Incorporation of Cr<Superscript>3+</Superscript> in dickite: a spectroscopic study

 We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm⁻¹ allows us to unambiguously identify the major contribution of octahedrally coordinated Cr³⁺ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr³⁺ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest the substitution of Cr³⁺ for Al³⁺ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion around Cr³⁺ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe³⁺ ions (λ≈ 0.6–0.8). Received: 29 June 2001 / Accepted: 22 October 2001     

Enzymatic degradation of polyhydroxyalkanoate using lipase from <Emphasis Type="Italic">Bacillus subtilis</Emphasis>

Polyhydroxyalkanoates (PHAs) are an important class of biodegradable polymers synthesized by a few bacteria under nutrient-limiting conditions. In this study, the lipase-catalysed degradation of PHA synthesized by Enterobacter sp. was monitored. For this, the lipase-encoding gene from Bacillus subtilis DI2 was PCR-amplified, cloned into a T vector system and sequenced. It was expressed in Escherichia coli DH5α cells, the recombinant enzyme was purified 24.25-fold, and its molecular weight was determined to be around 28 kDa. When PHA biodegradation studies were carried out with this enzyme, gel permeation chromatography showed 21.3 and 28.3 % molecular weight decrease and weight loss, respectively. Further, scanning electron micrographs revealed alterations in polymer surface morphology. Changes in molecular vibrations were noticed in the FTIR spectra. When the chemical shifts in NMR spectra were studied, a steep reduction in area under the peak at 1.57 ppm was observed. In the heating range of 30–930 °C employed during thermogravimetry analysis, the degraded sample showed a total of 45.82 % weight loss, as against 18.89 % for the native sample. The melting temperature (T _m) of the polymer was also brought down from 126.22 to 118.18 °C, as inferred from differential scanning calorimetry. Lipase-catalysed chain scission reactions could thus be used to generate low molecular weight functional biopolymers with wide-ranging pharmaceutical applications, such as in sustained drug release.     

Seasonal and solar cycle variations of night-time anomalous enhancements in total electron content

Seasonal and solar cycle variations of the various characteristics of night-time anomalous enhancements in total electron content (TEC) of the ionosphere are presented for a low latitude station, Hawaii by considering TEC data for a full solar cycle. All the characteristics of the TEC enhancements have seasonal and solar cycle dependence. TEC enhancement characteristics such as frequency of occurrence, amplitude and duration are positively correlated with solar activity. The possible source mechanisms for the observed enhancements are also discussed.     

Development of a continuous soil moisture accounting procedure for curve number methodology and its behaviour with different evapotranspiration methods

The curve number (CN) method is widely used for rainfall–runoff modelling in continuous hydrologic simulation models. A sound continuous soil moisture accounting procedure is necessary for models using the CN method. For shallow soils and soils with low storage, the existing methods have limitations in their ability to reproduce the observed runoff. Therefore, a simple one‐parameter model based on the Soil Conservation Society CN procedure is developed for use in continuous hydrologic simulation. The sensitivity of the model parameter to runoff predictions was also analysed. In addition, the behaviour of the procedure developed and the existing continuous soil moisture accounting procedure used in hydrologic models, in combination with Penman–Monteith and Hargreaves evapotranspiration (ET) methods was also analysed. The new CN methodology, its behaviour and the sensitivity of the depletion coefficient (model parameter) were tested in four United States Geological Survey defined eight‐digit watersheds in different water resources regions of the USA using the SWAT model. In addition to easy parameterization for calibration, the one‐parameter model developed performed adequately in predicting runoff. When tested for shallow soils, the parameter is found to be very sensitive to surface runoff and subsurface flow and less sensitive to ET. Copyright © 2007 John Wiley & Sons, Ltd.     

Structural control over equilibrium silicon and oxygen isotopic fractionation: A first-principles density-functional theory study

Isotopic fractionation factors for oxygen and silicon in selected silicates (quartz, enstatite, forsterite, lizardite, kaolinite) are calculated using first-principles methods based on density-functional theory. Good agreement between theory and experiment is found in the case of oxygen. In the case of silicon, agreement and differences with existing estimates of equilibrium fractionation factors are discussed. The relationship between silicon and oxygen fractionation factors, silicate polymerization degree and chemical composition is studied and compared with previous semi-empirical models.     

Induced modifications of kaolinite under ionizing radiation: an infrared spectroscopic study

Radiation effects on kaolinite were investigated using He⁺ ions of 1.5 MeV at radiation doses up to 4.3 × 10⁸ Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 × 10¹⁶ spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects.     

57Fe Mössbauer spectroscopy of tektites

Tektite glasses are investigated using ⁵⁷Fe Mössbauer spectroscopy. Room temperature spectra analysis is performed using two complementary analytical methods based on two-dimensional distributions of both isomer shift and quadrupole splitting. No a priori correlation between the two hyperfine parameters is considered. The first method, based on a shape independent distribution, provides the justification for the Gaussian distribution shape used in the second method. No ferric iron contribution is evidenced by Mössbauer spectra analysis in these samples, although several criteria are used. Ferrous iron sites are shown to be continuously distributed between four- and five-fold co-ordinated sites.     

Assessment of coastal bio-resources of the Palk Bay,India, using IRS-LISS-III data

Coastal resources viz., coral reefs, seagrasses, mangroves, and coastal land features viz., sandy beach, mudflats and salt pan/aquaculture ponds were classified and assessed in the Palk Bay region of the south-east coast of India using IRS LISS III satellite image (1996, 2000, 2002 and 2004). The study recorded an areal coverage of 286.95 ha of reef area during 2004, which is 177.54 ha lesser than that of the reef area of 1996. The reef vegetation composed mainly of seaweeds has gained over 29.44 ha during the same period. Likewise, sand over reef area has also increased alarmingly i.e. 120.34 ha between 1996 and 2004. The seagrass beds of Munaikkadu region of the Palk Bay are comparatively protected and have gained over 7.5 ha between 1996 and 2004. It has been found that both the dense (2.99 ha) and sparse (36.45 ha) mangroves have gained their areal coverage considerably between 1996 and 2004. Whereas in Devipattinam region, many anthropogenic pressures are exerted only on the seagrass resources which has led to the reduction of over 785.5 ha of dense seagrass beds between 1996 and 2004. The study clearly indicated that the resources are under the pressures of low to high threats, especially the coral reefs and seagrasses, if the pressures continue, coastal resources of the Palk Bay may face serious threats of destruction in this part of the Bay in the years to come.