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.     

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.     

exofit: orbital parameters of extrasolar planets from radial velocities

Retrieval of orbital parameters of extrasolar planets poses considerable statistical challenges. Due to sparse sampling, measurement errors, parameters degeneracy and modelling limitations, there are no unique values of basic parameters, such as period and eccentricity. Here, we estimate the orbital parameters from radial velocity data in a Bayesian framework by utilizing Markov Chain Monte Carlo (MCMC) simulations with the Metropolis–Hastings algorithm. We follow a methodology recently proposed by Gregory and Ford. Our implementation of MCMC is based on the object-oriented approach outlined by Graves. We make our resulting code, exofit , publicly available with this paper. It can search for either one or two planets as illustrated on mock data. As an example we re-analysed the orbital solution of companions to HD 187085 and HD 159868 from the published radial velocity data. We confirm the degeneracy reported for orbital parameters of the companion to HD 187085, and show that a low-eccentricity orbit is more probable for this planet. For HD 159868, we obtained slightly different orbital solution and a relatively high 'noise' factor indicating the presence of an unaccounted signal in the radial velocity data. exofit is designed in such a way that it can be extended for a variety of probability models, including different Bayesian priors.     

First-principles study of the structural and isotopic properties of Al- and OH-bearing hematite

A series of hematite structures containing various amounts of aluminum and hydroxyl groups was modeled using first-principles methods based on the density functional theory. Evolution of the lattice parameters was quantified as a function of Al and H concentrations. The a and c lattice parameters decrease with the aluminum content and increase with the water content. This allows explaining experimental data reported for synthetic hematites, in particular the observed deviation from the Vegard’s rule. Investigation of several hydroxyl configurations associated with cationic vacancies suggests that the speciation of water also significantly affects the hematite structure. The ⁵⁷Fe and ¹⁸O reduced partition functions (β-factor) were determined. Results show a linear dependence of the iron and oxygen β-factors on the aluminum content. An incorporation of 18 mole % Al₂O₃ in hematite would increase the iron β-factor of about 0.6‰ and the oxygen β-factor of about 5.5‰ at 0 °C. This effect is sufficiently large to be measurable and to affect the interpretation of natural isotopic compositions. On the other hand, the effect of water is found to be negligible for the hydroxyl configuration investigated.     

Multiple current sheets in a double auroral oval observed from the MAGION-2 and MAGION-3 satellites

A case is described of multiple current sheets crossed by the MAGION-2 satellite in the near-midnight quieting auroral oval. The data were obtained by the magnetometer experiment onboard. Results show during a quieting period after a preceding substorm, or during an early growth phase of the next substorm, two double-sheet current bands, POLE and EQUB, located at respectively the polar and equatorial borders of the auroral oval separated by about 500 km in latitude. This is consistent with the double-oval structure during recovery introduced by Elphinstone et al. (1995). Within the POLE, the magnetic field data show simultaneous existence of several narrow parallel bipolar current sheets within the upward current branch (at 69.5–70.3° invariant latitude) with an adjacent downward current branch at its polar side at (70.5–71.3°). The EQUB was similarly stratified and located at 61.2–63.5° invariant latitude. The narrow current sheets were separated on average by about 35 km and 15 km, respectively, within the POLE and EQUB. A similar case of double-oval current bands with small-scale structuring of their upward current branches during a quieting period is found in the data from the MAGION-3 satellite. These observations contribute to the double-oval structure of the late recovery phase, and add a small-scale structuring of the upward currents producing the auroral arcs in the double- oval pattern, at least for the cases presented here. Other observations of multiple auroral current sheets and theories of auroral arc multiplicity are briefly discussed. It is suggested that multiple X-lines in the distant tail, and/or leakage of energetic particles and FA currents from a series of plasmoids formed during preceding magnetic activity, could be one cause of highly stratified upward FA currents at the polar edge of the quieting double auroral oval.     

Sustainable for whom? Green urban development,environmental gentrification,and the Atlanta Beltline

Large-scale, sustainable urban development projects can transform surrounding neighborhoods. Without precautionary policies, environmental amenities produced by these projects, such as parks, trails, walkability, and higher-density development, tend to result in higher land and housing costs. This will make it harder for a low- and moderate-income households to live near the projects, and neighborhoods are likely to become increasingly affluent. The Atlanta Beltline will ultimately connect 45 Atlanta neighborhoods via a 22-mile loop of trails, parks, and eventually a streetcar, all of which follow abandoned railroad tracks. This paper examines the effect of the Beltline on housing values within one half mile. From 2011 to 2015, depending on the segment of the Beltline, values rose between 17.9 percent and 26.6 percent more for homes within a half-mile of the Beltline than elsewhere. The implications for housing affordability and neighborhood change of projects like the Beltline, and associated policy questions, are addressed.