Coupling efficiency in grating tuned carbon dioxide waveguide lasers

The coupling efficiency in typical CO₂ waveguide lasers when the feedback element is a diffraction grating is investigated theoretically. A scalar diffraction integral approach is adopted, and the laser is assumed to operate on its lowest loss waveguide mode.     

Phase diagram of carbon dioxide: update and challenges

We present the phase diagram of carbon dioxide with the most recent finding of coesite-like carbon dioxide, a missing analog to SiO₂, address several controversies on phase VII and phase IV in terms of the phase metastabilities and thermal path-dependent phase transitions, and discuss the implications to the generalized phase diagram of simple molecular solids.     

Ion hydration and hydrogen bond structure in NaCl solutions at temperatures and pressures for carbon dioxide sequestration: the effects of solvated CO2 molecules

In the present study, we focus on the phase properties of CO₂–brine systems in geologic media. Molecular dynamics simulation methods were used to investigate the ion hydration and hydrogen bond structure in CO₂–brine and brine solutions at temperatures and pressures for CO₂ sequestration. By comparing the results of CO₂–brine solutions with those of brine solutions, the effects of solvated CO₂ were analysed and discussed.     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO 2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO ₂ mixing ratios and their carbon isotope composition (¹³C/¹²C and ¹⁴C/¹²C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO ₂ load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered ‘background’ CO ₂. In Krakow, the average contribution of fossil fuel CO ₂ was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO ₂ budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO ₂ mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO ₂ loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO ₂ fluxes.     

Molecular dynamics simulations of carbon dioxide hydrate growth in electrolyte solutions of NaCl and MgCl2

Molecular dynamics simulations are performed to study the growth of carbon dioxide (CO₂) hydrate in electrolyte solutions of NaCl and MgCl₂. The kinetic behaviour of the hydrate growth is examined in terms of cage content, density profile, and mobility of ions and water molecules, and how these properties are influenced by added NaCl and MgCl₂. Our simulation results show that both NaCl and MgCl₂ inhibit the CO₂ hydrate growth. With a same mole concentration or ion density, MgCl₂ exhibits stronger inhibition on the growth of CO₂ hydrate than NaCl does. The growth rate of the CO₂ hydrate in NaCl and MgCl₂ solutions decreases slightly with increasing pressure. During the simulations, the Na⁺, Mg²⁺, and Cl^? ions are mostly excluded by the growing interface front. We find that these ions decrease the mobility of their surrounding water molecules, and thus reduce the opportunity for these water molecules to form cage-like clusters toward hydrate formation. We also note that during the growth processes, several 5¹²6³ cages appear at the hydrate/solution interface, although they are finally transformed to tetrakaidecahedral (5¹²6²) cages. Structural defects consisting of one water molecule trapped in a cage with its hydrogen atoms being attracted by two Cl^? ions have also been observed.     

Near infrared spectroscopy of carbon dioxide. II: OCO and OCO line positions

High-resolution near-infrared (4000-8500 cm⁻¹) spectra of ¹³C-enriched carbon dioxide have been recorded using the McMath-Pierce Fourier transform spectrometer at the Kitt Peak National Solar Observatory. We observed over 1000 line positions for the ¹⁶O¹³C¹⁶O isotopologue, the majority of which have previously been observed only in spectra of the Venusian atmosphere [J. Mol. Spectrosc. 67 (1977) 304]. These have been analyzed to determine spectroscopic constants for 28 different vibrational states. The analysis yielded RMS fitting residuals <1.5 × 10⁻⁴ cm⁻¹ for the strongest bands and RMS residuals <5 × 10⁻⁴ cm⁻¹ for most other fitted bands. A 5% ¹⁸O-enrichment in the sample enabled us to observe 410 line positions from 5 near-infrared vibrational bands of the ¹⁶O¹³C¹⁸O isotopologue. Analysis of the ¹⁶O¹³C¹⁸O bands yielded RMS fitting residuals <2 × 10⁻⁴ cm⁻¹. Additionally, the first fits for the ¹⁶O¹³C¹⁸O 11101 ← 01101 and 11102 ← 01101 hot bands yielded RMS residuals of 2.3 × 10⁻⁴ and 2.2 × 10⁻⁴ cm⁻¹, respectively. Critical reevaluations of the spectroscopic constants for the low lying vibrational states for both isotopologues have been performed as part of the analysis.     

