Ground based observations of stratospheric nitrogen dioxide

1980 ◽  
Vol 58 (6) ◽  
pp. 788-802 ◽  
Author(s):  
M. Q. Syed ◽  
A. W. Harrison

Ground based measurements of stratospheric NO2, using four different established methods based on twilight sky observations in the spectral region 437.0–451.0 nm have been made at two locations: Primrose Lake (54.78°N, 110.05°W) and at Priddis (50.86°N, 114.29°W), Alberta, Canada, during March and April 1979. The four methods differ from one another on the basis of: (a) whether or not stratospheric ozone is taken into account, (b) whether a continuous NO2 absorption spectrum or just the absorption at a few discrete wavelengths is used for analysis, and (c) the assumed altitude distribution of NO2 concentration. Two different independently developed altitude distribution models are employed in obtaining the NO2 vertical column abundance and its effective altitude from a set of slant column abundances, measured in the twilight sky at different solar zenith angles in the range 85–96°. A comparison shows that the use of one or the other of these two models alone could introduce a difference of as much as 30% in the derived vertical column abundance.

This study of the thallium fluoride spectrum was undertaken as part of a detailed investigation into the molecular spectra of the series of heavy diatomic fluorides HgF, TlF, PbF and BiF. Whereas the spectra of PbF (Rochester 1936) and BiF (Howell 1936), of which analyses have already been published, contain no very unusual features the TlF spectrum is particularly rich in them, so that it has seemed desirable to extend the original investigation in order to include the other halides of thallium. The absorption spectrum of the fluoride has already been examined by Boizova and Butkow (1936), their findings being summarized below: 1— A continuum at 2200 A appears when the absorption tube is at a temperature of 155° C. Its long-wave edge moves towards the red with increase of temperature, being at 2700 for the unsaturated vapour and at 3400 for the saturated vapour when the temperature is 280° C. They attributed this continuum to the dissociation of Tl 2 F 2 . Tl 2 F 2 → 2TlF + kinetic energy.


1987 ◽  
Vol 65 (9) ◽  
pp. 2013-2018 ◽  
Author(s):  
R. Manoharan ◽  
Sneh K. Dogra

The red shift observed in the absorption spectrum of 2,7-diaminofluorene (DAF) in ether and acetonitrile is either due to the proton-donating capacity of the solute or due to its dispersive interactions with the solvent and a blue shift in methanol and water is due to the proton-accepting nature of DAF. DAF acts as a proton donor in S1 state in all solvents. The red shift in the fluorescence spectrum of the monocation of DAF relative to that of DAF is not because of the —NH2 group becoming more basic but because of the large solvent relaxating in aqueous medium. On the other hand, the monocation of DAF in cyclohexane follows the normal blue shift in the fluorescence spectrum. pKa values for the various prototropic reactions in S0 and S1 states are determined and discussed.


2015 ◽  
Vol 11 (8) ◽  
pp. 1097-1105 ◽  
Author(s):  
R. V. Kochanov ◽  
I. E. Gordon ◽  
L. S. Rothman ◽  
S. W. Sharpe ◽  
T. J. Johnson ◽  
...  

Abstract. In the recent article by Byrne and Goldblatt, "Radiative forcing for 28 potential Archean greenhouse gases", Clim. Past. 10, 1779–1801 (2014), the authors employ the HITRAN2012 spectroscopic database to evaluate the radiative forcing of 28 Archean gases. As part of the evaluation of the status of the spectroscopy of these gases in the selected spectral region (50–1800 cm−1), the cross sections generated from the HITRAN line-by-line parameters were compared with those of the PNNL database of experimental cross sections recorded at moderate resolution. The authors claimed that for NO2, HNO3, H2CO, H2O2, HCOOH, C2H4, CH3OH and CH3Br there exist large or sometimes severe disagreements between the databases. In this work we show that for only three of these eight gases a modest discrepancy does exist between the two databases and we explain the origin of the differences. For the other five gases, the disagreements are not nearly at the scale suggested by the authors, while we explain some of the differences that do exist. In summary, the agreement between the HITRAN and PNNL databases is very good, although not perfect. Typically differences do not exceed 10 %, provided that HITRAN data exist for the bands/wavelengths of interest. It appears that a molecule-dependent combination of errors has affected the conclusions of the authors. In at least one case it appears that they did not take the correct file from PNNL (N2O4 (dimer)+ NO2 was used in place of the monomer). Finally, cross sections of HO2 from HITRAN (which do not have a PNNL counterpart) were not calculated correctly in BG, while in the case of HF misleading discussion was presented there based on the confusion by foreign or noise features in the experimental PNNL spectra.


