Optical absorption of electronic Fe–Ti charge-transfer transition in natural andalusite: the thermal stability of the charge-transfer band

Differently colored natural Brazilian andalusite crystals heat-treated under reducing and oxidizing conditions were analyzed by optical spectroscopy. The intensity of a broad intense band at around 20,500 cm⁻¹ in the optical absorption spectra of all color zones of the sample is proportional to the product of Ti- and Fe-concentrations and herewith proves its attribution to electronic Fe²⁺/Ti⁴⁺ IVCT transition. The band is strictly E||c-polarized, causing an intense red coloration of the samples in this polarization. The polarization of the Fe²⁺/Ti⁴⁺ IVCT band in andalusite, E||c, shows that the electronic charge-transfer process takes place in Al–O octahedral groups that share edges with neighbors on either side, forming chains parallel to the c-axis of the andalusite structure. Under thermal treatments in air, the first noticeable change is some intensification of the band at 800°C. However, at higher temperatures its intensity decreases until it vanishes at 1,000°C in lightly colored zones and 1,100°C in darkly colored ones. Under annealing in reducing conditions at 700 and 800°C, the band also slightly increases and maintains its intensity at treatments at higher temperatures up to 1,000°C. These results demonstrate that weakening and disappearance of the Fe²⁺/Ti⁴⁺ IVCT band in spectra of andalusite under annealing in air is caused by oxidization of Fe²⁺ to Fe³⁺ in IVCT Fe²⁺/Ti⁴⁺-pairs. Some intensification of the band at 800°C is, most probably, due to thermally induced diffusion of Fe²⁺ and Ti⁴⁺ in the structure that leads to aggregation of “isolated” Ti⁴⁺ and Fe²⁺ ions into Fe²⁺–Ti⁴⁺-pairs. At higher temperatures, the competing process of Fe²⁺ → Fe³⁺ oxidation overcomes such “coupling” and the band continues to decrease. The different thermal stability of the band in lightly and darkly colored zones of the samples evidence some self-stabilization over an interaction of Fe²⁺/Ti⁴⁺-pairs involved in IVCT process.     

On the origin and the spreading of the shallow Mediterranean water core in the Iberian basin

The origin and the spreading of the shallow Mediterranean water core (Ms) in the Iberian basin is discussed with a quasi-synoptic hydrographic data set enhanced by chlorofluoromethane (CFM) measurements. Its characteristic density level is found to be σ_t = 27.4. Characterized by high temperature and CFM values, Ms enters the Iberian basin in the region of Cape St Vincent between depths of 500–750 dbar. A heat anomaly of >11.8 × 10⁹ J m⁻² is chosen as the boundary between the presence of Ms and the background field. The core is found in a tongue-like shape as well as in separate isolated eddies of both cyclonic and anticyclonic circulation. Using the optimum multiparameter analysis (Tomczak and Large, 1989, Journal of Geophysical Research, 94, 16141–16149), the North Atlantic Central Water (NACW), which mixes with the Mediterranean outflow to form Ms, turned out to be in the mean 1°C warmer and 0.11 saltier than in regions with minor Mediterranean influence. This points to the Gulf of Cadiz as the origin of Ms, where the Mediterranean oufflows is in contact with NACW of the appropriate characteristics.     

High-resolution seabed imagery as a tool for biodiversity conservation planning on continental margins

Submarine canyons increase seascape diversity on continental margins and harbour diverse and abundant biota vulnerable to fishing. Because many canyons are fished, there is an increasing emphasis on including them in conservation areas on continental margins. Here we report on sponge diversity and bottom cover in three canyons of South-eastern Australia, test the performance of biological and abiotic surrogates, and evaluate how biological data from detailed seabed surveys can be used in conservation planning in these habitats. The biological data on sponge assemblage structure and species richness were obtained from 576 seafloor images taken between 148 and 472 m depth, yielding 65 morphospecies. Seafloor characteristics were similar within and between canyons, being almost exclusively composed of sediments with very few rocky substrates of higher relief. This environmental homogeneity did not, however, translate into biological uniformity of the megabenthos, and environmental factors were consequently poor predictors of biological features. By contrast, total bottom cover of sponges was highly correlated with species richness and served as a good proxy for species-level data in this situation. Design strategies that employ information on cover or richness of sponges provided a large dividend in conservation effort by dramatically reducing the number of spatial units required to achieve a specified conservation target of 50–90% of species to be included in reserves. This demonstrates that image-derived data are useful for the design of reserves in the deep sea, particularly where extractive sampling is not warranted. Using biological data on the sponge megabenthos to identify conservation units can also minimise socio-economic costs to fisheries because of a smaller geographic and bathymetric ambit of conservation areas.     

