2010, Yasmeen, F., Vermeylen, R., Szmigielski, R., Iinuma, Y., Böge, O., Herrmann, H., Maenhaut, W., Claeys, M.

In the present study, we have characterized the structure of a higher-molecular weight (MW) 358 α- and β-pinene dimeric secondary organic aerosol (SOA) product that received ample attention in previous molecular characterization studies and has been elusive. Based on mass spectrometric evidence for deprotonated molecules formed by electrospray ionization in the negative ion mode and chemical considerations, it is suggested that diaterpenylic acid is a key monomeric intermediate for dimers of the ester type. It is proposed that cis-pinic acid is esterified with the hydroxyl-containing diaterpenylic acid, which can be explained through acid-catalyzed hydrolysis of the recently elucidated lactone-containing terpenylic acid and/or diaterpenylic acid acetate, both first-generation oxidation products. To a minor extent, higher-MW 358 and 344 diester products are formed containing other terpenoic acids as monomeric units, i.e., diaterpenylic acid instead of cis-pinic acid, and diaterebic acid instead of diaterpenylic acid. It is shown that the MW 358 diester and related MW 344 compounds, which can be regarded as processed SOA products, also occur in ambient fine (PM2.5) rural aerosol collected at night during the warm period of the 2006 summer field campaign conducted at K-puszta, Hungary, a rural site with coniferous vegetation. This indicates that, under ambient conditions, the higher-MW diesters are formed in the particle phase over a longer time-scale than that required for gas-to-particle partitioning of their monomeric precursors in laboratory α-/β-pinene ozonolysis experiments.

2017, Leck, C., Bigg, E.K., Covert, D.S., Heintzenberg, J., Maenhaut, W., Nilsson, E.D., Wiedensohler, A.

The broad aim of the Atmospheric program of the International Arctic Ocean Expedition (IAOE-91) was to test the hypothesis that marine biogenically produced dimethyl sulfide (DMS) gas can exert a significant global climatic control. The hypothesis states that DMS is transferred to the atmosphere and is oxidised to form airborne particles. Some of these grow large enough to act as cloud condensation nuclei (CCN) which help determine cloud droplet concentration. The latter has a strong influence on cloud albedo and hence on the radiation balance of the area affected. In summer, the central Arctic is a specially favourable region for studying the natural sulfur cycle in that the open waters surrounding the pack ice are the only significant sources of DMS and there are almost no anthropogenic particle sources. Concentrations of seawater and atmospheric DMS decreased at about the same rate during the period of measurements, (1 August to 6 October, latitudes 75°N to 90°N) spanning about three orders of magnitude. Methane sulfonate and nonsea salt sulfate in the submicrometer particles, which may be derived from atmospheric DMS, also decreased similarly, suggesting that the first part of the hypothesis under test was true. Influences on cloud droplet concentration and radiation balance could not be measured. Size-resolved aerosol chemistry showed a much lower proportion of methane sulfonate to be associated with supermicrometer particles than has been found elsewhere. Its molar ratio to nonsea salt sulfate suggested that the processes controlling the particulate chemistry do not exhibit a net temperature dependence. Elemental analysis of the aerosol also revealed the interesting possibility that debris from Siberian rivers transported on the moving ice represent a fairly widespread source of supermicrometer crustal material within the pack ice. Highly resolved measurements of aerosol number size distributions were made in the diameter range 3 nm to 500 nm. 3 distinct modal sizes were usually present, the “ultrafine”, “Aitken” and “accumulation” modes centred on 14, 45 and 170 nm diameter, respectively. The presence of ultrafine particles, implying recent production, was more frequent than has been found in lower latitude remote marine areas. Evidence suggests that they were mixed to the surface from higher levels. Sudden and often drastic changes in aerosol concentration and size distribution were surprisingly frequent in view of the relatively slowly changing meteorology of the central Arctic during the study period and the absence of strong pollution sources. They were most common in particles likely to have taken part in cloud formation (> 80 nm diameter). 2 factors appear to have been involved in these sudden changes. The 1st was the formation of vertical gradients in aerosol concentration due to interactions between particles and clouds or favoured regions for new particle production during periods of stability. The 2nd was sporadic localised breakdowns of the stability, bringing changed particle concentrations to the measurement level. Probable reasons for these sporadic mixing events were indicated by the structure of the Marine Boundary Layer (MBL) investigated with high resolution rawinsondes. Low level jets were present about 60% of the time, producing conditions conductive to turbulence and shear-induced waves. It is concluded that an even more detailed study of meteorological processes in the MBL in conjunction with more highly time-resolved measurements of gas-aerosol physics and chemistry appears to be essential in any future research aimed at studying the indirect, cloud mediated, effect of aerosol particles.

