Magmatic-hydrothermal ore deposits are formed in association with aqueous fluids that exsolve from hydrous silicate melts during ascent and crystallization. These fluids are invariably trapped as inclusions in vein-filling minerals associated with hydrothermal fluid flow, and their composition may be modeled based on the H₂O-NaCl system. Thus, if we know the pressure-volume-temperature-composition (PVTX) properties of H₂O-NaCl solutions, it is possible to interpret the PTX trapping conditions, which is important for understanding the processes leading to the generation of the hydrothermal system and ore mineralization. High salinity (> 26 wt. % NaCl) fluid inclusions contain liquid, vapor, and halite at room temperature, and are common in magmatic-hydrothermal ore deposits. These inclusions homogenize in one of three ways: A) halite disappearance (Tmhalite) followed by liquid-vapor homogenization (ThL-V), B) simultaneous ThL-V and Tmhalite, or C) ThL-V followed by Tmhalite. The PVTX properties of H₂O-NaCl solutions three phase (L+V+H) and liquid-vapor (L+V) phase boundaries are well constrained, allowing researchers to interpret the minimum trapping pressure of inclusion types A and B. However, data that describe the pressure at Tmhalite for inclusion type C are limited to a composition of 40 wt. % NaCl. To resolve this problem, the synthetic fluid inclusion technique was used to determine the relationship between homogenization temperature and minimum trapping pressure for inclusions that homogenize by mode C. These results allow researchers to interpret the minimum trapping pressure of these inclusions, and by extension the depth at which the inclusions formed. The temporal and spatial distribution of fluid inclusions formed in associated with porphyry copper mineralization has been predicted using a computer model. A simple geologic model of an epizonal intrusion was developed based on a Burnham-style model for porphyry systems and thermal models of the evolution of epizonal intrusions. The phase stability fields and fluid inclusion characteristics at any location and time were predicted based on PVTX properties of H₂O-NaCl solutions. These results provide vectors towards the center of a magmatic-hydrothermal system that allow explorationists to use fluid inclusion petrography to predict position with the overall porphyry environment when other indicators of position are absent. / Ph. D.

The system H₂O-CH₄ is found in a variety of geological environments in the earth’s crust, from sedimentary basins to low grade metamorphic terrains. Knowledge of the PressureVolume-Temperature-Composition (PVTX) properties of the H₂O-CH₄ system is necessary to understand the role that these fluids play in different geological environments. In this study the properties of the H₂O-CH₄ fluid system at elevated temperatures and pressures has been investigated experimentally to determine the PVTX properties of H₂O-CH₄ fluids in the P-T range equivalent to late diagenetic to low grade metamorphic environments, and XCH₄≤4mol%. A study has also been conducted to determine methane hydrate stability over the temperature range of -40~20°C. Synthetic fluid inclusions were employed in both studies as miniature autoclaves. Experimental data for the PVTX properties of H₂O-CH₄ fluids under late diagenetic to low grade metamorphic conditions was used to calculate the slopes of isoTh lines (the line connecting the P-T conditions of the inclusions at formation and at homogenization) at different PTX conditions. An empirical equation to describe the slope of iso-Th line as a function of homogenization temperature and fluid composition was developed. The equation is applicable to natural H₂O-CH₄ fluid inclusions up to 500°C and 3 kilobars, for fluid compositions ≤4 mol% CH₄. The Raman peak position of CH₄ gas is a function of the pressure and temperature. This relationship was used to determine the pressure along the methane hydrate stability curve in the H₂O-CH₄ system. The combined synthetic fluid inclusion, microthermometry and Raman spectroscopy method is a novel experimental approach to determine the P-T stability conditions of methane hydrates. The method is fast compared to conventional methods, and has the potential to be applied to study other gas hydrate systems. / Ph. D.

Phase equilibria and volumetric properties in the system water-sodium chloride-carbon dioxide were determined experimentally for pressures between about 1 to 6 kbar, temperatures of 300° to 800°C, and fluid compositions up to 40 wt% NaCl and 20 mol% carbon dioxide, both relative to water. This was accomplished by using the synthetic fluid inclusion technique in conjunction with conventional microthermometry, a hydrothermal diamond-anvil cell and Raman spectroscopy. At constant salinity, the high-pressure portion of the solvus migrates to higher pressures and temperatures with increasing carbon dioxide concentration. Immiscibility is possible in this ternary system over almost the entire range of crustal P-T conditions at salinities equal to or in excess of 20 wt% NaCl and carbon dioxide concentrations between about 30 and 70 mol% carbon dioxide. The dP/dT slopes of lines of equal homogenization temperature decrease nonlinearly with increasing homogenization temperature; at constant homogenization temperature, these slopes become steeper (higher) along pseudobinaries with addition of carbon dioxide and particularly with addition of sodium chloride. Up to concentrations of 20 wt% NaCl and 20 mol% carbon dioxide, a sharp rise in the critical temperature was observed with increasing salinity at a fixed water/carbon dioxide ratio. The critical point shifts rapidly towards higher pressures with increasing carbon dioxide concentration. Addition of carbon dioxide to an aqueous 40 wt% NaCl solution results in a slight elevation of the halite dissolution temperature under vapor-saturated conditions. A significant error can be associated with the calculation of molar volumes from measured densities of the carbonic phase of water-sodium chloride-carbon dioxide inclusions. To avoid such errors, phase diagrams were constructed based on the obtained lines of equal homogenization temperature for salinities between 6 and 40 wt% NaCl and carbon dioxide concentrations between 5 and 20 mol% relative to water. These diagrams are of direct applicability to the interpretation of natural fluid inclusions from a wide variety of geologic environments. / Ph. D.