A study of the bonded interactions in nitride molecules in terms of bond critical point properties and relative electronegativities

Bond critical point properties calculated for the MN bonds in a number of geometry optimized nitride molecules containing first- and second-row M cations are compared with those calculated for a number of oxide molecules. As reported for the oxides, the value of the electron density, ρ(r _c ), at the bond critical points, r _c , increases with decreasing bond length while for the more electronegative cations, the local energy density, H(r _c ) decreases nonlinearly in value as the relative electronegativities of the M-cations, χ _M , tend to increase. In the majority of cases, χ_M, |λ₁|/λ₃ and ∇²ρ(r _c ) increase with decreasing minimum energy bond lengths. The bond lengths adopted by the molecules are indicated to be an important determinant of the critical point properties of the electron density distributions. The relative electronegativities derived from the electron density distributions of the nitrides agree with those derived for the oxides and Pauling’s electronegativities to within ∼5%, on average. Received: 3 February 1997 / Revised, accepted: 11 July 1997     

Electron density distribution of FeTiO<Subscript>3</Subscript> ilmenite under high pressure analyzed by MEM using single crystal diffraction intensities

Many of ilmenites ABO₃ compounds bearing transition elements have semiconductive, ferroelectric and antiferromagnetic properties. The high-pressure diffraction studies of FeTiO₃ have been conducted up to 8.2 GPa using synchrotron radiation in KEK at Tsukuba with diamond anvil cell. The compression mechanism of FeTiO₃ ilmenite has been investigated by the structure refinements converged to the reliable factors R = 0.05. The deformations of the FeO₆ and TiO₆ octahedra were reduced with increasing pressure. In order to elucidate the electric conductivity change with pressure, electron density distribution of ilmenite have been executed by maximum entropy method (MEM) using single-crystal diffraction intensity data. MEM based on F _obs(hkl) of FeTiO₃ clearly shows electron density in comparison with the difference Fourier synthesis based on F _obs(hkl) − F _calc(hkl). The radial distribution of the electron density indicates electron localization around the cation positions. The bonding electron density found in bond Fe–O and Ti–O is lowered with pressure. The isotropic temperature factors B _iso become smaller with increasing pressure. Nevertheless the thermal vibration is considerably restrained by the compression, the electric conductivity is enhanced with pressure. Neither charge transfer nor electron hopping between Fe and Ti along the c axis in FeTiO₃ is plausible under high pressure. But the electric conductivity due to electron super-exchange in Fe–Fe and Ti–Ti has been clarified by the MEM electron density distribution. The anisotropy in the electric conductivity has been clarified.     

Practically Applicable Central Limit Theorem for Spatial Statistics

Let {Z(s):s∈D⊆ℝ ^d } be a zero mean stationary random field observed at a finite number of locations. Lahiri (Sankhya Ser. A 65:356–388, 2003) proved spatial central limit theorems (CLT) for ∑ _i=1 ⁿ Z(s _i ) assuming a ‘nearly infill domain sampling’. Applications of his results depended on the underlying spatial sampling region and the design in a complicated fashion. The main objective of this paper is to provide CLTs that could be applied easily in practice. We present two main results assuming a ‘nearly infill domain sampling’ defined mainly in terms of dependence. Theorem 1 establishes a CLT for ∑ _i=1 ⁿ Z(s _i ) and Theorem 2 is obtained mainly for applications to density estimates. We report on a simulation study for illustrating a way of applying our results in practice.     

