A hydrocode calculation coupled with reaction kinetics of carbon compounds within an impact vapor plume and its implications for cometary impacts on Galilean satellites

The synthesis of organic molecules via chemical reactions within impact vapor plumes has been proposed as a mechanism to supply organics on a planet. However, the kinetics of chemical reactions within a rapidly expanding vapor plume or quenching process of the reactions has not been studied extensively. In this study, we constructed a new numerical model that calculates kinetics of the entire chemical reactions within an impact vapor plume. Numerical results revealed that the semi-analytical models proposed so far, in which the final amount of a chemical species was given by the equilibrium abundance at the quenching temperature of the fastest reaction path involving the species, underestimates the yield of organic molecules, such as HCN, by up to a factor of 10. This is because the previously used assumption that a species can achieve equilibrium with the rest of the reaction system via the fastest reaction path involving the species is not necessarily valid. Our analysis of the high-temperature H/C/N/O reaction system suggests that the quenching of slow reactions divides the reaction network into smaller reaction sub-systems isolated from the rest of the reaction system. Then, the fastest reaction path cannot equilibrate an isolated reaction sub-system with the rest of the reaction system. Simulation of this actual disequilibrium mechanism requires a simultaneous numerical calculation of the entire reaction network, which is equivalent to conducting a full kinetic model calculation, such as our model. Our numerical code makes it possible to discuss quantitatively the impact chemistry for various situations, such as the Galilean satellites. In this study, our numerical model is applied to the delivery of organic molecules via cometary impact on the Galilean satellites. Our numerical results indicate that small-particle impacts would produce HCN efficiently. Resulting HCN may freeze out immediately and be deposited on satellite surfaces, where it may be eventually converted into complex organics via irradiation of charged particle. On the other hand, large-size impacts may form transient CH₄-N₂ atmospheres, in which complex organics (tholin) may be formed via energy deposition of UV and/or charged particle. Resulting complex organics may subsequently precipitate on the satellite surfaces without clear correlation with the locations of impact craters. Such distribution of complex organics created by chemical reactions within vapor plumes due to cometary impacts may explain an absorption (4.57 μm) on Galilean satellites nonassociated with observable (moderate- and large-size) impact craters.     

Fast and slow timescales in the tropical low-cloud response to increasing CO2 in two climate models

To obtain physical insights into the response and feedback of low clouds (C _l ) to global warming, ensemble 4?×?CO₂ experiments were carried out with two climate models, the Model for Interdisciplinary Research on Climate (MIROC) versions 3.2 and 5. For quadrupling CO₂, tropical-mean C _l decreases, and hence, acts as positive feedback in MIROC3, whereas it increases and serves as negative feedback in MIROC5. Three time scales of tropical-mean C _l change were identified—an initial adjustment without change in the global-mean surface air temperature, a slow response emerging after 10–20?years, and a fast response in between. The two models share common features for the former two changes in which C _l decreases. The slow response reflects the variability of C _l associated with the El Ni?o-Southern Oscillation in the control integration, and may therefore be constrained by observations. However, the fast response is opposite in the two models and dominates the total response of C _l . Its sign is determined by a subtle residual of the C _l increase and decrease over the ascending and subsidence regions, respectively. The regional C _l increase is consistent with a more frequent occurrence of a stable condition, and vice versa, as measured by lower-tropospheric stability (LTS). The above frequency change in LTS is similarly found in six other climate models despite a large difference in both the mean and the changes in the low-cloud fraction for a given LTS. This suggests that the response of the thermodynamic constraint for C _l to increasing CO₂ concentrations is a robust part of the climate change.     

A multiple-code simulation study of the long-term EDZ evolution of geological nuclear waste repositories

This simulation study shows how widely different model approaches can be adapted to model the evolution of the excavation disturbed zone (EDZ) around a heated nuclear waste emplacement drift in fractured rock. The study includes modeling of coupled thermal-hydrological-mechanical (THM) processes, with simplified consideration of chemical coupling in terms of time-dependent strength degradation or subcritical crack growth. The different model approaches applied in this study include boundary element, finite element, finite difference, particle mechanics, and elasto-plastic cellular automata methods. The simulation results indicate that thermally induced differential stresses near the top of the emplacement drift may cause progressive failure and permeability changes during the first 100 years (i.e., after emplacement and drift closure). Moreover, the results indicate that time-dependent mechanical changes may play only a small role during the first 100 years of increasing temperature and thermal stress, whereas such time-dependency is insignificant after peak temperature, because of decreasing thermal stress.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

Computer simulation of the MgSiO3 polymorphs

Six polymorphs of MgSiO₃ have been studied using molecular dynamic (MD) simulation techniques, based on the empirical potential (MAMOK), which is composed of terms to describe pairwise additive Coulomb, van der Waals attraction, and repulsive interactions. Crystal structures, bulk moduli, volume thermal expansivities, and enthalpies were simulated for the known MgSiO₃ polymorphs; orthoenstatite, clinoenstatite, protoenstatite, garnet, ilmenite, and perovskite. The simulated values compare very well with the available experimental data, and the results are quite satisfactory in view of the diversity of the crystal structures of the six polymorphs, the wide range of simulated properties, and the simplicity of the MAMOK potential. MD simulation was further successfully used to study the possibile existence of a post-protoenstatite phase at high temperature, and a C2/c phase at high pressure, both phases being suggested or inferred previously from experimental works.     

