Transport and fate of nitrate within soil units of glacial origin

Questions concerning the influence of soil type and crop cover on the fate and transport of nitrate (NO₃⁻) were examined. During a growing season, soils derived from glacial material underlying either corn or soybeans were sampled for levels of NO₃⁻ within the pore water. Measured levels of NO₃⁻ ranged from below detection limit to 14.9 g NO₃⁻ per kilogram of soil (g/kg). In fields with the same crop cover, the silty-clayey soil exhibited a greater decrease in NO₃⁻ levels with depth than the sandier soil. Crop uptake of NO₃⁻ occurs within the root zone; however, the type of crop cover did not have a direct impact on the fate or transport during the growing season. The soils underlying soybeans had an increase in NO₃⁻ levels following harvest, suggesting that the decomposition of the soybean roots contributed to the net gain of NO₃⁻ in the shallow soil. For all of the soil types, conditions below 100 cm are conducive for microbial denitrification, with both a high water saturation level (>60%) and moderate organic carbon content (1–2%). At depths below 100 cm, temporal differences in NO₃⁻ levels of over a magnitude, up to a 95% reduction, were recorded in the soil units as the growing season progressed. Physical properties that control the transport of NO₃⁻ or denitrification have a larger influence on NO₃⁻ levels than crop type.

Optical spectroscopy study of variously colored gem-quality topazes from Ouro Preto,Minas Gerais,Brazil

Variously colored gem-quality topazes from Ouro Preto, Minas Gerais, Brazil, were studied by optical absorption spectroscopy and photoluminescence methods. In the near infrared range (750–2500 nm) the absorption spectra display an identical pattern of narrow intense absorption lines caused by overtones and combination vibrations of OH groups, which do not relate to the coloration of the topazes studied. Their colors were found to be caused by combination of three sets of absorption features, (1), (2), and (3) in the visible and near-UV range, which are due to different color center. (1) denotes a pair of broad split bands with maxima 18 000 and 25 000 cm^–1 caused by electronic spin-allowed dd transitions of Cr³⁺ ions. They cause a light rose to deep violet color and characteristic pleochroism of Cr³⁺-containing topazes. Photoluminescence evidences of at least three different types of Cr³⁺ complexes which, most probably, differ by ligand surroundings, O₄F₂, O₄F(OH) and O₄(OH) (2) Corresponds to the intense weakly polarized UV absorption edge. Two different parts, the thermally stable one, caused by ligand-to-metal charge transfer, and the thermally unstable one, caused by some defect center(s), contribute to the edge. (3) denotes a system of two broad unstructured bands with maxima around 19 000 cm^–1 (X>Y Z) and 24 000 cm^–1 (Y Z X). They cause the unique orange color and characteristic pleochroism of Brazilian Imperial topazes. Combinations of (1) and (3) absorption features cause various yellow-rose colors of the samples. Investigations of natural irradiated and thermally treated topazes show that the color centers (1) and (3) transform to each other at annealing and X- or gamma irradiation. The color of natural orange-red Imperial topazes is assumed to be caused by Cr⁴⁺, stabilized by other impurity ions and/or defect irradiation EPR centers. At T=300 °C Cr⁴⁺ reduces to Cr³⁺, the color of Imperial topazes changes to pale rose, caused by spin-allowed bands of Cr³⁺. In artificially irradiated crystals the (3)-center, Cr⁴⁺, may be induced according to the reaction 2Cr³⁺ Cr⁴⁺ + Cr²⁺, which involves chromium pairs in adjacent Al sites of the structure. Such artificially induced color is unstable at room temperature and in daylight. The process of the decay of (3)-centers may be described as a recombination Cr⁴⁺+Cr²⁺ 2Cr³⁺ that results in vanishing of the (3)-bands accompanied by the appearance or increase in Cr³⁺ dd bands, the original orange color turning to a pale rose.     

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     

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Vibrational states of H<Subscript>2</Subscript>O in beryl: physical aspects

Single-crystal polarized Raman spectra (3,000–4,000 cm⁻¹ at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be₂Al₃Si₆O₁₈·xH₂O, to determine the behavior of H₂O molecules of both Type I and Type II in the cavities. At low temperature, the H₂O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H₂O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm⁻¹. Water Type II is characterized by a free rotation with respect to the C ₂ molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

On the miscibility gap in monazite–xenotime systems

The regular solid solution model has been applied to solid solubility in the monazite–xenotime systems and is verified against the available experimental data for LaPO₄–YPO₄ and CePO₄–YPO₄ systems. The model is then used to predict the miscibility gaps in a number of other monazite–xenotime systems. The implications for prospective two-phase monazite–xenotime fiber coatings for applications in ceramic matrix composites (CMCs) are discussed.

