Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

Identification of key parameters controlling dissolved oxygen migration and attenuation in fractured crystalline rocks

In the crystalline rocks of the Canadian Shield, geochemical conditions are currently reducing at depths of 500-1000 m. However, during future glacial periods, altered hydrologic conditions could potentially result in enhanced recharge of glacial melt water containing a relatively high concentration of dissolved oxygen (O2). It is therefore of interest to investigate the physical and geochemical processes, including naturally-occurring redox reactions, that may control O2 ingress. In this study, the reactive transport code MIN3P is used in combination with 2k factorial analyses to identify the most important parameters controlling oxygen migration and attenuation in fractured crystalline rocks. Scenarios considered are based on simplified conceptual models that include a single vertical fracture, or a fracture zone, contained within a rock matrix that extends from the ground surface to a depth of 500 m. Consistent with field observations, Fe(II)-bearing minerals are present in the fractures (i.e. chlorite) and the rock matrix (biotite and small quantities of pyrite). For the parameter ranges investigated, results indicate that for the single fracture case, the most influential factors controlling dissolved O2 ingress are flow velocity in the fracture, fracture aperture, and the biotite reaction rate in the rock matrix. The most important parameters for the fracture zone simulations are flow velocity in the individual fractures, pO2 in the recharge water, biotite reaction rate, and to a lesser degree the abundance and reactivity of chlorite in the fracture zone, and the fracture zone width. These parameters should therefore receive increased consideration during site characterization, and in the formulation of site-specific models intended to predict O2 behavior in crystalline rocks.     

An evaluation of global QSAR models for the prediction of the toxicity of phenols to Tetrahymena pyriformis

This study presents an analysis of the ability of a two-parameter response surface, a multiple linear regression and a neural network model to produce global quantitative structure-activity relationships (QSARs) to predict the toxic potency of phenols to Tetrahymena pyriformis. The phenolic toxicity data set analysed is characterised by multiple mechanisms of toxic action. The study aimed to evaluate the confidence that can be applied to the modelling of the differing mechanisms of action. Assessment of confidence was decided in terms of whether the statistics for the global models reflect the ability of the QSARs to model the individual mechanisms of toxic action present in the data set. The results showed that the global statistics only reflected the ability of models to predict the two non-covalent mechanisms (polar narcosis and respiratory uncoupling), with the metabolically transformed and electrophilic mechanism (pre-electrophiles and soft electrophiles) being modelled poorly by all three model building methods. The results confirm the difficulty in modelling electrophilic mechanisms of toxic action. The results also highlight the fact that this poor predictivity is often 'hidden' in good statistical fit of some global models. In particular these results emphasise that for practical predictive purposes the mechanistic applicability domain is required to give confidence to estimated toxicity values.     

Corruption in emergency procurement

Corruption in emergency procurement reduces the resources available for life‐saving operations, lowers the quality of products and services provided, and diverts aid from those who need it most. ¹ 1 The paper is based on a study for a project of the Chr Michelsen Institute (CMI)'s U4 Anti‐Corruption Resource Centre entitled ‘Corruption in Emergencies’ (see http://www.u4.no ).
It also negatively influences public support for humanitarian relief, both in the affected country and abroad. This paper aims to unpack and analyse the following question in order to mitigate risk: how and where does corruption typically occur, and what can be done? Suggested strategies reflect a multi‐layered approach that stresses internal agency control mechanisms, conflict‐sensitive management, and the need for common systems among operators.     

Experimental Study of the Criteria of Flow Laminarization in Two-Dimensional Dense Gas Plumes

Laminarization of flow in a two-dimensional dense gas plume was experimentally investigated in this study. The plume was created by releasing CO₂ through a ground-level line source into a simulated turbulent boundary layer over an aerodynamically rough surface in a meteorological wind tunnel. The bulk Richardson number (Ri_*), based on negative plume buoyancy, plume thickness, and friction velocity, was varied over a wide range so that the effects of stable stratification on plume laminarization could be observed. A variety of ambient wind speeds as well as three different sizes of roughness arrays were used so that possible effects of roughness Reynolds number (Re_*) on plume laminarization could also be identified. Both flow visualization methods and quantitative measurements of velocity and intermittency of turbulence were used to provide quantitative assessments of plume laminarization.Flow visualization provided an overall picture of how the plume was affected by the negative buoyancy. With increasing Ri_*, both the plume depth and the vertical mixing were significantly suppressed, while upstream propagation of the plume from the source was enhanced. The most important feature of the flow revealed by visualization was the laminarization of flow in the lower part of the plume, which appeared to be closely related to both Ri_* and Re_*.Measurements within the simulated dense gas plumes revealed the influence of the stable stratification on mean velocity and turbulence intensity profiles. Both the mean velocity and turbulence intensity were significantly reduced near the surface; and these reductions systematically depended on Ri_*. The roughness Reynolds number also had considerable influence on the mean flow and turbulence structure of the dense gas plumes.An intermittency analysis technique was developed and applied to the digitized instantaneous velocity signals. It not only confirmed the general flow picture within the dense plume indicated by the flow visualization, but also clearly demonstrated the changes of flow regime with variations in Ri_* and Re_*. Most importantly, based on this intermittency analysis, simple criteria for characterizing different flow regimes are formulated; these may be useful in predicting when plume laminarization might occur.     

