scholarly journals Abiotic stress impact on aerosol mass spectra over a forest site in Lithuania

2019 ◽  
Vol 59 (3) ◽  
Author(s):  
Julija Pauraitė ◽  
Steigvilė Byčenkienė ◽  
Kristina Plauškaitė ◽  
Algirdas Augustaitis ◽  
Vitas Marozas ◽  
...  
Keyword(s):  
Abiotic Stress ◽  
Mass Spectra ◽  
Organic Aerosol ◽  
Response Analysis ◽  
Forest Site ◽  
Tree Trunk ◽  
Integrated Monitoring ◽  
Aerosol Mass ◽  
Volatile Organic ◽  
Normal Increase

Volatile organic compounds (VOCs) emitted by trees in response to abiotic stress evoke high levels of secondary organic aerosol (SOA) compounds. Few techniques exist to provide chemically-resolved submicron (PM1) particle mass concentrations and source apportionment of stress-induced emissions from trees and SOA formation. The chemical composition of atmospheric aerosol particles was characterized using an aerosol chemical speciation monitor (ACSM) at a mixed-mature forest site – the Aukštaitija Integrated Monitoring Station in the eastern part of Lithuania. The organic fraction of PM1 consisted of SOA (76%) and of anthropogenic combustion related primary organic aerosol (POA) (24%). The analysis of tree trunk circumference revealed three shrinkage and three normal increase episodes. During the episodes of tree trunk circumference shrinkage, several m/z signal (m/z 42, 43, 45, 48, 50) intensities were found to be magnified together with the daily SOA concentration. The stress response analysis confirm that tree trunk circumference shrinkage may be observed through the enhancement of selected m/z signals and result in increased SOA levels.

scholarly journals Chemical characterization of biogenic secondary organic aerosol generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

2015 ◽  
Vol 15 (7) ◽  
pp. 3629-3646 ◽  
Author(s):  
C. L. Faiola ◽  
M. Wen ◽  
T. M. VanReken
Keyword(s):  
Mass Spectra ◽  
Secondary Organic Aerosol ◽  
Plant Stress ◽  
Chemical Characterization ◽  
Organic Aerosol ◽  
Aerosol Mass ◽  
Treatment Conditions ◽  
Volatile Organic ◽  
Plant Emissions ◽  
Pre Treatment

Abstract. The largest global source of secondary organic aerosol (SOA) in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic volatile organic compound (BVOC) profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate (MeJA), a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six different coniferous plant types. Volatile organic compounds (VOCs) emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA chemical composition was measured using a Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+), m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, MeJA, is also presented. Elemental analysis results demonstrated an O : C range of baseline biogenic SOA between 0.3 and 0.47. The O : C of standard MeJA SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient data sets collected in forest environments.

scholarly journals Constructing a data-driven receptor model for organic and inorganic aerosol – a synthesis analysis of eight mass spectrometric data sets from a boreal forest site

2019 ◽  
Vol 19 (6) ◽  
pp. 3645-3672 ◽  
Author(s):  
Mikko Äijälä ◽  
Kaspar R. Daellenbach ◽  
Francesco Canonaco ◽  
Liine Heikkinen ◽  
Heikki Junninen ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Organic Aerosol ◽  
Mass Spectrometric ◽  
Chemical Components ◽  
Forest Site ◽  
Aerosol Composition ◽  
Mass Spectrometric Data ◽  
Spectrometric Data ◽  
Aerosol Mass ◽  
Inorganic Aerosol

Abstract. 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, ion-balance-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 statistics-based approaches offer significant potential for un- or semi-supervised machine-learning applications in future analyses of aerosol mass spectrometric data.

scholarly journals A new method to discriminate secondary organic aerosols from different sources using high-resolution aerosol mass spectra

2012 ◽  
Vol 12 (4) ◽  
pp. 2189-2203 ◽  
Author(s):  
M. F. Heringa ◽  
P. F. DeCarlo ◽  
R. Chirico ◽  
T. Tritscher ◽  
M. Clairotte ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectra ◽  
Principal Component ◽  
Particle Growth ◽  
Organic Aerosol ◽  
Diesel Emissions ◽  
Anthropogenic Sources ◽  
Inlet System ◽  
Alpha Pinene ◽  
Aerosol Mass