2009, Hallquist, M., Wenger, J.C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N.M., George, C., Goldstein, A., Hamilton, J.F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M.E., Jimenez, J.L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th.F., Monod, A., Prévôt, A.S.H., Seinfeld, J.H., Surratt, J.D., Szmigielski, R., Wildt, J.

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

2015, Yttri, K.E., Schnelle-Kreis, J., Maenhaut, W., Abbaszade, G., Alves, C., Bjerke, A., Bonnier, N., Bossi, R., Claeys, M., Dye, C., Evtyugina, M., García-Gacio, D., Hillamo, R., Hoffer, A., Hyder, M., Iinuma, Y., Jaffrezo, J.-L., Kasper-Giebl, A., Kiss, G., López-Mahia, P.L., Pio, C., Piot, C., Ramirez-Santa-Cruz, C., Sciare, J., Teinilä, K., Vermeylen, R., Vicente, A., Zimmermann, R.

The monosaccharide anhydrides (MAs) levoglucosan, galactosan and mannosan are products of incomplete combustion and pyrolysis of cellulose and hemicelluloses, and are found to be major constituents of biomass burning (BB) aerosol particles. Hence, ambient aerosol particle concentrations of levoglucosan are commonly used to study the influence of residential wood burning, agricultural waste burning and wildfire emissions on ambient air quality. A European-wide intercomparison on the analysis of the three monosaccharide anhydrides was conducted based on ambient aerosol quartz fiber filter samples collected at a Norwegian urban background site during winter. Thus, the samples' content of MAs is representative for BB particles originating from residential wood burning. The purpose of the intercomparison was to examine the comparability of the great diversity of analytical methods used for analysis of levoglucosan, mannosan and galactosan in ambient aerosol filter samples. Thirteen laboratories participated, of which three applied high-performance anion-exchange chromatography (HPAEC), four used high-performance liquid chromatography (HPLC) or ultra-performance liquid chromatography (UPLC) and six resorted to gas chromatography (GC). The analytical methods used were of such diversity that they should be considered as thirteen different analytical methods. All of the thirteen laboratories reported levels of levoglucosan, whereas nine reported data for mannosan and/or galactosan. Eight of the thirteen laboratories reported levels for all three isomers. The accuracy for levoglucosan, presented as the mean percentage error (PE) for each participating laboratory, varied from −63 to 20%; however, for 62% of the laboratories the mean PE was within ±10%, and for 85% the mean PE was within ±20%. For mannosan, the corresponding range was −60 to 69%, but as for levoglucosan, the range was substantially smaller for a subselection of the laboratories; i.e. for 33% of the laboratories the mean PE was within ±10%. For galactosan, the mean PE for the participating laboratories ranged from −84 to 593%, and as for mannosan 33% of the laboratories reported a mean PE within ±10%. The variability of the various analytical methods, as defined by their minimum and maximum PE value, was typically better for levoglucosan than for mannosan and galactosan, ranging from 3.2 to 41% for levoglucosan, from 10 to 67% for mannosan and from 6 to 364% for galactosan. For the levoglucosan to mannosan ratio, which may be used to assess the relative importance of softwood versus hardwood burning, the variability only ranged from 3.5 to 24 . To our knowledge, this is the first major intercomparison on analytical methods used to quantify monosaccharide anhydrides in ambient aerosol filter samples conducted and reported in the scientific literature. The results show that for levoglucosan the accuracy is only slightly lower than that reported for analysis of SO42- (sulfate) on filter samples, a constituent that has been analysed by numerous laboratories for several decades, typically by ion chromatography and which is considered a fairly easy constituent to measure. Hence, the results obtained for levoglucosan with respect to accuracy are encouraging and suggest that levels of levoglucosan, and to a lesser extent mannosan and galactosan, obtained by most of the analytical methods currently used to quantify monosaccharide anhydrides in ambient aerosol filter samples, are comparable. Finally, the various analytical methods used in the current study should be tested for other aerosol matrices and concentrations as well, the most obvious being summertime aerosol samples affected by wildfires and/or agricultural fires.