Low-temperature sol-gel preparation of ordered nanoparticles of tungsten carbide/oxide

Tungsten carbide/oxide particles have been prepared by the gel precipitation of tungstic acid in the presence of an organic gelling agent [10% ammonium poly(acrylic acid) in water, supplied by Ciba Specialty Chemicals]. The feed solution; a homogeneous mixture of sodium tungstate and ammonium poly(acrylic acid) in water, was dropped from a 1-mm jet into hydrochloric acid saturated hexanol/concentrated hydrochloric acid to give particles of a mixture of tungstic acid and poly(acrylic acid), which, after drying in air at 100 degrees C and heating to 900 degrees C in argon for 2 h, followed by heating in carbon dioxide for a further 2 h and cooling, gives a mixture of WO, WC, and a trace of NaxWO3, with the carbon for the formation of WC being provided by the thermal carbonization of poly(acrylic acid). The pyrolyzed product is friable and easily broken down in a pestle and mortar to a fine powder or by ultrasonics, in water, to form a stable colloid. The temperature of carbide formation by this process is significantly lower (900 degrees C) than that reported for the commercial preparation of tungsten carbide, typically > 1400 degrees C. In addition, the need for prolonged grinding of the constituents is obviated because the reacting moieties are already in intimate contact on a molecular basis. X-ray diffraction, particle sizing, transmission electron microscopy, surface area, and pore size distribution studies have been carried out, and possible uses are suggested. A flow diagram for the process is described.

Evaluation of data for atmospheric models: master equation/RRKM calculations on the combination reaction, BrO+NO2 -> BrONO2, a conundrum

Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.

A study of the effect of heat source location in a ventilated room using multiple regression analysis

Multiple regression analysis is a statistical technique which allows to predict a dependent variable from m ore than one independent variable and also to determine influential independent variables. Using experimental data, in this study the multiple regression analysis is applied to predict the room mean velocity and determine the most influencing parameters on the velocity. More than 120 experiments for four different heat source locations were carried out in a test chamber with a high level wall mounted air supply terminal at air change rates 3-6 ach. The influence of the environmental parameters such as supply air momentum, room heat load, Archimedes number and local temperature ratio, were examined by two methods: a simple regression analysis incorporated into scatter matrix plots and multiple stepwise regression analysis. It is concluded that, when a heat source is located along the jet centre line, the supply momentum mainly influences the room mean velocity regardless of the plume strength. However, when the heat source is located outside the jet region, the local temperature ratio (the inverse of the local heat removal effectiveness) is a major influencing parameter.

Theoretical and experimental investigation of wall confluent jets ventilation and comparison with wall displacement ventilation

This paper reports CFD and experimental results of the characteristics of wall confluent jets in a room. The results presented show the behaviour of wall confluent jets in the form of velocity profiles, the spreading rate of jets on the surface, jets decay, etc. The empirical equations derived are compared with other types of air jets. In addition, the flow in wall confluent jets is compared with the flow in displacement ventilation supply, with regards to the vertical and horizontal spreading on the floor. It is concluded that the jet momentum of wall confluent jets can be more conserved than other jets. Thus, wall confluent jets have a greater spread over the floor than displacement flow.

The air distribution index as an indicator for energy consumption and performance of ventilation systems

This paper deals with the energy consumption and the evaluation of the performance of air supply systems for a ventilated room involving high- and low-level supplies. The energy performance assessment is based on the airflow rate, which is related to the fan power consumption by achieving the same environmental quality performance for each case. Four different ventilation systems are considered: wall displacement ventilation, confluent jets ventilation, impinging jet ventilation and a high level mixing ventilation system. The ventilation performance of these systems will be examined by means of achieving the same Air Distribution Index (ADI) for different cases. The widely used high-level supplies require much more fan power than those for low-level supplies for achieving the same value of ADI. In addition, the supply velocity, hence the supply dynamic pressure, for a high-level supply is much larger than for low-level supplies. This further increases the power consumption for high-level supply systems. The paper considers these factors and attempts to provide some guidelines on the difference in the energy consumption associated with high and low level air supply systems. This will be useful information for designers and to the authors' knowledge there is a lack of information available in the literature on this area of room air distribution. The energy performance of the above-mentioned ventilation systems has been evaluated on the basis of the fan power consumed which is related to the airflow rate required to provide equivalent indoor environment. The Air Distribution Index (ADI) is used to evaluate the indoor environment produced in the room by the ventilation strategy being used. The results reveal that mixing ventilation requires the highest fan power and the confluent jets ventilation needs the lowest fan power in order to achieve nearly the same value of ADI.