Three-Dimensional Modelling of Concentration Fluctuations in Complicated Geometry

The strong fluctuating component in the measured concentration time series of a dispersing gaseous pollutant in the atmospheric boundary layer, and the hazard level associated to short-term concentration levels, demonstrate the necessity of calculating the magnitude of turbulent fluctuations of concentration using computational simulation models. Moreover the computation of concentration fluctuations in cases of dispersion in realistic situations, such as built-up areas or street canyons, is of special practical interest for hazard assessment purposes. In this paper, the formulation and evaluation of a model for concentration fluctuations, based on a transport equation, are presented. The model is applicable in cases of complex geometry. It is included in the framework of a computational code, developed for simulating the dispersion of buoyant pollutants over complex geometries. The experimental data used for the model evaluation concerned the dispersion of a passive gas in a street canyon between 4 identical rectangular buildings performed in a wind tunnel. The experimental concentration fluctuations data have been derived from measured high frequency concentrations. The concentration fluctuations model is evaluated by comparing the model's predictions with the observations in the form of scatter plots, quantile-quantile plots, contour plots and statistical indices as the fractional bias, the geometrical mean variance and the factor-of-two percentage. From the above comparisons it is concluded that the overall model performance in the present complex geometry case is satisfactory. The discrepancies between model predictions and observations are attributed to inaccuracies in prescribing the actual wind tunnel boundary conditions to the computational code.     

Identifying the largest individual sample value from a two-way composite sampling design

Composite sampling techniques for identifying the largest individual sample value seem to be cost effective when the composite samples are internally homogeneous. However, since it is not always possible to form homogeneous composite samples, these methods can lead to higher costs than expected. In this paper we propose a two-way composite sampling design as a way to improve on the cost effectiveness of the methods available to identify the largest individual sample value.     

南部非洲的一体化电力计划

本文概括了12个南部非洲国家电力联营的一体化电力计划(IEP)过程,阐述了使用IEP的长期计划,本文同时也着重讨论了关于未来生产量的决策过程,提出了有利于在南非采纳更清洁技术的角色和措施.     

城市及其遗产：保存的根源和条件

城市遗产的保存和利用将都市管理的负责人置于艰难选择的境地.下面的文字对城市的构成进行了简短的历史回顾,得出了在场所利用及其保存之间保持平衡发展条件.     

Unprecedented bleaching-induced mortality in Porites spp. at Rangiroa Atoll, French Polynesia

In April-May 1998, mass coral bleaching was observed in the lagoon of Rangiroa Atoll, Tuamotu Archipelago, French Polynesia. Six months later, the extent of bleaching-induced coral mortality was assessed at three sites. Corals in the fast-growing genus Pocillopora had experienced >99% mortality. Many large colonies of the slow-growing genus Porites (mean horizontal cross-sectional area 5.8 m²) had also died - a phenomenon not previously observed in French Polynesia and virtually unprecedented world-wide. At one site, 25% of colonies, or 44% of the pre-bleaching cover of living Porites, experienced whole-colony mortality. At the two other sites, recently dead Porites accounted for 41% and 82% of the pre-bleaching live cover. Mortality in Porites was negatively correlated with depth between 1.5 and 5 m. Using a 50-year dataset of mean monthly sea surface temperature (SST), derived from ship- and satellite-borne instruments, we show that bleaching occurred during a period of exceptionally high summer SST. 1998 was the first year in which mean monthly SSTs exceeded the 1961-1990 upper 95% confidence limit (29.4°C) for a period of three consecutive months. We suggest that the sustained 3-month anomaly in local summer SST was a major cause of coral mortality, but do not discount the synergistic effect of solar radiation. Recovery of the size-frequency distribution of Porites colonies to pre-bleaching levels may take at least 100 years.