Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

Ebben, C. J.; Martinez, Imee Su; Shrestha, Mona; Buchbinder, Avram M.; Corrigan, A. L.; Karl, T.; Petäj̈ä, Tuukka; Song, Weihua; Zorn, S. R.; Artaxo, Paulo; Kulmala, Markku; Martin, Scot T.; Russell, Lynn M.; Williams, Jonathan; Geiger, Franz M.

doi:10.5194/acp-11-10317-2011

Cited by 32 publications

(36 citation statements)

References 52 publications

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“…The growth of the newly formed particles over the boreal forest is triggered by organic molecules (Tunved et al, 2006) and each monoterpene has a specific aerosol yield leading to different growth rates and cloud condensation nucleus concentrations with important impacts on the radiative aerosol properties. Ebben et al (2011) show that the organic fraction of submicron aerosol particles collected from SMEAR II site closely resembles the molecular signature of α-pinene, thus confirming the importance of α-pinene emissions in the secondary organic aerosol formation processes at this site. A detailed study on the quantitative influence of chemotypic heterogeneity on the OH-and NO 3 -radical budget will be presented in further studies.…”

Section: Chemodiversity and Atmospheric Chemistrymentioning

confidence: 50%

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

et al. 2012

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Abstract. Atmospheric chemistry in background areas is strongly influenced by natural vegetation. Coniferous forests are known to produce large quantities of volatile vapors, especially terpenes. These compounds are reactive in the atmosphere, and contribute to the formation and growth of atmospheric new particles.Our aim was to analyze the variability of mono-and sesquiterpene emissions between Scots pine trees, in order to clarify the potential errors caused by using emission data obtained from only a few trees in atmospheric chemistry models. We also aimed at testing if stand history and seed origin has an influence on the chemotypic diversity. The inherited, chemotypic variability in mono-and sesquiterpene emission was studied in a seemingly homogeneous 48 yr-old stand in Southern Finland, where two areas differing in their stand regeneration history could be distinguished. Sampling was conducted in August 2009. Terpene concentrations in the air had been measured at the same site for seven years prior to branch sampling for chemotypes.Two main compounds, α-pinene and 3 -carene formed together 40-97 % of the monoterpene proportions in both the branch emissions and in the air concentrations. The data showed a bimodal distribution in emission composition, in particular in 3 -carene emission within the studied population. 10 % of the trees emitted mainly α-pinene and no 3 -carene at all, whereas 20 % of the trees where characterized as high 3 -carene emitters ( 3 -carene forming >80 % of total emitted monoterpene spectrum). An intermediate group of trees emitted equal amounts of both α-pinene and 3 -carene. The emission pattern of trees at the area established using seeding as the artificial regeneration method differed from the naturally regenerated or planted trees, being mainly high 3 -carene emitters. Some differences were also seen in e.g. camphene and limonene emissions between chemotypes, but sesquiterpene emissions did not differ significantly between trees. The atmospheric concentrations at the site were found to reflect the species and/or chemodiversity rather than the emissions measured from any single tree, and were strongly dominated by α-pinene. We also tested the effect of chemodiversity on modeled monoterpene concentrations at the site and found out that since it significantly influences the distributions and hence the chemical reactions in the atmosphere, it should be taken into account in atmospheric modeling.

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Section: Chemodiversity and Atmospheric Chemistrymentioning

confidence: 50%

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

et al. 2012

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“…In our previous report of the first vibrational SFG spectrum of α-pinene collected using conventional BB-SFG, 21 we referred to published SFG spectra of compounds containing linear hydrocarbon chains 24,33−49 to attribute the SFG signal at 2960 cm −1 to the asymmetric methyl C−H stretch, the intensity at 2940 cm −1 to a methyl Fermi resonance, and the one at 2880 cm −1 to the symmetric methyl C−H stretch. Guided by literature precedent, 33,50−53 we also stated that the methylene group on the four-membered ring of α-pinene may contribute SFG signal intensity between 2950 and 2990 cm −1 due to ring strain.…”

Section: Resultsmentioning

confidence: 99%

“…21,22 At NU, the visible probe pulse at 800 nm features a full width at half-maximum (fwhm) of about 1.5 ps, providing a spectral resolution of ∼10−15 cm −1 , and the broad IR pulse is 150 fs long and covers about 150 cm −1 in each measurement, requiring use of Walker's hybrid scanning broadband method, 23 as described earlier. 24 The incident angles and pulse energies for the NU system are 61°and ∼1.5−2.5 μJ for the IR pulse and 42°and ∼2 μJ for the upconverter pulse.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

Accurate Line Shapes from Sub-1 cm^–1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature

