Northwestern Mexico is characterized by different metallogenic provinces that are included along the Basin and Range, the Sierra Madre Occidental, and the Baja California geological provinces. With the purpose of contribute to the current understanding of the mineralizing processes, the present study focused on two important copper metallogenic provinces: the Cananea Porphyry District in Sonora, and the Sediment-hosted Stratiform Copper- and Mn-deposits in Baja California Sur. The U-Pb zircon ages from the mineralizing porphyries from Cananea district suggest a continued magmatic activity period of ~6 Ma. Also suggests a period of ~20 Ma for the entire magmatic activity in the district. The Re-Os molybdenite ages demonstrate five well-constrained mineralization events in the district; the main mineralization is constrained over a short period of time (~4 Ma). The new molybdenite age from the Pilar deposit documents the oldest mineralizing pulse, suggesting possibly the initiation of the Laramide mineralization in northern Sonora. A detailed study of Mariquita porphyry Cu and Lucy Cu-Mo deposits in the Cananea district was performed. Four hydrothermal stages were defined in Mariquita, whereas a single hydrothermal pulse characterizes Lucy. Emplacement depths between 1-1.2 km, and temperatures between 430-380ºC characterized the mineralization from Mariquita, whereas deeper emplacement depths and higher mineralization temperatures characterized Lucy. The stable isotope systematic and fluid inclusion data determined that the mineralizing fluids in Mariquita deposit are essentially magmatic during the earlier hydrothermal stages, whereas the last stage is the mixing between magmatic and winter meteoric-waters. The mineralizing fluids from Lucy deposit are magmatic in origin. A comprehensive study was performed in the Cu-Co-Zn-Mn ineralization of the Boléo District, and Mn-oxide mineralization along the eastern coast Baja California Sur. The REE and trace element in the Mn-oxides demonstrated the exhalative nature of the mineralizing hydrothermal fluids, and exclude the hydrogenous nature. The stable isotope systematic in ore and gangue minerals, along with the Cu-isotope data helped to decipher the nature of mineralizing and non-mineralizing fluids. The application of Pb, Sr and Re-Os isotope systems was applied to constrain the nature of the fluids involved during the mineralization processes and that the metal sources.

In the Basin and Range province of southwestern North America, Oligocene and Miocene normal faults are superimposed upon the Late Cretaceous-early Tertiary magmatic arc. This study examines tilted fault blocks containing dismembered pieces of porphyry systems, including pieces below and peripheral to ore bodies, that are exposed at the modern surface. Features in the magmatic-hydrothermal porphyry systems are used to place constraints on the style of extension in Arizona, and reconstructions of extension are used to examine the deep and peripheral portions of porphyry systems to provide a more complete understanding of porphyry systems as a whole. The Eagle Pass, Tea Cup, and Sheep Mountain porphyry systems of Arizona are examined in this study. In all the study areas, previous interpretations of the style of extension involved strongly listric normal faults. However, similar amounts of tilting observed in hanging wall and footwall rocks, as well as structure contour maps of fault planes, require that down dip curvature on faults was minimal (<1°/km. Instead, extension is shown here to have occurred as sets of nearly planar, "domino-style" normal faults were superimposed upon one another, including in the Pinaleño metamorphic core complex. Reconstructions of Tertiary extension reveal that sodic (-calcic) alteration is occurs 2-4 km peripheral to, and greisen alteration is found structurally below and overlapping with, potassic alteration. In addition, a preliminary reconstruction of extension across the Laramide magmatic arc reveals that the geometry, as revealed by known porphyry systems, is of similar scale to that of other magmatic arcs. These results help further the debate surrounding competing models of continental extension, and combine with previous work to provide a more complete understanding of the geometries of Arizona porphyry systems at the district and arc scale.