Precision improvements in the geo-fit retrieval of pressure and temperature from MIPAS limb observations by modeling CO2 line-mixing

In this paper, we present an improvement of the retrieval of pressure and temperature from the observations of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board of the environmental satellite (ENVISAT). The improvement has been obtained by integrating a state-of-the-art CO₂ line-mixing model in a two-dimensional inversion system (Geo-fit). We describe the implementation of this model in the Geo-fit system and we show its capability to reproduce the CO₂ spectral features affected by line-mixing. The upgraded analysis algorithm provides a better fit of the set of MIPAS observations analyzed by the European Space Agency (ESA) ground segment although these observations have been selected with criteria that should avoid line-mixing effects. Moreover, we show that this set of observations can be extended improving the precision of the retrieved pressure and temperature fields without increasing the computing demands. Since the CO₂Q branches are very sensitive to pressure and temperature, the capability to model accurately the line-mixing effects opens the possibility to exploit at best these spectral regions to infer pressure and temperature distributions. According to this idea, we propose a new set of spectral intervals, including the most intense CO₂Q branches. It is shown that the analysis of these intervals provides a significant improvement (up to 70%) in the precision of the retrieved pressure and temperature profiles, while using a smaller number of observations with respect to the ESA ground segment analysis. Since the knowledge of pressure and temperature is necessary for the retrieval of the altitude distribution of all the atmospheric constituents, the benefits of more precise pressure and temperature fields obtained in this work propagate into the quality of all the MIPAS products.     

Updated database plus software for line-mixing in CO2 infrared spectra and their test using laboratory spectra in the 1.5-2.3 μm region

In a previous series of papers, a model for the calculation of CO₂-air absorption coefficients taking line-mixing into account and the corresponding database/software package were described and widely tested. In this study, we present an update of this package, based on the 2008 version of HITRAN, the latest currently available. The spectroscopic data for the seven most-abundant isotopologues are taken from HITRAN. When the HITRAN data are not complete up to J″=70, the data files are augmented with spectroscopic parameters from the CDSD-296 database and the high-temperature CDSD-1000 if necessary. Previously missing spectroscopic parameters, the air-induced pressure shifts and CO₂ line broadening coefficients with H₂O, have been added. The quality of this new database is demonstrated by comparisons of calculated absorptions and measurements using CO₂ high-pressure laboratory spectra in the 1.5-2.3 μm region. The influence of the imperfections and inaccuracies of the spectroscopic parameters from the 2000 version of HITRAN is clearly shown as a big improvement of the residuals is observed by using the new database. The very good agreements between calculated and measured absorption coefficients confirm the necessity of the update presented here and further demonstrate the importance of line-mixing effects, especially for the high pressures investigated here. The application of the updated database/software package to atmospheric spectra should result in an increased accuracy in the retrieval of CO₂ atmospheric amounts. This opens improved perspectives for the space-borne detection of carbon dioxide sources and sinks.     

Ignition and devolatilization of pulverized bituminous coal particles during oxygen/carbon dioxide coal combustion

Oxygen/carbon dioxide recycle coal combustion is actively being investigated because of its potential to facilitate CO₂ sequestration and to achieve emission reductions. In the work reported here, the effect of enhanced oxygen levels and CO₂ bath gas is independently analyzed for their influence on single-particle pulverized coal ignition of a U.S. eastern bituminous coal. The experiments show that the presence of CO₂ and a lower O₂ concentration increase the ignition delay time but have no measurable effect on the time required to complete volatile combustion, once initiated. For the ignition process observed in the experiments, the CO₂ results are explained by its higher molar specific heat and the O₂ results are explained by the effect of O₂ concentration on the local mixture reactivity. Particle ignition and devolatilization properties in a mixture of 30% O₂ in CO₂ are very similar to those in air.     

基于Mie散射的CO_2激光大气传输特性测量

为了更准确地计算大气透过率,在Mie散射理论基础上,分析了雷达系统设计中需考虑的大气透过率的经验计算公式,指出了该经验公式的不足。考虑大气分析软件MODTRAN自身的优点,采用经验公式和软件计算相结合的方式计算大气透过率,给出了MODTRAN计算结果的修正表达式。在该理论指导下,进行了CO2激光大气传输实验。由于没有考虑大气湍流,理论计算和实验结果存在一定偏差,但不影响本文方法的实用性。实验测量显示,激光器出口处光斑能量抖动比为6.18%,而在50m和1km处能量抖动比分别为8.3%和50.2%,表明随着传输距离增加,能量抖动比增大。除掉激光器本身输出能量抖动外,在50m和1km处由大气传输造成的能量抖动比分别为2.12%和44.02%。实验结果提示,水平传输1km时能量抖动已相当剧烈,所以对更远距离的激光传输,自适应光学补偿显得尤为重要。     