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Alternative technologies for rural areas–what about the ‘alternative’ dimension of Wi-Fi?

Summary  The question of alternative technologies for high-speed Internet access lies at the heart of rural development problems. In this paper, we focus on one of those technologies, the system combining satellite technologies and Wi-Fi. Based on an empirical study carried out in three rural areas, we analyze the dynamics of the use and appropriation of that technology by the companies and organizations participating in the experiment. Considered both from a technical and social standpoint, the technology ‘in use’ appears here in its structuring dimensions.

Calcium diffusivity in alumino-silicate garnets: an experimental and ATEM study

Concentration gradients in calcium are common in metamorphic or magmatic garnets and can be used to determine the timescales of geological processes. However, the kinetics of Ca diffusion in garnet is poorly constrained and experimental studies have to date yielded widely varying diffusion coefficients. In this paper, we describe a new method for generating diffusion profiles in garnet. We incorporated polished and compositionally homogeneous garnet seeds in a finely ground powder of clinopyroxene and garnet. During the experiments (1.3 GPa, 1,050–1,250°C, and ƒO₂ ≤ the graphite-O₂ buffer), the mineral powder partially melted, recrystallized, and formed a 10–50 μm wide overgrowth zone of compositionally distinct garnet around the seeds. Long duration experiments generated measurable relaxation profiles at these seed/overgrowth interfaces. We performed analytical transmission electron microscope traverses across the interfaces in each experiment. Thirteen usable compositional profiles were obtained with characteristic distances of diffusion ranging from 300 to 1,000 nm. From these profiles, Ca–(Fe, Mg) interdiffusion coefficients were retrieved using an analytical solution for the diffusion equation and the data were cast in an Arrhenius relation. Linear regression of the data yields an activation energy Q _{Ca–(Fe, Mg)} equal to 188 ± 48 kJ mol⁻¹ and a frequency factor D ₀ equal to 6.6 × 10⁻¹⁴ m² s⁻¹. Within the compositional range studied, the composition of garnet has no major effect on the Ca–(Fe, Mg) interdiffusion coefficient. The very slow diffusion rate of Ca is in agreement with natural observations indicating that Ca diffuses more slowly than Fe and Mg. The Ca diffusion coefficients derived from this study are not model-dependent and can be used to determine the durations of geological events from Ca relaxation profiles in natural garnets.

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Isotope and trace element evidence for depleted lithosphere in the source of enriched Ko’olau basalts

We have measured the Hf and Nd isotopic compositions of 38 basalts from the Ko’olau drill hole, Hawai’i. The basalts show limited variations in both ¹⁷⁶Hf/¹⁷⁷Hf and ¹⁴³Nd/¹⁴⁴Nd (ε _Nd varies from +4.2 to +7.3 and ε _Hf from +8.0 to +12.3). Their correlated variation has an R ² of 0.86. The data form an array with a slope of 1.2 on an ε _Hf–ε _Nd isotope correlation diagram, while the slope of all Hawai’ian basalt data is 0.98. Both slopes are significantly shallower than that of the mantle array of 1.4 defined by ocean island basalts. Previous studies have shown that a shallow slope in Hf–Nd isotope space can be related to ancient pelagic sediments in the mantle source (Blichert-Toft et al. 1999; Salters and White 1998). However, the combined variations in Ko’olau basalts of Hf–Nd–Pb–Os isotopic compositions and trace element ratios, such as La/Nb, Th/La and Sr/Nd, are not consistent with the simple addition of a sediment component to the mantle. We instead propose that the shallow slope on the Hf–Nd isotope correlation diagram for Ko’olau shield stage basalts can be better explained if the enriched endmember contains either an ancient oceanic lithosphere component or the high-¹⁷⁶Hf/¹⁷⁷Hf component observed in the Salt Lake Crater (SLC) peridotite xenoliths (which also have a depleted lithosphere origin). Since Ko’olau basalts have high ¹⁸⁷Os/¹⁸⁸Os (0.135–0.160) and the SLC xenoliths have ¹⁸⁷Os/¹⁸⁸Os up to 0.13 (Lassiter et al. 2000) Os-isotopes are consistent with the latter being a component in the enriched Ko’olau source.

