Hydrogen isotopic substitution of solid methylamine through atomic surface reactions at low temperatures: A potential contribution to the D/H ratio of methylamine in molecular clouds

We experimentally studied hydrogen (H)–deuterium (D) substitution reactions of solid methylamine (CH₃NH₂) under astrophysically relevant conditions. We also calculated the potential energy surface for the H–D substitution reactions of methylamine isotopologues using quantum chemical methods. Despite the relatively large energy barrier of more than 18 kJ mol^?1, CH₃NH₂ reacted with D atoms to yield deuterated methylamines at 10 K, suggesting that the H–D substitution reaction proceeds through quantum tunneling. Deuterated methylamines reacted with H atoms as well. On the basis of present results, we propose that methylamine has potential for D enrichment through atomic surface reactions on interstellar grains at very low temperatures in molecular clouds. D enrichment would occur in particular in the methyl group of methylamine.     

A cyclone over Saudi Arabia on 5 January 2002: A case study

Summary A shallow and short-lived subsynoptic cyclone is discussed as one of typical events causing natural disasters over Saudi Arabia on 5 January 2002 using the Japan Meteorological Agency global analysis dataset. The main cause for its formation was vorticity stretching. On the same day widespread rainfall over Saudi Arabia with enhanced precipitation over the mountainous Jeddah region was also observed using the Global Precipitation Climatology Project dataset. Owing to eastward-moving wintertime synoptic-scale Mediterranean disturbances, this rainfall was associated with frontal activity, modified by the local orography.     

What controls equatorial Atlantic winds in boreal spring?

The factors controlling equatorial Atlantic winds in boreal spring are examined using both observations and general circulation model (GCM) simulations from the coupled model intercomparison phase 5. The results show that the prevailing surface easterlies flow against the attendant pressure gradient and must therefore be maintained by other terms in the momentum budget. An important contribution comes from meridional advection of zonal momentum but the dominant contribution is the vertical transport of zonal momentum from the free troposphere to the surface. This implies that surface winds are strongly influenced by conditions in the free troposphere, chiefly pressure gradients and, to a lesser extent, meridional advection. Both factors are linked to the patterns of deep convection. Applying these findings to GCM errors indicates, that, consistent with the results of previous studies, the persistent westerly surface wind bias found in most GCMs is due mostly to precipitation errors, in particular excessive precipitation south of the equator over the ocean and deficient precipitation over equatorial South America. Free tropospheric influences also dominate the interannual variability of surface winds in boreal spring. GCM experiments with prescribed climatological sea-surface temperatures (SSTs) indicate that the free tropospheric influences are mostly associated with internal atmospheric variability. Since the surface wind anomalies in boreal spring are crucial to the development of warm SST events (Atlantic Niños), the results imply that interannual variability in the region may rely far less on coupled air–sea feedbacks than is the case in the tropical Pacific.     

Characterization of locally available soil as a liner material for solid waste landfills in Sri Lanka

This study aimed to develop a low-cost and effective clay liner material for solid waste landfills in Sri Lanka. A locally available clayey soil and its admixtures with 5 and 10% bentonite were examined for this purpose. Laboratory experiments to determine soil plasticity and swell index were carried out on the tested samples. Hydraulic conductivity (k) tests were carried out in the laboratory using water and an aqueous solution of CaCl₂ on unconsolidated samples prepared by either dry or slurry packing and pre-consolidated samples with five different consolidation pressures (p) from 10 to 200 kPa. Measured liquid limits for tested admixtures increased with increasing bentonite contents and correlated well with measured values of the swell index. The difference in permeant solutions had little effect on measured k values for both unconsolidated and pre-consolidated samples. The hydraulic conductivities were highly affected by changing p, i.e., the k values decreased on two orders of magnitude as p increased from 10 to 200 kPa. The Kozeny–Carman equation, a theoretical permeability model that expresses the k-porosity relationship, was applied to measured data including reported values. Results showed the Kozeny–Carman equation captured well the porosity-dependent k values for tested soils and their admixtures with bentonite under a wide range of void ratios, suggesting that the Kozeny–Carman equation is a useful tool to estimate the magnitude of k values for differently compacted soil and its bentonite admixtures.     