Experimental multipole-refined and theoretical charge density study of LiGaSi<Subscript>2</Subscript>O<Subscript>6</Subscript> clinopyroxene at ambient conditions

The synthetic LiGaSi₂O₆ clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding, as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2 bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar to spodumene (LiAlSi₂O₆), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical topological properties of the electron density distribution on the Si₂O₆ group are very similar to those calculated for spodumene. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A characterisation of the physical properties of soil and the implications for landslide occurrence on the slopes of Mount Elgon,Eastern Uganda

Soil properties of major landslides that occurred recently on the mid-altitude slopes of Mount Elgon, eastern Uganda were analysed. A mudflow, located at the Kitati protected forest site, and two deep debris flows on the Nametsi and Buwabwala deforested steep slopes (36°–58°) were surveyed. In order to test the hypothesis that ‘soils at the landslide sites are particularly ‘problem soils’ and thus prone to landslides’, the following analyses were undertaken: particle size distribution, Atterberg limits, shear strength and factor of safety (F_s). Soils at the Kitati and Buwabwala sites exhibited expansive potential, owing to clay contents well above 20%. A clay content exceeding 32% was identified at the Nametsi debris flow site implying an extremely high expansive potential of the soil. High liquid limits (LLs) at Kitati (59%) and Buwabwala (53%) meant that the soils qualified as vertisols susceptible to landslides. High plasticity indices (PIs) (averaging 33%) also confirmed the vertic nature of soils at the Nametsi debris flow site. Whereas the value of F _s  < 1 for the Kitati site signifies an inherently unstable slope, Nametsi and Buwabwala are supposedly stable slopes (F _s  > 1). Despite this finding, the stable sites could be described as only conditionally stable because of the interplay of various physical, pedological and anthropogenic factors. The results point to the fact that soils at the landslide sites are inherently ‘problem soils’ where slope failure can occur even without human intervention. Therefore, the hypothesis that soils at three landslide sites are inherently ‘problem soils’ and prone to landslides, is accepted.     

Multipole-refined charge density study of diopside at ambient conditions

The experimental multipole electron density, ρ(r), of diopside was derived from high-resolution single-crystal diffraction at room temperature. Its topological analysis revealed predominantly ionic Si–O bonding, as found in electron density studies of other silicates. In particular, the non-bridging Si–O bonds are slightly less ionic in character than the bridging Si–O bonds. The Ca–O and Mg–O bonds are classified as pure closed-shell ionic interactions. An analysis of –∇²ρ(r) showed the presence of maxima around the oxygen atoms, associated to lone pairs domains that are involved in bonds with the surrounding ions. Calculation of atomic basins gave net charges of –1.56(12), 3.11(17), 1.79(13) and 1.88(18) e for O (averaged), Si, Ca and Mg atoms, respectively. O···O interactions between the O atoms at the vertices of the SiO₄ tetrahedron were also detected from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. All these results were also confirmed by periodic restricted Hartree–Fock (RHF) calculations. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

A physical basis for Pauling's definition of bond strength

 The average strength, s, of the bonded interactions comprising a cation containing oxide anion coordination polyhedron and the value of the electron density, ρ(r _c ), at the bond-critical points are inversely correlated with bond length. In each case, the observed bond lengths, R, were modeled with power-law expressions defined in terms of s/r and ρ(r _c )/r, respectively, where r is the Periodic Table row number of the cation involved in the bonded interaction. On the basis of the close connection between bond strength and the value of the electron density at the bond-critical point, we conclude that bond strength is a direct measure of bond type; the greater its value, the greater the localization of electron density in the binding region and the greater the shared–electron covalent character of the bonded interaction. Received: 15 October 2002 / Accepted: 17 February 2003 Present address:G. V. Gibbs in care of M. Spackman Department of Chemistry, University of New England, Armidale 2351, Australia Acknowledgements The NSF is thanked for supporting this study with grant EAR–9627458. The paper was written while GVG was a Visiting NSF Scholar at The University of Arizona. The faculty and graduate students of the Department of Geosciences and Bob Downs and Marelina Stimpf in particular are thanked for making the visit great fun.     