Abstract. Organic aerosol (OA) represents a significant and often major fraction of the non-refractory PM1 (particulate matter with an aerodynamic diameter da < 1 μm) mass. Secondary organic aerosol (SOA) is an important contributor to the OA and can be formed from biogenic and anthropogenic precursors. Here we present results from the characterization of SOA produced from the emissions of three different anthropogenic sources. SOA from a log wood burner, a Euro 2 diesel car and a two-stroke Euro 2 scooter were characterized with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and compared to SOA from α-pinene. The emissions were sampled from the chimney/tailpipe by a heated inlet system and filtered before injection into a smog chamber. The gas phase emissions were irradiated by xenon arc lamps to initiate photo-chemistry which led to nucleation and subsequent particle growth by SOA production. Duplicate experiments were performed for each SOA type, with the averaged organic mass spectra showing Pearson's r values >0.94 for the correlations between the four different SOA types after five hours of aging. High-resolution mass spectra (HR-MS) showed that the dominant peaks in the MS, m/z 43 and 44, are dominated by the oxygenated ions C2H3O+ and CO2+, respectively, similarly to the relatively fresh semi-volatile oxygenated OA (SV-OOA) observed in the ambient aerosol. The atomic O:C ratios were found to be in the range of 0.25–0.55 with no major increase during the first five hours of aging. On average, the diesel SOA showed the lowest O:C ratio followed by SOA from wood burning, α-pinene and the scooter emissions. Grouping the fragment ions revealed that the SOA source with the highest O:C ratio had the largest fraction of small ions. The HR data of the four sources could be clustered and separated using principal component analysis (PCA). The model showed a significant separation of the four SOA types and clustering of the duplicate experiments on the first two principal components (PCs), which explained 79% of the total variance. Projection of ambient SV-OOA spectra resolved by positive matrix factorization (PMF) showed that this approach could be useful to identify large contributions of the tested SOA sources to SV-OOA. The first results from this study indicate that the SV-OOA in Barcelona is strongly influenced by diesel emissions in winter while in summer at SIRTA at the southwestern edge of Paris SV-OOA is more similar to alpha-pinene SOA. However, contributions to the ambient SV-OOA from SOA sources that are not covered by the model can cause major interference and therefore future expansions of the PCA model with additional SOA sources is recommended.

scholarly journals Relating hygroscopicity and composition of organic aerosol particulate matter

2011 ◽  
Vol 11 (3) ◽  
pp. 1155-1165 ◽  
Author(s):  
J. Duplissy ◽  
P. F. DeCarlo ◽  
J. Dommen ◽  
M. R. Alfarra ◽  
A. Metzger ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Field Experiments ◽  
Organic Aerosol ◽  
Photochemical Oxidation ◽  
Ionization Mass ◽  
Hygroscopic Growth ◽  
Atmospheric Models ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Organic Precursors

Abstract. A hygroscopicity tandem differential mobility analyzer (HTDMA) was used to measure the water uptake (hygroscopicity) of secondary organic aerosol (SOA) formed during the chemical and photochemical oxidation of several organic precursors in a smog chamber. Electron ionization mass spectra of the non-refractory submicron aerosol were simultaneously determined with an aerosol mass spectrometer (AMS), and correlations between the two different signals were investigated. SOA hygroscopicity was found to strongly correlate with the relative abundance of the ion signal m/z 44 expressed as a fraction of total organic signal (f44). m/z 44 is due mostly to the ion fragment CO2+ for all types of SOA systems studied, and has been previously shown to strongly correlate with organic O/C for ambient and chamber OA. The analysis was also performed on ambient OA from two field experiments at the remote site Jungfraujoch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation between the hygroscopicity of OA at subsaturated RH, as given by the hygroscopic growth factor (GF) or "ϰorg" parameter, and f44 was determined and is given by ϰorg = 2.2 × f44 − 0.13. This approximation can be further verified and refined as the database for AMS and HTDMA measurements is constantly being expanded around the world. The use of this approximation could introduce an important simplification in the parameterization of hygroscopicity of OA in atmospheric models, since f44 is correlated with the photochemical age of an air mass.

scholarly journals Analysis of secondary organic aerosol formation and aging using positive matrix factorization of high-resolution aerosol mass spectra: application to the dodecane low-NO<sub>x</sub> system

2012 ◽  
Vol 12 (24) ◽  
pp. 11795-11817 ◽  
Author(s):  
J. S. Craven ◽  
L. D. Yee ◽  
N. L. Ng ◽  
M. R. Canagaratna ◽  
C. L. Loza ◽  
...  
Keyword(s):  
High Resolution ◽  
Matrix Factorization ◽  
Mass Spectra ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Positive Matrix Factorization ◽  
Aerosol Formation ◽  
Positive Matrix ◽  
Aerosol Mass ◽  
Van Krevelen Diagram

