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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 3134-3143 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-resolution (0.013 cm−1) spectra of the second overtone of the OH stretch of trans-nitrous acid were recorded between 10 230 and 10 350 cm−1. The spectra were analyzed to yield a complete set of rotational parameters, including the A, B, and C rotational constants and the 5 quartic distortion constants. Two groups of anharmonic perturbations were observed and analyzed, and for one of these groups, the spectra were fit with a second model to extract an improved set of parameters that took into account these interactions. Much less information could be obtained from our spectra about the second group of perturbations, except that the same dark vibrational state was probably not responsible for both groups of perturbations. The anharmonic coupling matrix element between the 3ν1 "bright" state and one "dark" vibrational state was found to be 0.0338(31) cm−1, and possible assignments for the "dark" level are discussed. In addition, we report the first measurement of the absolute intensity of the 3ν1 overtone band, which was found to be 2.1±0.6×10−21 cm2 molecule−1 cm−1. Our findings are discussed in the context of the contribution of overtone-mediated processes to OH radical production in the upper atmosphere. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2019-12-03
    Description: The applicability, methods and limitations of constrained peak-fitting on mass spectra of low mass resolving power (m/dm50 ~ 500) recorded with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) are explored. Calibration measurements as well as ambient data are used to exemplify the methods that should be applied to maximise data quality and assess confidence in peak-fitting results. Sensitivity analyses and basic peak fit metrics such as normalised ion separation are employed to demonstrate which peak-fitting analyses commonly performed in high-resolution aerosol mass spectrometry are appropriate to perform on spectra of this resolving power. Information on aerosol sulphate, nitrate, sodium chloride, methanesulphonic acid as well as semi-volatile metal species retrieved from these methods is evaluated. The constants in a commonly used formula for the estimation of the mass concentration of hydrocarbon-like organic aerosol may be refined based on peak-fitting results. Finally, application of a recently-published parameterisation for the estimation of carbon oxidation state to ToF-ACSM spectra is validated for a range of organic standards and its use demonstrated for ambient urban data.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
    Format: application/pdf
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  • 3
    Publication Date: 2022-05-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in O'Brien, R. E., Ridley, K. J., Canagaratna, M. R., Jayne, J. T., Croteau, P. L., Worsnop, D. R., Budisulistiorini, S. H., Surratt, J. D., Follett, C. L., Repeta, D. J., & Kroll, J. H. Ultrasonic nebulization for the elemental analysis of microgram-level samples with offline aerosol mass spectrometry. Atmospheric Measurement Techniques, 12(3), (2019):1659-1671, doi:10.5194/amt-12-1659-2019.
    Description: The elemental composition of organic material in environmental samples – including atmospheric organic aerosol, dissolved organic matter, and other complex mixtures – provides insights into their sources and environmental processing. However, standard analytical techniques for measuring elemental ratios typically require large sample sizes (milligrams of material or more). Here we characterize a method for measuring elemental ratios in environmental samples, requiring only micrograms of material, using a small-volume nebulizer (SVN). The technique uses ultrasonic nebulization of samples to generate aerosol particles (100–300 nm diameter), which are then analyzed using an aerosol mass spectrometer (AMS). We demonstrate that the technique generates aerosol from complex organic mixtures with minimal changes to the elemental composition of the organic material and that quantification is possible using internal standards (e.g., NH154NO3). Sample volumes of 2–4 µL with total solution concentrations of at least 0.2 g L−1 form sufficient particle mass for elemental ratio measurement by the AMS, despite only a small fraction (∼ 0.1 %) of the sample forming fine particles after nebulization (with the remainder ending up as larger droplets). The method was applied to aerosol filter extracts from the field and laboratory, as well as to the polysaccharide fraction of dissolved organic matter (DOM) from the North Pacific Ocean. In the case of aerosol particles, the mass spectra and elemental ratios from the SVN–AMS agree with those from online AMS sampling. Similarly, for DOM, the elemental ratios determined from the SVN–AMS agree with those determined using combustion analysis. The SVN–AMS provides a platform for the rapid quantitative analysis of the elemental composition of complex organic mixtures and non-refractory inorganic salts from microgram samples with applications that include analysis of aerosol extracts and terrestrial, aquatic, and atmospheric dissolved organic matter.
    Description: This work was supported by National Oceanic and Atmospheric Administration grant nos. NA13OAR4310072 and NA140AR4310132. Kelsey J. Ridley acknowledges support from the NSF Graduate Research Fellowship Program. Sri Hapsari Budisulistiorini and Jason D. Surratt acknowledges support from the U.S. Environmental Protection Agency award no. 835404, Electric Power Research Institute (EPRI), and National Oceanic and Atmospheric Administration grant no. NA13OAR4310064. Special thanks are due to David Karl and Eric Grabowski, University of Hawaii, for the CHNS elemental analysis of DOM. Daniel J. Repeta acknowledges support from the Gordan and Betty Moore Foundation award 6000 and the Simons Foundation SCOPE award 329108.
    Repository Name: Woods Hole Open Access Server
    Type: Article
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