Ingress of Brachyuran Crab Post-larvae to the Newport River Estuary

Planktonic larvae of estuarine species often develop in the coastal ocean and return to estuaries using favorable currents. This study investigated spatial distributions of brachyuran crab post-larvae during ingress to the Newport River estuary, North Carolina, USA (34°41′ N, 76°40′ W). Nearshore plankton tows were conducted across the inlet to the estuary. Settlement on passive ‘hog’s hair’ collectors was simultaneously monitored in each of four estuarine channels. Callinectes sapidus density was highest east of the inlet, whereas relative estuarine abundance was higher in western channels. In separate sampling with collectors at coastal and estuarine locations, spatial distributions of post-larvae were consistent through time but differed for C. sapidus, Uca spp., and Pachygrapsus transversus. The diel timing of C. sapidus settlement on collectors was determined at the coast and compared to previous studies of settlement in the estuary. Behavioral responses to environmental cues may alter transport pathways from those predicted by hydrodynamic models.     

Some constraints on the thermodynamic mixing properties of Fe-Mg orthopyroxenes and olivines

Existing data on the temperature and composition dependence of the Fe²⁺-Mg²⁺ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe²⁺ and Mg²⁺ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe²⁺ and Mg⁺ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe₂SiO₄ component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.     

Re-viewing the Entrapment controversy: Megaprojection, (mis)representation and postcolonial performance

Becoming the tallest building in the world in the mid-1990s, the Petronas Towers was the centre piece of an image of national progress and development that Malaysian authorities sought to project internationally. The release of Fox Movies' Entrapment in Malaysia in May 1999 provoked political outrage and popular disappointment at the way in which the Petronas Towers in Kuala Lumpur had been spliced alongside riverside ‘slums’ filmed in the town of Malacca some 150 km away. This paper provides a critical reading of the spliced scene in the movie. At one level, the angry response of the Malaysian Prime Minister, Dr Mahathir Mohamad, to the scene diagnoses a geopolitics of asymmetrical representational power. However, I show how Mahathir's criticism of Entrapment in Malaysia was as much a defence of domestic political legitimacy (and national economic investibility) as it was ‘opposition’ or ‘resistance’ to hegemonic ‘Western’ (mis)representation. In addition, while the material and symbolic work of reimaging Kuala Lumpur had sought to negate (neo)orientalist imaginings of ‘Asian’ cities, the controversial scene rendered visible environmental ‘underdevelopment’ that has no place in a modern (vision of) Malaysia. Entrapment thus performed something in inducing Malaysian cities and citizens to ‘clean up’ their act, to practice ‘fully developed’ ways of seeing, being and being seen. This revised version was published online in August 2006 with corrections to the Cover Date.     

Geospatial contour mapping of shear wave velocity for Mumbai city

Shear wave velocity is one of the most important input parameter in the analysis of geotechnical earthquake engineering problems, particularly to estimate site-specific amplification factor and ground response study. Dynamic in situ tests such as spectral analysis of surface waves (SASW) or multichannel analysis of surface waves (MASW) are very expensive. Also due to lack of specialized personnel, these tests are generally avoided in many soil investigation programs. Worldwide, several researchers have developed correlations between the SPT ‘N’ value and shear wave velocity ‘V _s’, which are useful for determining the dynamic soil properties. In the present study, more than 400 numbers of soil borehole data were collected from various geotechnical investigation agencies, government engineering institutes and geotechnical laboratories from different parts of Mumbai city, which is financial capital of India with highest population density. In this paper, an attempt has been made to develop the correlation between the SPT ‘N’ value and shear wave velocity ‘V _s’ for various soil profile of Mumbai city and compared with other existing correlations for different cities in India. Using Geographical Information System (GIS), a geospatial contour map of shear wave velocity profile for Mumbai city is prepared with contour intervals of 25 and 50 m/s. The scarcity of database or maps of shear wave velocity profile for Mumbai city will make the present geospatial contour maps extremely useful and beneficial to the designer, practitioners for seismic hazard study involved in geotechnical earthquake engineering.     

