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Author's School

Graduate School of Arts & Sciences

Author's Department/Program

Earth and Planetary Sciences


Jill Pasteris, Everett Shock, Ian Duncan, Robert Dymek, John Gleaves, John Bleeke


English (en)

Date of Award


Degree Type

Restricted Access Dissertation

Degree Name

Doctor of Philosophy (PhD)


The hydrothermal transport of platinum-group elements (PGE) was evaluated by integrating a petrologic study of a portion of the Duluth Complex, Minnesota, and a thermodynamic analysis of both PGE solubility in supercritical aqueous solutions and alteration of mafic intrusive rocks. Investigation of two drillcores (FHL-1 and FHL-2) from the basal zone of the southern Duluth Complex indicates multiple overprintings of hydrothermal alteration within these rocks. Primary mafic igneous silicates are replaced by hydrous phases such as amphibole, biotite, and chlorite. Earlier massive magmatic Fe-rich sulfides (pyrrhotite) are replaced by Cu-rich sulfides (chalcopyrite, cubanite). Cu-rich sulfides also occur as disseminated grains and veinlets in more intensely altered zones. Values of Cu/Ni and Pd/Ir covary in the less-altered upper section of FHL-1, but in the lower, highly-altered zone these element ratios vary inversely. The highest values of PGE in FHL-2 samples are found in an intensely hydrothermally altered zone immediately below a massive oxide horizon. Within the latter, coexisting spinels and ilmenite delineate a temperature-oxygen fugacity trajectory for fluid-rock reaction that extends from ~750ºC and 2 units below the value of the fayalite-magnetite-quartz buffer assemblage (i.e., FMQ-2) to ~350ºC and FMQ-9. This trend is more reduced than that for a PGE-rich oxide zone from the northern region. Development of a set of consistent thermodynamic data for Ru, Rh, Pd, and Pt minerals, aqueous ions, and aqueous chloride, hydroxide and sulfate complexes, combined with recent developments in theoretical geochemistry of supercritical aqueous solutions, has enabled quantitative evaluation of the solubility and transport of PGE in NaCl solutions to 1000ºC and 5 kbar. Solubilities are strong functions of pH, oxygen fugacity, temperature, and total chloride concentration. Theoretical investigation of supercritical alteration of troctolite, norite, and olivine gabbro indicates that at high temperatures and pressures (500º to 700ºC and 2 kbar) fluid pH becomes more alkaline and oxygen fugacity decreases during fluid/rock reaction. For these conditions, calculation of PGE solubility in a 3.0 m NaCl solution indicates that this process could produce a 1 ppm Pd deposit with steeply fractionated PGE patterns.


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