Insight into the molecular composition of laboratory organic residues produced from interstellar/pre-cometary ice analogues using very high resolution mass spectrometry

2016 ◽  
Vol 189 ◽  
pp. 184-196 ◽  
Author(s):  
G. Danger ◽  
A. Fresneau ◽  
N. Abou Mrad ◽  
P. de Marcellus ◽  
F.-R. Orthous-Daunay ◽  
...  
2017 ◽  
Author(s):  
Lauren T. Fleming ◽  
Peng Lin ◽  
Alexander Laskin ◽  
Julia Laskin ◽  
Robert Weltman ◽  
...  

Abstract. Emissions of airborne particles from biomass-burning are a significant source of black carbon (BC) and brown carbon (BrC) in rural areas of developing countries where biomass is the predominant energy source for cooking and heating. This study explores the molecular composition of organic particles from household cooking emissions, with a focus on identifying fuel-specific compounds and BrC chromophores. Traditional meals were prepared by a local cook with dung and brushwood-fueled cookstoves in a village of Palwal district, Haryana, India. The cooking events were carried out in a village kitchen while controlling for variables including stove type, fuel moisture content, and meal. The particulate matter (PM2.5) emissions were collected on filters, and then analyzed via nanospray desorption electrospray ionization/high resolution mass spectrometry (nano-DESI-HRMS) and high performance liquid chromatography/photodiode array/high resolution mass spectrometry (HPLC-PDA-HRMS) techniques. The nano-DESI-HRMS analysis provided an inventory of compounds present in the particle phase. Although several compounds observed in this study have been previously characterized using gas chromatography methods, a majority of species in nano-DESI spectra were newly observed biomass-burning compounds. Both the stove (chulha or angithi) and the fuel (brushwood or dung) affected the composition of organic particles. The geometric mean PM2.5 emissions factor and the molecular complexity of PM2.5 emissions increased in the following order: brushwood/chulha (4.9 ± 1.7 g kg-1 dry fuel, 93 compounds), dung/chulha (12.3 ± 2.5 g kg-1 dry fuel, 212 compounds), and dung/angithi (16.7 ± 6.7 g kg-1 dry fuel, 262 compounds). The lower limit for the mass absorption coefficient (MAC) at 365 nm and 405 nm for brushwood PM2.5 was 3.4 m2 g-1 and 1.8 m2 g-1, respectively, which was approximately a factor of two higher than that for dung PM2.5. The HPLC-PDA-HRMS analysis showed that, regardless of fuel type, the main chromophores were CxHyOz lignin fragments. The main chromophores accounting for the higher MAC values of brushwood PM2.5 were C8H10O3 (tentatively assigned syringol), possible nitrophenol species C8H9NO4, and C10H10O3 (tentatively assigned methoxycinnamic acid).


2018 ◽  
Author(s):  
Kaspar R. Daellenbach ◽  
Ivan Kourtchev ◽  
Alexander L. Vogel ◽  
Emily A. Bruns ◽  
Jianhui Jiang ◽  
...  

Abstract. This study presents the molecular composition of 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 wood burning emissions from Alpine valleys during wood burning pollution episodes and chamber investigations of wood smoke as well as samples from Hyytiälä 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 emission or formation pathways seem to be important at the latter location in winter. Samples from Zurich during summer are similar to those collected in Hyytiälä, predominantly impacted by oxygenated compounds with an H / C ratio of 1.5, indicating the importance of biogenic precursors for SOA formation at this location. 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 seasonally rather constant predominance of non-fossil organic carbon at European locations.


2010 ◽  
Vol 147 ◽  
pp. 495 ◽  
Author(s):  
Véronique Vuitton ◽  
Jean-Yves Bonnet ◽  
Maeliss Frisari ◽  
Roland Thissen ◽  
Eric Quirico ◽  
...  

2015 ◽  
Vol 15 (10) ◽  
pp. 5683-5695 ◽  
Author(s):  
I. Kourtchev ◽  
J.-F. Doussin ◽  
C. Giorio ◽  
B. Mahon ◽  
E. M. Wilson ◽  
...  

Abstract. Field observations over the past decade indicate that a significant fraction of organic aerosol in remote areas may contain highly oxidized molecules. Aerosol processing or further oxidation (aging) of organic aerosol has been suggested to be responsible for their formation through heterogeneous reaction with oxidants and multigenerational oxidation of vapours by OH radicals. In this study we investigated the influence of several aging processes on the molecular composition of secondary organic aerosols (SOA) using direct infusion and liquid chromatography high-resolution mass spectrometry. SOA was formed in simulation chamber experiments from ozonolysis of a mixture of four biogenic volatile organic compounds (BVOC): α-pinene, β-pinene, Δ3-carene and isoprene. The SOA was subsequently aged under three different sets of conditions: in the dark in the presence of residual ozone, with UV irradiation and OH radicals, and using UV light only. Among all studied conditions, only OH radical-initiated aging was found to influence the molecular composition of the aerosol and showed an increase in carbon oxidation state (OSC) and elemental O / C ratios of the SOA components. None of the aging processes produced an observable effect on the oligomers formed from ozonolysis of the BVOC mixture, which were found to be equally abundant in both "fresh" and "aged" SOA. Additional experiments using α-pinene as the sole precursor demonstrated that oligomers are an important group of compounds in SOA produced from both ozonolysis and OH radical-initiated oxidation processes; however, a completely different set of oligomers is formed under these two oxidation regimes. SOA from the OH-initiated oxidation of α-pinene had a significantly higher overall OSC and O / C compared to that from pure ozonolysis experiments confirming that the OH radical reaction is more likely to be responsible for the occurrence of highly oxidized species in ambient biogenic SOA.


Biostatistics ◽  
2009 ◽  
Vol 10 (3) ◽  
pp. 481-500 ◽  
Author(s):  
J. E. Eckel-passow ◽  
A. L. Oberg ◽  
T. M. Therneau ◽  
H. R. Bergen

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