Nomospace and genospace: A spatial matrix

We are concerned here with the notion of space as a primary condition for building social relations. From this stand, we have created two analytical matrixes that can help us characterize two modes: that of ‘being-there-in-space’ and that of ‘being-of-the-space’; the nomospace and the genospace. While the nomospace is characterized by ‘cold’ connotations, which are ideally defined as a result of a logical option, the genospace is mainly characterized by emotional or ‘warm’ connotations, which originate from a feeling of shared nature and common destiny. We believe that these matrixes could help us to identify the meanings of some behaviours and, therefore, make us more capable of interpreting many dynamics that occur in modern societies. The importance of geography is justified by the existing relationship between these behaviours and their proper spatial form. This revised version was published online in July 2006 with corrections to the Cover Date.     

Relations estimated at shock discontinuities excited by coronal mass ejections

An analysis of SOHO/LASCO C₃ data shows that there are discontinuities in the radial profiles of the plasma density within limited regions in front of each of ten coronal mass ejections, which represent shocks. The shock velocities in various events reach V ≈ 800–2500 km/s. A comparison of the dependence of the AlfvenicMach numberM _A on the shock strength ρ ₂/ρ ₁ detected at distancesR > 10R⊙ from the center of the Sun with calculations carried out using ideal magnetic hydrodynamics shows that the effective ratio of specific heats γ describing processes inside the shock front varies from 2 to 5/3 (ρ ₁ and ρ ₂ are the densities in front of and behind the shock, and R⊙ is the solar radius). This corresponds to an effective number of degrees of freedom between two and three. A similar dependenceMA(ρ ₂ /ρ ₁) was found for near-Earth bow shocks and interplanetary collisionless shocks. These features support the hypothesis that the studied discontinuities preceding coronal mass ejections are collisionless shocks.     

Electron density distributions and bonded interactions for the fibrous zeolites natrolite, mesolite and scolecite and related materials

 For the fibrous zeolites natrolite, Na₂[Al₂Si₃O₁₀]·2H₂O, mesolite, Na₂Ca₂[Al₂Si₃O₁₀]₃·8H₂O, and scolecite, Ca[Al₂Si₃O₁₀]·3H₂O, with topologically identical aluminosilicate framework structures, accurate single-crystal X-ray diffraction data have been analyzed by least-squares refinements using generalized scattering factor (GSF) models. The final agreement indices were R(F ) = 0.0061, 0.0165, and 0.0073, respectively. Ensuing calculations of static deformation [Δρ(r)], and total, [ρ(r)], model electron density distributions served to study chemical bonding, in particular by topological electron density analyses yielding bond critical point (bcp) properties and in situ cation electronegativities. The results for 32 SiO, 24 AlO, 14 CaO, and 12 NaO unique bonds are compiled and analyzed in terms of both mean values and correlations between bond lengths, bonded oxygen radii, bcp densities, curvatures at the bcps, and electronegativities. Comparison with recent literature data obtained from both experimental electron density studies on minerals and model calculations for geometry-optimized molecules shows that the majority of the present findings conforms well with chemical expectation and with the trends observed from molecular modeling. For the SiO bond, the shared interaction is indicated to increase with decreasing bond length, whereas the AlO bond is of distinctly more polar nature, as is the NaO bond compared to CaO. Also, the observed ranges of the Si and Al in situ electronegativities and their mean electronegativities agree well with both Pauling's values and model calculation results, and statistically significant correlations are obtained which are consistent with trends described for oxide and nitride molecules. Received: 10 May 1999 / Revised, accepted: 14 September 1999     

Imagining the border and Southern spaces: Cinematic explorations of race and gender