In order to improve our understanding of poorly studied Mexican Porphyry Copper Deposits in the SW regional metallogenetic province, a detailed study of the hydrothermal fluid evolution of La Caridad porphyry copper-molybdenum deposit, and its connection to a high sulfidation epithermal deposit, was performed using oxygen, hydrogen and sulfur stable isotopes combined with fluid inclusion studies. In addition, UPb and Re-Os geochronology from La Caridad, Milpillas and El Arco porphyry deposit were performed to constrain the timing of mineralization and magmatism in northwest Mexico. Uranium-lead zircon ages from La Caridad suggest a short period of magmatism, between 55.5 and 53.0 Ma. Re-Os molybdenite ages from potassic and phyllic hydrothermal veins yielded identical ages within error, 53.6 ± 0.3 Ma and 53.8 ± 0.3 Ma, respectively. Four stages of hypogene alteration and mineralization are recognized at La Caridad porphyry copper deposit. The isotopic composition of the water in equilibrium with hydrothermal alteration minerals is consistent with highly evaporated lacustrine waters mixed with magmatic waters or vapor separated from magmatic fluids, however, sulfur isotopes and fluid inclusions data support the lacustrine-magmatic water hypothesis. Milpillas porphyry copper deposit in the Cananea Mining District, yielded a crystallization age of 63.9 ± 1.3 Ma. Two Re-Os molybdenite ages yielded an identical age of 63.1 ± 0.4 Ma, Suggesting a restricted period of mineralization. Re-Os data indicate that mineralization in Cananea District, spanned ~4 m.y. in three discrete pulses at ~59 Ma, ~61 Ma and ~63Ma. El Arco porphyry copper deposit, Baja California, Mexico, yielded a Middle Jurassic crystallization age (U-Pb) of 164.7 ± 6.7 Ma and a Re-Os mineralization age of 164.1 ± 0.4 Ma and not ~100 Ma as previously determinated. Porphyry copper deposits in Mexico range in age from 164 Ma to 54 Ma and the mineralization in Sonora state occurred in two different periods, but magmatism overlaps in space and time.

xviii, 177 p. : ill., maps. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / This dissertation explores several important consequences of H 2 O-rich fluids in magmatic and ore-forming systems within continental arc crust. North Sister, a stratovolcano in the Oregon High Cascades, provides a window into magma generation processes in the deep crust. Eruption of a remarkably limited basaltic andesite composition over the lifespan of this volcano may reflect last equilibration of mantle derived magma within a deep crustal hot zone. High pressure, water-undersaturated phase equilibrium experiments show that an anhydrous, augite-rich gabbro at ∼12 kbar (40 km depth) and ∼ 1175°C is the most probable lithology with which North Sister basaltic andesite with ∼3.5 wt% H 2 O last equilibrated within the deep crust before erupting. While magma often erupts at the planets surface as at North Sister, a greater volume never reaches the surface and solidifies within the upper crust. Exsolution of magmatic fluids is an inevitable consequence of crystallization of hydrous crustal magmas. The fate of these fluids is the focus of the remainder of this dissertation. Modeling of CO 2 and H 2 O variations during crystallization of granitic magma reveals that exsolution of a large mass of fluid occurs only after CO 2 is largely degassed, creating ideal conditions for hydrofracturing and formation of porphyry copper deposits. CO 2 and H 2 O solubility relations suggest that H 2 O-rich magma was required to produce the porphyry-Cu-Mo deposit at Butte, Montana, which may explain its distinctively deep generation. Electron microprobe analyses of Ti in quartz and Zr in rutile in samples from Butte yield porphyry magma temperatures (630-770°C) that overlap substantially with hydrothermal vein temperatures (<430-750°C). Veins display large temperature ranges (50-250°C) that signify variable degrees of cooling of hot magmatic fluids upon contact with cooler wall rock during vein growth. Modeling of Ti diffusion in quartz suggests that individual dikes and veins likely cooled over short timescales (10s-1000s years), indicating that porphyry systems may evolve by episodic magmatic fluid injections with discrete thermal spikes. Modeling of Ti diffusion in quartz combined with electron backscatter diffraction maps show that small hydrothermal quartz veins likely formed by epitaxial growth. This dissertation includes co-authored material both previously published and in preparation for submission. / Committee in charge: A. Dana Johnston, Chairperson, Geological Sciences; Mark Reed, Member, Geological Sciences; Paul Wallace, Member, Geological Sciences; Richard P. Taylor, Outside Member, Physics

