| 1. |
- Hassler, B., et al.
(författare)
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Past changes in the vertical distribution of ozone - Part 1: Measurement techniques, uncertainties and availability
- 2014
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 7:5, s. 1395-1427
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Tidskriftsartikel (refereegranskat)abstract
- Peak stratospheric chlorofluorocarbon (CFC) and other ozone depleting substance (ODS) concentrations were reached in the mid- to late 1990s. Detection and attribution of the expected recovery of the stratospheric ozone layer in an atmosphere with reduced ODSs as well as efforts to understand the evolution of stratospheric ozone in the presence of increasing greenhouse gases are key current research topics. These require a critical examination of the ozone changes with an accurate knowledge of the spatial (geographical and vertical) and temporal ozone response. For such an examination, it is vital that the quality of the measurements used be as high as possible and measurement uncertainties well quantified. In preparation for the 2014 United Nations Environment Programme (UNEP)/World Meteorological Organization (WMO) Scientific Assessment of Ozone Depletion, the SPARC/IO3C/IGACO-O3/NDACC (SI2N) Initiative was designed to study and document changes in the global ozone profile distribution. This requires assessing long-term ozone profile data sets in regards to measurement stability and uncertainty characteristics. The ultimate goal is to establish suitability for estimating long-term ozone trends to contribute to ozone recovery studies. Some of the data sets have been improved as part of this initiative with updated versions now available. This summary presents an overview of stratospheric ozone profile measurement data sets (ground and satellite based) available for ozone recovery studies. Here we document measurement techniques, spatial and temporal coverage, vertical resolution, native units and measurement uncertainties. In addition, the latest data versions are briefly described (including data version updates as well as detailing multiple retrievals when available for a given satellite instrument). Archive location information for each data set is also given.
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| 2. |
- Sheese, P. E., et al.
(författare)
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Validation of ACE-FTS version 3.5 NO y species profiles using correlative satellite measurements
- 2016
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 9:12, s. 5781-5810
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Tidskriftsartikel (refereegranskat)abstract
- The ACE-FTS (Atmospheric Chemistry Experiment - Fourier Transform Spectrometer) instrument on the Canadian SCISAT satellite, which has been in operation for over 12 years, has the capability of deriving stratospheric profiles of many of the NOy (N + NO + NO2 + NO3 + 2 x N2O5 + HNO3 + HNO4 + ClONO2 + BrONO2) species. Version 2.2 of ACE-FTS NO, NO2, HNO3, N2O5, and ClONO2 has previously been validated, and this study compares the most recent version (v3.5) of these five ACE-FTS products to spatially and temporally coincident measurements from other satellite instruments - GOMOS, HALOE, MAESTRO, MIPAS, MLS, OSIRIS, POAM III, SAGE III, SCIAMACHY, SMILES, and SMR. For each ACE-FTS measurement, a photochemical box model was used to simulate the diurnal variations of the NOy species and the ACE-FTS measurements were scaled to the local times of the coincident measurements. The comparisons for all five species show good agreement with correlative satellite measurements. For
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| 3. |
- Imai, Koji, et al.
(författare)
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Validation of ozone data from the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES)
- 2013
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Ingår i: Journal of Geophysical Research. - : American Geophysical Union (AGU). - 0148-0227 .- 2156-2202 .- 2169-897X. ; 118:11, s. 5750-5769
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Tidskriftsartikel (refereegranskat)abstract
- The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) onboard the International Space Station provided global measurements of ozone profiles in the middle atmosphere from 12 October 2009 to 21 April 2010. We present validation studies of the SMILES version 2.1 ozone product based on coincidence statistics with satellite observations and outputs of chemistry and transport models (CTMs). Comparisons of the stratospheric ozone with correlative data show agreements that are generally within 10%. In the mesosphere, the agreement is also good and better than 30% even at a high altitude of 73km, and the SMILES measurements with their local time coverage also capture the diurnal variability very well. The recommended altitude range for scientific use is from 16 to 73km. We note that the SMILES ozone values for altitude above 26km are smaller than some of the correlative satellite datasets; conversely the SMILES values in the lower stratosphere tend to be larger than correlative data, particularly in the tropics, with less than 8% difference below similar to 24km. The larger values in the lower stratosphere are probably due to departure of retrieval results between two detection bands at altitudes below 28km; it is similar to 3% at 24km and is increasing rapidly down below.
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| 4. |
- Khosravi, Maryam, 1975, et al.