Investigation of air quality, comfort parameters and effectiveness for two floor-level air supply systems in classrooms

The method of distributing the outdoor air in classrooms has a major impact on indoor air quality and thermal comfort of pupils. In a previous study, ([11] Karimipanah T, Sandberg M, Awbi HB. A comparative study of different air distribution systems in a classroom. In: Proceedings of Roomvent 2000, vol. II, Reading, UK, 2000. p. 1013-18; [13] Karimipanah T, Sandberg M, Awbi HB, Blomqvist C. Effectiveness of confluent jets ventilation system for classrooms. In: Idoor Air 2005, Beijing, China, 2005 (to be presented).) presented results for four and two types of air distribution systems tested in a purpose built classroom with simulated occupancy as well as computational fluid dynamics (CFD) modelling. In this paper, the same experimental setup has been used to investigate the indoor environment in the classroom using confluent jet ventilation, see also ([12]Cho YJ, Awbi HB, Karimipanah T. The characteristics of wall confluent jets for ventilated enclosures. In: Proceedings of Roomvent 2004, Coimbra, Portugal, 2004.) Measurements of air speed, air temperature and tracer gas concentrations have been carried out for different thermal conditions. In addition, 56 cases of CFD simulations have been carried to provide additional information on the indoor air quality and comfort conditions throughout the classroom, such as ventilation effectiveness, air exchange effectiveness, effect of flow rate, effect of radiation, effect of supply temperature, etc., and these are compared with measured data.

Tracking and mean structure of easterly waves over the Intra-Americas Sea

Easterly waves (EWs) are prominent features of the intertropical convergence zone (ITCZ), found in both the Atlantic and Pacific during the Northern Hemisphere summer and fall, where they commonly serve as precursors to hurricanes over both basins.Alarge proportion of Atlantic EWs are known to form over Africa, but the origin of EWs over the Caribbean and east Pacific in particular has not been established in detail. In this study reanalyses are used to examine the coherence of the large-scale wave signatures and to obtain track statistics and energy conversion terms for EWs across this region. Regression analysis demonstrates that some EW kinematic structures readily propagate between the Atlantic and east Pacific, with the highest correlations observed across Costa Rica and Panama. Track statistics are consistent with this analysis and suggest that some individual waves are maintained as they pass from the Atlantic into the east Pacific, whereas others are generated locally in the Caribbean and east Pacific. Vortex anomalies associated with the waves are observed on the leeward side of the Sierra Madre, propagating northwestward along the coast, consistent with previous modeling studies of the interactions between zonal flow and EWs with model topography similar to the Sierra Madre. An energetics analysis additionally indicates that the Caribbean low-level jet and its extension into the east Pacific—known as the Papagayo jet—are a source of energy for EWs in the region. Two case studies support these statistics, as well as demonstrate the modulation of EW track and storm development location by the MJO.

U.K. HiGEM: Simulations of desert dust and biomass burning aerosols with a high-resolution atmospheric GCM

The atmospheric component of the United Kingdom’s new High-resolution Global Environmental Model (HiGEM) has been run with interactive aerosol schemes that include biomass burning and mineral dust. Dust emission, transport, and deposition are parameterized within the model using six particle size divisions, which are treated independently. The biomass is modeled in three nonindependent modes, and emissions are prescribed from an external dataset. The model is shown to produce realistic horizontal and vertical distributions of these aerosols for each season when compared with available satellite- and ground-based observations and with other models. Combined aerosol optical depths off the coast of North Africa exceed 0.5 both in boreal winter, when biomass is the main contributor, and also in summer, when the dust dominates. The model is capable of resolving smaller-scale features, such as dust storms emanating from the Bode´ le´ and Saharan regions of North Africa and the wintertime Bode´ le´ low-level jet. This is illustrated by February and July case studies, in which the diurnal cycles of model variables in relation to dust emission and transport are examined. The top-of-atmosphere annual mean radiative forcing of the dust is calculated and found to be globally quite small but locally very large, exceeding 20 W m22 over the Sahara, where inclusion of dust aerosol is shown to improve the model radiative balance. This work extends previous aerosol studies by combining complexity with increased global resolution and represents a step toward the next generation of models to investigate aerosol–climate interactions. 1. Introduction Accurate modeling of mineral dust is known to be important because of its radiative impact in both numerical weather prediction models (Milton et al. 2008; Haywood et