Porphyry copper deposits represent one of the largest copper reserves on Earth. They typically contain large, low-grade reserves of primary ore and higher-grade, supergene enrichment blankets of sulfide and oxide ores. Understanding the mineralogy of porphyry copper ores and ores related to porphyry copper systems is exceedingly important for several reasons, foremost of which are the information provided by ore mineral parageneses, assemblages, and mineral chemistry on evolution of these magmatic-hydrothermal systems, and information on mineral processing characteristics of the ores. The focus of this work is to better understand the mineralogy of supergene copper sulfides in porphyry copper systems and hypogene base metal lodes related to porphyry copper systems, and use this mineralogical knowledge to improve our understanding of the processes responsible for ore formation. The objectives of this study are accomplished by two means: focusing on the crystallography and crystal chemistry of minerals, and then applying this mineralogical knowledge to a supergene sulfide enrichment blanket and hypogene massive sulfides from base metal lodes in southeastern Arizona. The discovery of a new mineral, natropalermoite, NaSr2Al4(PO4)4(OH)4, provided the opportunity to use single-crystal X-ray diffraction to solve a crystal structure, and electron-probe microanalysis (EPMA) to study the crystal chemistry of natropalermoite and how the accommodation of Na in the structure changes lengthens the unit cell along [010] and shortens it along [100] and [001] compared to its lithium analogue, palermoite. Solution of the crystal structure of the mineral nickelskutterudite, (Ni,Co,Fe)As3, allowed for the investigation of anion deficiency in minerals of the skutterudite group, a problem whose solution has eluded researchers for nearly 100 years. Two skutterudite (CoAs3) and two nickelskutterudite samples were analyzed using single-crystal X-ray diffraction, EPMA, and procrystal electron density. The results showed fully-occupied anion sites and a cation surplus, which was accommodated in the icosahedral site, proving that minerals of the skutterudite group are not anion deficient. This mineralogical knowledge was applied to the supergene enrichment blanket in the Western Copper section of the Morenci mine, Greenlee County, and hypogene massive sulfide deposits associated with a porphyry copper deposit at Bisbee, Cochise County, Arizona. This is one of very few studies of supergene sulfide blankets ever completed. One drill hole through the supergene blanket at Western Copper was examined using ore microscopy and EPMA. Results showed dominant (Cu+Fe):S ratios of 1.80 ± 0.05, 1.92 ± 0.03, and 1.10 ± 0.10, with higher (Cu+Fe):S dominant high in the blanket and low ratios dominant near the base of the blanket. These values were interpreted to be controlled by activity of Cu2+, Fe2+, and Fe3+ in solution. Massive sulfide deposits at Bisbee were investigated using ore microscopy and EPMA in order to correct the previous conflicting reports of the mineralogy and paragenesis of this famous district and interpret constraints on conditions of ore-forming fluids. Results show four types of ore: chalcopyrite-rich with hematite and/or pyrite, bornite-rich, chalcocite-rich, and a Zn-Pb association. Chalcopyrite-rich ores formed first, followed by bornite-rich and chalcocite-rich ores. All ores were formed at relatively shallow depths from oxidized, moderately sulfur-rich fluids; early fluids were higher temperature and later fluids were lower temperature and considerably more sulfidized. Zinc-lead ores formed early and were continuously dissolved and reprecipitated distal to Cu-mineralization. These patterns are similar to many other base-metal lode districts worldwide, however Bisbee contains more Zn-Pb ore than other districts with hematite-containing ores and less than those without hematite.