Abstract. Positive matrix factorization (PMF) of high-resolution laboratory chamber aerosol mass spectra is applied for the first time, the results of which are consistent with molecular level MOVI-HRToF-CIMS aerosol-phase and CIMS gas-phase measurements. Secondary organic aerosol was generated by photooxidation of dodecane under low-NOx conditions in the Caltech environmental chamber. The PMF results exhibit three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. The slope of the measured high-resolution aerosol mass spectrometer (HR-ToF-AMS) composition data on a Van Krevelen diagram is consistent with that of other low-NOx alkane systems in the same O : C range. Elemental analysis of the PMF factor mass spectral profiles elucidates the combinations of functionality that contribute to the slope on the Van Krevelen diagram.

scholarly journals Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modeling of complete high time-resolution aerosol mass spectra

2014 ◽  
Vol 14 (15) ◽  
pp. 8017-8042 ◽  
Author(s):  
M. L. McGuire ◽  
R. Y.-W. Chang ◽  
J. G. Slowik ◽  
C.-H. Jeong ◽  
R. M. Healy ◽  
...  
Keyword(s):  
Mass Spectrum ◽  
Mass Spectra ◽  
Organic Aerosol ◽  
Mass Resolution ◽  
Receptor Modeling ◽  
Unit Mass ◽  
Organic Mass ◽  
Aerosol Mass ◽  
Inorganic Species ◽  
Unit Mass Resolution

Abstract. Receptor modeling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada's Canadian Regional and Urban Investigation System for Environmental Research (CRUISER) mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach compared to the more common method of analyzing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulfate- and oxygenated organic aerosol-containing factor (Sulfate-OA); an ammonium nitrate- and oxygenated organic aerosol-containing factor (Nitrate-OA); an ammonium chloride-containing factor (Chloride); a hydrocarbon-like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analyzing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case the Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR–ToF–AMS data, due to the ability to understand better the chemical nature of atypical factors from high-resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of the extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably resolved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

scholarly journals Evaluation of the new capture vaporizer for aerosol mass spectrometers: Characterization of organic aerosol mass spectra

2018 ◽  
Vol 52 (7) ◽  
pp. 725-739 ◽  
Author(s):  
Weiwei Hu ◽  
Douglas A. Day ◽  
Pedro Campuzano-Jost ◽  
Benjamin A. Nault ◽  
Taehyun Park ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Organic Aerosol ◽  
Mass Spectrometers ◽  
Aerosol Mass

scholarly journals Primary to secondary organic aerosol: evolution of organic emissions from mobile combustion sources

2014 ◽  
Vol 14 (10) ◽  
pp. 5015-5036 ◽  
Author(s):  
A. A. Presto ◽  
T. D. Gordon ◽  
A. L. Robinson
Keyword(s):  
Gas Turbine ◽  
Mass Spectra ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Turbine Engines ◽  
Gas Turbine Engines ◽  
Residual Method ◽  
Diesel Vehicles ◽  
Aerosol Mass ◽  
Oxidation Chemistry

Abstract. A series of smog chamber experiments were conducted to investigate the transformation of primary organic aerosol (POA) and formation of secondary organic aerosol (SOA) during the photooxidation of dilute exhaust from a fleet of gasoline and diesel motor vehicles and two gas-turbine engines. In experiments where POA was present in the chamber at the onset of photooxidation, positive matrix factorization (PMF) was used to determine separate POA and SOA factors from aerosol mass spectrometer data. A 2-factor solution, with one POA factor and one SOA factor, was sufficient to describe the organic aerosol for gasoline vehicles, diesel vehicles, and one of the gas-turbine engines. Experiments with the second gas-turbine engine required a 3-factor PMF solution with a POA factor and two SOA factors. Results from the PMF analysis were compared to the residual method for determining SOA and POA mass concentrations. The residual method apportioned a larger fraction of the organic aerosol mass as POA because it assumes that all mass at m / z 57 is associated with POA. The POA mass spectrum for the gasoline and diesel vehicles exhibited high abundances of the CnH2n+1 series of ions (m / z 43, 57, etc.) and was similar to the mass spectra of the hydrocarbon-like organic aerosol factor determined from ambient data sets with one exception, a diesel vehicle equipped with a diesel oxidation catalyst. POA mass spectra for the gas-turbine engines are enriched in the CnH2n−1 series of ions (m / z 41, 55, etc.), consistent with the composition of the lubricating oil used in these engines. The SOA formed from the three sources exhibits high abundances of m / z 44 and 43, indicative of mild oxidation. The SOA mass spectra are consistent with less-oxidized ambient SV-OOA (semivolatile oxygenated organic aerosols) and fall within the triangular region of f44 versus f43 defined by ambient measurements. However there is poor absolute agreement between the experimentally derived SOA mass spectra and ambient OOA factors, though this poor agreement should be expected based on the variability of ambient OOA factors. Van Krevelen analysis of the POA and SOA factors for gasoline and diesel experiments reveal slopes of −0.50 and −0.40, respectively. This suggests that the oxidation chemistry in these experiments is a combination of carboxylic acid and alcohol/peroxide formation, consistent with ambient oxidation chemistry.