(författare)
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Diurnal variation of stratospheric and lower mesospheric HOCl, ClO and HO2 at the equator: comparison of 1-D model calculations with measurements by satellite instruments
- 2013
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Ingår i: Atmospheric Chemistry and Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 13:15, s. 7587-7606
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Tidskriftsartikel (refereegranskat)abstract
- The diurnal variation of HOCl and the related species ClO, HO2 and HCl measured by satellites has been compared with the results of a one-dimensional photochemical model. The study compares the data from various limb-viewing instruments with model simulations from the middle stratosphere to the lower mesosphere. Data from three sub-millimetre instruments and two infrared spectrometers are used, namely from the Sub-Millimetre Radiometer (SMR) on board Odin, the Microwave Limb Sounder (MLS) on board Aura, the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES) on the International Space Station, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board ENVISAT, and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on board SCISAT. Inter-comparison of the measurements from instruments on sun-synchronous satellites (SMR, MLS, MIPAS) and measurements from solar occultation instruments (ACE-FTS) is challenging since the measurements correspond to different solar zenith angles (or local times). However, using a model which covers all solar zenith angles and data from the SMILES instrument which measured at all local times over a period of several months provides the possibility to verify the model and to indirectly compare the diurnally variable species. The satellite data were averaged for latitudes of 20 degrees S to 20 degrees N for the SMILES observation period from November 2009 to April 2010 and were compared at three altitudes: 35, 45 and 55 km. Besides presenting the SMILES data, the study also shows a first comparison of the latest MLS data (version 3.3) of HOCl, ClO, and HO2 with other satellite observations, as well as a first evaluation of HO2 observations made by Odin/SMR. The MISU-1D model has been carefully initialised and run for conditions and locations of the observations. The diurnal cycle features for the species investigated here are generally well reproduced by the model. The satellite observations and the model agree well in terms of absolute mixing ratios. The differences between the day and night values of the model are in good agreement with the observations although the amplitude of the HO2 diurnal variation is 10-20 % lower in the model than in the observations. In particular, the data offered the opportunity to study the reaction ClO+HO2 -> HOCl+O-2 in the lower mesosphere at 55 km. At this altitude the HOCl night-time variation depends only on this reaction. The result of this analysis points towards a value of the rate constant within the range of the JPL 2006 recommendation and the upper uncertainty limit of the JPL 2011 recommendation at 55 km.
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| 5. |
- Baron, P., et al.
(författare)
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Measurement of stratospheric and mesospheric winds with a submillimeter wave limb sounder: results from JEM/SMILES and simulation study for SMILES-2
- 2015
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Ingår i: Proceedings of SPIE - The International Society for Optical Engineering. - : SPIE. - 0277-786X .- 1996-756X. - 9781628418491 ; 9639, s. Article no. 96390N-
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Konferensbidrag (refereegranskat)abstract
- Satellite missions for measuring winds in the troposphere and thermosphere will be launched in a near future. There is no plan to observe winds in the altitude range between 30-90 km, though middle atmospheric winds are recognized as an essential parameter in various atmospheric research areas. Sub-millimetre limb sounders have the capability to fill this altitude gap. In this paper, we summarize the wind retrievals obtained from the Japanese Superconducting Submillimeter Wave Limb Emission Sounder (SMILES) which operated from the International Space Station between September 2009 and April 2010. The results illustrate the potential of such instruments to measure winds. They also show the need of improving the wind representation in the models in the Tropics, and globally in the mesosphere. A wind measurement sensitivity study has been conducted for its successor, SMILES-2, which is being studied in Japan. If it is realized, sub-millimeter and terahertz molecular lines suitable to determine line-of-sight winds will be measured. It is shown that with the current instrument definition, line-of-sight winds can be observed from 20 km up to more than 160 km. Winds can be retrieved with a precision better than 5 m s(-1) and a vertical resolution of 2-3 km between 35-90 km. Above 90 km, the precision is better than 10 m s(-1) with a vertical resolution of 3-5 km. Measurements can be performed day and night with a similar sensitivity. Requirements on observation parameters such as the antenna size, the satellite altitude are discussed. An alternative setting for the spectral bands is examined. The new setting is compatible with the general scientific objectives of the mission and the instrument design. It allows to improve the wind measurement sensitivity between 35 to 90 km by a factor 2. It is also shown that retrievals can be performed with a vertical resolution of 1 km and a precision of 5-10 m s(-1) between 50 and 90 km. RAGAM A, 1953, PHYSICAL REVIEW, V92, P1448
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| 6. |
- Baron, P., et al.
(författare)
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Performance Assessment of Superconducting Submillimeter-Wave Limb-Emission Sounder-2 (SMILES-2)
- 2019
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Ingår i: International Geoscience and Remote Sensing Symposium (IGARSS). ; , s. 7556-7559
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Konferensbidrag (refereegranskat)abstract
- © 2019 IEEE. SMILES2 is a mission prepared for the next call-for-proposals for JAXA/ISAS M-class scientific satellite mission. It aims at scanning the atmospheric limb from 20 to 160 km above the surface at frequencies near 700 GHz and 2 THz. It could provide the temperature and composition as well as, for the first time, the horizontal wind vector above 30 km, the atomic oxygen in its ground state above 90 km, and the atmospheric density and the geomagnetic field vector near the mesopause. The mission is proposed for the 2nd time and the instrument design has been improved for accounting for the recommendations of the review committee. In this publication, we discuss the measurement performances assessed from simulations including latest results showing the mission potential for measuring the geomagnetic field between 70-110 km.
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| 7. |
- Baron, P., et al.
