Natural and experimental structural evolution of dispersed organic matter in mudstones: The Shimanto accretionary complex,southwest Japan

Structural changes induced by thermal maturation of dispersed organic matter (OM) in the Shimanto accretionary complex, southwest Japan, were investigated using micro‐Fourier‐transform infrared spectroscopy and micro‐Raman spectroscopy. Natural dispersed OM exhibits systematic structural changes inferred from D1‐ and G‐band FWHM values, Raman band separation (RBS), and intensity ratios of the D1‐ and G‐bands (I_D1/I_G ratio) from diagenetic zone to anchizone (IC values: 0.75–0.30). Infrared spectra indicate a loss of aliphatic CH _x, aromatic CH _x, and oxygen‐containing structures as temperature increases. These changes are consistent with discontinuities in thermal structures bounded by out‐of‐sequence thrusts. Kinetic pyrolysis experiments indicate that the I_D1/I_G ratio of synthesized OM has a power law relationship with heat treatment time. Kinetic models of temperature dependence were fitted using the I_D1/I_G ratio, and an effective activation energy of 106 ±17 kJ/mol was estimated using an Arrhenius equation. The activation energies estimated by power law rate and Avrami models have a least‐square correlation coefficient of 0.93, indicating the temperature dependence of carbonization. The estimated effective activation energy is consistent with that of coal, lignin, cellulose, and hemicellulose during thermal degradation. On the other hand, RBS, and D1‐ and G‐band FWHM values of OM display more complex changes with increasing heating temperature and time, and it is difficult to constrain rate parameters during pyrolysis experiments. Our data indicate that the I_D1/I_G ratio is controlled by a simple thermally activated process, whereas RBS and D1‐ and G‐band FWHM values can be affected by lithostatic pressure, fluid activity, hydrogen index, and host lithology, as well as temperature. Structural evolution of dispersed OM in mudstones differs between natural and anhydrous closed experimental systems. Natural carbonization based on micro‐Raman spectroscopy should be applied for a limited indicator of thermal maturation, especially for dispersed OM in diagenetic zone.     

Chemical Features of White Micas from the Piemonte Calc-schists, Western Alps and Implications for K–Ar Ages of Metamorphism

Anomalously large chemical ranges in muscovite-paragonite and muscovite-celadonite systems are observed in white micas from the Piemonte calcschists in the Chisone valley area, internal western Alps. The petrographical and chemical observations on white mica strongly suggest that most mica crystals with high Na/K ratios in the chlorite zone are of detrital origin, and were derived from the pre-Alpine high-temperature metamorphic sequence such the Caledonian and/or Variscan. Submicroscopic muscovite (Ms) - paragonite (Pg) composite aggregates occur in the chlorite zone and their EPMA analyses give an apparent chemical composition range from Ms_0.6Pg_0.4 to Ms_0.2Pg_0.8. In the rutile zone, the paragonite content of the white micas is less than 20%, suggesting that the white micas have been homogenized during the Alpine metamorphism even if detrital white micas existed.Metamorphic mica is also very heterogeneous. The total range in Si content becomes wider with increasing of metamorphic grade: 3.22–3.39 pfu for the chlorite zone, 3.07–3.45 pfu for the chloritoid zone and 3.06–3.59 pfu for the rutile zone. This clearly indicates that the micas have experienced significant retrogressive chemical reactions during cooling and exhumations of the host schists.The detrital white mica in the chlorite zone has not reset well in its K-Ar system during the Alpine subduction-related metamorphism. The wide range of the white mica K-Ar ages from 115 to 41 Ma must be due to a mixture of various amounts of detrital white mica in the separates. This feature is also observed in the chloritoid zone though the age variation is not so large as that in the chlorite zone. In contrast, the mica in the rutile zone, which was higher than 450°C, has been reset completely during Alpine HP metamorphism.     

实时 Ｇ Ｐ Ｓ可降水量资料的变分同化个例研究

用实时GPS可降水量(Precipitable Water, PW)资料GPSPW,针对2007年7月2-3日发生在日本九州南部地区的一次梅雨锋降水过程,设计控制试验和4个同化试验,利用WRF和WRF-Var模式进行三维变分同化研究,并用ETS评分客观评价各方案的预报效果.结果表明:实时GPSPW同化能有效地改进模式初始时刻水汽场以及预报时间内(0～6 h)的PW.背景误差水平尺度调节系数的大小对水汽场的调整范围和PW的改进程度有一定影响.GPSPW的实时性能提高降水预报业务的实时性.     

