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  • Analytical Chemistry and Spectroscopy  (3)
  • aerosol particles  (2)
  • 1
    ISSN: 1573-0662
    Keywords: Antarctica ; Palmer ; Marsh ; Mawson ; aerosol particles ; biogeochemical cycles ; sulfate ; nitrate ; methanesulfonate ; lead-210 ; beryllium-7 ; sea-salt ; ammonium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract High volume bulk aerosol samples were collected continuously at three Antarctic sites: Mawson (67.60° S, 62.50° E) from 20 February 1987 to 6 January 1992; Palmer Station (64.77° S, 64.06° W) from 3 April 1990 to 15 June 1991; and Marsh (62.18° S, 58.30° W) from 28 March 1990, to 1 May 1991. All samples were analyzed for Na+, SO 4 2− , NO 3 − , methanesulfonate (MSA), NH 4 + ,210Pb, and7Be. At Mawson for which we have a multiple year data set, the annual mean concentration of each species sometimes vary significantly from one year to the next: Na+, 68–151 ng m−3; NO 3 − , 25–30 ng m−3; nss SO 4 2− , 81–97 ng m−3; MSA, 19–28 ng m−3; NH 4 + , 16–21 ng m−3;210Pb, 0.75–0.86 fCi m−3. Results from multiple variable regression of non-sea-salt (nss) SO 4 2− with MSA and NO 3 − as the independent variables indicates that, at Mawson, the nss SO 4 2− /MSA ratio resulting from the oxidation of dimethylsulfide (DMS) is 2.80±0.13, about 13% lower than our earlier estimate (3.22) that was based on 2.5 years of data. A similar analysis indicates that the ratio at Palmer is about 40% lower, 1.71±0.10, and more comparable to previous results over the southern oceans. These results when combined with previously published data suggest that the differences in the ratio may reflect a more rapid loss of MSA relative to nss SO 4 2− during transport over Antarctica from the oceanic source region. The mean210Pb concentrations at Palmer and Marsh and the mean NO 3 − concentration at Palmer are about a factor of two lower than those at Mawson. The210Pb distributions are consistent with a210Pb minimum in the marine boundary layer in the region of 40°–60° S. These features and the similar seasonalities of NO 3 − and210Pb at Mawson support the conclusion that the primary source regions for NO 3 − are continental. In contrast, the mean concentrations of MSA, nss SO 4 2− , and NH 4 + at Palmer are all higher than those at Mawson: MSA by a factor of 2; nss SO 4 2− by 10%; and NH 4 + by more than 50%. However, the factor differences exhibit substantial seasonal variability; the largest differences generally occur during the austral summer when the concentrations of most of the species are highest. NH 4 + /(nss SO 4 2− +MSA) equivalent ratios indicate that NH3 neutralizes about 60% of the sulfur acids during December at both Mawson and Palmer, but only about 30% at Mawson during February and March.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-0662
    Keywords: Antarctica ; aerosol particles ; ice ; biogeochemical cycles ; sulfate ; nitrate ; methanesulfonate ; lcad-210 ; boryllium-7 ; sea-salt
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract High volume aerosol samples were collected continuously at Mawson, Antarctica (67°36'S, 62°30'E), from February 1987 through October 1989. All samples were analyzed for Na+, Cl-, SO4 =, NO3 -, methanesulfonate (MSA), NH4 +,7Be, and210Pb. The annual mean concentrations of many of the species are very low, substantially lower than even those over the relatively pristine regions of the tropical and subtropical South Pacific. The concentrations at Mawson are comparable both in magnitude and in seasonality to those which have been measured in long term studies at the South Pole and at the coastal German Antarctic research station, Georg von Neumayer (GvN). This comparability suggests that the aerosol composition may be relatively uniform over a broad sector of the Antarctic. The concentrations of most of the species exhibit very strong and sharply-defined seasonal cycles. MSA, non-sea-salt (nss) SO4 = and NH4 + all exhibit similar cycles, with maxima during the austral summer (December through February) being more than an order of magnitude higher than the winter minima. The limited7Be data appears to exhibit a similar cycle. Although nitrate and210Pb also exhibit relatively high concentrations during the austral summer, their cycles are far more complex than those of the previous species with indications of multiple peaks. As expected, the concentration of sea-salt (as indicated by Na+ and Cl-) peaks during the winter. The results from multiple variable regression analyses indicate that the dominant source of nss SO4 = is the oxidation of dimethylsulfide (DMS) which produces MSA and nss SO4 = in a ratio of about 0.31 (about five times higher than that over the tropical and subtropical oceans). However, a very significant fraction (about 25%) of the nss SO4 = is associated with NO3 -, The seasonal cycle of NO3 - is similar to that of210Pb and distinctly different from that of7Be and MSA. These results indicate that the major source of NO3 - over Antarctica is probably continental as opposed to stratospheric or marine biogenic.