Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

Structure prediction of subtilisin BPN' mutants using molecular dynamics methods

In this paper we describe the achievements and pitfalls encounteredin doing structure predictions of protein mutants using moleculardynamics simulation techniques in which properties of atomsare slowly changed as a function of time. Basically the methodconsists of a thermodynamic integration (slow growth) calculationused for free energy determination, but aimed at structure prediction;this allows for a fast determination of the mutant structure.We compared the calculated structure of the mutants Met222Ala,Met222Phe and Met222Gln of subtilisin BPN' with the respectiveX-ray structures and found good agreement between predictedand X-ray structure. The conformation of the residue subjectto the mutation is relatively easy to predict and is mainlydetermined by packing criteria. When the side chain has polargroups its exact orientation may pose problems; long-range Coulombinteractions may generate a polarization feedback involvingsystem relaxation times beyond the simulation time. Changesinduced in the environment are harder to predict using thismethod. In particular, rearrangement of the hydration structurewas difficult to predict correctly, probably because of thelong relaxation times. In all conversions made the changes observedin the environment were found to be history-dependent and inparticular the hydrogen bonding patterns provided evidence formetastable substates. In all cases the structure predicted wascompared with available kinetic data and the reduced activitycould be explained in terms of changes in the configurationof the active site.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

The impact of particle filtration on indoor air quality in a classroom near a highway

A pilot study was performed to investigate whether the application of a new mechanical ventilation system with a fine F8 (MERV14) filter could improve indoor air quality in a high school near the Amsterdam ring road. PM10, PM2.5, and black carbon (BC) concentrations were measured continuously inside an occupied intervention classroom and outside the school during three sampling periods in the winter of 2013/2014. Initially, 3 weeks of baseline measurements were performed, with the existing ventilation system and normal ventilation habits. Next, an intervention study was performed. A new ventilation system was installed in the classroom, and measurements were performed during 8 school weeks, in alternating 2‐week periods with and without the filter in the ventilation system under otherwise identical ventilation conditions. Indoor/outdoor ratios measured during the weeks with filter were compared with those measured without filter to evaluate the ability of the F8 filter to improve indoor air quality. During teaching hours, the filter reduced BC exposure by, on average, 36%. For PM10 and PM2.5, a reduction of 34% and 30% was found, respectively. This implies that application of a fine filter can reduce the exposure of schoolchildren to traffic exhaust at hot spot locations by about one‐third.     

Ethnic differences in realising desires to leave urban neighbourhoods

Selective mobility into and out of urban neighbourhoods is one of the main driving forces of segregation. Earlier research has found group differences in who wants to leave or who leaves certain types of neighbourhoods. A factor that has received little attention so far is that some residents will have a desire to leave their neighbourhood, but are unable to do so. If there are differences between population groups in the realisation of desires to leave the neighbourhood, this might lead to involuntary segregation. This paper uses a unique combination of register data and survey data. We combine data from a large housing survey in the Netherlands (WoON) with longitudinal register data from the Netherlands (SSD) which contains individual-level information on residential mobility histories. This allows us to study whether households with a desire to leave their neighbourhood do realise this desire and which households are successful in leaving which neighbourhoods. A more thorough insight in who wants to leave which neighbourhoods but is unable to do so will contribute to a better understanding of selective mobility and segregation. We find that ethnic minorities and low-income households are less likely to realise a desire to leave their neighbourhood. We expected that ethnic minorities would be especially unsuccessful in realising desires to leave minority concentration neighbourhoods; however, for none of the ethnic groups we found an effect of neighbourhood ethnic composition on the realisation of desires to leave.     

Estimating the Impact of Water Pricing on Water Use Efficiency in Semi-arid Cropping System: An Application of Probabilistically Constrained Nonparametric Efficiency Analysis

By introducing proper pricing instruments, farm level water can be used more efficient. But it demands a proper estimation strategy to analyse the efficiency and the input use behavior of farms under the new pricing system. As most production relationships are stochastic in nature, excluding random errors and noise from model specifications often leads to criticism. By using a probabilistically constrained programming formulation, an empirical estimation of stochastic data envelopment analysis (DEA) is done to analyze the efficiency of irrigation water use in the agricultural production system in the Krishna river basin, India. The results illustrate that water demand is higher for farms at, or close to the frontier and lower for those with low efficiency levels. In a second step, a simulation model is developed by using the frontier and economic efficiency derived from stochastic DEA to analyse the impact of water pricing on water use efficiency and water use behaviour. It is shown that an increase in the water price would not cause sizeable profit loss, if the pricing system is administered on a volumetric basis, but water demand would decrease substantially.     

Drivers of change in agricultural water productivity and its improvement at basin scale in developing economies

We approach the issue of water productivity in agriculture by identifying five sets of drivers of change. We find that irrigation efficiencies at the field level can result in real water savings under certain conditions, but that small farmers in most of South Asia and Africa have little incentive to adopt the appropriate measures. Although water productivity improvement and water savings at the regional level are possible through a shift to economically efficient crops, such changes may be constrained by concerns with respect to domestic and regional food security, rural employment, and farming system resilience.     

Ecological strategies successfully predict the effects of river floodplain rehabilitation on breeding birds

To improve the ecological functioning of riverine ecosystems, large‐scale floodplain rehabilitation has been carried out in the Rhine–Meuse Delta since the 1990s. This paper evaluates changes in abundance of 93 breeding bird species over a period of 10 years in response to rehabilitation, by comparing population changes in 75 rehabilitated sites with 124 non‐rehabilitated reference sites. Such quantitative, multi‐species, large‐scale and long‐term evaluations of floodplain rehabilitation on biodiversity are still scarce, particularly studies that focus on the terrestrial component. We try to understand the effects by relating population trends to ecological and life‐history traits and strategies of breeding birds. More specifically, we try to answer the question whether rehabilitation of vegetation succession or hydro‐geomorphological river processes is the key driver behind recent population changes in rehabilitated sites. Populations of 35 species have significantly performed better in rehabilitated sites compared to non‐rehabilitated floodplains, whereas only 8 have responded negatively to rehabilitation. Differences in effects between species are best explained by the trait selection of nest location. Reproductive investment and migratory behaviour were less strong predictors. Based on these three traits we defined eight life‐history strategies that successfully captured a substantial amount of variation in rehabilitation effects. We conclude that spontaneous vegetation succession and initial excavations are currently more important drivers of population changes than rehabilitation of hydrodynamics. The latter are strongly constrained by river regulation. If rehabilitation of hydro‐geomorphological processes remains incomplete in future, artificial cyclic floodplain rejuvenation will be necessary for sustainable conservation of characteristic river birds. Copyright © 2010 John Wiley & Sons, Ltd.     

The deep waters of land reform: land,water and conservation area claims in Limpopo Province,Olifants Basin,South Africa

Through investigating the reactions of commercial farmers to land and water reforms in the Trichardtsdal-Ofcolaco area, Limpopo Province, Olifants Basin, South Africa, from 1997 to 2006, it is shown that water claims are key to land redistribution processes, and that commercial farmers make strategic use of arguments for nature conservation and ecological stewardship to defend their claims to water. Given these observations, caution is warranted with respect to the implementation of land and water reforms as separate policy packages; it may be more effective to design water and conservation policies as an integral part of land reform programmes.