CW-cavity ringdown spectroscopy of carbon dioxide isotopologues near 1.5 μm

The absorption spectra of carbon dioxide in natural isotopic abundance and with 99% enrichment in ¹³C have been recorded by CW-cavity ringdown spectroscopy in two specific spectral regions: 5957-6122 and 6745-6833 cm⁻¹. The spectra were obtained at Doppler limited resolution by using a CW-CRDS spectrometer based on fibered DFB lasers. The typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹, allowed for the detection of lines with intensity as weak as 5 × 10⁻²⁹ cm/molecule. More than 2900 line positions of the six major isotopologues contributing to the spectra (¹²C¹⁶O₂, ¹⁶O¹²C¹⁷O, ¹⁶O¹²C¹⁸O, ¹³C¹⁶O₂, ¹⁶O¹³C¹⁷O and ¹⁶O¹³C¹⁸O), were measured and assigned on the basis of their respective global effective Hamiltonian models. For comparison, only 507 lines are provided by the HITRAN database in these spectral regions. The band by band analysis has led to the determination of the rovibrational parameters of a total of 52 bands, 30 of them being newly reported. Most of the observed line positions show an agreement close to the experimental uncertainty (1-2 × 10⁻³ cm⁻¹) with the predictions of their respective effective Hamiltonian models. However, the quality of the predictions degrades for the minor isotopologues reaching maximum deviations of 0.35 cm⁻¹ in one specific case. For several bands, rovibrational transitions with J values between 60 and 90 could be newly detected. While an excellent agreement is observed with the line positions predicted by the Hamiltonian models, the comparison of these observations with the line positions listed in the HITRAN database or extrapolated by using the best FTS rotational constants available in the literature has evidenced significant deviations.     

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

The active catalysts for methane formation from the gas mixture of CO₂ + 4H₂ with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO₂ prepared by calcination of aqueous ZrO₂ sol with Sm(NO₃)₃ and Ni(NO₃)₂. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO₂, and the activity for methanation increased by an increase in inclusion of Sm³⁺ ions substituting Zr⁴⁺ ions in the tetragonal ZrO₂ lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.     

Stabilization of atmospheric carbon dioxide via zero emissions-An alternative way to a stable global environment. Part 1: Examination of the traditional stabilization concept

The concept of "stabilization" of atmospheric CO2 concentration is re-examined in connection with climate-change mitigation strategies. A new "zero-emissions stabilization (Z-stabilization)" is proposed, where CO2 emissions are reduced to zero at some time and thereafter the concentration is decreased by natural removal processes, eventually reaching an equilibrated stable state. Simplified climate experiments show that, under Z-stabilization, considerably larger emissions are permissible in the near future compared with traditional stabilization, with the same constraint on temperature rise. Over longer time scales, the concentration and temperature decrease close to their equilibrium values, much lower than those under traditional stabilization. The smaller temperature rise at final state is essential to avoid longer-term risk of sea level rise, a significant concern under traditional stabilization. Because of these advantages a Z-stabilization pathway can be a candidate of practical mitigation strategies as treated in Part 2.(Contributed by Taroh MATSUNO, M.J.A.).     

First global observations of atmospheric COClF from the Atmospheric Chemistry Experiment mission

Carbonyl chlorofluoride (COClF) is an important reservoir of chlorine and fluorine in the Earth's atmosphere. Satellite-based remote sensing measurements of COClF, obtained by the Atmospheric Chemistry Experiment (ACE) for a time period spanning February 2004 through April 2007, have been used in a global distribution study. There is a strong source region for COClF in the tropical stratosphere near 27 km. A layer of enhanced COClF spans the low- to mid-stratosphere over all latitudes, with volume mixing ratios of 40-100 parts per trillion by volume, largest in the tropics and decreasing toward the poles. The COClF volume mixing ratio profiles are nearly zonally symmetric, but they exhibit a small hemispheric asymmetry that likely arises from a hemispheric asymmetry in the parent molecule CCl₃F. Comparisons are made with a set of in situ stratospheric measurements from the mid-1980s and with predictions from a 2-D model.     

Seasonal variability of soil CO2 flux and its carbon isotope composition in Krakow urban area,Southern Poland

As urban atmosphere is depleted of ¹³CO₂, its imprint should be detectable in the local vegetation and therefore in its CO₂ respiratory emissions. This work was aimed at characterising strength and isotope signature of CO₂ fluxes from soil in urban areas with varying distances from anthropogenic CO₂ emissions. The soil CO₂ flux and its δ¹³C isotope signature were measured using a chamber method on a monthly basis from July 2009 to May 2012 within the metropolitan area of Krakow, Southern Poland, at two locations representing different levels of anthropogenic influence: a lawn adjacent to a busy street (A) and an urban meadow (B). The small-scale spatial variability of the soil CO₂ flux was also investigated at site B. Site B revealed significantly higher summer CO₂ fluxes (by approximately 46 %) than site A, but no significant differences were found between their δ¹³CO₂ signatures.     

