Applicability of molecular simulations for modelling the adsorption of the greenhouse gas CF4 on carbons

Tetrafluoromethane, CF4, is powerful greenhouse gas, and the possibility of storing it in microporous carbon has been widely studied. In this paper we show, for the first time, that the results of molecular simulations can be very helpful in the study of CF4 adsorption. Moreover, experimental data fit to the results collected from simulations. We explain the meaning of the empirical parameters of the supercritical Dubinin–Astakhov model proposed by Ozawa and finally the meaning of the parameter k of the empirical relation proposed by Amankwah and Schwarz.

Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.

Secular trends in daily precipitation characteristics: greenhouse gas simulation with a coupled AOGCM

Secular trends of daily precipitation characteristics are considered in the transient climate change experiment with a coupled atmosphere-ocean general circulation model ECHAM4/OPYC3 for 1900-2099. The climate forcing is due to increasing concentrations of the greenhouse gases in the atmosphere. Mean daily precipitation, precipitation intensity, probability of wet days and parameters of the gamma distribution are analyzed. Particular attention is paid to the changes of heavy precipitation, Analysis of the annual mean precipitation trends for 1900-1999 revealed general agreement with observations with significant positive trends in mean precipitation over continental areas. In the 2000-2099 period precipitation trend patterns followed the tendency obtained for 1900-1999 but with significantly increased magnitudes. Unlike the annual mean precipitation trends for which negative values were found for some continental areas, the mean precipitation intensity and scale parameter of the fitted gamma distribution increased over all land territories . Negative trends in the number of wet days were found over most of the land areas except high latitudes in the Northern Hemisphere. The shape parameter of the gamma distribution in general revealed a slight negative trend in the areas of the precipitation increase. Investigation of daily precipitation revealed an unproportional increase of heavy precipitation events for the land areas including local maxima in Europe and the eastern United States.

Intensified Asian summer monsoon and its variability in a coupled model forced by increasing greenhouse gas concentrations

The Asian summer monsoon response to global warming is investigated by a transient green-house warming integration with the ECHAM4/OPYC3 CGCM. It is demonstrated that increases of greenhouse gas concentrations intensify the Asian summer monsoon and its variability. The intensified monsoon results mainly from an enhanced land-sea contrast and a northward shift of the convergence zone. A gradual increase of the monsoon variability is simulated from year 2030 onwards. It seems to be connected with the corresponding increase of the sea surface temperature variability over the tropical Pacific.

Will greenhouse gas-induced warming over the next 50 years lead to higher frequency and greater intensity of hurricanes?

The use of a high resolution atmospheric model at T106 resolution, for studying the influence of greenhouse warming on tropical storm climatology, is investigated. The same method for identifying the storms has been used as in a previous study by Bengtsson et al. The sea surface temperature anomalies have been taken from a previous transient climate change experiment, obtained with a low resolution ocean-atmosphere coupled model. The global distribution of the storms, at the time when the CO2 concentration in the atmosphere had doubled, agrees in geographical position and seasonal variability with that of the present climate, but the number of storms is significantly reduced, particularly at the Southern Hemisphere. The main reason to this, appear to be connected to changes in the large scale circulation, such as a weaker Hadley circulation and stronger upper air westerlies. The low level vorticity in the hurricane genesis regions is generally reduced compared to the present climate, while the vertical tropospheric wind shear is somewhat increased. Most tropical storm regions indicate reduced surface windspeeds and a slightly weaker hydrological cycle.

Time-resolved gas-phase kinetic, quantum chemical, and RRKM studies of reactions of silylene with alcohols

Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.

The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed.

Hydrogen bonding in the gas-phase: the molecular structures of 2‑hydroxybenzamide (C7H7NO2) and 2‑methoxybenzamide (C8H9NO2), obtained by gas-phase electron diffraction and theoretical calculations

The structures of 2-hydroxybenzamide(C7H7NO2) and 2-methoxybenzamide (C8H9NO2) have been determined in the gas-phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict four stable conformers for both 2-hydroxybenzamide and 2-methoxybenzamide. For both compounds, evidence for intramolecular hydrogen bonding is presented. In 2-hydroxybenzamide, the observed hydrogen bonded fragment is between the hydroxyl and carbonyl groups, while in 2-methoxybenzamide, the hydrogen bonded fragment is between one of the hydrogen atoms of the amide group and the methoxy oxygen atom.

Are greenhouse gas signals of Northern Hemisphere winter extra-tropical cyclone activity dependent on the identification and tracking algorithm?

For Northern Hemisphere extra-tropical cyclone activity, the dependency of a potential anthropogenic climate change signal on the identification method applied is analysed. This study investigates the impact of the used algorithm on the changing signal, not the robustness of the climate change signal itself. Using one single transient AOGCM simulation as standard input for eleven state-of-the-art identification methods, the patterns of model simulated present day climatologies are found to be close to those computed from re-analysis, independent of the method applied. Although differences in the total number of cyclones identified exist, the climate change signals (IPCC SRES A1B) in the model run considered are largely similar between methods for all cyclones. Taking into account all tracks, decreasing numbers are found in the Mediterranean, the Arctic in the Barents and Greenland Seas, the mid-latitude Pacific and North America. Changing patterns are even more similar, if only the most severe systems are considered: the methods reveal a coherent statistically significant increase in frequency over the eastern North Atlantic and North Pacific. We found that the differences between the methods considered are largely due to the different role of weaker systems in the specific methods.

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.