(författare)
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The level 2 research product algorithms for the superconducting submillimeter-wave limb-emission sounder (SMILES)
- 2011
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Ingår i: Atmospheric Measurement Techniques Discussions. - : Copernicus GmbH. - 1867-8610. ; 4:3, s. 3593-3645
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Tidskriftsartikel (refereegranskat)abstract
- This paper describes the algorithms of the level-2 research (L2r) processingchain developed for the Superconducting Submillimeter-Wave Limb-EmissionSounder (SMILES). The chain has been developed in parallel to the operationalchain for conducting researches on calibration and retrieval algorithms. L2rchain products are available to the scientific community. The objective ofversion 2 is the retrieval of the vertical distribution of trace gases in thealtitude range of 18-90 km. An theoretical error analysis is conducted toestimate the retrieval feasibility of key parameters of the processing:line-of-sight elevation tangent altitudes (or angles), temperature and O3 profiles. The line-of-sight tangent altitudes are retrievedbetween 20 and 50 km from the strong ozone (O3) line at 625.371 GHz,with low correlation with the O3 volume-mixing ratio and temperatureretrieved profiles. Neglecting the non-linearity of the radiometric gain inthe calibration procedure is the main systematic error. It is large for theretrieved temperature (between 5-10 K). Therefore, atmospheric pressure cannot be derived from the retrieved temperature, and, then, in the altituderange where the line-of-sight tangent altitudes are retrieved, the retrievedtrace gases profiles are found to be better represented on pressure levelsthan on altitude levels. The error analysis for the retrieved HOCl profiledemonstrates that best results for inverting weak lines can be obtained byusing narrow spectral windows. Future versions of the L2r algorithms willimprove the temperature/pressure retrievals and also provide information inthe upper tropospheric/lower stratospheric region (e.g., water vapor, icecontent, O3) and on stratospheric and mesospheric line-of-sight winds.
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| 8. |
- Baron, P., et al.
(författare)
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The Level 2 research product algorithms for the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES)
- 2011
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 4, s. 2105-2124
-
Tidskriftsartikel (refereegranskat)abstract
- This paper describes the algorithms of the level-2 research (L2r) processing chain developed for the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES). The chain has been developed in parallel to the operational chain for conducting researches on calibration and retrieval algorithms. L2r chain products are available to the scientific community. The objective of version 2 is the retrieval of the vertical distribution of trace gases in the altitude range of 18–90 km. A theoretical error analysis is conducted to estimate the retrieval feasibility of key parameters of the processing: line-of-sight elevation tangent altitudes (or angles), temperature and ozone profiles. While pointing information is often retrieved from molecular oxygen lines, there is no oxygen line in the SMILES spectra, so the strong ozone line at 625.371 GHz has been chosen. The pointing parameters and the ozone profiles are retrieved from the line wings which are measured with high signal to noise ratio, whereas the temperature profile is retrieved from the optically thick line center. The main systematic component of the retrieval error was found to be the neglect of the non-linearity of the radiometric gain in the calibration procedure. This causes a temperature retrieval error of 5–10 K. Because of these large temperature errors, it is not possible to construct a reliable hydrostatic pressure profile. However, as a consequence of the retrieval of pointing parameters, pressure induced errors are significantly reduced if the retrieved trace gas profiles are represented on pressure levels instead of geometric altitude levels. Further, various setups of trace gas retrievals have been tested. The error analysis for the retrieved HOCl profile demonstrates that best results for inverting weak lines can be obtained by using narrow spectral windows.
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| 9. |
- Ejiri, M.K., et al.
(författare)
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Validation of the Improved Limb Atmospheric Spectrometer-II (ILAS-II) Version 1.4 nitrous oxide and methane profiles
- 2006
-
Ingår i: Journal of Geophysical Research. - 0148-0227 .- 2156-2202. ; 111:D22
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Tidskriftsartikel (refereegranskat)abstract
- This study assesses polar stratospheric nitrous oxide (N(2)O) and methane (CH(4)) data from the Improved Limb Atmospheric Spectrometer-II (ILAS-II) on board the Advanced Earth Observing Satellite-II (ADEOS-II) retrieved by the Version 1.4 retrieval algorithm. The data were measured between January and October 2003. Vertical profiles of ILAS-II volume mixing ratio (VMR) data are compared with data from two balloon-borne instruments, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) and the MkIV instrument, as well as with two satellite sensors, the Odin Sub-Millimetre Radiometer (SMR) for N(2)O and the Halogen Occultation Experiment (HALOE) for CH(4). Relative percentage differences between the ILAS-II and balloon/satellite data and their median values are calculated in 10-ppbv-wide bins for N(2)O (from 0 to 400 ppbv) and in 0.05-ppmv-wide bins for CH(4) (from 0 to 2 ppmv) in order to assess systematic differences between the ILAS-II and balloon/satellite data. According to this study, the characteristics of the ILAS-II Version 1.4 N(2)O and CH(4) data differ between hemispheres. For ILAS-II N(2)O VMR larger than 250 ppbv, the ILAS-II N(2)O agrees with the balloon/SMR N(2)O within +/- 20% in both hemispheres. The ILAS-II N(2)O in the VMR range from 30-50 to 250 ppbv (corresponding to altitudes of similar to 17-30 km in the Northern Hemisphere (NH, mainly outside the polar vortex) and similar to 13-21 km in the Southern Hemisphere (SH, mainly inside the polar vortex) is smaller by similar to 10-30% than the balloon/SMR N(2)O. For ILAS-II N(2)O VMR smaller than 30 ppbv (>similar to 21 km) in the SH, the differences between the ILAS-II and SMR N(2)O are within +/- 10 ppbv. For ILAS-II CH(4) VMR larger than 1 ppmv (similar to 30 km) and the ILAS-II CH(4) for its VMR smaller than 1 ppmv (>similar to 25 km) only in the NH, are abnormally small compared to the balloon/satellite data.
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| 10. |
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| 11. |
- Komaguchi, K., et al.