Silicate melt inclusions are ubiquitous in quartz phenocrysts, yet there are few studies of such inclusions from porphyry copper systems. A melt inclusion forms when magma is trapped in a growing phenocryst. If a phenocryst is able to preserve the original parent magma, then accurate information can be obtained for ancient volcanic systems. In recent igneous systems, melt inclusions are commonly preserved as optically clear homogeneous glass representative of magma stored at depth before eruption. Melt inclusions are difficult to recognize in quartz phenocrysts from porphyry copper system because they are crystalline and hidden by exsolved magmatic volatiles. The inclusions range in size from less than 5 to over 150 μm. In order to evaluate the magmatic contribution to economic mineralization, we conducted three separate studies to determine whether or not crystallized melt inclusions preserve representative samples of magma. The first study modeled the phase relationships that occur during equilibrium crystallization and melting of haplogranite magma trapped in quartz. Results from the model are similar to observations made during the heating of crystallized melt inclusions from porphyry copper systems. It is necessary to re-melt the crystal and volatile phases before chemical analysis. Micro-explosions caused by heating resulted in the loss of important chemical components. Our second study evaluated several microthermometric heating procedures using synthetic melt inclusions trapped at conditions similar to those inferred for porphyry copper systems. A synthetic hydrous melt was saturated with saline hydrothermal solutions allowing both melt and aqueous fluids to be trapped in quartz. Based on microthermometric measurements from these coeval melt and aqueous fluid inclusions we were able to predict the known trapping temperature and pressure of formation. This technique can be applied to natural samples to constrain trapping pressures and temperatures. It was found that slower heating rates could be used to avoid overheating and that heating under a confining pressure greatly minimizes the decrepitation of inclusions. The third study examined the copper concentrations in melt inclusions from the Red Mountain, Arizona porphyry copper system. Older andesite magma contains pyroxene with melt inclusions of higher copper concentrations compared to melt inclusions in quartz from quartz latite. The higher water concentrations in crystallized melt inclusions in the quartz, and abundant aqueous fluid inclusions indicates that the exsolution of water from the magma occurred prior to the trapping of melt inclusions in quartz. The lower water concentrations and the absence of aqueous fluid inclusions indicates that the andesite never reached the stage of water exsolution. The results obtained here are consistent with models that suggest that copper is extracted from the melt by saline magmatic fluids, producing a metal-charged hydrothermal solution and leaving behind a metal-depleted melt and serves to identify the potential contribution of melt inclusion studies to constrain the origin of ore metals in porphyry copper deposits. / Ph. D.

Magmatic-hydrothermal systems typically have vertical extents of several hundred<br />meters and their geochemical characteristics (e.g. mineral assemblages) vary considerably<br />over that vertical extent. As a consequence the expression in outcrop varies depending on<br />the level of erosion. Therefore understanding the geochemical zonation of magmatic-hydrothermal<br />ore deposits opens the possibility to detect deep magmatic-hydrothermal<br />systems, and to assess qualitatively the degree of erosion that has taken place in the area<br />and at which level the mineralization may occur. This dissertation presents the<br />characterization of two shallow hydrothermal systems and their potential relations with<br />deeper magmatic-hydrothermal systems. In addition, this dissertation develops the<br />equations to directly interpret thermometric data from the fluid inclusion type dominant in<br />one of those deposits (fluid inclusions that homogenize by halite disappearance).<br />Red Mountain, AZ is a porphyry copper system with a well-preserved lithocap<br />providing an ideal candidate to characterize the shallow expression of porphyry copper<br />systems in the southwestern US. The distribution of fluid inclusions, alteration mineralogy<br />and grade indicate that the intrusive responsible for the mineralization was only partially<br />intercepted during the exploration program and that one single magmatic event was likely<br />responsible for the mineralization detected. Fluid inclusion types and clay minerals are<br />systematically distributed within the deposit. The fluid responsible for the shallow<br />hypogene mineralization was a low pH-intermediate temperature-low density fluid while a<br />high salinity fluid was responsible for deep mineralization.<br />Wutong is a Pb-Zn-Ag deposit in the Nanling belt (southeast China). The combination<br />of fluid inclusion and mineral thermometry indicates that the Wutong deposit formed at<br />relatively low pressures. The age and isotopic composition of the mineralization indicates<br />that the deposit formed during the Cretaceous from crustal derived fluids. The occurrence<br />of a shallow magmatic-hydrothermal system of Cretaceous age in this region suggests that<br />Cretaceous intrusions, despite not outcropping very commonly in this particular region may<br />occur at deeper levels. / Ph. D.

