Simulation of stream flow components in a mountainous catchment in northern Thailand with SWAT,using the ANSELM calibration approach

Highland agriculture is intensifying rapidly in South‐East Asia, leading to alarmingly high applications of agrochemicals. Understanding the fate of these contaminants requires carefully planned monitoring programmes and, in most cases, accurate simulation of hydrological pathways into and through water bodies. We simulate run‐off in a steep mountainous catchment in tropical South‐East Asia. To overcome calibration difficulties related to the mountainous topography, we introduce a new calibration method, named A Nash–Sutcliffe Efficiency Likelihood Match (ANSELM), that allows the assignment of optimal parameters to different hydrological response units in simulations of stream discharge with the Soil and Water Assessment Tool (SWAT) hydrological model. ANSELM performed better than the Parasol calibration tool built into SWAT in terms of model efficiency and computation time. In our simulation, the most sensitive model parameters were those related to base flow generation, surface run‐off generation, flow routing and soil moisture change. The coupling of SWAT with ANSELM yielded reasonable simulations of both wet‐season and dry‐season storm hydrographs. Nash–Sutcliffe model efficiencies for daily stream flow during two validation years were 0.77 and 0.87. These values are in the upper range or even higher than those reported for other SWAT model applications in temperate or tropical regions. The different flow components were realistically simulated by SWAT, and showed a similar behaviour in all the study years, despite inter‐annual climatic differences. The realistic partitioning of total stream flow into its contributing components will be an important factor for using this hydrological model to simulate solute transport in the future. Copyright © 2014 John Wiley & Sons, Ltd.     

“You have to engage with life,or life will go away”: An intersectional life course analysis of older women’s social participation in a disadvantaged urban area

Social participation in later life has been studied as part of discourses around ‘active ageing’ but the promotion of participation in disadvantaged urban neighbourhoods meets with particular challenges. In this paper I argue that in order to effectively promote social participation in later life researchers and practitioners require an understanding of life-long relational practices which are embedded in social norms and places as they intersect with identities such as gender, class and age.The intersectional life course analysis traces complex relationalities between people and place across the life course of two women living in disadvantaged urban areas. It shows the effects of societal and structural changes on individuals’ opportunities for social participation as well as demonstrating how age-related relational practices may lead to spatial segregation of older people in society.     

Structural investigations of the two polymorphs of synthetic Fe-cordierite and Raman spectroscopy of hexagonal Fe-cordierite

The crystal structures of synthetic hexagonal and orthorhombic Fe-cordierite polymorphs with the space groups P6/mcc and Cccm were refined from single-crystal X-ray diffraction data to R _{1, hex}?=?3.14 % and R _{1, ortho}?=?4.48 %. The substitution of the larger Fe²⁺ for Mg leads to multiple structural changes and an increase of the unit cell volumes, with a, c (hex)?=?9.8801(16) Å, 9.2852(5) Å and a, b, c (ortho)?=?17.2306(2) Å, 9.8239(1) Å, 9.2892(1) Å in the end-members. Furthermore Fe incorporation results in an increase of the volumes of the octahedra, although the diameters of the octahedra in direction of the c-axis decrease in both polymorphs. X-ray powder diffraction analysis indicates a high degree of Al/Si ordering in the orthorhombic polymorph, the Miyashiro distortion index is ~0.24. Estimations of site occupancies based on the determined tetrahedral volumes result in the following values for hexagonal Fe-cordierite: ~73 % Al for T₁ and ~28 % Al for T₂. For the first time Raman spectroscopy was performed on the hexagonal Fe-cordierite polymorph. In the hexagonal Fe-cordierite polymorph most Raman peaks are shifted towards lower wavenumbers when compared with the Mg-end-member.     