Infrared device for simultaneous measurement of fluctuations of atmospheric carbon dioxide and water vapor

An infrared device designed to measure simultaneous fluctuations of atmospheric CO₂ and water vapor concentrations is described. The measuring frequency is 30 Hz. The sensing path length is 20 cm. It is compatible with the path length of the standard type of a sonic anemometer. The noise level of the device is equivalent to fluctuations of about 0.8 ppm peak-to-peak for CO₂ and 0.02 g kg^-1 peak-to-peak for water vapor. Field tests have showed that the device is suitable for simultaneous measurement of turbulent fluxes of CO₂ and water vapor in conjunction with a sonic anemometer.     

Seasonal Trend in the Occurrence of Nocturnal Drainage Flow on a Forested Slope Under a Tropical Monsoon Climate

Using data for one year, we examined the vertical wind speed profileson a mountain slope covered with forest in northern Thailand undera tropical monsoon climate. We defined two profile patterns: higherwind speeds at greater heights (Pattern 1) and lower wind speeds atgreater heights (Pattern 2). We classified 9.4% of the data as Pattern 2;this pattern tended to occur during the night, at low wind speeds, and with high outgoing longwave radiation. In addition, stable stratification anddecoupling between the canopy surface air and the overlying layers wereobserved when Pattern 2 occurred frequently. These facts suggested thatPattern 2 was caused by a nocturnal drainage flow. The occurrence ofPattern 2 showed a clear seasonal trend, indicating that there is a seasonaltrend in the occurrence of nocturnal drainage flows. Pattern 2 was observedmore frequently between August and February and less frequently betweenMarch and July. This corresponded to the seasonal trend in wind speed, butdid not correspond to the seasonal trend in the outgoing longwave radiation.     

Geochemical Cycles of Bio-essential Elements on the Early Earth and Their Relationships to Origin of Life

Abstract: The bio-essential elements are demanded for the metabolic action of all living organisms. These elements are continuously supplied to biosphere through the elemental cycle on the surface Earth. The geochemical cycle of bio-essential elements was most likely different in the pre-biotic era (ca. 4.4 to 4.0 Ga) compared to the modern Earth. The difference was probably made by the absence of continents and biological mediation in the pre-biotic environments. Geochemical cycle models of bio-essential elements (P, B and Mo) on the pre-biotic Earth are proposed in this study, and these models are examined using available geochemical data.
The input flux of phosphorous in pre-biotic oceans was probably dominated by submarine hydrothermal activities associated with carbonatized oceanic crusts. Such input flux by submarine hydrothermal activities is not known in the present-day oceans, and probably a unique flux in the pre-biotic oceans. Boron chemistry of pre-biotic oceans was also controlled by submarine hydrothermal input flux. The Mo exchange between the pre-biotic ocean and lithosphere may have restricted only at the submarine hydrothermal areas. These suggest that the submarine hydrothermal discharging areas were only locations to obtain bio-essential elements for the earliest life. This model is consistent with the previously proposed model for hydrothermal origin of life.     

Challenges posed by and approaches to the study of seasonal-to-decadal climate variability

The tasks of providing multi-decadal climate projections and seasonal plus sub-seasonal climate predictions are of significant societal interest and pose major scientific challenges. An outline is presented of the challenges posed by, and the approaches adopted to, tracing the possible evolution of the climate system on these various time-scales. First an overview is provided of the nature of the climate system’s natural internal variations and the uncertainty arising from the complexity and non-linearity of the system. Thereafter consideration is given sequentially to the range of extant approaches adopted to study and derive multi-decadal climate projections, seasonal predictions, and significant sub-seasonal weather phenomena. For each of these three time-scales novel results are presented that indicate the nature (and limitations) of the models used to forecast the evolution, and illustrate the techniques adopted to reduce or cope with the forecast uncertainty. In particular, the contributions (i) appear to exemplify that in simple climate models uncertainties in radiative forcing outweigh uncertainties associated with ocean models, (ii) examine forecast skills for a state-of-the-art seasonal prediction system, and (iii) suggest that long-lived weather phenomena can help shape intra-seasonal climate variability. Finally, it is argued, that co-consideration of all these scales can enhance our understanding of the challenges associated with uncertainties in climate prediction.