Dissolving multicomponent NAPL as a source of contamination in subsurface water is considered. In particular, two processes are analyzed with regard to how they alter inter-species concentration ratios at remote monitoring locations relative to inter-species molar ratios in the NAPL: nonlinear dissolution governed by Raoult’s Law and differential sorption during subsurface transport. An analytic solution for Raoult’s Law-governed dissolution is presented. Separately, it is shown how a variety of 1D analytic transport models for simple boundary conditions may be adapted to use arbitrary time-varying concentrations by use of some properties of Laguerre series. This is combined with the analytic solution so that Raoult’s Law-governed multicomponent NAPL dissolution may be employed as the boundary condition for analytic transport models. A new computer model implementing this technique in an environment of discrete, parallel fractures is presented, and its accuracy verified for specific conditions against an existing code. The new code is applied to a parametric study on the plume separation of PAH and phenolic compounds from the dissolution of creosote. Narrow fracture spacing as well as significant values of matrix organic carbon are seen as particularly conducive to separation of these types of plumes, which in some circumstances may be entirely disjoint. Concentration ratios downgradient are shown largely unrelated to concentration ratios at the source. Finally, a study of PCB speciation is undertaken in fractured rock with known parameters, for which a rigorous, least squares speciation approach is developed. Even at distances of 5 m from the source, given perfect information about the subsurface, it is found not possible to chemically fingerprint a source PCB mixture from a list of three absent a model of the weathering of the NAPL. Both the PCB and creosote studies demonstrate that forensic inference of source compositions from field data is unreliable and the need for coupled dissolution and transport models like the one developed here. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2012-09-25 21:43:29.04

La miniaturisation de circuits intégrés, les hautes fréquences de fonctionnement, la baisse des potentiels d'alimentation, les fortes densités d'intégration rendent les signaux numériques propagés sur les interconnexions très susceptibles à la dégradation voire à la corruption. En vue d’évaluer la compatibilité électromagnétique et l’intégrité du signal il est nécessaire de disposer dès les premières phases de développement de modèles précis de ces interconnexions pour les insérer dans les simulateurs temporels. Nos travaux s'inscrivent dans ce contexte et concernent plus particulièrement la modélisation comportementale des buffers et drivers de ligne de transmission. Ils ont abouti à une approche originale de modélisation notamment basée sur les séries de Volterra-Laguerre. Les modèles boites noires développés disposent d’une implémentation SPICE assez simple autorisant ainsi une très bonne portabilité. Ils sont faciles à identifier et disposent d’une complexité paramétrique permettant un gain important de temps de simulation vis-à-vis des modèles transistors des drivers. En outre les méthodes développées permettent une modélisation dynamique non linéaire plus précise du port de sortie, et une gestion plus générale des entrées autorisant notamment une très bonne prise en compte du régime de sur-cadencement ce que par exemple ne fait pas le standard IBIS. / Integrated circuits miniaturization, high operating frequencies, lower supply voltages, high-density integration make digital signals propagating on interconnects highly vulnerable to degradation. Assessing EMC and signal integrity in the early stages of the design flow requires accurate interconnect models allowing for efficient time-domain simulations. In this context, our work addressed the issue of behavioral modeling of transmission line buffers, and particularly that of drivers. The main result is an original modeling approach partially based on Volterra-Laguerre series. The black box models we developed have a fairly simple implementation in SPICE thus allowing a very good portability. They are easy to identify and have a parametric complexity allowing a large gain in simulation time with respect to transistor driver models. In addition, the developed methods allow a more accurate output port nonlinear dynamics modeling, and a more general management of inputs. A very good reproduction of driver behaviour in overclocking conditions provides a significant advantage over standard IBIS models.