Abstract
Ph.D. (Chemistry)
The main objective of this study was to develop sample preparation methods based on separation and preconcentration of trace metals in organic matrices (alcohols, diesel and gasoline). The presence of metals in organic matrices is undesirable, unless they are used as additives. Therefore, it is important to control and monitor their concentrations in fuel and petrochemical products as they tend to affect the quality of these products. Solid phase extraction (SPE), solid phase microextraction (SPME) and hollow fiber-liquid phase microextraction (HF-LPME were used for separation and preconcentration of Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Ti, V and Zn prior to their inductively coupled plasma optical emission/mass spectrometric (ICP OES/-MS) determination.
For solid phase extraction, the exchange efficiencies of different commercial ion exchange resins, namely Dowex 50W-x8, Dowex 1-x8, Dowex MAC-3 and Chelex 100, for preconcentration of metal ions in alcohol and fuel samples, were investigated. The results obtained indicated that Dowex 50W-x8 was suitable for simultaneous preconcentration of cations such as Cd, Co, Ni, Cu, Fe, Mn and Zn, among other metals while Dowex 1-x8 was suitable for metal ions that exists in more than one oxidation states, namely, As, Cr, Mo, Sb and V. Chelex-100 and Dowex MAC-3 were found to be selective to a limited number of target metal analytes. For further applications, Dowex 50W-x8 and Dowex 1-x8 were employed. Furthermore, the applicability of synthetic adsorbents such as nanometer-sized alumina and functionalized cellulose nanofibers for preconcentration of trace metals in gasoline samples, was investigated. Nanometer-sized alumina sorbent was found to be suitable for simultaneous separation and preconcentration of Co, Cr, Mn, Ni and Ti. Functionalized cellulose nanofibers on the hand, were suitable for simultaneous preconcentration of Cd, Cu, Fe, Pb and Zn. The optimization of the experimental parameters was achieved by both univariate and multivariate procedure.
The second preconcentration technique was solid phase microextraction which was also used for extraction and enrichment of metal ions in diesel samples using two approaches of the SPME method. The first approach was hollow fiber-solid phase microextraction (HF–SPME) method using fiber-supported sol-gel combined with a cation exchange resin (Dowex 50W-x8). This method showed satisfactory results for the preconcentration of Cd, Cu, Fe, Pb and Zn in diesel and gasoline samples. The second approach was based on membrane solid phase microextraction (MSPME) using titania-alumina hollow fiber. The MSPME method applied was used for extraction and
preconcentration of trace amounts of Co, Cr, Mo, Ni, Sb and V in liquid fuel samples. Multivariate techniques were used for optimization of experimental parameters for both approaches.
The last preconcentration technique that was developed was hollow fiber- liquid phase microextraction (HF-LPME). In this method fuel samples were first digested before being subjected to HF-LPME system. Ammonium pyrrolidine dithiocarbamate (APDC) and [C6MIM][PF6] ionic liquid were both used as chelating agent and acceptor phase, respectively. Two level factorial and central composite designs were used for multivariate optimization of experimental parameters. Satisfactory results were obtained for extraction and preconcentration of Ag, Al, As, Mn and Ti.