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  • 1
    ISSN: 1573-0662
    Keywords: tropospheric ozone ; atmospheric aerosol particles ; halogen chemistry ; Arctic regions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The halogen ions Br- and Cl- together with NO3 -, SO4 =, MSA- (methane sulfonate), Na+ and NH4 + were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m-3 (0.14 nmol m-3) was observed for the whole campaign, while maximum concentrations of 80 ng m-3 (1 nmol m-3) were detected during two total O3-depletion events (O3 drop to mixing ratios below the detection limit of 〈 2 ppb). Anticorrelation between f-Br and O3 was also seen during minor O3-depletion episodes (sudden drop in O3 by at least 10 ppb, but O3 still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O3-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O3-depletion periods. At O3 concentrations 〈 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-0662
    Keywords: Naphthalene ; bromine oxide ; differential absorption spectroscopy ; OH measurement ; interferences
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Naphthalene (C10H8), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (≤0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy. Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section σ′ was determined. The strongest naphthalene line at 308.002 nm is close to the Q 1(2) OH line, but about a factor of 200 weaker (σ′=(65.2±15.3)×10-20 cm2/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration. BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q 1(2) and Q 1(3) OH lines.
    Type of Medium: Electronic Resource
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