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  • 1
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 68 (1997), S. 230-239 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: Investigations of the relationship between changes in climate and the variation of composition of the atmosphere can be performed most directly and with the highest resolution possible by analyzing the air sampled and preserved in the polar ice sheets for hundreds of thousands of years by nature itself. For the determination of CO2, CH4, N2O, and CO in air samples of 1–3 cm3 extracted from ice cores, a high-frequency modulated tunable diode laser absorption spectrometer has been developed. The instrument can measure CO2, CH4, N2O, and CO at ambient mixing ratios of 300 ppmv (1 ppmv=10−6 volume mixing ratio), 1700, 300, and 100 ppbv (1 ppbv=10−9 volume mixing ratio), respectively, with a precision of 1%–2%. The measurement of high CO2 mixing ratios is not constrained by the detection limit. For other gases mixing ratios of 20 ppbv of CH4, 0.9 ppbv of N2O, and 1.6 ppbv of CO are detectable with the instrument in 2 cm3 standard temperature and pressure. These detection limits and the measurement precision are sufficient for the determination of past changes in atmospheric composition. The technique is also suitable for other applications in which several infrared active trace gases have to be determined in the low ppbv and possibly even in the upper pptv range in air samples of a few cm3 or small samples of other matrices. The sensitivity or the reproducibility of the instrument can be improved by another order of magnitude by using more powerful lasers and by averaging over longer periods. Such improvement could result in a capability to detect sub-ppbv mixing ratios in samples of the present size or ppbv measurements in even smaller air samples. The higher reproducibility would also make the technique interesting for measurements of isotope ratios. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Analytica Chimica Acta 110 (1979), S. 35-47 
    ISSN: 0003-2670
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 54 (1978), S. 444-447 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Publishing Ltd
    FEMS microbiology letters 62 (1989), S. 0 
    ISSN: 1574-6968
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Biology
    Notes: Abstract Fluxes of NO from three different soils have been studied by a flow-through system in the laboratory as a function of gas flow rate, of NO mixing ratio, and of incubation conditions. The dependence of net NO fluxes on gas flow rates and on NO mixing ratios could be described by a simple model of simultaneous NO production and NO uptake. By using this model, rates of gross NO production, rate constants of NO uptake, and NO compensation mixing ratios could be determined as function of the soil type and the incubation condition. Gross NO production rates were one to two orders of magnitude larger under anaerobic than under aerobic conditions. NO uptake rate constants, on the other hand, were only 5–8 times larger so that the compensation mixing ratios of NO were in a range of about 1600–2200 ppbv under anaerobic and of about 50–600 ppbv under aerobic conditions. The different soils exhibited similar NO uptake rate constants, but the gross NO production rate and compensation mixing ratio was significantly higher in an acidic (pH 4.7) sandy clay loam than in other less acidic soils. Experiments with autoclaved soil samples showed that both NO production and NO uptake was mainly due to microbial metabolism.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Applied physics 49 (1989), S. 99-108 
    ISSN: 1432-0649
    Keywords: 07.65
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Ultrasensitive absorption spectroscopy of NO2 was performed with a tunable lead-salt diode laser (TDL) using a single-tone high-frequency modulation (FM) technique. With a detection bandwidth of 200 kHz, an optical density of 2.7 × 10−5 was detectable at SNR of 1. The detectable optical density could be further improved by reducing the detection bandwidth in agreement with the √Δf relationship, reaching 2.5 × 10−6 at a detection bandwidth of 1.56 kHz. Normalized to 1 Hz bandwidth, the demonstrated performance would then correspond to a detectable optical density of 5.9 × 10−8. This detection limit agrees well with the calculated “quantum limited” performance based on the measured laser power, modulation index, noise figure of the electronic components, and other parameters of the apparatus. These measurements and calculations show that by implementation of the FM technique, the sensitivity of the present TDL absorption spectrometers (TDLAS) can be improved by at least a factor of 10 and possibly even of 100. Such a sensitivity improvement would greatly extend the applicability of TDLAS for trace gas analysis, especially in atmospheric monitoring.
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  • 6
    ISSN: 1432-0649
    Keywords: 07.65
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Modern research in atmospheric chemistry requires highly sensitive techniques for the measurement of concentrations of free radicals which determine the rate of photochemical destruction of most atmospheric pollutants. Tunable diode-laser absorption spectroscopy (TDLAS) has already been successfully used for measurements of very low concentrations of stable gases, but further improvement in its sensitivity by signal averaging has been limited by the stability of the instrument. In this paper the concept of the Allan variance is utilized to analyze the stability of an existing frequency-modulated (FM) TDLAS instrument leading to a detection limit for NO2 of 34 pptv at 6 Hz detection bandwidth. The stability of the instrument allows averaging over 60 s. Taking into account the measuring cycle consisting of the determination of the sample spectra and zero air spectra as well as gas exchange in the absorption cell, the detection limit achievable with this particular instrument was 10 pptv within 25 s under laboratory conditions. Possibilities of further improvement of the detection limit are discussed.