The geology, petrology and geochemistry of Catface porphyry Cu (Mo-Au) deposit, located on the west coast of Vancouver Island are examined in detail. Detailed core logging and sampling was carried out to characterize the geometry and identity of different intrusive phases and alteration styles prevalent during the emplacement and formation of the deposit, as well as their geochemical affinity. Early- and late-stage potassic alteration is identified, as well as main-stage sodic-calcic and calcic-sodic alteration. Four distinct Paleogene intrusive phases vary from quartz diorite to granodiorite in composition. The rocks are broadly calc-alkaline, weakly peraluminous to moderately metaluminous, and have typical arc geochemical affinity. The timing of emplacement and mineralization is constrained by U-Pb and Re-Os geochronology at 40.4-41.4 Ma and 40.9 ±0.2 Ma, respectively. All four Paleogene Catface intrusive phases were emplaced close in time with a direct temporal correlation to mineralization. The chalcopyrite- and pyrite-bearing miarolitic cavities in the Halo Porphyry intrusive, combined with U-Pb and Re-Os dates suggest this intrusive phase is the most likely source of mineralizing fluids. The intrusions were emplaced at depths of less four kilometers in the crust, as evidenced by the presence of miarolitic cavities and confirmed through amphibole-plagioclase thermobarometry, which record conditions of 615–700 °C and <200 MPa. The lack of primary anhydrite and hematite, and the presence of pyrrhotite in the ore system indicate a reduced magmatic-hydrothermal event. The SO3 contents in apatites are <450 ppm, indicative of a degassed and/or sulphate-free (reduced) magma. The assemblage K-feldspar-quartz-biotite-ilmenite yields oxygen fugacities (fO2) which are 0.5 to 3.0 log units below the quartz-fayalite-magnetite (QFM) buffer at an assumed pressure of 300 MPa; orders of magnitude more reduced than typical porphyry deposits. Parental magmas to the Catface deposit were either derived from intrinsically-reduced mantle, or more typical oxidized arc magma that was subsequently reduced during ascent and emplacement. Further isotopic work is required to determine which process contributed to the reduction of these magmas in an arc setting. Nevertheless, recognition of reduced porphyry-related magmatism on west-central Vancouver Island is of similar age to that of North Fork (~36.8-38.9 Ma) deposit in Washington suggesting a consanguinity of reduced magmatism with the Paleogene Cascade arc. / Graduate

Late-stage fissure-filling ore at the world class Bingham Canyon, Utah, porphyry copper deposit has long been recognized, but poorly studied. Physical and chemical characterization of the Pb-Zn-Cu-Ag-Au mineralized fissures in the porphyry-epithermal transition zone provides insight into the origin, timing, and controls of ore deposition. These sheared sulfide-rich fissures are dominated by pyrite and multiple generations of quartz, with lesser amounts of other sulfides and gangue minerals. Au (0.27 to 4.61 ppm) provides the most value to the ore in the transition zone. Host rocks include Eocene monzonite and Paleozoic limestone and quartzite"”all of which can contain economic ore bodies. Associated alteration is predominantly sericitic and argillic. Mineralization into the wall rocks is restricted, not exceeding 1.5 m from the fissure margins. Mineral assemblages vary with distance from the center of the main Cu-Mo deposit and the modal abundances are dependent on host rock. The appearance of both galena and sphalerite (and tennantite to an extent) mark the transition from a porphyry to an epithermal environment. This is accompanied by an increased concentration of chalcophile trace elements in sulfides as determined by EMPA and LA-ICP-MS. Significant hosts of Ag include galena and tennantite, while Cu is hosted primarily in chalcopyrite, tennantite, and sphalerite. Gold does not appear to be hosted in solid solution, but may be focused along fractures or inclusions in pyrite. δ3434S values of fissure pyrite has a narrow range (+2.3 to 3.4‰), while δ18O of quartz is more variable and high (+11.5 to 14.0‰) relative to typical hydrothermal quartz. This can be explained by increased fractionation at lower temperatures in the magmatic fluids, which could have additionally mixed with exchanged 18O-rich meteoric water. Ore grades improve with distance from the center of the deposit; however, this is accompanied by higher concentrations of elements (Pb, As, Bi, etc.) undesirable for downstream processing. The mineralized fissures were created sequentially throughout the formation of the deposit. Initial joints probably formed as a result of the intrusion of a barren equigranular monzonite. The NE orientation of the joints was controlled by the regional stress field, which is more apparent distal to the center of the deposit. A quartz monzonite porphyry then intruded, dilating the joints to allow precipitation of quartz and then pyrite during the Cu-Au-stage of mineralization in the main ore body. After dike-like intrusions of latite porphyry and quartz latite porphyry intruded, galena, sphalerite, and pyrite precipitated to form the Pb-Zn-Ag mineralization. This was followed by late precipitation of chalcopyrite and tennantite (and likely Au mineralization).