(författare)
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ESR and theoretical studies of trimer radical cations of coronene
- 2006
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 63:1, s. 76-84
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Tidskriftsartikel (refereegranskat)abstract
- Highly resolved ESR spectra of monomer, dimer and trimer radical cations of coronene (C24H12) were observed at room temperature for a solution of 1,1,1,3,3,3-hexafluoro-2-propan-2-ol (HFP) containing thallium(III) trifluoroacetate as oxidant. The spectra consisting of multiple lines with isotropic 1H-hyperfine splitting (hfs) constants of 0. 0766 mT (24H) and 0.013 mT (6H) were attributable to a mixture of the dimer with the trimer radical cations, (C24H12)2+ and (C24H12)3+. For (C24H12)2+, the 1H-hfs constant agreed well with the reported value, 0.077 mT. However, for (C 24H12)3+, the values were significantly different from the reported ones, 0.117 mT (12H) and 0.020 mT (24H), by Ohya Nishiguchi et al. [H. Ohya-Nishiguchi, H. Ide, N. Hirota, Chem. Phys. Lett. 66 (1979) 581], but rather similar to those reported by Willigen et al. [H. van Willigen, E. De Boer, J.T. Cooper, W.F. Forbes, J. Chem . Phys. 49 (1968) 1190]. In conflict with Willigen's report, however, no ESR line broadening which has been ascribed to a low stationary concentration of (C 24H12)3+ was detected. Based on ab initio MO calculations for benzene as a compact model of C24H 12, the structure of (C24H12)3+ was investigated in terms of the observed 1H-hfs constants. A staggered sandwich C2v structure was suggested being at the "global" minimum for the benzene trimer cation. In the structure, the unpaired electron spin is predominantly localized to the central ring, which is qualitatively in agreement with the previous ESR results of (C 24H12)3+ by Ohya-Nishiguchi et al. In addition, as a "local" minimum, the benzene trimer was indicated to have a slipped sandwich Cs structure, which is less stable by ca. 19 kJ mol-1 than the "global" minimum. In this structure, the unpaired electron spin was nearly equally distributed on both the central and one of the two side C24H12 molecules. The observed 1H-hfs constants were possibly attributable to the (C 24H12)3+ cation with the analogous slipped sandwich Cs structure.
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| 12. |
- Liu, W, et al.
(författare)
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Structure and dynamics of radicals in zeolite matrices : ESR and theoretical studies
- 2003
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Ingår i: Applied Magnetic Resonance. - 0937-9347 .- 1613-7507. ; 24:3-4, s. 285-302
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Tidskriftsartikel (refereegranskat)abstract
- Amine radical cations of the type R3N.+ and [R3NCH2](.+), R = CH3, C2H5, C3H7, and nitric oxide, NO, have been used to probe the bonding to the surface and the dynamics of the radicals trapped in the confined space of cages or channels in the zeolite. Regular continuous-wave electron spin resonance (ESR) was employed to study the internal motion of the cation radicals formed by gamma-irradiation of amines and related ammonium ions, introduced during the synthesis of the zeolites Al-offretite, SAPO-37, SAPO-42 and AlPO4-5. The ESR spectra of [(CH3)(3)NCH2](.+) radical cation in several studied systems changed reversibly with temperature, indicating dynamical effects. Free rotation about the >N-CH2 bond of the [(CH3)(3)NCH2](.+) species was found to occur in the temperature range of 110 to 300 K, while the rotation about the >N-CH3 bonds was hindered. The observations confirm the theoretical prediction on the basis of density functional theory calculations, which indicate that the corresponding barriers are of the order of 0.3 and 7 kJ/mol, respectively. The radical cations of the type R3N.+ with R = C2H5, C3H7 were found to undergo a different type of dynamics, involving a two-jump process of the methylene hydrogens next to the nitrogen. A cage or channel size effect on the stability and molecular dynamics was inferred in some cases. Pulsed ESR was employed to study the (NO)(2) triplet-state dimers in Na-A type zeolite, with the purpose to resolve the interaction with surface groups, and to elucidate the role of the zeolite on stabilizing the triplet rather than the usual singlet state. Measurements performed at 5 K gave rise to Fourier transform spectra that were assigned to the dimer species interacting with one or more Na-23 nuclei, with approximative parameters A(Na-23) = (4.6, 4.6, 8.2) MHz and Q(Na-23) = (-0.3, -0.3, 0.6) MHz for the hyperfine and nuclear quadrupole coupling tensors, respectively. The values are of similar magnitude as those determined for the NO---Na+ complex. The stability of the triplet-state structure was attributed to an unusual geometric structure imposed by the zeolite matrix, with the N-O bonds along a line as in [O-N---Na+---N-O], which according to UHF ab initio calculations has a triplet ground state.
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| 13. |
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| 14. |
- Baron, P., et al.
