The technique of extraction with supercritical carbon dioxide (SC-CO$ sb2$), which is now used routinely for the recovery of non-polar analytes from a variety of liquid and semipermeable solid media, was extended to the efficient extraction of metal ions. Measurements of the solubilities in SC-CO$ sb2$ corroborated the hypothesis that the non-polar character of a series of tetraalkylammoniun dialkyldithiocarbamates ion pairs was influenced (i) primarily by the chain length of the alkyl substituent(s) on the carbamate nitrogen and (ii) to a lesser extent, by the chain length of the alkyl substituent(s) on the ammonium counter ion. In operation, analyte metal(s) in aqueous medium was derivatized by in situ complexation with the dithiocarbamate complexing reagent and the product complex(es) was partitioned into the SC-CO$ sb2$ mobile phase then purged from the extractor by replacing the headspace with fresh solvent. A novel silica flame-in-tube interface was developed for the sensitive detection, by atomic absorption spectrometry (AAS), of As, Cd, Cu, Mn, Pb, Se, or Zn in SC-CO$ sb2$ extractor eluate. For different analyte elements, the limits of detection (LODs) ranged from sub-nanogram to low picogram if standard was flow injected into the mobile phase. These sensitivities permitted differences in the rates of mobilization of different forms of the analyte metal from various media to be explored as a technique for probing the interaction of the analyte metal with the matrix. A portion of the Zn burden in fresh bovine liver was mobilized rapidly in the absence of complexing agent and the remainder was solubilized more rapidly than the Zn in a freeze-dried reference material of this tissue. The nebulizer assembly of a conventional flame-AAS was modified to extend the range of metals amenable to on-line detection. Supplemental heating of the inlet air to 200$ sp circ$C resulted in an on line detector which provided approximately a ten-fold improvement over convention
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.39890 |
| Date | January 1995 |
| Creators | Wang, Jin, 1954- |
| Contributors | Marshall, William D. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Food Science and Agricultural Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001480204, proquestno: NN08165, Theses scanned by UMI/ProQuest. |
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