scholarly journals The link between organic aerosol mass loading and degree of oxygenation: an α-pinene photooxidation study

2013 ◽  
Vol 13 (13) ◽  
pp. 6493-6506 ◽  
Author(s):  
L. Pfaffenberger ◽  
P. Barmet ◽  
J. G. Slowik ◽  
A. P. Praplan ◽  
J. Dommen ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Organic Aerosol ◽  
Mass Loading ◽  
Smog Chamber ◽  
Organic Mass ◽  
Aerosol Composition ◽  
Ambient Aerosol ◽  
Aerosol Mass ◽  
Hygroscopic Properties ◽  
Mass Concentrations

Abstract. A series of smog chamber (SC) experiments was conducted to identify factors responsible for the discrepancy between ambient and SC aerosol degree of oxygenation. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer is used to compare mass spectra from α-pinene photooxidation with ambient aerosol. Composition is compared in terms of the fraction of particulate CO2+, a surrogate for carboxylic acids, vs. the fraction of C2H3O+, a surrogate for aldehydes, alcohols and ketones, as well as in the Van Krevelen space, where the evolution of the atomic hydrogen-to-carbon ratio (H : C) vs. the atomic oxygen-to-carbon ratio (O : C) is investigated. Low (near-ambient) organic mass concentrations were found to be necessary to obtain oxygenation levels similar to those of low-volatility oxygenated organic aerosol (LV-OOA) commonly identified in ambient measurements. The effects of organic mass loading and OH (hydroxyl radical) exposure were decoupled by inter-experiment comparisons at the same integrated OH concentration. An OH exposure between 3 and 25 × 107 cm−3 h is needed to increase O : C by 0.05 during aerosol aging. For the first time, LV-OOA-like aerosol from the abundant biogenic precursor α-pinene was produced in a smog chamber by oxidation at typical atmospheric OH concentrations. Significant correlation between measured secondary organic aerosol (SOA) and reference LV-OOA mass spectra is shown by Pearson's R2 values larger than 0.90 for experiments with low organic mass concentrations between 1.2 and 18 μg m−3 at an OH exposure of 4 × 107 cm−3 h, corresponding to about two days of oxidation time in the atmosphere, based on a global mean OH concentration of ~ 1 × 106 cm−3. α-Pinene SOA is more oxygenated at low organic mass loadings. Because the degree of oxygenation influences the chemical, volatility and hygroscopic properties of ambient aerosol, smog chamber studies must be performed at near-ambient concentrations to accurately simulate ambient aerosol properties.

scholarly journals Relating hygroscopicity and composition of organic aerosol particulate matter

2010 ◽  
Vol 10 (8) ◽  
pp. 19309-19341 ◽  
Author(s):  
J. Duplissy ◽  
P. F. DeCarlo ◽  
J. Dommen ◽  
M. R. Alfarra ◽  
A. Metzger ◽  
...  
Keyword(s):  
Mass Spectra ◽  
Field Experiments ◽  
Organic Aerosol ◽  
Photochemical Oxidation ◽  
Ionization Mass ◽  
Hygroscopic Growth ◽  
Atmospheric Models ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Organic Precursors

Abstract. A hygroscopicity tandem differential mobility analyzer (HTDMA) was used to measure the water uptake (hygroscopicity) of secondary organic aerosol (SOA) formed during the chemical and photochemical oxidation of several organic precursors in a smog chamber. Electron ionization mass spectra of the non-refractory submicron aerosol were simultaneously determined with an aerosol mass spectrometer (AMS), and correlations between the two different signals were investigated. SOA hygroscopicity was found to strongly correlate with the relative abundance of the ion signal m/z 44 expressed as a fraction of total organic signal (f44). m/z 44 is due mostly to the ion fragment CO2+ for all types of SOA systems studied, and has been previously shown to strongly correlate with organic O/C for ambient and chamber OA. The analysis was also performed on ambient OA from two field experiments at the remote site Jungfraujoch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation between the hygroscopicity of OA at subsaturated RH, as given by the hygroscopic growth factor (GF) or "κorg" parameter, and f44 was determined and is given by κorg=2.2×f44−0.13. This approximation can be further verified and refined as the database for AMS and HTDMA measurements is constantly being expanded around the world. The use of this approximation could introduce an important simplification in the parameterization of hygroscopicity of OA in atmospheric models, since f44 is correlated with the photochemical age of an air mass.

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