Rantala, Pekka; Kulmala, Markku; Petäjä, Tuukka; Worsnop, Douglas; Ehn, Mikael (2020)
    The Station for Measuring Ecosystem Atmosphere Relations (SMEAR) II is well known among atmospheric scientists due to the immense amount of observational data it provides of the Earth atmosphere interface. Moreover, SMEAR II plays an important role for the large European research infrastructure, enabling the large scientific community to tackle climate- and air-pollution-related questions, utilizing the high-quality long-term data sets recorded at the site. So far, this well-documented site was missing the description of the seasonal variation in aerosol chemical composition, which helps understanding the complex biogeochemical and physical processes governing the forest ecosystem. Here, we report the sub-micrometer aerosol chemical composition and its variability, employing data measured between 2012 and 2018 using an Aerosol Chemical Speciation Monitor (ACSM). We observed a bimodal seasonal trend in the sub-micrometer aerosol concentration culminating in February (2.7, 1.6, and 5.1 mu g m(-3) for the median, 25th, and 75th percentiles, respectively) and July (4.2, 2.2, and 5.7 mu g m(-3) for the median, 25th, and 75th percentiles, respectively). The wintertime maximum was linked to an enhanced presence of inorganic aerosol species (ca. 50 %), whereas the summertime maximum (ca. 80 % organics) was linked to biogenic secondary organic aerosol (SOA) formation. During the exceptionally hot months of July of 2014 and 2018, the organic aerosol concentrations were up to 70 % higher than the 7-year July mean. The projected increase in heat wave frequency over Finland will most likely influence the loading and chemical composition of aerosol particles in the future. Our findings suggest strong influence of meteorological conditions such as radiation, ambient temperature, and wind speed and direction on aerosol chemical composition. To our understanding, this is the longest time series reported describing the aerosol chemical composition measured online in the boreal region, but the continuous monitoring will also be maintained in the future.
  • de Jesus, Alma Lorelei; Thompson, Helen; Knibbs, Luke D.; Kowalski, Michal; Cyrys, Josef; Niemi, Jarkko V.; Kousa, Anu; Timonen, Hilkka; Luoma, Krista; Petäjä, Tuukka; Beddows, David; Harrison, Roy M.; Hopke, Philip; Morawska, Lidia (2020)
    Urbanisation and industrialisation led to the increase of ambient particulate matter (PM) concentration. While subsequent regulations may have resulted in the decrease of some PM matrices, the simultaneous changes in climate affecting local meteorological conditions could also have played a role. To gain an insight into this complex matter, this study investigated the long-term trends of two important matrices, the particle mass (PM2.5) and particle number concentrations (PNC), and the factors that influenced the trends. Mann-Kendall test, Sen's slope estimator, the generalised additive model, seasonal decomposition of time series by LOESS (locally estimated scatterplot smoothing) and the Buishand range test were applied. Both PM2.5 and PNC showed significant negative monotonic trends (0.03-0.6 mg m(-3).yr(-1) and 0.40-3.8 x 10(3) particles. cm(-3). yr(-1), respectively) except Brisbane (+0.1 mg m(-3). yr(-1) and +53 particles. cm(-3). yr(-1), respectively). For the period covered in this study, temperature increased (0.03-0.07 degrees C.yr(-1)) in all cities except London; precipitation decreased (0.02-1.4 mm.yr(-1)) except in Helsinki; and wind speed was reduced in Brisbane and Rochester but increased in Helsinki, London and Augsburg. At the change-points, temperature increase in cold cities influenced PNC while shifts in precipitation and wind speed affected PM2.5. Based on the LOESS trend, extreme events such as dust storms and wildfires resulting from changing climates caused a positive step-change in concentrations, particularly for PM2.5. In contrast, among the mitigation measures, controlling sulphur in fuels caused a negative step-change, especially for PNC. Policies regarding traffic and fleet management (e.g. low emission zones) that were implemented only in certain areas or in a progressive uptake (e.g. Euro emission standards), resulted to gradual reductions in concentrations. Therefore, as this study has clearly shown that PM2.5 and PNC were influenced differently by the impacts of the changing climate and by the mitigation measures, both metrics must be considered in urban air quality management. (C) 2020 Elsevier Ltd. All rights reserved.