(författare)
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Potential for the measurement of mesosphere and lower thermosphere (MLT) wind, temperature, density and geomagnetic field with Superconducting Submillimeter-Wave Limb-Emission Sounder 2 (SMILES-2)
- 2020
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Ingår i: Atmospheric Measurement Techniques. - : Copernicus GmbH. - 1867-1381 .- 1867-8548. ; 13:1, s. 219-237
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Tidskriftsartikel (refereegranskat)abstract
- Submillimeter-Wave Limb-Emission Sounder 2 (SMILES-2) is a satellite mission proposed in Japan to probe the middle and upper atmosphere (20-160 km). The main instrument is composed of 4K cooled radiometers operating near 0.7 and 2 THz. It could measure the diurnal changes of the horizontal wind above 30 km, temperature above 20 km, ground-state atomic oxygen above 90 km and atmospheric density near the mesopause, as well as abundance of about 15 chemical species. In this study we have conducted simulations to assess the wind, temperature and density retrieval performance in the mesosphere and lower thermosphere (60- 110 km) using the radiometer at 760 GHz. It contains lines of water vapor (H2O), molecular oxygen (O2) and nitric oxide (NO) that are the strongest signals measured with SMILES-2 at these altitudes. The Zeeman effect on the O2 line due to the geomagnetic field (B) is considered; otherwise, the retrieval errors would be underestimated by a factor of 2 above 90 km. The optimal configuration for the radiometer's polarization is found to be vertical linear. Considering a retrieval vertical resolution of 2.5 km, the line-of-sight wind is retrieved with a precision of 2-5ms-1 up to 90 km and 30ms-1 at 110 km. Temperature and atmospheric density are retrieved with a precision better than 5K and 7% up to 90 km (30K and 20% at 110 km). Errors induced by uncertainties on the vector B are mitigated by retrieving it. The retrieval of B is described as a side-product of the mission. At high latitudes, precisions of 30-100 nT on the vertical component and 100-300 nT on the horizontal one could be obtained at 85 and 105 km (vertical resolution of 20 km). SMILES-2 could therefore provide the first measurements of B close to the electrojets' altitude, and the precision is enough to measure variations induced by solar storms in the auroral regions.
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| 15. |
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| 16. |
- Itagaki, Y, et al.
(författare)
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An EPR and ENDOR study of quartet state nitrogen atoms trapped in irradiated NaN3 powder
- 2001
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 3:19, s. 4444-4448
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Tidskriftsartikel (refereegranskat)abstract
- The nature of quartet state nitrogen atoms formed in gamma -irradiated NaN3 powder was investigated by EPR, ENDOR and ENDOR-induced EPR (EIE). The ENDOR spectrum observed at 110 K clearly showed two sets of N-14 signal pairs centered at a(N)/2 (half the N-14-hyperfine splitting) and at 3a(N)/2, strongly suggesting the existence of quartet state N-14 atoms (S-4(3/2)). At 160 K, the EPR spectrum exhibited a clear fine structure. accompanied by a hyperfine coupling due to N-14. The zero-field splitting, D, gradually increased with decreasing temperature from 170 to 40 K, and then became nearly constant. The temperature dependence of D was explained in terms of a local lattice vibration coupled with spin states of N-14 atoms. At below 95 K, a new fine structure with larger D was observed. The observed two D-values were attributed to 14N atoms located at two different interstitial sites in the monoclinic NaN3 structure.
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| 17. |
- Kasai, Y., et al.
(författare)
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Stratospheric Ozone Isotope Enrichment Studied by Sub-Millimeter Wave Heterodyne Radiometry: The Observation Capabilities of SMILES
- 2006
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Ingår i: IEEE Transactions on Geoscience and Remote Sensing. - 0196-2892 .- 1558-0644. ; 44:3, s. 676-693
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Tidskriftsartikel (refereegranskat)abstract
- The isotopic ratio of molecules often provides valuable information about past or presently occurring processes in the atmosphere because chemical and physical processes may give rise to isotope fractionation of molecular species. However, there are so far no published satellite measurements on the spatial and temporal variations of ozone isotopes in the stratosphere. Spectroscopic remote sensing methods can theoretically be used to observe ozone isotope fractionation on a global scale, but sufficient accuracy has not yet been achieved. A new generation of submillimeter-wave receivers employing sensitive superconductor-insulator - superconductor (SIS) detector technology will provide new opportunities for precise remote sensing measurements of ozone isotopes on a global scale. We have estimated the observation capabilities of two different SIS instruments, namely the space-station-borne Japanese Experimental Module/Sub-Millimeter-wave Limb Emission Sounder (JEM/SMILES) instrument, currently planned for launch in 2008, as well as the airborne Submillimeter wave Atmospheric Sounder/Airborne Submillimeter SIS Radiometer (SUMAS/ASUR) sensor. Measurements of the airborne sensor, conducted in 1996, are presented in order to demonstrate the detection of normal-O 3 and asymmetric-18-O 3 in the SMILES frequency bands. In the ideal case, JEM/SMILES has the capability to measure the ozone isotope enrichment (δ M O 3 ) in the middle stratosphere with a precision of ∼12%∼11%‰‰, and ∼9%‰, for asymmetric-18-O 3 , symmetric-17-O 3 , asymmetric-17-O 3 , respectively, for a daily zonal mean product with resolution of 10° in latitude. The systematic error, including contributions of all instrumental and spectroscopic uncertainties, is estimated to be of the order of 100%‰ to 200%‰ and should be reduced by prelaunch laboratory measurements and in-flight calibrations. A remaining bias in the SMILES measurements will have to be quantified by dedicated validation campaigns. JEM/SMILES should then be capable to provide valuable information on the global distribution and seasonal variation of ozone isotope fractionation in the stratosphere. This new technology will allow us to shed new light on this still open issue in atmospheric sciences. © 2006 IEEE.
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| 18. |
- Komaguchi, K, et al.
