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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.
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  • 2
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] The field measurements were carried out at Scotia, Pennsylvania. The site is located in a forest preserve 10 km west of State College, remote from the influence of direct anthropogenic emissions. The site is a monitoring station of the National Acid Precipitation Assessment Program (NAPAP) with ...
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  • 3
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] According to current theory of the tropospheric ozone budget, photochemical production and stratospheric flux are principal sources of ozone, which are balanced by photochemical destruc-tion and surface deposition2"5. The photochemical production of ozone is mainly limited by the availability of ...
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  • 4
    ISSN: 0047-2670
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-0662
    Keywords: Ozone trends ; tropospheric ozone ; hydroxyls ; odd hydrogen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The response of tropospheric ozone to a change in solar UV penetration due to perturbation on column ozone depends critically on the tropospheric NO x (NO+NO2) concentration. At high NO x or a polluted area where there is net ozone production, a decrease in column ozone will increase the solar UV penetration to the troposphere and thus increase the tropospheric ozone concentration. However, the opposite will occur, for example, at a remote oceanic area where NO x is so low that there is net ozone destruction. This finding may have important implication on the interpretation of the long term trend of tropospheric ozone. A change in column ozone will also induce change in tropospheric OH, HO2, and H2O2 concentrations which are major oxidants in the troposphere. Thus, the oxidation capacity and, in turn, the abundances of many reduced gases will be perturbed. Our model calculations show that the change in OH, HO2, and H2O2 concentrations are essentially independent of the NO x concentration.
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  • 6
    ISSN: 1573-0662
    Keywords: Tropospheric ozone ; ozone precursors ; photochemistry ; nitrogen oxides ; rural ozone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO x (NO+NO2) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O3 can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O3 mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O3 levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O3 production.
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  • 7
    ISSN: 1573-0662
    Keywords: Stratospheric photochemistry ; HO2 -, NO2 +in situ data ; vertical profiles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Vertical profiles of stratospheric HO2 and NO2 concentrations were determined using matrix isolation and ESR. Up to 10 different samples per flight were collected in situ by a balloon borne cryosampler. Free radicals and trace constituents which are condensable at 68 K are trapped in a polycristalline H2O or D2O matrix. After collection, the samples are stored at a temperature below 83 K until they are analysed in the laboratory by X-band ESR spectroscopy at 4 K. The HO2 and NO2 were identified and calibrated by comparison with standard samples collected in the laboratory under typical stratospheric sampling conditions. From several flights over Southern France (44°N) we obtained two profiles of the stratospheric NO2 mixing ratio. One, from 21 October 1982, agrees well with previous measurements. The other, from 8 October 1981, is lower by one order of magnitude. The few HO2 data obtained around 35 km altitude agree with previous measurements. An isolated measurement at 17 km altitude is one order of magnitude higher than the model predicted HO2 concentration.
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  • 8
    ISSN: 1573-0662
    Keywords: Tropospheric ozone ; photochemistry ; nitrogen oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The mixing ratios for ozone and NOx (NO+NO2) have been measured at a rural site in the United States. From the seasonal and diurnal trends in the ozone mixing ratio over a wide range of NOx levels, we have drawn certain conclusions concerning the ozone level expected at this site in the absence of local photochemical production of ozone associated with NOx from anthropogenic sources. In the summer (June 1 to September 1), the daily photochemical production of ozone is found to increase in a linear fashion with increasing NOx mixing ratio. For NOx mixing ratios less than 1 part per billion by volume (ppbv), the daily increase is found to be (17±3) [NOx]. In contrast, the winter data (December 1 to March 1) indicate no significant increase in the afternoon ozone level, suggesting that the photochemical production of ozone during the day in winter approximately balances the chemical titration of ozone by NO and other pollutants in the air. The extrapolated intercept corresponding to [NOx]=0 taken from the summer afternoon data is 13% less than that observed from the summer morning data, suggesting a daytime removal mechanism for O3 in summer that is attributed to the effects of both chemistry and surface deposition. No significant difference is observed in the intercepts inferred from the morning and afternoon data taken during the winter. The results contained herein are used to deduce the background ozone level at the measurement site as a function of season. This background is equated with the natural ozone background during winter. However, the summer data suggest that the background ozone level at our site is elevated relative to expected natural ozone levels during the summer even at low NOx levels. Finally, the monthly daytime ozone mixing ratios are reported for 0≤[NOx]≤0.2 ppbv, 0.3 ppbv≤[NOx]≤0.7 ppbv and 1 ppbv≤[NOx]. These monthly ozone averages reflect the seasonal ozone dependence on the NOx level.
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  • 9
    ISSN: 1573-0662
    Keywords: OH-radicals ; troposphere ; long path absorption spectroscopy ; sensitivity study ; formaldehyde ; measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×106 to 3.2×106 cm-3. Simultaneously we measured the concentrations of O3, H2O, NO, NO2, CH4, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O3 and NO2. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO x concentrations. It is argued that additional, so far unidentified. HO x loss reactions must be responsible for that discrepancy.
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  • 10
    Publication Date: 2011-08-19
    Description: Measurements of NO, NO(x) (NO + NO2), O3, and CO are presented from seven aircraft flights made over the eastern Pacific Ocean and the southwestern United States in spring of 1984. The sampling region was characterized by large- and small-scale variability for all of the measurements, likely as a result of vigorous synoptic scale meteorology and the influence of tropopause folds. Median values for NO, NO(x), O3, and CO from the flights made over the ocean in the region of 5.8-7.6 km were 10 parts per trillion by volume (pptv), 32 pptv, 46 parts per billion by volume (ppbv), and 120 ppbv, respectively. Corresponding values from two flights made over the continent at similar altitudes were 16 pptv, 38 pptv, 42 ppbv, and 111 ppbv. There was a strong tendency for NO or NO(x) to be correlated positively with O3 and to be anticorrelated with dew-point/frost-point measurements. No significant overall correlation occurred between NO(x) and CO for the ocean data. The variability of NO(x) was such that regions of net destruction and regions of net production of O(3) were sampled both over the ocean and over the continent. However, in the middle free troposphere over the ocean, net O(3) destruction was predominant.
    Keywords: GEOPHYSICS
    Type: Journal of Geophysical Research (ISSN 0148-0227); 94; 5043-506
    Format: text
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