Platinum concentrations in urban road dust and soil, and in blood and urine in the United Kingdom

Increasing Pt concentrations from vehicle catalysts have been reported from a number of countries. Analysis of Pt and Pd in soils and road dusts taken from areas of high and low traffic flows in SE England show concentrations of Pt in the range < 0.30-40.1 ng g-1 and Pd in the range < 2.1-57.9 ng g-1. Higher concentrations of Pt are associated with high traffic densities. Samples taken from streets of lower traffic flows were found to contain the lower concentrations of the ranges. Pilot studies of Pt concentrations in blood and urine using ICP-MS have been carried out. Platinum concentrations in whole blood were: precious metal workers, 780-2170, mean 1263 pmol l-1 (0.152-0.423, mean 0.246 microgram l-1); motorway maintenance workers, 645-810, mean 744 pmol l-1 (0.126-0.158, mean 0.145 microgram l-1); Imperial College staff, 590-713, mean 660 pmol l-1 (0.115-0.139, mean 0.129 microgram l-1). Platinum concentrations in urine in pmol Pt per mmol creatinine were: precious metal workers, 122-682, mean 273 [0.21-1.18, mean 0.47 microgram Pt (g creatinine)-1]; motorway maintenance workers, 13-78, mean 33.7 [0.022-0.135, mean 0.058 microgram Pt (g creatinine)-1]; Imperial College staff, 28-130, mean 65.6 [0.048-0.224, mean 0.113 microgram Pt (g creatinine)-1]. Detection limits were 0.03 microgram l-1 for both blood and urine. The possible health effects of increasing Pt in the environment are discussed. Platinum provides an excellent example of the significance of speciation in metal toxicity. Platinum allergy is confined to a small group of charged compounds that contain reactive ligand systems, the most effective of which are chloride ligand systems. Metallic Pt is considered to be biologically inert and non allergenic and since the emitted Pt is probably in the metallic or oxide form, the sensitising potential is probably very low. Platinum from road dusts, however, can be solubilised, and enter waters, sediments, soils and the food chain. There is at present no evidence for any adverse health effects from Pt in the general environment, particularly allergic reactions.     

A functional equations approach to nonlinear discrete-time feedback stabilization through pole-placement

The present work proposes a new approach to the nonlinear discrete-time feedback stabilization problem with pole-placement. The problem's formulation is realized through a system of nonlinear functional equations and a rather general set of necessary and sufficient conditions for solvability is derived. Using tools from functional equations theory, one can prove that the solution to the above system of nonlinear functional equations is locally analytic, and an easily programmable series solution method can be developed. Under a simultaneous implementation of a nonlinear coordinate transformation and a nonlinear discrete-time state feedback control law that are both computed through the solution of the system of nonlinear functional equations, the feedback stabilization with pole-placement design objective can be attained under rather general conditions. The key idea of the proposed single-step design approach is to bypass the intermediate step of transforming the original system into a linear controllable one with an external reference input associated with the classical exact feedback linearization approach. However, since the proposed method does not involve an external reference input, it cannot meet other control objectives such as trajectory tracking and model matching.     

Deformation mechanism of aluminum–magnesium alloys at elevated temperatures

The study concentrates on the formulation of a reliable constitutive equation for plastic forming of Al–Mg-based alloys above 400 °C and at strain rates above 10^?3 s^?1. The deformation mechanisms of two coarse-grained Al–Mg alloys, also known as AA5182, with grain sizes 21 and 37 μm were investigated. They exhibited optimum extension at 10^?2 s^?1 and at T equal to 425 °C and above 475 °C, respectively, with uniform elongation above 300 %. The strain-rate sensitivity and the stress exponent were equal to 0.25 and 4, respectively, suggesting that the deformation is controlled by the solute drag of gliding dislocations whereas dislocation climb occurs also in grains whose orientation renders them hard. Grain boundary sliding may contribute to a small extent in the deformation process. The threshold stress was found to be small and the activation energy lies between 144 and 136 kJ mol^?1, i.e., that of Al self-diffusion and Mg diffusion in Al. It is concluded that coarse-grained materials may well fulfill the industrial requirements of forming and within this scope, the use of the low purity coarse-grained Al–Mg-based alloys of the AA5182 type would constitute the next step in the course for further cost reduction.     

The poison chain for mercury in the environment

The toxic effects of mercury in specific population groups, for example following occupational exposure or therapeutic application, has long been known, but mercury as a general environmental hazard has followed comparitively recent technological development. Contamination with both inorganic mercury and organic mercury compounds has resulted from industrial waste and from the use of the latter compounds as fungicides. Deposited eventually in rivers and lakes, this has led to raised levels of mercury in fish. Under appropriate conditions, methylation of mercury may occur in the natural environment, converting less toxic inorganic and aryl mercury compounds into the more toxic alkyl mercury form. In certain predominantly fish eating populations this has led to an increase in the body burden for organic mercury, resulting in localized outbreaks of methyl mercury poisoning. Raised levels of mercury in eggs and bird tissues have resulted from feeding on mercury contaminated fish and on organomercury treated seed. This has contributed to a reduction in some species of birds in certain areas. In addition to the direct toxic action of mercury, limited evidence suggests that methyl mercury compounds may possibly exert mutagenic and teratogenic effects, at levels below those usually associated with poisoning. Methyl mercury concentration should be monitored in exposed groups and where this is raised, epidemiological studies performed to evaluate a possible hazard.     