The Río Blanco–Los Bronces (Chile) is one of the richest endowed porphyry copper-molybdenum districts worldwide, where about 20% of the known mineralization is hosted by tourmaline-cemented hydrothermal breccia. This work seeks: (1) to find a relationship between tourmaline chemical and/or isotopic composition and the degree of mineralization in the breccia, (2) to constrain the source of the mineralizing fluid in the breccia, and (3) to determine of the composition and age of intrusive units in three new exploration projects and correlate them with the known intrusive rocks of the mine areas. Tourmaline from mineralized and barren breccias has similar boron isotopic compositions but differences in Mg/(Mg+Fe) ratios, Al-contents and Al-Fe correlation, which may have exploration value. Boron and sulfur isotopes results are consistent with a magmatic source of hydrothermal fluids. Results of whole rock geochemistry and U-Pb and 40Ar/39Ar geochronology of intrusive units, breccia and late-stage veins are combined with previous U-Pb, Ar/Ar and Re-Os ages to elucidate the magmatic and hydrothermal history of the district.:1 Introduction 1.1 Motivation of the study and statement of research questions 1.2 Scope of the study 2 Porphyry copper deposits (PCDs) 2.1 Introduction 2.1.1 Global copper inventory 2.1.2 Definition and classification of PCDs 2.2 Regional scale characteristics of PCDs 2.2.1 Tectonic setting 2.2.2 Space and time distribution 2.2.3 Porphyry stocks and their pluton and volcanic connections 2.2.4 Wall-rock Influence 2.3 Deposit-scale characteristics 2.3.1 Porphyry stocks and dikes 2.3.2 Hydrothermal breccia 2.3.3 Alteration-mineralization zoning 2.4 Processes of PCD formation 2.4.1 Arc magmatism 2.4.2 Magmatic volatiles 2.4.3 Genetic models 3 Regional setting of the study area 3.1 Tectono-magmatic setting 3.2 Metallogenic belts 4 Río Blanco – Los Bronces mining district 4.1 Mining history 4.2 District geology 4.2.1 Stratified rocks 4.2.2 Plutonic and hypabyssal intrusions 4.2.3 Structures 4.2.4 Alteration and mineralization 4.2.1 Geochronology database 5 Results 5.1 Plutonic units 5.1.1 Petrography 5.1.2 Whole rock (WR) geochemistry 5.1.3 Geochronology 5.2 Mineralization 5.2.1 Petrography 5.2.2 Tourmaline occurrence and composition 5.2.3 Sulfides and sulfates 6 Discussion 6.1 Time-space relationships of intrusion, brecciation and hydrothermal alteration 6.2 Stable isotope constraints on fluid source and evolution 6.2.1 Oxygen, hydrogen and sulfur isotopes 6.2.2 Boron isotopes 6.3 Tourmaline as a redox indicator and significance for exploration 7 Summary and conclusions 8 References Digital supplement Appendix (Methods) 9 Appendix Methods 9.1 Optical microscopy (OM) 9.2 Scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDS) 9.3 Whole rock chemical analysis 9.4 Electron microprobe analyses (EMPA) 9.5 Boron isotopes 9.6 Sulfur isotopes 9.7 40Ar/39Ar dating 9.8 Zircon separation and characterization 9.9 U-Pb zircon LA-ICP-MS dating 9.10 U-Pb zircon CA-ID-TIMS dating 9.11 Single zircon evaporation as screening method