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 6 (1992), S. 173-178 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Peptides and proteins with molecular weights of ca 20 000 have been mass measured with accuracies of ±0.5 Da using electrospray ionization interfaced to a double-focusing magnetic sector mass spectrometer. Factors affecting mass measurement accuracy such as resolution, peak profiles, calibration, data processing, and mass calculations are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 20 (1989), S. 1-9 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman spectra of gaseous, liquid and solid 1,1,1,3,3,3-hexafluoro-2-methoxypropane, (CF3)2 CHOCH3, and the corresponding methoxy-d3 isotope, (CF3)2 CHOCD3, together with the infrared spectra of the gases and solids, have been recorded from 3500 to 30 cm-1. A comparison of the vibrational spectra obtained for the fluid phases with those obtained for the amorphous and annealed solids indicates the predominance of a single conformer at ambient temperature in the fluid phases with the same conformer present in the solid state. Based on the lack of depolarized Raman lines in the fluid phases, and a predominance of nondescript infrared band contours, it is concluded that the stable conformer is the gauche form which has the methoxy group rotated approximately 60° from eclipsing the secondary carbon—hydrogen bond. Thirty-eight of the 39 normal modes have been assigned based on group frequencies, isotopic shifts, depolarization values and infrared band contours. There appears to be coupling of the CF3 and methoxy torsional modes. Utilizing a coupled-top barrier calculation, the barrier to internal rotation of the perfluoromethyl groups is estimated to be 2858 ± 100 cm-1 (8.2 ± 0.3 kcal mol-1) based on the torsional frequencies of 107 and 64 cm-1 observed in the solid phase. Several of the fundamentals appear as doublets in the spectra of the solids, which indicates that there are at least two molecules per primitive cell. These results are compared with similar data for some corresponding molecules.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 21 (1990), S. 109-122 
    ISSN: 0377-0486
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Raman spectra of gaseous, liquid and solid 1, 1, 1-trifluoro-2-methoxypropane, CF3(CH3)CHOCH3, and the corresponding methoxy-d3 isotope, CF3(CH3)CHOCD3, together with the infrared spectra of the gases and solids were recorded from 3500 to 30 cm-1. A comparison of the vibrational spectra obtained for the fluid phases with those obtained for the amorphous and annealed solids indicates the predominance of two conformers in the fluid phases at ambient temperature. Owing to possible steric hindrance, it is suggested that the most stable conformer is the gauche-2 form, which has the methoxy group trans with respect to the carbon-carbon bond of the perfluoromethyl group. This conformer is the one present in the solid. The other conformer in appreciable abundance in the fluid states is probably the gauche-1 form, which has the methoxy group trans to the carbon-carbon bond of the methyl group. From a temperature study of the Raman spectrum of the liquid, the enthalpy difference between these conformers was determined to be 180 ± 100 cm-1 (515 ± 286 cal mol-1). The asymmetric torsional frequencies for the gauche-2 and gauche-1 conformers are 93 and 53 cm-1, respectively, and from these data and the enthalpy difference the values for the potential constants governing the internal rotation have been estimated. The normal modes have been assigned based on group frequencies, isotopic shifts, depolarization values and infrared band contours. The barrier to internal rotation of the methyl group is calculated to be 1275 cm-1 (3.65 kcal mol-1) from the torsional frequency of 234 cm-1 of the solid.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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