Geochemical evolution of historical lavas from Askja Volcano, Iceland: Implications for mechanisms and timescales of magmatic differentiation

The mechanisms and the timescales of magmatic evolution were investigated for historical lavas from the Askja central volcano in the Dyngjufjöll volcanic massif, Iceland, using major and trace element and Sr, Nd, and Pb isotopic data, as well as ²³⁸U-²³⁰Th-²²⁶Ra systematics. Lavas from the volcano show marked compositional variation from magnesian basalt through ferrobasalt to rhyolite. In the magnesian basalt-ferrobasalt suite (5-10 wt% MgO), consisting of lavas older than 1875 A.D., ⁸⁷Sr/⁸⁶Sr increases systematically with increasing SiO₂ content; this suite is suggested to have evolved in a magma chamber located at ∼600 MPa through assimilation and fractional crystallization. On the other hand, in the ferrobasalt-rhyolite suite (1-5 wt% MgO), including 1875 A.D. basalt and rhyolite and 20th century lavas, ⁸⁷Sr/⁸⁶Sr tends to decrease slightly with increasing SiO₂ content. It is suggested that a relatively large magma chamber occupied by ferrobasalt magma was present at ∼100 MPa beneath the Öskjuvatn caldera, and that icelandite and rhyolite magmas were produced by extraction of the less and more evolved interstitial melt, respectively, from the mushy boundary layer along the margin of the ferrobasalt magma chamber, followed by accumulation of the melt to form separate magma bodies. Ferrobasalt and icelandite lavas in the ferrobasalt-rhyolite suite have a significant radioactive disequilibrium in terms of (²²⁶Ra/²³⁰Th), and its systematic decrease with magmatic evolution is considered to reflect aging, along with assimilation and fractional crystallization processes. Using a mass-balance model in which simultaneous fractional crystallization, crustal assimilation, and radioactive decay are taken into account, the timescale for the generation of icelandite magma from ferrobasalt was constrained to be <∼3 kyr which is largely dependent on Ra crystal-melt partition coefficients we used.     

Iron oxidation state of a 2.45-Byr-old paleosol developed on mafic volcanics

The 2.45-Byr-old weathering profile developed on early Proterozoic mafic volcanics located near Cooper Lake, Ontario, Canada, was examined geochemically and mineralogically for a better understanding of the atmospheric oxygen evolution. Ferrous to ferric ion, Fe(II) and Fe(III), respectively, ratios of the bulk rock samples were analyzed by Mössbauer spectrometry. The total Fe (Fe(T)) and Fe(II) concentrations decrease from 12.0 and 11.2 wt.% to 1.85 and 0.89 wt.%, respectively, from the bottom to the top of the weathering profile. The Fe(T) and Fe(II) concentrations normalized to Ti and Zr, as well as the Fe(II)/Fe(III) ratio of raw data, linearly decrease with depth toward the top, while the Fe(III) concentration remains nearly constant throughout the profile. The linear decrease of Fe(II), accompanied by the nearly constant distribution of Fe(III), is difficult to be explained by the scenario of oxidizing weathering and subsequent reducing hydrothermal alteration. The behaviors of Fe(II) and Fe(III) can be simply explained by anoxic weathering. The anoxic weathering suggests that the 2.45-Ga atmosphere was anoxic. The slight increase of Fe/(Fe+Mg) in the octahedral sites of chlorite toward the top and no Ce anomaly in the REE patterns are also consistent with anoxic weathering.     