Optimal controller tuning for nonlinear processes

The present work proposes a systematic methodology for the optimal selection of controller parameters in the sense of minimizing a performance index, which is a quadratic function of the tracking error and the control effort. The performance index is calculated explicitly as an algebraic function of the controller parameters by solving Zubov's partial differential equation (PDE). Standard optimization techniques are then employed for the calculation of the optimal values of the controller parameters. The solution of Zubov's PDE is also used to estimate the closed-loop stability region for the chosen values of the controller parameters. The proposed approach is finally illustrated in a chemical reactor control problem.     

Nonlinear observer design for state and disturbance estimation

A new systematic framework for nonlinear observer design that allows the concurrent estimation of the process state variables together with key unknown process or sensor disturbances is proposed. The nonlinear observer design problem is addressed within a similar methodological framework as the one introduced in [N. Kazantzis, C. Kravaris, Nonlinear observer design using Lyapunov's auxiliary theorem, Systems Control Lett. 34 (1998) 241; A.J. Krener, M. Xiao, Nonlinear observer design in the Siegel domain, SIAM J. Control Optim. 41 (2002) 932.] for state estimation purposes only. From a mathematical standpoint, the problem under consideration is addressed through a system of first-order singular PDEs for which a rather general set of solvability conditions is derived. A nonlinear observer is then designed with a state-dependent gain that is computed from the solution of the system of singular PDEs. Under the aforementioned conditions, both state and disturbance estimation errors converge to zero with assignable rates. The convergence properties of the proposed nonlinear observer are tested through simulation studies in an illustrative example involving a biological reactor.     

Molecular simulation studies of adsorption of hydrogen cyanide and methyl ethyl ketone on zeolite NaX and activated carbon

In the present research study the primary aim is to understand and characterize the physical adsorption of polar molecules namely, hydrogen cyanide and methyl ethyl ketone (MEK) in zeolite NaX, and activated carbon through detailed Monte-Carlo simulations and computational quantum chemistry techniques. The sorption capacity and affinity of the zeolite is compared with activated carbon with different acid site concentrations, type of acid site, and pore sizes by simulating single component isotherms and Henry's constant at 25 degrees C. The role/contribution of certain types of electrostatic interactions namely charge-dipole, charge-induced dipole with zeolite NaX and activated carbon, as well as dipole-dipole interactions among polar molecules is analyzed and discussed.     

High pressure palladium membrane reactor for the high temperature water-gas shift reaction

The water-gas shift (WGS) catalytic membrane reactor (CMR) incorporating a composite Pd-membrane and operating at elevated temperatures and pressures can greatly contribute to the efficiency enhancement of several methods of H₂ production and green power generation. To this end, mixed gas permeation experiments and WGS CMR experiments have been conducted with a porous Inconel supported, electroless plated Pd-membrane to better understand the functioning and capabilities of those processes. Binary mixtures of H₂/He, H₂/CO₂, and a ternary mixture of H₂, CO₂ and CO were separated by the composite membrane at 350, 400, and 450 °C, 14.4 bar (P_tube = 1 bar), and space velocities up to 45,000 h⁻¹. H₂ permeation inhibition caused by reversible surface binding was observed due to the presence of both CO and CO₂ in the mixtures and membrane inhibition coefficients were estimated. Furthermore, WGS CMR experiments were conducted with a CO and steam feed at 14.4 bar (P_tube = 1 bar), H₂O/CO ratios of 1.1-2.6, and GHSVs of up to 2900 h⁻¹, considering the effect of the H₂O/CO ratio as well as temperature on the reactor performance. Experiments were also conducted with a simulated syngas feed at 14.0 bar (P_tube  = 1 bar), and 400-450 °C, assessing the effect of the space velocity on the reactor performance. A maximum CO conversion of 98.2% was achieved with a H₂ recovery of 81.2% at 450 °C. An optimal operating temperature for high CO conversion was identified at approximately 450 °C, and high CO conversion and H₂ recovery were achieved at 450 °C with high throughput, made possible by the 14.4 bar reaction pressure.     

Concluding causation from correlation: Comment on Burns and Spangler (2000).

This commentary critiques the study conducted by D. D. Burns and D. Spangler (2000) (see record 2000-13544-005) in which the relationship between homework compliance and therapy outcome was estimated using structural equation modeling (SEM). Although the authors, of the commentary advocate the use of SEM, they suggest greater caution in the indiscriminate endorsement of a causal relationship based on (a) correlational data and (b) retrospective accounts of the main predictor variable within a cross-sectional design. This discussion also highlights a need to address the issue of therapist competence in homework administration. The results of Burns and Spangler's report are consistent with existing empirical evidence suggesting that compliance with homework facilitates therapeutic outcome. However, the gold standard for determining causal inferences rests on prospective, experimental research rather than on retrospective, correlational models. (PsycINFO Database Record (c) 2010 APA, all rights reserved)