Ca2Mg(NO3)6×12H2O–structural investigations on a new compound retrieved from chimney deposits of a combined heat and power plant

Phase analysis of incrustations retrieved from chimney deposits of a combined heat and power plant in Malchow/Germany by X-ray powder diffraction gave evidence for the existence of a previously unknown hydrous calcium magnesium nitrate. Optical investigations of the sample showed the presence of colorless platy crystals with a maximum diameter of about 250 μm embedded in a partly polycrystalline and partly glassy matrix. Aided by EDX-analysis and Raman spectroscopy, a single-crystal diffraction study performed at ambient conditions demonstrated that the material represents a phase with composition Ca₂Mg(NO₃)₆×12H₂O. Basic crystallographic data are as follows: trigonal symmetry, space group type R \( \overline{3} \) , a?=?10.5583(5) Å, c?=?19.5351(10) Å, V?=?1885.97(16) ų, Z?=?3, (R(|F|) = 0.0248). The magnesium ions are coordinated by water molecules to form distorted Mg(H₂O)₆-octahedra. The calcium atoms are surrounded by nine ligands. The resulting CaO₉ tricapped trigonal prisms involve oxygen atoms from additional water moieties as well as from three different bidentate nitrate groups, respectively. Hydrogen bonds link one octahedron with two adjacent prisms into trimers. The trimers in turn are stacked in columns running parallel to [001]. Further hydrogen bonding between neighboring columns results in the formation of a three-dimensional network. To our best knowledge, Ca₂Mg(NO₃)₆×12H₂O represents a new structure type. However, column-like topologies with rods consisting of different types of polyhedra have been also observed in other trigonal hydrous nitrates. The structural relationships between these compounds are discussed. It is interesting to note that in previous phase equilibrium studies on the ternary system Ca(NO₃)₂-Mg(NO₃)₂-H₂O no other hydrous double salt has been described. Finally, the results of the structure analysis allowed a qualitative and quantitative phase analysis of the crystalline part of the chimney deposit by the Rietveld method.     

A first principles study of the oxidation energetics and kinetics of realgar

Quantum-mechanical calculations allow resolving and quantifying in detail important aspects of reaction mechanisms such as spin transitions and oxygen dissociation that can be the major rate-limiting steps in redox processes on sulfide and oxide surfaces. In addition, this knowledge can help experimentalists in setting up the framework of rate equations that can be used to describe the kinetics of, e.g., oxidation processes. The unique molecular crystal structure of realgar, As₄S₄ clusters held together by van der Waals bonds, allows for a convenient quantum-mechanical (q.m.) cluster approach to investigate the thermodynamics and kinetic pathways of oxidation. The interaction of As₄S₄ clusters with oxygen and co-adsorbed ions provides a model system for understanding the molecular-scale processes that underpin empirically-derived rate expressions, and provides clues to the oxidation mechanisms of other sulfides and oxides. Two activated processes are shown to dominate the kinetics of oxidation by molecular oxygen: (i) a paramagnetic ³O₂ to diamagnetic ¹O₂ spin transition and (ii) oxygen dissociation on the surface, in that order. The activation energies for the spin transition and O₂ dissociation step were determined to be 1.1 eV (106 kJ/mol) and 0.9 eV (87 kJ/mol), respectively, if molecular oxygen is the only reactant on the surface. In the case of As₄S₄, q.m. calculations reveal that ³O₂ transfers its spin to the cluster and forms a low-spin, peroxo intermediate on the surface before dissociating. The adsorption of a hydroxide ion on the surface proximate to the ³O₂ adsorption site changes the adsorption mechanism by lowering the activation energy barriers for both the spin transition (0.30 eV/29 kJ/mol) and the O₂ dissociation step (0.72 eV/69 kJ/mol). Thus, while spin transition is rate limiting for oxidation with O₂ alone, dissociation becomes the rate-limiting step for oxidation with co-adsorption of OH⁻. First-principles, periodic calculations of the realgar surface show that the energetics and structural changes that accompany oxidation of As₄S₄ clusters on the surface are similar to those involving individual As₄S₄ clusters. Thus, assuming that an As₄S₄ cluster with an adsorbed hydroxyl group is a reasonable approximation of the surface of As₄S₄ at high pH, the theoretically calculated oxidation rate (∼1 × 10⁻¹⁰ mol m⁻² s⁻¹) is of the same order as empirically-derived rates from experiments at T = 298 K, pH = 8, and similar dissolved oxygen concentrations. In addition, the co-adsorption of other anions found in alkaline waters (i.e. carbonate, bicarbonate, sulfate, and sulfite) were shown to energetically promote the oxidation of As₄S₄ (on the order of 5-40 kJ/mol depending on the co-adsorbed anion, OH⁻, , , , or , and accounting for changes in the hydration of products and reactants). The effect of the co-adsorbate on the kinetics and thermodynamics of oxidation is due to each adsorbate modifying the electronic and structural environment of the other adsorption site.Activation-energy barriers due to spin transitions are rarely discussed in the literature as key factors for controlling oxidation rates of mineral surfaces, even though the magnitude of these barriers is enough to alter the kinetics significantly. The attenuation of the activation energy by co-adsorbed anions suggests the possibility of pH− or p(co-adsorbate)-dependent activation energies that can be used to refine oxidation rate laws for sulfide minerals and other, especially semiconducting minerals, such as oxides.     

