Development of solid phase extraction flow-based tools for environmental monitoring

Abstract

The development of new analytical tools can be considered a non-stop challenge due to the constant search for new improved features and also to the emerging environmental contaminants. Flow-based methodologies stand out in contributing for this analytical challenge, providing the automation and miniaturization of the analysis including sample pre-treatment. This thesis was developed based on two major objectives, one of them was to develop new miniaturized and automated analytical tools based on flow analysis for environmental monitoring. When designing new methodologies, another essential objective was to simplify sample preparation by coupling these techniques, based on solid phase extraction (SPE), within the developed flow-based system. The developed methodologies were optimized based on the same principles: minimize the use of reagent, make greener choices of the reagents, minimize the effluent production, lower the limits of detection and quantification, simplify and minimize sample/reagent handling. The use of the in-line SPE strategy showed to bring advantageous features to the analytical method (lowering limits of detection and quantification). The in-line SPE was achieved by using commercial resins (NTA and Chelex 100) and also a lab-made polymer inclusion membrane (Chapter 3). A biparametric sequential injection system for the determination of copper and zinc in water and soil leachates was developed (Chapter 3). The strategy was to use a non-specific coulour reagent (4-(2-Pyridylazo)resorcinol – PAR) and explore the use of two different sorbent materials to selectively separate the two different metal ions in the same manifold. A polymer inclusion membrane (PIM) and the commercial resin Chelex 100 were the chosen materials to selectively retain zinc and copper, respectively. It was the first time that a PIM was used with this purpose in a flow system. A spectrophotometric method for iron quantification using a newly designed chromogenic chelator was developed (Chapter 4). This low toxicity iron chelator was a specially designed 3-hydroxy-4-pyrydinone functionalized with ethers. Furthermore, this reagent demonstrated to display high affinity and specificity for iron ions. With the main objective of quantifying iron in a variety of water samples (fresh and marine water) a strategy including SPE was added to the manifold. By using an in-line SPE process, resorting to a NTA resin column coupled to the flow system, sample matrix clean-up and also the enrichment of the analyte was achieved. A method for the screening of biogenic amines in waters was developed (Chapter 5). The system was divided in two analytical parts. The first one was devoted to the pre-concentration of the analyte using a column packed with Chelex 100; the second was the derivatization of the biogenic amines using fluorescamine for the fluorescent detection of the analyte. This method intended to be a suitable and ease to operate system to obtain real-time information about biogenic amines content in water. A flow injection system for the spectrophotometric determination of the total zinc content in plant digests was developed (Chapter 6). By using a NTA resin column, zinc pre-concentration and the removal of possible interferences was accomplished. A specially designed multi-reflection flow cell coupled with a light emitting diode was the chosen detection system for the spectrophotometric determination of zinc using Zincon as colour reagent. The physical configuration of the flow cell contributed to improve the limit of detection and minimize refractive index gradients produced by the mixture of the reagents.

Date of Award	10 Jul 2020
Original language	English
Awarding Institution	Universidade Católica Portuguesa
Supervisor	António O. S. S. Rangel (Supervisor) & Ildikó Vargáné Tóth (Co-Supervisor)