Mifflin

Velarde

et al. 2015

J. Phys. Chem. A

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Despite the importance of terpenes in biology, the environment, and catalysis, their vibrational spectra remain unassigned. Here, we present subwavenumber high-resolution broad-band sum frequency generation (HR-BB-SFG) spectra of the common terpene (+)-α-pinene that reveal 10 peaks in the C-H stretching region at room temperature. The high spectral resolution resulted in spectra with more and better resolved spectral features than those of the Fourier transform infrared, femtosecond stimulated Raman spectra in the bulk condensed phase and those of the conventional BB-SFG and scanning SFG spectroscopy of the same molecule on a surface. Experiment and simulation show the spectral line shapes with HR-BB-SFG to be accurate. Homogeneous vibrational decoherence lifetimes of up to 1.7 ps are assigned to specific oscillators and compare favorably to lifetimes computed from density functional tight binding molecular dynamics calculations. Phase-resolved spectra provided their orientational information. We propose the new spectroscopy as an attractive alternative to time domain vibrational spectroscopy or heterodyne detection schemes for studying vibrational energy relaxation and vibrational coherences in molecules at molecular surfaces or interfaces.

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“…20,31 The sample was moved so that at least three spots were analyzed per sample. The SFG spectra were recorded at the same incident up-converter pulse energy.…”

Section: Methodsmentioning

confidence: 99%

Vibrational Sum Frequency Generation Spectroscopy of Secondary Organic Material Produced by Condensational Growth from α-Pinene Ozonolysis

et al. 2013

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Secondary organic material (SOM) was produced in a flow tube from α-pinene ozonolysis, and collected particles were analyzed spectroscopically via a nonlinear coherent vibrational spectroscopic technique, namely sum frequency generation (SFG). The SOM precursor α-pinene was injected into the flow tube reactor at concentrations ranging from 0.125 ± 0.01 ppm to 100 ± 3 ppm. The oxidant ozone was varied from 0.15 ± 0.02 to 194 ± 2 ppm. The residence time was 38 ± 1 s. The integrated particle number concentrations, studied using a scanning mobility particle sizer (SMPS), varied from no particles produced up to (1.26 ± 0.02) × 10(7) cm(-3) for the matrix of reaction conditions. The mode diameters of the aerosols increased from 7.7 nm (geometric standard deviation (gsd), 1.0) all the way to 333.8 nm (gsd, 1.9). The corresponding volume concentrations were as high as (3.0 ± 0.1) × 10(14) nm(3) cm(-3). The size distributions indicated access to different particle growth stages, namely condensation, coagulation, or combination of both, depending on reaction conditions. For filter collection and subsequent spectral analysis, reaction conditions were selected that gave a mode diameter of 63 ± 3 nm and 93 ± 3 nm, respectively, and an associated mass concentration of 12 ± 2 μg m(-3) and (1.2 ± 0.1) × 10(3) μg m(-3) for an assumed density of 1200 kg m(-3). Teflon filters loaded with 24 ng to 20 μg of SOM were analyzed by SFG. The SFG spectra obtained from particles formed under condensational and coagulative growth conditions were found to be quite similar, indicating that the distribution of SFG-active C-H oscillators is similar for particles prepared under both conditions. The spectral features of these flow-tube particles agreed with those prepared in an earlier study that employed the Harvard Environmental Chamber. The SFG intensity was found to increase linearly with the number of particles, consistent with what is expected from SFG signal production from particles, while it decreased at higher mass loadings of 10 and 20 μg, consistent with the notion that SFG probes the top surface of the SOM material following the complete coverage of the filter. The linear increase in SFG intensity with particle density also supports the notion that the average number of SFG active oscillators per particle is constant for a given particle size, that the particles are present on the collection filters in a random array, and that the particles are not coalesced. The limit of detection of SFG intensity was established as 24 ng of mass on the filter, corresponding to a calculated density of about 100 particles in the laser spot. As established herein, the technique is applicable for detecting low particle number or mass concentrations in ambient air. The related implication is that SFG is useful for short collection times and would therefore provide increased temporal resolution in a locally evolving atmospheric environment.

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Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

Cited by 32 publications

References 52 publications

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

Accurate Line Shapes from Sub-1 cm^–1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature

Vibrational Sum Frequency Generation Spectroscopy of Secondary Organic Material Produced by Condensational Growth from α-Pinene Ozonolysis

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Contrasting organic aerosol particles from boreal and tropical forests during HUMPPA-COPEC-2010 and AMAZE-08 using coherent vibrational spectroscopy

Cited by 32 publications

References 52 publications

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

Chemodiversity of a Scots pine stand and implications for terpene air concentrations

Accurate Line Shapes from Sub-1 cm–1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature

Vibrational Sum Frequency Generation Spectroscopy of Secondary Organic Material Produced by Condensational Growth from α-Pinene Ozonolysis

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Product

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Accurate Line Shapes from Sub-1 cm^–1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature