Rainfall threshold for hillslope outflow: an emergent property of flow pathway connectivity

Nonlinear relations between rain input and hillslope outflow are common observations in hillslope hydrology field studies. In this paper we use percolation theory to model the threshold relationship between rainfall amount and outflow and show that this nonlinear relationship may arise from simple linear processes at the smaller scale. When the rainfall amount exceeds a threshold value, the underlying elements become connected and water flows out of the base of the hillslope. The percolation approach shows how random variations in storage capacity and connectivity at the small spatial scale cause a threshold relationship between rainstorm amount and hillslope outflow. <br><br> As a test case, we applied percolation theory to the well characterized experimental hillslope at the Panola Mountain Research Watershed. Analysing the measured rainstorm events and the subsurface stormflow with percolation theory, we could determine the effect of bedrock permeability, spatial distribution of soil properties and initial water content within the hillslope. The measured variation in the relationship between rainstorm amount and subsurface flow could be reproduced by modelling the initial moisture deficit, the loss of free water to the bedrock, the limited size of the system and the connectivity that is a function of bedrock topography and existence of macropores. The values of the model parameters were in agreement with measured values of soil depth distribution and water saturation

Electronic characterization of redox (non)-innocent Fe2S2 reference systems:a multi K-edge X-ray spectroscopic study

Di-iron dithiolate hydrogenase model complexes are promising systems for electrocatalytic production of dihydrogen and have therefore been spectroscopically and theoretically investigated in this study. The direct effect of ligand substitution on the redox activity of the complex is examined. In order to understand and eventually optimize such systems, we characterised both metal and ligand in detail, using element specific X-ray absorption Fe- and S-K edge XAS. The (electronic) structure of three different [Fe2S2] hydrogenase systems in their non-reduced state was investigated. The effect of one- and two-electron reduction on the (electronic) structure was subsequently investigated. The S K-edge XAS spectra proved to be sensitive to delocalization of the electron density into the aromatic ring. The earlier postulated charge and spin localization in these complexes could now be measured directly using XANES. Moreover, the electron density (from S K-edge XANES) could be directly correlated to the Fe–CO bond length (from Fe K-edge EXAFS), which are in turn both related to the reported catalytic activity of these complexes. The delocalization of the electron density into the conjugated π-system of the aromatic moieties lowers the basicity of the diiron core and since protonation occurs at the diiron (as a rate determining step), lowering the basicity decreases the extent of protonation and consequently the catalytic activity

Annual survey air quality 2001

The air quality for 2001 is found to strongly resemble that for 2000. The decreasing trend in concentrations seen in the nineties, is still valid on the whole. Concerning the meteorological influences, 2001 can be considered as a normal year. Widespread exceedances occurred for ozone and PM10, and in the deposition of potential acid and total nitrogen. In the urban environment, exceedances of the annual mean limit value for NO2 occurred along road length of about 2000 km. Calculations for benzene and benzo[a]pyrene showed that exceedances were incidental. This annual air quality survey provides an overview of the air quality and the load placed on soils and surface water by atmospheric deposition in the Netherlands, on the basis of measurements and model calculations. The report describes global, photochemical, acidifying, particulate and local air pollution. Special attention has been paid to the Dutch air quality in relation to the new European legislation on air quality.Als we de luchtkwaliteit over 2001 vergelijken met die van 2000 blijken deze in grote lijnen met elkaar overeen te komen. De trendmatige daling van concentraties heeft zich in grote lijnen doorgezet. 2001 was wat meteorologische invloed betreft een normaal jaar. Normoverschrijdingen op landelijke schaal hebben zich voorgedaan van ozon, zwevende deeltjes (PM10), depositie van potentieel zuur en stikstof. In de stedelijke omgeving is de jaargemiddelde norm NO2 overschreden langs een weglengte van circa 2000 km. Voor benzeen en benzo[a]pyreen geven berekeningen aan dat incidenteel overschrijdingen van grenswaarden kunnen zijn voorgekomen. In het jaaroverzicht luchtkwaliteit 2001 wordt op basis van metingen en modelberekeningen een samenvattend beeld gegeven van de luchtkwaliteit en de belasting van bodem en oppervlaktewater door atmosferische depositie in Nederland over 2001. Het rapport beschrijft de onderwerpen: mondiale, fotochemische, verzurende, deeltjesvormige en lokale luchtverontreiniging. Als extra onderwerp is een hoofdstuk opgenomen over de Nederlandse luchtkwaliteit in relatie tot de nieuwe Europese wetgeving voor luchtkwaliteit