(författare)
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An ESR and ENDOR study of irradiated 6Li-formate
- 2007
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 66:3, s. 754-760
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Tidskriftsartikel (refereegranskat)abstract
- Lithium formate (6LiOOCH·H2O), 95% 6Li enrichment, combined with an exchange of crystallization water with D2O was investigated. The ESR spectrum of the radiation induced free radicals stable at room temperature consists of a singlet with a narrow line width, 0.92 mT. 6Li has smaller magnetic moment and nuclear spin, which resulted in the narrower line width accompanied with an increase in peak amplitude. In comparison with lithium formate with natural isotopic composition, 6Li (7.5%, I = 1) and 7Li (92.5%, I = 3/2), the sensitivity was increased by a factor of two. With optimised spectrometer settings 6Li formate had seven times higher sensitivity compared to alanine. Therefore this material is proposed as a dosimeter material in a dose range down to 0.1 Gy. The g and the 13C-hyperfine (hf) tensors of the CO2- radical anion, major paramagnetic products, were evaluated to be g = (2.0037, 1.9975, 2.0017), and A(13C) = (465.5, 447.5, 581.3) MHz for polycrystalline samples at room temperature. Furthermore, the 1H-hf and 6Li-hf tensors observed for the surroundings of CO2- by ENDOR technique were in fairly good agreement with DFT calculations. The CO2- radicals are found to be so stable that the formate is applicable to the ESR dosimetry, because of fully relaxing in a fully relaxed geometrical structure of the CO2- component and remaining tight binding with the surroundings after the H atom detachment from HCO2-. © 2006 Elsevier B.V. All rights reserved.
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| 19. |
- Liu, W, et al.
(författare)
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Cage effect on stability and molecular dynamics of [(CH3)(3)N](center dot+) and [(CH3)(3)NCH2](center dot+) generated in gamma-irradiated zeolites
- 2001
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 3:17, s. 3532-3535
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Tidskriftsartikel (refereegranskat)abstract
- An EPR study was carried out to elucidate the zeolite cage effect on the stability and molecular dynamics of [(CH3)(3)N](.+) and [(CH3)(3)NCH2](.+) radical cations generated in gamma -irradiated Al-offretite, SAPO-37 and SAPO-42, which contained (CH3)(4)N+ ions as organic template. The [(CH3)(3)N](.+) radical cation was stable at room temperature when it was generated in relatively small size cages such as the sodalite cages of SAPO-37 and the beta -cages of SAPO-42. On the other hand, the [(CH3)(3)NCH2](.+) radical cation was stable not only in the sodalite cages of SAPO-37, but also in relatively large cages such as gmelinite cages or the main channels of Al-offretite and the alpha -cages of SAPO-42. Strongly temperature dependent EPR spectra were observed for the [(CH3)(3)NCH2](.+) radical cation stabilized in Al-offretite and SAPO-42. They were successfully analyzed by a spectral simulation method assuming a three-site exchange for the methyl protons. The evaluated exchange rates were in the order SAPO-37 (sodalite cages) < Al-offretite (gmelinite cages or main channels) < SAPO-42 (alpha -cages) in the temperature range 110-300 K.
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| 20. |
- Liu, W., et al.
(författare)
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Structure and dynamics of [(CH3)3N-CH2]+· radical generated in ?- irradiated Al-offretite
- 2000
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 2:11, s. 2515-2519
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Tidskriftsartikel (refereegranskat)abstract
- An EPR study was carried out to investigate the structure and motional dynamics of the [(CH3)3N-CH2]+· radical formed in a ?-irradiated Al- offretite. Strongly temperature-dependent EPR spectra were observed in the temperature range between 4 and 300 K. The observed 1H hyperfine (hf) splitting was a1 = 0.46 mT for three magnetically equivalent hydrogens, one of each methyl group at 110 K and a1 = 0.15 mT for three of each methyl group at 300 K, the hf splittings due to two equivalent CH2 hydrogens and the central 14N were a2 = 2.24 and a3 = 0.35 mT, respectively, independent of the temperature. This result suggests that rotation of the methyl group around the N-CH3 bond is responsible for the temperature dependent line shapes. Assuming a three-site jump model in which three methyl protons interchange their positions with each other, the EPR line shapes were successfully analyzed by a simulation method using the jump rate as a variable parameter in the temperature range from 140 to 270 K. The rate was found to increase from 7.0 x 106 s-1 (140 K) to 4.1 x 108 s-1 (270 K) with temperature. From an Arrhenius plot of the rate constants, an activation energy of 8.1 kJ mol-1 was evaluated for the methyl group rotation of [(CH3)3N-CH2]+· in Al-offretite.
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| 21. |
- Liu, W, et al.
(författare)
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Structure and dynamics of triethylamine and tripropylamine radical cations generated in AlPO4-5 by ionizing radiation : an EPR and MO study
- 2001
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - 1463-9076 .- 1463-9084. ; 3:9, s. 1611-1616
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Tidskriftsartikel (refereegranskat)abstract
- An EPR study was carried out to investigate both the structure and molecular dynamics of triethylamine (Et3N) and tripropylamine (Pr3N) radical cations generated in gamma -irradiated AlPO4-5 from neutral mother molecules incorporated as an organic template. Both Et3N+. and Pr3N+. radical cations were stable at 300 K and showed strongly temperature-dependent EPR spectral line-shapes in the temperature range from 77 to 300 K. The spectral change was successfully explained by assuming a two-site exchange model in which two inequivalent beta -hydrogens interchange their positions with each other. The experimental spectra were quantitatively analyzed by a simulation method using the exchange rate as a variable parameter. From an Arrhenius plot of the rate constants, activation energies of 9.1 and 11.4 kJ mol(-1) were evaluated for Et3N+. and Pr3N+. in AlPO4-5, respectively.