Ultraviolet-visible and fluorescence spectral evidence of natural organic matter (NOM) changes along an estuarine salinity gradient

A transect of the St Marys River estuary from above the point of maximum salt wedge penetration to coastal salinities was conducted in July 1999. None of the parameters examined—dissolved organic carbon (DOC) content, UV light absorbance at 254 nm, and Total Luminescence spectra—follow the rule of conservative mixing. The characteristics of the different molecular size fractions of the St Marys River natural organic matter (NOM), as well as the results of a laboratory mixing experiment, provided evidence that loss of larger molecular size compounds from riverine NOM may occur by coagulation at salinities up to 10. An apparent gain of carbon in the lower estuary was attributed to exports from abundant coastal marshes in this area. The Total Luminescence spectra of the riverine NOM can be described by two peaks, centered respectively around 340/445 nm, and 230/430 nm Excitation/Emission Wavelength Pair (EEWP), which are characteristic of humic materials of aquatic origin. The samples from the high salinity stations exhibit peaks at lower emission wavelength EEWP 320/424 nm, which can be considered as marine humic-like material. The presence of amino acid-tryptophan like peaks were observed, with EEWP 300/350 nm in some of the high salinity samples. This peak was of high relative fluorescence intensity. It is hypothesized that the intense biological activity of the salt marsh and near coastal area is responsible for the carbon addition as well as the appearance of the highly fluorescence amino acid-protein like material.     

Trajectory analysis at intersections for traffic rule identification

In this paper,we focus on trajectories at intersections regulated by various regulation types such as traffic lights,priority/yield signs,and right-of-way rules.We test some methods to detect and recognize movement patterns from GPS trajectories,in terms of their geometrical and spatio-temporal components.In particular,we first find out the main paths that vehicles follow at such locations.We then investigate the way that vehicles follow these geometric paths(how do they move along them).For these scopes,machine learning methods are used and the performance of some known methods for trajectory similarity measurement(DTW,Hausdorff,and Fréchet distance)and clustering(Affinity propagation and Agglomerative clustering)are compared based on clustering accuracy.Afterward,the movement behavior observed at six different intersections is analyzed by identifying certain movement patterns in the speed-and time-profiles of trajectories.We show that depending on the regulation type,different movement patterns are observed at intersections.This finding can be useful for intersection categorization according to traffic regulations.The practicality of automatically identifying traffic rules from GPS tracks is the enrichment of modern maps with additional navigation-related information(traffic signs,traffic lights,etc.).     

Strange pulsar hypothesis

It appears that there is a genuine shortage of radio pulsars with surface magnetic fields significantly smaller than ∼10⁸ G. We propose that the pulsars with very low magnetic fields are actually strange stars locked in a state of minimum free energy and therefore at a limiting value of the magnetic field which cannot be lowered by the system spontaneously.     

The role of Fischer‐Tropsch catalysis in solar nebula chemistry

Abstract— Fischer‐Tropsch catalysis, the iron/nickel catalyzed conversion of CO and H₂ to hydrocarbons, would have been the only thermally‐driven pathway available in the solar nebula to convert CO into other forms of carbon. A major issue in meteoritics is to determine the origin of meteoritic organics: are they mainly formed from CO in the solar nebula via a process such as Fischer‐Tropsch, or are they derived from interstellar organics? In order to determine the role that Fischer‐Tropsch catalysis may have played in the organic chemical evolution of the solar nebula, we have developed a kinetic model for this process. Our model results agree well with experimental data from several existing laboratory studies. In contrast, empirical rate equations, which have been derived from experimental rate data for a limited temperature (T) and pressure (P) range, are inconsistent with experimental rate data for higher T and lower P. We have applied our model to pressure and temperature profiles for the solar nebula, during the epoch in which meteorite parent bodies condensed and agglomerated. We find that, under nebular conditions, the conversion rate of CO to CH₄ does not simply increase with temperature as the empirically‐derived equations suggest. Instead, our model results show that this process would have been most efficient in a fairly narrow region that coincides with the present position of the asteroid belt. Our results support the hypothesis that Fischer‐Tropsch catalysis may have played a role in solar nebula chemistry by converting CO into less volatile materials that can be much more readily processed in the nebula and in parent bodies.     

Scenarios of the spread of a waste heat discharge in a river — Vistula River case study

The problem of two-dimensional mathematical modelling of heated cooling water discharges into running waters is considered in the paper. Two models — one for the evaluation of 2D turbulent velocity field and the other, developed by authors of the study, for 2D heat transport in open-channels — were used in the calculations. Relevant scenarios of the spread of heated water discharged from a designed gas-stem power plant to be constructed at the Vistula River were presented. Environmentally most friendly variant of the discharge of the thermal pollution was selected from among four various variants.