Baroclinic stationary waves in aquaplanet models

An aquaplanet model is used to study the nature of the highly persistent low-frequency waves that have been observed in models forced by zonally symmetric boundary conditions. Using the Hayashi spectral analysis of the extratropical waves, the authors find that a quasi-stationary wave 5 belongs to a wave packet obeying a well-defined dispersion relation with eastward group velocity. The components of the dispersion relation with k ≥ 5 baroclinically convert eddy available potential energy into eddy kinetic energy, whereas those with k < 5 are baroclinically neutral. In agreement with Green’s model of baroclinic instability, wave 5 is weakly unstable, and the inverse energy cascade, which had been previously proposed as a main forcing for this type of wave, only acts as a positive feedback on its predominantly baroclinic energetics. The quasi-stationary wave is reinforced by a phase lock to an analogous pattern in the tropical convection, which provides further amplification to the wave. It is also found that the Pedlosky bounds on the phase speed of unstable waves provide guidance in explaining the latitudinal structure of the energy conversion, which is shown to be more enhanced where the zonal westerly surface wind is weaker. The wave’s energy is then trapped in the waveguide created by the upper tropospheric jet stream. In agreement with Green’s theory, as the equator-to-pole SST difference is reduced, the stationary marginally stable component shifts toward higher wavenumbers, while wave 5 becomes neutral and westward propagating. Some properties of the aquaplanet quasi-stationary waves are found to be in interesting agreement with a low frequency wave observed by Salby during December–February in the Southern Hemisphere so that this perspective on low frequency variability, apart from its value in terms of basic geophysical fluid dynamics, might be of specific interest for studying the earth’s atmosphere.

The impact of the state of the troposphere on the response to stratospheric heating in a simplified GCM

Previous studies have made use of simplified general circulation models (sGCMs) to investigate the atmospheric response to various forcings. In particular, several studies have investigated the tropospheric response to changes in stratospheric temperature. This is potentially relevant for many climate forcings. Here the impact of changing the tropospheric climatology on the modeled response to perturbations in stratospheric temperature is investigated by the introduction of topography into the model and altering the tropospheric jet structure. The results highlight the need for very long integrations so as to determine accurately the magnitude of response. It is found that introducing topography into the model and thus removing the zonally symmetric nature of the model’s boundary conditions reduces the magnitude of response to stratospheric heating. However, this reduction is of comparable size to the variability in the magnitude of response between different ensemble members of the same 5000-day experiment. Investigations into the impact of varying tropospheric jet structure reveal a trend with lower-latitude/narrower jets having a much larger magnitude response to stratospheric heating than higher-latitude/wider jets. The jet structures that respond more strongly to stratospheric heating also exhibit longer time scale variability in their control run simulations, consistent with the idea that a feedback between the eddies and the mean flow is both responsible for the persistence of the control run variability and important in producing the tropospheric response to stratospheric temperature perturbations.

Sting jets in simulations of a real cyclone by two mesoscale models

The existence of sting jets as a potential source of damaging surface winds during the passage of extratropical cyclones has recently been recognized However, there are still very few published studies on the subject Furthermore, although ills known that other models are capable of reproducing sting jets, in the published literature only one numerical model [the Met Office Unified Model (MetUM)] has been used to numerically analyze these phenomena This article alms to improve our understanding of the processes that contribute to the development of sting jets and show that model differences affect the evolution of modeled sting jets A sting jet event during the passage of a cyclone over the United Kingdom on 26 February 2002 has been simulated using two mesoscale models namely the MetUM and the Consortium for Small Scale Modeling (COSMO) model to compare their performance Given the known critical importance of vertical resolution in the simulation of sting jets the vertical resolution of both models has been enhanced with respect to their operational versions Both simulations have been verified against surface measurements of maximum gusts, satellite imagery and Met Office operational synoptic analyses, as well as operational analyses from the ECMWF It is shown that both models are capable of reproducing sting jets with similar, though not identical. features Through the comparison of the results from these two models, the relevance of physical mechanisms, such as evaporative cooling and the release of conditional symmetric instability, in the generation and evolution of sting jets is also discussed

Distributed water ingress and water potential measurements using fibre optics

We report on a distributed moisture detection scheme which uses a cable design based on waterswellable hydrogel polymers. The cable modulates the loss characteristic of light guided within a multi-mode optical fibre in response to relative water potentials in the surrounding environment. Interrogation of the cable using conventional optical time-domain reflectometry (OTDR) instruments allows water ingress points to be identified and located with a spatial resolution of 50 cm. The system has been tested in a simulated tendon duct grouting experiment as a means of mapping the extent of fill along the duct during the grouting process. Voided regions were detected and identified to within 50 cm. A series of salt solutions has been used to determine the sensor behaviour over a range of water potentials. These experiments predict that measurements of soil moisture content can be made over the range 0 to – 1500 kPa. Preliminary data on soil measurements have shown that the sensor can detect water pressure changes with a resolution of 45 kPa. Applications for the sensor include quality assurance of grouting procedures, verification of waterproofing barriers and soil moisture content determination (for load-bearing calculations).

