Interstellar cyanomethane

We have made an observational study of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of (1) elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and (2) providing a possible test of Bates's models of dissociative electron recombination. We find a remarkably different abundance ratio CH2CN/CH3CN in TMC-1 and Sgr B2, which we deduce is a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O. If this reaction does not proceed, then CH2CN and CH3CN are concluded to form via different chemical pathways. Thus, they do not provide a test of Bates's conjectures (they do not both form from CH3CNH+). CH2CN is then likely to form via C2H4(+) + N --> CH2CNH+, thus demonstrating the viability of this important reaction in astrochemistry. The T dependence of the CH2CN/CH3CN ratio would then reflect the increasing rate of the C2H4(+) + N reaction with decreasing temperature.     

Laboratory detection of a new interstellar free radical CH2CN(2B1)

An asymmetric-top free radical CH2CN, which as a 2B1 ground state, was detected for the first time by laboratory microwave spectroscopy. The radical was produced in a free-space absorption cell by a DC glow discharge in pure CH3CN gas. About 60 fine-structure components were observed for the N = 11-10 to 14-13 a-type rotational transitions in the frequency region of 220-260 GHz, and many hyperfine resolved components for the N = 4-3 and 5-4 transitions in the 80 and 100 GHz regions, respectively. The molecular constants, including the rotational constants, centrifugal distortion constants, and spin-rotation coupling constants with centrifugal distortion correction terms were determined from the fine-structure resolved transitions, and the hyperfine coupling constants due to the hydrogen and nitrogen nuclei were obtained from the low-N transitions. As a result we assigned U100602 and U80484 from Sgr B2, and U40240 and U20120 from TMC-1, to the N = 5-4, 4-3, 2-1, and 1-0 transitions with K-1 = 0 of the CH2CN radical.     

Ca isotopic compositions of dolomite, phosphorite and the oldest animal embryo fossils from the Neoproterozoic in Weng'an, South China

Deciphering the drastic changes of surface environment and the emergence of animals after the Neoproterozoic Snowball Earth event are important for understanding the changes of surface environment and its influence on the evolution of life through geologic time. Especially, the emergence of two types of Metazoan animals such as animal embryo fossils, cnidarians or sponges, and Ediacaran fauna in the late Neoproterozoic was one of the critical turning points in the biological evolution.Calcium is one of the essential elements for the growth of most animals. In this study, in order to evaluate the Ca cycles in the Neoproterozoic, we have measured Ca isotopic ratios (⁴⁴Ca/⁴²Ca and ⁴³Ca/⁴²Ca) for phosphorite, dolostone and phosphatic animal embryo fossils with a multiple collector, inductively coupled plasma-mass spectrometer (MC-ICP-MS). The resulting ⁴⁴Ca/⁴²Ca ratio defined by the relative deviation from the ratio of NIST SRM915a (δ^44/42Ca_NIST915) for phosphorite and dolostone ranges from 0.83 to 0.95‰, demonstrating that the fractionation between phosphorite/dolostone and seawater was very small. This evidence indicates that at the emergence of the Weng'an biota seawater was deficient in Ca probably due to mass deposition of phosphorite/dolostone and to the beginning of Ca-biomineralization.Three phosphatic animal embryo fossils have lower δ^44/42Ca values than the phosphorite and dolomite, implying that the precursor of the phosphatic embryo fossils was able to fractionate Ca isotopes through Ca-biomineralization, consistent with marine gastropods.     

Ba isotopic signature for early differentiation between Cs and Ba in natural fission reactors

Ba isotopic studies of the Oklo and Bangombé natural fission reactors in east Gabon provide information on the geochemical behavior of radioactive Cs (¹³⁵Cs and ¹³⁷Cs) in a geological medium. Large isotopic deviations derived from fissiogenic Ba were found in chemical leachates of the reactor uraninites. The fissiogenic Ba isotopic patterns calculated by subtracting the non-fissiogenic component are classified into three types that show different magnifications of chemical fractionation between Cs and Ba. In addition, the isotopic signatures of fissiogenic ¹³⁵Ba, ¹³⁷Ba and ¹³⁸Ba suggest an early differentiation between Cs and Ba of less than 20 years after the production of fissiogenic Cs and Ba. On the other hand, only small excesses of ¹³⁵Ba (ε < +1.8) and/or ¹³⁷Ba (ε < +1.3) were identified in some clay samples, which might have resulted from selective adsorption of ¹³⁵Cs and ¹³⁷Cs that migrated from the reactors by differentiation.     

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.     

Crystal-field theory calculations for Fe2+ Ions in bronzite,augite, and olivine

Crystal-field theory was applied to Fe²⁺ ions in three types of silicates in an attempt to assign all the major absorption bands with only one parameter to adjust. Coulomb potential energy field were calculated by Fourier method based on all the actual atomic coordinates refined by X-ray diffraction studies. Perturbed d-electron splitting energies of the central Fe²⁺ ion were calculated by introducing Configuration Interaction (CI) method for the lowest energy spectral states. All the major absorption bands observed in powdered bronzite, augite, and olivine, were assigned to the transitions between those calculated energy levels by optimizing only one parameter that expresses expansion or contraction of d-electron cloud. The result of the calculations gives almost the same assignments as the other previous works for bronzites, different assignments for augites, and a possibility of the existence of the fourth band hidden in the composite 1-μm band of olivines.     