1938 ◽  
Vol 21 (4) ◽  
pp. 411-430 ◽  
Author(s):  
Aurin M. Chase ◽  
Charles Haig

The absorption spectra of visual purple solutions extracted by various means were measured with a sensitive photoelectric spectrophotometer and compared with the classical visual purple absorption spectrum. Hardening the retinas in alum before extraction yielded visual purple solutions of much higher light transmission in the blue and violet, probably because of the removal of light-dispersing substances. Re-extraction indicated that visual purple is more soluble in the extractive than are the other colored retinal components. However, the concentration of the extractive did not affect the color purity of the extraction but did influence the keeping power. This suggests a chemical combination between the extractive and visual purple. The pH of the extractive affected the color purity of the resulting solution. Over the pH range from 5.5 to 10.0, the visual purple color purity was greatest at the low pH. Temperature during extraction was also effective, the color purity being greater the higher the temperature, up to 40°C. Drying and subsequent re-dissolving of visual purple solutions extracted with digitalin freed the solution of some protein impurities and increased its keeping power. Dialysis against distilled water seemed to precipitate visual purple from solution irreversibly. None of the treatments described improved the symmetry of the unbleached visual purple absorption spectrum sufficiently for it to resemble the classical absorption spectrum. Therefore it is very likely that the classical absorption spectrum is that of the light-sensitive group only and that the absorption spectra of our purest unbleached visual purple solutions represent the molecule as a whole.


An analysis of the 1650-1350 Å band system of nitrogen dioxide has been carried out. A pattern of band spacings and intensities is found that is complex but regular. It is shown that this pattern is qualitatively, and to a large extent quantitatively, just what would be expected for a transition in which the shape of the molecule changes from bent to linear. The transition is a parallel one and the upper state has 2 Σ + u symmetry. The symmetrical stretching frequency is increased from its ground-state value to ca. 1420 cm -1 in the upper state. The upper-state bending frequency is ca. 600 cm -1 . The N — O length is decreased from its groundstate value, probably to 1·1(3) Å. The upper state resembles closely the ground state of NO + 2 . The transition is to be classed as one of the Rydberg transitions leading to the first ionization potential of NO 2 ; and the orbital to which the odd electron is transferred in the transition is (pσ) in type. The anharmonic constant g 22 for the linear upper state is found to be 2·(3) cm -1 . Other Rydberg transitions may well be present in the region, but have not been definitely identified.


2020 ◽  
Author(s):  
Ioan Bratu ◽  
Constantin Marutoiu ◽  
Antonio Hernanz ◽  
Olivia Florena Nemes ◽  
M Tiplic ◽  
...  

Abstract Three Transylvanian fragments of some 18th century Saxon tiles obtained from excavations in the Central Railway Station Square in Sibiu (Romania) have been studied by Raman microscopy, FTIR, SEM-EDX and XRF techniques. A lead-rich aluminosilicate was found to have been used as enamel/glaze for the tile fragments. An analysis of the band components of the Raman spectra of the enamel of one fragment in the 400–1200 cm− 1 spectral region indicates that their processing temperature was in the 600–800 °C range, in good agreement with the temperature obtained from FTIR spectra of the other two tile fragments.