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| 22. |
- Lund, Anders, et al.
(författare)
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Automatic fitting to 'powder' EPR spectra of coupled paramagnetic species employing Feynman's theorem
- 2006
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 63:4, s. 830-835
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Tidskriftsartikel (refereegranskat)abstract
- A previous automatic fitting procedure of EPR spectra has been extended with the purpose to characterise coupled paramagnetic complexes in powders and frozen solutions. The theoretical EPR spectra were obtained by matrix diagonalization of a general spin Hamiltonian. A least-squares fitting procedure using analytical derivatives of the calculated spectrum with respect to the spectroscopic, fine structure, nuclear quadrupole, electron-electron, and hyperfine coupling tensors was used to refine those parameters. The powder spectra of matrix isolated CF3 and RCF2CF2 radicals, previously measured at low temperature, were reanalysed with this method. A theoretically modeled complex consisting of a Cu2+ ion, featuring an axially symmetric g-tensor and 63Cu hyperfine structure anisotropy, and a free radical located at different orientations, with respect to the symmetry axis of the Cu2+ ion, was examined in order to investigate the possibility to recover the magnetic parameters of the separate units and the magnetic couplings between them. © 2005 Elsevier B.V. All right reserved.
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| 23. |
- Millán, L., et al.
(författare)
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SMILES ice cloud products
- 2013
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Ingår i: Journal of Geophysical Research: Atmospheres. - : American Geophysical Union (AGU). - 2169-8996 .- 2169-897X. ; 118:12, s. 6468-6477
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Tidskriftsartikel (refereegranskat)abstract
- Upper tropospheric water vapor and clouds play an important role in Earth's climate, but knowledge of them, in particular diurnal variation in deep convective clouds, is limited. An essential variable to understand them is cloud ice water content. The Japanese Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on board the International Space Station (ISS) samples the atmosphere at different local times allowing the study of diurnal variability of atmospheric parameters. We describe a new ice cloud data set consisting of partial Ice Water Path and Ice Water Content. Preliminary comparisons with EOS-MLS, CloudSat-CPR and CALIOP-CALIPSO are presented. Then, the diurnal variation over land and over open ocean for partial ice water path is reported. Over land, a pronounced diurnal variation peaking strongly in the afternoon/early evening was found. Over the open ocean, little temporal dependence was encountered. This data set is publicly available for download in HDF5 format.
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| 24. |
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| 25. |
- Shiotani, M., et al.
(författare)
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Structures of tetrafluorocyclopropene, hexafluorocyclobutene, octafluorocyclopentene and related perfluoroalkene radical anions revealed by electron spin resonance spectroscopic and computational studies
- 2006
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 110:19, s. 6307-6323
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Tidskriftsartikel (refereegranskat)abstract
- Isotropic and anisotropic ESR spectra were observed for the radical anions of hexafluorocyclobutene (c-C4F6-), octafluorocyclopentene (c-C5F8-) and perfluoro-2-butene (CF3CF=CFCF3-) in ?-irradiated plastically crystalline neopentane, tetramethylsilane (TMS) and TMS-d12 matrices, or the rigid 2-methyltetrahydrofuran (MTHF) matrix. The isotropic spectra of c-C4F6- and c-C5F8- are characterized by three different sets of pairs of 19F nuclei with the isotropic hyperfine (hf) splittings of 15.2 (2F), 6.5 (2F), 1.1 (2F) mT for oC4F 6- and 14.7 (2F), 7.4 (2F), 1.0 (2F) mT for c-C 5F8-. By comparison with the results of ab initio quantum chemical computations, the large triplet 19F hf splittings of ca. 15 mT are assigned to the two fluorines attached to the C=C bond. The UHF, B3LYP and MP2 computations predict that the geometrical structures of the perfluoroalkenes are strongly distorted by one-electron reduction to form their radical anions, c-C3F4-: C2 symmetry (2A state) ? C2v (1A1), c-C4F6-: C 1 (2A) ? C2v (1A1) and c-C5F8-: C1 (2A) ? Cs (1A'). The structural distortion arises from a mixing of the p* and higher-lying s* orbitals at the C=C carbons similar to that previously found for CF2=CF 2- with a C2h, distortion. The isotropic 19F hf splittings computed with the B3LYP method with 6-311+G(2df,p) basis set for the geometry optimized by the UHF and/or MP2 methods are within 6% error of the experimental values. The experimental anisotropic spectra of c-C4F6-, c-C5F8- and CF2=CF2- were satisfactorily reproduced by the ESR spectral simulation method using the computed hf principal values and orientation of 19F nuclei. In addition, the electronic excitation energies and oscillator strengths for the CF2=CF 2-, c-C3F4-, c-C 4F6- and c-C5F8- radical anions were computed for the first time by TD-DFT methods. © 2006 American Chemical Society.
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| 26. |
- Volodin, A, et al.