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Sensitivity of high-resolution tropical cyclone intensity forecasts to surface flux parameterization

Surface flux parameterization schemes used in current dynamic models are primarily based upon measurements at low and moderate wind speeds. Recent studies show that these parameterization schemes may be incorrect at high wind speeds (e.g., tropical cyclone forecasts). Five high-resolution numerical model experiments are designed to assess the sensitivity of tropical cyclone intensity forecasts to changes in the surface flux parameterization. The sensitivity experiments are conducted by running 48 h forecasts of the Coupled Ocean/Atmosphere Mesoscale Prediction System (COAMPS) for six selected tropical cyclones with individual modifications to surface flux calculation that include: (1) limiting the surface stress for wind speeds greater than 33 m s⁻¹, or 64 knots (kt); (2) computing the stress at the top of the model bottom grid layer (MBGL) by averaging results from surface layer similarity and turbulence mixing parameterization for wind speeds greater than 33 m s⁻¹; (3) increasing the roughness lengths for heat and moisture transfer by a factor of ten; (4) setting the roughness lengths for heat and moisture transfer to 1/10 of the momentum roughness length; and (5) cooling the sea surface temperature (SST) by a prescribed rate at high winds. Averaged responses for the six storms to these sensitivity tests show that: (i) the limit on surface stress at high winds significantly increases the cyclone intensity in 48 h forecasts; (ii) the averaged surface layer stress at high winds increases the cyclone intensity but to a much lesser degree than limiting the surface stress; (iii) large increases in the roughness lengths for heat and moisture transfer are needed to significantly impact the intensity forecast; (iv) the different roughness length formula for surface transfer coefficients notably increases C _h/C _d ratio from 0.59 to 0.79 for 25 m s⁻¹ and 0.41 to 0.75 for 50 m s⁻¹ that significantly increases the predicted cyclone intensity; and (v) cooling of the SST by −5.8°C in 48 h reduces the maximum surface wind speed by −32 kt, or 16.5 m s⁻¹, at 48 h forecast. These results suggest that a surface flux parameterization scheme suitable for tropical cyclone intensity forecast must correctly model the leveling-off character of surface stress and C _h/C _d ratio at high winds. All modifications to surface flux calculation have little influence on 48 h track forecasts, even though they may significantly impact the intensity forecasts.

The formation and recombination kinetics of [Si<Stack><Subscript>4</Subscript><Superscript>5−</Superscript></Stack>] centers in zircon

The radiation sensitivity, time stability and optical sensitivity of [Si₄⁵⁻] paramagnetic centers in natural zircon crystals, particularly those from the Late Neopleistocenic tuff of the Elbrus Volcano, have been studied. Optical bleaching was shown to result in the recombination of [Si₄⁵⁻] centers, while the concentration of centers increases in the absence of light due to the internal radiation background. The data obtained show the infeasibility of using [Si₄⁵⁻] centers in zircons as paleodosimeters in conventional dating methods using electron paramagnetic resonance (EPR) spectroscopy. New specific techniques need to be developed for EPR dating of zircons.     

Erosion rates on subalpine paleosurfaces in the western Mediterranean by in-situ <Superscript>10</Superscript>Be concentrations in granites: implications for surface processes and long-term landscape evolution in Corsica (France)

A study of erosion rates by in-situ ¹⁰Be concentrations in granites of Miocene high-elevation paleosurfaces in Corsica indicates maximum erosion rates between 8 and 24 mm/kyear. The regional distribution of measured erosion rates indicates that the local climatic conditions, namely precipitation, the petrographic composition of granites, and the degree of brittle deformation govern erosion rates. Chemical erosion dominates even at elevations around 2,000 m in presently subalpine climate conditions. Field evidence indicates that erosion operates by continuous dissolution and/or disintegration to grains (grusification). The erosion rates are relatively high with respect to the preservation of inferred Early Miocene landscapes. We infer temporal burial in the Middle Miocene and significantly lower erosion rates in the Neogene until ∼3 Ma to explain the preservation of paleosurfaces, in line with fission track data. Valley incision rates that are a magnitude higher than erosion rates on summit surfaces result in relief enhancement and long-term isostatic surface uplift. On the other hand, widening and deepening of valleys by cyclic glaciation progressively destroys the summit surface relics.

Melt inclusion formation mechanisms and compositional effects in high-An feldspar and high-Fo olivine in anhydrous mafic silicate liquids

Important aspects of melt inclusion formation and potential compositions effects have been addressed through a series of experiments using anorthite/fosterite saturated anhydrous mafic liquids. Experimental charges were cooled from 1,300 to 1,230 and 1,210°C at rates of 1–10°/min followed by 0–24 h isothermal periods. Hopper and skeletal crystal morphologies with variable degrees of completeness developed during the cooling period. Planar overgrowth of these textures during isothermal periods led to the formation of inclusions, the majority of which formed after 6 h of isothermal run time. We suggest that the change in morphologies is related to a decrease in growth rates and changes in dominant growth mechanisms. In general, inclusion compositions were uniform and similar to the host glass, indicating that with the isothermal times required for most inclusions to form, a boundary layer was not entrapped that could be detected within the limits of our analyses.