1909 ◽  
Vol 29 ◽  
pp. 68-74
Author(s):  
Robert A. Houstoun ◽  
Alexander S. Russell

In the third volume of his Spectroscopie, p. 91, Kayser has raised the question whether on mixing two coloured solutions which do not act on one another chemically the absorption spectrum of each of the components remains unchanged. Melde thought he had discovered such an effect; he stated that when a solution of carmine in ammonia which has two sharp bands in the green, was added to a solution of potassium dichromate which absorbs the violet end of the spectrum, or to an ammoniacal solution of copper sulphate which absorbs the red end, that the carmine bands were in each case displaced towards the end absorption in question. He ascribed this to a physical action between the molecules. It was, however, pointed out by Schuster that a shift of this nature would be seen if, instead of mixing, the one solution was merely placed behind the other. Bostwick and Krüss repeated Melde's work, and came to the conclusion that there was a real shift in addition to the apparent shift pointed out by Schuster. Since then additional evidence has been adduced by Formánek and has been quoted by Kayser in the section cited above. The object of the research recorded in this paper was to investigate those cases with the most accurate means possible, and, if a shift was established, to decide if it was physical.


1977 ◽  
Vol 213 ◽  
pp. L139 ◽  
Author(s):  
R. G. Danehy ◽  
B. L. Lutz ◽  
T. Owen ◽  
T. W. Scattergood ◽  
W. Goetz

2015 ◽  
Vol 8 (6) ◽  
pp. 2417-2435 ◽  
Author(s):  
F. Tack ◽  
F. Hendrick ◽  
F. Goutail ◽  
C. Fayt ◽  
A. Merlaud ◽  
...  

Abstract. We present an algorithm for retrieving tropospheric nitrogen dioxide (NO2) vertical column densities (VCDs) from ground-based zenith–sky (ZS) measurements of scattered sunlight. The method is based on a four-step approach consisting of (1) the differential optical absorption spectroscopy (DOAS) analysis of ZS radiance spectra using a fixed reference spectrum corresponding to low NO2 absorption, (2) the determination of the residual amount in the reference spectrum using a Langley-plot-type method, (3) the removal of the stratospheric content from the daytime total measured slant column based on stratospheric VCDs measured at sunrise and sunset, and simulation of the rapid NO2 diurnal variation, (4) the retrieval of tropospheric VCDs by dividing the resulting tropospheric slant columns by appropriate air mass factors (AMFs). These steps are fully characterized and recommendations are given for each of them. The retrieval algorithm is applied on a ZS data set acquired with a multi-axis (MAX-) DOAS instrument during the Cabauw (51.97° N, 4.93° E, sea level) Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI) held from 10 June to 21 July 2009 in the Netherlands. A median value of 7.9 × 1015 molec cm−2 is found for the retrieved tropospheric NO2 VCDs, with maxima up to 6.0 × 1016 molec cm−2. The error budget assessment indicates that the overall error σTVCD on the column values is less than 28%. In the case of low tropospheric contribution, σTVCD is estimated to be around 39% and is dominated by uncertainties in the determination of the residual amount in the reference spectrum. For strong tropospheric pollution events, σTVCD drops to approximately 22% with the largest uncertainties on the determination of the stratospheric NO2 abundance and tropospheric AMFs. The tropospheric VCD amounts derived from ZS observations are compared to VCDs retrieved from off-axis and direct-sun measurements of the same MAX-DOAS instrument as well as to data from a co-located Système d'Analyse par Observations Zénithales (SAOZ) spectrometer. The retrieved tropospheric VCDs are in good agreement with the different data sets with correlation coefficients and slopes close to or larger than 0.9. The potential of the presented ZS retrieval algorithm is further demonstrated by its successful application on a 2-year data set, acquired at the NDACC (Network for the Detection of Atmospheric Composition Change) station Observatoire de Haute Provence (OHP; Southern France).


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