Reaction of forsterite with hydrogen molecules at high pressure and temperature

High pressure and temperature reactions of a mixture of forsterite and hydrogen molecules have been carried out using a laser heated diamond anvil cell at 9.8–13.2 GPa and ~1,000 K. In situ X-ray diffraction measurements showed no sign of decomposition or phase transitions of the forsterite under these experimental conditions, indicating that the olivine structure was maintained throughout all runs. However, a substantial expansion of the unit cell volume of the forsterite was observed for samples down to ~3 GPa upon quenching to ambient pressure at room temperature. The Raman spectroscopy measurements under pressure showed significant shifts of the Raman peaks of the Si–O vibration modes for forsterite and of the intramolecular vibration mode for H₂ molecules toward a lower frequency after heating. Additionally, no OH vibration modes were observed by Raman and FT-IR spectroscopic measurements. These lines of evidence show that the observed volume expansion in forsterite is not explained by the incorporation of hydrogen atoms as hydroxyl, but suggest the presence of hydrogen as molecules in the forsterite structure under these high pressure and temperature conditions.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Diurnal Variation in the Vertical Profile of the Raindrop Size Distribution for Stratiform Rain as Inferred from Micro Rain Radar Observations in Sumatra

The diurnal variation in the vertical structure of the raindrop size distribution(RSD) associated with stratiform rain at Kototabang, West Sumatra(0.20°S, 100.32°E), was investigated using micro rain radar(MRR) observations from January 2012 to August 2016. Along with the MRR data, the RSD from an optical disdrometer and vertical profile of precipitation from the Tropical Rainfall Measuring Mission were used to establish the microphysical characteristics of diurnal rainfall.Rainfall during 0000–...     

A method for extending a general constitutive model to consider the electro-chemo-mechanical phenomena of mineral crystals in expansive soils

The mechanical behavior of expansive soils varies according to the chemical composition of the pore fluid. It is well known that electrochemical phenomena on the surface of clay mineral crystals considerably affect their macrostructural behavior. In particular, a change in the pore fluid composition causes osmotic consolidation or swelling. In this study, a model is constructed to describe the characteristic behavior of expansive soils by coupling the interlaminar behavior of clay mineral crystals and the soil skeleton behavior. The interlaminar behavior is derived from the electro-chemo-mechanical coupling equilibrium of mineral crystals, and the soil skeleton behavior is given by a general elastoplastic constitutive model for soils. This modeling approach extends a general model to consider the electro-chemo-mechanical phenomena of mineral crystals. Oedometer tests with the replacement of the cell fluid and the swelling pressure and deformation tests on expansive clays are simulated with the proposed model. The simulation results indicate that the proposed method can reasonably represent the typical behavior of expansive soils.     

Observations of Coherent Turbulence Structures in the Near-Neutral Atmospheric Boundary Layer

Turbulence structures of high Reynolds number flow in the near-neutral atmospheric boundary layer (ABL) are investigated based on observations at Shionomisaki and Shigaraki, Japan. A Doppler sodar measured the vertical profiles of winds in the ABL. Using the integral wavelet transform for the time series of surface wind data, the pattern of a descending high-speed structure with large vertical extent (from the surface to more than 200-m level) is depicted from the Doppler sodar data. Essentially this structure is a specific type of coherent structure that has been previously shown in experiments on turbulent boundary-layer flows. Large-scale high-speed structures in the ABL are extracted using a long time scale (240 s) for the wavelet transform. The non-dimensional interval of time between structures is evaluated as 3.0–6.2 in most cases. These structures make a large contribution to downward momentum transfer in the surface layer. Quadrant analyses of the turbulent motion measured by the sonic anemometer (20-m height) suggest that the sweep motion (high-speed downward motion) plays a substantial role in the downward momentum transfer. In general, the contribution of sweep motions to the momentum flux is nearly equal to that of ejection motions (low-speed upward motions). This contribution of sweep motions is related to the large-scale high-speed structures.     

Shattering and coagulation of dust grains in interstellar turbulence

We investigate shattering and coagulation of dust grains in turbulent interstellar medium (ISM). The typical velocity of dust grain as a function of grain size has been calculated for various ISM phases based on a theory of grain dynamics in compressible magnetohydrodynamic turbulence. In this paper, we develop a scheme of grain shattering and coagulation and apply it to turbulent ISM by using the grain velocities predicted by the above turbulence theory. Since large grains tend to acquire large velocity dispersions as shown by earlier studies, large grains tend to be shattered. Large shattering effects are indeed seen in warm ionized medium within a few Myr for grains with radius   a ≳ 10⁻⁶  cm. We also show that shattering in warm neutral medium can limit the largest grain size in ISM  ( a ∼ 2 × 10⁻⁵ cm)  . On the other hand, coagulation tends to modify small grains since it only occurs when the grain velocity is small enough. Coagulation significantly modifies the grain size distribution in dense clouds (DC), where a large fraction of the grains with   a < 10⁻⁶ cm  coagulate in 10 Myr. In fact, the correlation among   R_V   , the carbon bump strength and the ultraviolet slope in the observed Milky Way extinction curves can be explained by the coagulation in DC. It is possible that the grain size distribution in the Milky Way is determined by a combination of all the above effects of shattering and coagulation. Considering that shattering and coagulation in turbulence are effective if dust-to-gas ratio is typically more than ∼1/10 of the Galactic value, the regulation mechanism of grain size distribution should be different between metal-poor and metal-rich environments.