(författare)
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ESR study of monomer and triplet state dimer NO adsorbed on sulfated zirconia
- 2000
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Ingår i: Chemical Physics Letters. - 0009-2614 .- 1873-4448. ; 327:3-4, s. 165-170
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Tidskriftsartikel (refereegranskat)abstract
- Triplet state NO dimers stabilized on the surface of sulfated zirconia (g(perpendicular to)= 1.993, g(parallel to) = 1.942, D-perpendicular to = 195 G, E approximate to 0) have been observed by ESR. They are formed by adsorption of NO molecules on pair (acceptor) surface sites represented, most likely, by two adjacent (d=5.2 Angstrom) low-coordinated Zr4+ ions. A new single line (Lorentz line with g = 1.993 and line width 18 G) of NO monomers adsorbed on active sites of sulfated zirconia has been observed. The sites where this form is stabilized seem to be very strong electron accepters responsible for the formation of radical cations after adsorption of aromatic molecules, (C) 2000 Elsevier Science B.V. All rights reserved.
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| 27. |
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| 28. |
- Yahiro, H, et al.
(författare)
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An EPR study on nitrogen monoxide adsorbed on sodium ion-exchanged A-type zeolite
- 2000
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Ingår i: Chemistry Letters. - 0366-7022 .- 1348-0715. ; :7, s. 736-737
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Tidskriftsartikel (refereegranskat)abstract
- Temperature-dependent EPR spectra of nitrogen monoxide (NO) introduced into sodium ion-exchanged A-type (Na-A) zeolite demonstrated that two types of NO monoradical and one NO-NO radical pair were formed on the zeolites and that the thermally less stable NO monoradical was converted into the thermally stable one upon warming from 30 K to 100 K.
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| 29. |
- Yahiro, H., et al.
(författare)
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Association forms of NO in sodium ion-exchanged A-type zeolite : Temperature-dependent Q-band EPR spectra
- 2000
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 104:34, s. 7950-7956
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Tidskriftsartikel (refereegranskat)abstract
- Nitrogen monoxide (NO) introduced into sodium ion-exchanged A-type (Na-A) zeolite was studied by temperature- and NO pressure-dependent EPR measurements at Q-band in the temperature range between 5 and 140 K. The experimental spectra were successfully utilized to determine accurate values of the g and A(14N) tensors of NO monoradical and the g tensors and zero field splitting (ZFS) parameters, D and E, of the NO-NO biradical. Two different EPR spectra corresponding to low and high temperature forms of the NO monoradical were observed when the NO pressure was low (PNO=3.1 kPa). Based on the g and A tensors, the former was attributed to a rigid form and the latter to a rotational form of the monoradical. For higher NO pressure, the biradical became dominant. The structure of the biradical was discussed in terms of the D and g tensors combined with the spectral line shape simulation method.
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| 30. |
- Yahiro, H, et al.
(författare)
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EPR study on NO introduced into lithium ion-exchanged LTA zeolites
- 2002
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 4:17, s. 4255-4259
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Tidskriftsartikel (refereegranskat)abstract
- Nitrogen monoxide (NO) introduced into partially and fully lithium ion (Li+)-exchanged A-type zeolite was studied by X-band EPR measurements. Two types of NO species, NO monoradical and NO-NO biradical, were detected for the partially ion-exchanged zeolite, while the latter was less detectable for the fully ion-exchanged one. The EPR parameters of the NO monoradical provided evidence that the electrostatic field associated with Li+ ions in A-type zeolites is weaker than that with Na+ ions. It was found that the molecular distance of NO biradical formed in partially Li+-exchanged zeolite was shorter than that in sodium ion-exchanged A-type zeolite.
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| 31. |
- Yahiro, H, et al.
(författare)
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Nitric oxide adsorbed on zeolites : EPR studies
- 2004
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Ingår i: Spectrochimica Acta Part A - Molecular and Biomolecular Spectroscopy. - : Elsevier BV. - 1386-1425 .- 1873-3557. ; 60:6, s. 1267-1278
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Tidskriftsartikel (refereegranskat)abstract
- CW-EPR studies of NO adsorbed on sodium ion-exchanged zeolites were focused on the geometrical structure of NO monoradical and (NO)(2) biradical formed on zeolites. The EPR spectrum of NO monoradical adsorbed on zeolite can be characterized by the three different g-tensor components and the resolved y-component hyperfine coupling with the N-14 nucleus. Among the g-tensor components, the value of g,, is very sensitive to the local environment of zeolite and becomes a measure of the electrostatic field in zeolite. The temperature dependence of the g-tensor demonstrated the presence of two states of the Na-NO adduct, in rigid and rotational states. The EPR spectra of NO adsorbed on alkaline metal ion-exchanged zeolite and their temperature dependency are essentially the same as that on sodium ion-exchanged zeolite. On the other hand, for NO adsorbed on copper ion-exchanged zeolite it is known that the magnetic interaction between NO molecule and paramagnetic copper ion are observable in the spectra recorded at low temperature. The signals assigned to (NO)(2) biradical were detected for EPR spectrum of NO adsorbed on Na-LTA. CW-EPR spectra as well as their theoretical calculation suggested that the two NO molecules are aligned along their N-O bond axes. A new procedure for automatical EPR simulation is described which makes it possible to analyze EPR spectrum easily. In the last part of this paper, some instances when other nitrogen oxides were used as a probe molecule to characterize the zeolite structure, chemical properties of zeolites, and dynamics of small molecules were described on the basis of selected literature data reported recently. (C) 2003 Published by Elsevier B.V.
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