For some time the US-Mexico border has been a symbol – and site – of conflict, collaboration, and transnational mobility. Related to the border, the topic of undocumented immigration, and Mexican migrants in particular, has received considerable attention in US mainstream media. Cinema in particular, provides a context for producing and interrogating discourses of nationalism, nativism, and fear. The cinematic examples I draw on illustrate an ongoing fear (and terror) about borders and border crossing of various forms. In this paper I explore how narratives of borders and nationhood are mapped onto immigrant bodies and border spaces through specific filmic representations. In order to undertake this study I focus on three cinematic examples exploring immigration at the US-Mexico border – Touch of Evil, The Border and Lone Star. I examine how concepts of borders, race, and gender, and tropes of ‘The South’ are reterritorialized around immigrant bodies and specific locales. I argue that an inability to control and ‘fix’ boundaries around possible ‘threats’ to specific US spaces and identities is counteracted by displacing this fear onto more easily marked targets that are viewed as posing challenges to US national (and personal) security, i.e., undocumented immigrants. At the same time, cinematic images illustrate that the threats and spaces for immigrants themselves become increasingly marginalized, blurred, and frequently erased. This revised version was published online in August 2006 with corrections to the Cover Date.     

Contesting Chinatown: Place-making and the Emergence of ‘Ethnoburbia’ in Brisbane,Australia

This paper juxtaposes the actual areas of settlement and settlement activities of Chinese migrants in Brisbane’s southern suburbs since the mid-1980s, with the concomitant, ‘government planned’ construction of the city’s Chinatown as an ‘exotic,’ ‘ethnic,’ and ‘cosmopolitan’ landmark. It argues that while the latter, as with Chinatowns in other Australian and world cities, has continued to appropriate the symbols of so-called ‘Chineseness’ to sell the locale to non-Chinese, the former, in recalling the notion of ‘ethnoburbia,’ significantly evinces actual Chinese migrants’ agency and role in place-making. In the process, these migrants have not only established a local, ethnically meaningful environment, but also challenged the still current metonymic Western image of the Chinese as preferring life in ‘ethnic’ urban enclaves that had its origin from early Chinese settlement and fundamentally detached from the lives of other ethnic groups per se. Indeed greater recognition and comprehension of such locales may go a long way to illustrate that many Chinese living in Australia today do not fit the territorial, place-based identity often associated with them in the imagination of mainstream society.     

Melt variability in percolated peridotite: an experimental study applied to reactive migration of tholeiitic basalt in the upper mantle

Melt-rock reaction in the upper mantle is recorded in a variety of ultramafic rocks and is an important process in modifying melt composition on its way from the source region towards the surface. This experimental study evaluates the compositional variability of tholeiitic basalts upon reaction with depleted peridotite at uppermost-mantle conditions. Infiltration-reaction processes are simulated by employing a three-layered set-up: primitive basaltic powder (‘melt layer’) is overlain by a ‘peridotite layer’ and a layer of vitreous carbon spheres (‘melt trap’). Melt from the melt layer is forced to move through the peridotite layer into the melt trap. Experiments were conducted at 0.65 and 0.8 GPa in the temperature range 1,170–1,290°C. In this P-T range, representing conditions encountered in the transition zone (thermal boundary layer) between the asthenosphere and the lithosphere underneath oceanic spreading centres, the melt is subjected to fractionation, and the peridotite is partially melting (T _s ~ 1,260°C). The effect of reaction between melt and peridotite on the melt composition was investigated across each experimental charge. Quenched melts in the peridotite layers display larger compositional variations than melt layer glasses. A difference between glasses in the melt and peridotite layer becomes more important at decreasing temperature through a combination of enrichment in incompatible elements in the melt layer and less efficient diffusive equilibration in the melt phase. At 1,290°C, preferential dissolution of pyroxenes enriches the melt in silica and dilutes it in incompatible elements. Moreover, liquids become increasingly enriched in Cr₂O₃ at higher temperatures due to the dissolution of spinel. Silica contents of liquids decrease at 1,260°C, whereas incompatible elements start to concentrate in the melt due to increasing levels of crystallization. At the lowest temperatures investigated, increasing alkali contents cause silica to increase as a consequence of reactive fractionation. Pervasive percolation of tholeiitic basalt through an upper-mantle thermal boundary layer can thus impose a high-Si ‘low-pressure’ signature on MORB. This could explain opx + plag enrichment in shallow plagioclase peridotites and prolonged formation of olivine gabbros.     