Revisit of event-based rainfall characteristics at Shapotou area in northern China

Distribution of rainfall event sizes and interval lengths between events are important characteristics of arid and semi-arid climates. Understanding their importance will contribute to our ability to understand ecosystem dynamics in these regions. Rainfall event timing and magnitude are important drivers of ecosystem processes and are instrumental in creating landscape heterogeneity in arid and semi-arid regions. Rainfall event characteristics were analyzed using an automatic tipping-bucket rain-gauge record across the entire summer monsoon season from 2008 to 2015 at the arid desert area of Shapotou in the Tengger Desert, China. Changing the minimum inter-event time (MIT) from 30 min to 24 h alters the number of rainfall events from 64 to 25 for the event depth larger than 0.1 mm. The mean rainfall intensity declined from 0.95 mm/h to 0.53 mm/h, and the geometric mean event duration rose from 0.55 h to 4.4 h. The number of rainfall events, mean rainfall intensity, and geometric mean event duration differed under different criteria of individual rainfall depths, except that for an individual rainfall depth of 0.5, 1.0, and 5.0 mm. The aforementioned features differed only at the lowest range of the mean rainfall intensity and depth for MIT=3 and 6 h. These findings suggest that identification of event-based rainfall in this specific arid region can be better achieved by setting the MIT at six hours. The wide variation in rainfall event properties indicate the need for paying more attention to the proper selection and reporting of event criteria in studies that adopt event-based data analysis. This is especially true in quantifying effective rainfall for soil water replenishment in terms of rainfall depth and intensity with infrequent rainfall events.     

Relationships between textural and photoluminescence spectral features of carbonado (natural polycrystalline diamond) and implications for its origin

Field Emission SEM (FESEM) textural observations, crystal size distribution (CSD) analyses, UV-excited luminescence imaging, and photoluminescence (PL) microspectroscopy excited by 488 nm laser were conducted on two texturally contrasting samples of carbonado, a kind of natural polycrystalline diamond from the Central African Republic (CAR). The investigated carbonado samples A and B show extremely different textures: sample A is made up of faceted crystals accompanied by abundant, small rectangular pores, whereas sample B has a granular texture with coarser crystals and scarce, large pores. Diamond crystals smaller than 2–3 µm are enriched in sample A but depleted in sample B. These textural features indicate that sample B diamonds were annealed under thermodynamically stable P–T conditions. The pore characteristics indicate that fluid permeability was higher for sample A than sample B. Photoluminescence (PL) spectra indicate that samples A and B correspond to Group A and B carbonados in the classification of Kagi et al. (1994), respectively, so that sample A reveals emissions from the H3 center without any N–V⁰ derived emission at 575 nm, whereas sample B shows emissions from the 3H center and the N–V⁰ defect. In addition, UV-excited luminescence images and photoluminescence spectra for sample B indicate that the rims of diamond crystals within several microns of a pore show luminescence features similar to those of Group AB carbonados (Kagi et al., 1994), indicating that this Group AB material was formed from Group B by irradiation from pore-filling, radioactive-element-bearing materials at a low temperature. The extent of the low-temperature irradiation is considered to depend on fluid permeability, and the Group A material was strongly irradiated due to its permeable texture whereas the Group B material was not significantly irradiated due to its less permeable granular texture. These results indicate that Group B carbonados have retained their original PL spectral features produced under high pressures and temperatures at mantle depths.     

Seasonal variations of dissolved organic matter and nutrients in sediment pore water in the inner part of Tokyo Bay

At four stations in Tokyo Bay, pore water profiles of dissolved organic carbon (DOC), nitrogen (DON), phosphorus (DOP), and inorganic nutrients were determined at 3-month intervals over 6 years. Concentrations of dissolved organic matter (DOM) and nutrients were significantly higher in pore waters than in the overlying waters. Pore water DOC, DON, and DOP concentrations in the upper most sediment layer (0–1 cm) ranged from 246 to 888 μM, from 14.6 to 75.9 μM, and from 0.02 to 9.83 μM, respectively. Concentrations of DOM and nutrients in pore waters occasionally showed clear seasonal trends and were highest in the summer and lowest in the winter. The seasonal trends in the pore water DOM concentrations were coupled with trends in the overlying water temperature and dissolved oxygen concentration. Benthic effluxes of DON and DOP were low compared with those of inorganic nutrients, accounting for only 1.0 and 1.5 % of the total benthic effluxes of nitrogen and phosphorus, respectively; thus benthic DOM fluxes were quantitatively insignificant to the inorganic nutrient fluxes in Tokyo Bay. The DOM fluxes represented about 7, 3, and 10 % of the riverine discharge of DOC, DON, and DOP to Tokyo Bay, respectively.     

Numerical study for specifying the major origin of low salinity water associated with <Emphasis Type="Italic">Chattonella</Emphasis> (Raphidophyceae) blooms in Tachibana Bay,Japan

In both 2009 and 2010, massive Chattonella blooms occurred in Tachibana Bay. Observation results show that high cell densities of Chattonella were distributed in the central area of Tachibana Bay with low salinity water. Model results indicate that the low salinity water originated from the Ariake Sea and intruded into Tachibana Bay during the northerly or weak winds. It is suggested that low salinity water was mainly discharged from the northern area of the Ariake Sea. Northerly wind enhanced the horizontal advection of the low salinity water intruding into Tachibana Bay originating from the northern area of the Ariake Sea.