DFT study on coupling reaction of carbon dioxide with ethylene oxide catalyzed by 1,4,6-triaza-bicyclo[3.3.0]oct-4-enium bromide (TBO.HBr)

ABSTRACT

Chemical fixation of CO₂ with epoxides catalyzed by organic-base salts were found to be efficient among the various catalysts tested due to synergetic effects of HBDs and halide-ions for ring-opening. In this study, 1,4,6-Triaza–bicyclo[3.3.0]oct-4-enium bromide catalyzed conversion of CO₂ and epoxide into cyclic-carbonate has been studied by using DFT method to understand the reaction mechanism and the catalytic performance of TBO.HBr. Two hypothetical reaction mechanisms were proposed for the coupling reaction. Thermodynamic and kinetic parameters were computed for each steps to determine the more favorable route. Mechanism II is more favorable path whereby Br^- ion first interacts with epoxide to form bromo-alcohol, which directed to form carbonate-ion and finally ring-closure step yielded cyclic-carbonate with catalyst-regeneration. Cyclization step is rate-determining step with reaction barrier of 22.696?kcal/mol in gas phase. Ensuing the favorable mechanism, solvent-effects on the reaction barrier has been investigated using water and THF. Mechanism II is still more favorable reaction path in both THF and water. However, the rate-determining step is found to be ring-opening of the epoxide with reaction barrier of 22.658?kcal/mol (wate) and 21.969?kcal/mol (THF). In this study, TBO.HBr exhibited good catalytic activity for the title reaction investigated in both gas phase and solvents.     

Diffusion of CO2/CH4 confined in narrow carbon nanotube bundles

ABSTRACT

The diffusion of a CO₂/CH₄ mixture in carbon nanotube (CNT) bundles was studied using molecular simulations. The effect of diameter and temperature on the diffusion of the mixture was investigated. Our results show that the single-file diffusion occurs when CO₂ and CH₄ are confined in CNTs of diameter less than 1.0 nm. In CNTs of diameter larger than 1.0 nm, both molecules diffuse in the Fickian style. The transition from single-file to Fickian diffusion was demonstrated for both CO₂ and CH₄ molecules. A dual diffusion mechanism was observed in the studied (20, 0) CNT bundle, single-file diffusion of CO₂ in the interstitial sites of (20, 0) CNT bundle and Fickian diffusion of CO₂ and CH₄ in the pores. For CO₂, the interaction energies (CO₂–CO₂ and CO₂–CNT) are larger than that of CH₄ in all cases. But only a very small difference in the diffusion coefficient was observed between CO₂ and CH₄. Temperature has a negligible effect on the difference between diffusion coefficients of CO₂ and CH₄ in the studied CNT bundles. The adsorption, diffusion and permeation selectivities are discussed and compared, and the adsorption is demonstrated to be the rate limiting step for the separation of CO₂/CH₄ in CNT bundle membranes.     

Remote detection of sulfur dioxide by means of a CO2 laser

The possibility of remote detection of SO₂ in the 9-μm region of the spectrum by means of a TEA CO₂ laser was theoretically and experimentally investigated with regard to the real state of the atmosphere and the contribution of background concentrations of H₂O, CO₂ and NH₃ to absorption. For sounding along short paths (2L=2 km), the method of detection of small concentrations of SO₂ (at the MPC level) with the use of the lines of the CO₂-molecule regular transitions (00^o1–02^o0 band) has been devised and experimentally tested. It is shown that in sounding along longer paths (2L=6 km), a noticeable increase in sensitivity can be achieved by the generation lines of the CO₂-molecule sequential 00^o2–02^o1 band. B. I. Stepanov Institute of Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 508–515, July–August, 1998.     

RHEED study of titanium dioxide with pulsed laser deposition

Reflection high-energy electron diffraction (RHEED) operated at high pressure has been used to monitor the growth of thin films of titanium dioxide (TiO₂) on (1 0 0) magnesium oxide (MgO) substrates by pulsed laser deposition (PLD). The deposition is performed with a synthetic rutile TiO₂ target at low fluence. The topography and structure of the deposited layers are characterized using in situ high pressure RHEED and atomic force microscope (AFM). Based on these observations the growth mode of the films is discussed. The results will be compared to earlier results obtained for the growth of TiN films on (1 0 0) MgO.