Validating a Tsunami Vulnerability Assessment Model (the PTVA Model) Using Field Data from the 2004 Indian Ocean Tsunami

The “PTVAM” tsunami vulnerability assessment model [Papathoma and Dominey-Howes: 2003, Nat. Hazards Earth Syst. Sci. 3, 733–744; Papathoma et al.: 2003, Nat. Hazards Earth Syst. Sci. 3, 377–389], like all models, requires validation. We use the results from post-tsunami surveys in the Maldives following the December 26, 2004 Indian Ocean tsunami to ‘evaluate’ the appropriateness of the PTVAM attributes to understanding spatial and temporal vulnerability to tsunami damage and loss. We find that some of the PTVAM attributes are significantly important and others moderately important to understanding and assessing vulnerability. Some attributes require further investigation. Based upon the ground-truth data, we make several modifications to the model framework and propose a revised version of the PTVAM (PTVAM 2).     

Application of Markov chain and entropy analysis to lithologic succession — an example from the early Permian Barakar Formation,Bellampalli coalfield,Andhra Pradesh,India

A statistical approach by a modified Markov process model and entropy function is used to prove that the early Permian Barakar Formation of the Bellampalli coalfield developed distinct cyclicities during deposition. From results, the transition path of lithological states typical for the Bellampalli basin is as: coarse to medium-grained sandstone → interbedded fine-grained sandstone/shale → shale → coal and again shale. The majority of cycles are symmetrical but asymmetrical cycles are present as well. The chi-square stationarity test implies that these cycles are stationary in space and time. The cycles are interpreted in terms of in-channel, point bar and overbank facies association in a fluvial system. The randomness in the occurrence of facies within a cycle is evaluated in terms of entropy, which can be calculated from the Markov matrices. Two types of entropies are calculated for every facies state; entropy after deposition E(post) and entropy before deposition E(pre), which together form entropy set; the entropy for the whole system is also calculated. These values are plotted and compared with Hattori’s idealized plots, which indicate that the sequence is essentially a symmetrical cycle (type-B of Hattroi). The symmetrical cyclical deposition of early Permian Barakar Formation is explained by the lateral migration of stream channels in response to varying discharge and rate of deposition across the alluvial plain. In addition, the fining upward cycles in the upper part enclosing thick beds of fine clastics, as well as coal may represent differential subsidence of depositional basin.     

Thermophysical properties of the α–β–γ polymorphs of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>: a computational study

Thermophysical properties of the various polymorphs (i.e. α-, β- and γ) of Mg₂SiO₄ were computed with the CRYSTAL06 code within the framework of CO-LCAO-GTF approach by using the hybrid B3LYP density functional method. Potential wells were calculated through a symmetry preserving, variable cell-shape structure relaxation procedure. Vibrational frequencies were computed at the long-wavelength limit corresponding to the center of the Brillouin zone (k → 0). Thermodynamic properties were estimated through a semiclassical approach that combines B3LYP vibrational frequencies for optic modes and the Kieffer’s model for the dispersion relation of acoustic modes. All computed values except volume (i.e. electronic energy, zero point energy, optical vibrational modes, thermal corrections to internal energy, standard state enthalpy and Gibbs free energy of reaction, bulk modulus and its P and T derivatives, entropy, C _V, C _P) are consistent with available experimental data and/or reasonable estimates. Volumes are slightly overestimated relative to those determined directly by X-ray diffraction. A set of optimized volumetric properties that are consistent with the other semiclassical properties of the phases α, β and γ have been derived by optimization procedure such that the calculated boundaries for the α/β and β/γ equilibria have the best overall agreement with the experimental data for these transitions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.