Multimodel climate and variability of the stratosphere

The stratospheric climate and variability from simulations of sixteen chemistry‐climate models is evaluated. On average the polar night jet is well reproduced though its variability is less well reproduced with a large spread between models. Polar temperature biases are less than 5 K except in the Southern Hemisphere (SH) lower stratosphere in spring. The accumulated area of low temperatures responsible for polar stratospheric cloud formation is accurately reproduced for the Antarctic but underestimated for the Arctic. The shape and position of the polar vortex is well simulated, as is the tropical upwelling in the lower stratosphere. There is a wide model spread in the frequency of major sudden stratospheric warnings (SSWs), late biases in the breakup of the SH vortex, and a weak annual cycle in the zonal wind in the tropical upper stratosphere. Quantitatively, “metrics” indicate a wide spread in model performance for most diagnostics with systematic biases in many, and poorer performance in the SH than in the Northern Hemisphere (NH). Correlations were found in the SH between errors in the final warming, polar temperatures, the leading mode of variability, and jet strength, and in the NH between errors in polar temperatures, frequency of major SSWs, and jet strength. Models with a stronger QBO have stronger tropical upwelling and a colder NH vortex. Both the qualitative and quantitative analysis indicate a number of common and long‐standing model problems, particularly related to the simulation of the SH and stratospheric variability.

Dependence of Indian monsoon rainfall on moisture fluxes across the Arabian Sea and the impact of coupled model sea surface temperature biases

The Arabian Sea is an important moisture source for Indian monsoon rainfall. The skill of climate models in simulating the monsoon and its variability varies widely, while Arabian Sea cold sea surface temperature (SST) biases are common in coupled models and may therefore influence the monsoon and its sensitivity to climate change. We examine the relationship between monsoon rainfall, moisture fluxes and Arabian Sea SST in observations and climate model simulations. Observational analysis shows strong monsoons depend on moisture fluxes across the Arabian Sea, however detecting consistent signals with contemporaneous summer SST anomalies is complicated in the observed system by air/sea coupling and large-scale induced variability such as the El Niño-Southern Oscillation feeding back onto the monsoon through development of the Somali Jet. Comparison of HadGEM3 coupled and atmosphere-only configurations suggests coupled model cold SST biases significantly reduce monsoon rainfall. Idealised atmosphere-only experiments show that the weakened monsoon can be mainly attributed to systematic Arabian Sea cold SST biases during summer and their impact on the monsoon-moisture relationship. The impact of large cold SST biases on atmospheric moisture content over the Arabian Sea, and also the subsequent reduced latent heat release over India, dominates over any enhancement in the land-sea temperature gradient and results in changes to the mean state. We hypothesize that a cold base state will result in underestimation of the impact of larger projected Arabian Sea SST changes in future climate, suggesting that Arabian Sea biases should be a clear target for model development.

Boundary layer dynamics over London, UK, as observed using Doppler lidar during REPARTEE-II

Urban boundary layers (UBLs) can be highly complex due to the heterogeneous roughness and heating of the surface, particularly at night. Due to a general lack of observations, it is not clear whether canonical models of boundary layer mixing are appropriate in modelling air quality in urban areas. This paper reports Doppler lidar observations of turbulence profiles in the centre of London, UK, as part of the second REPARTEE campaign in autumn 2007. Lidar-measured standard deviation of vertical velocity averaged over 30 min intervals generally compared well with in situ sonic anemometer measurements at 190 m on the BT telecommunications Tower. During calm, nocturnal periods, the lidar underestimated turbulent mixing due mainly to limited sampling rate. Mixing height derived from the turbulence, and aerosol layer height from the backscatter profiles, showed similar diurnal cycles ranging from c. 300 to 800 m, increasing to c. 200 to 850 m under clear skies. The aerosol layer height was sometimes significantly different to the mixing height, particularly at night under clear skies. For convective and neutral cases, the scaled turbulence profiles resembled canonical results; this was less clear for the stable case. Lidar observations clearly showed enhanced mixing beneath stratocumulus clouds reaching down on occasion to approximately half daytime boundary layer depth. On one occasion the nocturnal turbulent structure was consistent with a nocturnal jet, suggesting a stable layer. Given the general agreement between observations and canonical turbulence profiles, mixing timescales were calculated for passive scalars released at street level to reach the BT Tower using existing models of turbulent mixing. It was estimated to take c. 10 min to diffuse up to 190 m, rising to between 20 and 50 min at night, depending on stability. Determination of mixing timescales is important when comparing to physico-chemical processes acting on pollutant species measured simultaneously at both the ground and at the BT Tower during the campaign. From the 3 week autumnal data-set there is evidence for occasional stable layers in central London, effectively decoupling surface emissions from air aloft.