Diffusive Gradients in Thin Films for Inorganic Arsenic Speciation and Electrothermal Atomic Absorption Spectrometry with a Coupled Microcolumn for Trace Metal Speciation
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
This thesis is directed towards the development of the diffusive gradients in thin films (DGT) technique for the measurement of total dissolved As, and for As speciation measurements. In addition, a preliminary investigation of a novel laboratory-based method for measuring labile metal species was carried out; this method involved the coupling of a microcolumn of adsorbent with a standard electrothermal atomic absorption spectrometer. An iron-oxide adsorbent was utilized for As measurements by DGT. The diffusion coefficients of inorganic Asv and AsIII> were measured through the polyacrylamide diffusive gel using both a diffusion cell and DGT devices. A variety of factors that may affect the measurement of total As by DGT were investigated. These factors, which included pH, anions, cations, fulvic acid, FeIII-fulvic acid complexes, and colloidal Fe, may affect the adsorption of the As species to the iron-oxide, or may affect the diffusion coefficients of the individual As species. The DGT method was further developed to selectively accumulate the AsIII species in the presence of Asv. This was achieved by the placement of a negatively charged Nafion membrane at the front of the DGT device which slowed the diffusion of the negatively charged Asv species (H₂AsO₄₂ ⁻) considerably, relative to the uncharged AsIII species (H₃AsO₃). The effect that pH, anions, and cations may have on the selective accumulation of AsIII, in the presence of Asv, was investigated. DGT devices without a Nafion membrane and with a Nafion membrane were deployed in natural waters to determine the total inorganic As and AsIII> concentrations, and to evaluate its performance. A preliminary investigation of the coupling of a microcolumn of Chelex-100 resin with a standard electrothermal atomic absorption spectrometer was undertaken to establish its value as a laboratory-based speciation method. This involved the examination of various microcolumn materials to accommodate the Chelex-100 resin, and finding an appropriate buffer that could be used to buffer the Chelex-100 resin without interfering with the ETAAS measurement. Furthermore, factors that may affect the uptake of metal by the Chelex-100 resin, such as concentration of buffer in solution, ionic strength, and conditioning of the Chelex-100 resin, were investigated.