Development of chemical separation processes for the treatment and monitoring of metallic cations and oxoanions in polluted waters

The chemical contamination of natural waters is a global problem with a worldwide impact. Considering the relevance of this problem, this thesis is intended, on one hand, to develop different separation/preconcentration techniques based on membranes ability to permeate anions for the transport of toxic oxyanions of chromium(VI) and arsenic contained in aqueous matrices. In particular, we have investigated supported liquid membranes and polymer inclusion membranes, both of which contain the commercial quaternary ammonium salt Aliquat 336 as a carrier, as well as commercial anion exchange membranes. On the other hand, we have focused on the development of chemical sensors to facilitate the monitoring of several metals from different aqueous matrices. Thus, a selective optical sensor for Cr(VI) based on polymeric membranes containing Aliquat 336 as an ionophore has been designed. Additionally, mercury-based screen-printed electrodes have been evaluated for for cadmium, lead, copper and zinc detection.

DAI-DEPUR: an integrated and distributed architecture for wastewater treatment plants supervision

The activated sludge process - the main biological technology usually applied to wastewater treatment plants (WWTP) - directly depends on live beings (microorganisms), and therefore on unforeseen changes produced by them. It could be possible to get a good plant operation if the supervisory control system is able to react to the changes and deviations in the system and can take the necessary actions to restore the system’s performance. These decisions are often based both on physical, chemical, microbiological principles (suitable to be modelled by conventional control algorithms) and on some knowledge (suitable to be modelled by knowledge-based systems). But one of the key problems in knowledge-based control systems design is the development of an architecture able to manage efficiently the different elements of the process (integrated architecture), to learn from previous cases (spec@c experimental knowledge) and to acquire the domain knowledge (general expert knowledge). These problems increase when the process belongs to an ill-structured domain and is composed of several complex operational units. Therefore, an integrated and distributed AI architecture seems to be a good choice. This paper proposes an integrated and distributed supervisory multi-level architecture for the supervision of WWTP, that overcomes some of the main troubles of classical control techniques and those of knowledge-based systems applied to real world systems

Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence

Treatment of nonlinear optical properties due to large amplitude anharmonic vibrational motions: umbrella motion in NH3

A general reduced dimensionality finite field nuclear relaxation method for calculating vibrational nonlinear optical properties of molecules with large contributions due to anharmonic motions is introduced. In an initial application to the umbrella (inversion) motion of NH3 it is found that difficulties associated with a conventional single well treatment are overcome and that the particular definition of the inversion coordinate is not important. Future applications are described