The Evolutionary Status of Early-type Galaxies in Abell 2390

We explore the evolution of the early-type galaxy population in the rich cluster Abell 2390 at z=0.23. For this purpose, we have obtained spectroscopic data of 51 elliptical and lenticular galaxies with MOSCA at the 3.5 m telescope on Calar Alto Observatory. As our investigation spans both a broad range in luminosity (–22.3≤M_B≤–:19.3)and a wide field of view (10′×10′), the environmental dependence of different formation scenarios can be analysed in detail as a function of radius from the cluster center. In this paper, we present first results on the Faber-Jackson relation and, for a subsample of 14 galaxies with morphological and structural parameters from HST, we also investigate the evolution of the Kormendy relation and the Fundamental Plane. We find a mild luminosity evolution of the early-type galaxies in Abell 2390: our objects are on average brighter by m _B∼0.4 mag. This revised version was published online in July 2006 with corrections to the Cover Date.     

Intragroup diffuse light in compact groups of galaxies – II. HCG 15, 35 and 51

This continuing study of intragroup light in compact groups of galaxies aims to establish new constraints to models of formation and evolution of galaxy groups, specially of compact groups, which are a key part in the evolution of larger structures, such as clusters. In this paper we present three additional groups (HCG 15, 35 and 51) using deep wide-field B - and R -band images observed with the LAICA camera at the 3.5-m telescope at the Calar Alto observatory (CAHA). This instrument provides us with very stable flat-fielding, a mandatory condition for reliably measuring intragroup diffuse light. The images were analysed with the ov_wav package, a wavelet technique that allows us to uncover the intragroup component in an unprecedented way. We have detected that 19, 15 and 26 per cent of the total light of HCG 15, 35 and 51, respectively, are in the diffuse component, with colours that are compatible with old stellar populations and with mean surface brightness that can be as low as 28.4 B mag arcsec⁻². Dynamical masses, crossing times and mass-to-light ratios were recalculated using the new group parameters. Also tidal features were analysed using the wavelet technique.     

Hillslope runoff and erosion as affected by rolled erosion control systems: a field study

A replicated field study using rainfall simulation and overland flow application was conducted in central Oahu, Hawaii, on a clay‐dominated Oxisol with a 9% slope. Three main treatment groups were examined: a bare treatment, a group of four rolled erosion control systems (RECSs) with open weave designs, and a group of five randomly oriented fibre RECSs. A total of 1122 measurements of runoff and erosion were made to examine treatment differences and to explore temporal patterns in runoff and sediment flux. All erosion control systems significantly delayed the time required to generate plot runoff under both simulated rainfall (35 mm h^?1) and the more intense trickle flow application (114 mm h^?1). Once runoff was generated during the rainfall application phase, the bare treatment runoff coefficients were significantly lower than those from the two groups of RECSs, as surface seal disruption by rilling is inferred to have enhanced infiltration in the bare treatments. During the more intense phase of overland flow application, the reverse pattern was observed. Interrill contributing‐area roughness was reduced on the bare treatment, facilitating increased runoff to well‐developed rill networks. Meanwhile, the form roughness associated with the RECSs delayed interrill flow to the poorly organized rills that formed under some of the RECSs. Regardless of runoff variations between treatments, sediment output was significantly lower from all surfaces covered by RECSs. The median cumulative sediment output from the bare surfaces was 6·9 kg, compared with 1·2 kg from the open‐weave RECSs and 0·2 kg from the random‐fibre RECSs. The random‐fibre systems were particularly effective under the more stressful overland flow application phase, with 63 times less sediment eroded than the bare treatments and 12 times less than that from the open‐weave systems. Architectural design differences between the two groups of RECSs are discussed in light of their relation to erosion process dynamics and shear stress partitioning. Copyright © 2006 John Wiley & Sons, Ltd.