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  • 1
    ISSN: 1420-9136
    Keywords: Electron paramagnetic resonance ; Free radicals ; Matrix isolation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract With some special adaptations the technique of matrix isolation followed by detection through electron paramagnetic resonance (EPR) can also be used for the measurement of atmospheric radical concentrations. A light weight cryogenic sampling device has been constructed. It uses condensation of atmospheric CO2 or H2O at 77 K for matrix formation and trapping of the radicals. The sampler has been flown on a balloon for stratospheric sampling. First data on stratospheric, HO2 and NO2 at 32 km altitude have been obtained on a flight on 8 August 1976 and will be reported.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 81 (1977), S. 1543-1545 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 253 (1975), S. 333-334 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 3 (1985), S. 341-361 
    ISSN: 1573-0662
    Keywords: Peroxyradicals ; NO2 ; in-situ measurement ; matrix isolation ; electron spin resonance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract A cryogenic system for the airborne and ground based sampling of ambient radicals by matrix isolation is described. The trapped radicals, e.g., NO2 and RO2, are analyzed by ESR. The technique has been improved, mainly by addition of water vapor to the sampled air, to yield a collection efficiency of (90±10)% and a lower detection limit of about 20 ppt, but it still does not distinguish between the different RO2. Careful calibration reduced the measurement error (1 σ) to ±10% for NO2 and ±15% for HO2. Two diurnal variations of RO2 and NO2 at ground level and vertical profiles in the lower troposphere are presented.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 16 (1993), S. 313-335 
    ISSN: 1573-0662
    Keywords: HO2-, RO2-, and NO3-radicals ; tropospheric measurements ; matrix isolation/electron spin resonance ; nighttime chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract We present simultaneous field measurements of NO3 and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O3, NO x , NO y , and hydrocarbons, as well as meteorological parameters. NO2, NO3, HO2, and ∑(RO2) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO3 and HO2 were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO3, RO2, and HO2 exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO3 and RO2 radical concentrations at night. The measured trace gas set allows the calculation of NO3 and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO2 concentrations. The chemical budget of both NO3 and RO2 radicals can be understood if emissions of monoterpenes are included. The measured HO2 can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO2 radicals implies the presence of hydroxyl radicals at night in concentrations of up to 105 cm−3.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 11 (1990), S. 271-297 
    ISSN: 1573-0662
    Keywords: Matrix isolation/electron spin resonance ; peroxy radicals ; NO3 ; NO2 ; numerical analysis ; atmospheric measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Improvements of the matrix isolation/electron spin resonance technique for the measurement of NO2, NO3, and RO2 radicals in the atmosphere are described. The use of D2O instead of H2O as the matrix yields a better spectral resolution and, as a consequence, larger a signal-to-noise ratio as well as better identification of the different species. Reference spectra of the different radicals in H2O and D2O matrices are compared. While a large degree of correlation exists amongst the spectra of the different (unsubstituted and substituted) alkylperoxy radicals, the spectra of HO2, CH3C(O)O2, and NO3 show significant differences that allow their distinction in atmospheric samples. A numerical procedure for the analysis of the composite ESR spectra obtained from atmospheric samples was developed. Subtraction of the dominant NO2 signal is performed by matching a reference NO2 spectrum with respect to amplitude, spectral position, and line width to the sample spectrum. The manipulations are performed with the virtually noise-free reference spectrum and are based on physical information. The residual spectrum is then analyzed for RO2 (and/or NO3) by simultaneously fitting up to six different reference spectra. The method was applied to laboratory samples as well as to atmospheric samples in order to demonstrate the ability of retrieving small amounts of HO2 in the presence of large amounts of NO2 and other peroxy radicals. The new algorithm allowed, for the first time, the identification of the HO2 and CH3C(O)O2 radical in tropospheric air at concentrations ranging up to 40 ppt.
    Type of Medium: Electronic Resource
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