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  • 7
    Electronic Resource
    Electronic Resource
    [s.l.] : Nature Publishing Group
    Nature 355 (1992), S. 434-437 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] We measured total gaseous mercury (TGM) in air over the Atlantic Ocean during four ship cruises in the years 1977-1980 (refs 18, 19). There was a pronounced interhemispherical difference in latitudinal TGM distribution, with 1.96± 0.35 ng m~3 in the Northern Hemisphere and 1.33 ...
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Pure and applied geophysics 118 (1980), S. 964-974 
    ISSN: 1420-9136
    Keywords: Atmospheric chemistry ; Interhemispheric differences ; Mercury
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Atmospheric mercury concentrations were measured during a nautical expedition on the Atlantic Ocean between Hamburg (54°N, 10°E) and Santo Domingo (20°N, 67°W). In addition, samples were taken during flights on a commerical aircraft in the upper and middle troposphere between 60°N and 55°S, mostly over the Pacific Ocean. The data obtained in the lower troposphere over the Northern Atlantic show considerable variation in the Hg concentrations, with values ranging between 1 and 11 ng/m3; the average concentration was found to be 2.8 ng/m3. The upper tropospheric data show an interhemispheric difference with average values of 1.45 ng/m3 and 1.08 ng/m3 in the Northern and Southern Hemisphere, respectively. This suggests that mercury production occurs predominantly over the continents both by natural and anthropogenic processes. The mercury content in aerosols was found to be ≤0.3 ng/m3, or one-tenth of the atmospheric concentration. The data indicate a mean residence time of mercury in the atmosphere of a few months to one year.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 1 (1984), S. 159-169 
    ISSN: 1573-0662
    Keywords: N2O emission ; nitrogen fertilizer ; soil ; subtropics ; atmospheric budget
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Field measurements of N2O emission rates were carried out from August until October 1982 in a subtropical region in Europe, i.e. in Andalusia, Spain. The measurements were performed by using an automatic sampling and analysis technique allowing the semi-continuous determination of N2O emission rates. The N2O emission rates were positively correlated to the soil surface temperature and exhibited a diurnal rhythm with maximum rates in the afternoon and minimum rates in the early morning with average values of 1 μg N2O−N/m2/h for the grass lawn and 15 μg N2O−N/m2/h for cultivated land. Application of urea and ammonium nitrate resulted in elevated N2O emission rates when compared to the unfertilized control. The loss of fertilizer-nitrogen as N2O was 0.18% for urea and 0.04% for NH4NO3 which compares very well with data obtained in a temperate climate (Germany). The total source strength of fertilizer-derived N2O is estimated to be 0.01–2.2 Tg N2O−N per year. The N2O flux from unfertilized natural soils may be as high as 4.5 Tg N2O−N, indicating that the N2O emission from soils contributes significantly to the global N2O budget.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of atmospheric chemistry 2 (1984), S. 1-24 
    ISSN: 1573-0662
    Keywords: NO ; NO2 ; soil ; decomposition ; production ; global budget ; mineral fertilizer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Field measurements of NO and NO2 emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO x detector allowing the determination of minimum flux rates of 2 μg N m-2 h-1 for NO and 3 μg m-2 h-1 for NO2. The NO and NO2 flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO2, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO2. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO2 emission rates were positively correlated with soil moisture in the upper soil layer. The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO2 equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO2. The soil acted as a net sink for ambient air NO and NO2 mixing ratios higher than the equilibrium values and a net source for NO and NO2 mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO2 are formed and destroyed concurrently in the soil. Average flux rates measured on bare unfertilized soils were about 10 μg N m-2 h-1 for NO2 and 8 μg N m-2 h-1 for NO. The NO and NO2 flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO2. Application of mineral fertilizers increased the NO and NO2 emission rates. Highest emission rates were observed for urea followed by NH4Cl, NH4NO3 and NaNO3. The fertilizer loss rates ranged from 0.1% for NaNO3 to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate. The total NO x emission from soil is estimated to be 11 Tg N yr-1. This figure is an upper limit and includes the emission of 7 Tg N yr-1 from natural unfertilized soils, 2 Tg N yr-1 from fertilized soils as well as 2 Tg N yr-1 from animal excreta. Despite its speculative character, this estimation indicates that NO x emission by soil is important for tropospheric chemistry especially in remote areas where the NO x production by other sources is comparatively small.
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