IR active orientation of OH bending mode in topaz

Infrared (IR) and nearinfrared (NIR) absorption spectra of hydrous and F-rich topazes were measured to assign an OH bending mode of topaz. Three absorption peaks at 1165, 3650, and 4803 cm⁻¹ are assigned to OH related absorption peaks. Since a peak at 4803 cm⁻¹ can be assigned to a combination mode of 1165 and 3650 cm⁻¹, the 1165 cm⁻¹ peak is harmonic with the 3650 cm⁻¹ peak. Polarized IR absorption spectra of (100), (010), and (001) planes of the hydrous topaz were measured to examine IR active orientation of the 1165 cm⁻¹ OH related mode. Three pleochroic distributions of the absorption peak at 1165 cm⁻¹ on (100), (010), and (001) planes indicate an active orientation of the 1165 cm⁻¹ OH related mode. The IR active orientation of the 1165 cm⁻¹ OH related mode in topaz is normal to the OH dipole. The orthogonality and harmonic combination mode indicate that the 1165 cm⁻¹ peak is OH bending mode. The active orientation of OH bending mode is polarized in the plane normal to the OH dipole. The polarization suggests that anisotropic thermal vibration of protons on the hydroxyl is maximum along the IR active orientation. Received: August 16, 1996 / Revised, accepted: April 20, 1997     

Interlayer proton transfer in brucite under pressure by polarized IR spectroscopy to 5.3 GPa

In order to investigate the behaviour of proton in brucite under pressure, polarized IR absorption spectra and polarized absorbance distributions of (001) and (110) oriented single crystal of brucite under high pressure were measured by Fourier transform polarized infrared microspectroscopy with diamond anvil cell. A pressure-induced absorption peak at 3645 cm⁻¹ observed under pressures over 2.9 GPa was confirmed to be due to a secondarily formed OH dipole. Polarized absorbance distribution measured under pressure of (110) suggests that the secondary OH dipole is oriented 136.0° to c-axis under 5.3 GPa. Isotropic absorbance distribution of (001) suggests that the secondary OH dipole is disorderly trifurcated. Abrupt onset of the secondary peak and its reverse pleochroism suggest that the process of secondary OH dipole formation is due to proton transfer between layers in brucite. The calculated orientation of the secondary OH dipole consistent with the O-H···O′ angle revealed by neutron diffraction supports the existence of proton transfer along H···O′. The secondary OH dipole implies a new site of proton in brucite under pressure. Received: 6 March 1997 / Revised, accepted: 9 June 1997     

Characteristics of rainfall systems accompanied with Changma front at Chujado in Korea

The rainy season from June to July in the East Asia is called the Changma in Korea, the Meiyu in China, or the Baiu in Japan. The mesoscale convective systems which occur near a front frequently lead to severe weather phenomenon such as localized gust and heavy rainfall. An intensive field experiment was conducted at Chujado (33.95°N, 126.28°E) to find out the characteristics of the precipitating system using information such as the raindrop size distribution, kinematic features during a Changma period between June 21 2007 and July 11 2007. Different characteristics of three identified rainfall cases in a Changma frontal precipitation system occurred from 5 to 6 July in 2007 at Chujado area have been identified. Based on the radar reflectivity and raingage at Chujado, each rainfall system maintained for 7 hours, 4 hours, and 9 hours, respectively. According to the analysis of a total vertical wind shear (TVWS) and a directional vertical wind shear (DVWS), the temperature gradient was the strongest near the surface and both warm and cold advections were occurred in all cases but at different levels. The deep warm advection was related to the longer rainfall lifetime and stronger rainrate, but smaller raindrop size. The unstable atmospheric condition, which has cold advection at the surface and warm advection in higher level, caused the larger size diameter of raindrop. The echo top height of 30 dBZ was around 6 km in the two rainfall systems and around 4 km in the other one. The number concentrations of raindrop has turning point at the drop size of 2 mm in diameter. The stronger (weaker) updraft and downdraft were also related to the decreased number concentration of smaller (larger) size drops and increased that of the larger (smaller) drops.     

Estimation of surface soil water content from surface temperatures in dust source regions of Mongolia and China

Surface conditions, such as surface roughness and soil moisture, control wind erosion and dust emission in northeast Asia. Data on spatial and temporal changes of surface soil water content are needed for dust-modeling systems used to predict dust events with the aim of preventing damage from them. A modified temperature-vegetation dryness index (MTVDI) was tested to see if it could reproduce surface soil water contents measured during the dust event season in Bayan Unjuul, Mongolia, and Shenmu, China. MTVDI was calculated from land surface temperature and aerodynamic minimum and maximum surface temperatures estimated from meteorological data. The standard deviation of the error of estimations of soil water content from MTVDI was ±1.5% in Bayan Unjuul when soil water content was lower than 4%. This compares favorably with the observational error of ±1% of the soil moisture sensors used.     

