Determination of cadmium, lead, and nickel by simultaneous multielement flame atomic absorption spectrometry in burned and unburned Venezuelan crude oil

This work describes the use of simultaneous multielement flame atomic absorption spectrometry for the determination of cadmium, lead, and nickel in burned and unburned Venezuelan crude oil (5 ml volumes) in controlled laboratory experiments. The simultaneous detection limits were 0.010 mug ml(-1) (Cd), 0.04 mug ml(-1) (Pb), and 0.40 mug ml(-1) (Ni) with precision's of these elements at concentrations of 10x above these detections limits, and in the crude oil, of 1-2%. Loss of elemental concentrations in the crude oil in a 3-5 ml volume when burned were 4% (Cd), 50% (Pb), and 22% (Ni). These results suggest that the form of the elements and the temperature attained in the burning crude oil effect the removal of the elements. The type of surface affected the volume of oil removed. Soil gave a 15% and a smooth surface almost 50% volume reduction.     

Adsorption of liquid mixtures on silicalite-1 zeolite: a density-bottle method

A technique that measures the effective density of a zeolite after adsorption from the liquid phase was developed to measure the absolute amounts of liquid mixtures adsorbed on zeolites without using a nonadsorbing solvent. Since the fugacities of the adsorbing components in solution can be dramatically different with or without the addition of a nonadsorbing solvent, this technique measures mixture isotherms that can be used for analyzing pervaporation through zeolite membranes. A nonideal solution, methanol/acetone, was used as an example to show that its adsorption isotherms on silicalite-1 zeolite at 294 K differ dramatically from those measured with the nonadsorbing solvent method. The methanol/acetone fugacity ratio is different for the two methods because of different concentrations in the liquid phase. Methanol preferentially adsorbs on silicalite-1 at low methanol concentrations and acetone preferentially adsorbs at high methanol concentrations. The density bottle method was used to show that n-hexane preferentially adsorbs from n-hexane/3-methylpentane liquid mixtures, and at high n-hexane concentrations, essentially no 3-methylpentane adsorbs, as has been predicted previously by simulations. A larger molecule, 2,2-dimethylbutane, adsorbed so slowly at 294 K that silicalite had only 16% of saturation coverage after 370 h, but it was saturated after 1650 h; at 423 K, saturation was obtained in less than 24 h.     

Analysis of transient permeation as a technique for determination of sorption and diffusion in supported membranes

Systematic membrane selection, process design as well as elucidation of structure–property relationships for pervaporation and vapor permeation require knowledge of sorption and diffusion properties. Direct measurement of sorption is not possible in the case of commercial membranes due to the presence of a support layer. Sorption measurements may also be difficult if the polymer is synthesized or crosslinked directly on the support and its properties are different from the bulk polymer. This work describes a technique to obtain sorption as well as diffusion parameters for supported membranes using transient permeation data. Computer simulations for transient permeation were carried out using sorption and diffusion data from the literature. It was demonstrated that the desired parameters could be estimated using data having a reasonable degree of error (±2%) by the least squares method. Alternatively, a time-lag analysis may be used instead of direct regression of the parameters by the least squares method. A general method for estimating the sorption as well as diffusion parameters using the time-lag and steady-state flux is described. Analytical solutions are derived for the various transport models, wherever possible.     

Two-stage application of the optimised uncertainty method: a practical assessment

Uncertainty estimates from routine sampling and analytical procedures can be assessed as being fit for purpose using the optimised uncertainty (OU) method. The OU method recommends an optimal level of uncertainty that should be reached in order to minimise the expected financial loss, given a misclassification of a batch as a result of the uncertainty. Sampling theory can used as a predictive tool when a change in sampling uncertainty is recommended by the OU method. The OU methodology has been applied iteratively for the first time using a case study of wholesale butter and the determination of five quality indicators (moisture, fat, solids-not-fat (SNF), peroxide value (PV) and free fatty acid (FFA)). The sampling uncertainty (s(samp)) was found to be sub-optimal for moisture and PV determination, for 3-fold composite samples. A revised sampling protocol was devised using Gy's sampling theory. It was predicted that an increase in sample mass would reduce the sampling uncertainty to the optimal level, resulting in a saving in expectation of loss of over pounds 2000 per 20 tonne batch, when compared to current methods. Application of the optimal protocol did not however, achieve the desired reduction in s(samp) due to limitations in sampling theory. The OU methodology proved to be a useful tool in identifying broad weaknesses within a routine protocol and assessing fitness for purpose. However, the successful routine application of sampling theory, as part of the optimisation process, requires substantial prior knowledge of the sampling target.     

A conformal decomposition finite element method for modeling stationary fluid interface problems

A method is developed for modeling fluid transport in domains that do not conform to the finite element mesh. One or more level set functions are used to describe the fluid domain. A background, non‐conformal mesh is decomposed into elements that conform to the level set interfaces. Enrichment takes place by adding nodes that lie on the interfaces. Unlike other enriched finite element methods, the proposed technique requires no changes to the underlying element assembly, element interpolation, or element quadrature. The complexity is entirely contained within the element decomposition routines. It is argued that the accuracy of the method is no less than that for eXtended Finite Element Methods (XFEM) with Heaviside enrichment. The accuracy is demonstrated using multiple numerical tests. In all cases, optimal rates of convergence are obtained for both volume and surface quantities. Jacobi preconditioning is shown to remove the ill‐conditioning that may result from the nearly degenerate conformal elements. Copyright © 2009 John Wiley & Sons, Ltd.     

Modelling LGD for unsecured retail loans using Bayesian methods

Loss Given Default (LGD) is the loss borne by the bank when a customer defaults on a loan. LGD for unsecured retail loans is often found difficult to model. In the frequentist (non-Bayesian) two-step approach, two separate regression models are estimated independently, which can be considered potentially problematic when trying to combine them to make predictions about LGD. The result is a point estimate of LGD for each loan. Alternatively, LGD can be modelled using Bayesian methods. In the Bayesian framework, one can build a single, hierarchical model instead of two separate ones, which makes this a more coherent approach. In this paper, Bayesian methods as well as the frequentist approach are applied to the data on personal loans provided by a large UK bank. As expected, the posterior means of parameters that have been produced using Bayesian methods are very similar to the frequentist estimates. The most important advantage of the Bayesian model is that it generates an individual predictive distribution of LGD for each loan. Potential applications of such distributions include the downturn LGD and the stressed LGD under Basel II.