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Patterns of population change in Ghana (1984–2000): urbanization and frontier development

The study addresses population dynamics in Ghana on the urban and regional levels between 1984 and 2000. At the urban level, the development trends are analyzed for urban localities (population above 5,000) on the basis of geo-coded census data. Potential driving forces for rapid population growth related to size, location, accessibility and facility counts are examined using bivariate and multivariate analysis. An index of weighted accessibility relative to other urban localities provides significant explanation at the national level, as does initial locality size. At the regional level, population development is analyzed to provide insight into the rural–urban relations. The level of urbanization is steadily increasing but varies considerably between regions. Areas of high population growth are found in some rural areas that have a remote location relative to the large urban centers. This seems to indicate the existence of ‘frontier’ regions, i.e. areas that experience a high degree of in-migration by people aiming to undertake specific farming activities. A high proportion of the population growth in these areas appears to take place in relatively small towns. The paper concludes with a more in-depth discussion of the development characteristics of Ghana’s Western Region. This region has experienced one of the highest regional population growth rates, mainly due to its status as a ‘frontier’ for cocoa production.

Crystal field and covalency of octahedral chromium in natural [8](Mg1?xCax) 3[6] (Al0.67Cr0.33)2Si3O12 garnets from upper mantle rocks

In the course of a thorough study of the influences of the second coordination sphere on the crystal field parameters of the 3d ^N -ions and the character of 3d ^N –O bonds in oxygen based minerals, 19 natural Cr³⁺-bearing (Mg,Ca)-garnets from upper mantle rocks were analysed and studied by electronic absorption spectroscopy, EAS. The garnets had compositions with populations of the ^[8] X-sites by 0.881 ± 0.053 (Ca + Mg) and changing Ca-fractions in the range 0.020 ≤ w _Ca[8] ≤ 0.745, while the ^[6] Y-site fraction was constant with x _Cr³⁺ _[6] = 0.335 ± 0.023. The garnets had colours from deeply violet-red for low Ca-contents (up to x _Ca = 0.28), grey with 0.28 ≤ x _Ca ≤ 0.4 and green with 0.4 ≤ x _Ca. The crystal field parameter of octahedral Cr³⁺ 10Dq decreases strongly on increasing Ca-fraction from 17,850 cm⁻¹ at x _Ca[8] = 0.020 to 16,580 cm⁻¹ at x _Ca[8] = 0.745. The data could be fit with two model which do statistically not differ: (1) two linear functions with a discontinuity close to x _Ca[8] ≈ 0.3,

Gendered access to customary land in East Timor

Land tenure rights reflect the deeper structures of society, particularly gender distinctions in relation to land. Considering the structural differences between patrilineal and matrilineal customary tenure systems in East Timor are understudied, this paper explores men and women’s experiences in accessing land under such arrangements. The comparative analysis of two patrilineal with one matrilineal land tenure systems in Ainaro and Manufahi districts suggests a significant degree of flexibility within both systems with respect to the norms of gendered inheritance. Therefore, the binary constructs of ‘patrilineal’ and ‘matrilineal’ societies are limiting. Both men and women in these communities may acquire land rights under different circumstances, mainly through negotiations with their parents or hamlet chief. Daughters in the patrilineal communities could inherit family land upon their parents’ death and sons in the matrilineal community could gain land by cultivating and maintaining unclaimed customary land. Empirical evidence show that inheritance principally determines usufruct rights to land, but marriage exchange practices complicates a deeper understanding of traditional East Timorese land rights.

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Church–state relations in Spain: Variations on a National-Catholic theme?

Contrary to the absence of a uniform Spanish identity (a phenomenon that is often referred to as Spain being a ‘nation of nations’), Spain’s confessional map is remarkably homogeneous. From the beginning of its existence as a political conglomeration, Spain has been a mono-confessional Catholic territory. Even at present, Catholicism is an intrinsic feature of Spanish society and – though officially a secular state – of state policy. A closer look at Spain’s religious situation and its corresponding pattern of church–state relations reveals, however, some recent cracks in the century’s old bond between Spain and Catholicism. Particularly secularization and religious pluralism challenge Spain’s mono-confessional Catholic nature, a development that fits well into Spain’s post-Francoist focus on Europe and European (secular) values. This paper discusses Spanish church–state relations from the beginning of its political existence until present times. Special attention will be paid to more recent societal developments and their impact on religious Spain and church–state relations.