The development of Fe-nodules surrounding biological material mediated by microorganisms

Takashikozo is a phenomenon of Quaternary sediments in Japan. They are cylindrical Fe-oxyhydroxide nodules that form as plaques round plant roots, where Fe is preferentially concentrated to develop a solid wall. Structural features suggest that after the roots have decayed, the central space where the roots were situated acts as a flow path for oxidized water. Analysis of microbial 16S rDNA extracted from the nodules identified iron-oxidizing bacteria encrusted round the roots where they are the likely initiators of nodule formation. Direct microscopic observation revealed an accumulation of Fe-oxyhydroxides that fill the pore spaces and is also likely to be linked with the encrusting microbial colonies. Geological history and nanofossil evidence suggest that these Fe-nodules may have been buried at a depth of up to several tens of meters for at least 10⁵ years in reducing Quaternary sediments. Thus Fe-oxyhydroxide nodules that have formed in a geological environment at the interfaces between water and rock by microbial mediation can persist under reducing conditions. If this is the case, the phenomenon is significant as an analogue of post-closure conditions in radioactive waste repositories, since it could influence nuclide migration.     

Present environment of Dam Lake Sambe,southwestern Japan: a geochemical study of bottom sediments

Geochemical analyses of lakebed and core sediments from Lake Sambe on the outskirts of Oda City in Shimane prefecture in southwestern Japan were carried out in order to assess the water quality and the concentration and distribution patterns of sixteen elements. The lake water showed a stratified condition with respect to dissolved O₂, and As, Fe, and Mn concentrations in the bottom layers which increased in the summer. The chemical composition of the sediments, as measured by X-ray fluorescence, included major and trace elements (P, Ca, Sc, Ti, V, Cr, Fe, Ni, Cu, Zn, As, Sr, Zr, Pb, and Th), and total sulfur (TS). Elevated values of As, Zn, V, Fe, P, and TS were present in several layers of the upper cores (from 0 to 5 cm) and other surface sediments. Increases in the abundances of these metals in lake sediments are probably related to the reducing condition of the sediments, fine-grained organic rich sediments, and post-depositional diagenetic remobilization. Moreover, correlations between the concentrations of trace metals and iron in the sediments suggest their adsorption onto Fe (oxy)hydroxides, whereas correlations with sulfur indicate that they were precipitated as Fe-sulfides. The average abundances of As, Pb, Zn, and Cu exceeded the lowest effect level and Interim Sediment Quality Guideline values that the New York State Department of Environmental Conservation and the Canadian Council of Ministers of the Environment determined to have moderate impact on aquatic organisms. In addition, concentrations of As and Zn exceeded the Coastal Ocean Sediment Database threshold value, indicating potentially toxic levels. Therefore, the presence of trace metals in the lake sediments may result in adverse effects on biota health.     

Magmatic fluids of Tatun volcanic group,Taiwan

Two distinctive magmatic fluids were recognized in the Tatun volcanic group (TVG), Taiwan. One is a relatively reduced fluid represented by the fumarolic gases at Hsiao-you-ken (HYK) geothermal field. Another is an oxidized fluid containing high concentrations of HCl represented by the fumarolic gases at Da-you-ken (DYK). An intermediate gas was recognized at Gung-tze-ping (GTP) and She-hung-ping (SHP). The fumarolic gases at HYK and GTP possess the features of so-called primary steam generated on mixing of magmatic gas and meteoric groundwater. The fumarolic gases at DYK are a simple mixture between magmatic gas and water vapor of meteoric origin. The CO₂/H₂O molar ratio of the magmatic component in the fumarolic gases at DYK was estimated to be 0.018, meanwhile it was estimated to be 0.027 for the fumarolic gases at HYK and GTP, suggesting the magma beneath DYK is depleted in volatiles relative to the magma beneath HYK and GTP. The estimated CO₂/H₂O ratio for the magmatic component is comparable to that of some active volcanoes in Japan, suggesting the enrichment of volatiles in the magmas beneath TVG.