Diurnal surface temperature difference index derived from ground-based meteorological measurements for assessment of moisture availability

Droughts have become widespread in the Northern Hemisphere, including in China, where they have affected farmland resources on the Loess Plateau. Given this background, we proposed a new index, the Normalized Day-Night Surface Temperature Index (NTDI), to estimate moisture availability (m_a), defined as the ratio of actual to reference evapotranspiration. The NTDI is defined as the ratio of the difference between the maximum daytime surface temperature and the minimum nighttime surface temperature, to the difference between the maximum and minimum surface temperatures estimated from meteorological data by applying energy balance equations.To calculate the index, we used data of 20 clear-sky meteorological observations made during the 2005 growing season at a natural grassland station in the Liudaogou River basin on the Loess Plateau. The NTDI showed a significant inverse exponential correlation with m_a (R² = 0.97, p < 0.001), whereas the numerator of the index (the maximum daytime surface temperature minus the minimum nighttime surface temperature) was only weakly correlated with m_a (R² = 0.24, p = 0.03). This result indicates that normalization relative to the index denominator (maximum surface temperature − minimum surface temperature) dramatically improved the accuracy of the estimate.     

Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na⁺ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm⁻¹. On the basis of experimental and theoretical studies, we assigned these pairs of bands to the ν₁ and ν₂ modes of doubly coordinated type II H₂O and to singly coordinated type II H₂O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750°C, suggested the dehydration of type I and type II water, respectively.     

Induction of female‐to‐male sex change in a large protogynous fish,Choerodon schoenleinii

Most behavioral studies on hermaphroditic fishes have focused on small‐sized species, which are tractable for research. Although many species of large hermaphroditic fishes are important fishery resources, their proximate mechanisms (visual, chemical and/or behavioral cues) in the social regulation of sex change have not been determined. Determination of these would inform resource management and aquaculture. In order to get closer to understanding the proximate mechanisms underlying the social regulation of female‐to‐male sex change in large hermaphroditic fishes, this study reports situations that induced female‐to‐male sex change in black‐spot tuskfish, Choerodon schoenleinii, a species of large protogynous fish, in massive laboratory tanks. The situations differed in the possibility of male‐to‐female tactile contact and in the group sex ratio, enabling us to infer plausible proximate mechanisms underlying sex change induction. Tactile contact between individuals is suspected to be closely related to the incidence of female‐to‐male sex change in C. schoenleinii. Visual and chemical cues alone may be insufficient to inhibit such sex changes. Male‐to‐female tactile contact may have an important influence on female‐to‐male sex change, i.e., inhibition of this sex change, in this species. The effect of sex ratio of a social group on the incidence of sex change may be due to the relative frequency and intensity of male tactile contact with each female, which may vary with the number of females. In the absence of a dominant male, tactile contact among females may affect the incidence of sex change, as well as determine which individuals change sex.     

Response of plant growth to surface water balance during a summer dry period in the Kazakhstan steppe

In drylands, water deficit is the primary factor limiting plant growth. In the present study, surface energy balance and plant growth (above‐ground and below‐ground biomass) were measured continuously during the 2002 growing season in semiarid grassland in the northern part of Kazakhstan, Central Asia. Although there was above normal total rainfall during the 2002 growing season (May–November; 244 mm over 183 days), there was a dry period during July and August. Evaporative water was effectively supplied by precipitation and surface soil moisture during the wet season (May and June), during which time above‐ground biomass increased. During the early stages of the dry period, mature plants were likely to tap deeper sources of soil moisture, representing stored snowmelt water. As the soil moisture content decreased during the summer dry period due to the high levels of evapotranspiration and lack of precipitation, the evaporative fraction and above‐ground biomass rapidly decreased, whereas the below‐ground biomass increased. These results suggest that in summer, soil moisture acts to store water, and that soil moisture is essential for plant growth as a direct source of water during the dry period in natural grasslands in the Kazakhstan steppe. Copyright © 2007 John Wiley & Sons, Ltd.     

The orientation of the OH− dipole in an optically anisotropie crystal: An application to the OH− dipole in topaz

For the purpose of determining the orientation of the OH^? dipole in an optically anisotropic crystal, distribution of polarized IR absorbance is formulated under Fourier transform microspectroscopy. The formulatd absorbance distribution suggests that the degree of pleochroism of absorbance depends on the angle between the orientation of the OH^? dipole and the principal orientation of the optically anisotropic crystal. As its application, the general orientation of the OH^? dipole in topaz is determined to be inclined 27.3° from the c-axis in (010).     

Water molecules in beryl and cordierite: high-temperature vibrational behavior,dehydration, and coordination to cations

Natural samples of typical cyclosilicates beryl and cordierite include water and carbon dioxide molecules in channels formed by the open cavities. Water molecules in the channels have two forms that are distinguished by whether they coordinate to extra-framework cations (type II) or not (type I). We measured polarized infrared (IR) spectra for thin sections of the (100) plane of beryl or the (100) and (010) planes (cb and ca planes) of cordierite under various temperature conditions. The spectral features of major bands clearly showed the distinguishable behavior of types I and II water molecules under high temperature as follows. Over the temperature range from room temperature to 800°C where rapid dehydration did not occur, the decrease in band heights for type II water molecules were smaller than those for type I, and band shifts were more predominant for type II water molecules. The decrease in band heights and band shifts of type I/II bands differed also for beryl and cordierite, which arises from the different ways in which water molecules are fixed in the channels. Dehydration was enhanced at 850°C. The IR spectra at room temperature quenched from 850°C both for beryl and cordierite showed that the vibrational bands related to type II water molecules were stable after those related to type I water molecules disappeared. In addition, frequency changes of type II bands were observed, possibly because of changes of coordination states of type II water molecules to extra-framework cations in the channels.