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

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) × 10⁷ 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) × 10¹⁴ nm³ 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) × 10³ 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

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.National Science Foundation Atmospheric Chemistry divisionNational Science Foundation Atmospheric Chemistry division[NSF ATM-0533436]U.S. Department of Energy (DOE)Office of Science (BES), U.S. Department of Energy (DOE)[DE-FG02-08ER64529

On molecular chirality within naturally occurring secondary organic aerosol particles from the central Amazon Basin

In this perspectives article, we reflect upon the existence of chirality in atmospheric aerosol particles. We then show that organic particles collected at a field site in the central Amazon Basin under pristine background conditions during the wet and dry seasons consist of chiral secondary organic material. We show how the chiral response from the aerosol particles can be imaged directly without the need for sample dissolution, solvent extraction, or sample preconcentration. By comparing the chiral-response images with optical images, we show that chiral responses always originate from particles on the filter, but not all aerosol particles produce chiral signals. The intensity of the chiral signal produced by the size resolved particles strongly indicates the presence of chiral secondary organic material in the particle. Finally, we discuss the implications of our findings on chiral atmospheric aerosol particles in terms of climate-related properties and source apportionment.Northwestern Initiative for Sustainability and Energy at Northwestern (ISEN)National Science Foundation NSFAchievement Rewards for College Scientists (ARCS)Schlumberger Oilfield Chemical Products, LLCFAPESPCNPqOffice of Science (BES), U.S. Department of Energy (DOE)[DE-FG02-08ER64529]National Science Foundation Atmospheric Chemistry division[NSF ATM-0533436]Division of Chemistry[CHE-0937460]Irving

Vibrational Mode Assignment of α‑Pinene by Isotope Editing: One Down, Seventy-One To Go

This study aims to reliably assign the vibrational sum frequency generation (SFG) spectrum of α-pinene at the vapor/solid interface using a method involving deuteration of various methyl groups. The synthesis of five deuterated isotopologues of α-pinene is presented to determine the impact that removing contributions from methyl group C–H oscillators has on its SFG response. 0.6 cm^–1 resolution SFG spectra of these isotopologues show varying degrees of differences in the C–H stretching region when compared to the SFG response of unlabeled α-pinene. The largest spectral changes were observed for the isotopologue containing a fully deuterated vinyl methyl group. Noticeable losses in signal intensities allow us to reliably assign the 2860 cm^–1 peak to the vinyl methyl symmetric stretch. Furthermore, upon removing the vinyl methyl group entirely by synthesizing apopinene, the steric influence of the unlabeled C₉H₁₄ fragment on the SFG response of α-pinene SFG can be readily observed. The work presented here brings us one step closer to understanding the vibrational spectroscopy of α-pinene

Size-Resolved Sea Spray Aerosol Particles Studied by Vibrational Sum Frequency Generation

We present vibrational sum frequency generation (SFG) spectra of the external surfaces and the internal interfaces of size-selected sea spray aerosol (SSA) particles generated at the wave flume of the Scripps Hydraulics Laboratory. Our findings support SSA particle models that invoke the presence of surfactants in the topmost particle layer and indicate that the alkyl chains of surfactant-rich SSA particles are likely to be disordered. Specifically, the SFG spectra suggest that across the range of sizes studied, surfactant-rich SSA particles contain CH oscillators that are subject to molecular orientation distributions that are broader than the narrow molecular distribution functions associated with well-ordered and well-aligned alkyl chains. This result is consistent with the interpretation that the permeability of organic layers at SSA particle surfaces to small reactive and nonreactive molecules may be substantial, allowing for much more exchange between reactive and nonreactive species in the gas or the condensed phase than previously thought. The SFG data also suggest that a one-component model is likely to be insufficient for describing the SFG responses of the SSA particles. Finally, the similarity of the SFG spectra obtained from the wave flume microlayer and 150 nm-sized SSA particles suggests that the SFG active CH oscillators in the topmost layer of the wave flume and the particle accumulation mode may be in similar chemical environments. Needs for additional research activities are discussed in the context of the results presented

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

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

Size-Dependent Changes in Sea Spray Aerosol Composition and Properties with Different Seawater Conditions

A great deal of uncertainty exists regarding the chemical diversity of particles in sea spray aerosol (SSA), as well as the degree of mixing between inorganic and organic species in individual SSA particles. Therefore, in this study, single particle analysis was performed on SSA particles, integrating transmission electron microscopy with energy dispersive X-ray analysis and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy, with a focus on quantifying the relative fractions of different particle types from 30 nm to 1 μm. SSA particles were produced from seawater in a unique ocean-atmosphere facility equipped with breaking waves. Changes to the SSA composition and properties after the addition of biological (bacteria and phytoplankton) and organic material (ZoBell growth media) were probed. Submicrometer SSA particles could be separated into two distinct populations: one with a characteristic sea salt core composed primarily of NaCl and an organic carbon and Mg²⁺ coating (SS-OC), and a second type consisting of organic carbon (OC) species which are more homogeneously mixed with cations and anions, but not chloride. SS-OC particles exhibit a wide range of sizes, compositions, morphologies, and distributions of elements within each particle. After addition of biological and organic material to the seawater, a change occurs in particle morphology and crystallization behavior associated with increasing organic content for SS-OC particles. The fraction of OC-type particles, which are mainly present below 180 nm, becomes dramatically enhanced with increased biological activity. These changes with size and seawater composition have important implications for atmospheric processes such as cloud droplet activation and heterogeneous reactivity

ClNO2 yields from aircraft measurements during the 2015 WINTER campaign and critical evaluation of the current parameterization

Nitryl chloride (ClNO2) plays an important role in the budget and distribution of tropospheric oxidants, halogens, and reactive nitrogen species. ClNO2 is formed from the heterogeneous uptake and reaction of dinitrogen pentoxide (N2O5) on chloride-containing aerosol, with a production yield, ϕ(ClNO2), defined as the moles of ClNO2 produced relative to N2O5 lost. The ϕ(ClNO2) has been increasingly incorporated into 3-D chemical models where it is parameterized based on laboratory-derived kinetics and currently accepted aqueous-phase formation mechanism. This parameterization models ϕ(ClNO2) as a function of the aerosol chloride to water molar ratio. Box model simulations of night flights during the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) aircraft campaign derived 3,425 individual ϕ(ClNO2) values with a median of 0.138 and range of 0.003 to 1. Comparison of the box model median to those predicted by two other field-based ϕ(ClNO2) derivation methods agreed within a factor of 1.3, within the uncertainties of each method. In contrast, the box model median was 75–84% lower than predictions from the laboratory-based parameterization (i.e., [parameterization − box model]/parameterization). An evaluation of factors influencing this difference reveals a positive dependence of ϕ(ClNO2) on aerosol water, opposite to the currently parameterized trend. Additional factors may include aqueous-phase competition reactions for the nitronium ion intermediate and/or direct ClNO2 loss mechanisms. Further laboratory studies of ClNO2 formation and the impacts of aerosol water, sulfate, organics, and ClNO2 aqueous-phase reactions are required to elucidate and quantify these processes on ambient aerosol, critical for the development of a robust ϕ(ClNO2) parameterization