Theory of Ferromagnetism in Doped Excitonic Condensates

Nesting in a semimetal can lead to an excitonic insulator state with spontaneous coherence between conduction and valence bands and a gap for charged excitations. In this paper we present a theory of the ferromagnetic state that occurs when the density of electrons in the conduction band and holes in the valence band differ. We find an unexpectedly rich doping-field phase diagram and an unusual collective excitation spectrum that includes two gapless collective modes. We predict regions of doping and external field in which phase-separated condensates of electrons and holes with parallel spins and opposing spins coexist.Comment: 5 pages, 3 postscript file

Cationic Copper Iminophosphorane Complexes as CuAAC Catalysts:A Mechanistic Study

We have combined Cu K-edge X-ray absorption spectroscopy with NMR spectroscopy (1H and 31P) to study the Cu-catalyzed azide–alkyne cycloaddition (CuAAC) reaction under operando conditions. A variety of novel, well-defined CuI iminophosphorane complexes were prepared. These ligands, based on the in situ Staudinger reduction when [Cu(PPh3)3Br] is employed, were found to be active catalysts in the CuAAC reaction. Here, we highlight recent advances in mechanistic understanding of the CuAAC reaction using spectroscopic and kinetic investigations under strict air-free and operando conditions. A mononuclear Cu triazolide intermediate is identified to be the resting state during catalysis; cyclization and protonation both have an effect on the rate of the reaction. A key finding of this study includes a novel group of highly modular CuI complexes that are active in the base-free CuAAC reaction

A risk profile for identifying community-dwelling elderly with a highrisk of recurrent falling: results of a 3-year prospective study

Introduction: The aim of the prospective study reported here was to develop a risk profile that can be used to identify community-dwelling elderly at a high risk of recurrent falling. Materials and methods: The study was designed as a 3-year prospective cohort study. A total of 1365 community-dwelling persons, aged 65 years and older, of the population-based Longitudinal Aging Study Amsterdam participated in the study. During an interview in 1995/1996, physical, cognitive, emotional and social aspects of functioning were assessed. A follow-up on the number of falls and fractures was conducted during a 3-year period using fall calendars that participants filled out weekly. Recurrent fallers were identified as those who fell at least twice within a 6-month period during the 3-year follow-up. Results: The incidence of recurrent falls at the 3-year follow-up point was 24.9% in women and 24.4% in men. Of the respondents, 5.5% reported a total of 87 fractures that resulted from a fall, including 20 hip fractures, 21 wrist fractures and seven humerus fractures. Recurrent fallers were more prone to have a fall-related fracture than those who were not defined as recurrent fallers (11.9% vs. 3.4%; OR: 3.8; 95% CI: 2.3-6.1). Backward logistic regression analysis identified the following predictors in the risk profile for recurrent falling: two or more previous falls, dizziness, functional limitations, weak grip strength, low body weight, fear of falling, the presence of dogs/cats in the household, a high educational level, drinking 18 or more alcoholic consumptions per week and two interaction terms (high educationx18 or more alcohol consumptions per week and two or more previous falls x fear of falling) (AUC=0.71). Discussion: At a cut-off point of 5 on the total risk score (range 0-30), the model predicted recurrent falling with a sensitivity of 59% and a specificity of 71%. At a cut-off point of 10, the sensitivity and specificity were 31% and 92%, respectively. A risk profile including nine predictors that can easily be assessed seems to be a useful tool for the identification of community-dwelling elderly with a high risk of recurrent falling. © International Osteoporosis Foundation and National Osteoporosis Foundation 2006

CaB_6: a new semiconducting material for spin electronics

Ferromagnetism was recently observed at unexpectedly high temperatures in La-doped CaB_6. The starting point of all theoretical proposals to explain this observation is a semimetallic electronic structure calculated for CaB_6 within the local density approximation. Here we report the results of parameter-free quasiparticle calculations of the single-particle excitation spectrum which show that CaB_6 is not a semimetal but a semiconductor with a band gap of 0.8 eV. Magnetism in La_xCa_{1-x}B_6 occurs just on the metallic side of a Mott transition in the La-induced impurity band.Comment: 4 pages, 1 postscript figur

Point defects, ferromagnetism and transport in calcium hexaboride

The formation energy and local magnetic moment of a series of point defects in CaB$_6$ are computed using a supercell approach within the generalized gradient approximation to density functional theory. Based on these results, speculations are made as to the influence of these defects on electrical transport. It is found that the substitution of Ca by La does not lead to the formation of a local moment, while a neutral B$_6$ vacancy carries a moment of 2.4 Bohr magnetons, mostly distributed over the six nearest-neighbour B atoms. A plausible mechanism for the ferromagnetic ordering of these moments is suggested. Since the same broken B-B bonds appear on the preferred (100) cleavage planes of the CaB$_6$ structure, it is argued that internal surfaces in polycrystals as well as external surfaces in general will make a large contribution to the observed magnetization.Comment: Calculated defect formation energies had to be corrected, due to the use of a wrong reference energy for the perfect crystal in the original pape